86029-WO-PCT/DOW 86029 WO GAS PHASE POLYMERIZATION PROCESSES FOR MAKING ETHYLENE-BASED POLYMER HAVING ULTRA-HIGH MOLECULAR WEIGHT TAILING CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application claims the benefit of U.S. Provisional Application Serial No. 63/665,918 filed June 28, 2024, the contents of which are incorporated in their entirety herein. BACKGROUND [0002] Polyethylene is manufactured for a wide variety of articles. The polyethylene and polypropylene polymerization process can be varied in a number of respects to produce a wide variety of resultant polyethylene resins having different physical properties tha t render the various resins suitable for use in different applications. Polyethylene is produced via various catalyst systems. Selection of such catalyst systems used in the polymerization process of the polyethylene is an important factor contributing to the characteristics and properties of the polyethylene. BRIEF SUMMARY [0003] Despite previous research efforts in developing catalyst systems suitable for polyethylene polymerization, there is still a need to increase the efficiencies of catalyst systems to reduce their cost-in-use, particularly without compromising other critical properties, as well as developing new catalyst systems that produce polymers with improved attributes and performance. These polyethylene polymers may be utilized for a number of products including films, fibers, pipes, nonwoven and/or woven fabrics, extruded articles, and/or molded articles, among others. There is continued focus in the industry on developing new and improved materials and/or processes that may be utilized to form these polymers. Embodiments of the present disclosure meet this need by providing methods of making polyethylene in a gas phase polymerization, which utilize a catalyst system described herein to produce a polyethylene having advantageous polydispersity index as well as ultra-high molecular weight tailing, ultra-high Mz and/or broad Mz/Mw. Further embodiments
86029-WO-PCT/DOW 86029 WO accomplish the aforementioned advantageous properties while also maintaining low-to-no observed long-chain branching (LCB), or ≤ 0.01 long-chain branches per 1,000 carbons (LCBf). [0004] Embodiments of the present disclosure are directed to methods of making polyethylene comprising: polymerizing in a gas phase reactor ethylene monomer and optionally at least one C3 to C81-alkene comonomer and a catalyst system, thereby forming a polyethylene, the catalyst system comprising a procatalyst having a structure according to Formula (I):
[0005] where: M is a metal selected from titanium, zirconium, and hafnium, the metal having a formal oxidation state of +2, +3, or +4; each X is a monodentate or bidentate ligand independently selected from unsaturated (C2−C30)hydrocarbon, unsaturated (C2−C30)heterohydrocarbon, (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6-C30)aryl, (C3-C30)aryl, halogen, −N(RX)2, and −(CH2)wSi(RX)3, where w is 1 to 10 and each RX is independently selected from (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6-C30)aryl, and (C3-C30)heteroaryl; n is 1 or 2; Q is a monoanionic spectator ligand selected from (C1−C50)hydrocarbyl, (C1−C50)heterohydrocarbyl, (C5-C30)aryl, and (C3-C30)heteroaryl, wherein Q is different from each X; RY is a (C1−C30)hydrocarbyl or (C1−C30)heterohydrocarbyl; R1 is a (C1-C50)hydrocarbyl, (C1−C50)heterohydrocarbyl, (C6- C30)aryl, or (C3-C30)heteroaryl; each of R2 and R3 is independently selected from the group consisting of (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6-C30)aryl, (C3- C30)heteroaryl, −ORC, −Si(RC)3, −Ge(RC)3, halogen, and –H, wherein RC is independently selected from the group consisting of (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6-
86029-WO-PCT/DOW 86029 WO C30)aryl, (C3-C30)heteroaryl, and -H; and optionally, R2 and R3 are covalently linked to form an aromatic or non-aromatic ring. [0006] Additionally, the polyethylene has a polydispersity index (PDI=Mw/Mn) greater than 11, wherein Mw is weight averaged molecular weight and Mn is number averaged molecular weight as measured according to Gel Permeation Chromatography; and the polyethylene has a Mz/Mw ≥ 3.5, where Mz is defined as the z-average molecular weight. [0007] These and other embodiments are described in more detail in the Detailed Description. It is to be understood that both the foregoing general description and the following detailed description present embodiments of the presently disclosed technology, and are intended to provide an overview or framework for understanding the nature and character of the technology as it is claimed. BRIEF DESCRIPTION OF THE DRAWINGS [0008] FIG. 1 depicts a Gel Permeation Chromatography (GPC) plot for some example polymers produced using catalyst system S-1; [0009] FIG.2 depicts a GPC plot for some example polymers produced with catalyst system S-2; [0010] FIG.3 depicts a GPC plot for some example polymers produced with catalyst system S-3; and [0011] FIG. 4 depicts a GPC plot for some example polymers produced with catalyst systems S-1, S-2, and S-3. DETAILED DESCRIPTION [0012] Common abbreviations are listed below: [0013] R, Q, M, X and n: as defined above; Me : methyl; Et : ethyl; Ph : phenyl; Bn: benzyl; Mes: mesityl (2,4,6-trimethylphenyl); i-Pr : iso-propyl; t-Bu : tert-butyl; t-Oct : tert- octyl (2,4,4-trimethylpentan-2-yl); Tf : trifluoromethane sulfonate; : Et2O : diethyl ether; EtOH : ethanol; DCM or CH2Cl2 : dichloromethane; DME : dimethoxyethane; DIW :
86029-WO-PCT/DOW 86029 WO deionized water; C6D6 : deuterated benzene or benzene-d6 : CDCl3 : deuterated chloroform; Na2SO4 : sodium sulfate; MgSO4 : magnesium sulfate; HCl : hydrogen chloride; K2CO3: potassium carbonate; NaHCO3 : sodium bicarbonate; NH4Cl : ammonium chloride; Pd(Ph3)4 : tetrakis(triphenylphosphine)palladium(0); HfBn4 : hafnium(IV) tetrabenzyl; ZrCl4 : zirconium(IV) chloride; ZrBn4 : zirconium(IV) tetrabenzyl; IMesNH : 1,3-bis(2,4,6- trimethylphenyl)imidazol-2-ylidene; tBuNH : 1,3-di(tert-butyl)imidazol-2-ylidene; Cy3PNH: tricyclohexyl-phosphinimine; tBu3PN-SiMe3: 1,1,1-tri(tert-butyl)-N- trimethylsilyl-λ5-phosphanimine; CpZrBn3: cyclopentadienylzirconium(IV) tribenzyl; nBuCpZrBn3: n-butylcyclopentadienylzirconium(IV) tribenzyl; Cp*ZrBn3: pentamethylcyclopentadienylzirconium(IV) tribenzyl; MeCpZrBn3: methylcyclopentadienylzirconium(IV) tribenzyl; CpHfBn3: cyclopentadienylhafnium(IV) tribenzyl; MeCpHfBn3: methylcyclopentadienylhafnium(IV) tribenzyl ; IPrNZrBn3: 1,3- bis(2,6-diisopropylphenyl)imidazol-2-ylidenezirconium(IV) tribenzyl; tBuNHfBn3: 1,3- di(tert-butyl)imidazol-2-ylidenehafnium(IV) tribenzyl; tBuNZrBn3: 1,3-di(tert- butyl)imidazol-2-ylidenezirconium(IV) tribenzyl; (Me2N)TiCl3: dimethylamidotitanium(IV) trichloride (IMesN)TiCl3(HNMe2): 1,3-bis(2,4,6-trimethylphenyl)imidazol-2- ylidenetitanium(IV) trichloride dimethylamine adduct; (IMesN)TiMe3: 1,3-bis(2,4,6- trimethylphenyl)imidazol-2-ylidenetitanium(IV) trimethyl; Cy3PNZrBn3: tricyclohexyl- phosphinimideziconium(IV) tribenzyl; tBu3PNTiCl3 : tri(tert- butyl)phosphinimidetitanium(IV) trichloride; tBu3PNTiMe3 : tri(tert- butyl)phosphinimidetitanium(IV) trimethyl; N2 : nitrogen gas; PhMe: toluene; PPR : parallel pressure reactor; MAO : methylaluminoxane; MMAO : modified methylaluminoxane; GC : gas chromatography; LC : liquid chromatography; NMR : nuclear magnetic resonance; MS: mass spectrometry; mmol : millimoles; mL : milliliters; M : molar; min or mins: minutes; h or hrs : hours; d: days; rpm: revolution per minute. [0014] 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 “activating co-catalyst” and “activator” are interchangeable terms. [0015] The term “spectator ligand” refers to a ligand that occupies a coordination site on the metal center of a metal–ligand complex and influences the reactivity of the metal center,
86029-WO-PCT/DOW 86029 WO but remains bound and does not de-coordinate from the metal center during the course of polymerization. Spectator ligands are also referred to as “ancillary ligands” and are generally less basic or less easily protonated than ligands that de-coordinate from the metal center during polymerization. [0016] In this disclosure, a “heteroleptic” metal–ligand complex refers to a metal–ligand complex bearing a spectator ligand and one or more additional ligands that are the same or different from one another. At minimum, a heteroleptic complex contains both a spectator ligand and a ligand that participates in chemical reactions carried out by the metal–ligand complex, such as olefin polymerization, by de-coordinating from the metal center of the metal–ligand complex. [0017] The term “polymer” refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type. The generic term “polymer” thus embraces the term “homopolymer,” usually employed to refer to polymers prepared from only one type of monomer as well as “copolymer” which refers to polymers prepared from two or more different monomer types. [0018] “Polyethylene” or “ethylene-based polymer” refers to polymers comprising greater than 50% by weight derived from ethylene monomer. This includes polyethylene homopolymers or copolymers (meaning units derived from two or more monomer types). Common forms of polyethylene known in the art include Low-density polyethylene (LDPE); Linear Low-density polyethylene (LLDPE); Ultra Low-density polyethylene (ULDPE); Very Low-density polyethylene (VLDPE); single-site catalyzed Linear Low-density polyethylene, including both linear and substantially linear low-density resins (m-LLDPE); Medium Density Polyethylene (MDPE); and High Density Polyethylene (HDPE). [0019] The term “LDPE” may also be referred to as “high-pressure ethylene polymer” or “highly branched polyethylene” and is defined to mean that the polymer is partly or entirely homopolymerized or copolymerized in autoclave or tubular reactors at pressures above 14,500 psi (100 MPa) with the use of free-radical initiators, such as peroxides (see, for example, U.S. Patent No. 4,599,392, which is hereby incorporated by reference in its entirety). LDPE resins typically have a density in the range of 0.916 g/cm 3 to 0.930 g/cm3.
