Aromatic hydrocarbon solvent-free supported metallocene catalyst systems for olefin polymerization and associated methods

Abstract

Formation of catalyst systems in the absence of an aromatic solvent may be desirable. Catalyst systems effective for olefin polymerization may comprise a support material, an alumoxane formed in situ on the support material from a trialkylaluminum compound and water in the absence of an aromatic solvent, such as toluene, and a metallocene having C1 symmetry and comprising a Group 4 metal. To form the catalyst systems, a support material may be slurried in an aliphatic hydrocarbon solvent in the presence of water and contacted with a trialkylaluminum compound to form a supported activator, and contacting the supported activator with a metallocene having C1 symmetry and comprising a Group 4 metal.

Description

AROMATIC HYDROCARBON SOLVENT-FREE SUPPORTED METALLOCENE CATALYST SYSTEMS FOR OLEFIN POLYMERIZATION AND ASSOCIATED METHODSFIELD

[0001] The present disclosure relates to supported metallocene catalyst systems and, more particularly, to supported metallocene catalyst systems containing an alumoxane and prepared in the absence of aromatic hydrocarbon solvents.BACKGROUND

[0002] Polyolefins are commonly employed commercial polymers because of their robustness and wide-ranging and tunable physical properties. Polyolefins are typically prepared using a catalyst to promote the polymerization of one or more olefinic monomers, frequently in the presence of a co-catalyst or activator. Methyalumoxane (MAO) is a popular activator used to activate single-site catalysts, such as metallocenes, to form active catalyst systems for use in commercial gas-phase polymerization processes. Commercial MAO is commonly sold as a toluene solution because aromatic hydrocarbon solvents can dissolve MAO without causing issues observed with other solvents. For example, donor-containing solvents (e.g.. an ether or THF) may deactivate MAO through complexation, active proton-containing solvents (e.g., an alcohol) may react with MAO, and aliphatic hydrocarbon solvents (e.g., hexane) may insufficiently dissolve MAO. Even so, toluene solutions of MAO are commonly stored in a cold environment, such as about -20°C to -30°C, to reduce decomposition and gelation thereof. Gelled MAO solutions may be unsuitable to activate a catalyst for promoting olefin polymerization.

[0003] Polyolefin products, particularly polypropylene, are often used as plastic packaging for sensitive products. As such, it may be desirable to minimize the amount of non-polyolefin compounds, such as toluene and other aromatic hydrocarbon solvents, present in such polyolefin products. Recent efforts have sought to eliminate or significantly lower amounts of aromatic hydrocarbon solvents, such as toluene, used in polymerization processes, both as a delivery vehicle or as a reaction solvent, in response to potential toxicity concerns during polymerization and to eliminate residual aromatic hydrocarbon solvent in the resulting polymer product, which may be problematic for some applications. From a production standpoint, eliminating aromatic hydrocarbon solvents from polymerization processes may allow post-polymerization devolatilization operations to be minimized, thereby decreasing process costs and complexity.Unfortunately, the foregoing goals have not yet been fully realized in the case of polyolefins produced through MAO activation of metallocenes and other polymerization catalysts as a consequence of the limited solubility and compatibility of MAO with other types of solvents.SUMMARY

[0004] In some aspects, the present disclosure provides catalyst systems comprising: a support material; an alumoxane formed in situ on the support material from a trialkylaluminum compound and water in the absence of an aromatic hydrocarbon solvent; and a metallocene having Cl symmetry and comprising a Group 4 metal.

[0005] In some or other aspects, polymerization methods comprise: providing a catalyst system of the present disclosure; and contacting the catalyst system with an olefinic feed under polymerization reaction conditions to form a polyolefin.

[0006] In still other aspects, methods for making catalyst systems of the present disclosure comprise: providing a support material slurried in an aliphatic hydrocarbon solvent in the presence of water; contacting the support material with a trialkylaluminum compound in the aliphatic hydrocarbon solvent in the absence of an aromatic hydrocarbon solvent; wherein the water and the trialkylaluminum compound react to form an alumoxane upon the support material, thereby generating a supported activator; and contacting the supported activator with a metallocene having Cl symmetry and comprising a Group 4 metal to form a catalyst system.

[0007] These and other features and attributes of the disclosed systems and methods of the present disclosure and their advantageous applications and / or uses will be apparent from the detailed description which follows.BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Not applicable.DETAILED DESCRIPTION

[0009] The present disclosure relates to supported metallocene catalyst systems and, more particularly, to supported metallocene catalyst systems containing an alumoxane and prepared in the absence of aromatic hydrocarbon solvents.

[0010] Embodiments of the present disclosure include catalyst systems comprising a support material; an alumoxane formed in situ on the support material from a trialkylaluminum compound and water in the absence of an aromatic hydrocarbon solvent; and a metallocene having Cl symmetry and comprising a Group 4 metal. By forming the alumoxane in situ upon the supportmaterial in the absence of an aromatic hydrocarbon solvent, the catalyst systems may be overall free or substantially free of aromatic hydrocarbon solvents, since Cl symmetric metallocenes and optionally other metallocenes may be readily deposited upon the support material without utilizing such aromatic hydrocarbon solvents. Additional description in regard to the foregoing, as well as methods for making and using the catalyst systems in polymerization processes, is provided herein. Because the catalyst systems and associated polymerization processes may be substantially free of detectable toluene or other aromatic hydrocarbon solvents, various processing and health and safety benefits may be realized. Further advantageously, the catalyst activity and resulting polymer properties afforded with the catalyst systems of the present disclosure may be substantially identical to values obtained when aromatic hydrocarbon solvents are alternately used.

[0011] Metallocenes having Cl symmetry may afford particular advantages in regard to the foregoing. Such metallocenes are asymmetric, meaning the metallocenes have no planes of symmetry about any axis. The asymmetry is advantageous as no isomers (rac / meso) are formed during synthesis of the metallocenes, thereby providing a much higher yield or usable catalyst relative to metallocenes that are symmetric but are capable of forming optical isomers. That is, metallocenes having Cl symmetry may be advantageous in terms of subverting the need to separate optical isomers of the metallocene prior to polymerization. In some instances, Cl symmetric metallocenes may promote formation of isotactic propylene homopolymers (iPP) or long-chain branched polypropylene copolymers, for instance. In some instances, an optionally substituted adamantyl or similar bulky alkyl group in the 4-position of an indacenyl group of the Cl symmetric metallocenes may promote predominately vinyl termination of the resulting polymer. Aryl group substitution in the 4-position may promote increased polymer melting points, higher catalytic activity, and higher polymer molecular weights in some instances.Definitions

[0012] For the purposes of the present disclosure, the new numbering scheme for groups of the Periodic Table is used. In said numbering scheme, the groups (columns) are numbered sequentially from left to right from 1 through 18, excluding the f-block elements (lanthanides and actinides). Under this scheme, the term “transition metal” refers to any atom from Groups 3-12 of the Periodic Table, inclusive of the lanthanide and actinide elements. Ti, Zr, and Hf are Group 4 transition metals, for example.

[0013] As used herein, Mn is number average molecular weight, Mw is weight average molecular weight, and Mz is z average molecular weight, wt% is weight percent, and mol% is mole percent. Molecular weight distribution (MWD), also referred to as poly dispersity index (PDI), is defined to be Mw divided by Mn. Unless otherwise noted, all molecular weight units (e.g., Mw, Mn, and Mz) are in units of g / mol (g’moF1).

[0014] For purposes of this disclosure, when a polymer, copolymer, or oligomer, particularly a polyolefin, is referred to as comprising an olefin, the olefin present in such polymer, copolymer, or oligomer is the polymerized form of the olefin. For example, when a copolymer is said to have an "ethylene" content of 0 wt% to 5 wt%, it is to be understood that the mer unit in the copolymer is derived from the monomer ethylene in the polymerization reaction and said derived units are present at 0 wt% (z.e., absent) to 5 wt%, based upon the weight of the copolymer. As used herein, the terms “polymer” and oligomer” (and grammatical variations thereof) are used interchangeably to refer to a molecule having two or more of the same or different mer units. As used herein, the term “polymerize” (and grammatical variations thereof, e.g., polymerization) is used to refer to a process of generating a molecule having two or more of the same or different mer units from two or more of the same or different monomers. A “homopolymer” is a polymer (or oligomer) having mer units that are the same. A “copolymer” is a polymer (or oligomer) having two or more mer units that are different from each other. A “terpolymer” is a polymer (or oligomer) having three mer units that are different from each other. “Different,” as used to refer to mer units, indicates that the mer units differ from each other by at least one atom or are different isomerically. Accordingly, the definition of copolymer, as used herein, includes terpolymers and like higher polymers. A "decene polymer" or "decene copolymer," for example, is a polymer or copolymer comprising at least 50 mol% decene-derived units.

[0015] The term “independently,” when referenced to selection of multiple items from within a given group, means that the selected choice for a first item does not necessarily influence the choice of any second or subsequent item. That is, independent selection of multiple items within a given group means that the individual items may be the same or different from one another.

[0016] As used herein, the term “detectable aromatic hydrocarbon solvent” means 0.1 mg / m2or more aromatic hydrocarbons (e.g., toluene), as determined by gas-phase chromatography.

[0017] The terms “group,” “radical,” and “substituent” may be used interchangeably herein.

[0018] The term “hydrocarbon” refers to a class of compounds having hydrogen bound to carbon, and encompasses saturated hydrocarbon compounds, unsaturated hydrocarbon compounds, and mixtures of hydrocarbon compounds (saturated and / or unsaturated), including mixtures of hydrocarbon compounds having different numbers of carbon atoms. The term “Cn” refers to hydrocarbon(s) or a hydrocarbyl group having n carbon atom(s) per molecule or group, wherein n is a positive integer. Such hydrocarbon compounds may be one or more of linear, branched, cyclic, acyclic, saturated, unsaturated, aliphatic, and / or aromatic. As used herein, a cyclic hydrocarbon may be referred to as “carbocyclic,” which includes saturated, unsaturated, and partially unsaturated carbocyclic compounds, as well as aromatic compounds. The term “heterocyclic” refers to a carbocyclic ring containing at least one ring heteroatom as a replacement for a ring carbon atom.

[0019] The terms “hydrocarbyl radical,” “hydrocarbyl,” and “hydrocarbyl group” may be used interchangeably throughout this disclosure and refer to a group containing hydrogen atoms and carbon atoms and bearing at least one unfilled valence position when removed from a parent compound. Hydrocarbyl radical may be optionally substituted in some cases. Suitable “hydrocarbyl radicals” may refer to C1-C100 radicals that may be linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic in nature. Examples of saturated hydrocarbyl radicals include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tertbutyl, pentyl, iso-amyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like including their substituted analogues.

[0020] Substituted hydrocarbyl radicals are radicals in which at least one hydrogen atom of the hydrocarbyl radical has been substituted with at least a non-hydrogen group, such as a hydrocarbyl group, a halogen (e.g., Br, Cl, F or I), or at least one functional group such as NR*2, OR*, SeR*, TeR*, PR* 2, ASR*2, SbR*2, SR*, BR*2, SiR*3, GeR*3, SnR*3, PbR*3, and the like, or where at least one heteroatom has been inserted within a hydrocarbyl ring, wherein each R* is independently hydrogen, a hydrocarbyl or halocarbyl radical, or two or more R* may j oin together to form a substituted or unsubstituted, saturated, unsaturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure.

[0021] The term “substituted” refers to replacement of at least one hydrogen atom or carbon atom of a hydrocarbon or hydrocarbyl group with a heteroatom or heteroatom functional group. Heteroatoms may include, but are not limited to, B, O, N, S, P, F, Cl, Br, I, Si, Pb, Ge, Sn, As, Sb,Se, and Te. Heteroatom functional groups that may be present in substituted hydrocarbons or hydrocarbyl groups include, but are not limited to, functional groups such as O, S, S=O, S(=O)2, NO2, F, Cl, Br, I, NR2, OR, SeR, TeR, PR2, AsR2, SbR2, SR, BR2, SiR3, GeR3, SnRg, PbR3, where R is a hydrocarbyl group or H. Suitable hydrocarbyl R groups may include alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocyclyl, and the like, any of which may be optionally substituted.

[0022] The term “optionally substituted” means that a hydrocarbon or hydrocarbyl group can be unsubstituted or substituted. For example, the term “optionally substituted hydrocarbyl” refers to replacement of at least one hydrogen atom or carbon atom in a hydrocarbyl group with a heteroatom or heteroatom functional group. Unless otherwise specified as being expressly unsubstituted, any of the hydrocarbyl groups herein may be optionally substituted.

[0023] The term “saturated hydrocarbon” means a hydrocarbon that contains zero carbon-carbon double bonds. The saturated hydrocarbon can be a linear or cyclic hydrocarbon, either of which may be optionally branched. The saturated hydrocarbon can be a C2-C40 hydrocarbon, such as a C4-C7 hydrocarbon. In at least one embodiment, a C4-C7 hydrocarbon may be isobutane, pentane, cyclopentane, cyclohexane, isopentane, isohexane, hexane, heptane, or mixtures thereof.

