Polyethylenes and films thereof

Abstract

The present disclosure relates to polyethylene copolymers. The polyethylene copolymers include 90 wt% or greater ethylene units and a remainder balance of C3-C20 comonomer units. The polyethylene copolymers have a melt index of about 0.1 g / 10min to about 2.2 g / min, a high load melt index (HLMI) of about 10 g / 10 min to about 50 g / 10 min, a melt index ratio (MIR) of about 20 to about 35, a molecular weight distribution (MWD) of about 3 to about 7, a melt strength of about 0.03 N to about 0.10 N, a ∆CWF / ∆T of about wt% / 0.02 °C to about 0.03 wt% / °C, a SignCDI *ɳ0*1032 / (Tan delta (ω=0.1) * MW6.82) of about 2 Pa*s / [(g / mol)6.82]to about 8 Pa*s / [(g / mol)6.82], and a CDI_NWZ,w of about 0.200 to about 0.33.

Description

POLYETHYLENES AND FILMS THEREOFFIELD

[0001] This disclosure relates to polyethylene polymers and films made therefrom.BACKGROUND

[0002] A linear low density polyethylene (LLDPE) is a substantially linear polymer composed of ethylene monomeric units and alpha-olefin comonomeric units. The typical comonomeric units used are derived from 1 -butene, 1 -hexene, or 1 -octene. An LLDPE may be distinguished from a conventional low density polyethylene (LDPE) in several ways including their different manufacturing processes. In addition, LLDPE has little or no detectable long chain branching (LCB) per 1,000 carbon atoms, whereas conventional LDPEs contain a relatively high degree of long chain branching. Long chain branching provides reduced neck-in and increased draw stability during extrusion processes. In addition, LLDPEs often have a narrower molecular weight distribution (MWD) relative to MWD of LDPEs, especially metallocene-catalyzed LLDPEs (“mLLDPE”). LLDPEs also have different rheological and mechanical properties, such as tear properties, as compared to LDPEs.

[0003] While mLLDPEs typically provide superior mechanical properties to incumbent LDPEs in films and other articles made therefrom, they are generally more difficult to process than LDPEs, e.g, having lower melt strength and decreased shear thinning. These factors can impact bubble stability in many film formation processes, as well as lead to melt fracture -surface roughness or similar irregularities - in films produced at typical commercial extrusion rates.

[0004] Thus, various levels of LDPE have been blended with mLLDPEs to increase melt strength, to increase shear sensitivity, e.g. to increase flow at commercial shear rates in extruders, and to reduce the tendency to melt fracture. However, such blending generally has a negative impact on mechanical properties of films made from the polymers. Indeed, it has been a challenge to improve mLLDPE processability without sacrificing physical properties.

[0005] Overall, there is a need for new polyethylene copolymers having a combination of desirable properties (such as density, melt index, broad compositional distribution, and long chain branching) while also providing commercially desirable polymerizations and extrusions of the polyethylene copolymers.

[0006] Other references of potential interest in this regard include: W02023 / 060075.SUMMARY

[0001] The present disclosure relates to gas phase polymerizations and methods thereof.

[0002] In some embodiments, the present disclosure provides polyethylene copolymers. The polyethylene copolymers include 90 wt% or greater ethylene units and a remainder balance of C3-C20 comonomer units. The polyethylene copolymers have a melt index of about 0.1 g / lOmin to about 2.2 g / min, a high load melt index (HLMI) of about 10 g / 10 min to about 50 g / 10 min, a melt index ratio (MIR) of about 20 to about 35, a molecular weight distribution (MWD) of about 3 to about 7, a melt strength of about 0.03 N to about 0.10 N, a ACWF / AT of about 0.01 wt% / °C to about 0.03 wt% / °C, a SigncDi *pp*I032 / (Tan delta (ra=o.i) * MW6 82) of about 2 to about 8, and a CDI_NWZ,w of about 0.20 to about 0.33.

[0003] In some embodiments, the present disclosure provides polyethylene copolymers. The polyethylene copolymers include 90 wt% or greater ethylene units and a remainder balance of C3-C20 comonomer units. The polyethylene copolymers have a melt index of about 0.1 g / lOmin to about 2.2 g / min, a high load melt index (HLMI) of about 10 g / 10 min to about 50 g / 10 min, a melt index ratio (MIR) of about 20 to about 35, a molecular weight distribution (MWD) of about 3 to about 7, a melt strength of about 0.03 N to about 0.10 N, a MD 1 % Secant Modulus, at 23°C of about 25,000 psi to about 35,000 psi. a TD 1% Secant Modulus, at 23°C of about 30,000 psi to about 45,000 psi, an Elmendorf Tear value (MD) of about 150 g / mil to about 350 g / mil, a Dart Drop Impact of about 500 g / mil to about 785 g / mil, a puncture energy at break energy of about 35 in-lbs / mil to about 51 in-lbs / mil, a ACWF / AT of about 0.01 wt% / °C to about 0.03 wt% / °C, a SigncDi *i]p*1032 / (Tan delta (ro=o.i) * MW682) of about 2 to about 8, and a CDI NWZ.w of about 0.20 to about 0.33.

[0004] In some embodiments, the present disclosure provides methods for producing polyethylene copolymers. The methods include contacting a first composition and a second composition in a line to form a third composition. The first composition includes a contact product of a first diluent, a first catalyst compound, a support material, and an activator. The second composition includes a contact product of a second diluent and a second catalyst compound. A third composition is introduced from the line into a gas-phase fluidized bed reactor. The third composition is exposed to polymerization conditions by polymerizing ethylene and at least one C3-C20 alpha-olefin by introducing the ethylene and the at least one C3-C20 alpha-olefin into the gas-phase fluidized bed reactor. The polyethylene copolymer is obtained. The first catalyst compound is represented by Formula (I).CpACpBMXn (I)in which:M of Formula (I) is titanium, zirconium, or hafnium;n of Formula (I) is an integer from 0 to 4;each CpA and CpB of Formula (I) is independently selected from the group consisting of substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, substituted or unsubstituted tetrahydroindenyL and substituted or unsubstituted fluorenyl; and each X of Formula (I) is independently selected from the group consisting of a halogen, a hydride, a Ci to C12 alky l, a C2 to C12 alkenyls, a Ce to C12 aryl, a C7 to C20 alkylaryl, a Ci to C12 alkoxy, a Ce to Ci6 aryloxy, a C7 to Cs alkylaryloxy, a Ci to C12 fluoroalkyl, a Ce to C12 fluoroaryl, a Ci to C12 heteroatom containing hydrocarbon, an amide, an amines, a phosphine, an ether, a carboxylate, a diene, and substituted derivatives thereof;the second catalyst is represented by Formula (III) or Formula (V):M of Formula (III) is a group 4 metal;each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10. R11, R12, R13and R14of Formula (III) is independently hydrogen, substituted or unsubstituted hydrocarbyl, a substituted or unsubstituted heteroatom, or a substituted or unsubstituted heteroatom-containing group, or one or more of R1and R2, R4and R5, R5and R6, R6and R7, R9and R10, R11and R12, R12and R13, and R13and R14are joined to form a substituted or unsubstituted completely saturated ring or a substituted or unsubstituted aromatic ring;each X of Formula (in) is independently a halide, a substituted or unsubstituted hydrocarbyl, a hydride, an amide, a substituted or unsubstituted alkoxide, a sulfide, a phosphide, or a combination thereof, or two of X are joined together to form a substituted orunsubstituted metallocycle ring, or two of X are joined to form a chelating ligand, a diene ligand, or an alkylidene;in which:M of Formula (V) is a group 4 metal;each of R1, R2, R3, R4, R5, R6, R7, R7, R8, R8, R9, R9, R10and R10’ of Formula (V) is independently hydrogen, substituted or unsubstituted hydrocarbyl, a substituted or unsubstituted heteroatom, or a substituted or unsubstituted heteroatom-containing group, one or more of R5and R6, R7and R8, R8and R9, and R9and R10are joined to form a substituted or unsubstituted completely saturated ring or a substituted or unsubstituted aromatic ring, or one or more of R7and R8, R8and R9, and R9and R10are absent such that a carbon-carbon double bond is present between the corresponding carbon atoms of the hydroindenyl ring shown in Formula (V);T of Formula (V) is represented by formula RhJ. (Ra)4J2, or (Ra)eJ3 in which each J is independently C, Si, or Ge, and each Rais independently hydrogen, halide, a substituted or unsubstituted Ci to C40 hydrocarbyl, or two Racan form a substituted or unsubstituted cyclic structure including a substituted or unsubstituted completely saturated ring, a substituted or unsubstituted partially saturated ring, or a substituted or unsubstituted aromatic ring; and

[0005] each of X1and X2is independently a univalent anionic ligand, a diene ligand, an alkylidene ligand, or X1and X2are joined to form a metallocyclic ring.

[0006] These and other features and attributes of the disclosed methods and systems of the present disclosure and their advantageous applications and / or uses will be apparent from the detailed description that follows.BRIEF DESCRIPTION OF THE DRAWINGS

[0007] To assist those of ordinary skill in the relevant art in making and using the subject matter hereof, reference is made to the appended drawings, wherein:

[0008] FIG. 1 is a graph illustrating a gel permeation chromatograph using quadrupole detection (GPC-4D), infrared based molecular weight, and hexene distribution of polyethylene copolymers in accordance with various embodiments described herein.

[0009] FIG. 2 is a graph illustrating a small amplitude oscillatory shear testing (SAGS) of polyethylene copolymers in accordance with various embodiments described herein.

[0010] FIG. 3 is a graph illustrating a Rheotens melt strength profde of polyethylene copolymers in accordance with various embodiments described herein.

[0011] FIG. 4 is a graph illustrating TREFIR5 of polyethylene copolymers in accordance with various embodiments described herein.

[0012] FIG. 5 is a graph illustrating SigncDi *qp*1032 / (Tan delta (ro-o.i) * MW6 82) vs ACWF / AT (Below 80 °C at 5 °C intervals) of polyethylene copolymers in accordance with various embodiments described herein.DETAILED DESCRIPTION

[0013] Various embodiments, versions of the disclosed compounds, processes, and articles of manufacture, will now be described, including specific embodiments and definitions that are adopted herein. While the following detailed description gives specific embodiments, those skilled in the art should appreciate that these embodiments are exemplary only, and that embodiments of the present disclosure can be practiced in other ways. Any reference to embodiments may refer to one or more, but not necessarily all, of the compounds, processes, or articles of manufacture defined by the claims. The use of headings is for purposes of convenience only and does not limit the scope of the present disclosure.

[0014] This disclosure relates to polyethylene polymers and films made therefrom. Polyethylene polymers are copolymers formed by dual catalyst systems, such as systems provided to a polymerization reactor using “trim"’ processes, such that the polyethylene polymers can have a combination of low density, low melt index, high melt index ratio, controllable broad compositional distribution, and controllable long chain branching (introduced by a trim process) while also providing commercially desirable polymerizations and extrusions of the polyethylene copolymers.

[0015] As compared to conventional LLDPEs, polyethylene copolymers of the present disclosure can include increased long chain branching (also referred to as 'LCB’?) in the copolymers, thereby providing reduced neck-in and increased draw stability. Polyethylenecopolymers of the present disclosure can include increased broad compositional distribution (also referred to as ' BCD ") and reduced broad orthogonal compositional distribution (also referred to as " BOCD ") compared to conventional LLDPEs due to an increase in the reaction temperature, thereby providing increased toughness of the polyethylene copolymers. Polyethylene copolymers of the present disclosure can be produced using less trim solution when produced using higher reaction temperatures than conventional reaction temperatures, while maintaining similar or improved mechanical properties, e.g., puncture energy, MD tear, and TD tear. Polyethylene copolymers of the present disclosure can include reduced extruder melt pressure and increased bubble stability (melt strength), thereby leading to lower motor torque during extrusion, providing increased output of the extruded polyethylene copolymer product having enhanced mechanical properties compared to conventional LLDPEs.

[0016] Polyethylene copolymers of the present disclosure further can provide films having increased LCB while maintaining similar and / or improved processing properties, e.g., reduced motor loads and melt pressures (which increases throughput) due to improved flow behavior, as compared to conventional LLDPEs. For example, a reduction in melt pressure and decrease in melt temperature may be provided during blown film fabrication. Films of the present disclosure can be particularly useful as shrink wrap films (improved by the presence of LCB in the polyethylene copolymers of the present disclosure).Definitions

[0007] As used herein, an “olefin,” alternatively referred to as “alkene,” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond. For purposes of this specification and the claims appended thereto, when a polymer or copolymer is referred to as “comprising” an olefin, the olefin present in such polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is described as having an “ethylene” content of 35 wt % to 55 wt %, it is understood that the mer unit in the copolymer is derived from ethylene in the polymerization reaction and the derived units are present at 35 wt % to 55 wt %, based upon the weight of the copolymer.

[0008] As used herein, the terms “polyethylene polymer,” “polyethylene copolymer,” “polyethylene,” “ethylene polymer,” “ethylene copolymer,” and “ethylene based polymer” mean a polymer or copolymer comprising at least 50 mol % ethylene units, or at least 70 mol % ethylene units, or at least 80 mol % ethylene units, or at least 90 mol % ethylene units, or at least 95 mol % ethylene units or 100 mol % ethylene units (in the case of a homopolymer).

[0009] As used herein, a “polymer” may refer to homopolymers, copolymers, interpolymers, terpolymers, etc. A “polymer” has two or more of the same or differentmonomer units. A “homopolymer” is a polymer having monomer units that are the same. A “copolymer” is a polymer having two or more monomer units that are different from each other. A “terpolymer” is a polymer having three monomer units that are different from each other. The term “different” as used to refer to monomer units indicates that the monomer 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 the like. Likewise, the definition of polymer, as used herein, includes copolymers and the like.

[0010] An ethylene polymer having a density of more than 0.860 to less than 0.910 g / cm3is referred to as an ethylene plastomer or plastomer; an ethylene polymer having a density of 0.910 to 0.925 g / cm3is referred to as a “linear low density polyethylene” (LLDPE) when substantially linear (having minor or no long chain branching) as is typically the case for Ziegler-Nata or metallocene-catalyzed PE or branched low density polyethylene (LDPE) when significantly branched (having a high degree of long chain branching), as is often the case with free-radical polymerized PE; and an ethylene polymer having a density of more than 0.940 g / cm3is referred to as a “high density polyethylene” (HDPE). Density is determined according to ASTM D792. Specimens are prepared according to ASTM D4703 - Annex 1 Procedure C followed by conditioning according to ASTM D618 - Procedure A prior to testing.

[0011] As used herein, and unless otherwise specified, the term “hydrocarbon” means a class of compounds containing hydrogen bound to carbon, and encompasses (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated or unsaturated), including mixtures of hydrocarbon compounds having different values of n.

[0012] As used herein, a composition or film “free of’ a component refers to a composition / film substantially devoid of the component, or comprising the component in an amount of less than about 0.01 wt %, by weight of the total composition.

[0013] As used herein, the term “polymerization conditions” refers to conditions conducive to the reaction of one or more olefin monomers when contacted with an activated olefin polymerization catalyst to produce a polyolefin polymer, including a skilled artisan's selection of temperature, pressure, reactant concentrations, optional solvent / diluents, reactant mixing / addition parameters, and other conditions within at least one polymerization reactor.

[0014] For the sake of brevity7, only certain ranges are explicitly disclosed herein. How ever, ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit maybe combined with any other upper limit to recite a range not explicitly recited. Additionally, "‘in a range” or "within a range” includes every point or individual value between its end points even though not explicitly recited and includes the end points themselves. Thus, every point or individual value may serve as its own low er or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.

[0015] For the purposes of the present disclosure, the numbering scheme for the Periodic Table Groups is used as described in Chemical and Engineering News, 63(5), pg. 27 (1985).

[0016] The following abbreviations may be used herein: MAO is methylalumoxane, SMAO is supported methylalumoxane, NMR is nuclear magnetic resonance, ppm is part per million, THF is tetrahydrofuran.

[0017] As used herein, olefin polymerization catalyst(s) refer to any catalyst, such as an organometallic complex or compound that is capable of coordination polymerization addition w here successive monomers are added in a monomer chain at the organometallic active center.

[0018] The terms “substituent,” “radical,” “group,” and “moiety” may be used interchangeably.

[0019] The term “alpha-olefin” refers to an olefin having a terminal carbon-to-carbon double bond in the structure thereof ((R R )-C=CH2, where R and R can be independently hydrogen or any hydrocarbyl group; such as R is hydrogen and R is an alkyl group). A “linear alpha-olefin” is an alpha-olefin defined in this paragraph wherein R is hydrogen, and R is hydrogen or a linear alkyl group.

[0020] For the purposes of the present disclosure, ethylene shall be considered an alphaolefin.

[0021] As used herein, and unless otherwise specified, the term “Cn” means hydrocarbon(s) having n carbon atom(s) per molecule, wherein n is a positive integer. The term “hydrocarbon” means a class of compounds containing hydrogen bound to carbon, and encompasses (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and or unsaturated), including mixtures of hydrocarbon compounds having different values of n. Likewise, a “Cm-Cy” group or compound refers to a group or compound including carbon atoms at a total number thereof from m to y. Thus, a Ci-Cso alkyl group refers to an alkyl group including carbon atoms at a total number thereof of about 1 to about 50.

[0022] Unless otherwise indicated, (e.g., the definition of "substituted hydrocarbyl", "substituted aromatic", etc.), the term “substituted” means that at least one hydrogen atom has been replaced with at least one non-hydrogen group, such as a hydrocarbyl group, a heteroatom.or a heteroatom containing group, such as halide (such as 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, where each R* is independently a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted completely saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), or where at least one heteroatom has been inserted within a hydrocarbyl ring.

[0023] The term "substituted hydrocarbyl" means a hydrocarbyl radical in which at least one hydrogen atom of the hydrocarbyl radical has been substituted with at least one heteroatom (such as halide, e.g., Br, Cl, F or I) or heteroatom-containing group (such as a functional group, e g., -NR*2, -OR*, -SeR*, -TeR*, -PR*2. -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*3, -GeR*3, -SnR*3, -PbR*3, where each R* is independently a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted completely saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), or where at least one heteroatom has been inserted within a hydrocarbyl ring.

[0024] The term "substituted aromatic," means an aromatic group having 1 or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom containing group.

[0025] The terms “hydrocarbyl radical,’' “hydrocarbyl group,” or “hydrocarbyl” may be used interchangeably and are defined to mean a group including hydrogen and carbon atoms only. For example, a hydrocarbyl can be a Ci-Cioo radical that may be linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic. Examples of such radicals may include, but are not limited to, alky l groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and aryl groups, such as phenyl, benzyl, naphthyl.

[0026] The terms “alkoxy” and “alkoxide” mean an alkyl or aryl group bound to an oxygen atom, such as an alkyl ether or aryl ether group / radical connected to an oxygen atom and can include those where the alkyl / aryl group is a Ci to Cio hydrocarbyl. The alky l group may be straight chain, branched, or cyclic. The alkyl group may be saturated or unsaturated. Examples of suitable alkoxy radicals can include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, phenoxyl.

[0027] The term "alkenyl" means a straight-chain, branched-chain, or cyclic hy drocarbon radical having one or more double bonds. These alkeny l radicals may be optionally substituted. Examples of suitable alkenyl radicals can include ethenyl, propenyl, allyl. 1,4-butadienyl,cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloctenyl, including their substituted analogues.