86029-WO-PCT/DOW 86029 WO [0020] The term “LLDPE,” includes resin made using Ziegler-Natta catalyst systems as well as resin made using single-site catalysts, including, but not limited to, bis-metallocene catalysts (sometimes referred to as “m-LLDPE”), phosphinimine, and constrained geometry catalysts, and resins made using post-metallocene, molecular catalysts, including, but not limited to, bis(biphenylphenoxy) catalysts (also referred to as polyvalent aryloxyether catalysts). LLDPE includes linear, substantially linear, or heterogeneous ethylene-based copolymers. LLDPEs contain less long chain branching than LDPEs and include the substantially linear ethylene polymers, which are further defined in U.S. Patent No. 5,272,236, U.S. Patent No. 5,278,272, U.S. Patent No. 5,582,923 and U.S. Patent No. 5,733,155 each of which are incorporated herein by reference in their entirety; the homogeneously branched linear ethylene polymer compositions such as those in U.S. Patent No. 3,645,992 which is incorporated herein by reference in its entirety; the heterogeneously branched ethylene polymers such as those prepared according to the process disclosed in U.S. Patent No. 4,076,698 which is incorporated herein by reference in its entirety; and blends thereof such as those disclosed in U.S. Patent No. 3,914,342 and U.S. Patent No. 5,854,045 which are incorporated herein by reference in their entirety. The LLDPE resins can be made via gas-phase, solution-phase, or slurry polymerization or any combination thereof, using any type of reactor or reactor configuration known in the art. [0021] The term “HDPE” generally refers to polyethylenes having densities greater than about 0.940 g/cm3 and up to about 0.970 g/cm3, which are generally prepared with Ziegler- Natta catalysts, chrome catalysts or single-site catalysts including, but not limited to, substituted mono- or bis-cyclopentadienyl catalysts (typically referred to as metallocene), constrained geometry catalysts, phosphinimine catalysts & polyvalent aryloxyether catalysts (typically referred to as bisphenyl phenoxy). [0022] The term “independently selected” followed by multiple options is used herein to indicate that the individual R groups appearing before the term, such as R 1, R2, R3, R4, R5, and RC can be identical or different, without dependency on the identity of any other group also appearing before the term (e.g., R1, R2, R3, R4, and R5 may all be substituted alkyls or R1 and R2 may be a substituted alkyl and R3 may 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
86029-WO-PCT/DOW 86029 WO having that name. These definitions are intended to supplement and illustrate, not preclude, the definitions known to those of skill in the art. [0023] When used to describe certain carbon atom-containing chemical groups, a parenthetical expression having the form “(Cx−Cy)” means that the unsubstituted form of the chemical group has from x carbon atoms to y carbon atoms, inclusive of x and y. For example, a (C1−C30)alkyl is an alkyl group having from 1 to 30 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups may be substituted by one or more substituents such as RS. An RS substituted 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 RS is 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. [0024] The term “substitution” means that at least one hydrogen atom (−H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., RS). The term “persubstitution” means that every hydrogen atom (H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., RS). The term “polysubstitution” means that at least two, but fewer than all, hydrogen atoms bonded to carbon atoms or heteroatoms of a corresponding unsubstituted compound or functional group are replaced by a substituent. The term “−H” means a hydrogen or hydrogen radical that is covalently bonded to another atom. When describing chemical structures of various compounds, “hydrogen” and “−H” are interchangeable, and unless clearly specified have identical meanings. [0025] The term “(C1−C30)hydrocarbyl” means a hydrocarbon radical of from 1 to 30 carbon atoms and the term “(C1−C30)hydrocarbylene” means a hydrocarbon diradical of from 1 to 30 carbon atoms, in which each hydrocarbon radical and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, straight chain or branched chain, cyclic (having three carbons or more, and including mono- and poly-cyclic, fused and non-fused polycyclic,
86029-WO-PCT/DOW 86029 WO and bicyclic) or acyclic, and substituted by one or more RS or unsubstituted. Examples of (C1−C30)hydrocarbyl are unsubstituted or substituted (C1−C30)alkyl, (C3−C30)cycloalkyl, (C3−C20)cycloalkyl-(C1−C10)alkylene, (C6−C30)aryl, or (C6−C20)aryl-(C1-C10)alkylene (such as benzyl (−CH2−C6H5)). Examples of (C1−C50)hydrocarbyl are unsubstituted or substituted (C1−C50)alkyl, (C3−C50)cycloalkyl, (C3−C20)cycloalkyl-(C1−C20)alkylene, (C6−C40)aryl, or (C6−C20)aryl-(C1-C20)alkylene (such as benzyl (−CH2−C6H5)). [0026] The term “(C1−C50)alkyl” means a saturated straight or branched hydrocarbon radical of from 1 to 50 carbon atoms that is unsubstituted or substituted by one or more R S. Other alkyl groups (e.g., (Cx−Cy)alkyl) are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more R S. Examples of unsubstituted (C1−C50)alkyl are unsubstituted (C1−C20)alkyl; unsubstituted (C1−C10)alkyl; unsubstituted (C1−C5)alkyl; methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2- butyl; 2-methylpropyl; 1,1-dimethylethyl; 1-pentyl; 1-hexyl; 1-heptyl; 1-nonyl; and 1-decyl. Examples of substituted (C1−C40)alkyl are substituted (C1−C20)alkyl (such as benzyl (−CH2−C6H5)), substituted (C1−C10)alkyl, trifluoromethyl, and [C45]alkyl. The term “[C45]alkyl” means there is a maximum of 45 carbon atoms in the radical, including substituents, and is, for example, a (C27−C40)alkyl substituted by one RS, which is a (C1−C5)alkyl, respectively. Each (C1−C5)alkyl may be methyl, trifluoromethyl, ethyl, 1- propyl, 1-methylethyl, or 1,1-dimethylethyl. [0027] The term “(C6−C40)aryl” means an unsubstituted or substituted (by one or more RS) mono-, bi- or tricyclic aromatic hydrocarbon radical of from 6 to 40 carbon atoms, of which at least from 6 to 14 of the carbon atoms are aromatic ring carbon atoms. Other aryl groups (e.g., (Cx−Cy)aryl) are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more RS. A monocyclic aromatic hydrocarbon radical includes one aromatic ring; a bicyclic aromatic hydrocarbon radical has two rings; and a tricyclic aromatic hydrocarbon radical has three rings. When the bicyclic or tricyclic aromatic hydrocarbon radical is present, at least one of the rings of the radical is aromatic. The other ring or rings of the aromatic radical may be independently fused or non- fused and aromatic or non-aromatic. Examples of unsubstituted (C6−C40)aryl include: unsubstituted (C6−C20)aryl, unsubstituted (C6−C18)aryl; 2-(C1−C5)alkyl-phenyl; phenyl;
86029-WO-PCT/DOW 86029 WO fluorenyl; tetrahydrofluorenyl; indacenyl; hexahydroindacenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene. Examples of substituted (C 6−C40)aryl include: substituted (C1−C20)aryl; substituted (C6−C18)aryl; 2,4-bis([C20]alkyl)-phenyl; polyfluorophenyl; pentafluorophenyl; and fluoren-9-one-l-yl. [0028] The term “(C3−C50)cycloalkyl” means a saturated cyclic hydrocarbon radical of from 3 to 50 carbon atoms that is unsubstituted or substituted by one or more RS. Other cycloalkyl groups (e.g., (Cx−Cy)cycloalkyl) are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more RS. Examples of unsubstituted (C3−C40)cycloalkyl are unsubstituted (C3−C20)cycloalkyl, unsubstituted (C3−C10)cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Examples of substituted (C3−C40)cycloalkyl are substituted (C3−C20)cycloalkyl, substituted (C3−C10)cycloalkyl, cyclopentanon-2-yl, and 1- fluorocyclohexyl. [0029] Examples of (C1−C50)hydrocarbylene include unsubstituted or substituted (C6−C50)arylene, (C3−C50)cycloalkylene, and (C1−C50)alkylene (e.g., (C1−C20)alkylene). The diradicals may be on the same carbon atom (e.g., −CH2−) or on adjacent carbon atoms (i.e., 1,2-diradicals), or are spaced apart by one, two, or more than two intervening carbon atoms (e.g., 1,3-diradicals, 1,4-diradicals, etc.). Some diradicals include 1,2-, 1,3-, 1,4-, or an α,ω- diradical, and others a 1,2-diradical. The α,ω-diradical is a diradical that has maximum carbon backbone spacing between the radical carbons. Some examples of (C2−C20)alkylene α,ω- diradicals include ethan-1,2-diyl (i.e. −CH2CH2−), propan-1,3-diyl (i.e. −CH2CH2CH2−), 2- methylpropan-1,3-diyl (i.e. −CH2CH(CH3)CH2−). Some examples of (C6−C50)arylene α,ω- diradicals include phenyl-1,4-diyl, napthalen-2,6-diyl, or napthalen-3,7-diyl. [0030] The term “(C1−C50)alkylene” means a saturated straight chain or branched chain diradical (i.e., the radicals are not on ring atoms) of from 1 to 50 carbon atoms that is unsubstituted or substituted by one or more RS. Other alkylenee groups (e.g., (Cx−Cy)alkylene) are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more RS. Examples of unsubstituted (C1−C50)alkylene are unsubstituted (C1−C20)alkylene, including unsubstituted −CH2CH2−, −(CH2)3−, −(CH2)4−, −(CH2)5−, −(CH2)6−, −(CH2)7−, −(CH2)8−, −CH2C*HCH3, and