[0024] The term “alkyl” means a straight-chain, branched-chain, or cyclic hydrocarbon radical having only carbon-carbon single bonds. Such alkyl radicals may be substituted. Examples of alkyl radicals include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like, including their substituted analogues.

[0025] The term “alkylene” means a divalent alkyl radical. For example, a methylene group is a divalent alkylene radical.

[0026] The term “olefin” (alternatively referred to as “alkene”) means a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond.

[0027] The term “alkenyl” means a straight-chain, branched-chain, or cyclic hydrocarbon radical having one or more carbon-carbon double bonds. These alkenyl radicals may be substituted. Examples of suitable alkenyl radicals include, but are not limited to, ethenyl, propenyl, allyl, 1,4- butadienyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloctenyl, and the like, including their substituted analogues.

[0028] The term “aromatic” means a hydrocarbyl compound or group containing a planar unsaturated ring of atoms that is stabilized by interaction of the bonds forming the ring. Suchcompounds are often six-membered rings such as benzene and its derivatives. As used herein, the term “aromatic” also refers to pseudoaromatics which are compounds that have similar properties and structures (nearly planar) to aromatics, but are not by definition aromatic; likewise, the term aromatic also refers to substituted aromatic compounds and radicals. Aromatic (but not pseudoaromatic) hydrocarbons obey the Hiickel Rule and contain a cyclic cloud of 4n+2 n- electrons, where n is a positive integer.

[0029] The term “aryl” or “aryl group” means a carbon-containing aromatic ring or substituted variants thereof, including but not limited to, phenyl, 2-methylphenyl, xylyl, 4-bromoxylyl, and the like. Likewise, the term “heteroaryl” or “heteroaryl group” means an aryl group where a ring carbon atom (or two or three ring carbon atoms) has been replaced with a heteroatom, preferably N, O, or S. As used herein, the term “aromatic” also refers to pseudoaromatic heterocycles which are heterocyclic substituents that have similar properties and structures (nearly planar) to aromatic heterocyclic groups, but are not by definition aromatic.

[0030] A substituted aryl is an aryl group where at least one hydrogen atom of the aryl radical has been substituted with at least a non-hydrogen group, such as a hydrocarbyl group, a heteroatom, or a heteroatom-containing group, such as halogen (e.g., Br, Cl, F or I) or at least one functional group such as -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*, -SiR*3, -GeR*,-GeR*3, -SnR*, -SnR*3, -PbR*3, and the like, where each R* is independently hydrogen, a hydrocarbyl or halocarbyl radical, or two or more R* may join together to form a substituted or unsubstituted, saturated, unsaturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure, or where at least one heteroatom has been inserted within a hydrocarbyl ring. For example, 3,5-dimethylphenyl and 2-methylphenyl are substituted aryl groups. The term “arylalkyl” may also refer to an aryl group where a hydrogen has been replaced with an alkyl or substituted alkyl group. The term “alkylaryl” means an alkyl group where a hydrogen has been replaced with an aryl or substituted aryl group. Thus, for example, 2-methylphenyl is an arylalkyl or substituted aryl group, and benzyl and phenethyl are alkylaryl groups.

[0031] The term “substituted phenyl,” or “substituted phenyl group” means a phenyl group having one or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom-containing group, such as halogen e.g., F, Cl, Br, I) or at least one functional group such as -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*,-BR*2, -SiR*, -SiR*3, -GeR*, -GeR*3, -SnR*, -SnR*3, -PbR*3, and the like, where each R* is independently hydrogen, a hydrocarbyl, halogen, or halocarbyl radical, or two or more R* may join together to form a substituted or unsubstituted, saturated, unsaturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure, or where at least one heteroatom has been inserted within a hydrocarbyl ring.

[0032] The term “heterocyclic” means a cyclic group where a ring carbon atom (or two or three ring carbon atoms) has been replaced with a heteroatom, such as N, O, or S. A heterocyclic ring is a ring having a heteroatom in the ring structure as opposed to a heteroatom-substituted ring where a hydrogen on a ring atom is replaced with a heteroatom. For example, tetrahydrofuran is a heterocyclic ring, and 4-N,N-dimethylaminophenyl is a heteroatom-substituted ring.

[0033] The term “substituted heterocyclic” means a heterocyclic group where at least one hydrogen atom of the heterocyclic radical has been substituted with at least a non-hydrogen group, such as a hydrocarbyl group, a heteroatom, or a heteroatom-containing group, such as halogen (e.g., F, Cl, Br, I) or at least one functional group such as -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -ASR*2, -SbR*2, -SR*, -BR*2, -SiR*, -SiR*3, -GeR*, -GeR*3, -SnR*, -SnR*3, -PbR*3, and the like, where each R* is independently hydrogen, a hydrocarbyl or halocarbyl radical.

[0034] The term “ring atom” means an atom that is part of a cyclic ring structure. By this definition, a benzyl group has 6 ring atoms and tetrahydrofuran has 5 ring atoms.

[0035] Where isomers of a named alkyl, alkenyl, alkoxide, or aryl group exist (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl), reference to one member of the group (e.g., n-butyl) shall expressly disclose the remaining isomers (e.g., iso-butyl, sec-butyl, and tert-butyl) in the family. Likewise, reference to an alkyl, alkenyl, alkoxide, or aryl group without specifying a particular isomer (e.g., butyl) expressly discloses all isomers (e.g., n-butyl, iso-butyl, sec-butyl, and tertbutyl).

[0036] The terms “catalyst productivity” and “catalyst activity” interchangeably refer to a measure of how many grams of polymer (P) are produced using a polymerization catalyst comprising W g of catalyst (cat), over a period of time of T hours; and may be expressed by the following formula: P / (TxW) and expressed in units of gPgcat’1hr’1. Conversion is the amount of monomer that is converted to polymer product, and is reported as mol % and is calculated based on the polymer yield (weight) and the amount of monomer fed into the reactor. Catalyst activityis a measure of the level of activity of the catalyst and is reported as the mass of product polymer (P) produced per mass of supported catalyst (cat) (gP / g supported cat).

[0037] The term “catalyst system” refers to a combination of at least one catalyst compound, a support material, and an optional activator. The catalyst system may further include at least one activator and / or at least one co-activator. When catalyst systems are described as comprising neutral stable forms of the foregoing components, it is to be understood that the ionic form of the component is the form that reacts with monomers to produce polymers. For purposes of the present disclosure, a “catalyst system” may include both neutral and ionic forms of the components of the catalyst system.

[0038] In the present disclosure, a “catalyst” may be described as any of a catalyst precursor, a pre-catalyst compound, catalyst compound, a catalyst, or a transition metal compound, and these terms are used interchangeably herein. An “anionic ligand” is a negatively charged ligand which donates one or more pairs of electrons to a metal ion. A “neutral donor ligand” is a neutrally charged ligand which donates one or more pairs of electrons to a metal ion.

[0039] The term “alkoxide” means entities containing a Ci to Cio hydrocarbyl group bound to oxygen. The hydrocarbyl group may be straight chain, branched, or cyclic, and be saturated or unsaturated, including aromatic. The terms “alkoxy” and “alkoxide” therefore refer to an alkyl ether or aryl ether radical. Examples of hydrocarbyl ether radicals include, but are not limited to, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, phenoxy, and the like.

[0040] The term “complex” means molecules in which an ancillary ligand is coordinated to a central metal atom. The ligand is stably bonded to the metal atom so as to maintain its influence during use of the complex during a catalytic process, such as polymerization. The ligand may be coordinated to the metal atom by a covalent bond and / or electron donation coordination or intermediate bonds. Metal complexes may be subjected to activation to perform their catalytic function, such as polymerization, using an activator which is believed to create a cation as a result of the removal of an anionic group, often referred to as a leaving group, from the metal atom.

[0041] The term “metallocene” means an organometallic compound with at least one 7c-bound cyclopentadienyl moiety or substituted cyclopentadienyl moiety (such as substituted or unsubstituted cyclopentadienyl (Cp) and / or indenyl (Ind)) and more frequently two (or three) 7i- bound cyclopentadienyl moieties or substituted cyclopentadienyl moieties.

[0042] When used in the present disclosure, the following abbreviations may be used: dme is 1,2-dimethoxy ethane, Me is methyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl, n-Pr is normal propyl, cPr is cyclopropyl, Bu is butyl, iBu is isobutyl, tBu is tertiary butyl, p-tBu is para- tertiary butyl, nBu is normal butyl, sBu is sec-butyl, TMS is trimethyl silyl, TIBAL is triisobutylaluminum, TNOAL is tri(n-octyl)aluminum, MAO is methylalumoxane, sMAO is supported methylalumoxane, Bn is benzyl (z.c., CEEPh), THF (also referred to as tetrahydrofuran, RT is room temperature (and is 23°C. unless otherwise indicated), tol is toluene, EtOAc is ethyl acetate, and Cy is cyclohexyl.

[0043] The term “scavenger” refers to a compound that may be added to a catalyst system to facilitate polymerization by scavenging impurities. Some scavengers may also act as activators and may be referred to as co-activators. A co-activator that is not a scavenger may also be used in conjunction with an activator in order to form an active catalyst system. In at least one embodiment, a co-activator can be pre-mixed with a complex to form an alkylated metal complex.

[0044] The term “continuous” means a system that operates without interruption or cessation for a period of time. For example, a continuous process to produce a polymer may continually introduce monomer into one or more reactors and polymer product is continually withdrawn therefrom.

[0045] The term “bulk polymerization” or “slurry polymerization” means a polymerization process in which the monomers and / or co-monomers being polymerized are used as a solvent or diluent using little or no inert solvent or diluent. A small fraction of inert solvent might be used as a carrier for catalyst and scavenger. A bulk polymerization system contains less than about 25 wt% of inert solvent or diluent, such as less than about 10 wt%, such as less than about 1 wt%, such as 0 wt%.Supports

[0046] The catalyst systems of the present disclosure include a support material upon which an alumoxane may be prepared in situ. The support material may be capable of absorbing water in an amount of at least 0.5 mmol of water per gram of support material. The support material may be a porous support material such as, for example, talc, inorganic oxides, zeolites, clays, organoclays, or any other organic or inorganic support materials, or mixtures thereof. In at least one example, the support material may comprise silica. Optionally, the support material may bedried (e.g., through calcination) prior to forming a catalyst system according to the disclosure herein.

[0047] The support material may be an inorganic oxide in a finely divided form. Suitable inorganic oxides for catalyst systems containing a supported alumoxane formed in accordance with the present disclosure may include Groups 2, 4, 13, or 14 metal oxides, such as silica, alumina, and mixtures thereof. Other inorganic oxides may be employed, either alone or in combination with the silica or alumina, such as magnesia, titania, zirconia, or the like. Particularly useful support materials may include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolites, talc, silica, clays, silica clay, silicon oxide clay, and the like. Combinations of these support materials may be used such as, for example, silica-chromium, silica-alumina, silica-titania, and the like. In at least one embodiment, the support material may be selected from AI2O3, ZrO2, SiO2, SiCh / AhCh, silica clay, silicon oxide / clay, or mixtures thereof. Other suitable support materials may be employed as well such as, for example, finely divided functionalized polyolefins, such as finely divided polyethylene, polypropylene, and polystyrene with functional groups that are able to absorb water, (e.g., oxygen- or nitrogen-containing groups such as -OH, -RC=O, -OR, and - NR2).

[0048] The support material may be optionally treated with an electron-withdrawing anion. The electron-withdrawing anion may increase the Lewis or Bronsted acidity of the support material, as compared to the support material that is not treated. The electron-withdrawing anion may be derived from a salt, an acid, or other compounds, such as a volatile organic compound, that serve as a source or precursor for the electron-withdrawing anion. Electron-withdrawing anions may include sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, tri fluoroacetate, triflate, fluorozirconate, fluorotitanate, phosphotungstate, or any combination thereof. Combinations of one or more different electronwithdrawing anions, in varying proportions, may be used to tailor the specific acidity of the support material to a desired level. Such combinations of electron-withdrawing anions may be contacted with the support material simultaneously or individually and in any order that provides a desired specific acidity.

[0049] The support material may be optionally fluorided by introducing a fluoride-containing anion. For example, a fluorided support may be a silicon dioxide support wherein a portion of the silica hydroxyl groups have been replaced with fluorine or a fluorine-containing compound.Suitable fluorine-containing compounds include, but are not limited to, inorganic fluorine- containing compounds and / or organic fluorine-containing compounds, either of which may be utilized for providing fluorine to the support material. Illustrative inorganic fluorine-containing compounds that may be used for fluoriding a support material include, for example, NH4BF4, (NH4)2SiF6, NH4PF6, NH4F, (NH4)2TaF7, NH4NbF4, (NH4)2GeF6, (NH4)2SmF6, (NH4)2TiF6, (NH4)2ZrF6, MOF6, ReF6, GaF3, SO2C1F, F2, SiF4, SF6, C1F3, C1F5, BrF5, IF7, NF3, HF, BF3, NHF2, NH4HF2, and combinations thereof.