[0028] The terms "alkyl radical,” “alkyl group,” and “alkyl” are used interchangeably throughout this disclosure. For purposes of this disclosure, "alkyl radical" is defined to be Ci-Cioo alky ls that may be linear, branched, or cyclic. Examples of such radicals can include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyd, cyclohexyl, cyclooctyl, including their substituted analogues.

[0029] The term "aryl" or "aryl group" means an aromatic ring and the substituted variants thereof, such as pheny l, 2-methyl-phenyl, xylyl, 4-bromo-xylyl. Likewise, “heteroaryl” means an aryl 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. 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 ligands, but are not by definition aromatic; likewise the term aromatic also refers to substituted aromatics.

[0030] Where isomers of a named alkyl, alkenyl, alkoxide, or aryl group exist (e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl), 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 tert-butyl).

[0031] The term "ring atom" means an atom that is part of a cyclic ring structure. By this definition, a benzyl group has six ring atoms and tetrahydrofuran has five ring atoms.

[0032] 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-dimethylamino-phenyl is a heteroatom-substituted ring. Other examples of heterocycles may include pyridine, imidazole, and thiazole.

[0033] 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 polydispersity (PDI), is defined to be Mw divided by Mn. Unless otherwise noted, all molecular weight units (e.g., Mw, Mn, Mz) are g / moL

[0034] The terms “catalyst compound”, “catalyst complex”, “transition metal complex”, “transition metal compound”, “precatalyst compound”, and “precatalyst complex” are used interchangeably.

[0035] A ‘‘catalyst system” is a combination of at least one catalyst compound, at least one activator, an optional coactivator, and an optional support material. When "catalyst system" is used to describe such a pair before activation, it means the unactivated catalyst complex (precatalyst) together with an activator and, optionally, a coactivator. When it is used to describe such a pair after activation, it means the activated complex and the activator or other charge-balancing moiety. The catalyst compound may be neutral as in a precatalyst, or a charged species with a counter ion as in an activated catalyst system. For the purposes of the present disclosure and the claims thereto, when catalyst systems are described as including neutral stable forms of the components, it is well understood by one of ordinary skill in the art, that the ionic form of the component is the form that reacts with the monomers to produce polymers. A polymerization catalyst system is a catalyst system that can polymerize monomers to polymer. Furthermore, catalyst compounds and activators represented by formulae herein are intended to embrace both neutral and ionic forms of the catalyst compounds and activators.

[0036] An “anionic ligand” is a negatively charged ligand which donates one or more pairs of electrons to a metal ion. A “Lewis base” or “neutral donor ligand” is a neutrally charged ligand which donates one or more pairs of electrons to a metal ion. Examples of Lewis bases include ethylether, trimethylamine, pyridine, tetrahydrofuran, dimethylsulfide, and triphenylphosphine. The term “heterocyclic Lewis base” refers to Lewis bases that are also heterocycles. Examples of heterocyclic Lewis bases include pyridine, imidazole, thiazole, and furan.

[0037] A scavenger is a compound that can be added to facilitate polymerization by scavenging impurities. Some scavengers may also act as activators and may be referred to as coactivators. A coactivator, that is not a scavenger, may also be used in conjunction with an activator in order to form an active catalyst. In at least one embodiment, a coactivator can be pre-mixed with the transition metal compound to form an alkylated transition metal compound.

[0038] The term "continuous" means a system that operates without interruption or cessation for an extended period of time. For example a continuous process to produce a polymer would be one where the reactants are continually introduced into one or more reactors and polymer product is continually withdrawn.

[0039] A solution polymerization means a polymerization process in which the polymer is dissolved in a liquid polymerization medium, such as an inert diluent or monomer(s) or their blends. A solution polymerization can be homogeneous. A homogeneous polymerization is one where the polymer product is dissolved in the polymerization medium. Suitable systemsmay be not turbid as described in J. Vladimir Oliveira, C. Dariva and J. C. Pinto, Ind. Eng. Chem. Res.. 2000, Vol. 29, p. 4627.

[0040] A bulk polymerization means a polymerization process in which the monomers and or comonomers being polymerized are used as a solvent or diluent using little or no inert solvent as a solvent or diluent. A small fraction of inert solvent / diluent might be used as a carrier for catalyst and scavenger. A bulk polymerization system contains less than 25 wt% of inert solvent or diluent, such as less than 10 wt%, such as less than 1 wt%, such as 0 wt%.

[0041] The term ‘'single catalyst compound” refers to a catalyst compound corresponding to a single structural formula, although such a catalyst compound may comprise and be used as a mixture of isomers, e.g., stereoisomers.

[0042] A catalyst system that utilizes a single catalyst compound means a catalyst system that is prepared using only a single catalyst compound in the preparation of the catalyst system. Thus, such a catalyst system is distinguished from, for example, “dual” catalyst systems, which are prepared using two catalyst compounds having different structural formulas, e.g., the connectivity between the atoms, the number of atoms, and / or the type of atoms in the two catalyst compounds is different. Thus, one catalyst compound is considered different from another if it differs by at least one atom, either by number, type, or connection. For example bisindenyl zirconium dichloride is different from (indenyl)(2-methylindenyl) zirconium dichloride which is different from (indenyl)(2-methylindenyl) hafnium dichloride. Catalyst compounds that differ only in that they are stereoisomers of each other are not considered to be different catalyst compounds. For example, rac-dimethylsilylbis(2-methyl 4-phenyl)hafnium dimethyl and / wcs«-dimethylsilylbis(2-methyl 4-phenyl)hafnium dimethyl are considered to be not different.

[0043] The terms “cocatalyst” and “activator” are used herein interchangeably and are defined to be any compound which can activate any one of the catalyst compounds described above by converting the neutral catalyst compound to a catalytically active catalyst compound cation.Polymerization Processes

[0044] A polymerization process can include a gas phase polymerization reaction, and in particular a fluidized bed gas phase polymerization reaction. Generally, in a fluidized gas bed process used for producing polymers, a gaseous stream containing one or more monomers is continuously cycled through a fluidized bed in the presence of a catalyst under reactive conditions. In some embodiments, the reaction medium includes condensing agents, which aretypically non-coordinating inert liquids that are converted to gas in the polymerization processes, such as isopentane, isohexane, or isobutane. The gaseous stream is withdrawn from the fluidized bed and recycled back into the reactor. Simultaneously, polymer product is withdrawn from the reactor and fresh monomer is added to replace the polymerized monomer. (See, for example, US Patent Nos. 4,543,399; 4,588,790; 5,028,670; 5,317,036; 5,352,749; 5,405,922; 5,436,304; 5,453,471; 5,462,999; 5,616,661; and 5,668,228; all of which are incorporated herein by reference.) The gas-phase polymerization may be carried out in any suitable reactor system, e g., a stirred- or paddle-type reactor system. See U. S. Pat. Nos.7,915,357; 8,129,484; 7,202,313; 6,833,417; 6,841,630; 6,989,344; 7,504,463; 7,563,851; and 8,101,691 for discussion of suitable gas phase fluidized bed polymerization systems, which are incorporated herein by reference.

[0045] In such polymerization processes, a gas-phase, fluidized-bed process is conducted by passing a stream containing ethylene and an olefin comonomer continuously through a fluidized-bed reactor under reaction conditions and in the presence of a catalyst composition at a velocity sufficient to maintain a bed of solid particles in a suspended state. A stream (which may be called a “cycle gas’’ stream) containing unreacted ethylene and olefin comonomer is continuously withdrawn from the reactor, compressed, cooled, optionally partially or fully condensed, and recycled back to the reactor. Prepared polyethylene copolymer is withdrawn from the reactor and replacement ethylene and olefin comonomer are added to the recycle stream. In some embodiments, gas inert to the catalyst composition and reactants is present in the gas stream.

[0046] The reactor pressure during polymerization may be about 100 psig (680 kPag)-about 500 psig (3448 kPag), such as about 200 psig (1379 kPag)- about 400 psig (2759 kPag), such as about 250 psig (1724 kPag)- about 350 psig (2414 kPag). In some embodiments, the reactor is operated at a temperature of about 60°C to about 120°C, such as about 60°C to about 115°C, such as about 70°C to about 110°C, such as about 70°C to about 95°C, such as about 80°C to about 90°C. A ratio of hydrogen gas to ethylene can be about 10 to about 30 ppm / mol%, such as about 15 to about 25 ppm / mol%. such as about 16 to about 20 ppm / mol%.

[0047] The mole percent of ethylene (based on total monomers) may be about 25- about 90 mole percent, such as about 50- about 90 mole percent, or about 70- about 85 mole percent, and the ethylene partial pressure (in the reactor) can be about 75 psia (517 kPa)- about 300 psia (2069 kPa), or about 100 psia - about 275 psia (689-1894 kPa), or about 150 psia - about 265 psia(1034-1826 kPa), or about 180 psia- about 200 psia. Ethylene concentration in the reactor can also range from about 35 mol% - about 95 mol%, such as within the range from a low of35, 40, 45, 50, or 55 mol% to a high of 70, 75, 80, 85, 90, or 95 mol% and further where ethylene mol% is measured on the basis of total moles of gas in the reactor (including, if present, ethylene and / or comonomer gases as well as inert gases such as one or more of nitrogen, isopentane or other ICA(s), etc.); as with vol-ppm hydrogen, this measurement may for convenience be taken in the cycle gas outlet rather than in the reactor itself. Comonomer concentration can be about 0.2 - about 1 mol%, such as from a low of 0.2, 0.3, 0.4 or 0.5 mol% to a high of 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95. or 1.0 mol%.Polymerizations Using Trim

[0048] Polymerization processes of the present disclosure can be performed using a “trim’’ process. Trim processes are described, e.g., in U. S. Patent Publication No. 2021 / 0395404, especially in connection with FIG. 1 therein, and at Paragraphs

[0113] -

[0124] therein, which description is incorporated herein by reference. An overview of such processes of particular use for the present disclosure is also provided below.

[0049] For delivery of a catalyst slurry7to a reactor, a high solids concentration of the slurry7typically increases the slurry viscosity. A high solids concentration also increases the amount of foaming which is typically generated in a catalyst slurry vessel. A high slurry7viscosity and foaming can cause handling problems, storage problems as well as reactor injection problems. Low viscosity7diluents can be added to the slurry7to reduce the viscosity7. However, the reduced viscosity promotes settling of the slurry in the solution, which can result in plugging of reactor components and accumulation of solids on the walls of catalyst slurry vessels.

[0050] A second catalyst solution can be added (i.e. "‘trimmed’’) to the slurry to adjust one or more properties “in-situ” of polymer being formed in a reactor. Such “trim” processes are very economical because they do not require a polymerization to cease in order to adjust polymer properties in the event a catalyst system is not behaving in a desirable way. However, a second catalyst is typically delivered to the slurry as a low viscosity solution, which can promote settling of the slurry^ solution and subsequent gelling and / or plugging of reactor components.

[0051] Accordingly, processes for polymerizing olefin(s) can include using dual catalyst systems (e.g., by supporting a second catalyst in situ). In particular, methods include combining a catalyst component slurry with a catalyst component solution (to “trim”) to form a third catalyst composition and introducing the third composition into a polymerization reactor (e.g., gas phase reactor).

[0052] In some embodiments, a method includes: contacting a first composition with a second composition in a line leading to the reactor to form a third composition. The firstcomposition includes a first catalyst (or catalyst compound), a support, and a diluent. The first catalyst or catalyst compound may be referred to herein as a "primary catalyst’" or "base catalyst.” The second composition includes a second catalyst (or catalyst compound) and a second diluent. The second catalyst or catalyst compound can be referred to as a “trim catalyst”, particularly insofar as in methods described herein, the trim process is preferably used to adjust ratio of first to second catalyst by increasing or decreasing relative amount of trim catalyst to primary catalyst. The method includes introducing the third composition from the line into a gas-phase fluidized bed reactor and exposing the third composition to polymerization conditions. The method includes obtaining a polyolefin.

[0053] Processes can include adjusting reactor conditions, such as an amount of second catalyst fed to the reactor (via the line to the reactor), to control one or more polymer properties of the polyolefin obtained from the reactor.

[0054] By using metallocene catalysts of the present disclosure as the second catalyst trimmed on-line at various ratios onto slurry feeding the first catalyst, or vice versa, along with varying reactor conditions involving temperature, reaction mixture component concentrations, and the like, beneficial polyolefin products may be formed.

[0055] Additionally, it should also be contemplated that for the distinct catalysts selected, some of the second catalyst may be initially co-deposited with the first catalyst on a common support, and the remaining amount of the first catalyst or second catalyst added as trim.

[0056] The catalyst system may include a catalyst compound in a slurry and an added solution catalyst component that is added to the slurry. Generally, the first catalyst and / or second catalyst will be supported in the initial slurry, depending on solubility. However, in at least one embodiment, the initial catalyst component slurry may have no catalysts. In this case, two or more solution catalysts may be added as “trim” to the slurry to cause each to be supported.

[0057] Furthermore, notwithstanding the above distinctions between “primary catalyst” or “base catalyst” and “trim catalyst” as noted above, it is contemplated that one could easily swap the role of primary catalysts described herein with trim catalysts, to achieve a similar effect (that is, in various embodiments, any “primary catalyst” described herein could be used as the “second catalyst” in methods just described; and any “trim catalyst” could be used as the “first catalyst” in methods just described).

[0058] The slurry may include one or more activators and supports, and one or more catalyst compounds. For example, the slurry may include two or more activators (such as alumoxane and a modified alumoxane) and a catalyst compound, or the slurry may include asupported activator and more than one catalyst compounds. In at least one embodiment, the slurry includes a support, an activator, and two catalyst compounds. In another embodiment the slurry includes a support, an activator and two different catalyst compounds, which may be added to the slurry separately or in combination. The slurry, containing silica and alumoxane, may be contacted with a catalyst compound, allowed to react, and thereafter the slurry is contacted with another catalyst compound, for example, as ‘“trim.”

[0059] One or more diluents can be used to facilitate the combination of any two or more components of the catalyst system in the slurry or in the trim catalyst solution. For example, the single site catalyst compound and the activator can be combined together in the presence of toluene or another non-reactive hydrocarbon or hydrocarbon mixture to provide the catalyst mixture. In addition to toluene, other suitable diluents can include, but are not limited to, ethylbenzene, xylene, pentane, hexane, heptane, octane, other hydrocarbons, or any combination thereof. The support, either dry or mixed with toluene can then be added to the catalyst mixture or the catalyst / activator mixture can be added to the support.

[0060] The diluent can be or include mineral oil. Mineral oil can have a density of about 0.85 g / cm3to about 0.9 g / cm3at 25°C according to ASTM D4052, such as about 0.86 g / cm3to about 0.88 g / cm3. Mineral oil can have a kinematic viscosity at 25°C of about 150 cSt to about 200 cSt according to ASTM D341, such as about 160 cSt to about 190 cSt, such as about 170 cSt. Mineral oil can have an average molecular weight of about 400 g / mol to about 600 g / mol according to ASTM D2502, such as about 450 g / mol to about 550 g / mol, such as about 500 g / mol. In at least one embodiment, a mineral oil is HYDROBRITE® 380 PO White Mineral Oil (“HB380”) from Sonnebom, LLC.

[0061] The diluent can further include a wax, which can provide increased viscosity to a slurry (such as a mineral oil slurry). A wax is a food grade petrolatum also known as petroleum jelly. A wax can be a paraffin wax. Paraffin waxes include SONO JELL® paraffin waxes, such as SONO JELL® 4 and SONO JELL® 9 from Sonnebom, LLC. In at least one embodiment, a slurry has 5 wt% or greater of wax, such as 10 wt% or greater, such as 25 wt% or greater, such as 40 wt% or greater, such as 50 wt% or greater, such as 60 wt% or greater, such as 70 wt% or greater. For example, a mineral oil slurry can have about 70 wt% mineral oil, about 10 wt% wax, and about 20 wt% supported catalyst(s) (e g., supported dual catalysts). The increased viscosity provided by a wax in a slurry, such as a mineral oil slurry7, provides reduced settling of supported catalyst(s) in a trim vessel or catalyst pot (for introducing supported catalyst to the line); while at the same time trim efficiency can be suitably maintained. In at least one embodiment, a wax has a density of about 0.7 g / cm3(at 100°C) toabout 0.95 g / cm3(at 100°C), such as about 0.75 g / cm3(at 100°C) to about 0.87 g / cm3(at 100°C). A wax can have a kinematic viscosity of about 5 mm2 / s (at 100°C) to about 30 mm2 / s (at 100°C). A wax can have a boiling point of about 200°C or greater, such as about 225°C or greater, such as about 250°C or greater. A wax can have a melting point of about 25°C to about 100°C, such as about 35°C to about 80°C.

[0062] The catalyst component solution (referred to as the “trim” solution) may include only catalyst compound(s) or may include an activator. In at least one embodiment, the catalyst compound(s) in the catalyst component solution is unsupported. The catalyst solution used in a trim process can be prepared by dissolving the catalyst compound and optional activators in a liquid diluent. The liquid diluent may be an alkane, such as a Cs to C30 alkane, or a C5 to C10 alkane. Cyclic alkanes such as cyclohexane and aromatic compounds such as toluene may also be used. Mineral oil may be used as a diluent alternatively or in addition to other alkanes such as a Cs to C30 alkane. Mineral oil can have a density of about 0.85 g / cm3to about 0.9 g / cm3at 25°C according to ASTM D4052, such as about 0.86 g / cm3to about 0.88 g / cm3. Mineral oil can have a kinematic viscosity at 25°C of about 150 cSt to about 200 cSt according to ASTM D341, such as about 160 cSt to about 190 cSt, such as about 170 cSt. Mineral oil can have an average molecular weight of about 400 g / mol to about 600 g / mol according to ASTM D2502, such as about 450 g / mol to about 550 g / mol, such as about 500 g / mol. In at least one embodiment, a mineral oil is HYDROBRITE® 380 PO White Mineral Oil (“HB380”) from Sonnebom, LLC.

[0063] The solution used should be liquid under the conditions of polymerization and relatively inert. In at least one embodiment, the liquid utilized in the catalyst compound solution is different from the diluent used in the catalyst component slurry. In another embodiment, the liquid utilized in the catalyst compound solution is the same as the diluent used in the catalyst component solution.

[0064] In alternative embodiments, the catalyst is not limited to a slurry arrangement, as a mixed catalyst system may be made on a support and dried. The dried catalyst system can then be fed to the reactor through a dry’ feed system.

[0065] In gas-phase polyethylene production processes, it may be desirable to use one or more static control agents to aid in regulating static levels in the reactor. As used herein, a static control agent is a chemical composition which, when introduced into a fluidized bed reactor, may influence or drive the static charge (negatively, positively, or to zero) in the fluidized bed. The specific static control agent used may depend upon the nature of the staticcharge, and the choice of static control agent may vary dependent upon the polymer being produced and the single site catalyst compounds being used.

[0066] Static control agents such as aluminum stearate may be used. The static control agent used may be selected for its ability to receive the static charge in the fluidized bed without adversely affecting productivity. Other suitable static control agents may also include aluminum distearate, ethoxylated amines, and anti-static compositions.Primary Catalysts

[0067] The catalysts employed in a polymerization of the present disclosure can be metallocene catalysts. The catalysts employed can be supported catalysts introduced via a line to a reactor. For example, metallocene catalysts may be selected from the catalysts described in Patent Cooperation Treaty Publication Nos. U. S. 5,278,272; U. S. 5,763,543; U. S. 6,255.426; and U. S. 7,951,873, each of which is incorporated herein by reference. In some embodiments, a catalyst is bis(n-propyl cyclopentadienyl)2 hafnium dimethyl. In general, metallocene catalyst compounds can include catalyst compounds having one or more Cp ligands (cyclopentadieny l and ligands isolobal to cyclopentadienyl) bound to at least one Group 3 to Group 12 metal atom (preferably Zn, Hf, or Ti), and one or more (preferably two) leaving group(s) bound to the at least one metal atom (preferably wherein each leaving group is independently Ci to C4 alkyl, such as methyl, or halide, such as Cl).