86029-WO-PCT/DOW 86029 WO −(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 RS may 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. [0031] The term “(C3−C50)cycloalkylene” means a cyclic diradical (i.e., the radicals are on ring atoms) of from 3 to 50 carbon atoms that is unsubstituted or substituted by one or more RS. Other cycloalkylene groups (e.g., (Cx−Cy)cycloalkylene) are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more RS. [0032] The term “heteroatom” refers to an atom other than hydrogen or carbon. Examples of groups containing one or more than one heteroatom include O, S, S(O), S(O)2, Si(RC)2, P(RP), N(RN), −N=C(RC)2, −Ge(RC)2−, or −Si(RC)−, where each RC and each RP is unsubstituted (C1−C18)hydrocarbyl or −H, and where each RN is unsubstituted (C1−C18)hydrocarbyl. The term “heterohydrocarbon” refers to a molecule or molecular framework in which one or more carbon atoms of a hydrocarbon are replaced with a heteroatom. The term “(C1−C50)heterohydrocarbyl” means a heterohydrocarbon radical of from 1 to 50 carbon atoms, and the term “(C1−C50)heterohydrocarbylene” means a heterohydrocarbon diradical of from 1 to 50 carbon atoms. The heterohydrocarbon of the (C1−C50)heterohydrocarbyl or the (C1−C50)heterohydrocarbylene has one or more heteroatoms. The radical of the heterohydrocarbyl may be on a carbon atom or a heteroatom. The two radicals of the heterohydrocarbylene may be on a single carbon atom or on a single heteroatom. Additionally, one of the two radicals of the diradical may be on a carbon atom and the other radical may be on a different carbon atom; one of the two radicals may be on a carbon atom and the other on a heteroatom; or one of the two radicals may be on a heteroatom and the other radical on a different heteroatom. Each (C1−C50)heterohydrocarbyl and (C1−C50)heterohydrocarbylene may be unsubstituted or substituted (by one or more RS), aromatic or non-aromatic, saturated or unsaturated, straight chain or branched chain, cyclic
86029-WO-PCT/DOW 86029 WO (including mono- and poly-cyclic, fused and non-fused polycyclic), or acyclic. Other heterohydrocarbyl groups (e.g., (Cx−Cy) heterohydrocarbyl) are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more RS. [0033] The (C1−C50)heterohydrocarbyl may be unsubstituted or substituted. Non-limiting examples of the (C1−C50)heterohydrocarbyl include (C1−C50)heteroalkyl, (C1−C50)hydrocarbyl-O−, (C1−C50)hydrocarbyl-S−, (C1−C50)hydrocarbyl-S(O)−, (C1−C50)hydrocarbyl-S(O)2−, (C1−C50)hydrocarbyl-Si(RC)2−, (Cl−C50)hydrocarbyl-N(RN)−, (Cl−C50)hydrocarbyl-P(RP)−, (C2−C50)heterocycloalkyl, (C2−C19)heterocycloalkyl- (C1−C20)alkylene, (C3−C20)cycloalkyl-(C1−C19)heteroalkylene, (C2−C19)heterocycloalkyl- (C1−C20)heteroalkylene, (C1−C50)heteroaryl, (C1−C19)heteroaryl-(C1−C20)alkylene, (C6−C20)aryl-(C1−C19)heteroalkylene, or (C1−C19)heteroaryl-(C1−C20)heteroalkylene. [0034] The (C1−C30)heterohydrocarbyl may be unsubstituted or substituted. Non-limiting examples of the (C1−C30)heterohydrocarbyl include (C1−C30)heteroalkyl, (C1−C30)hydrocarbyl-O−, (C1−C30)hydrocarbyl-S−, (C1−C30)hydrocarbyl-S(O)−, (C1−C30)hydrocarbyl-S(O)2−, (C1−C30)hydrocarbyl-Si(RC)2−, (Cl−C30)hydrocarbyl-N(RN)−, (Cl−C30)hydrocarbyl-P(RP)−, (C2−C30)heterocycloalkyl, (C2−C20)heterocycloalkyl- (C1−C10)alkylene, (C3−C20)cycloalkyl-(C1−C10)heteroalkylene, (C2−C20)heterocycloalkyl- (C1−C10)heteroalkylene, (C1−C30)heteroaryl, (C1−C20)heteroaryl-(C1−C10)alkylene, (C6−C20)aryl-(C1−C10)heteroalkylene, or (C1−C20)heteroaryl-(C1−C10)heteroalkylene. [0035] The term “(C3−C50)heteroaryl” means an unsubstituted or substituted (by one or more RS) mono-, bi-, or tricyclic heteroaromatic hydrocarbon radical of from 3 to 50 total carbon atoms and from 1 to 10 heteroatoms. A monocyclic heteroaromatic hydrocarbon radical includes one heteroaromatic ring; a bicyclic heteroaromatic hydrocarbon radical h as two rings; and a tricyclic heteroaromatic hydrocarbon radical has three rings. When the bicyclic or tricyclic heteroaromatic hydrocarbon radical is present, at least one of the rings in the radical is heteroaromatic. The other ring or rings of the heteroaromatic radical may be independently fused or non-fused and aromatic or non-aromatic. Other heteroaryl groups (e.g., (Cx−Cy)heteroaryl generally, such as (C4−C12)heteroaryl) are defined in an analogous manner as having from x to y carbon atoms (such as 4 to 12 carbon atoms) and being
86029-WO-PCT/DOW 86029 WO unsubstituted or substituted by one or more than one RS. The monocyclic heteroaromatic hydrocarbon radical is a 5-membered ring or a 6-membered ring. The 5-membered ring has 5 minus h carbon atoms, wherein h is the number of heteroatoms and may be 1, 2, or 3; and each heteroatom may be O, S, N, or P. Examples of 5-membered ring heteroaromatic hydrocarbon radicals include pyrrol-1-yl; pyrrol-2-yl; furan-3-yl; thiophen-2-yl; pyrazol-1- yl; isoxazol-2-yl; isothiazol-5-yl; imidazol-2-yl; oxazol-4-yl; thiazol-2-yl; 1,2,4-triazol-1-yl; 1,3,4-oxadiazol-2-yl; 1,3,4-thiadiazol-2-yl; tetrazol-1-yl; tetrazol-2-yl; and tetrazol-5-yl. The 6-membered ring has 6 minus h carbon atoms, wherein h is the number of heteroatoms and may be 1 or 2 and the heteroatoms may be N or P. Examples of 6-membered ring heteroaromatic hydrocarbon radicals include pyridine-2-yl; pyrimidin-2-yl; and pyrazin-2-yl. The bicyclic heteroaromatic hydrocarbon radical can be a fused 5,6- or 6,6-ring system. Examples of the fused 5,6-ring system bicyclic heteroaromatic hydrocarbon radical are indol- 1-yl; and benzimidazole-1-yl. Examples of the fused 6,6-ring system bicyclic heteroaromatic hydrocarbon radical are quinolin-2-yl; and isoquinolin-1-yl. The tricyclic heteroaromatic hydrocarbon radical can be a fused 5,6,5-; 5,6,6-; 6,5,6-; or 6,6,6-ring system. An Example of the fused 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indol-1-yl. An Example of the fused 5,6,6-ring system is 1H-benzo[f] indol-1-yl. An Example of the fused 6,5,6-ring system is 9H-carbazol-9-yl. An Example of the fused 6,5,6-ring system is 9H-carbazol-9-yl. An Example of the fused 6,6,6-ring system is acrydin-9-yl. [0036] The term “(C1−C50)heteroalkyl” means a saturated straight or branched chain radicals containing one to fifty carbon atoms, or fewer carbon atoms and one or more of the heteroatoms. The term “(C1−C50)heteroalkylene” means a saturated straight or branched chain diradicals containing from 1 to 50 carbon atoms and one or more than one heteroatoms. The heteroatoms of the heteroalkyls or the heteroalkylenes may include Si(RC)3, Ge(RC)3, Si(RC)2, Ge(RC)2, P(RP)2, P(RP), N(RN)2, N(RN), N, O, ORC, S, SRC, S(O), and S(O)2, wherein each of the heteroalkyl and heteroalkylene groups are unsubstituted or are substituted by one or more RS. [0037] Examples of unsubstituted (C2−C40)heterocycloalkyl include unsubstituted (C2−C20)heterocycloalkyl, unsubstituted (C2−C10)heterocycloalkyl, aziridin-l-yl, oxetan-2- yl, tetrahydrofuran-3-yl, pyrrolidin-l-yl, tetrahydrothiophen-S,S-dioxide-2-yl, morpholin-4-