[0050] Non-limiting examples of cations suitable for use in the present disclosure in combination with the electron-withdrawing anion include ammonium, trialkylammonium, tetraalkylammonium, tetraalkylphosphonium, H+, [H(OEt2)2]+, [HNR3]+(Ris a Ci-C2o hydrocarbyl group, which may be the same or different and optionally substituted), or combinations thereof.

[0051] The method by which the support material is contacted with the electron-withdrawing anion, may include, but is not limited to, gelling, co-gelling, impregnation of one compound onto another, the like, or combinations thereof. Following a particular contacting method, the treated support material may then be calcined.

[0052] The support material, preferably an inorganic oxide and more preferably silica, may have a surface area about 10 m2 / g to about 800 m2 / g, or about 10 m2 / g to about 500 m2 / g, or about 10 m2 / g to about 100 m2 / g, or about 10 m2 / g to about 50 m2 / g, or about 50 m2 / g to about 800 m2 / g, or about 50 m2 / g to about 500 m2 / g, or about 50 m2 / g to about 100 m2 / g, or about 100 m2 / g to about 800 m2 / g, or about 100 m2 / g to about 500 m2 / g, or about 500 m2 / g to about 800 m2 / g.

[0053] The support material, preferably an inorganic oxide and more preferably silica, may have a pore volume of about 0.1 cc / g to about 4.0 cc / g, or about 0.1 cc / g to about 1 cc / g, or about 1 cc / g to about 4 cc / g. The average pore size of the support material may be about 10 A to about 1000 A, or about 10 A to about 500 A, or about 10 A to about 100 A, or about 100 A to about 1000 A, or about 100 A to about 500 A, or about 500 A to about 1000 A.

[0054] The support material, preferably an inorganic oxide and more preferably silica, may have an average particle size of about 5 pm to about 500 pm, or about 5 pm to about 100 pm, or about 5 pm to about 50 pm, or about 50 pm to about 500 pm, or about 50 pm to about 100 pm, or about 100 pm to about 500 pm.

[0055] The support material, preferably an inorganic oxide and more preferably silica, may contain about 0.5 mmol absorbed water per gram of support material to about 30 mmol absorbedwater per gram of support material, or about 0.5 mmol / g to about 20 mmol / g, or about 0.5 mmol / g to about 10 mmol / g, or about 0.5 mmol / g to about 1 mmol / g, or about 1 mmol / g to about 30 mmol / g, or about 1 mmol / g to about 20 mmol / g, or about 1 mmol / g to about 10 mmol / g, or about 10 mmol / g to about 30 mmol / g, or about 10 mmol / g to about 20 mmol / g, or about 20 mmol / g to about 30 mmol / g. The amount of absorbed water may be determined by adding a known amount of water into the support material in a closed container and agitating to allow the water to distribute in the pores of the support material and / or by a standard thermogravimetric analysis method (e.g., loss on drying at 300°C for 4 hours). Most commercial support materials may contain some absorbed water, and, in some cases, the amount of absorbed water may be sufficient to facilitate formation of an alumoxane in situ according to the disclosure herein. In other cases, additional water may be added to the support material, or the support material may be initially dried (e.g., through calcination above the boiling point of water) and then contacted with an amount of water. The latter approach may be advantageous in that the amount of water that is present may be more precisely known. The foregoing may be accomplished, for example, by slurrying the support material e.g., silica) in an aliphatic hydrocarbon solvent (e.g., hexane) containing an amount of water sufficient to promote in situ formation of an alumoxane upon the surface of the support material according to the disclosure herein once absorbed onto the support material.Supported Activators, Aliphatic Hydrocarbon Solvents, and Trialkylaluminum Compounds

[0056] An alumoxane may be formed in situ upon the support material by contacting the support material with a trialkylaluminum compound in an aliphatic hydrocarbon solvent in the presence of water. As indicated above, the water may be present upon the support material and / or additional water may be added to the support material in the presence of the aliphatic hydrocarbon solvent.

[0057] Suitable aliphatic hydrocarbon solvents include those in which the trialkylaluminum compound is at least partially soluble and which are liquid at reaction temperatures. Non-limiting examples of suitable aliphatic hydrocarbon solvents include, for example, non-cyclic alkanes of formula CnH(2n+2) wherein n is 4-30 (e.g., isopentane, pentane, hexane, isohexane, n-heptane, octane, nonane, decane, and the like), cycloalkanes of parent formula CnH2n wherein n is 5-30 (e.g., cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and the like), the like, and any combination thereof. As such, the catalyst systems of the present disclosure and polymers derived therefrom may be substantially free of aromatic hydrocarbon solvents, such as toluene.

[0058] Suitable trialkylaluminium compounds that may form an alumoxane upon the support material may comprise alkyl groups having up to about 10 carbon atoms, such as octyl, isobutyl, ethyl or methyl. Thus, suitable trialkylaluminum compounds may include, but are not limited to, trimethyl aluminum, triethylaluminum, tripropylaluminum, tri-n-butylaluminum, tri-isobutyl- aluminum, tri(2-methylpentyl)aluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-n- decylaluminum, and the like. Preferably, the trialkylaluminum compound may be trimethylaluminum, and the alumoxane formed therefrom may be MAO.

[0059] When forming the alumoxane upon the support material, the molar ratio of water to the trialkylaluminum compound may be about 1 :0.95 to about 1 : 100, or about 1 : 0.95 to about 1 :50, or about 1 :0.95 to about 1 : 10, or about 1 : 10 to about 1 : 100, or about 1 : 10 to about 1 :50, or about 1 :50 to about 1 : 100. The trialkylaluminum compound may be present in an amount sufficient to provide aluminum upon the support material in an amount of about 1.5 wt% to about 30 wt%, or about 1.5 wt% to about 10 wt%, or about 1.5 wt% to about 5 wt%, or about 5 wt% to about 30 wt%, or about 5 wt% to about 10 wt%, or about 10 wt% to about 30 wt% based on the weight of the support material.

[0060] Alumoxanes may be prepared in situ upon the support material by contacting the support material with a trialkylaluminum compound and water in an aliphatic hydrocarbon solvent, thereby forming a supported activator comprising the alumoxane and lacking aromatic hydrocarbon solvents associated therewith. The support material and water may be slurried in a first portion of the aliphatic hydrocarbon solvent and then be combined with the trialkylaluminum compound dissolved in a second portion of the aliphatic hydrocarbon solvent. The slurry of the support material and water in the aliphatic hydrocarbon solvent may be agitated (e.g, stirred) prior to being contacted with the trialkylaluminum compound. The support material and water may be added to the trialkylaluminum compound or vice versa. Optionally, the water may be adsorbed to the support material when added to the aliphatic hydrocarbon solvent, and the water need not necessarily be visible when the support material is slurried in the aliphatic hydrocarbon solvent. Preferably, the slurry of the support material and the water in the aliphatic hydrocarbon solvent may be added to the trimethylaluminum compound dissolved in the second portion of the aliphatic hydrocarbon solvent. In one example, the slurry of the support material may be added slowly to the trialkylaluminum solution at a temperature of about 0°C to about -60°C, or about 0°C to about -25°C, or about 0°C to about -10°C, or about -10°C to about -60°C, or about -10°C to about -25°C,or about -25°C to about -60°C. Mineral oil or similar inert materials may be added to the slurry of the support material to produce a viscous slurry so as to avoid fast settlement of particles, for example.

[0061] After being prepared in situ, the alumoxane and the support material may be optionally treated at a higher temperature for a period of time, either within the aliphatic hydrocarbon solvent slurry or after being isolated therefrom. For example, such treatment may take place at about 60°C to about 200°C, or about 60°C to about 150°C, or about 60°C to about 100°C, or about 100°C to about 200°C, or about 100°C to about 150°C, or about 150°C to about 200°C.

[0062] The resulting supported activator may be isolated from the aliphatic hydrocarbon solvent through, for example, filtration, decantation, evaporation, or any combination thereof. After isolation of the supported activator from the aliphatic hydrocarbon solvent, additional washing of the supported activator with an aliphatic hydrocarbon solvent may take place and / or drying under vacuum and / or with application of heat may take place. As another option, the supported activator may also be spray dried in a spray drying reactor at a high temperature to evaporate the solvents and / or volatiles and form the supported activator with a desired average particle size and particle size distribution.Ligands and Metallocene Complexes

[0063] The supported activators described above may further be converted into a catalyst system by contacting the supported activator with a metallocene, preferably a metallocene having Cl symmetry and comprising a Group 4 metal (e.g., Ti, Zr, or Hf). In non-limiting examples, the catalyst systems may be effective for promoting polymerization of ethylenically unsaturated compounds, such as one or more alpha-olefins, under suitable polymerization reaction conditions. The metallocenes may be loaded onto the support material in combination with the alumoxane, and the catalyst systems may be isolated prior to performing a polymerization reaction, or formation of the catalyst systems may take place in situ during a polymerization reaction by contacting the supported alumoxanes with a suitable metallocene in the presence of an ethylenically unsaturated compound.

[0064] Metallocenes suitable for use in the catalyst systems and associated processes of the present disclosure may have a structure represented by Formula 1Formula 1 wherein:

[0065] M is a transition metal of Group 3, 4, or 5 of the Periodic Table of Elements, such as a Group 4 metal, for example Zr, Hf, or Ti;

[0066] T is a bridging group;

[0067] X1and X2are each a univalent anionic ligand, or X1and X2are joined to form a metallocycle ring, a chelating ligand, a diene ligand, or an alkylidene;

[0068] R1is hydrogen, halogen, optionally substituted C1-C40 alkyl, optionally substituted Ce- C14 aryl, optionally substituted C3-C13 heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, where R" is C1-C10 alkylene and each R' is hydrogen, C1-C10 alkyl, or Cg-Cio aryl; preferably, R1is C1-C10 alkyl, and more preferably, R1is methyl;

[0069] R2and R6are independently hydrogen, halogen, optionally substituted C1-C40 alkyl, optionally substituted Ce-Ci4 aryl, an optionally substituted C3-C13 heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2, or -R"-SiR’3, wherein R" is C1-C10 alkylene and each R' is hydrogen, C1-C10 alkyl, or Cg-Cio aryl; preferably, at least one of R2and R6are hydrogen, and more preferably, R2and R6are both hydrogen;

[0070] R3is an optionally substituted C1-C40 alkyl, an optionally substituted Ce-Cis aryl, or an optionally substituted C3-C13 heteroaryl; more preferably R3is a bulky alkyl group, such as optionally substituted cyclohexyl, optionally substituted norbomanyl, optionally substituted adamantanyl, or optionally substituted tert-butyl, such as cyclohexyl, 1-adamantyl, 2-adamantyl, (ls,4s)-bicyclo[2.2.1]heptan-7-ide, (lR,4S)-bicyclo[2.2.1]heptan-2-ide, or (Is, 4s)- bicyclo[2.2.1]heptan-l-ide; or R3is an optionally substituted aryl group, more preferably an optionally substituted phenyl group, an optionally substituted naphthyl group, or an optionally substituted anthracenyl group;

[0071] R4and R5are independently H, R1", or OR'", wherein R1" is an optionally substituted Ci- C40 alkyl, or R4and R5are joined to form a C3-C62 substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic ring structure, or a combination thereof;

[0072] R7, R8, R9, and R10are independently hydrogen, halogen, optionally substituted C1-C40 alkyl, optionally substituted C6-C14 aryl, optionally substituted C3-C13 heteroaryl, -NR'2, -SR', - OR', -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10 alkylene and R' is hydrogen, C1-C10 alkyl, or C6-C10 aryl, or one or more of R5and R6, R6and R7, or R7and R8are joined to form a C3- Cg2 substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic ring structure, or a combination thereof; preferably R7, R8, R9, and R10are methyl.

[0073] As a non-limiting illustration, in Formula 1 when R4and R5are joined to form a polycyclic ring structure, the polycyclic ring structure may comprise a 5- or 6-membered ring, preferably a 5- or 6-membered carbocyclic ring lacking heteroatoms as ring atoms. For example, an indacenyl ligand contains such a 5-membered carbocyclic ring and a hexahydrobenz[ / ]indenyl ligand contains such a 6-membered carbocyclic ring.hexahydrobenz[ / ]indenyl ligandThe carbocyclic ring in the indacenyl ligand or the hexahydrobenz[f]indenyl ligand can be substituted or unsubstituted and can be part of multi-cyclic groups where the additional cyclic groups may be saturated or unsaturated, and substituted or unsubstituted. Typical substituents on the carbocyclic ring may include optionally substituted Ci to C40 hydrocarbyls, heteroatoms (such as halogens, such as Br, F, Cl, or I), heteroatom-containing groups (such as a halocarbyl), or two or more substituents are joined together to form a cyclic or polycyclic ring structure (which may contain saturated and / or unsaturated rings), or a combination thereof. Examples ligands in which R4and R5are fused to form a carbocyclic ring include those having structures represented by Formulas 2-4:Formula 2 Formula 3 Formula 4 where the wavy lines indicate a connection to M in Formula 1 (such as to Hf or Zr) and T (such as MesSi). The corresponding ligands lacking methyl group substitution on the unsaturated carbocyclic ring are also suitable for use herein. In any of the foregoing, R3may be a bulky alkyl group, preferably an optionally substituted cyclohexyl, optionally substituted norbornanyl, optionally substituted adamantyl, or optionally substituted tert-butyl, or an optionally substituted aryl group, such as an optionally substituted phenyl group, optionally substituted naphthyl group, or optionally substituted anthracenyl group.