[0068] More particularly, a primary catalyst in accordance with various embodiments can include an unbridged hafnocene or zirconocene, such as the hafnocenes described in U. S. Patent No. 7,078,467 at col. 3, line 62to col. 4, line 51, which description is incorporated herein by reference, as well as the zirconocene analogues thereof; and / or the catalysts described in U. S. Patent No. 6,936,675 at col. 4, line 22 to col. 7, line 36, which description is also incorporated herein by reference. For instance, a suitable primary catalyst can include an unbridged bis-indenyl hafnocene or zirconocene, such as one or more of the followingAs used herein, all references to the Periodic Table of the Elements and groups thereof is to the NEW NOTATION published in HAWLEYS CONDENSED CHEMICAL DICTIONARY. Thirteenth Edition, John Wiley & Sons, Inc., (1997) (reproduced there with permission from IUPAC), unless reference is made to the Previous IUPAC form noted with Roman numerals (also appearing in the same), or unless otherwise noted.

[0069] The Cp ligands are one or more rings or ring system(s), at least a portion of which includes n-bonded systems, such as cycloalkadienyl ligands and heterocyclic analogues. The ring(s) or ring system(s) typically include atoms selected from Groups 13 to 16 atoms, and. in at least one embodiment, the atoms that make up the Cp ligands are selected from carbon.nitrogen, oxygen, silicon, sulfur, phosphorous, germanium, boron, aluminum, and combinations thereof, where carbon makes up at least 50% of the ring members. In a more particular exemplary embodiment, the Cp ligand(s) are selected from the group consisting of substituted and unsubstituted cyclopentadienyl ligands and ligands isolobal to cyclopentadienyl, non-limiting examples of which include cyclopentadienyl, indenyl, fluorenyl and other structures. Further non-limiting examples of such ligands include cyclopentadienyl, cyclopentaphenanthreneyl, indenyl, benzindenyl, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, phenanthrindenyl, 3,4-benzofluorenyl, 9-phenylfluorenyl, 8-H-cyclopent[a]acenaphthylenyl, 7-H-dibenzofluorenyl, indeno[l,2-9]anthrene, thiophenoindenyl, thiophenofluorenyl, hydrogenated versions thereof (e.g..4,5,6,7-tetrahydroindenyl, or ”H4 Ind”), substituted versions thereof, and heterocyclic versions thereof.

[0070] The metal atom “M” of the metallocene catalyst compound can be selected from Groups 3 through 12 atoms and lanthanide Group atoms; and selected from Groups 3 through 10 atoms some embodiments; and selected from the group of Sc, Ti, Zr, Hf, V, Nb, Ta, Mn, Re, Fe, Ru, Os, Co. Rh, Ir, and Ni in some embodiments; and selected from Groups 4, 5, and 6 atoms in some embodiments; and Ti, Zr, Hf atoms in some embodiments; and Zr in at least one embodiment. The oxidation state of the metal atom “M” can range from 0 to +7 in one exemplary embodiment; and in a more particular exemplary embodiment, can be +1, +2, +3, +4, or +5; and in yet a more particular exemplary embodiment can be +2. +3 or +4. The groups bound to the metal atom “M” are such that the compounds described below in the formulas and structures are electrically neutral, unless otherwise indicated. The Cp ligand forms at least one chemical bond with the metal atom M to form the “metallocene catalyst compound.” The Cp ligands are distinct from any leaving groups bound to the catalyst compound in that they are not highly susceptible to substitution / abstraction reactions.

[0071] In some embodiments, the one or more metallocene catalyst compounds can be represented by Formula (I):CpACpBMXn (I).in which M is as described above; each X is chemically bonded to M, each Cp group is chemically bonded to M and n is 0 or an integer from 1 to 4, and either 1 or 2 in a particular exemplary' embodiment.

[0072] The ligands represented by CpA and CpB in Formula (I) can be the same or different cyclopentadienyl ligands or ligands isolobal to cyclopentadienyl, either or both of which can contain heteroatoms and either or both of which can be substituted by a group R. In at leastone embodiment, CpA and Cpn are independently selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, and substituted derivatives of each.

[0073] Independently, each Cp. and CpB of Formula (I) can be unsubstituted or substituted with any one or combination of substituent groups R. Non-limiting examples of substituent groups R as used in structure of Formula (I) as well as ring substituents in structures discussed and described below, include groups selected from hydrogen radicals, alkyls, alkenyls, alkynyls, cycloalkyls, aryls, acyls, aroyls, alkoxys, aryloxys, alkylthiols, dialkylamines, alkylamidos, alkoxycarbonyls, aryloxycarbonyls, carbamoyls, alkyl- and dialkyl-carbamoyls, acyloxys, acylaminos, aroylaminos, and combinations thereof. More particular non-limiting examples of alkyl substituents R associated with any of the catalyst structures of the present disclosure (e.. Formula (I)) include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzy l, phenyl, methylphenyl, and tert-butylphenyl groups and the like, including all their isomers, for example, tertiary butyl, isopropyl, and the like. Other possible radicals include substituted alky ls and aryls such as, for example, fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl, hydrocarbyl substituted organometalloid radicals including trimethylsilyl, trimethylgermyl, methyldiethylsilyl, and the like, and halocarbyl-substituted organometalloid radicals, including tris(trifluoromethyl)silyl, methylbis(difluoromethyl)silyl, bromomethyldimethylgermyl and the like; and disubstituted boron radicals including dimethylboron, for example; and disubstituted Group 15 radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, as well as Group 16 radicals including methoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide. Other substituent groups R include olefins such as olefinically unsaturated substituents including vinyl-terminated ligands such as, for example, 3-butenyl, 2-propenyl, 5-hexenyl, and the like. In one exemplary embodiment, at least two R groups (two adjacent R groups in a particular exemplary embodiment) are joined to form a ring structure having from 3 to 30 atoms selected from carbon, nitrogen, oxygen, phosphorous, silicon, germanium, aluminum, boron, and combinations thereof. Also, a substituent group R, such as 1-butanyl, can form a bonding association to the element M.

[0074] Each X in the Formula (I) (and X of the catalyst structures shown below) is independently selected from halogen, hydrides. Ci to C12 alkyls, C2 to C12 alkenyls, Ce to C12 aryls, C7 to C20 alkylaryls, Ci to C12 alkoxys, Ce to C16 ary loxys, C7 to Cs alkylaryloxys, Ci to C12 fluoroalkyls, Ce to C12 fluoroaryls, and Ci to C12 heteroatom containing hydrocarbons and substituted derivatives thereof; such as hydride, halogen ions, Ci to Ce alkyls, C2 to C6 alkenyls, C7 to Cis alkylaryls. Ci to Ce alkoxys, Ce to C14 aryloxys, C7 to Cie alkylaryloxys. Ci to Cealkylcarboxylates, Ci to Ce fluorinated alkylcarboxylates, Ce to C12 arylcarboxylates, C7 to Cis alkylarylcarboxylates, Ci to Ce fluoroalkyls, C2 to Ce fluoroalkenyls, and C7 to Cis fluoroalkylaryls; such as hydride, chloride, fluoride, methyl, phenyl, phenoxy, benzoxy, tosyl, fluoromethyls and fluorophenyls; such as Ci to C12 alkyds, C2 to C12 alkenyls, Ce to C12 ary ls, C7 to C20 alkylaryls, substituted Ci to C12 alky ls, substituted Ce to C12 ary ls, substituted C7 to C20 alkylaryls and Ci to C12 heteroatom-containing alkyls, Ci to C12 heteroatom-containing aryls, and Ci to C12 heteroatom-containing alkylaryls; such as chloride, fluoride, Ci to Ce alkyls, C2 to Ce alkenyls, C7 to Cis alkylaryls, halogenated Ci to Ce alkyls, halogenated C2 to Ce alkenyls, and halogenated C7 to Cis alkylaryls; such as chloride, methyl, ethyl, propyl, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, fluoromethyls (mono-, di- and trifluoromethyls) and fluorophenyls (mono-, di-, tri-, tetra- and pentafluorophenyls).

[0075] Other examples of X groups include amides, amines, phosphines, ethers, carboxylates, dienes, hydrocarbon radicals having from 1 to 20 carbon atoms, fluorinated hydrocarbon radicals (e.g., -CeFs (pentafluorophenyl)), fluorinated alkylcarboxylates (e.g., CF3C(O)O-), hydrides, halogen ions and combinations thereof. Other examples of X ligands include alkyl groups such as cyclobutyl, cyclohexyl, methyl, heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy, bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and the like. In one exemplary embodiment, two or more X’s form a part of a fused ring or ring system. In at least one specific embodiment, X can be a leaving group selected from the group consisting of chloride ions, bromide ions, Ci to C10 alkyls, and C2 to C12 alkenyls, carboxylates, acetylacetonates, and alkoxides.

[0076] The metallocene catalyst compound can include a structure where CpA and Cpn are bridged to each other by at least one bridging group. (A) such that the structure is represented by Formula (II):CpA(A)CpBMXn (II).These bridged compounds represented by Formula (II) are known as “bridged metallocenes.'’ The elements CpA, Cpn. M, X and n in Formula (II) are as defined above for formula (I); where each Cp ligand is chemically bonded to M, and (A) is chemically bonded to each Cp. The bridging group (A) can include divalent hydrocarbon groups containing at least one Group 13 to 16 atom, such as, but not limited to, at least one of a carbon, oxygen, nitrogen, silicon, aluminum, boron, germanium, tin atom, and combinations thereof; where the heteroatom can also be Ci to C12 alkyl, or and substituted to satisfy neutral valency. In at least one embodiment, the bridging group (A) can also include substituent groups R as defined above(for Formula (I)) including halogen radicals and iron. In at least one embodiment, the bridging group (A) can be represented by Ci to Ce alkylenes, substituted Ci to Ce alkylenes, oxygen, sulfur, R2C=R.2Si, -Si(R')2Si(OR')2-, RhGe-. and RP=, where “=” represents two chemical bonds, R is independently selected from hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted Group 15 atoms, substituted Group 16 atoms, and halogen radical; and where two or more R' can be joined to form a ring or ring system. In at least one embodiment, the bridged metallocene catalyst compound of Formula (II) includes two or more bridging groups (A). In one or more embodiments, (A) can be a divalent bridging group bound to both CpA and CpB selected from divalent Ci to C20 hydrocarbyls and Ci to C20 heteroatom containing hydrocarbonyls. where the heteroatom containing hydrocarbonyls include from one to three heteroatoms.

[0077] The bridging group (A) can include methylene, ethylene, ethylidene, propylidene, isopropylidene, diphenylmethylene, 1,2-dimethylethylene, 1,2-diphenylethylene, 1, 1,2,2-tetramethylethylene, dimethyl silyl, diethylsilyl, methyl-ethylsilyl, trifluoromethylbutylsilyl, bis(trifluoromethyl)silyl, di(n-butyl)silyl, di(n-propyl)silyl, di(i-propyl)silyl, di(n-hexyl)silyl, dicyclohexylsilyl, diphenylsilyl cyclohexylphenylsilyl, t-butylcyclohexylsilyl, di(t-butylphenyl) silyl, di(p-toly Ijsilyl and the corresponding moieties where the Si atom is replaced by a Ge or a C atom; as well as dimethylsilyl, diethylsilyl, dimethylgermyl and diethylgermyl.

[0078] The bridging group (A) can also be cyclic, having, for example. 4 to 10 ring members; in at least one embodiment, bridging group (A) can have 5 to 7 ring members. The ring members can be selected from the elements mentioned above, and, in some embodiments, can be selected from B, C, Si, Ge, N, and O. Non-limiting examples of ring structures which can be present as, or as part of the bridging moiety are cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclooctylidene and the corresponding rings where one or two carbon atoms are replaced by at least one of Si, Ge, N and O. In one or more embodiments, one or two carbon atoms can be replaced by at least one of Si and Ge. The bonding arrangement between the ring and the Cp groups can be cis-, trans-, or a combination thereof.

[0079] The cyclic bridging groups (A) can be saturated or unsaturated and / or can carry one or more substituents and / or can be fused to one or more other ring structures. If present, the one or more substituents can be, in at least one specific embodiment, selected from the group consisting of hydrocarbyl (e.g., alkyl, such as methyl) and halogen (e.g., F, Cl). The one or more Cp groups to which the above cyclic bridging moieties can optionally be fused can be saturated or unsaturated, and are selected from the group consisting of those having 4 to 10,more particularly 5, 6, or 7 ring members (selected from the group consisting of C, N, O, and S in a particular exemplary embodiment) such as. for example, cyclopentyl, cyclohexyl and phenyl. Moreover, these ring structures can themselves be fused such as, for example, in the case of a naphthyl group. Moreover, these (optionally fused) ring structures can carry one or more substituents. Illustrative, non-limiting examples of these substituents are hydrocarbyl (particularly alkyl) groups and halogen atoms. The ligands CpA and Cpn of formula (II) and (II) can be different from each other. The ligands CpA and Cpn of formula (I) and (II) can be the same.

[0080] A metallocene catalyst compound of the present disclosure can, alternatively, include bridged mono ligand metallocene compounds (e.g., mono cyclopentadienyl catalyst components).

[0081] It is considered that the metallocene catalyst components discussed and described above include their structural or optical or enantiomeric isomers (racemic mixture), and, in some embodiments, can be a pure enantiomer. As used herein, a single, bridged, asymmetrially substituted metallocene catalyst compound having a racemic and / or meso-isomer does not, itself, constitute at least two different bridged, metallocene catalyst components.

[0082] The metallocene catalyst compounds can include any suitable combination. For example, the metallocene catalyst compound can include: bis(ethylcyclopentadienyl)Zr(CH3)2,bis(ethylcyclopentadienyl)ZrCh,bis(ethylcyclopentadienyl)Hf(CH3)2,bis(ethylcyclopentadienyl)HfC12,(ethylcyclopentadi enyl)(pentamethylcyclopentadienyl)ZrC12, (ethylcyclopentadienyl)(pentamethylcyclopentadienyl)Zr(CH3)2, (ethylcyclopentadienyl)(pentamethylcyclopentadienyl)HfC12, (ethylcyclopentadienyl)(pentamethylcyclopentadienyl)Hf(CH3)2,bis(n-propylcyclopentadienyl)Zr(CH3)2,bis(n-propylcyclopentadienyl)ZrC12,bis(n-propylcyclopentadienyl)Hf(CH3)2,bis(n-propylcyclopentadienyl)HfC12,(n-propylc clopentadienyl.pentamethylcyclopenladienyl)ZrC 2.(n-propylcyclopentadienyl,pentamethylcyclopentadienyl)Zr(CH3)2,(n-propylcyclopentadienyl,pentamethylcyclopentadienyl)HfC12,(n-propylcyclopentadienyl,pentamethylcyclopentadienyl)Hf(CH3)2,bis(n-butylcyclopentadienyl)Zr(CH3)2,bisfn-bulylcyclopenladienyljZrCb.bis(n-butylcyclopentadienyl)Hf(CH3)2,bis(n-butylcyclopentadienyl)HfC12,(n-butylcyclopentadienyl, pentamethylcyclopentadi enyl)ZrC12,(n-butylcyclopentadienyl.pentamethylcyclopentadienyl)Zr(CH3)2,(n-butylcyclopentadienyLpentamethylcyclopentadienyl)HfC(n-butylcyclopentadienyl,pentamethylcyclopentadienyl)Hf(CH3)2,or combinations thereof.

[0083] In yet other embodiments, the primary catalyst can be a bridged metallocene catalyst, such as in accordance with those described in one or more of US 5,314.973; US 6,255,426 (esp. at col. 2, line 61 to col. 3, line 17 therein, which description is incorporated herein by reference) and US 5,763,543 (esp. at col. 2, line 42 to col. 4, line 22, which description is incorporated herein by reference). Particular examples include bridged bis-indenyl catalysts, such as bridged bis-indenyl zirconocenes or bridged bis-indenyl hafnocenes, particularly those in which each indenyl ligand is unsubstituted (e.g., is a tetrahydroindenyl ligand), and wherein the bridge is Ci - Cio alkyl or R1R2S1. wherein Ri and R2 are each independently selected from methyl, ethyl, propyl, buty l, and penty l. Examples of such bridged bis-indenyl hafnocenes and zirconocenes can include (CH3)2Si(4, 5,6,7-tetrahydroindenyl)2Zr(CH3)2. (CH3)2Si(4.5.6.7-tetrahydroindenyl)2ZrC12, (CH2CH3)2Si(4,5,6,7-tetrahydroindenyl)2Zr(CH3)2, (CH2CH3)2SI(4,5,6,7-tetrahydroindenyl)2ZrC12, ((CH3)2Si)2(4,5,6,7-tetrahydroindenyl)2Zr(CH3)2, ((CH3)2Si)2(4,5,6,7-tetrahydroindenyl)2ZrC12, (CH3)2Si(4,5,6,7-tetrahydroindenyl)2Hf(CH3)2, (CH3)2Si(4,5,6,7-tetrahydroindenyl)2HfC12, (CH2CH3)2Si(4, 5,6,7-tetrahydroindenyl)2Hf(CH3)2, (CH2CH3)2Si(4,5,6,7-tetrahydroindenyl)2HfC12, ((CH3)2Si)2(4,5,6,7-tetrahydroindenyl)2Hf(CH3)2, ((CHs)2Si)2(4, 5,6,7-tetrahydroindenyl)2HfC12, or combinations thereof.

[0084] Although the catalyst compounds may be written or shown with methyl-, chloro-, or phenyl-leaving groups attached to the central metal, it can be understood that these groups may' be different. For example, each of these ligands may independently be a benzyl group (Bn), a methyl group (Me), a chloro group (Cl), a fluoro group (F), or any number of other groups, including organic groups, or heteroatom groups. Further, these ligands will change during the reaction, as a pre-catalyst is converted to the active catalyst for the reaction.Second Catalysts (e.g.. “trim’’ catalysts)

[0085] A second catalyst of the present disclosure includes a second catalyst that is supported onto a support along with the first catalyst to form a dual catalyst system. The second catalyst can be supported, and the dual catalyst system can be isolated. Alternatively, the second catalyst can be supported as a “trim” catalyst onto supported first catalyst in line on its way to the reactor. The dual catalyst system (e.g., also with activator) is introduced into a reactor (e.g., gas phase reactor).

[0086] In some embodiments, a second catalyst is represented by Formula (III):K (Hl), where M is a group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf); each of R1, R2, R3, R4, R5, R6. R7. R8, R9, R10, R11, R12, R13and R14is independently hydrogen, substituted or unsubstituted hydrocarbyl, a substituted or unsubstituted heteroatom, or a substituted or unsubstituted heteroatom-containing group, or one or more of R1and R2, R4and R5, R5and R6, R6and R7, R9and R10, R11and R12, R12and R13, and R13and R14are joined to form a substituted or unsubstituted completely saturated ring or a substituted or unsubstituted aromatic ring; where at least one of (1) R4and R3, (2) R3and R6, or (3) R6and R7are joined to form a first substituted or unsubstituted completely saturated ring fused to the first indenyl ring shown in Formula (III), and at least one of (1) R11and R12, (2) R12and R13, or (3) R13and R14are joined to form a second substituted or unsubstituted completely saturated ring fused to the second indenyl ring shown in Formula (III); and each X is independently a halide, a substituted or unsubstituted hydrocarbyl, a hydride, an amide, substituted or unsubstituted alkoxide, sulfide, phosphide, or a combination thereof, or two of X are joined together to form asubstituted or unsubstituted metallocycle ring, or two of X are joined to form a chelating ligand, a diene ligand, or an alkylidene.