86029-WO-PCT/DOW 86029 WO yl, 1,4- dioxan-2-yl, hexahydroazepin-4-yl, 3-oxa-cyclooctyl, 5-thio-cyclononyl, and 2-aza- cyclodecyl. [0038] The term “halogen atom” or “halogen” means the radical of a fluorine atom (F), chlorine atom (Cl), bromine atom (Br), or iodine atom (I). The term “halide” means the anionic form of the halogen atom: fluoride (F−), chloride (Cl−), bromide (Br−), or iodide (I−). [0039] The term “saturated” means lacking carbon–carbon double bonds, carbon–carbon triple bonds, and (in heteroatom-containing groups) carbon–nitrogen, carbon–phosphorous, and carbon–silicon double bonds. Where a saturated chemical group is substituted by one or more substituents RS, one or more double and/or triple bonds optionally may or may not be present in substituents RS. The term “unsaturated” means containing one or more carbon– carbon double bonds, carbon–carbon triple bonds, or (in heteroatom-containing groups) one or more carbon–nitrogen, carbon–phosphorous, or carbon–silicon double bonds, not including double bonds that may be present in substituents RS, if any, or in (hetero) aromatic rings, if any. Polymerization Methods [0040] According to embodiments disclosed herein, a method of making polyethylene may comprise polymerizing, in a gas phase reactor ethylene monomer and optionally at least one C3 to C8 1-alkene comonomer and a catalyst system, thereby forming a polyethylene. [0041] In embodiments, the polymerization may occur 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. 0 517 868 and 0 794 200. The 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, particles of the catalyst system may be fed directly to the gas-phase polymerization reactor. In other embodiments, a slurry of catalyst system in a liquid, such as an inert hydrocarbon liquid, solvent, or mineral oil, may be fed to the reactor. [0042] 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
86029-WO-PCT/DOW 86029 WO particles, and a minor amount of the 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. 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. [0043] In embodiments, the gas phase polymerization occurs in the reactor at a temperature of less than or equal to 130 °C. For example, the reactor temperature of the gas -phase polymerization reactor may be from 75 ºC to 115 ºC, from 30 °C to 45 °C, from 45 °C to 60 °C, from 60 °C to 70 °C, from 70 °C to 75 °C, from 75 °C to 80 °C, from 80 °C to 85 °C, from 85 °C to 90 °C, from 90 °C to 95 °C, from 95 °C to 100 °C, from 100 °C to 105 °C, from 105 °C to 110 °C, from 110 °C to 115 °C, from 115 °C to 130 °C,, or any combination of two or more of these ranges. [0044] 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 1,379 kPa (200 psig), from 1,379 kPa (200 psig) to 2068 kPa (300 psig), from 2068 kPa (300 psig) to 2,759 kPa (400 psig), from 2,759 kPa (400 psig) to 3,448 kPa (500 psig), or any combination of two or more of these ranges. [0045] In embodiments, ethylene may be one of the gasses used to pressurize the gas-phase polymerization reactor. In embodiments, the ethylene partial pressure (C2PP) may be up to 2413 kPa (350 psig), such as from 35 kpa (5 psig) to 137 kPa (20 psig), from 137 kPa (20 psig) to 345 kPa (50 psig), from 345 kPa (50 psig) to 689 kPa (100 psig), from 689 kPa (100 psig) to 1034 kPa (150 psig), from 1034 kPa (150 psig) to 1378 kPa (200 psig), from 1378 kPa (200 psig) to 1723 kPa (250 psig), from 1723 kPa (250 psig) to 2068 kPa (300 psig), from 2068 kPa (300 psig) to 2413 kPa (350 psig), or any combination of two or more of these ranges.
86029-WO-PCT/DOW 86029 WO [0046] In embodiments, hydrogen gas may be used during polymerization to control the final properties of the polyethylene. The amount of hydrogen used during polymerization may be expressed as a molar ratio relative to the total polymerizable monomer, such as, fo r example, ethylene or a blend of ethylene and C3 to C81-alkene. The amount of hydrogen used in the polymerization process may be an amount necessary to achieve the desired properties of the polyethylene, such as, for example, melt flow rate. In embodiments, the mole ratio of hydrogen to total polymerizable monomer (e.g., H2:monomer, also referred to herein as “H2:C2” or “H2/C2”) is greater than 0.0001. For example, the mole ratio of hydrogen to total polymerizable monomer (H2:C2) may be from 0.0001 to 1.8, from 0.0001 to 1.0, from 0 to 0.1, from 0.0001 to 0.10, from 0.0001 to 0.001, from 0.0001 to 0.0005, from 0.0005 to 1.8, from 0.0005 to 1.0, from 0.0005 to 0.10, from 0.0005 to 0.001, from 0.001 to 1.8, from 0.001 to 1.0, from 0.001 to 0.10, from 0.001 to 0.05, or from 0.001 to 0.005, or any combination of two or more of these ranges. It should be understood that “total polymerizable monomer” refers to the amount of ethylene in the reactor which has not yet been covalently bonded to another compound. [0047] In some embodiments where the at least one C3 to C81-alkene comonomer is used during polymerization, the molar ratio between the at least one C3 to C81-alkene comonomer to the ethylene monomer (also referred to herein as a comonomer-to-ethylene ratio) in the polymerization reactor may be from 0 to 0.04, such as from 0 to 0.0001, from 0.0001 to 0.001, from 0.001 to 0.04, from 0.001 to 0.02, from 0.001 to 0.01, from 0.01 to 0.02, from 0.02 to 0.03, from 0.03 to 0.04, or any combination of two or more of these ranges. [0048] In one or more embodiments, the polymerization process produces greater than or equal to 300 grams of the polyethylene per gram of the spray-dried catalyst system per hour (gpoly/gcat·hour). In some embodiments, the process produces at to 400 gpoly/gcat·hour, at least 450 gpoly/gcat·hour, at least 500 gpoly/gcat·hour, at least 600 gpoly/gcat·hour, at least 700 gpoly/gcat·hour, at least 800 gpoly/gcat·hour, at least 900 gpoly/gcat·hour, at least 1000 gpoly/gcat·hour, at least 1200 gpoly/gcat·hour, at least 1500 gpoly/gcat·hour, at least 2000 gpoly/gcat·hour, at least 5,000 gpoly/gcat·hour, or at least 75,000 gpoly/gcat·hour. [0049] In one or more embodiments, the polymerization process consumes both ethylene and C3 to C8 1-alkene comonomer resulting in a comonomer uptake as defined by (wt. of C 3
86029-WO-PCT/DOW 86029 WO to C8 1-alkene comonomer consumed / wt. of ethylene consumed) x 100%. Generally, comonomer uptake is a direct indicator of how well a catalyst system incorporates the comonomer. It is believed that ultra-low incorporation of comonomer, as is achieved in some embodiments by catalyst systems described herein, allows for the production of particular resins. In embodiments, the comonomer uptake is ≤ 4.0%, ≤ 3.5%, ≤ 3.0%, ≤ 2.5%, ≤ 2.0%, ≤ 1.5%, ≤ 1.0%., ≤ 0.5%, from 0.001 to 4 %, from 0.001 to 0.01 %, from 0.01 % to 0.1 %, from 0.1 % to 0.15 %, from 0.15% to 0.2%, from 0.2 % to 0.25%, from 0.25% to 0.3%, from 0.3% to 0.35%, from 0.35% to 0.4%, or any combination of two or more of these ranges. Reaction Constituents [0050] As mentioned above, the method of making polyethylene may comprise polymerizing, in a gas phase reactor, ethylene monomer and optionally at least one C 3 to C8 1-alkene comonomer and a catalyst system. The optional at least one C3 to C8 1-alkene comonomer, may comprise any C3 to C81-alkene comonomer, such as a 1-propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, or 1-octene. [0051] The catalyst system may comprise at least a procatalyst. The term “procatalyst” refers to a compound that has catalytic activity when combined with an activator. The term “activator” refers to a compound that chemically reacts with a procatalyst in a manne r that converts the procatalyst to a catalytically active catalyst. As used herein, the terms “activating co-catalyst” and “activator” are interchangeable terms. [0052] The procatalyst may have a structure according to Formula (I):
Formula (I) [0053] In Formula (I), M is a metal selected from titanium, zirconium, and hafnium, the metal having a formal oxidation state of +2, +3, or +4. n is 1 or 2. Each X is a monodentate or bidentate ligand independently selected from unsaturated (C2−C30)hydrocarbon,