[0074] When R4and R5are not joined to form a polycyclic ring structure, preferably both R4and R5may be hydrogen, or R4may be OR'" and R5may be R1", wherein each R’" is independently selected. In specific examples, R4may be OR'", preferably OCH3, and R5may be hydrogen, or R4may be OR'", preferably OCH3, and R may be an alkyl group, preferably t-butyl.

[0075] In some embodiments of the present disclosure, X1and X2are each independently an optionally substituted C1-C40 hydrocarbyl (such as an optionally substituted C2-C20 hydrocarbyl), an optionally substituted C4-C62 aryl, an optionally substituted C4-C62 heteroaryl, hydride, amide, alkoxide, sulfide, phosphide, halide, diene, amine, phosphine, ether, or a combination thereof. For example, each of X1and X2may be independently a halide or a Ci-Ce hydrocarbyl or a C1-C10 hydrocarbyl, such as methyl. In some embodiments, each of X1and X2is independently chloro, bromo, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl. In some embodiments of the present disclosure, X1and X2may form a part of a fused ring or a ring system, which may define a metallocycle, a chelating ligand, or a diene ligand bound to M.

[0076] In some embodiments, T is represented by the formula, (R*2G)g, wherein each G is C, Si, or Ge, g is 1 or 2, and each R* is, independently, hydrogen, an optionally substituted C1-C20 hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or phenyl), or the two or more R* are joined to form a substituted orunsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic ring structure. In some embodiments, the bridging group may be represented by R'2C, R'2Si, R'2Ge, R'2CCR'2, R'2CCR'2CR'2, R'2CCR'2CR'2CR'2, R'C=CR', R'C=CR'CR'2, R'2CCR'=CR'CR'2, R'C=CR'CR'=CR', R'C=CR'CR'2CR'2, R'2CSiR'2, R'2SiSiR'2, R2CSiR'2CR'2, R^SiCR^SiR^, R'C=CR'SiR'2, R'2CGeR'2, R'2GeGeR'2, R'2CGeR'2CR'2, R'2GeCR'2GeR'2, R'2SiGeR'2, R'C=CR'GeR'2, R'B, R'2C- BR', R'2C-BR'-CR'2, R'2C-O-CR'2, R'2CR'2C-O-CR'2CR'2, R'2C-O-CR'2CR'2, R'2C-0-CR'=CR', R2C-S-CR2, R'2CR'2C-S-CR'2CR'2, R'2C-S-CR'2CR'2, R'2C-S-CR'=CR', R'2C-Se-CR'2, R'2CR'2C-Se-CR'2CR'2, R'2C-Se-CR2CR'2, R'2C-Se-CR'=CR', R'2C-N=CR', R'2C-NR'-CR'2, R'2C -NR' CR2CR2, R'2C NR' CR-CR', R'2CR'2C NR' CR'2CR'2, R'2C-P=CR', or R'2C PR' CR'2 where each R' is independently hydrogen or an optionally substituted C1-C20 hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or phenyl), a C1-C20 halocarbyl, a C1-C20 silylcarbyl, or a C1-C20 germylcarbyl substituent, or two or more adjacent R' are joined to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic ring structure. In some embodiments of the present disclosure, T may be CH2, CH2CH2, C(CH3)2, (Ph)2C, (p-(Et)3SiPh)2C, SiMe2, SiPh2, SiMePh, Si(CH2)s, or Si(CH2)4. Preferably, T is CH2or SiMe2, and more preferably SiMe2or SiPh2.

[0077] Suitable alkyl groups in any selection herein may be optionally substituted and independently chosen from, but not limited to, methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl, nonacosenyl, triacontenyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonadecynyl, eicosynyl, heneicosynyl, docosynyl, tricosynyl, tetracosynyl, pentacosynyl, hexacosynyl, heptacosynyl, octacosynyl, nonacosynyl, triacontynyl, butadienyl, pentadienyl, hexadienyl, heptadienyl, octadienyl, nonadienyl, and decadienyl.

[0078] Suitable aryl groups in any selection herein may be optionally substituted and independently chosen from, but not limited to, phenyl, 1 -naphthyl, 2-naphthyl, 9-anthracenyl, 2- biphenyl, 3-biphenyl, 4-biphenyl, 2-methylphenyl, 3 -methylphenyl, 4-methylphenyl, 2,3- dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4- dimethylphenyl, 3,5-dimethylphenyl, 2,4,5-trimethylphenyl, 3,4,5-trimethylphenyl, 2, 3, 4,5,6- pentamethylphenyl, 2-ethylphenyl, 3 -ethyl phenyl, 4-ethylphenyl, 2,3-diethylphenyl, 2,4- diethylphenyl, 2,5-diethylphenyl, 2,6-diethylphenyl, 3,4-diethylphenyl, 3,5-diethylphenyl, 2- isopropylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 3,5-di-isopropylphenyl, 2,5-di- isopropylphenyl, 2-tert-butylphenyl, 3-tert-butylphenyl, 4-tert-butylphenyl, 3,5-di-tert- butylphenyl, 3,5-di-tert-butyl-4-methoxyphenyl, 3,5-di-tert-butyl-4-dimethylaminophenyl, 2,5-di- tert-butylphenyl, 2-trimethylsilylphenyl, 3-trimethylsilylphenyl, 4-trimethylsilylphenyl, 3,5- bis(trimethylsilyl)phenyl, 2-trifluoromethylphenyl, 3 -trifluoromethylphenyl, 4- trifluoromethylphenyl, and 3,5-bis(trifluoromethyl)phenyl.

[0079] Suitable cycloalkyl groups in any selection herein may be optionally substituted and independently chosen from, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, cycloheptyl, cycloheptenyl, norbomanyl, norbornenyl, adamantyl, and the like.

[0080] In more specific examples, metallocenes suitable for forming a catalyst system herein and having a structure represented by Formula 1 with alkyl substitution at R3may include variables defined in accordance with the following:

[0081] M is a Group 4 metal, preferably zirconium or hafnium, and more preferably hafnium;

[0082] T is a bridging group; preferably CRnR12or SiRnR12, wherein R11and R12are independently hydrogen, an optionally substituted C1-C40 hydrocarbyl, or optionally substituted Ce-C62 aryl, or R11and R12are joined to form a substituted or unsubstituted C4-C62 saturated or unsaturated cyclic or polycyclic ring structure; more preferably T is CH2, CH2CH2, C(CH3)2, (Ph)2C, (p-(Et)3SiPh)2C, SiMe2, SiPh2, SiMePh, Si(CH2)3, Si(CH2)4, or Si(CH2)4; still more preferably T is CH2or SiMe2or more preferably, T is SiMe2or SiPh2;

[0083] X1and X2are each a univalent anionic ligand, or X1and X2are joined to form a metallocycle ring, a chelating ligand, a diene ligand, or an alkylidene, preferably X1and X2are independently a halide (F, Cl, Br, I) or a Ci-Ce hydrocarbyl, such as a Ci-Ce alkyl or phenyl, more preferably methyl;

[0084] R1is hydrogen, a halogen, an optionally substituted C1-C40 hydrocarbyl, an optionally substituted C4-C62 aryl, an optionally substituted C4-C62 heteroaryl, -NR'2, -SR', -OR’, -SiR'3, - OSiR'3, -PR' 2, or -R"-SiR'3, wherein R" is C1-C10 alkylene and R' is hydrogen, C1-C10 alkyl, or Ce- C10 aryl; preferably R1is C1-C10 alkyl; more preferably R1is methyl;

[0085] R2and R6are independently hydrogen, a halogen, an optionally substituted C1-C40 hydrocarbyl, an optionally substituted C4-C62 aryl, an optionally substituted C4-C62 heteroaryl, - NR'2, -SR', -OR’, -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10 alkylene and R' is hydrogen, C1-C10 alkyl, or Ce-Cio aryl; preferably R2and R6are hydrogen or R2is hydrogen and R6is H or optionally substituted phenyl;

[0086] R3is a bulky alkyl group; preferably R3is an optionally substituted cyclohexyl, optionally substituted norbornanyl, optionally substituted adamantyl (e.g., 1-adamantyl, 2-adamantyl, (ls,4s)-bicyclo[2.2.1]heptan-7-yl, (lR,4S)-bicyclo[2.2.1]heptan-2-yl, (Is, 4s)- bicyclo[2.2.1]heptan-l-yl) , or optionally substituted t-butyl;

[0087] R4and R3are independently H, R'", or OR'", wherein R'" is an optionally substituted Ci- C40 alkyl, or R4and R5are joined to form a C3-C62 substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic ring structure, or a combination thereof; and

[0088] R7, R8, R9, and R10are independently hydrogen, a halogen, an optionally substituted Ci- C40 hydrocarbyl, an optionally substituted C4-C62 aryl, an optionally substituted C4-C62 heteroaryl, -NR'2, -SR', -OR’, -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10 alkylene and R' is hydrogen, C1-C10 alkyl, or Ce-Cio aryl, or one or more of R3and R6, R6and R7, or R7and R8are joined to form a substituted or unsubstituted C4-C62 saturated or unsaturated cyclic or polycyclic ring structure, or a combination thereof; preferably R5, R6, R7, and R8are each C1-C10 alkyl; more preferably R5, R6, R7, and R8are each methyl.

[0089] If R4and R5are not joined to form a cyclic or polycyclic ring structure, preferably both R4and R5may be hydrogen, or R4may be OR'" and R5may be R'", wherein each R"' is independently selected. In specific examples, R4may be OR'", preferably OCH3, and R5may be hydrogen, orR4may be OR'", preferably OCH3, and R5may be an alkyl group, preferably t-butyl.

[0090] Accordingly, in some embodiments, suitable metallocenes having Cl symmetry and a bulky alkyl group at R3may have a structure represented by Formula 5Formula 5 wherein:

[0091] M is a Group 4 metal, preferably Zr or Hf, more preferably Hf;

[0092] X1and X2are independently a halide (F, Cl, Br, I) or a Ci-Ce alkyl; preferably X1and X2are each chloride or methyl;

[0093] R1is Ci-Cio alkyl group, preferably methyl;

[0094] R3is a bulky alkyl group, preferably optionally substituted cyclohexyl, optionally substituted norbomanyl, optionally substituted adamantyl, or optionally substituted t-butyl; preferable groups include 1-adamantyl, 2-adamantyl, (ls,4s)-bicyclo[2.2.1]heptan-7-ide, (1R,4S)- bicyclo[2.2.1]heptan-2-ide, or (ls,4s)-bicyclo[2.2.1]heptan-l-ide;

[0095] R4and R3are independently H, R'", or OR'", wherein R'" is an optionally substituted Ci- C40 alkyl, or R4and R5are joined to form a C3-C62 substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic ring structure, or a combination thereof;

[0096] R6is hydrogen, halogen, optionally substituted C1-C40 alkyl, optionally substituted Ce- C14 aryl, an optionally substituted C3-C13 heteroaryl, -NR'2, -SR', -OR',-SiR'3, -OSiR'3, -PR'2, or -R"-SiR’3, wherein R" is C1-C10 alkylene and each R' is hydrogen, C1-C10 alkyl, or Ce-Cio aryl; preferably R6is hydrogen or optionally substituted phenyl;

[0097] R7, R8, R9, and R10are independently hydrogen, a halogen, an optionally substituted Ci- C40 hydrocarbyl, an optionally substituted C4-C62 aryl, an optionally substituted C4-C62 heteroaryl, -NR'2, -SR', -OR’, -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10 alkylene and R' is hydrogen, C1-C10 alkyl, or Ce-Cio aryl, or one or more of R5and R6, R6and R7, or R7and R8are joined to form a substituted or unsubstituted C4-C62 saturated or unsaturated cyclic or polycyclic ring structure, or a combination thereof; preferably R3, R6, R7, and R8are each C1-C10 alkyl; more preferably R5, R6, R7, and R8are each methyl; and

[0098] R11and R12are independently optionally substituted C1-C10 alkyl, or optionally substituted Ce-Cio aryl, or R11and R12are joined to form a substituted or unsubstituted C2-C22saturated or unsaturated cyclic or polycyclic ring structure; preferably R11and R12are each methyl or phenyl; and more preferably, R11and R12are each methyl.