[0087] In some embodiments, each of R4, R5, R6, R7, R11, R12, R13and R14of Formula (III) is independently hydrogen or Ci-Cio alkyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octy l, nonyl, or decyl), wherein at least one of (1) R4and R5, (2) R5and R6, or (3) R6and R7are joined to form a first substituted or unsubstituted completely saturated ring fused to the indenyl ring shown in Formula (III), and at least one of (1) R11and R12, (2) R12and R13, or (3) R13and R14are joined to form a second substituted or unsubstituted completely saturated ring fused to the indenyl ring shown in Formula (III).

[0088] In some embodiments, at least one of (1) R4and R5, (2) R5and R6, or (3) R6and R7are joined to form a first substituted or unsubstituted completely saturated ring fused to the indenyl ring shown in Formula (III). In some embodiments, R4and R5are joined to form a substituted or unsubstituted saturated C4 ring, a substituted or unsubstituted saturated C5 ring, a substituted or unsubstituted saturated Ce ring, or a substituted or unsubstituted saturated C7 ring, where the C4 ring, C5 ring, Ce ring, or C7 ring is fused to the indenyl ring shown in Formula (HI) In some embodiments, R5and R6are joined to form a substituted or unsubstituted saturated C4 ring, a substituted or unsubstituted saturated Cs ring, a substituted or unsubstituted saturated Ce ring, or a substituted or unsubstituted saturated C7 ring, where the C4 ring, Cs ring, Ce ring, or C7 ring is fused to the indenyl ring shown in Formula (III). In some embodiments, if R5and R6are joined to form a substituted or unsubstituted completely saturated ring, then R2is not substituted or unsubstituted hydrocarbyl. In some embodiments, R6and R7are joined to form a substituted or unsubstituted saturated C4 ring, a substituted or unsubstituted saturated Cs ring, a substituted or unsubstituted saturated Ce ring, or a substituted or unsubstituted saturated C7 ring, where the C4 ring. Cs ring, Ce ring, or C7 ring is fused to the indenyl ring shown in Formula (HI)

[0089] In some embodiments, at least one of (1) R11and R12, (2) R12and R13, or (3) R13and R14are joined to form a first substituted or unsubstituted completely saturated ring fused to the indenyl ring shown in Formula (III). In some embodiments, R11and R12are joined to form a substituted or unsubstituted saturated C4 ring, a substituted or unsubstituted saturated Cs ring, a substituted or unsubstituted saturated Ce ring, or a substituted or unsubstituted saturated C7 ring, w here the C4 ring, Cs ring, Ce ring, or C7 ring is fused to the indenyl ring shown in Formula (HI) In some embodiments, R12and R13are joined to form a substituted or unsubstituted saturated C4 ring, a substituted or unsubstituted saturated Cs ring, a substituted or unsubstituted saturated Ce ring, or a substituted or unsubstituted saturated C7 ring, where the C4 ring, Cs ring.Ce ring, or C7 ring is fused to the indenyl ring shown in Formula (III). In some embodiments, where R12and R13are joined to form a substituted or unsubstituted completely saturated ring, then R9is not substituted or unsubstituted hydrocarbyl. In some embodiments, R13and R14are joined to form a substituted or unsubstituted saturated C4 ring, a substituted or unsubstituted saturated Cs ring, a substituted or unsubstituted saturated Ce ring, or a substituted or unsubstituted saturated C7 ring, where the C4 ring. Cs ring, Ce ring, or C7 ring is fused to the indenyl ring shown in Formula (III).

[0090] In some embodiments, each of R1, R2, R3, R8, R9, and R10of Formula (III) is independently hydrogen or C1-C10 alkyd (such as methyl, ethyl, propyl, buty l, penty l, hexyl, heptyl, octyl, nonyl, or decyl). In some embodiments, each of R1, R2, R3, R8, R9, and R10is independently hydrogen, methyl, ethyl, or propyl. In some embodiments, each of R1, R2, R3, R8, R9, and R10is hydrogen. In some embodiments, each of R1, R2, R3, R8, R9, and R10is methyl. In some embodiments, at least one of R3and R10is C1-C10 alkyl. In some embodiments, each of R3and R10is independently C1-C10 alkyl. In some embodiments, each of R3and R10are Ci-C10 alkyl (such as methy 1) and R1. R2. R4, R5, R6, R7, R8, R9, R11, R12. R13and R14are hydrogen.

[0091] In some embodiments, one or more of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13and R14of Formula (III) is independently hydrogen, hydrocarbyl, silylcarbyl, alkoxyl, halide, or siloxyl.

[0092] In some embodiments of Formula (III), M is a group 4 metal, such as titanium (Ti), zirconium (Zr). or hafnium (HI), such as Zr or Hf. In some embodiments, each X is independently a halide, such as chloro. In yet other embodiments, each X is independently a C1-C4 alkyd, such as methy l. In some embodiments, each X is independently selected from substituted or unsubstituted hydrocarbyl, a heteroatom or substituted or unsubstituted heteroatom-containing group, such as methyl, benzyl, trimethylsilyl, methyl(trimethylsilyl), neopentyl, ethyl, propyl, butyl, phenyl, hydrido, chloro, fluoro, bromo, iodo, trifluoromethanesulfonate, dimethylamido, diethylamido, dipropy lamido, and diisopropylamido.

[0093] In some embodiments of Formula (III), (1) M is Zr or Hf, (2) X is C1-C4 alkyl, (3) R1, R2, R3, R4, R5. R6, and R7is independently hydrogen or substituted or unsubstituted C1-C10 alkyl, (4) R8, R9, R10, R11, R12, R13and R14is independently hydrogen or substituted or unsubstituted C1-C10 alkyl, (5) at least one of R4and R5, R5and R6, or R6and R7are joined to form a substituted completely saturated ring fused to the indenyl ring shown in Formula (I), and (6) R11and R12, R12and R13, or R13and R14are joined to form a substituted completely saturated ring fused to the indenyl ring shown in Formula (III).

[0094] In some embodiments, a catalyst compound is an unbridged metallocene represented by Formula (IV):where M is a group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf); each of R1R2R2R4R2R8R9R^9R^\ R^ R^ R^ R^ R^ R^2R^2R^8R^8R^9R^9R29R20. R21, R21, R22. and R22is independently hydrogen, a substituted or unsubstituted hydrocarbyl, a substituted or unsubstituted heteroatom, or a substituted or unsubstituted heteroatom-containing group; and each X is independently a halide, a substituted or unsubstituted hydrocarbyl, a hydride, an amide, substituted or unsubstituted alkoxide, a sulfide, a phosphide, or a combination thereof, or two of X are joined together to form a substituted or unsubstituted metallocycle ring, or two of X are joined to form a chelating ligand, a diene ligand, or an alkylidene.

[0095] In some embodiments, each of R4, R7, R11, R14, R15, R15, R16, R16, R17, R17, R18, R18’. R19, R19, R20, R20, R21, R21, R22, and R22of Formula (IV) is independently hydrogen or Ci-Cio alkyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl). In some embodiments, each of R13, R15, R18, R18, R19, R19, R22, and R22is independently hydrogen, methyl, ethyl, or propyl. In some embodiments, each of R15, R15, R18, R18, R19, R19’. R22, and R22’is hydrogen. In some embodiments, each of R15, R15, R18, R18, R19, R19’, R22, and R22is Ci-Cio alkyl (such as methyl). In some embodiments, each of R4, R7, R11, R14. R16, R16, R17, R17, R20, R20, R21, and R21is hydrogen.

[0096] In some embodiments, each of R1, R2, R3, R8, R9, and R10of Formula (IV) is independently hydrogen or Ci-Cio alky l (such as methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, or decyl). In some embodiments, each of R1, R2, R3, R8, R9, and R10is independently hydrogen, methyl, ethyl, or propyl. In some embodiments, each of R1, R2, R3, R8, R9, and R10is hydrogen. In some embodiments, each of R1, R2, R3, R8, R9, and R10is methyl. In some embodiments, at least one of R3and R10is C1-C10 alkyl. In some embodiments, each of R3and R10is independently C1-C10 alkyl. In some embodiments, R3and R10are C1-C10 alkyl (such as methyl), and R1, R2, R8, and R9are hydrogen.

[0097] In some embodiments of Formula (IV), M is a group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf), such as Zr or Hf. In some embodiments, each X is independently a halide, such as chloro. In yet other embodiments, each X is independently a C1-C4 alkyl, such as methyl. In some embodiments, each X is independently selected from substituted or unsubstituted hydrocarbyl, a heteroatom or substituted or unsubstituted heteroatom-containing group, such as methyl, benzyl, trimethylsilyl, methyl(trimethylsilyl), neopentyl, ethyl, propyl, butyl, phenyl, hydrido, chloro, fluoro, bromo, iodo, trifluoromethanesulfonate, dimethylamido, diethylamido, dipropylamido, and diisopropylamido.

[0098] In some embodiments of Formula (IV), (1) M is Zr or Hf, (2) X is C1-C4 alkyl, (3) R1, R2, R1, R4, R7, R15, R15, R16, R16, R17, R17, R18, and R18is independently hydrogen or substituted or unsubstituted C1-C10 alkyl, and (4) R8, R9, R10, R11, R14, R19, R19, R20, R20, R21, R21. R22, and R22is independently hydrogen or substituted or unsubstituted C1-C10 alkyl.

[0100] In some embodiments, a catalyst is represented by Formula (V):where M is a group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf); each of R1, R2, R?, R4, R5, R6, R7, R7, R8, R8, R9, R9, R10and R10is independently hydrogen, substituted or unsubstituted hydrocarbyl, a substituted or unsubstituted heteroatom, or a substituted or unsubstituted heteroatom-containing group, one or more of R5and R6, R7and R8, R8and R9, and R9and R10are joined to form a substituted or unsubstituted completely saturated ring or a substituted or unsubstituted aromatic ring, or one or more of R7and R8, R8and R9, and R9and R10are absent such that a carbon-carbon double bond is present between the corresponding carbon atoms of the hydroindenyl ring shown in Formula (V); T represents the formula Ra2J,(Ra)4J2, or (Ra)6J3 wherein each J is independently C, Si, or Ge, and each Rais independently hydrogen, halide, a substituted or unsubstituted Ci to C40 hydrocarbyl, or two Racan form a substituted or unsubstituted cyclic structure including a substituted or unsubstituted completely saturated ring, a substituted or unsubstituted partially saturated ring, or a substituted or unsubstituted aromatic ring; and each of X1and X2is independently a univalent anionic ligand, a diene ligand, an alkylidene ligand, or X1and X2are joined to form a metallocyclic ring.

[0101] Each of X1and X2can be independently a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group. In at least one embodiment, each of X1and X2is independently Ci to C20 hydrocarbyl radical, a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements, or X1and X2join together to form a C4 to C62 cyclic or polycyclic ring structure. In at least one embodiment, each of X1and X2is independently- selected from hydrocarbyl radicals having from 1 to 20 carbon atoms, aryls, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof, (each of X1and X2may form a part of a fused ring or a ring system), such as X1and X2is independently selected from halides, aryls, and Ci to C5 alkyl groups, such as phenyl, methyl, ethyl, propyl, butyl, pentyl, or chloride group. In at least one embodiment, each of X1and X2are chloride.

[0102] In at least one embodiment, R7, R7, R8, R8, R9, R9, R10and R10is independently selected from hydrogen, halogen. C1-C40 hydrocarbyl, substituted C1-C40 hydrocarbyl. a functional group comprising elements from Groups 13 to 17 of the periodic table of the elements (such as -NR'2, -SR', -OR’, -OSiR'3, or -PR'2, wherein each R' is independently hydrogen, halogen, C1-C10 alkyd, or Ce-Cio aryl), or two of R7, R7, R8, R8, R9, R9, R10and R10are joined to form a saturated ring, unsaturated ring, substituted saturated ring, or substituted unsaturated ring, such as a substituted or unsubstituted C4 to C62 cyclic or polycyclic ring. In at least one embodiment, each of R7, R8, R9, R10, R11, R12, and R13is hydrogen.

[0103] In at least one embodiment, R1, R2, R3, R4, R5, R6, R7, R7, R8, R8, R9, R9, R10and R10is independently hydrogen, halide, alkoxide or Ci to C40 substituted or unsubstituted hydrocarbyl (such as Ci to C12 substituted or unsubstituted hydrocarbyl), or - R"-SiR'3 or -R"-CR's where R" is Ci to C4 hydrocarbyl (such as -CH2-; -CH2CH2-; - (Me)CHCH2-; or -(Me)CH-, and each R' is independently Ci to C20 substituted or unsubstituted hydrocarbyl and at least one R' is Ci to C20 substituted or unsubstituted hydrocarbyl. In at least one embodiment, each R' is independently selected from methyl, ethyl, propyl, buty l, pentyl, hexyl, phenyl, biphenyl, or an isomer thereof. R' is a Ci to C20 alkyl or aryl, such as methyl, methyl phenyl,phenyl, biphenyl, pentamethylphenyl, tetramethylphenyl, or di-t-butylphenyl, provided that at least one R' is not H, alternatively 2 R' are not H. alternatively 3 R' are not H.

[0104] In at least one embodiment, C1-C40 hydrocarbyl, C1-20 hydrocarbyl, or C1-C12 hydrocarbyl is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl, sec-octyl, n-nonyl, isononyl, sec-nonyl, n-decyl, isodecyl, or sec-decyl.

[0105] In at least one embodiment. R1. R2, R3, R4, R5, R6, R7, R7, R8, R8, R9, R9, R10and R10’ is independently hydrogen,, -CH2-SiMe3, -CH2-SiEt, -CFb-SiPn, -CEh-SiBus, -CH2-SiCys, CH2 C(CH3)3, CH2 CH(CHS)2, CH2CPI13, CH2(C6Me5), CH2 C(CH3)2Ph, CH2-C(Cy)Ph2, -CH2-SiPh3, -CH2-Si(CH3)2Ph, -CH2-Si(CH3)2Ph, -CH2-Si(CH3)Ph2, -CH2-Si(Et)2Ph, -CH2-Si(Et)Ph2. -CH2-Si(Cy)Ph2. or-CH2-Si(Cy)2Ph.

[0106] In at least one embodiment, R7, R7, R8, R8, R9, R9, R10and R10is hydrogen and each of R1, R2, R3, R4, R5, and R6is independently hydrogen, -CEE-SiMes, -CEE-SiEts, -CFE-SiPrs, -CH2-SiBu3, -CH2-SiCy3, -CH2-C(CH3)3, -CH2-CH(CH3)2, -CH2CPh3, -CH2(C6Me5), -CH2-C(CH3)2Ph, -CH2-C(Cy)Ph2, -CH2SiPh3, -CH2-Si(CH3)2Ph. -CH2-Si(CH3)2Ph, -CH2-Si(CH3)Ph2, -CH2-Si(Et)2Ph, -CH2-Si(Et)Ph2, -CH2-Si(Cy)Ph2. or -CH2-Si(Cy)2Ph, where at least one of R1, R2, R\ R4, R5, or R6is not hydrogen.

[0107] In at least one embodiment, a catalyst can be represented by Formula (V) wherein M is zirconium (Zr), each of R5, R7, R7, R8, R8, R9, R9, R10and R10is independently hydrogen or C1-C5 alkyl, each of R1, R2, R3, R4, and R6is C1-C5 alkyl, each of X1and X2is methyl or a halogen, and T is represented by the formula Ra2J wherein J is Si and each Rais C1-C5 alkyl.In at least one embodiment, a catalyst can be represented by Activators

[0108] The terms “cocatalyst” and “activator” are used herein interchangeably.

[0109] The catalyst systems described herein may include catalyst compound(s) as described above and an activator such as alumoxane or a non-coordinating anion and may be formed by combining the catalyst compounds described herein with activators in any manner known from the literature including combining them with supports, such as silica. The catalyst systems may also be added to or generated in solution polymerization or bulk polymerization (in the monomer). Catalyst systems of the present disclosure may have one or more activatorsand one, two or more catalyst components. Activators are defined to be any compound which can activate any one of the catalyst compounds described above by converting the neutral metal compound to a catalytically active metal compound cation. Non-limiting activators, for example, may include alumoxanes, aluminum alkyls, ionizing activators, which may be neutral or ionic, and conventional-type cocatalysts. Suitable activators may include alumoxane compounds, modified alumoxane compounds, and ionizing anion precursor compounds that abstract a reactive, o -bound, metal ligand making the metal compound cationic and providing a charge-balancing non-coordinating or weakly coordinating anion, e.g., a non-coordinating anion.

[0110] In at least one embodiment, the catalyst system includes an activator, a catalyst compound of Formula (I), Formula (II), Formula (III), Formula (IV), and / or Formula (V), and a support.Alumoxane Activators

[0111] Alumoxane activators are utilized as activators in the catalyst systems described herein. Alumoxanes are generally oligomeric compounds containing -Al(Ra)-O- sub-units, where Rais an alkyl group. Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, such as when the abstractable ligand is an alkyl, halide, alkoxide or amide. Mixtures of different alumoxanes and modified alumoxanes may also be used. It may be suitable to use a visually clear methylalumoxane. A cloudy or gelled alumoxane can be filtered to produce a clear solution or clear alumoxane can be decanted from the cloudy solution. A useful alumoxane is a modified methyl alumoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A, as described in U. S. Pat. No. 5,041,584, which is incorporated by reference herein). Another useful alumoxane is solid polymethylaluminoxane as described in U. S. Pat. Nos. 9,340,630, US 8,404,880, and US 8,975,209, which are incorporated by reference herein.

[0112] When the activator is an alumoxane (modified or unmodified), and in at least one embodiment, an amount of activator at up to a 5,000-fold molar excess Al / M over the catalyst compound (per metal catalytic site) may be used. The minimum activator-to-catalyst-compound may be a 1:1 molar ratio. Alternate ranges may include about 1:1 to about 500:1, alternately about 1:1 to about 200:1. alternately about 1:1 to about 100:1, or alternately about 1: 1 to about 50: 1.

[0113] In an alternate embodiment, little or no alumoxane is used in the polymerization processes described herein. For example, alumoxane can be present at zero mol%, alternately the alumoxane can be present at a molar ratio of aluminum to catalyst compound transition metal less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1 lonizing / Non-Coordinating Anion Activators

[0114] The term "non-coordinating anion" (NCA) means an anion which either does not coordinate to a cation or which is only weakly coordinated to a cation thereby remaining sufficiently labile to be displaced by a Lewis base. " Compatible" non-coordinating anions are those which are not degraded to neutrality when the initially formed complex decomposes. Further, the anion will not transfer an anionic substituent or fragment to the cation so as to cause it to form a neutral transition metal compound and a neutral by-product from the anion. Non-coordinating anions useful in accordance with the present disclosure are those that are compatible, stabilize the transition metal cation in the sense of balancing its ionic charge at +1, and yet retain sufficient lability to permit displacement during polymerization. Suitable ionizing activators may include an NCA, such as a compatible NCA.