86029-WO-PCT/DOW 86029 WO unsaturated (C2−C30)heterohydrocarbon, (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6-C30)aryl, (C3-C30)heteroaryl, halogen, −N(RX)2, and −(CH2)wSi(RX)3, where w is 1 to 10 and each RX is independently selected from (C1−C30)hydrocarbyl (C1−C30)heterohydrocarbyl, (C6-C30)aryl, and (C3-C30)heteroaryl. Formula (I) is overall charge neutral. [0054] In Formula (I), Q is a monoanionic spectator ligand selected from (C1−C50)hydrocarbyl, (C1−C50)heterohydrocarbyl, (C5-C30)aryl, and (C3-C30)heteroaryl, wherein Q is different from each X. In particular embodiments, Q may be unsubstituted or substituted cyclopentadienyl. Without intent to be bound by theory, it is believed that the heteroleptic nature of the 2-amino-imidazole complexes described herein, i.e., wherein Q is different from each X, may be advantageous for achieving improved catalyst activity and tunable polymer properties, relative to homoleptic 2-amino-imidazole complexes wherein the ligands bonded to the metal center, other than the 2-amino-benzamidazole ligand, are the same (e.g., three benzyl ligands). Further, it has been unexpectedly found that embodiments of the heteroleptic 2-amino-imidazole complexes described herein have increased catalyst activities relative to their homoleptic analogs while also producing polymers with low comonomer incorporation and variable weight-average molecular weight, the combination of which is believed to be favorable for polymer processability. [0055] RY is (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6-C30)aryl, and (C3- C30)heteroaryl. R1 is (C1−C50)hydrocarbyl, (C1−C50)heterohydrocarbyl, (C6-C30)aryl, or (C3- C30)heteroaryl. Each of R2 and R3 is independently selected from the group consisting of (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6-C30)aryl, and (C3-C30)heteroaryl, −ORC, −Si(RC)3, −Ge(RC)3, halogen, and –H, wherein R2 and R3 are optionally covalently linked to form an aromatic or non-aromatic ring. Each RC is independently selected from the group consisting of (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6-C30)aryl, and (C3- C30)heteroaryl, and –H. [0056] In some optional embodiments, R2 and R3 are covalently linked to form a ring. In such embodiments, the procatalyst has a structure according to Formula (II):
86029-WO-PCT/DOW 86029 WO
(II) [0057] In one or more embodiments, in Formula (II), each R1, RY, Q, X, M, and n are defined as in Formula (I) and each of R4, R5, R6, and R7 is independently (C1−C40)hydrocarbyl, (C1−C40)heterohydrocarbyl, (C6-C40)aryl, and (C3-C40)heteroaryl, halogen, or −H. In one or more embodiments, each of R5, R6, and R7 is −H. [0058] In one or more embodiments, R4 is (C6−C40)aryl or (C3−C40)heteroaryl. In some embodiments, R4 is (C6−C40)aryl or (C3−C40)heteroaryl, and each of R5, R6, and R7 is –H. [0059] In one or more embodiments, R4 is phenyl, 2,4,6-tri(isopropyl)phenyl, 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 3,5-di-tert-butylphenyl, unsubstituted naphthyl, substituted naphthyl, unsubstituted carbozolyl, or substituted carbozolyl. In some embodiments, R4 is phenyl, 2,4,6-tri(isopropyl)phenyl, 2,4,6-trimethylphenyl, 2,6- dimethylphenyl, 3,5-di-tert-butylphenyl, unsubstituted naphthyl, substituted naphthyl, unsubstituted carbozolyl, or substituted carbozolyl, anthracenyl, or substituted anthracenyl, and each of R5 , R6, and R7 is –H. [0060] In various embodiments, R1 is (C6−C30)aryl; R4 is phenyl, 2,4,6-tri(isopropyl)phenyl, 2,4,6-trimethylphenyl, 2,6-dimethylphenyl, 3,5-di-tert-butylphenyl, unsubstituted naphthyl, substituted naphthyl, unsubstituted carbozolyl, or substituted carbozolyl, anthracenyl, or substituted anthracenyl; and each of R5, R6, and R7 is −H. [0061] In some embodiments, Q has a structure according to any one of formulas Q-1 through Q-3, where the wavy line indicates a point of attachment to the M of Formula (I):
86029-WO-PCT/DOW 86029 WO
[0062] In Formula Q-1, each of R8-10 can be independently selected from (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6-C30)aryl, and (C3-C30)heteroaryl. In Formula Q-2, each of R11-14 can be independently selected from (C1−C50)hydrocarbyl, (C1−C50)heterohydrocarbyl, (C6-C30)aryl, (C3-C30)heteroaryl, −Si(RC)3, −Ge(RC)3, −N(RN)2, −ORC, and –H, wherein is each RC and RN independently selected from (C1−C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6-C30)aryl, (C3-C30)heteroaryl, and –H, and wherein optionally R11 and R12, or R11 and R13, or R11 and R14, or R13 and R14, or R12 and R13, or R12 and R14 may be covalently connected to form an aromatic ring or non-aromatic ring, or a multi-ring structure. In Formula Q-3, each of R15-19 is independently selected from (C1–C30)hydrocarbyl, (C1−C30)heterohydrocarbyl, (C6-C30), (C3-C30)heteroaryl, −Si(RC)3, −Ge(RC)3, and –H, wherein optionally, any of R15–19 are covalently connected to form one or more ring or multi- ring structures. [0063] In illustrative embodiments, the catalyst systems include a procatalyst according to Formula (I) having the structure of any one of Procatalysts 1–3 below:
Procatalyst 1 Procatalyst 2
86029-WO-PCT/DOW 86029 WO
Procatalyst 3 Supported Catalyst Systems [0064] In some embodiments, the catalyst system is a supported catalyst system comprising: the procatalyst; an activator; and a support. [0065] As mentioned above, the procatalyst may be rendered catalytically active by contacting it to, or combining it with, an activator. The term “activator” may include any combination of reagents that increases the rate at which a procatalyst oligomerizes or polymerizes unsaturated monomers, such as olefins. An activator may also affect the molecular weight, degree of branching, comonomer content, or other properties of the oligomer or polymer produced. The procatalyst may be activated for oligomerization and/or polymerization catalysis in any manner sufficient to allow coordination or cationic oligomerization and or polymerization. In some embodiments, the activator is a supported activator, that is, the activator is supported on a support material. [0066] 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;
86029-WO-PCT/DOW 86029 WO 5,204,419; 4,874,734; 4,924,018; 4,908,463; 4,968,827; 5,329,032; 5,248,801; 5,235,081; 5,157,137; 5,103,031; and EP 0561476; EP 0279586; EP 0516476; EP 0594218; and WO 94/10180. In embodiments, the activator comprises methylalumoxane (MAO). [0067] Aluminum alkyl or organoaluminum compounds that may be utilized as activators (or scavengers) including trimethylaluminum, triethylaluminum, triisobutylaluminum, tri -n- hexylaluminum, tri-n-octylaluminum and the like. [0068] In embodiments, the molar ratio of metal in the activator to metal in the procatalyst is from 0.5:1 to 3500:1, such as from 0.5:1 to 1:1, from 1:1 to 5:1, from 5:1 to 10:1, from 10:l to 20:1, from 20:1 to 50:1, from 50:1 to 100:1, from 100:1 to 250:1, from 250:1 to 500:1, from 500:1 to 1000:1, from 1000:1 to 1500:1, from 1500:1 to 2000:1, from 2000:1 to 2500:1, from 2500:1 to 3000:1, from 3000:1 to 3500:1, or any combination of two or more of these ranges. [0069] In embodiments, the procatalyst can be utilized to make supported catalyst systems or compositions. In some embodiments the procatalyst and support material are contacted together in an inert hydrocarbon liquid to give a suspension in the inert hydrocarbon liquid, then the suspension is contacted with the activator to give a suspension of the supported catalyst system in the inert hydrocarbon liquid, and then inert hydrocarbon liquid is removed to give the supported catalyst system. [0070] In embodiments, the procatalyst, the activator, or both, may be disposed on one or more support materials. For example, the procatalyst may be deposited on, contacted with, vaporized with, bonded to, or incorporated within, adsorbed or absorbed in, or on, one or more support materials. The procatalyst, the activator, or both, may be combined with one or more support materials using one of the support methods well known in the art or as described below. As used in the present disclosure, the procatalyst, the activator, or both, may be in a supported form, for example, when deposited on, contacted with, or incorporated within, adsorbed or absorbed in, or on, one or more support materials. [0071] In some embodiments the activator and the support material are contacted together in an inert hydrocarbon liquid to give a suspension of a supported activator in the inert hydrocarbon liquid, then the suspension is contacted with the procatalyst to give a suspension