[0099] In some examples, R4and R3may form a 5-membered carbocyclic ring. Specific examples of such metallocenes having a bulky alkyl group at R3may have a structure represented by Formula 6A, preferably wherein R6is hydrogen or optionally substituted phenyl. The metallocene represented by Formula 6B lacks the 5-membered carbocyclic ring fused to thewherein in Formula 6 A:

[0100] Q is an optional Ci-Ce alkyl group, and q is 0, 1, 2, 3, 4, 5, or 6. When present (q 0), optional substitution Q may be present at any non-aromatic carbon atom of the 5-membered ring defined by R4and R3. Preferably, each occurrence of Q is a methyl group.

[0101] Illustrative examples of metallocenes having a structure represented by Formulas 5, 6A, and 6B may include, but are not limited to:

[0102] In other specific examples, suitable metallocenes having Cl symmetry and a structure represented by Formula 1 may have an optionally substituted aryl at R3, preferably an optionally substituted phenyl group, an optionally substituted naphthyl group, or optionally substitutedanthracenyl group. Such metallocenes having an optionally substituted phenyl group at R3may have a structure represented by Formula 7Formula 7 wherein:

[0103] R13-R17are independently hydrogen, an optionally substituted C1-C40 hydrocarbyl, an optionally substituted C4-C62 aryl, an optionally substituted C4-C62 heteroaryl, -NR'2, -SR', -OR’, -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10 alkyl and each R1is hydrogen, Ci- C10 alkyl, or Ce-Cio aryl, or R13and R14, R14and R15, R15and R16, or R16and R17, or any combination thereof are joined to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic ring structure;

[0104] M is a Group 4 metal, preferably Zr or Hf, more preferably Hf;

[0105] X1and X2are independently a halide (F, Cl, Br, I) or a Ci-Ce alkyl; preferably X1and X2are each chloride or methyl;

[0106] R1is C1-C10 alkyl group, preferably methyl;

[0107] R4and R5are independently H, R1", or OR'", wherein R'" is an optionally substituted Ci- C40 alkyl, or R4and R5are joined to form a C3-C62 substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic ring structure, or a combination thereof;

[0108] R6is hydrogen, halogen, optionally substituted C1-C40 alkyl, optionally substituted Ce- C14 aryl, an optionally substituted C3-C13 heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2, or -R"-SiR’3, wherein R" is C1-C10 alkylene and each R' is hydrogen, C1-C10 alkyl, or G-Cio aryl; preferably R6is hydrogen or optionally substituted phenyl;

[0109] R7, R8, R9, and R10are independently hydrogen, a halogen, an optionally substituted Ci- C40 hydrocarbyl, an optionally substituted C4-C62 aryl, an optionally substituted C4-C62 heteroaryl, -NR'2, -SR', -OR’, -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10 alkylene and R' ishydrogen, C1-C10 alkyl, or Ce-Cio aryl, or one or more of R5and R6, R6and R7, or R7and R8are joined to form a substituted or unsubstituted C4-C62 saturated or unsaturated cyclic or polycyclic ring structure, or a combination thereof; preferably R5, R6, R7, and R8are each C1-C10 alkyl; more preferably R5, R6, R7, and R8are each methyl; and

[0110] R11and R12are independently optionally substituted C1-C10 alkyl, or optionally substituted Ce-Cio aryl, or R11and R12are joined to form a substituted or unsubstituted C2-C22 saturated or unsaturated cyclic or polycyclic ring structure; more preferably R11and R12are each methyl or phenyl.

[0111] In some examples, R4and R may form a 5-membered carbocyclic ring. Specific examples of such metallocenes having an optionally substituted phenyl group at R3may have a structure represented by Formula 8A, preferably wherein R6is hydrogen or optionally substituted phenyl. The metallocene represented by Formula 8B lacks the 5-membered carbocyclic ring fused to the indeny 1 group.wherein in Formula 8A:

[0112] Q is an optional Ci-Ce alkyl group, and q is 0, 1, 2, 3, 4, 5, or 6. When present (q 0), optional substitution Q may be present at any non-aromatic carbon atom of the 5-membered ring defined by R4and R3. Preferably, each occurrence of Q is a methyl group.

[0113] Illustrative examples of metallocenes having a structure represented by Formulas 7, 8A, or 8B include, but are not limited to:5Hf may replace Zr in any of the foregoing metallocenes.

[0114] For nomenclature purposes, the following numbering scheme is used for an indenyl ring.It should be noted that an indenyl ring can be considered a cyclopentadienyl group fused with a benzene ring. The structure below is drawn and named as an anion.Indenyl

[0115] Also for clarity, the following ring structures are substituted indenyl groups, where substitutions at the 5- and 6- positions collectively define a ring structure. For specific compound nomenclature purposes, these ligands are described below. A similar numbering and nomenclature scheme is used for these types of substituted indenyls that include indacenyls, cyclopenta[b]naphthalenyls, heterocyclopentanaphthyls, heterocyclopentaindenyls, and the like, as illustrated below. Each structure is drawn and named as an anion.1 ,2,3-trihydro-s-indacenyl 5,6,7,8-tetrahydro-cyclopenta[&]naphthalenylcyclopenta[6]naphthalenyl 5,8-dihydro-cyclopenta[fe]naphthalenyl7,8-dihydro-cyclopenta[Z>]naphthalenylCatalyst Systems

[0116] The present disclosure further provides catalyst systems comprising a support material; an alumoxane formed in situ on the support material from a trialkylaluminum compound and waterin the absence of an aromatic hydrocarbon solvent; and a metallocene having Cl symmetry and comprising a Group 4 metal, each component being described in further detail above.

[0117] Methods for forming the catalyst systems may comprise: providing a support material slurried in an aliphatic hydrocarbon solvent in the presence of water; contacting the support material with a trialkylaluminum compound in the aliphatic hydrocarbon solvent in the absence of an aromatic solvent; wherein the water and the trialkylaluminum compound react to form an alumoxane upon the support material, thereby generating a supported activator; and contacting the supported activator with a metallocene having Cl symmetry and comprising a Group 4 metal to form a catalyst system. Optionally, the supported activator may be separated from the aliphatic hydrocarbon solvent before contacting the supported activator with the metallocene.

[0118] In non-limiting examples, the alumoxane may be present in the catalyst system in up to a 5000-fold molar excess relative to the metallocene, as evaluated based on a ratio of aluminum to Group 4 metal in the metallocene (A1:M molar ratio). The minimum aluminum: Group 4 molar ratio is generally a 1 : 1 molar ratio. Accordingly, preferred ranges of molar ratios may include A1:M ratios of 1 :1 to 500: 1, 1 : 1 to 200: 1, 1 : 1 to 100: 1, or 1 : 1 to 50: 1.

[0119] Together, the support material and the alumoxane formed in situ on the support material may be described as a supported activator. The supported activator may be heated in a first portion of aliphatic hydrocarbon solvent, followed by separation therefrom, prior to contacting the metallocene in a second portion of the aliphatic hydrocarbon solvent. For example, the supported activator may be slurried in an aliphatic hydrocarbon solvent (first portion of aliphatic hydrocarbon solvent) and the resulting slurry may be contacted with a solution of at least one metallocene in the aliphatic hydrocarbon solvent (second portion of aliphatic hydrocarbon solvent). Alternately, the metallocene may be combined as a solid with the slurry of the supported activator in the aliphatic hydrocarbon solvent. The slurry of the supported activator may be contacted with the metallocene for a period of time ranging from about 0.02 hours to about 24 hours, or about 0.02 hours to about 12 hours, or about 0.02 hours to about 6 hours, or about 0.02 hours to about 1 hour, or about 1 hour to about 24 hours, or about 1 hour to about 12 hours, or about 1 hour to about 6 hours, or about 6 hours to about 24 hours, or about 6 hours to about 12 hours, or about 12 hours to about 24 hours.

[0120] The slurry of the supported activator may be heated while contacting the metallocene at a temperature ranging from about 0°C to about 70°C, or about 0°C to about 50°C, or about 0°C toabout 10°C, or about 10°C to about 70°C, or about 10°C to about 50°C, or about 50°C to about 70°C.

[0121] Similarly, an aliphatic hydrocarbon solvent may be charged into a reactor, followed by the supported activator that is pre-formed and isolated from an aliphatic hydrocarbon solvent. A metallocene may then be charged into the reactor, such as a metallocene solution in an aliphatic hydrocarbon solvent or as a solid. The mixture may be stirred at a temperature of about 0°C to about 70°C, or about 0°C to about 50°C, or about 0°C to about 10°C, or about 10°C to about 70°C, or about 10°C to about 50°C, or about 50°C to about 70°C. Additional solvent may be added to the mixture to form a slurry having a desired consistency, such as about 2 cc / g silica to about 20 cc / g silica, or about 2 cc / g silica to about 10 cc / g silica, or about 2 cc / g silica to about 5 cc / g silica, or about 5 cc / g silica to about 20 cc / g silica, or about 5 cc / g silica to about 10 cc / g silica, or about 10 cc / g silica to about 20 cc / g silica, each of the foregoing representing the total volume ratio of aliphatic hydrocarbon solvent in the reactor. The foregoing ratios of solvent to silica may also be applicable to other support materials.

[0122] After slurrying, the solvent may be removed to isolate the catalyst system. Removal of the solvent may be performed under a vacuum, by purging with inert atmosphere, by heating the mixture, or any combination thereof. When heating is conducted, any suitable temperature may be used that evaporates the aliphatic hydrocarbon solvent but without substantially altering the catalytic activity of the catalyst system.Polymerization Methods

[0123] Embodiments of the present disclosure may include polymerization methods comprising providing a catalyst system described herein; and contacting the catalyst system with an olefinic feed under polymerization reaction conditions to form a polyolefin. In non-limiting examples, contacting may be performed under gas-phase polymerization reaction conditions or slurry-phase polymerization reaction conditions. Such processes can be run in a batch, semi-batch, or continuous mode.

[0124] Slurry- and gas-phase polymerizations may be conducted in the presence of an aliphatic hydrocarbon solvent / diluent / condensing agent, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; preferably aromatics are present in the solvent / diluent / condensing agent at lessthan 1 wt%, preferably less than 0.5 wt%, preferably at 0 wt% based upon the weight of the solvents / diluent / condensing agent.

[0125] Monomers useful herein include substituted or unsubstituted C2 to C40 alpha-olefins, preferably C2 to C20 alpha-olefins, preferably C2 to C12 alpha-olefins, preferably ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecane, and isomers thereof. In a preferred embodiment, suitable olefins that may undergo polymerization with the catalyst systems include propylene and one or more optional co-monomers comprising one or more of ethylene or a C4 to C40 olefin, preferably a C4 to C20 olefin, or more preferably a Ce to C12 olefin. The C4 to C40 olefin monomers may be linear, branched, or cyclic. The C4 to C40 cyclic olefin may be strained or unstrained, monocyclic or polycyclic, and may include one or more heteroatoms and / or one or more functional groups. In another preferred embodiment, suitable monomers that may undergo polymerization with the catalyst systems include ethylene and an optional co-monomer comprising one or more of a C3 to C40 olefin, preferably a C4 to C20 olefin, or more preferably a Ce to C12 olefin. The C3 to C40 olefin monomers may be linear, branched, or cyclic. The C3 to C40 cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may include heteroatoms and / or one or more functional groups.

[0126] Illustrative C2 to C40 olefin monomers and optional co-monomers that may undergo polymerization according to the disclosure herein include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7- oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof, preferably hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, l-hydroxy-4-cyclooctene, 1 -acetoxy -4-cyclooctene, 5-methyl cyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene, vinylnorbornene, and substituted derivatives thereof, preferably norbomene, norbornadiene, and dicyclopentadiene.

[0127] One or more dienes may be present in a polymer produced according to the disclosure herein in an amount up to about 10 wt%, such as about 0.00001 to about 1.0 wt%, or about 0.002 to about 0.5 wt%, or about 0.003 to about 0.2 wt%, based upon the total weight of the polymer. In at least one embodiment, about 500 ppm or less of diene is added to the polymerization reaction, or about 400 ppm or less, or about 300 ppm or less. In at least one embodiment, at least about 50ppm of diene is added to the polymerization reaction, or about 100 ppm or more, or about 150 ppm or more.

[0128] Diene monomers may include any hydrocarbon structure, preferably a C4 to C30 hydrocarbon, having at least two unsaturated carbon-carbon bonds that may be conjugated or nonconjugated with one another. Particularly suitable diene monomers may include a, co -diene monomers (z.e., di-vinyl monomers), wherein olefinic groups are non-conjugated and the diolefin monomer contains 4 to 30 carbon atoms. Non-limiting examples of suitable diene monomers may include butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, particularly preferred dienes include 1,6-heptadiene, 1,7-octadiene, 1,8 -nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11 -dodecadiene, 1,12-tri decadiene, 1,13- tetradecadiene, and low molecular weight polybutadienes (Mw less than 1000 g / mol). Nonlimiting example cyclic dienes include cyclopentadiene, vinylnorbornene, norbornadiene, ethylidene norbomene, vinylnorbornene, divinylbenzene, dicyclopentadiene or higher ring containing diolefins with or without substituents at various ring positions.