[0115] It is within the scope of the present disclosure to use an ionizing activator, neutral or ionic. It is also within the scope of the present disclosure to use neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators. For descriptions of some suitable activators and activator combinations, as well as relative amounts of activators and catalyst compounds, and optional chain transfer agents for use in conjunction with these catalyst compounds, please see US 8,658,556 and US 6,211,105, incorporated by reference herein; as well as U. S. Patent Publication 2021 / 0179650, and in particular Paragraphs

[0084] -

[0135] of WIPO Patent Publication No. WO2021 / 257264, which description is incorporated by reference herein (including the various descriptions that are incorporated by reference therein, such as W02004 / 026921 page 72, paragraph

[0119] to page 81, paragraph

[0151] and W02004 / 046214 page 72, paragraph

[0177] to page 74, paragraph

[0178] )

[0116] Furthermore, a catalyst system of the present disclosure may include a metal hydrocarbenyl chain transfer agent represented by the formula:A1(R')3-V(R")Vwhere each R1can be independently a Ci-Cso hydrocarbyl group, and or each R", can be independently a C4-C20 hydrocarbenyl group having an end-vinyl group; and v can be from 0.1 to 3.Materials

[0117] In embodiments herein, the catalyst system may include an inert support material. The support material can be a porous support material, for example, talc, and inorganic oxides. Other support materials include zeolites, clays, organoclays, or another organic or inorganic support material, or mixtures thereof.

[0118] The support material can be an inorganic oxide. The inorganic oxide can be in a finely divided form. Suitable inorganic oxide materials for use in catalyst systems herein may include groups 2, 4, 13, and 14 metal oxides, such as silica, alumina, and mixtures thereof. Other inorganic oxides that may be employed either alone or in combination with the silica, or alumina can be magnesia, titania, zirconia. Other suitable support materials, however, can be employed, for example, finely divided functionalized polyolefins, such as finely divided polyethylene. Examples of suitable supports may include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolites, talc, clays. Also, combinations of these support materials may be used, for example, silica-chromium, silica-alumina, silica-titania. In at least one embodiment, the support material is selected from AI2O3, ZrCh, SiCh, SiCh / AhOs, SiCh / TiCh, silica clay, silicon oxide / clay, or mixtures thereof.

[0119] The support material, such as an inorganic oxide, can have a surface area of about 2 2 210 m / g to about 700 m / g, pore volume of about 0.1 cm / g to about 4.0 cm / g and average particle size of about 5 pm to about 500 pm. The surface area of the support material can be of about 50 m / g to about 500 m / g, pore volume of about 0.5 cm3 / g to about 3.5 cm3 / g and average particle size of about 10 pm to about 200 pm. For example, the surface area of the 2 2support material can be about 100 m Zg to about 400 m / g, pore volume of about 0.8 cm7g to about 3.0 cm3 / g and average particle size can be about 5 pm to about 100 pm. The average pore size of the support material useful in the present disclosure can be of about 10 A to about 1000 A, such as about 50 A to about 500 A, and such as about 75 A to about 350 A. In at least one embodiment, the support material is a high surface area, amorphous silica (surface 2 3area=300 m / gm; pore volume of 1.65 cm / gm). For example, suitable silicas can be the silicas marketed under the tradenames of DAVISON™ 952 or DAVISON™ 955 by the Davison Chemical Division of W. R. Grace and Company. In other embodiments, DAVISON™ 948 is used. Alternatively, a silica can be ES-70™ silica (PQ Corporation, Malvern, Pennsylvania) that has been calcined, for example (such as at 875°C).

[0120] The support material should be dry, that is, free or substantially free of absorbed water. Drying of the support material can be effected by heating or calcining at about 100°Cto about 1000°C, such as at least about 600°C. When the support material is silica, it is heated to at least 200°C, such as about 200°C to about 850°C, and such as at about 600°C; and for a time of about 1 minute to about 100 hours, about 12 hours to about 72 hours, or about 24 hours to about 60 hours. The calcined support material must have at least some reactive hydroxyl (OH) groups to produce supported catalyst systems of the present disclosure. The calcined support material is then contacted with at least one polymerization catalyst including at least one catalyst compound and an activator.

[0121] The support material, having reactive surface groups, such as hydroxyl groups, is slurried in anon-polar diluent and the resulting slurry is contacted with a solution of a catalyst compound and an activator. In at least one embodiment, the slurry of the support material is first contacted with the activator for a period of time of about 0.5 h to about 24 h. about 2 h to about 16 h, or about 4 h to about 8 h. The solution of the catalyst compound is then contacted with the isolated support / activator. In at least one embodiment, the supported catalyst system is generated in situ. In alternate embodiments, the slurry of the support material is first contacted with the catalyst compound for a period of time of about 0.5 h to about 24 h, about 2 h to about 16 h, or about 4 h to about 8 h. The slurry of the supported catalyst compound is then contacted with the activator solution.

[0122] The mixture of the catalyst(s), activator(s) and support is heated about 0°C to about 70°C. such as about 23°C to about 60°C, such as at room temperature. Contact times can be about 0.5 hours to about 24 hours, such as about 2 hours to about 16 hours, or about 4 hours to about 8 hours.

[0123] Suitable non-polar diluents are materials in which all of the reactants used herein, e.g., the activator and the catalyst compound, are at least partially soluble and which are liquid at reaction temperatures. Non-polar diluents can be alkanes, such as isopentane, hexane, n-heptane, octane, nonane, and decane, although a variety of other materials including cycloalkanes, such as cyclohexane, aromatics, such as benzene, toluene, and ethylbenzene, may also be employed.

[0124] In at least one embodiment, the support material is a supported methylalumoxane (SMAO), which is an MAO activator treated with silica (e.g., ES-70-875 silica).Polyethylene Copolvmers

[0125] The present disclosure provides polyethylene copolymers having a combination of low density, high melt index, long chain branching, and broad compositional distribution. In addition, the polyethylene copolymers and films thereof can be formed by commercially desirable polymerizations and extrusions of the polyethylene copolymers.

[0126] Thus, polyethylene copolymers of various embodiments herein can exhibit one or more of the following properties:• Density of about 0.915 to about 0.925 g / cm3, such as from a low of any one of 0.914, 0.915, 0.916, 0.917, 0.918, 0.919, or 0.92 g / cm3to a high of any one of 0.925, 0.924, 0.923, 0.922, 0.921, 0.920, or 0.919 g / cm3, such as about 0.915 g / cm3to about 0.920 g / cm3. alternatively about 0.918 g / cm3to about 0.93 g / cm3, with combinations from any low to any high contemplated (provided the high end is greater than the low end), e.g., about 0.916 to about 0.921 g / cm3.• Melt Index (MI, also referred to as b or I2.16 in recognition of the 2.16 kg loading used in the test) of about 0.1 or greater g / 10 min (ASTM DI 238, 190°C, 2.16 kg), such as from a low of any one of 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, or 1.5 g / 10 min to ahigh end of any one of 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 4, or 5 g / 10 min, with ranges from any low end to any high end contemplated herein (provided the high end is greater than the low end), such as about 0.1 to about 1 g / 10 min, such as about 0.3 to about 0.8 g / 10 min, such as about 0.2 to about 0.5 g / 10 min.• Melt Strength of about 0.03 N to about 0.10 N, such as from a low of any one of 0.03, 0.032, 0.034, 0.036. 0.038, or 0.04 N to a high of any one of 0.10, 0.095, 0.090, 0.085, or 0.080 N, such as about 0.04 to about 0.09 N, alternatively about 0.05 to about 0.08 N, with combinations from any low to any high contemplated (provided the high end is greater than the low end) e.g., about 0.03 to about 0.095 N. Without being bound by theory a melt strength of about 0.03 N to about 0.10 N can indicate increased LCB, thereby increasing processability. Melt strength of a polymer at 190°C is determined with a Gottfert Rheotens Melt Strength Apparatus. To determine melt strength, a polymer melt strand extruded from the capillary die is gripped between two counterrotating wheels on the apparatus. The take-up speed is increased at a constant acceleration of 2.4 mm / sec2The maximum pulling force (in the unit of cN) achieved before the strand breaks or starts to show draw-resonance is determined as the melt strength. The draw ratio is defined as the ratio between take up speed at maximum pulling force and the extrusion rate at the die exit. The temperature of the rheometer is set at I90°C. The capillary die has a length of 30 mm and a diameter of 2 mm. The polymer melt is extruded from the die at a speed of 18 mm / sec. The distance between the die exit and the wheel contact point should be 122 mm.• DART A of about 400 g / mil to about 800 g / mil, such as from a low of any one of 400, 420. 440, 460. 480, or 500 g / mil to a high of any one of 800, 780, 760, 740, 720, or 700 N, such as about 500 to about 750 g / mil, alternatively about 600 to about 700 g / mil, with combinations from any low to any high contemplated (provided the high end is greater than the low end) e.g, about 450 to about 780 g / mil.• TD Tear of about 500 g / mil to about 800 g / mil, such as from a low of any one of 500. 520, 540, 560, 580, or 600 g / mil to a high of any one of 800, 780, 760, 740, 720, or 700 N, such as about 600 to about 750 g / mil, alternatively about 650 to about 720 g / mil, with combinations from any low to any high contemplated (provided the high end is greater than the low end) e.g.. about 550 to about 740 g / mil.• Puncture at break energy of about 15 in-lbs / mil to about 60 in-lbs / mil, such as from a low of any one of 15, 16, 17, 18, 19, or 20 in4bs / mil to ahigh of any one of 60, 59, 58, 57, 56, or 55 in-lbs / mil, such as about 20 to about 55 in-lbs / mil, alternatively about 35 to about 52 in-lbs / mil, with combinations from any low to any high contemplated (provided the high end is greater than the low end) e.g, about 35 to about 51 in-lbs / mil.

[0127] The polyethylene copolymer may be the polymerization product of an ethylene monomer and one or more olefin comonomers, such as alpha-olefin comonomers. Alpha-olefin comonomers can have 3 to 12 carbon atoms, or from 4 to 10 carbon atoms, or from 4 to 8 carbon atoms. Olefin comonomers can be selected from the group consisting of propylene, 1-butene, 1 -pentene, 1 -hexene, 1 -heptene, 1 -octene, 4-methylpent-l-ene, 1 -nonene, 1 -decene, 1-undecene, 1 -dodecene, 1 -hexadecene, and the like, and any combination thereof, such as 1-butene, 1-hexene, and / or 1-octene. In some embodiments, a polyene is used as a comonomer. In some embodiments, the polyene is selected from the group consisting of 1,3-hexadiene. 1,4-hexadiene, cyclopentadiene, dicyclopentadiene, 4-vinylcyclohex-l-ene, methyloctadiene, 1-methyl-l,6-octadiene, 7-methyl-l,6-octadiene, 1,5-cyclooctadiene, norbomadiene, ethylidene norbomene, 5-vinylidene-2-norbomene, 5-vinyl-2-norbomene, and olefins formed in situ in the polymerization medium. In some embodiments, comonomers are selected from the group consisting of isoprene, styrene, butadiene, isobutylene, chloroprene, acrylonitrile, and cyclic olefins. In some embodiments, combinations of the olefin comonomers are utilized. In some embodiments, the olefin comonomer is selected from the group consisting of 1 -butene and 1-hexene. The olefin comonomer content of the polyethylene copolymer can range from a low of about 0.1, 5, 5.5. 6, 6.5, 7. 7.5, 8, or 8.5 wt% to a high of about 20, 15, 13, 12.5, 12, 11.5, 11, 10.5, 10, 9.5, or 9 wt%, on the basis of total weight of monomers in the polyethylene copolymer. The balance of the polyethylene comonomer is made up of units derived fromethylene (e.g., from a low of about 80, 85, 88, 90, 91, 92, 92.5, 93, 93.5, or 94 wt% to a high of about 90. 91. 92. 92.5. 93. 93.5. 94. 94.5, 95, 95.5, 96, 97, 99, or 99.9 wt%). Ranges from any foregoing low end to any foregoing high end are contemplated herein (e.g., about 90 to about 97 wt%, such as about 91 to about 93 wt% ethylene-derived units and the balance olefin comonomer-derived content).

[0128] The polyethylene copolymers can also have a high load melt index (HLMI) (also referred to as I21 or I21.6 in recognition of the 21.6 kg loading used in the test) within the range from a low of about 2, 3, 5, 8, 10, 12, 15, 17, 20, or 25 g / 10 min to a high of about 50, 45, 40, 45, 30, 28, 25, 22, 20, 18, 15, 12, 10, or 8 g / 10 min; with ranges from any of the foregoing lows to any of the foregoing highs contemplated herein (e.g., about 3 to about 30 g / 10 min, such as about 3 to about 10 g / 10 min, alternatively about 15 to about 30 g / 10 min). The term “high load melt index” (“HLMI”), is the number of grams extruded in 10 minutes under the action of a standard load (21.6 kg) and is an inverse measure of viscosity, at the specified load. As provided herein, HLMI (I21) is determined according to ASTM D1238 (190 °C / 21.6 kg) and is also sometimes referred to as I21 or I21.6.

[0129] The polyethylene copolymers can also have a melt index ratio (MIR, defined as the ratio of I21.6 / I2.16) within the range from a low of any one of about 20, 21, 22, 23, 24, or 25 to a high of any one of about 35, 34, 33, 32, 31, or 30 with ranges from any of the foregoing lows to any of the foregoing highs contemplated herein (e g., about 22 to about 29, alternatively about 22 to about 26).

[0130] The polyethylene copolymers can also have a molecular weight distribution (MWD) of about 2 to about 8. The MWD can also range from a low of about 2, 2.5, 3, 3.5, 4, 4.2, 4.4, 4.6, 4.8, 5, 5.1, 5.2, 5.3, 5.4, 5.5, or 6 to ahigh of about 3.5, 4, 4.5, 5, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9. 6, 6.5, or 7, with ranges from any foregoing low to any foregoing high contemplated, provided the high end of the range is greater than the low end, such as about 3 to about 5. MWD is defined as the weight average molecular weight (Mw) divided by numberaverage molecular weight (Mn).

[0131] Weight-average molecular weight (Mw) of polyethylene copolymers of various embodiments may be within the range from about 90,000 to about 400,000 g / mol, such as about 100,000 to about 300,000 g / mol, such as about 90,000 to about 140,000 g / mol, such as about 110,000 to about 135,000 g / mol, alternatively about 120,000 to about 150,000 g / mol, with ranges from any foregoing low end to any foregoing high end contemplated, such as about 120.000 g / mol to about 130.000 g / mol, alternatively about 130,000 g / mol to about 140,000 g / mol, alternatively about 140,000 g / mol to about 150,000 g / mol.

[0132] Number-average molecular weight (Mn) of polyethylene copolymers of various embodiments may be within the range from about 10,000 to about 50,000 g / mol, such as about 10,000 to about 30,000 g / mol, such as about 20,000 to about 30,000 g / mol, with ranges from any foregoing low end to any foregoing high end contemplated.

[0133] Z-average molecular weight (Mz) of polyethylene copolymers of various embodiments may be within the range from about 150,000 to about 1,000,000 g / mol, such as about 150,000 to about 350,000 g / mol, or about 180,000 to about 320,000 g / mol, alternatively about 200,000 g / mol to about 330,000 g / mol, alternatively about 180,000 g / mol to about 340,000 g / mol, or about 220,000 g / mol to about 340,000 g / mol, with ranges from any foregoing low end to any foregoing high end contemplated. The polyethylene copolymers of various embodiments may include a C6 wt% of about 7.0 wt % to about 9.0 wt %, e.g., about 7.0 wt % to about 8.5 wt %, about 7.5 wt % to about 8.5 wt %, or about 7.5 wt % to about 8.5 wt %.

[0134] Polyethylene copolymers of various embodiments may also exhibit a CDI_NWZ,w of about 0.200 to about 0.330, e.g., about 0.207 to about 0.328, about 0.212 to about 0.303, or about 0.220 to about 0.254., in which the CDI_NWZ,w defines the composition distribution. The CDI_NWZ,w may be calculated by (w2, WZ-w2, N) / (w2, Wz+w2, N), where w2 is the wt % of comonomer, w2, WZ is the average of w2 between weight average molecular weight Mw and Z-average molecular weight (IR), w2, N is is the average of w2 around number average molecular weight from infrared spectroscopy (IR), Mn (IR), e.g, about 0.5*Mn to about 2*Mn (IR). Without being bound by theory, a positive CDI NWZ,w can indicate increased BOCD, a negative CDI_NWZ,w can indicate an increased CCD, and a near 0 CDI_NWZ,w can indicate increased BCD compared to conventional polyethylene copolymers.

[0135] Polyethylene copolymers of various embodiments may also exhibit long-chain branching, which may be evidenced through, e.g., SigncDi *r[o* 1032 / (Tan delta (co=o. i) * MW6'82, which defines the rheology and composition of the polymer, in which a higher absolute value indicates both increased viscosity and elasticity (representative of increased long chain branching), where SigncDi is determined by the CDI_NWZ,w divided by the absolute value of CDI_NWZ,w, in which the SigncDi may distinguish the composition as CCD or BOCD, qp is the zero shear viscosity value specifically obtained using the cross model fitted across the angular frequency range of 0.1 to 100 s-1, Tan delta (<»=o.i) is the tan delta specifically taken at 0.1 rad / s, in which a low er Tan delta («>=o.i) value can indicate increased elasticity compared to conventional polyethylene copolymers, and MW is the weight average molecular weight from dynamic light scattering (LS).

[0136] The distributions and the moments of molecular weight (Mw, Mn, Mw / Mn, etc.) are determined by using a high temperature Gel Permeation Chromatography (Polymer Char GPC-IR) equipped with a multiple-channel band-filter based Infrared detector IR5, an 18-angle Wyatt Dawn Heleos light scattering detector and a 4-capillary viscometer with Wheatstone bridge configuration. Three Agilent PLgel 10-pm Mixed-B LS columns are used to provide polymer separation. Aldrich reagent grade 1,2,4-trichlorobenzene (TCB) with 300 ppm antioxidant butylated hydroxytoluene (BHT) is used as the mobile phase. The TCB mixture is filtered through a 0.1 -pm Teflon filter and degassed with an online degasser before entering the GPC instrument. The nominal flow' rate is 1.0 ml / min and the nominal injection volume is 200 pL. The whole system including transfer lines, columns, and viscometer detector are contained in ovens maintained at 145°C. The polymer sample is weighed and sealed in a standard vial with 80-pL flow marker (Heptane) added to it. After loading the vial in the autosampler, polymer is automatically dissolved in the instrument with 8 ml added TCB solvent. The polymer is dissolved at 160 °C with continuous shaking for about 2 hours. The concentration (c), at each point in the chromatogram is calculated from the baseline-subtracted IR5 broadband signal intensity (I), using the following equation: c = l, where fi is the mass constant. The mass recovery is 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 10 million g / mol. The MW at each elution volume is calculated with the following equation:., * log( T,, / K) aps+ 1logAT = ' - - + — - log A7....a +1 a +1where the variables with subscript “PS” stand for polystyrene while those without a subscript are the test samples. In this method, otps = 0.67 and KPS = 0.000175 while a and K are for ethylene-hexene copolymers as calculated from empirical equations (Sun, T. et al. Macromolecules 2001, 34, 6812), in which a = 0.695 and K = 0.000579(1 -0.75Wt), where Wt is the weight fraction for hexene comonomer. It should be noted that the comonomer composition is determined by the ratio of the IR5 detector intensity corresponding to CH2 and CH? channel calibrated with a series of PE and ethylene-hexene homo / copolymer standards whose nominal values are predetermined by NMR or FTIR. Here the concentrations areexpressed in g / cm3, molecular weight is expressed in g / mol, and intrinsic viscosity (hence K in the Mark-Houwink equation) is expressed in dL / g.