86029-WO-PCT/DOW 86029 WO of the supported catalyst system in the inert hydrocarbon liquid, and then the inert hydrocarbon liquid is removed to give the supported catalyst system. [0072] 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. [0073] Suitable support materials, such as inorganic oxides, include oxides of metals of Group 2, 3, 4, 5, 13 or 14 of the IUPAC periodic table. In embodiments, support materials include silica, which may include dehydrated silica, fumed silica, alumina (e.g., as described in International Patent Application No.1999/060033), silica-alumina, and mixtures of these. The fumed silica may be hydrophilic (untreated), alternatively hydrophobic (treated). In embodiments, the support material is hydrophobic fumed silica, which may be prepared by treating an untreated fumed silica with a treating agent, such as dimethyldichlorosilane, a polydimethylsiloxane fluid, or hexamethyldisilazane. In some embodiments, support materials include magnesia, titania, zirconia, magnesium chloride (e.g., as described in U.S. Patent No.5,965,477), montmorillonite (e.g., as described in European Patent No.0511665), phyllosilicate, zeolites, talc, clays (e.g., as described in U.S. Patent No. 6,034,187), and mixtures of these. In other embodiments, combinations of these support materials may be used, such as, for example, silica-chromium, silica-alumina, silica-titania, and combinations of these. Additional support materials may also include those porous acrylic polymers described in European Patent No. 0 767 184. Other support materials may also include nanocomposites described in International Patent Application No. 1999/047598; aerogels described in International Patent Application No.1999/048605; spherulites described in U.S. Patent No.5,972,510; and polymeric beads described in International Patent Application No. 1999/050311. An example of a support material is fumed silica available under the trade name CABOSIL TS- 610, or other TS- or TG-series supports, available from Cabot Corporation. Fumed silica is typically a silica with particles 7 to 30 nanometers in size that have been treated with dimethylsilyldichloride such that a majority of the surface hydroxyl groups are capped.
86029-WO-PCT/DOW 86029 WO [0074] The support material may comprise silica, alternatively amorphous silica (not quartz), alternatively a high surface area amorphous silica, e.g., from 500 to 1000 m2/g. Such silicas are commercially available from several sources including the Davison Chemical Division of W.R. Grace and Company, e.g., Davison 952 and Davison 955 products, and PQ Corporation, e.g., ES70 product. The silica may be in the form of spherical particles, which may be obtained by a spray-drying process. Alternatively, MS3050 product is a silica from PQ Corporation that is not spray-dried. As procured, these silicas are not calcined (i.e., not dehydrated). Silica that is calcined prior to purchase may also be used as the support material. [0075] 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. [0076] 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. [0077] In embodiments, the supported catalyst system may be produced by spray drying. For example, at least one of the procatalyst, the activator, and the support may be spray dried. As used herein, a “spray-dried” material refers to a material comprising components that have
86029-WO-PCT/DOW 86029 WO 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. [0078] In some embodiments, a mixture of procatalyst, support, activator, and inert hydrocarbon liquid may be formed. The mixture may then be spray dried to form a spray - dried supported catalyst system. Spray-drying the mixture removes the inert hydrocarbon solvent to produce spray-dried particles, though spray-drying the mixture may not result in complete removal of liquids from the resulting catalyst system. That is, the spray-dried catalyst system may include residual amounts (i.e., from 1 wt. % to 3 wt. %) of the inert hydrocarbon solvent. A number of other known components may be utilized in the spray - drying process. An atomizer, such as an atomizing nozzle or a centrifugal high speed disc, for example, may be used to create a spray or dispersion of droplets of the composition. The droplets of the composition may then be rapidly dried by contact with an inert drying gas. The inert drying gas may be any gas that is non-reactive under the conditions employed during atomization, such as nitrogen, for example. The inert drying gas may meet the composition at the atomizer, which produces a droplet stream on a continuous basis. Dried particles of the composition may be trapped out of the process in a separator, such as a cyclone, for example, which can separate solids formed from a gaseous mixture of the drying gas, solvent, and other volatile components. Generally, it is believed that spray drying may improve the productivity, efficiency, and/or resulting polymer properties of at least some of the catalyst systems described herein. [0079] In some embodiments, methods for producing the spray-dried catalyst system include spray-drying a mixture comprising an inert hydrocarbon liquid, a support material, and an activator, thereby forming a spray-dried supported activator, and then contacting the spray-dried supported activator with an inert hydrocarbon liquid and the procatalyst to make the spray-dried supported catalyst system. Further embodiments include preparing a trim solution comprising the second inert hydrocarbon liquid and the procatalyst and then contacting the trim solution with the spray-dried supported activator. In embodiments where a spray-dried supported activator is contacted with an inert hydrocarbon liquid and the procatalyst, the resulting mixture may be added directly, i.e., without an additional drying step, to a polymerization reactor (e.g., a gas polymerization reactor), or may be conventionally-dried or spray-dried to produce a dried supported catalyst system which is
86029-WO-PCT/DOW 86029 WO added to a polymerization reactor, or the dried supported catalyst system may be resuspended in an inert hydrocarbon liquid, and the resulting slurry is added to a polymerization reactor. [0080] In some embodiments, a mixture of the procatalyst, the support, and the activator in an inert hydrocarbon liquid are used without drying. For example, the supported catalyst system in the inert hydrocarbon liquid may be made in-line prior to entry or injection into the gas phase polymerization reactor and is utilized for a polymerization reaction in the reactor directly without a drying or decanting step. In some embodiments, contacting a mixture of the procatalyst and an inert hydrocarbon liquid with a supported or spray dried activator particle is performed in-line to a polymerization reactor. [0081] 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. [0082] In some embodiments, a mixture of the procatalyst, the support, and the activator in an inert hydrocarbon liquid are spray-dried to form a spray-dried catalyst system, and the supported catalyst system is contacted with the procatalyst in an inert hydrocarbon liquid, prior to entry or injection into the gas phase polymerization reactor, and is utilized for a polymerization reactor in the reactor directly without a drying or decanting step. [0083] The inert hydrocarbon liquid may comprise a mineral oil, a hydrocarbon solvent, or a combination thereof. The second inert hydrocarbon liquid may have the same or a different composition from the first inert hydrocarbon liquid. Polyethylenes [0084] In embodiments, the supported catalyst system of the present disclosure may be utilized to polymerize a single type of olefin, producing a homopolymer. However, additional 1-alkenes (also called alpha-olefins) may be incorporated into the polymerization scheme in other embodiments. The additional 1-alkene comonomers typically have no more than 8
86029-WO-PCT/DOW 86029 WO carbon atoms. For example, the supported catalyst systems of the present disclosure may be utilized to polymerize ethylene monomer and at least one 1-alkene comonomer. Exemplary 1-alkene comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1- hexene, 1-heptene, 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. [0085] As mentioned above, the method produces a polyethylene. In some embodiments, from 95 – 99.99 wt. %, such as from 95 to 96 wt. %, from 96 to 97 wt. %, from 97 to 98 wt. %, from 98 to 99 wt. %, from 99 to 99.5 wt. %, from 99.5 to 99.9 wt. %, or any combination of two or more of these ranges of units of the polyethylene comprise ethylene based on a total weight of the polyethylene, and 0.01-5 wt. %, such as from 0.01 to 0.05 wt. %, from 0.05 to 0.1 wt. %, from 0.1 wt. % to 0.5 wt. %, from 0.5 wt. % to 1 wt. %, from 1 wt. % to 2 wt. %, from 2 wt. % to 3 wt. %, from 3 wt. % to 4 wt. %, from 4 wt. % to 5 wt. %, or any combination of two or more of these ranges of units of the polyethylene comprise the at least one C 3 to C8 1-alkene comonomer, based on the total weight of the polyethylene. [0086] In some embodiments, the polyethylene may have a melt temperature from 125 °C to 140 °C, such as from 125 °C to 130 °C, from 130 °C to 135 °C, from 135 °C to 140 °C, or any combination of two or more of these ranges. [0087] In some embodiments, the polyethylene may have a melt index (I2) from 0.001 to 130 dg/min, such as from 0.001 to 0.1 dg/min, from 0.1 to 0.2 dg/min, from 0.2 to 0.3 dg/min, from 0.3 to 0.4 dg/min, from 0.4 to 0.5 dg/min, from 0.5 to 0.6 dg/min, from 0.6 to 0.7 dg/min, from 0.7 to 0.8 dg/min, from 0.8 to 0.9 dg/min, from 0.9 to 1.0 dg/min, from 1.0 to 1.1 dg/min, from 1.1 to 1.2 dg/min, from 1.2 to 1.3 dg/min, from 1.3 to 1.4 dg/min, from 1.4 to 1.5 dg/min, from 1.5 to 1.6 dg/min, from 1.6 to 1.7 dg/min, from 1.7 to 1.8 dg/min, from 1.8 to 1.9 dg/min, from 1.9 to 2.0 dg/min, from 2.0 to 2.5 dg/min, from 2.5 to 3.0 dg/min, from 3.0 to 3.5 dg/min, from 3.5 to 4.0 dg/min, from 4.0 to 4.5 dg/min, from 4.5 to 5.0 dg/min, from 5.0 to 7.0 dg/min, from 7.0 to 10.0 dg/min, from 10.0 to 15.0 dg/min, from 15.0 to 20.0 dg/min, from 20.0 to 30.0 dg/min, 30.0 to 40.0 dg/min, 40.0 to 50.0 dg/min, 50.0 to 80.0 dg/min, 80.0 to 100.0