[0129] Where butene is the co-monomer, the butene source may be a mixed butene stream comprising various isomers of butene. In such a mixed stream, 1-butene monomers are expected to be preferentially consumed by the polymerization process as compared to other butene monomers. Use of such mixed butene streams will provide an economic benefit, as these mixed streams are often waste streams from refining processes, for example, C4 raffinate streams, and can therefore be substantially less expensive than pure 1-butene.

[0130] Preferred polymerizations can be run at any temperature and / or pressure suitable to obtain the desired polyolefins. Typical temperatures and / or pressures include a temperature from about 0°C to about 300°C, or about 20°C to about 200°C, or about 35°C to about 150°C, or about 40°C to about 120°C, or about 65°C to about 95°C; and at a pressure from about 0.35 MPa to about 10 MPa, or about 0.45 MPa to about 6 MPa, or preferably from about 0.5 MPa to about 4 MPa. The run time of the polymerization reaction may be up to about 400 minutes, such as from about 5 minutes to about 250 minutes, or about 10 minutes to about 120 minutes.

[0131] Hydrogen may be added during the polymerization reaction to promote molecular weight control of the polyolefin being produced. In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of about 0.001 psig to about 50 psig (0.007 kPa to 345 kPa), or about 0.01 psig to about 25 psig (0.07 kPa to 172 kPa), or about 0.1 psig and 10 psig (0.7 kPa to 70 kPa). In one embodiment, 600 ppm or less of hydrogen is added, or 500 ppm or less of hydrogen is added, or 400 ppm or less, or 300 ppm or less. In other embodiments, at least 50 ppm of hydrogen is added, or 100 ppm or more, or 150 ppm or more.

[0132] The activity of the catalyst system may be at least about 50 g / mmol / hour, such as about 500 or more g / mmol / hour, or about 5,000 or more g / mmol / hr, or about 750,000 or more g / mmol / hr where the amount of metallocene is in the denominator. In an alternative embodiment, the conversion of olefin monomer is at least about 10%, based upon polymer yield (weight) and the weight of the monomer entering the reaction zone of the polymerization reactor, such as about 20% or more, or about 30% or more, or about 50% or more, or about 80% or more.

[0133] Preferably, little or no scavenger is used in the process to produce the polyolefin, such that scavenger is present at 0 mol%. Alternatively, the scavenger may be present at a molar ratio of scavenger metal to transition metal of the metallocene of less than about 100: 1, such as less than about 50: 1, or less than about 15: 1, or less than about 10: 1.

[0134] Other additives may also be used in the polymerization, as desired, such as one or more promoters, modifiers, chain transfer agents (such as diethyl zinc or a trialkylaluminum compound), reducing agents, oxidizing agents, hydrogen, or silanes.

[0135] Gas-phase polymerization processes may be used herein. Generally, in a fluidized gasphase process for producing polymers, a gaseous stream containing one or more monomers is continuously cycled through a fluidized bed comprising a catalyst system of the present disclosure under reactive conditions. The monomers within the gaseous stream need not necessarily be introduced to the reactor as a gas (i.e., they may be introduced as a condensed liquid), but they are in a gas state at least while contacting the catalyst system. The gaseous stream is withdrawn from the fluidized bed and recycled back into the reactor to continue polymerization of the monomers contained therein. Simultaneously, polymer product is withdrawn from the reactor and fresh monomer may be added to replace the polymerized monomer in the recycled gaseous stream.

[0136] Slurry-phase polymerization processes may also be used herein. In a slurry polymerization, a suspension of solid, particulate polymer is formed in a liquid polymerizationdiluent medium to which monomer and co-monomers, along with catalysts, are added. The suspension including diluent is intermittently or continuously removed from the reactor where the volatile components are separated from the polymer and recycled, optionally after a distillation, to the reactor. The liquid diluent employed in the polymerization medium is typically an alkane having from 3 to 7 carbon atoms, preferably a branched alkane. The medium employed should be liquid under the conditions of polymerization reaction and relatively inert. When a propane medium is used, for example, the process may be operated above the reaction diluent critical temperature and pressure. Preferably, a hexane or an isobutane medium may be employed.Polyolefins

[0137] Embodiments of the present disclosure may include utilizing a catalyst system of the present disclosure to produce olefin polymers, preferably polypropylene homopolymers or copolymers. Alternatively, the polymers produced herein may be homopolymers or copolymers of ethylene, preferably having from about 0 mol% to about 25 mol%, of one or more C3 to C20 olefin co-monomers, such as from about 0.5 mol% to about 20 mol%, or about 1 mol% to about 15 mol%, or about 3 mol% to about 10 mol%. Olefin co-monomers for use in combination with ethylene may be C3 to C12 alpha-olefins, for example, such as one or more of propylene, butene, hexene, octene, decene, or dodecene, preferably propylene, butene, hexene, or octene. Olefin co-monomers for use in combination with propylene may include one or more of ethylene or a C4 to C12 alphaolefin, preferably ethylene, butene, hexene, octene, decene, or dodecene, preferably ethylene, butene, hexene, or octene.

[0138] Polymers produced herein may have an Mw of about 5,000 to about 1,000,000 g / mol, such as from about 25,000 g / mol to about 750,000 g / mol, or about 50,000 g / mol to about 500,000 g / mol, and / or an Mw / Mn of about 1 to about 40, such as about 1.2 to about 20, or about 1.3 to about 10, or about 1.4 to about 5, or about 1.5 to about 4, or about 1.5 to about 3, as determined by GPC-4D.

[0139] The polyolefins produced herein may be essentially free of detectable aromatic hydrocarbons, such as toluene.Additional Embodiments

[0140] The present disclosure is further directed to the following non-limiting embodiments:

[0141] Embodiment !. A catalyst system comprising: a support material;an alumoxane formed in situ on the support material from a tri alkyl aluminum compound and water in the absence of an aromatic hydrocarbon solvent; and a metallocene having Cl symmetry and comprising a Group 4 metal.

[0142] Embodiment 2. The catalyst system of Embodiment 1, wherein the Group 4 metal isHf or Zr.

[0143] Embodiment s. The catalyst system of Embodiment 1 or Embodiment 2, wherein the metallocene has a structure represented bywherein:M is the Group 4 metal;T is a bridging group;X1and X2are each a univalent anionic ligand, or X1and X2are joined to form a metallocycle ring, a chelating ligand, a diene ligand, or an alkylidene;R1is hydrogen, halogen, optionally substituted C1-C40 alkyl, optionally substituted G>- C14 aryl, optionally substituted C3-C13 heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10 alkylene and R' is hydrogen, C1-C10 alkyl, or Ce-Cio aryl;R2and R6are independently hydrogen, halogen, optionally substituted C1-C40 alkyl, optionally substituted Ce-Cu aryl, optionally substituted C3-C13 heteroaryl, -NR'2, -SR', -OR', - SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10 alkylene and R' is hydrogen, C1-C10 alkyl, or Ce-Cio aryl;R3is optionally substituted C1-C40 alkyl or optionally substituted Ce-Ci8 aryl;R4and R5are independently H, R'", or OR'", wherein R'" is an optionally substituted Ci- C40 alkyl, optionally substituted Ce-Cu aryl, optionally substituted C3-C 13 heteroaryl, or R4and R?are joined to form a C3-C62 substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic ring structure, or a combination thereof; andR7, R8, R9, and R10are independently hydrogen, halogen, optionally substituted C1-C40 alkyl, optionally substituted Ce-Cu aryl, optionally substituted C3-C13 heteroaryl, -NR'2, -SR', - OR', -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10 alkylene and R' is hydrogen, C1-C10 alkyl, or Ce-Cio aryl, or one or more of R and R6, R6and R7, or R7and R8are joined to form a C3- Cg2 substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic ring structure, or a combination thereof.

[0144] Embodiment 4. The catalyst system of Embodiment 3, wherein T is selected from the group consisting of CH2, CH2CH2, C(CH3)2, (Ph)2C, (p-(Et)sSiPh)2C, SiMe2, SiPh2, SiMePh, Si(CH2)3, Si(CH2)4, and Si(CH2)4.

[0145] Embodiment 5. The catalyst system of Embodiment 3 or Embodiment 4, wherein X1and X2are independently halogen or Ci-Ce hydrocarbyl.

[0146] Embodiment 6. The catalyst system of any one of Embodiments 3-5, wherein R3is optionally substituted cyclohexyl, optionally substituted norbomanyl, optionally substituted adamantanyl, optionally substituted tert-butyl, optionally substituted phenyl, optionally substituted naphthyl, or optionally substituted anthracenyl.

[0147] Embodiment 7. The catalyst system of any one of Embodiments 1-6, wherein the alumoxane comprises methylalumoxane and the trialkylaluminum compound comprises trimethylaluminum.

[0148] Embodiment s. The catalyst system of any one of Embodiments 1-7, wherein the support material comprises silica.

[0149] Embodiment 9. A method comprising: providing the catalyst system of any one of Embodiments 1-8; and contacting the catalyst system with an olefinic feed under polymerization reaction conditions to form a polyolefin.

[0150] Embodiment 10. The method of Embodiment 9, wherein the olefinic feed comprises an alpha-olefin.

[0151] Embodiment 11. The method of Embodiment 10, wherein the alpha-olefin comprises at least propylene and the polyolefin comprises a polypropylene that is a homopolymer or a copolymer.

[0152] Embodiment 12. The method of any one of Embodiments 9-11, wherein contacting is performed under gas-phase polymerization reaction conditions or slurry-phase polymerization reaction conditions.

[0153] Embodiment 13. The method of any one of Embodiments 9-12, wherein providing the catalyst system comprises: providing a supported activator comprising the support material and the alumoxane formed in situ on the support material in the absence of the aromatic hydrocarbon solvent; and contacting the supported activator with the metallocene to form the catalyst system.

[0154] Embodiment 14. The method of Embodiment 13, wherein the supported activator is contacted with the metallocene in an aliphatic hydrocarbon solvent.

[0155] Embodiment 15. The method of Embodiment 14, further comprising: separating the catalyst system from the aliphatic hydrocarbon solvent prior to contacting the catalyst system with the olefinic feed.

[0156] Embodiment 16. A method comprising: providing a support material slurried in an aliphatic hydrocarbon solvent in the presence of water; contacting the support material with a tri alkyl aluminum compound in the aliphatic hydrocarbon solvent in the absence of an aromatic hydrocarbon solvent; wherein the water and the trialkylaluminum compound react to form an alumoxane upon the support material, thereby generating a supported activator; and contacting the supported activator with a metallocene having Cl symmetry and comprising a Group 4 metal to form a catalyst system.

[0157] Embodiment 17. The method of Embodiment 16, further comprising: separating the supported activator from the aliphatic hydrocarbon solvent before contacting the supported activator with the metallocene.

[0158] Embodiment 18. The method of Embodiment 17, wherein the supported activator is contacted with the metallocene in a second portion of the aliphatic hydrocarbon solvent.

[0159] Embodiment 19. The method of any one of Embodiments 16-18, wherein the Group 4 metal is Hf or Zr.

[0160] Embodiment 20. The method of any one of Embodiments 16-19, wherein the metallocene has a structure represented bywherein:M is the Group 4 metal;T is a bridging group;X1and X2are each a univalent anionic ligand, or X1and X2are joined to form a metallocycle ring, a chelating ligand, a diene ligand, or an alkylidene;R1is hydrogen, halogen, optionally substituted C1-C40 alkyl, optionally substituted Ce- C14 aryl, optionally substituted C3-C13 heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10 alkylene and R' is hydrogen, C1-C10 alkyl, or Ce-Cio aryl;R2and R6are independently hydrogen, halogen, optionally substituted C1-C40 alkyl, optionally substituted Ce-Cw aryl, optionally substituted C3-C13 heteroaryl, -NR'2, -SR', -OR', - SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10 alkylene and R' is hydrogen, C1-C10 alkyl, or Ce-Cio aryl;R3is optionally substituted C1-C40 alkyl or optionally substituted Ce-Cis aryl;R4and R5are independently H, R'", or OR'", wherein R'" is an optionally substituted Ci- C40 alkyl, optionally substituted C6-C14 aryl, optionally substituted C3-C 13 heteroaryl, or R4and R5are joined to form a C3-C62 substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic ring structure, or a combination thereof; andR7, R8, R9, and R10are independently hydrogen, halogen, optionally substituted C1-C40 alkyl, optionally substituted Cg-Ci4 aryl, optionally substituted C3-C13 heteroaryl, -NR'2, -SR', - OR', -SiR'3, -OSiR'3, -PR'2, or -R"-SiR' , wherein R" is C1-C10 alkylene and R' is hydrogen, C1-C10 alkyl, or Ce-Cio aryl, or one or more of R5and R6, R6and R7, or R7and R8are joined to form a C3- C62 substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic ring structure, or a combination thereof.