[0137] 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-^ - ^+2A cAR(e) MP(e)2Here, 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 Ko is the optical constant for the system:47r2n2(dn / dc)= - - -2A4NAwhere 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 purposes of the present disclosure and the claims thereto (dn / dc) = 0.1048 for ethylene-hexene copolymers.

[0138] A high temperature Polymer Char 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, T|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.Blends and additives

[0139] In some embodiments, the polyethylene copolymers can be formulated (e.g, blended) with one or more other polymer components. In some embodiments, those other polymer components are alpha-olefin polymers such as polypropylene or polyethylene homopolymer and copolymer compositions. In some embodiments, those other polyethylene polymers are selected from the group consisting of linear low density polyethylene, high density polyethylene, medium density polyethylene, low density polyethylene, and other differentiated polyethylenes.

[0140] In some embodiments, the formulated blends can contain additives, which are determined based upon the end use of the formulated blend. In some embodiments, theadditives are selected from the group consisting of fillers, antioxidants, phosphites, anti-cling additives, tackifiers, ultraviolet stabilizers, heat stabilizers, antiblocking agents, release agents, antistatic agents, pigments, colorants, dyes, waxes, silica, processing aids, neutralizers, lubricants, surfactants, and nucleating agents. In some embodiments, additives are present in an amount from about 0.1 ppm to about 5 wt %.

[0141] Polyethylene copolymers of the present disclosure can be optionally blended with one or more processing aids to form a polyethylene blend. Because of the improved properties of polyethylene copolymers of the present disclosure, advantageously, such processing aids can be omitted even in blown films (e.g., films, and particularly blown films, of some embodiments may be free of or substantially free of polymer processing aids, and especially polymer processing aids comprising fluorine; where “substantially free’7means free of any intentionally added components, but allowing for up to 100 ppm of such component(s) as impurities) ARTICLES OF MANUFACTURE

[0142] The polyethylene copolymers of the present disclosure can be particularly suitable for making end-use articles of manufacture such as films (e.g., as may be formed by lamination, extrusion, coextrusion, casting, and / or blowing); as well as other articles of manufacture as may be formed, e.g., by rotomolding or injection molding. Polyethylene copolymers can be formed into articles of manufacture by cast film extrusion, blown film extrusion, rotational molding or injection molding processes. In some embodiments, the polyethylene copolymer can be used in a blend.

[0143] It has been discovered that polyethylene copolymers of the present disclosure can provide similar and / or improved mechanical properties, e.g., puncture energy, MD tear, and TD tear while increasing the processability, such as by increasing melt strength, reducing motor load, melt pressure, and / or melt temperature, due to the increased long chain branching and increased broad compositional distribution. Further, polyethylene copolymers of the present disclosure can provide films formed using reduced extruder melt pressure and increased bubble stability (melt strength), thereby leading to lower motor torque during extrusion, providing increased output of the extruded polyethylene copolymer product having enhanced mechanical properties compared to conventional LLDPEs.

[0144] A polyethylene copolymer (or blend thereof) of the present disclosure can be useful in such forming operations as film, sheet, and fiber extrusion and co-extrusion as well as blow molding, injection molding, and rotary molding. Films include blown or cast films formed by co-extrusion or by lamination useful as shrink film, cling film, stretch film, sealing films, oriented films, snack packaging, heavy duty bags, grocery sacks, baked and frozen foodpackaging, medical packaging, industrial liners, membranes, etc., in food-contact and non-food contact applications. Fibers include melt spinning, solution spinning and melt blown fiber operations for use in woven or non-woven form to make filters, diaper fabrics, medical garments, geotextiles, etc. Extruded articles include medical tubing, wire and cable coatings, pipe, geomembranes, and pond liners. Molded articles include single and multi-layered constructions in the form of bottles, tanks, large hollow articles, rigid food containers and toys, etc.

[0145] The polyethylene copolymers (or blends thereof) may be formed into monolayer or multilayer films. These films may be formed by any of the conventional techniques including extrusion, co-extrusion, extrusion coating, lamination, blowing and casting. The film may be obtained by the flat film or tubular process which may be followed by orientation in a uniaxial direction or in two mutually perpendicular directions in the plane of the film. One or more of the layers of the film may be oriented in the transverse and / or longitudinal directions to the same or different extents. This orientation may occur before or after the individual layers are brought together. For example a polyethylene copolymer (or blend thereof) layer can be extrusion coated or laminated onto an oriented polypropylene layer or the polyethylene copolymer (or blend thereof) and polypropylene can be coextruded together into a film then oriented. Likewise, oriented polypropylene could be laminated to oriented polyethylene copolymer (or blend thereof), or oriented polyethylene copolymer (or blend thereof) could be coated onto polypropylene then optionally the combination could be oriented even further.

[0146] Films include monolayer or multilayer films. Particular end use films include, for example, blown films, cast films, stretch films, stretch / cast films, stretch cling films, stretch handwrap films, machine stretch wrap, shrink films, shrink wrap films, greenhouse films, laminates, and laminate films. Exemplary films are prepared by any conventional technique known to those skilled in the art, such as for example, techniques utilized to prepare blown, extruded, and / or cast stretch and / or shrink films (including shrink-on-shrink applications).

[0147] In at least one embodiment, multilayer films (multiple-layer films) may be formed by any suitable method. The total thickness of multilayer films may vary based upon the application desired. A total film thickness of 5-100 pm, such as 10-50 pm, is suitable for most applications. Those skilled in the art will appreciate that the thickness of individual layers for multilayer films may be adjusted based on desired end-use performance, polymer(s) employed, equipment capability, and other factors. The materials forming each layer may be coextruded through a coextrusion feedblock and die assembly to yield a film with two or more layers adhered together but differing in composition. Coextrusion can be adapted for use in both castfilm or blown film processes. Exemplary' multilayer films have at least two, at least three, or at least four layers. In one embodiment the multilayer films are composed of five to ten layers.

[0148] In at least one embodiment, a film of the present disclosure has a MD Tear (g / mil), according to ASTM D1922 of about 150 g / mil to about 340 g / mil, e.g., about 164 g / mil to about 332 g / mil, about 200 g / mil to about 332 g / mil, or about 256 g / mil to about 275 g / mil.

[0149] In at least one embodiment, a film of the present disclosure has a TD Tear (g / mil), according to ASTM D1922 of about 550 g / mil to about 730 g / mil, e.g.. about 550 g / mil to about 725 g / mil, about 650 g / mil to about 720 g / mil, or about 680 g / mil to about 715 g / mil.

[0150] In at least one embodiment, a film of the present disclosure has a MD 1 % Modulus (M). according to a ASTM D882 of about 20,000 psi to about 40,000 psi, such as about 25,000 psi to about 35.000 psi. such as about 26,000 to about 34,000 psi, alternatively about 27,000 psi to about 31,000 psi.

[0151] In at least one embodiment, a film of the present disclosure has a TD 1% Secant Modulus (M), according to a ASTM D882 of about 25,000 psi to about 46,000 psi, such as about 28,000 psi to about 36,000 psi, such as about 30,000 to about 35,000 psi, alternatively about 30,000 psi to about 32,000 psi.

[0152] A film of the present disclosure can have a Dart Drop Impact (or Impact Failure or Dart F50 or Dart Drop Impact Strength (DIS)), reported in grams (g) or grams per mil (g / mil), in accordance with ASTM D-l 709, method A. A film of the present disclosure can have a Dart Drop Impact of from about 400 g / mil to about 800 g / mil. e.g., about 500 g / mil to about 800 g / mil, about 500 g / mil to about 700 g / mil, or about 500 g / mil to about 600 g / mil.

[0153] In some embodiments, the film may have a puncture energy at break (also known as puncture break energy), in accordance with a modified ASTM D5748 (ExxonMobil BTEC Method Bl (stainless steel)) probe used with two 0.25mil HDPE slip sheets. Machine Model: United SFM-1. Testing speed: 10 in / min), of at least about 15 in-lbs / mil, such as at least about 20 in-lbs / mil, such as at least about 25 in-lbs / mil, such as about 15 in-lbs / mil to about 55 in-Ibs / mil, such as about 15 in4bs / mil to about 30 in-lbs / mil, such as about 20 in-lbs / mil to about 30 in-lbs / mil.

[0154] A film of the present disclosure can have an MD 1% Secant modulus in accordance with ASTM D-882. A film of the present disclosure can have an MD 1% secant modulus of from about 20,000 psi to about 35,000 psi, e.g., about 20,000 psi to about 34,000 psi, about 26,000 psi to about 32,000 psi, or about 27,000 psi to about 31,000 psi.

[0155] A film of the present disclosure can have a TD 1% Secant modulus in accordance with ASTM D-882. A film of the present disclosure can have a TD 1% Secant modulus offrom about 30,000 psi to about 46,000 psi, e.g, about 30,000 psi to about 45,000 psi, about 31,000 psi to about 38,000 psi, or about 32,000 psi to about 37,000 psi.

[0156] A film of the present disclosure can have a puncture peak force in accordance with a modified ASTM D5748 (ExxonMobil BTEC Method Bl (stainless steel)) probe used with two 0.25mil HDPE slip sheets, of from about 10 Ib / mil to about 15 Ib / mil, e.g, about 10 Ib / mil to about 14 Ib / mil, about 11 Ib / mil to about 14 Ib / mil, or about 11 Ib / mil to about 13 Ib / mil.

[0157] A film of the present disclosure can have an MD Yield Strength in accordance with ASTM D-882. A film of the present disclosure can have an MD Yield Strength of from about 1,100 psi to about 1,600 psi, e.g., about 1,200 psi to about 1,550 psi, about 1,200 psi to about 1,450 psi, or about 1,300 psi to about 1,380 psi.

[0158] A film of the present disclosure can have a TD yield strength in accordance with ASTM D-882. A film of the present disclosure can have a TD yield strength of from about 1,200 psi to about 1,800 psi, e.g., about 1,200 psi to about 1,600 psi, about 1,200 psi to about 1,500 psi, or about 1,300 psi to about 1,700 psi.

[0159] A film of the present disclosure can have an MD Elongation at yield in accordance with ASTM D-882. A film of the present disclosure can have an MD Elongation at yield of from about 5.0 % to about 5.6 %, e.g., about 5.0 % to about 5.5 % to about 5.1 % to about 5.5 %, or about 5.2 % to about 5.5 %.

[0160] A film of the present disclosure can have a TD Elongation at yield in accordance with ASTM D-882. A film of the present disclosure can have a TD Elongation at yield of from about 4.5 % to about 5.2 %, e.g, about 4.5 % to about 5.1 % to about 4.6 % to about 5.2 %, or about 4.6 % to about 5.1 %.

[0161] A film of the present disclosure can have an MD Tensile strength in accordance with ASTM D-882. A film of the present disclosure can have an MD Tensile strength of from about 7,000 psi to about 11,000 psi, e.g., about 7,000 psi to about 10,000, ab about 8,000 psi to about 10,000, or about 9,000 psi to about 11,000.

[0162] A film of the present disclosure can have a TD Tensile strength in accordance with ASTM D-882. A film of the present disclosure can have a TD Tensile strength of from about 6,000 psi to about 9,000 psi, e.g.. about 6,000 psi to about 8,000, ab about 6,500 psi to about 9,000, or about 7,000 psi to about 8,000.

[0163] A film of the present disclosure can have an MD elongation at break in accordance with ASTM D-882. A film of the present disclosure can have an MD elongation at break of from about 350 % to about 600 %, e.g., about 400 % to about 590 % to about 450 % to about 580 %, or about 380 % to about 510 %.

[0164] A film of the present disclosure can have a TD elongation in accordance with ASTM D-882. A film of the present disclosure can have a TD elongation of from about 600 % to about 750 %, e.g, about 600 % to about 700 % to about 650 % to about 750 %, or about 650 % to about 700 %.

[0165] A film of the present disclosure can have an MD gloss 45° in accordance with ASTM D-2457. A film of the present disclosure can have an MD gloss 45° of from about 35 GU to about 75 GU, e.g., about 36 GU to about 71 GU, about 40 GU to about 65 GU, or about 50 GU to about 70 GU.

[0166] A film of the present disclosure can have a TD gloss 45° in accordance with ASTM D-2457. A film of the present disclosure can have a TD gloss 45° of from about 35 GU to about 75 GU, e.g.. about 36 GU to about 71 GU, about 40 GU to about 65 GU. or about 50 GU to about 70 GU.

[0167] A film of the present disclosure can have a total haze percent in accordance with ASTM D-1003. A film of the present disclosure can have a total haze percent of from about 5 % to about 30 %, e.g., about 5 % to about 10 %, about 5 % to about 19 %, or about 9 % to about 30 %.

[0168] A film of the present disclosure can have a CDI_NWZ,w of from about 0.200 to about 0.330, e.g., about 0.207 to about 0.328, about 0.212 to about 0.303, or about 0.220 to about 0.254.

[0169] A film of the present disclosure can have a ACWF / AT (Below 80 °C at 5 °C intervals), in which the ACWF / AT is determined based on the slope of the cumulative weight fraction vs temperature below 80 °C when measured at 5 °C intervals, of from about 0.01 wt% / °C to about 0.03 wt% / °C, e.g., about 0.012 wt% / °C to about 0.028 wt% / °C, about 0.014 wt% / °C to about 0.027 wt% / °C, or about 0.016 wt% / °C to about 0.026 wt% / °C.

[0170] A film of the present disclosure can have a Signcoi *r| *1032 / (Tan delta (ra=o.i) * MW6'82) of from about 2 Pa*s / [(g / mole)682] to about 8 Pa*s / [(g / mole)682], e.g., about 2.05 Pa*s / [(g / mole)682] to about 7.95 Pa*s / [(g / mole)6 82], about 2.10 Pa*s / [(g / mole)682] to about 7.90 Pa*s / [(g / mole)682], or about 2.25 Pa*s / [(g / mole)682] to about 7.885 Pa*s / [(g / mole)682].

[0171] A film of the present disclosure can have a T75-T25 of from about 20 °C to about 24 °C, e.g., about 20.22 °C to about 23.68 °C, about 20.35 °C to about 23.54 °C, or about 20.44 °C to about 23.16 °C, where the T75-T25 values represent a temperature range to elute the middle 50 wt% of material. Without being bound by theory', a larger temperature difference can indicate a broader comonomer distribution.EXAMPLESSmall angle Oscillatory Shear Rheology:

[0172] SAGS Rheology Test measures dynamic shear melt rheological data with an ARES-G2 model rheometer using parallel plates (diameter=25 mm) at 190° C. using a compression molded sample at the specified temperature. The measurements were made over a range of angular frequencies that encompass 100 rad / s to 0.1 rad / s. Strains of 5%, 4%, or 3% were used and linearity of the response was verified. A nitrogen stream was circulated through the sample oven to minimize chain extension or cross-linking during the experiments. A sinusoidal shear strain is applied to the material. If the strain amplitude is sufficiently small, the material behaves linearly.Melt Strength MeasurementThe melt strength of a polymer at a particular temperature may be determined with a Gottfert Rheotens 71.97 Melt Strength Apparatus. To determine the melt strength, a polymer melt strand extruded from a capillary' die (Ceast SmartRheo rheometer) is gripped between two counter-rotating wheels on the apparatus. The take-up speed is increased at a constant acceleration of 12 mm / sec2. The maximum pulling force (in the unit of N) achieved before the strand breaks or starts to show draw resonance is determined as the melt strength. Once the strand breaks or starts to show draw resonance the test is stopped and repeated until the barrel is empty. The data from these measurements is then averaged into a mean curve which is fitted as described in J. Rheol. 42, 917-928 (1998). The reported melt strength is the maximum pulling force provided by the model fit. The temperature of the rheometer is set at 190 °C. The capillary' die has a length of 30 mm and a diameter of 2 mm. The polymer melt is extruded from the die at a speed of 18 min / sec. Hie distance between the die exit and the wheel contact point should be 105 mm.Temperature Rising Elution Fractionation:

[0173] ‘’Temperature Rising Elution Fractionation (TREF) analysis was done using a Crystallization Elution Fractionation (CEF) instrument from Polymer Char, S. A., Valencia, Spain. The principles of CEF analysis and a general description of the particular apparatus used are given in the article Monrabal, B. et al. Crystallization Elution Fractionation. A New Separation Process for Polyolefin Resins. Macromol. Symp. 2007, 257, 71. In particular, a process conforming to the “TREF separation process” shown in Figure la of this article, in which Fc=0, was used. Pertinent details of the analysis method and features of the apparatus used are as follows.

[0174] The solvent used for preparing the sample solution and for elution was 1,2-Dichlorobenzene (ODCB) filtered using a 0.1-pm Teflon filter (Millipore). The sample (16 mg) to be analyzed was dissolved in 8 ml of ODCB metered at ambient temperature by stirring (Medium setting) at 150°C for 90 min. A small volume of the polymer solution was first filtered by an inline filter (stainless steel, 10 gm), which is back-flushed after every7filtration. The filtrate was then used to completely fill a 200-pl injection-valve loop. The volume in the loop was then introduced near the center of the CEF column (15-cm long SS tubing, 3 / 8" o.d., 7.8 mm i.d.) packed with an inert support (SS balls) at 140°C, and the column temperature was stabilized at 125°C for 20 min.

[0175] The sample volume was then allowed to crystallize in the column by reducing the temperature to 0°C at a cooling rate of 1 °C / min. The column was kept at 0°C for 10 min before injecting the ODCB flow (1 ml / min) into the column for 10 min to elute and measure the polymer that did not cry stallize (soluble fraction). The wide-band channel of the infrared detector used (Polymer Char IR5) generates an absorbance signal that is proportional to the concentration of polymer in the eluting flow. A complete TREF curve was then generated by increasing the temperature of the column from 0 to 140°C at a rate of 2°C / min while maintaining the ODCB flow at 1 ml / min to elute and measure the concentration of the dissolving polymer. The TREF curve was further processed as follows: The solvent-only response of the instrument was generated and subtracted from the TREF curve of the sample. The solvent-only response is generated by running, typically before, the same method as used for the polymer sample, but without any polymer added to the sample vial; using the same solvent reservoir as for the polymer sample and without replenishing with fresh solvent; and within a reasonable proximity' of time from the run for the polymer sample.

[0176] The temperature axis of the TREF curve was appropriately shifted to correct for the delay in the IR signal caused by the column-to-detector volume. This volume is obtained by first filling the injection-valve loop with a ~1 mg / ml solution of an HDPE resin; then loading the loop volume in the same location within the column where a sample is loaded for TREF analysis; then directly flowing, at a constant flow rate of 1 ml / min, the hot solution towards the detector using an isothermal method; and then measuring the time after injection for the HDPE probe’s peak to appear in the IR signal. The delay volume (ml) is therefore equated to the time (min).

[0177] The curve was baseline corrected and appropriate integration limits were selected. And the curve was normalized so that the area of the curve is 100 wt%.”Synthesis:

[0178] All manipulations were performed under an inert atmosphere using glove box techniques unless otherwise stated. All reagents were purchased from commercial vendors (Sigma Aldrich, Fisher Scientific, Oakwood Chemical or Combi-Blocks) and used as received unless otherwise noted. Diethyl ether, pentane, hexane, toluene, 1,2-dimethoxy ethane, and dichloromethane (Sigma Aldrich) were sparged with N2 and dried over 3A molecular sieves overnight prior to use. Deuterated solvents were purchased from Cambridge Isotope Laboratories and were degassed and dried over molecular sieves prior to use. n-Butyl Lithium in hexane, iodomethane were purchased from Sigma Aldrich and used as received. ZrCh was purchased from Strem chemicals and used as received. 5,5,8,8-tetramethyl-6,7-dihydro-lH-cyclopenta[b]naphthalene was purchased from BLDpharm and used as received. Catalyst 1 bis(5,5,8,8-tetramethyl-6,7-dihydro-lH-cyclopenta[b]naphthalen-l-yl) zirconium dimethyl and [Tetramethylylcyclopentadienyldimethylsilyl(3-methyltetrahydroindenyl)]zirconium dichloride (shown below) were prepared as described in US patent applications 2023EM091 and 2020EM034, respectively.