86029-WO-PCT/DOW 86029 WO dg/min, 100.0 to 130.0 dg/min, or any combination of two or more of these ranges. Melt index (I2) is measured according to ASTM-1238 Condition B (190 °C, 2.16 kg). [0088] In some embodiments, the polyethylene may have a melt index (I5) from 0.001 to 600 dg/min, such as from 0.001 to 0.1 dg/min, from 0.1 to 0.5 dg/min, from 0.5 to 1 dg/min, from 1 to 5 dg/min, from 5 to 10 dg/min, from 10 to 20 dg/min, from 20 to 50 dg/min, from 50 to 80 dg/min, from 80 to 100 dg/min, from 100 to 120 dg/min, 120 to 150 dg/min, 150 to 200 dg/min, 200 to 300 dg/min, 300 to 400 dg/min, 400 to 500 dg/min, 500 to 600 dg/min, or any combination of two or more of these ranges. Melt index (I5) is measured according to ASTM-1238 Condition B (190 °C, 5 kg). [0089] The polyethylene may have a density according to ASTM D792 (incorporated herein by reference in its entirety) from 0.850 g/cm3 to 0.970 g/cm3, from 0.870 g/cm3 to 0.950 g/cm3, from 0.880 g/cm3 to 0.920 g/cm3, from 0.880 g/cm3 to 0.910 g/cm3, from 0.900 g/cm3 to 0.950 g/cm3, from 0.920 g/cm3 to 0.950 g/cm3, from 0.950 g/cm3 to 0.970 g/cm3, or from 0.880 g/cm3 to 0.900 g/cm3, for example. [0090] In some embodiments, the polyethylene may have a melt flow index (I21) from 0.001 to 2,000 dg/min, such as from 0.001 to 0.1 dg/min, from 0.1 to 0.5 dg/min, from 0.5 to 1 dg/min, from 1 to 5 dg/min, from 5 to 10 dg/min, from 10 to 20 dg/min, from 20 to 50 dg/min, from 50 to 100 dg/min, from 100 to 200 dg/min, from 200 to 300 dg/min, from 300 to 400 dg/min, from 400 to 500 dg/min, from 500 to 1000 dg/min, from 1000 to 1500 dg/min, from 1500 to 2000 dg/min, or any combination of two or more of these ranges. Melt flow index (I21) is measured according to ASTM-1238 Condition B (190 °C, 21.6 kg). [0091] In some embodiments, the polyethylene may have a polydispersity index (PDI=Mw/Mn) greater than 11, such as at least 12, at least 14, at least 16, at least 18, at least 20, at least 25, at least 30, at least 40, at least 50, at least 75, from 11 to 100, from 11 to 15, from 11 to 20, from 11 to 25, from 15 to 20, from 15 to 25, from 30 to 45, from 45 to 50, from 50 to 75, from 75 to 85 from 85 to 90, from 90 to 100, or any combination of two or more of these ranges. In PDI, Mw refers to the weight averaged molecular weight and Mn refers to the number averaged molecular weight, as determined by conventional gel permeation chromatography (GPC).
86029-WO-PCT/DOW 86029 WO [0092] In some embodiments, the polyethylene may have a z-average molecular weight (Mz) of greater than 1,000,000 g/mol, such as greater than 1,100,000 g/mol, greater than 1,250,000 g/mol, greater than 1,500,000 g/mol, greater than 1,750,000 g/mol, greater than 2,000,000 g/mol, greater than 3,000,000 g/mol, from 1,000,000 to 5,000,000 g/mol, from 1,000,000 to 1,100,000 g/mol, from 1,100,000 to 1,250,000 g/mol, from 1,250,000 to 1,500,000 g/mol, from 1,500,000 g/mol to 2,000,000 g/mol, from 2,000,00 to 3,500,000 g/mol, from 3,500,000 to 7,000,000 g/mol, or any combination of two or more of these ranges. A polymer with a z - average molecular weight higher than 1,000,000 g/mol may have improved mechanical properties including better toughness, abuse, and melt strength. [0093] In some embodiments, the polyethylene may have a Mz/Mw ≥ 3.5, such as ≥ 4.0, ≥ 5.0, ≥ 10.0, from 3.0 to 50, from 3.0 to 4.0, from 4.0 to 5.0, from 5.0 to 10, from 10 to 15, from 15 to 20, from 20 to 25, from 25 to 30, from 30 to 35, from 35 to 40, from 40 to 45, from 45 to 50, or any combination of two or more of these ranges. M z is defined as the z- average molecular weight. A broad Mz/Mw, for example an Mz/Mw ≥ 3.5 can lead to a polymer having a high molecular weight tail, or ultra-high molecular weight tail, which may improve mechanical properties including better toughness, abuse, and/or melt strength of the resin, and can lead to improved product performance. [0094] In some embodiments, the polyethylene may have a long chain branching factor of (LCBf) ≤ 0.01, such as < 0.008, < 0.005, or even < 0.003. Low-to-no observable LCBf may lead to improved mechanical properties and overall product performance. LCB f may be determined by Mark-Houwink analysis, as further described herein. [0095] The polyethylenes may further comprise one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. The ethylene-based polymers may contain any amounts of additives. The polyethylenes may compromise from about 0 to about 10 percent by the combined weight of such additives, based on the weight of the polyethylenes and the one or more additives. The polyethylenes may further comprise fillers, which may include, but are not limited to, organic or inorganic fillers. The polyethylenes may contain from about 0 to about 20 weight percent fillers such as, for example, calcium carbonate, talc, or Mg(OH)2, based on the
86029-WO-PCT/DOW 86029 WO combined weight of the polyethylenes and all additives or fillers. The polyethylenes may further be blended with one or more polymers to form a blend. [0096] 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, 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. [0097] Some embodiments of the methods described in this disclosure yield unique polymer properties (e.g., broad melt flow ratios of the polymers formed) and the amount of the comonomers incorporated into the polymers. [0098] One or more features of the present disclosure are illustrated in view of the examples as follows: TEST METHODS Melt Indices (I2, I5, I21)
86029-WO-PCT/DOW 86029 WO [0099] Melt index (I2) is measured according to ASTM-1238 Condition B (190 °C, 2.16 kg). Melt index (I5) is measured according to ASTM-1238 Condition B (190 °C, 5 kg). Melt flow index (I21) is measured according to ASTM-1238 Condition B (190 °C, 21.6 kg). Differential Scanning Calorimetry (DSC): [0100] Melt temperature was determined via Differential Scanning Calorimetry according to ASTM D 3418-08. In general, a scan rate of 10° C/min on a sample of 10 mg was used, and the second heating cycle was used to determine Tm. Comonomer Consumption or Uptake [0101] 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. Conventional Gel Permeation Chromatography (GPC) [0102] Details of the GPC method can be found in U.S. Patent Application Number 17/632,598, the entirety of which is incorporated by reference herein. Triple Detector GPC [0103] 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. [0104] 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
86029-WO-PCT/DOW 86029 WO the determination of the molecular weight, was obtained from the mass detector area and the mass detector constant, derived from a suitable linear polyethylene homopolymer, or one of the polyethylene standards of known weight-average molecular weight. The calculated molecular weights (using GPCOne™) were obtained using a light scattering constant, derived from one or more of the polyethylene standards mentioned below, and a refractive index concentration coefficient, dn/dc, of -0.104. Generally, the mass detector response (IR5) and the light scattering constant (determined using GPCOne™) should be determined from a linear standard with a molecular weight in excess of about 50,000 g/mole. The viscometer calibration (determined using GPCOne™) can be accomplished using the methods described by the manufacturer, or, alternatively, by using the published values of suitable linear standards, such as Standard Reference Materials (SRM) 1475a (available from National Institute of Standards and Technology (NIST)). A viscometer constant (obtained using GPCOne™) is calculated which relates specific viscosity area (DV) and injected mass for the calibration standard to its intrinsic viscosity. The chromatographic concentrations are assumed low enough to eliminate addressing 2nd viral coefficient effects (concentration effects on molecular weight). [0105] 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 1–3 as follows :