[0161] Embodiment 21 . The method of Embodiment 20, wherein T is selected from the group consisting of CH2, CH2CH2, C(CHa)2, (Ph)2C, (p-(Et)3SiPh)2C, SiMe2, SiPh2, SiMePh, Si(CH2)3, Si(CH2)4, and Si(CH2)4.

[0162] Embodiment 22. The method of Embodiment 20 or Embodiment 21, wherein X1and X2are independently halogen or Ci-Ce hydrocarbyl.

[0163] Embodiment 23. The method of any one of Embodiments 20-22, wherein R3 is optionally substituted cyclohexyl, optionally substituted norbomanyl, optionally substituted adamantanyl, optionally substituted tert-butyl, optionally substituted phenyl, optionally substituted naphthyl, or optionally substituted anthracenyl.

[0164] Embodiment 24. The method of any one of Embodiments 16-23, wherein the alumoxane comprises methylalumoxane and the trialkylaluminum compound comprises trimethylaluminum.

[0165] Embodiment 25. The method of any one of Embodiments 16-24, wherein the support material comprises silica.

[0166] To facilitate a better understanding of the embodiments of the present disclosure, the following examples of preferred or representative embodiments are given. In no way should the following examples be read to limit, or to define, the scope of the invention.EXAMPLES

[0167] Comparative Supported Activator Prepared Using an Aromatic Hydrocarbon Solvent (Comparative Activator). In a CELSTIR®, 10.0 g of DM-L403 silica (AGC Chemicals, dehydrated at 200°C) was suspended in 100 mb of dry toluene and cooled to -30°C. While stirring, 15.8 g of a cold MAO solution (30 wt% in toluene) was slowly added to the stirring silica suspension over 10 minutes. After stirring for 1.5 hours, the temperature was raised to 100°C, and the suspension was stirred for an additional 2.5 hours. Upon cooling, the resulting slurry was filtered, and the solids were washed with toluene (2 x 50 mL), followed by pentane (2 x 50 m ). After drying in vacuo for at least 2 hours, a white free-flowing powder was obtained.

[0168] Experimental Supported Activator Prepared in the Absence of an Aromatic Hydrocarbon Solvent (Experimental Activator 1). 8.0 g of DM-L403 silica (8.0 g) was calcined at 200°C and slurried in 30 mL of heptane in a CELSTIR® vessel. While stirring, 0.864 mL of water was added to the slurry via syringe through a side port that was capped and taped tightly. The slurry was then stirred for 2 hours at room temperature, followed by cooling to -20°C.Separately, 4.61 g of tri methyl aluminum was dissolved in 40 mL of heptane and cooled to -20°C. The silica slurry was cannulated into the cooled heptane solution. Addition of the silica slurry to the trimethylaluminum solution was carried out in two portions with additional intermittent cooling in a glovebox freezer. The combined slurry was stirred at room temperature for 1 hour and then heated to 90°C for 2.5 hours. After cooling to 45°C, the slurry was filtered and solids were washed pentane (2 x 50 mL). After drying in vacuo, 10.8 g of a free-flowing solid was obtained.

[0169] Experimental Supported Activator Prepared in the Absence of an Aromatic Hydrocarbon Solvent (Experimental Activator 2). 300 g of ES70 silica (PQ Corporation) was calcined at 400°C and slurried in 1080 g of isohexane. The slurry was then split between three 1 L bottles. Water (11.7 g) was added to each bottle, and each of the bottles containing the silica slurries was placed on a roller for 2 hours. A 4 L reactor was charged with 1100 mL of isohexane and 184.2 g of trimethylaluminum, and the solution was cooled to -20°C. Each of the silica slurries was then slowly transferred to the trimethylaluminum solution while maintaining the temperature no higher than -10°C. After the trimethylaluminum addition was complete, the temperature was gradually raised to 25°C, followed by stirring for 1 hour. The solvent was removed in vacuo, and the residue was dried overnight. After 18 hours, the residue was further heated at 100°C for 4 hours to obtain 461 g of a free-flowing powder.

[0170] Experimental Supported Activator Prepared in the Absence of an Aromatic Hydrocarbon Solvent (Experimental Activator 3). 100 g of ES70 silica (PQ Corporation) was calcined at 400°C and slurried in 360 g of heptane. The slurry was then placed in a 1 L bottle. Water (11.7 g) was added to the bottle, and the bottle containing the silica slurry was placed on a roller for 2 hours. A 4 L reactor was charged with 685 mL of heptane and 61.4 g of trimethyl aluminum, and the solution was cooled to -20°C. The silica slurry was then slowly transferred to the trimethylaluminum solution while maintaining the temperature no higher than - 10°C. After the trimethylaluminum addition was complete, the temperature was gradually raised to 25°C, followed by stirring for 1 hour. The slurry was then heated to 100°C for 4 hours, followed by filtration and drying of the residue to obtain 147 g of a free-flowing powder.

[0171] Metallocene. Dimethylsilyl-(tetramethylcyclopentadienyl)(2-Me-4(4-tertbutylphenyl) tetrahydroindacenyl) zirconium di chloride was used as the Cl -symmetric metallocene in the further experiments below. The substituted phenyl group was introduced onto the 6-methyl- 1,2,3,5-tetrahydro-s-indacene parent ring system through Suzuki coupling of a phenylboronic acidto the corresponding brominated parent ring system, followed by lithiation, dimethylsilyl bridge introduction, and metallocene formation. Illustrative synthetic procedures may be found in International Patent Application Publication WO 2023 / 034889.

[0172] Comparative Catalyst System Prepared Using a Supported Activator Prepared with an Aromatic Hydrocarbon Solvent (Comparative Catalyst System).

[0173] 1.08 g of the Comparative Supported Activator prepared above was slurried in 8 mb of toluene and placed on a shaker. While shaking, 0.56 mL of 1 M TIBAL in hexane was slowly added to the slurry, followed by 30 minutes of additional shaking. Thereafter, 2 mL of a toluene solution of Cl-symmetric metallocene (see above, 7.61 mg total metallocene) was added to the slurry. After shaking for an additional 4 hours, the mixture was filtered to collect the residue on a glass frit. The solids were then washed toluene (2 x 5 mL) and pentane (2 x 5 mL), followed by drying in vacuo. The final solid was slurried in mineral oil to obtain a 5 wt% slurry.

[0174] Experimental Catalyst System Prepared Using a Supported Activator Prepared in the Absence of an Aromatic Hydrocarbon Solvent (Experimental Catalyst System 1).

[0175] 1.0 g of Experimental Supported Activator 1 was slurried in 10 mL of pentane. The slurry was treated with 0.52 mL of 1 M TIBAL in hexane and placed on a shaker for 15 minutes. Thereafter, a pentane slurry of Cl-symmetric metallocene (see above, 7.6 mg total metallocene) was transferred to the slurry. The mixture became a dark orange-red color, indicating catalyst activation. The slurry was shaken for three additional hours, and the slurry was then fdtered. The resulting residue was washed with pentane (2 x 5 mL) and dried in vacuo. The resulting catalyst system was slurried in mineral oil to obtain a 5 wt% slurry.

[0176] Experimental Catalyst System Prepared Using a Supported Activator Prepared in the Absence of an Aromatic Hydrocarbon Solvent (Experimental Catalyst System 2). 0.6 gof Experimental Supported Activator 2 was slurried in 10 mL of heptane. The slurry was treated with 0.31 mL of 1 M TIB AL in hexane and placed on a shaker for 15 minutes. Thereafter, a pentane slurry of Cl -symmetric metallocene (see above, 5.2 mg total metallocene) was transferred to the slurry. The mixture because a dark orange-red color, indicating catalyst activation. The slurry was shaken for three additional hours then the catalyst system was filtered, washed with two additions of 5 mL pentane, and dried in vacuo. The solid catalyst system was slurried in mineral oil to obtain a 5 wt% slurry.

[0177] Experimental Catalyst System Prepared Using a Supported Activator Prepared in the Absence of an Aromatic Hydrocarbon Solvent (Experimental Catalyst System 3). Experimental Catalyst System 3 was prepared in a similar manner to Experimental Catalyst System 2, except Experimental Supported Activator 3 was used.

[0178] Bulk Polymerization Procedure. A I L autoclave reactor equipped with a mechanical stirrer was used for the polymer preparation. Prior to use, the reactor was placed under a nitrogen purge while maintaining a temperature of 90°C for 30 minutes. Upon cooling the reactor to ambient temperature, 500 mL of propylene feed, 0.2 mL of 1 M TIB AL scavenger, and, optionally, 2 mmol hydrogen (charged from a 50 mL bomb at a desired pressure) were introduced to the reactor and mixed for 5 minutes. Approximately 12.5 mg of a given supported catalyst system was then introduced to the reactor by flushing a pre-determined amount of the mineral oil slurry containing each catalyst system from a catalyst tube with 100 mL of liquid propylene. The reactor was kept at room temperature for 5 minutes before raising the temperature to 70°C. The reaction was allowed to proceed at 70°C for about 30 minutes, followed by cooling to 25°C. Excess propylene was then vented off, and the resulting polypropylene granules were collected and dried in vacuo overnight at 60°C. Properties of the respective polypropylenes and other experimental parameters are shown in Table 1. Molecular weight values were determined using GPC-4D analyses, as described in U.S. Patent Application Publication 2019 / 0127497, which is incorporated herein by reference in its entirety, and further summarized below.

[0179] The distribution and the moments of molecular weight (Mw, Mn, Mz, Mw / Mn, etc.), the co-monomer content, and the branching index (g1) were determined by using a high temperature Gel Permeation Chromatography (Polymer Char GPC-IR) equipped with a multiple-channel bandfilter based Infrared detector IR5 with a multiple-channel band filter based infrared detector ensemble IR5 with band region covering from about 2,700 cm-1to about 3,000 cm-1(representingsaturated C-H stretching vibration), an 18-angle light scattering detector and a viscometer. Three Agilent PLgel 10-pm Mixed-B LS columns were used to provide polymer separation. Reagent grade 1,2,4-trichlorobenzene (TCB) (from Sigma-Aldrich) comprising -300 ppm antioxidant BHT can be used as the mobile phase at a nominal flow rate of -1.0 mL / min and a nominal injection volume of -200 pL. The whole system including transfer lines, columns, and detectors can be contained in an oven maintained at ~145°C. A given amount of sample can be weighed and sealed in a standard vial with -10 pL flow marker (heptane) added thereto. After loading the vial in the auto-sampler, the oligomer or polymer may automatically be dissolved in the instrument with -8 m added TCB solvent at ~160°C with continuous shaking. The sample solution concentration can be from -0.2 to -2.0 mg / ml, with lower concentrations used for higher molecular weight samples. The concentration, c, at each point in the chromatogram can be calculated from the baseline-subtracted IR5 broadband signal, I, using the equation: c=al, where a is the mass constant determined with polyethylene or polypropylene standards. The mass recovery can be calculated from the ratio of the integrated area of the concentration chromatography over elution volume and the injection mass which is equal to the pre-determined concentration multiplied by injection loop volume. The conventional molecular weight (IR MW) is determined by combining universal calibration relationship with the column calibration which is performed with a series of monodispersed polystyrene (PS) standards ranging from 700 to 10M gm / mole. The MW at each elution volume is calculated with Equation 1 : logMEquation 1 where the variables with subscript “PS” stand for polystyrene while those without a subscript are for the test samples. In this method, aps = 0.67 and Kps = 0.000175, a and K for other materials are as calculated as described in the published in literature (e.g., Sun, T. et al. (2001) Macromolecules, v.34, pg. 6812), except that for purposes of this present disclosure and claims thereto, a = 0.705 and K = 0.0000229 for ethyl ene-propylene copolymers and ethyl ene-propylene- diene terpolymers, oc = 0.695 and K = 0.000579 for linear ethylene polymers, oc = 0.705 and K = 0.0002288 for linear propylene polymers, and a = 0.695 and K = 0.000181 for linear butene polymers. Concentrations are expressed in g / cm3, molecular weight is expressed in g / mole, andintrinsic viscosity (hence K in the Mark-Houwink equation) is expressed in dL / g unless otherwise noted.

[0180] The co-monomer composition is determined by the ratio of the IR5 detector intensity corresponding to CH2 and CH3 channel calibrated with a series of PE and PP homo / copolymer standards whose nominal value are predetermined by NMR or FTIR. In particular, this provides the methyls per 1,000 total carbons (CH3 / IOOOTC) as a function of molecular weight. The shortchain branch (SCB) content per l,000TC (SCB / 1000TC) is then computed as a function of molecular weight by applying a chain-end correction to the CH3 / IOOOTC function, assuming each chain to be linear and terminated by a methyl group at each end. The weight % co-monomer is then obtained from Equation 2 in which f is 0.3, 0.4, 0.6, 0.8, and so on for C3, C4, Ce, Cs, and so on co-monomers, respectively: w2 = / * SCB / 1000TC .Equation 2

[0181] The bulk composition of the polymer from the GPC-1R and GPC-4D analyses is obtained by considering the entire signals of the CH3 and CH2 channels between the integration limits of the concentration chromatogram. First, the following ratio in Equation 3 is obtained> , . > . Area of CI I? signal within integration limitsBulk IR ratio = - - ~ . — . - : — — — .Area oi CH2 signal within integration limitsEquation 3Then the same calibration of the CH3 and CH2 signal ratio, as mentioned previously in obtaining the CH3 / 1000TC as a function of molecular weight, is applied to obtain the bulk CH3 / 1000TC. A bulk methyl chain ends per l,000TC (bulk CH3end / 1000TC) is obtained by weight-averaging the chain-end correction over the molecular- weight range. Then, Equations 4 and 5 apply w2b = f * bulk CH3 / 1000TCEquation 4 bulk SCB / 1000TC = bulk CH3 / 1000TC - bulk CH3end / 1000TCEquation 5 and bulk SCB / 1000TC is converted to bulk w2 in the same manner as described above.