[0179] The following chemicals may be abbreviated as indicated in either lower case or capital letters: iodomethane (Mel), silver triflate (AgOTf), diethyl ether (Et20). tetrahydrofuran (thf).Synthesis of Catalyst 2

[0180] Synthesis of [Tetramethylylcyclopentadienyldimethylsilyl(3-methyltetrahydroindenyl)]zirconium dimethyl (Catalyst 2)

[0181] To a solution of [tetramethylylcyclopentadienyldimethylsilyl(3-methyltetrahydroindenyl)]zirconium dichloride (1.1 g. 2.33 mmol, 1.0 equiv) in diethyl ether at -35 °C was added 3 M MeMgBr in Et20 (3.1 mL, 9.31 mmol, 4 equiv). The reaction mixture was stirred at room temperature overnight. Solvent was removed under vacuum. The product was extracted with pentane and toluene. The solvents were then removed under vacuum to afford a dirty white solid. Yield 0.979 g, 97%. 'H NMR (CeDe) 4.79 (s, 1H), 2.70 -2.40 (m. 4H), 2.08 (s, 3H), 2.03 (s, 3H), 1.98 (s, 3H), 1.91 - 1.76 (m, 1H), 1.77 (s, 3H), 1.72 -1.56 (m, 2H), 1.63 (s. 3H), 1.50 - 1.37 (m, 1H), 0.52 (s, 3H), 0.45 (s, 3H), -0.38 (s, 3H), -0.44 (s, 3H).

[0182] Preparation of Supported Catalyst:

[0183] Supported catalyst was added to a container with a sufficient amount of slurry' mixture (SJCS-380. Sonnebom) to yield 20 wt% slurried catalyst.

[0184] Preparation of Trim Solution:

[0185] Under an inert atmosphere, catalyst was added to a container, followed by anhydrous isohexane in sufficient quantity to produce a 6 kg solution with a catalyst content of 0.04 wt%.

[0186] Polymerizations:

[0187] Polymerizations were performed in a 22 foot tall gas-phase fluidized bed reactor with a 13 inch straight section inner diameter and a wider conical expanded section above. Cycle and feed gases were fed into the reactor body through a perforated distributor plate, and the reactor was controlled at 290 psig and 64 mol% ethylene. The reactor temperature was maintained at constant temperature of 78 °C or 85 °C throughout the polymerization by controlling the temperature of the cycle gas loop.

[0188] The supported catalyst (20 wt% slurry) was optionally contacted in line with trim catalyst solution (0.04 wt% total trim catalyst in iC6) at an adjustable ratio, mixed to homogenize, and given sufficient time to enable trim catalyst diffusion, anchoring, and activation to thereby adjust the active catalyst ratio.

[0189] The references and examples are shown in Tables 1 & 2. Addition of catalysts 1 or catalyst 2 provided increased MIR values while maintaining comparable densities.Table 1:Polymer R1 El R2 E2 E3n-propyl n-propyl n-propyl n-propyl n-propyl cyclopentadi cyclopentadi cyclopentadi cyclopentadi cyclopentadi enyl)2 enyl)2 enyl)2 enyl)2 enyl)2 hafnium hafnium hafnium hafnium hafnium Catalyst dimethvl dimethyl dimethyl dimethyl dimethyl Trim none Catalyst 1 none Catalyst 1 Catalyst 1 Ml (g / 10min) 0.49 0.50 0.94 1.01 2.09 HLMI / MI 27.58 32.09 21.27 23.78 23.27 Density(g / cm3) 0.918 0.920 0.918 0.918 0.918BedTemperature (°F) 172.39 172.39 185.00 184.98 185.00 ReactorPressure(psig) 289.48 289.67 289.76 289.70 289.56 EthyleneConcentration (mol%) 64.00 63.99 63.98 64.00 63.99 H2 / C2=Gas Ratio(ppm / mol%) 4.45 5.36 6.09 6.72 8.98 C6 / C2=Gas Ratio(mol / mol) 0.01 0.02 0.01 0.01 0.02 C6 / C2=Flow Ratio(Ib / lb) 0.09 0.09 0.08 0.09 0.10 1C5Composition (mol%) 8.99 9.06 9.26 9.06 9.06 ResidenceTime(measuredbasis) (hr) 3.35 3.68 3.80 3.41 3.37 CatalystFeed Rate(dry orslurrv)(g / hr) 3.78 3.02 3.21 3.27 3.21 Cat feederSP (dry orslurry)(cc / hr or s’1) 20.00 16.00 17.00 17.30 17.00 TrimCatalystFeed Rate(g / hr) 0.00 0.02 0.00 0.01 0.01 TRIM soln / CATslurry (g / hr / cc / hr) 0.00 3.02 0.00 0.85 0.88 Table 2:Polymer E4 E5 E6 E7n-propyl n-propyl n-propyl n-propyl cyclopentadieny cyclopentadieny cyclopentadieny cyclopentadieny 1)2 hafnium 1)2 hafnium 1)2 hafnium 1)2 hafniumCatalyst dimethyl dimethyl dimethyl dimethylTrim Catalyst 1 Catalyst 1 Catalyst 2 Catalyst 2 MI (g / lO min) 0.55 0.46 0.47 0.46 HLMI / MI 24.64 25.28 25.27 31.46 Density7(g / cm3) 0.918.917.917.919 BedTemperature(°F) 184.99 190.37 185.02 172.38 ReactorPressure (psig) 289.68 289.67 289.65 289.69 EthyleneConcentration(mol%) 63.98 64.04 64.03 64.05 H2 / C2= GasRatio(ppm / mol%) 5.48 5.47 4.84 4.85 C6 / C2= GasRatio (mol / mol) 0.01 0.01 0.01 0.01 C6 / C2= FlowRatio (Ib / lb) 0.09 0.09 0.09 0.091C5Composition(mol%) 9.10 9.11 9.13 8.97 Residence Time(measuredbasis) (hr) 3.41 3.75 3.79 3.55 Catalyst FeedRate (dry orslurry ) (g / hr) 3.40 3.40 3.40 3.40 Cat feeder SP(dry or slurry)(cc / hr or s-1) 18.00 18.00 18.00 18.00 Trim CatalystFeed Rate (g / hr) 0.01 0.01 0.01 0.01 TRIM soln / CAT slurry(g / hr / cc / hr) 0.87 0.87 1.29 1.30 Preparation of Film

[0190] Films (1 mil thickness) were produced on a 2.5 inch blown film line with a 2.5: 1 blowup ratio, a 60 mil die gap, at a rate of 10 Ibs / hr / in die circumference. The reduced melt pressure and increase bubble stability (melt strength), e.g., about 0.03 N to about 0.10 N, indicate increased LCB of polymers E1-E7. When incorporating LCB at a reactor temperature of 78°C, a 44% and 34% decay in MD tear and dart occurred, respectively, as shown in polymer El of Table 3. By increasing the reactor temperature to 85°C, an increase of LCB occurred in examples E2-E7, providing a 28% reduction in MD tear and a similar dart relative to the polymer Rl, as shown in Table 3. The ACWF / AT (Below 80 °C at 5 °C intervals) reduced inthe polymers E1-E7 compared to R1 -R8, indicating an increased breadth of the low temperature eluents (less distinct low temperature peaks), as shown in Table 3. Additionally, the CDI_NWZ,w remained positive but decreased for the polymers E1-E7, compared to R1-R8, thereby indicating a reduction in their BOCD character, and an increased BCD, as shown in Table 3. Moreover, the polymers E1-E7 maintained a higher T75-T25, despite their reduced BOCD character, thereby indicating a broader comonomer distribution, and thereby greater BCD. The absolute value of the Signcoi *r|p*1032 / (Tan delta (ro=o.i) * MW6 82) also indicated that the polymers E1-E7 had a greater influence of LCB on the rheology compared to R1-R8. Additionally, melt strength, TD tear, and puncture increased by 23%, 58%, and 60%, respectively, as shown in Table 3, which can indicate enhanced processability and mechanical properties. Accordingly, polymers E2-E8 included a combination of melt strength and mechanical properties.Table 3:Polymer R1 R2 R3 R4 R5 R6 R7 R8 MI (g / 10 min @ load 0.49 0.94 1.02 1.08 0.79 0.86 0.80 0.89 of 2.16 kg)HLMI (g / 10 min @ 13.40 19.94 16.05 29.06 23.08 25.39 32.38 28.46 load of 21.6 kg)MIR = HLMI / MI 27.58 21.27 15.70 26.88 29.26 29.52 40.47 32.05 Density (g / cm3) 0.918 0.918 0.919 0.919 0.920 0.919 0.929 0.913 Mn (LS) (g / mole) 39084 36028 44563 28601 22568 33414 20248 28059 Mw (LS) (g / mole) 14874 11672 11636 13014 12867 12076 11842 120769 9 4 0 6 0 5 4 Mz (LS) (g / mole) 34159 22889 18544 44907 29133 25544 30953 264158 9 6 1 6 8 7 5 Mw / Mn (LS) 3.8 3.2 2.6 4.6 5.7 3.6 5.9 4.3 Mn (IR) (g / mole) 38923 35782 42868 29415 23626 30479 20065 26162 Mw (IR) (g / mole) 14488 11385 11294 12454 12400 10997 11356 114657 5 4 3 7 9 3 4 Mz (IR) (g / mole) 38272 23977 20126 39849 30600 25367 33472 271884 5 3 0 7 5 9 4 Mw / Mn (IR) (g / mole) 3.7 3.2 2.6 4.2 5.3 3.6 5.7 4.4 C6 wt% 7.84% 7.08% 6.36% 9.70% 8.82% 9.07% 6.63% 12.14% " CDI_NWZ.w"=(w2, 0.394 0.224 0.051 -0.199 0.425 0.370 0.682 0.303 WZ- w2, N) / (w2, WZ+w2. N)Signcoi 1 1 1 -1 1 1 1 1 CDIZABS(CDI)rjp (cross model roo.i - 18952 7947 7192 9359 10994 12810 11856 11104 coioo ) (Pa*s)Tan deltaro=o.i 11.35 26.36 42.74 10.16 16.33 6.35 6.69 6.48T75-T25 (°C) 22.5 15.5 11.4 31.2 25.5 26.5 20.1 21.6ACWF / AT (Below 0.018 0.031 0.037 0.016 0.021 0.048 0.062 0.050 80°C at 5°C intervals)SigncDi *r[o*lO32 / (Tan 0.884 0.834 0.475 -1.213 0.958 4.427 4.443 3.757 delta (a>=o.i) * MW6 82)Melt strength (N) 0.076 0.046 0.043 0.043 0.052 0.061 0.053 0.054 MD Tear (g / mil) 359 284 242 388 223 270NA TD Tear (g / mil) 454 449 374 667 586 628MD 1% Secant 31409 26376 24100 25300 33700 33380 48075 modulus (psi)TD 1% Secant 39701 30820 27500 35100 44700 41823 59476 modulus (psi)Dart A (g / mil) 737 663 677 144 786 922 725 Break Energy / mil 32 38 48 29 29 29 19 (in / lb / mil)Peak Force / mil 11.0 11.3 13.2 8.6 9.9 10.5 8.9 (Ib / mil)MD Yield Strength 1349 1250 1260 1320 1480 1406(psi)TD Yield Strength 1513 1320 1260 1450 1660 1588(psi)MD Elongation at 5.3 5.3 6.2 5.4 5.2 6.1NAYield (%)TD Elongation at 5.0 4.9 5.6 5 4.5 5.8Yield (%)MD Tensile Strength 10023 9180 11000 7280 10800 8324(psi) NATD Tensile Strength 7703 7930 9060 6370 7000 6587(psi)MD Elongation at 395 480 560 510 438 416Break (%)TD Elongation at 679 690 720 830 666 632Break (%)Gloss 45° @ MD 71 36 26 43 54 32(GU)Gloss 45° @ TD (GU) 71 36 26 43 54 33Haze Total (%) 7.9 18.3 28.0 >30.0 11.8 12.1 >30.0 Die factor ( lb / (in.hr) 10.0 10.0 10.0 10.0 10.0 9.9 10.0 Die diameter (in) 6 6 6 6 6 6 6Die gap (mil) 60 60 60 60 60 60 60BUR 2.5 2.5 2.5 2.5 2.5 2.5 2.5FLH (in) 18 24 23 23 21 24 14 Average thickness ( 0.99 0.99 1.00 1.00 1.00 0.99 1.02NAmil )Motor load (%) 64 52 42 72 57 63 66 Melt Temperature (°F) 405 401 393 410 411 410 407 Melt Pressure 1 (psi) 4910 4090 2790 5430 5840 5800 5130Melt Pressure 2 (psi) 3590 3020 1910 3930 4150 4150 3870Table 3 (continued):Polymer El E2 E3 E4 E5 E6 E7 MI (g / 10 min @ load of0.50 1.01 2.09 0.55 0.46 0.47 0.46 2.16 kg)HLMI (g / 10 min (a} load16.36 23.96 48.73 13.56 11.74 11.93 14.52 of 21.6 kg)MIR 32.09 23.78 23.27 24.64 25.28 25.27 31.46 Density (g / cm3) 0.920 0.918 0.918 0.918 0.917 0.917 0.919 Mn (LS) (g / mole) 37478 34120 28092 41511 40198 36934 35330 Mw (LS) (g / mole) 12614 11059 13231 13457 14071 13828935361 4 8 7 6 4 Mz (LS) (g / mole) 26028 21408 18199 25695 25932 28277 309500 9 2 8 5 1 4 Mw / Mn (LS) 3.4 3.2 3.3 3.2 3.4 3.8 3.9 Mn (IR) (g / mole) 36218 33858 27787 39627 38694 36032 33665 Mw (IR) (g / mole) 11940 10644 12406 13028 13420 131746 2 90623 1 9 9 8 Mz (IR) (g / mole) 26502 22059 18734 25807 28420 31046 330667 9 2 0 0 7 5 Mw / Mn (IR) 3.3 3.1 3.3 3.1 3.4 3.7 3.9 C6 wt% 7.19% 7.30% 8.25% 7.34% 7.93% 7.71% 7.55% " CDI_NWZ,w"=(w2, WZ- w2, N) / (w2. WZ+w2, N) 0.303 0.224 0.212 0.220 0.207 0.254 0.328 SigncDi =CDI / ABS(CDI) 1 1 1 1 1 1 1 r|p (cross model oo i - coioo21318 8506 4253 17355 19175 19589 24713 ) (Pa*s)Tan delta 0j=o.i 4.41 11.20 21.70 6.16 6.83 6.73 4.36 T75-T25 (°C) 23.2 21.6 22.5 22.2 22.2 20.4 21.1 ACWF / AT (Below 80°C0.016 0.026 0.025 0.024 0.026 0.024 0.016 at 5°C intervals)SigncDi *qp*1032 / (Tandelta (ro=o.i) * MW6 82) 7.885 3.035 2.456 3.312 2.942 2.250 4.931 Melt strength (N) 0.089 0.057 0.035 0.087 0.089 0.094 0.094 MD Tear (g / mil) 200 275 332 260 256 260 164 TD Tear (g / mil) 688 653 554 703 715 719 726 MD 1% Secant modulus33151 27654 26996 26399 27578 30679 34424 (psi)TD 1% Secant modulus39488 31549 30388 31024 32349 37718 45351 (psi)Dart A (g / mil) 483 560 572 719 783 718 776 Break Energy / mil36 45 35 42 51 51 39 (m / lb / mil)Peak Force / mil (Ib / mil) 11.4 12.4 10.3 12.8 14.5 14.9 12.9 MD Yield Strength (psi) 1426 1300 1220 1336 1333 1378 1501 TD Yield Strength (psi) 1560 1400 1300 1382 1382 1599 1732 MD Elongation at Yield5.4 5.5 5.3 5.4 5.5 5.4 5.5 (%)TD Elongation at Yield5.0 5.1 5.0 4.8 4.8 4.6 4.7(%)MD Tensile Strength10292 9150 7340 10828 11327 10824 11032 (psi)TD Tensile Strength (psi) 7682 6840 6870 8277 8804 7433 7523 MD Elongation at Break434 510 580 401 389 336 389 (%)TD Elongation at Break748 670 710 683 696 678 699 (%)Gloss 45° @ MD (GU) 56 53 34 71 66 69 55 Gloss 45° @ TD (GU) 58 52 33 70 67 67 56 Haze Total (%) 9.5 8.5 30.0 6.4 5.2 5.9 9.2 Die factor ( lb / (in.hr) 10.0 10.1 10.1 10.0 10.1 9.5 10.1 Die diameter (in) 6 6 6 6 6 6 6 Die gap (mil) 60 60 60 60 60 60 60 BUR 2.5 2.5 2.5 2.5 2.5 2.5 2.5 FLH (in) 18 24 30 23 23 23 23 Average thickness (mil) 1.02 1.01 0.99 1.03 1.02 0.98 1.00 Motor load (%) 64 52 42 72 57 63 66 Melt Temperature (°F) 405 401 393 410 411 410 407 Melt Pressure 1 (psi) 4910 4090 2790 5430 5840 5800 5130Melt Pressure 2 (psi) 3590 3020 1910 3930 4150 4150 3870

[0191] FIG. 1 is a graph illustrating GPC-4D, infrared based molecular weight, and hexene distribution in accordance with various embodiments of PE copolymers R1-R8 and E1-E7. FIG. 2 is a graph illustrating a small amplitude oscillatory shear testing (SAGS) of PE copolymers R1-R8 and E1-E7. As shown in FIG. 3, PE copolymers E1-E7 had increased extensional force at higher draw ratios as compared to polymers R1-R8, thereby offering increased bubble stability when forming the PE copolymer films. A concentration of a monomer over temperature of PE copolymers R1-R8 and E1-E7 is shown in FIG. 4. Additionally, the CDI_NWZ,w remained positive but decreased for the polymers E1-E7, compared to Rl, thereby indicating a reduction in their BOCD character, and increased BCD, as shown in Table 3. Furthermore, the PE copoly mers E2-E7 showed a reduced ACWF / AT (Below 80 °C at 5 °C intervals) an increased breadth of the low temperature eluents from TREF (less distinct low temperature peaks) and 3) increased LCB compared to PE polymers R1-R8, as show n in FIG. 5.ADDITIONAL EMBODIMENTS