86029-WO-PCT/DOW 86029 WO
Calculation of LCB frequency (LCBf) [0106] The long chain branching frequency is calculated based on the differences between the g’ values (g’ is a ratio of the intrinsic viscosity of a polymer sample over a linear polymer reference with the same molecular weight). In 3D GPC practice, a reference polyethylene homopolymer, containing no detectable LCB or SCB, and with a Mw of approximately 120,000 g/mol and polydispersity around 3.0, is injected at the beginning of each run queue to establish the Mark-Houwink linear reference line. A first-order linear fit is applied to the obtained log of the intrinsic viscosity and log of the molecular weight data within the log of the molecular weight range of 4.5 to 5.8 to provide the linear reference K and α values. [0107] A polyethylene sample of interest is analyzed to obtain intrinsic viscosity, molecular weight values, and the value of gi’ is calculated at each chromatographic slice (i) according to Equation 4: gi’ = (IVSample,i / IVlinear reference,i) (Eq.4), where the calculation utilizes the IVSample,i at equivalent absolute molecular weight values and same SCB content values to the linear reference within the log molecular weight range of 4.5 to 5.8 g/mol. If a difference in SCB content exists, the IV linear reference,i line is vertically shifted by adjusting the K value from the Mark-Houwink Plot to account for the SCB correction compared to the IVSample,i. The shift is done until the linear reference line makes a single point of contact to make a tangent with the sample Mark-Houwink line at a log molecular weight of 4.5. [0108] A Zimm-Stockmayer branching factor g was calculated from g’, g’= g^, using an epsilon factor of 0.5. The number of branches along the polymer sample (B n) at each data slice (i) can be determined by using Equation 6, (B. H. Zimm and W. H. Stockmayer, J. Chem. Phys.17, 1301 (1949)):
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[0109] Finally, the average LCBf quantity per 1000 carbons in the polymer across all of the slices (i) can be determined using Equation 6:
[0110] Estimated LCBf of the polymers produced from the gas phase batch reactor experiments is shown in Table 5. LCBf is a measurement, or quantification, of the number of long-chain branches per 1000 carbon atoms (LCB/1000C) based on analysis of Mark- Houwink plots, where the higher the LCBf, the higher the amount of long-chain branching. A model fit for LCBf was calculated using Microsoft Solver using Equation 8 below to fit a model curve to the experimental data, where the Log(IV) is calculated at a given log(Mw) (a) of a sample with an LCBf (b), weight percent comonomer (c), number of carbons in comonomer (d), and (IV) is intrinsic viscosity. Equation 7 (Eq.7): Log(IV) = LOG((0.000381478441772065*(10^a)^0.732)*((6/(b*(10^a)/14,000)*(0.5*SQRT ((2+(b*(10^a)/14,000))/(b*(10^a)/14,000))*LN((SQRT(2+(b*(10^a)/14,000))+SQRT((b*(1 0^a)/14,000)))/(SQRT(2+(b*(10^a)/14,000))-SQRT((b*(10^a)/14,000))))-1))^0.5)*(1- c/100*(d-2)/d)^2). EXAMPLES [0111] The following examples illustrate features of the present disclosure but are not intended to limit the scope of the disclosure. The following experiments analyzed the performance of embodiments of the ethylene-based polymers described herein. Procatalysts
86029-WO-PCT/DOW 86029 WO [0112] The structures of procatalysts 1-3 are shown below. Procatalysts 1-3 were synthesized according to the methods described in U.S. Provisional Patent Application Nos. 63/665,576 and 63/665,580, the entirety of both of which is incorporated by reference herein.
Spray-Dried Catalyst Production [0113] Spray-dried catalyst samples were prepared and sprayed in a nitrogen-purged glove box as follows. In an oven-dried jar, Cabosil™ TS-610 fumed silica 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 15 minutes, then the procatalyst 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
86029-WO-PCT/DOW 86029 WO rotations per minute (rpm), and pump speed of 130 rpm. Table 1 describes the amounts of the procatalyst, fumed silica, 10% MAO solution, and toluene used to make each of the spray - dried catalysts. Table 1
Gas-Phase Semi-Batch Reactor Testing: [0114] The spray dried catalysts prepared above were used for ethylene/1-hexene copolymerization conducted in the gas-phase in a 2-liter semi-batch autoclave polymerization reactor. The gas phase reactor employed was a 2-liter, stainless steel autoclave equipped with a mechanical agitator. For the experimental runs, the reactor was first dried, or “baked out,” for 1 hour by charging the reactor with 400 g of NaCl and heating at 105 °C under nitrogen for 60 minutes. After baking out the reactor, 5 g of spray-dried methyl aluminoxane (SDMAO) was introduced as a scavenger under nitrogen pressure. After adding SDMAO, the reactor was sealed and components were stirred. The reactor was then charged with hydrogen and 1-hexene, and pressurized with ethylene. Once the system reached a steady state, the catalyst was charged into the reactor at 80 °C to start polymerization. The reactor was brought to the indicated reaction temperature and maintained at this temperature, while keeping the ethylene, 1-hexene, and hydrogen feed ratios consistent throughout the 1-hour run. At the end of the run, the reactor was cooled down, vented, and opened. The resulting product mixture was washed with water and methanol, then dried. Polymerization activity or productivity (grams polymer/gram catalyst-hour) and polymerization efficiency (grams polymer / gram metal (Ti, Zr or Hf)) 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. The individual run conditions and some properties of the polymers produced in these runs are tabulated in Table 2 below. C6 uptake/consumption, or 1-hexene uptake/consumption, is the ratio of the amount of 1-hexene (grams) consumed in the reactor divided by the amount of ethylene (grams) consumed, multiplied by 100%.
86029-WO-PCT/DOW 86029 WO [0115] The gas-phase batch reactor test was carried out using each of spray-dried catalyst samples S-1 through S-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. Further evaluated in terms of resulting polymer melt flow (I2, I21), melt flow ratio and DSC is shown in Table 3. Table 2
C6/C2 & H2/C2 are molar ratios, C2PP = 220 psi, run time = 1 hr, catalyst injection temp. = 80 °C. Table 3
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C6/C2 and H2/C2 are molar ratios, C2PP = 220 psi, run time = 1 hr, catalyst injection temp. = 80 °C, NF = No Flow. Table 4
C6/C2 and H2/C2 are molar ratios, C2PP = 220 psi, run time = 1 hr, catalyst injection temp. = 80 °C, NF = No Flow. Table 5: LCBf for Select Examples
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[0116] Based on the melt flow data (I2, I5, I21, shown in Table 3) under these commercially relevant process conditions, these catalysts are capable of producing ethylene/hexene copolymers with broad melt flow ratios (MFRs) (I21/I2 > 25), a range of weight average molecular weights (Mw), and fractional melt index (capability (I2 ≤ 0.5). Based on triple detector GPC (Table 4), these catalysts are capable of producing ethylene/hexene copolymers with broad molecular weight distributions (PDI > 11) with ultra-high weight average molecular weight tails (Mz > 1,000,000 g/mol and/or broad Mz/Mw ≥ 3.5). Representative GPC plots of the extreme broadness inherent to these polymers are shown in FIGS. 1-4. It is important to note, the broad MFRs, PDIs, and ultra-high molecular weight tails are all produced with minimal-to-no observable long-chain branching (LCBf ≤ 0.01 by Mark-Houwink analysis, Table 5). [0117] The ability of these catalyst systems to produce ethylene/hexene copolymers having a range of Mw, broad PDI, ultra-high molecular weight tails including high Mz and/or broad Mz/Mw, combined with minimal-to-no observable LCB combined with their high efficiency make them potentially useful for both single and multi-catalyst applications that produce ethylene copolymers with advantageous properties for single and/or multi-reactor processes.
86029-WO-PCT/DOW 86029 WO [0118] While particular embodiments of the present disclosure have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the disclosure. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this disclosure.