[0182] The LS detector is the 18-angle Wyatt Technology High Temperature DAWN HELEOSII. The LS molecular weight (M) at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering Light Scattering from Polymer Solutions, Huglin, M. B., Ed.; Academic Press, 1972.), as specified in Equation 6:Equation 6Here, AR(0) is the measured excess Rayleigh scattering intensity at scattering angle 0, c is the polymer concentration determined from the IR5 analysis, A2 is the second virial coefficient, P(0) is the form factor for a monodisperse random coil, and Kois the optical constant for the system, as specified in Equation 7:Equation 7 where NA is Avogadro’ s number, and (dn / dc) is the refractive index increment for the system. The refractive index, n = 1.500 for TCB at 145°C and = 665 nm. For analyzing polyethylene homopolymers, ethylene-hexene copolymers, and ethylene-octene copolymers, dn / dc = 0.1048 ml / mg and A2 = 0.0015; for analyzing ethylene-butene copolymers, dn / dc = 0.1048*(l-0.00126*w2) ml / mg and A2 = 0.0015 where w2 is weight percent butene comonomer.

[0183] A high temperature Agilent (or Viscotek Corporation) viscometer, which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers, is used to determine specific viscosity. One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure. The specific viscosity, r|s, for the solution flowing through the viscometer is calculated from their outputs. The intrinsic viscosity, [q], at each point in the chromatogram is calculated from the equation [q]= qs / c, where c is concentration and is determined from the IR5 broadband channel output. The viscosity MW at each point is calculated as M = KpsMaps+1 / [ri] , where apsis 0.67 and Kpsis 0.000175.

[0184] The branching index (g'vis) is calculated using the output of the GPC-IR5-LS-VIS method as follows. The average intrinsic viscosity, [r|]avg, of the sample is calculated by Equation 8:Equation 8 where the summations are over the chromatographic slices, i, between the integration limits.

[0185] The branching index g'vis is defined as Equation 9:Equation 9 where Mvis the viscosity-average molecular weight based on molecular weights determined byLS analysis and the K and a are for the reference linear polymer, which are, for purposes of this present disclosure and claims thereto, oc = 0.705 and K = 0.0000229 for ethylene-propylene copolymers and ethylene-propylene-diene terpolymers, oc = 0.695 and K = 0.000579 for linear ethylene polymers, oc = 0.705 and K = 0.0002288 for linear propylene polymers, oc = 0.695 and K = 0.000181 for linear butene polymers. Concentrations are expressed in g / cm3, molecular weight is expressed in g / mole, and intrinsic viscosity (hence K in the Mark-Houwink equation) is expressed in dL / g unless otherwise noted. Calculation of the w2b values is as discussed above.Table 1

[0186] As shown, comparable catalyst activities and polymer properties were realized with the Experimental Catalyst Systems, and the data compared very favorably to values obtained using the Comparative Catalyst System. Of particular interest is the comparison between the Comparative Catalyst System and Experimental Catalyst System 1, as these two catalyst systemscomprise the same silica component (DM-L403). Not only were the activities of the two catalyst systems very comparable, but the properties of the polypropylene products were nearly replicated.

[0187] All documents described herein are incorporated by reference herein for purposes of all jurisdictions where such practice is allowed, including any priority documents and / or testing procedures to the extent they are not inconsistent with this text. As is apparent from the foregoing general description and the specific embodiments, while forms of the disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of the disclosure. Accordingly, it is not intended that the disclosure be limited thereby. For example, the compositions described herein may be free of any component, or composition not expressly recited or disclosed herein. Any method may lack any step not recited or disclosed herein. Likewise, the term “comprising” is considered synonymous with the term “including.” Whenever a method, composition, element or group of elements is preceded with the transitional phrase “comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “is” preceding the recitation of the composition, element, or elements and vice versa.

[0188] Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth used in the present specification and associated claims are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by one or more embodiments described herein. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claim, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0189] Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range is specifically disclosed. In particular, every range of values (of the form, “from about a to about b,” or, equivalently, “from approximately a to b,” or, equivalently, “from approximately a-b”) disclosed herein is to be understood to set forth every number and range encompassed within the broader range of values. Also, the terms in the claims have their plain, ordinary meaning unless otherwise explicitly andclearly defined by the patentee. Moreover, the indefinite articles “a” or “an,” as used in the claims, are defined herein to mean one or more than one of the element that it introduces.

[0190] One or more illustrative embodiments are presented herein. Not all features of a physical implementation are described or shown in this application for the sake of clarity. It is understood that in the development of a physical embodiment of the present disclosure, numerous implementation-specific decisions must be made to achieve the developer's goals, such as compliance with system-related, business-related, government-related and other constraints, which vary by implementation and from time to time. While a developer's efforts might be timeconsuming, such efforts would be, nevertheless, a routine undertaking for one of ordinary skill in the art and having benefit of this disclosure.

[0191] Therefore, the present disclosure is well adapted to attain the ends and advantages mentioned as well as those that are inherent therein. The particular embodiments disclosed above are illustrative only, as the present disclosure may be modified and practiced in different but equivalent manners apparent to one having ordinary skill in the art and having the benefit of the teachings herein. Furthermore, no limitations are intended to the details of construction or design herein shown, other than as described in the claims below. It is therefore evident that the particular illustrative embodiments disclosed above may be altered, combined, or modified and all such variations are considered within the scope and spirit of the present disclosure. The embodiments illustratively disclosed herein suitably may be practiced in the absence of any element that is not specifically disclosed herein and / or any optional element disclosed herein.

Claims

CLAIMSThe invention claimed is:

1. A cataly st sy stem compri si ng : a support material; an alumoxane formed in situ on the support material from a trialkylaluminum compound and water in the absence of an aromatic hydrocarbon solvent; and a metallocene having Cl symmetry and comprising a Group 4 metal.

2. The catalyst system of claim 1, wherein the Group 4 metal is Hf or Zr.

3. The catalyst system of claim 2, wherein the metallocene has a structure represented bywherein:M is the Group 4 metal;T is a bridging group;X1and X2are each a univalent anionic ligand, or X1and X2are joined to form a metallocycle ring, a chelating ligand, a diene ligand, or an alkylidene;R1is hydrogen, halogen, optionally substituted C1-C40 alkyl, optionally substituted Cs-Cu aryl, optionally substituted C3-C13 heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10 alkylene and R' is hydrogen, C1-C10 alkyl, or Ce- C10 aryl;R2and R6are independently hydrogen, halogen, optionally substituted C1-C40 alkyl, optionally substituted Ce-Ci4 aryl, optionally substituted C3-C 13 heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10 alkylene and R' is hydrogen,Ci-Cio alkyl, or Ce-Cio aryl;R3is optionally substituted C1-C40 alkyl or optionally substituted Ce-Cis aryl;R4and R5are independently H, R'", or OR'", wherein R'" is an optionally substituted C1-C40 alkyl, optionally substituted C6-C14 aryl, optionally substituted C3-C13 heteroaryl, or R4and R5are joined to form a C3-C62 substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic ring structure, or a combination thereof; andR7, R8, R9, and R10are independently hydrogen, halogen, optionally substituted Ci- C40 alkyl, optionally substituted Ce-Cu aryl, optionally substituted C3-C13 heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10 alkylene and R' is hydrogen, C1-C10 alkyl, or Ce-Cio aryl, or one or more of R5and R6, R6and R7, or R7and R8are joined to form a C3-C62 substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic ring structure, or a combination thereof.

4. The catalyst system of claim 3, wherein: a) T is selected from the group consisting of CH2, CH2CH2, C(CH3)2, (Ph)2C, (p- (Et)3SiPh)2C, SiMe2, SiPh2, SiMePh, Si(CH2)3, Si(CH2)4, and Si(CH2)4; b) wherein X1and X2are independently halogen or Ci-Ce hydrocarbyl; or, c) both a) and b).

5. The catalyst system of claim 3, wherein R3is optionally substituted cyclohexyl, optionally substituted norbornanyl, optionally substituted adamantanyl, optionally substituted tertbutyl, optionally substituted phenyl, optionally substituted naphthyl, or optionally substituted anthracenyl.

5. The catalyst system of any preceding claim, wherein the alum oxane comprises methylalumoxane and the trialkylaluminum compound comprises trimethylaluminum.

6. A method comprising: providing the catalyst system of claim 1; and contacting the catalyst system with an olefinic feed under polymerization reaction conditions to form a polyolefin.

7. The method of claim 6, wherein the olefinic feed comprises an alpha-olefin.

8. The method of claim 7, wherein the alpha-olefin comprises at least propylene and the polyolefin comprises a polypropylene that is a homopolymer or a copolymer.

9. The method of any of claims 6-8, wherein contacting is performed under gas-phase polymerization reaction conditions or slurry-phase polymerization reaction conditions.

10. The method of any of claims 6-9, wherein providing the catalyst system comprises: providing a supported activator comprising the support material and the alumoxane formed in situ on the support material in the absence of the aromatic hydrocarbon solvent; and contacting the supported activator with the metallocene to form the catalyst system.

11. The method of claim 10, wherein the supported activator is contacted with the metallocene in an aliphatic hydrocarbon solvent.

12. The method of claim 11, further comprising: separating the catalyst system from the aliphatic hydrocarbon solvent prior to contacting the catalyst system with the olefinic feed.

13. A method comprising: providing a support material slurried in an aliphatic hydrocarbon solvent in the presence of water; contacting the support material with a trialkylaluminum compound in the aliphatic hydrocarbon solvent in the absence of an aromatic hydrocarbon solvent; wherein the water and the trialkylaluminum compound react to form an alumoxane upon the support material, thereby generating a supported activator; contacting the supported activator with a metallocene having Cl symmetry and comprising a Group 4 metal to form a catalyst system; and,separating the supported activator from the aliphatic hydrocarbon solvent before contacting the supported activator with the metallocene..

14. The method of claim 13, wherein the Group 4 metal is Hf or Zr.

15. The method of claim 13, wherein the metallocene has a structure represented bywherein:M is the Group 4 metal;T is a bridging group;X1and X2are each a univalent anionic ligand, or X1and X2are joined to form a metallocycle ring, a chelating ligand, a diene ligand, or an alkylidene;R1is hydrogen, halogen, optionally substituted C1-C40 alkyl, optionally substituted C6-C14 aryl, optionally substituted C3-C13 heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10 alkylene and R' is hydrogen, C1-C10 alkyl, or Ce- C10 aryl;R2and R6are independently hydrogen, halogen, optionally substituted C1-C40 alkyl, optionally substituted C6-C14 aryl, optionally substituted C3-C 13 heteroaryl, -NR'2, -SR', - OR', -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10 alkylene and R' is hydrogen, C1-C10 alkyl, or Ce-Cio aryl;R3is optionally substituted C1-C40 alkyl or optionally substituted C -C IX aryl;R4and R5are independently H, R'", or OR'", wherein R'" is an optionally substituted C1-C40 alkyl, optionally substituted Ce-Cu aryl, optionally substituted C3-C13 heteroaryl, or R4and R5are joined to form a C3-C62 substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic ring structure, or a combination thereof; andR7, R8, R9, and R10are independently hydrogen, halogen, optionally substituted Ci- C40 alkyl, optionally substituted Ce-Cu aryl, optionally substituted C3-C13 heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C10 alkylene and R' is hydrogen, C1-C10 alkyl, or Ce-Cio aryl, or one or more of R5and R6, R6and R7, or R7and R8are joined to form a C3-C62 substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic ring structure, or a combination thereof.

16. The method of claim 15, wherein a) T is selected from the group consisting of CH2, CH2CH2, C(CH3)2, (Ph)2C, (p- (Et)3SiPh)2C, SiMe2, SiPh2, SiMePh, Si(CH2)3, Si(CH2)4, and Si(CH2)4; b) X1and X2are independently halogen or Ci-Ce hydrocarbyl; c) R3is optionally substituted cyclohexyl, optionally substituted norbornanyl, optionally substituted adamantanyl, optionally substituted tert-butyl, optionally substituted phenyl, optionally substituted naphthyl, or optionally substituted anthracenyl; or, d) all of a), b), and c).

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