[0192] The present disclosure provides, among others, the following embodiments, each of which may be considered as optionally including any alternate embodiments.Clause 1. A polyethylene copolymer comprising: 90 wt% or greater ethylene units; and a remainder balance of C3-C20 comonomer units; the polyethylene copolymer having one or more of the following properties: a melt index of about 0.1 g / lOmin to about 2.2 g / min, a high loadmelt index (HLMI) of about 10 g / 10 min to about 40 g / 10 min, a melt index ratio (MIR) of about 20 to about 35, a molecular weight distribution (MWD) of about 3 to about 7, a melt strength of about 0.03 N to about 0.10, a ACWF / AT of about 0.01 wt% / °C to about 0.03 wt% / °C, a Signcm *r|p*1032 / (Tan delta (m=o.i) * MW682) of about 2 Pa*s / [(g / mole)682] to about 8 Pa*s / [(g / mole)682], and a CDI_NWZ,w of about 0.200 to about 0.330.Clause 2. The polyethylene copolymer of clause 1, wherein the polyethylene copolymer has a melt index of about 0.4 g / 10 min to about 1.1 g / 10 min.Clause 3. The polyethylene copolymer of clause 1 or 2, wherein the polyethylene copolymer has a content of the Ce comonomer units of about 7 wt% to about 9 wt%.Clause 4. The polyethylene copolymer of any one of clauses 1 to 3, wherein the polyethylene copolymer has a weight average molecular weight (Mw) of about 90,000 g / mol to about 150,000 g / mol.Clause 5. The polyethylene copolymer of any one of clauses 1 to 4, wherein the polyethylene copolymer has a number-average molecular weight (Mn) of about 10,000 to about 40,000 g / mol.Clause 6. The polyethylene copolymer of any of clauses 1 to 5, wherein the polyethylene copolymer has a z-average molecular weight (Mz) of about 150,000 g / mol to about 400,000 g / mol.Clause 7. A film comprising a polyethylene copolymer comprising the polyethylene copolymer of clause 1.Clause 8. The film of clause 7, wherein the polyethylene copolymer has a melt index of about 0.4 g / 10 min to about 1.1 g / 10 min.Clause 9. The film of clauses 7 or 8, wherein the polyethylene copolymer has a content of the Ce comonomer units of about 7 wt% to about 9 wt%.Clause 10. The film of any one of clauses 7 to 9, wherein the polyethylene copolymer has a weight average molecular weight (Mw) of about 90,000 g / mol to about 150,000 g / mol. Clause 11. The film of any one of clauses 7 to 10, wherein the polyethylene copolymer has a number-average molecular weight (Mn) of about 10,000 to about 40,000 g / mol.Clause 12. The film of any one of clauses 7 to 11, wherein the polyethylene copolymer has a z-average molecular weight (Mz) of about 150,000 g / mol to about 400,000 g / mol.Clause 13. The film of any one of clauses 7 to 12, wherein the polyethylene copolymer has a viscosity ratio (T]IOO / T|O. I) of about 0.1 to about 0.4.Clause 14. The film of any one of clauses 7 to 13, wherein the film has: an MD Secant Modulus, of about 20,000 psi to about 40,000 psi, a TD Secant Modulus, of about 25,000 psito about 46,000 psi, an Elmendorf Tear value (MD) of about 100 g / mil to about 350 g / mil, a Dart Drop Impact of about 100 g / mil to about 800 g / mil, and a puncture energy at break energy of about 15 in-lbs / mil to about 40 in-lbs / mil.Clause 15. The film of any one of clauses 7 to 14, wherein the film has: an MD Secant Modulus of about 25,000 psi to about 35,000 psi, a TD Secant Modulus of about 30,000 psi to about 45,000 psi, an Elmendorf Tear value (MD) of about 150 g / mil to about 350 g / mil, a Dart Drop Impact of about 500 g / mil to about 785 g / mil, and a puncture energy at break energy of about 35 in-lbs / mil to about 51 in-lbs / mil.Clause 16. The film of any one of clauses 7 to 15, wherein the film has a haze value of about 30% or less.Clause 17. A polyethylene copolymer comprising: 90 wt% or greater ethylene units; and a remainder balance of C3-C20 comonomer units; the polyethylene copolymer having one or more of the following properties: a melt index of about 0.1 g / lOmin to about 2.2 g / min, a high load melt index (HLMI) of about 10 g / 10 min to about 40 g / 10 min, a melt index ratio (MIR) of about 20 to about 35. a molecular weight distribution (MWD) of about 3 to about 7, a melt strength of about 0.03 N to about 0.10, a ACWF / AT of about 0.01 wt% / °C to about 0.03 wt% / °C, a Signcm *ipo*lO32 / (Tan delta (ro=o.i) * MW6 82) of about 2 Pa*s / [(g / mol)6 82] to about 8 Pa*s / [(g / mol)682], and a CDI_NWZ,w of about 0.200 to about 0.330.Clause 18. The polyethylene copolymer of clause 17, wherein the polyethylene copolymer has: a weight average molecular weight (Mw) of about 90,000 g / mol to about 150,000 g / mol, a number-average molecular weight (Mn) of about 10,000 to about 40,000 g / mol, and a z-average molecular weight (Mz) of about 150,000 g / mol to about 400,000 g / mol.Clause 19. A film comprising the polyethylene copolymer of claim 17.Clause 20. A method for producing a polyethylene copolymer comprising: contacting a first composition and a second composition in a line to form a third composition, wherein: the first composition comprises a contact product of a first diluent, a first catalyst compound, a support material, and an activator; and the second composition comprises a contact product of a second diluent and a second catalyst compound; introducing the third composition from the line into a gas-phase fluidized bed reactor: exposing the third composition to polymerization conditions by polymerizing ethylene and at least one C3-C20 alpha-olefin by introducing the ethylene and the at least one C3-C20 alpha-olefin into the gas-phase fluidized bed reactor; and obtaining the poly ethylene copolymer, wherein: the first catalyst compound is represented by Formula (I):CPACPBMX, (I)wherein: M of Formula (I) is titanium, zirconium, or hafnium; n of Formula (I) is an integer from 0 to 4; each CpA and CpB of Formula (I) is independently selected from the group consisting of substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, substituted or unsubstituted tetrahydroindenyl, and substituted or unsubstituted fluorenyl; and each X of Formula (I) is independently selected from the group consisting of a halogen, a hydride, a Ci to C12 alkyl, a C2 to C12 alkenyls, a Co to C12 aryl, a C7 to C20 alkylaryl, a Ci to C12 alkoxy, a Ce to Ci6 aryloxy, a C7 to Cs alkylaryloxy, a Ci to C12 fluoroalkyl, a Ce to C12 fluoroaryl, a Ci to C12 heteroatom containing hydrocarbon, an amide, an amines, a phosphine, an ether, a carboxylate, a diene, and substituted derivatives thereof; the second catalyst is represented by Formula (III) or Formula (V):wherein: M of Formula (III) is a group 4 metal; each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13and R14is independently hydrogen, substituted or unsubstituted hydrocarbyl, a substituted or unsubstituted heteroatom, or a substituted or unsubstituted heteroatomcontaining group, or one or more of R1and R2, R4and R5, R5and R6, R6and R7, R9and R10, R11and R12, R12and R13, and R13and R14are joined to form a substituted or unsubstituted completely saturated ring or a substituted or unsubstituted aromatic ring; each X of Formula (III) is independently a halide, a substituted or unsubstituted hydrocarbyl, a hydride, an amide, a substituted or unsubstituted alkoxide, a sulfide, a phosphide, or a combination thereof, or two of X are joined together to form a substituted or unsubstituted metallocycle ring, or two of X are joined to form a chelating ligand, a diene ligand, or an alkylidene;wherein: M of Formula (V) is a group 4 metal; each of R1, R2. R3. R4. R5. R6. R7, R7. R8. R8, R9, R9, R10and R10is independently hydrogen, substituted or unsubstituted hydrocarbyl, a substituted or unsubstituted heteroatom, or a substituted or unsubstituted heteroatomcontaining group, one or more of R5and R6, R7and R8, R8and R9, and R9and R10are joined to form a substituted or unsubstituted completely saturated ring or a substituted or unsubstituted aromatic ring, or one or more of R7and R8, R8and R9, and R9and R10are absent such that a carbon-carbon double bond is present between the corresponding carbon atoms of the hydroindenyl ring shown in Formula (V); T of Formula (IV) is represented by formula Ra2J, (Ra)4J2, or (Ra)6J3 wherein each J is independently C, Si, or Ge, and each Rais independently hydrogen, halide, a substituted or unsubstituted Ci to C40 hydrocarbyl, or two Racan form a substituted or unsubstituted cyclic structure including a substituted or unsubstituted completely saturated ring, a substituted or unsubstituted partially saturated ring, or a substituted or unsubstituted aromatic ring; and each of X1and X2is independently a univalent anionic ligand, a diene ligand, an alkylidene ligand, or X1and X2are joined to form a metallocyclic ring. Clause 21. The method of clause 20, wherein the first catalyst is bi(n-propylcyclopentadienyl)Zr(CH3)2.Clause 22. The method of clause 21, wherein the second catalyst is represented by the Formula (III).Clause 23. The method of clause 22, wherein R5and Rs, are joined to form a substituted or unsubstituted completely saturated ring or a substituted or unsubstituted aromatic ring.Clause 24. The method of clause 22 or 23, wherein R12and R13, are joined to form a substituted or unsubstituted completely saturated ring or a substituted or unsubstituted aromatic ring.Clause 25. The method of any one of clause 22 to 24, wfierein each of R1, R2, R3, R4, R7, R8, R9, R10R11, R14, and R15of Formula (III) is independently hydrogen or a C1-C10 alkyl.Clause 26. The method of clause 24, wherein each of R1, R2, R3, R4, R7, R8, R9, R10Rn, R14, and R15of Formula (III) is hydrogen.Clause 27. The method of any one of clauses 22 to 26, wherein T of Formula (III) is selected from the group consisting of Si(CH2)s, Si(CH2)4, and Si(CH2)s.Clause 28. The method of any one of clauses 22 to 27, wherein: M of Formula (III) is zirconium or hafnium, and each X of Formula (III) is independently a C1-C5 alkyl.Clause 29. The method of any one of clauses 22 to 28, wherein the catalyst compound ofMeFormula (HI) is represented byClause 30. The method of clause 20, wherein the second catalyst is represented by the Formula (IV).Clause 31. The method of clause 30, wherein each of R7. R8. R9. R10, R7, R8, R9, and R10of Formula (V) is independently hydrogen or Ci-Cio alkyl.Clause 32. The method of clause 30 or 31, wherein each of R1, R2, R3, and R4of Formula (V) is independently hydrogen or a Ci-Cio alkyl.Clause 33. The method of any one of clauses 30 to 32. wherein each of R1, R2, R3, and R4of Formula (IV) is methyl.Clause 34. The method of any one of clauses 30 to 33, wherein T of Formula (V) is selected from the group consisting of SiMe2, SiEt2, and SiMeEt.Clause 35. The method of any one of clauses 30 to 34, wherein: M is zirconium or hafnium, and each X is independently a C1-C5 alkyl.Clause 36. The method of any one of clauses 30 to 35, wherein the catalyst compound ofMejSi Zrt / e>Formula (IV) is represented by'Clause 37. The method of any one of clauses 30 to 35, wherein the polymerization conditions comprise: a reactor pressure of about 250 psig to about 350 psig; and a reactor temperature of about 85°C to about 110°C.

[0193] The phrases, unless otherwise specified, "consists essentially of' and "consisting essentially of' do not exclude the presence of other steps, elements, or materials, whether or not, specifically mentioned in this specification, so long as such steps, elements, or materials, do not affect the basic and novel characteristics of the present disclosure, additionally, they do not exclude impurities and variances normally associated with the elements and materials used.

[0194] For the sake of brevity, only certain ranges are explicitly disclosed herein. However, ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited. Additionally, within a range includes every point or individual value between its end points even though not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.

[0195] All documents described herein are incorporated by reference herein, 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 present disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Accordingly, it is not intended that the present disclosure be limited thereby. Likewise, the term ‘’comprising” is considered synonymous with the term “including” for purposes of United States law; Likewise, whenever a composition, an element or a 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.

[0196] While the present disclosure has been described with respect to a number of embodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope and spirit of the present disclosure.

Claims

CLAIMS;1. A polyethylene copolymer comprising:90 wt% or greater ethylene units; anda remainder balance of C3-C20 comonomer units;the polyethylene copolymer having:a melt index of about 0.1 g / lOmin to about 2.2 g / min,a high load melt index (HLMI) of about 10 g / 10 min to about 50 g / 10 min, a melt index ratio (MIR) of about 20 to about 35,a molecular weight distribution (MWD) of about 3 to about 7,a melt strength of about 0.03 N to about 0.10 N,a ACWF / AT of about 0.01 wt% / °C to about 0.03 wt% / °C,a SigncDi *ijp* 1032 / (Tan delta (ra=o.i) * MW6,82) of about 2 Pa*s / [(g / mol)682] to about 8 Pa*s / [(g / mol)6 82], anda CDI_NWZ,w of about 0.200 to about 0.330.

2. The polyethylene copolymer of claim 1, wherein the polyethylene copolymer has a T75-T25 of about 20 °C to about 24 °C.

3. The polyethylene copolymer of claim 1, wherein the polyethylene copolymer has a melt index of about 0.4 g / 10 min to about 1.1 g / 10 min.

4. The polyethylene copolymer of claim 1, wherein the polyethylene copolymer has a content of the Ce comonomer units of about 7 wt% to about 9 wt%.

5. The polyethylene copolymer of claim 1, wherein the polyethylene copolymer has a weight average molecular weight (Mw) of about 90,000 g / mol to about 150,000 g / mol.

6. The polyethylene copolymer of claim 1, wherein the polyethylene copolymer has a numberaverage molecular weight (Mn) of about 10,000 to about 40,000 g / mol.

7. The polyethylene copolymer of claim 1, wherein the polyethylene copolymer has a z-av erage molecular weight (Mz) of about 150,000 g / mol to about 400,000 g / mol.

8. A film comprising a polyethylene copolymer comprising the polyethylene copolymer of claim 1.

9. The film of claim 8, wherein the film has:a MD 1% Secant Modulus, of about 20,000 psi to about 40,000 psi,aTD 1% Secant Modulus, of about 25,000 psi to about 46,000 psi,an Elmendorf Tear value (MD) of about 100 g / mil to about 350 g / mil,a Dart Drop Impact of about 100 g / mil to about 800 g / mil, anda puncture energy at break energy of about 15 in-lbs / mil to about 40 in-lbs / mil.

10. The film of claim 8, wherein the film has:a MD 1% Secant Modulus, of about 25,000 psi to about 35,000 psi,aTD 1% Secant Modulus, of about 30,000 psi to about 45,000 psi,an Elmendorf Tear value (MD) of about 150 g / mil to about 350 g / mil,a Dart Drop Impact of about 500 g / mil to about 785 g / mil, anda puncture energy at break energy of about 35 in-lbs / mil to about 51 in-lbs / mil.

11. The film of claim 8, wherein the film has a haze value of about 30% or less.

12. A polyethylene copolymer comprising:90 wt% or greater ethylene units; anda remainder balance of C3-C20 comonomer units;the polyethylene copolymer having:a melt index of about 0.40 g / lOmin to about 2.1 g / min,a high load melt index (HLMI) of about 11 g / 10 min to about 49 g / 10 min, a melt index ratio (MIR) of about 21 to about 32,a molecular weight distribution (MWD) of about 3 to about 6,a melt strength of about 0.03 N to about 0.10 N,a ACWF / AT of about 0.01 wt% / °C to about 0.03 wt% / °C,a Signcm *r<p*1032 / (Tan delta (m=o.i) * MW682) of about 2 Pa*s / [(g / mol)682]to about 8 Pa*s / [(g / mol)6 82], anda CDI_NWZ,w of about 0.200 to about 0.330.

13. The polyethylene copolymer of claim 12, wherein the polyethylene copolymer has:a weight average molecular weight (Mw) of about 90,000 g / mol to about 150,000 g / mol, a number-average molecular weight (Mn) of about 10,000 to about 40,000 g / mol, and a z-average molecular weight (Mz) of about 150,000 g / mol to about 400,000 g / mol; and aT75-T25 of about 20 °C to about 24 °C.

14. A film comprising the polyethylene copolymer of claim 12, wherein the film has:a MD Secant Modulus, at 23°C of about 25,000 psi to about 35,000 psi, a TD Secant Modulus, at 23°C of about 30,000 psi to about 45,000 psi, an Elmendorf Tear value (MD) of about 150 g / mil to about 350 g / mil, a Dart Drop Impact of about 500 g / mil to about 785 g / mil, anda puncture energy at break energy of about 35 in-lbs / mil to about 51 in-lbs / mil.

15. A method for producing a polyethylene copolymer comprising:contacting a first composition and a second composition in a line to form a third composition, wherein:the first composition comprises a contact product of a first diluent, a first catalyst compound, a support material, and an activator; andthe second composition comprises a contact product of a second diluent and a second catalyst compound;introducing the third composition from the line into a gas-phase fluidized bed reactor; exposing the third composition to polymerization conditions by polymerizing ethylene and at least one C3-C20 alpha-olefin by introducing the ethylene and the at least one C3-C20 alpha-olefin into the gas-phase fluidized bed reactor; andobtaining the polyethylene copolymer.wherein:the first catalyst compound is represented by Formula (I):CpACpBMXn(I)wherein:M of Formula (I) is titanium, zirconium, or hafnium;n of Formula (I) is an integer from 0 to 4;each CpA and CpBof Formula (I) is independently selected from the group consisting of substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, substituted or unsubstituted tetrahydroindenyl. and substituted or unsubstituted fluorenyl; andeach X of Formula (I) is independently selected from the group consisting of a halogen, a hydride, a Ci to C12 alkyl, a C2 to C12 alkenyls, a C6 to C12 aryl, a C7 to C20 alkylaryl, a Ci to C12 alkoxy, a Ce to C16 aryloxy, a C7 to Cs alkylaryloxy, a Ci to C12 fluoroalkyl, a Ce to C12 fluoroaryl, a Ci to C 12 heteroatom containing hydrocarbon, an amide, an amines, a phosphine, an ether, a carboxylate, a diene, and substituted derivatives thereof;the second catalyst is represented by Formula (III) or Formula (V):K (Hl) wherein:M of Formula (III) is a group 4 metal;each of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13and R14of Formula (III) is independently hydrogen, substituted or unsubstituted hydrocarbyl, a substituted or unsubstituted heteroatom, or a substituted or unsubstituted heteroatom-containing group, or one or more of R1and R2. R4and R5, R3and R6, R6and R7, R9and R10, R11and R12, R12and R13, and R13and R14are joined to form a substituted or unsubstituted completely saturated ring or a substituted or unsubstituted aromatic ring;each X of Formula (HI) is independently a halide, a substituted or unsubstituted hydrocarbyl, a hydride, an amide, a substituted or unsubstituted alkoxide, a sulfide, a phosphide, or a combination thereof, or two of X are joined together to form a substituted or unsubstituted metallocycle ring, or two of X are joined to form a chelating ligand, a diene ligand, or an alky lidene;wherein:M of Formula (V) is a group 4 metal;each of R1, R2, R3, R4, R5, R6, R7, R7, R8, R8, R9, R9, R10and R10of Formula (V) is independently hydrogen, substituted or unsubstituted hydrocarbyl, a substituted or unsubstituted heteroatom, or a substituted or unsubstituted heteroatom-containing group, one or more of R5and R6, R7and R8, R8and R9, and R9and R10are joined to form a substituted or unsubstituted completely saturated ring or a substituted or unsubstituted aromatic ring, or one or more of R7and R8, R8and R9, and R9and R10are absent such that a carbon-carbon double bond is present between the corresponding carbon atoms of the hydroindenyl ring shown in Formula (V);T of Formula (V) is represented by formula Ra2J, (Ra)4J2, or (Ra)eJ3 wherein each J is independently C, Si, or Ge, and each Rais independently hydrogen, halide, a substituted or unsubstituted Ci to C40 hydrocarbyl, or two Racan form a substituted or unsubstituted cyclic structure including a substituted or unsubstituted completely saturated ring, a substituted or unsubstituted partially saturated ring, or a substituted or unsubstituted aromatic ring; and each of X1and X2is independently a univalent anionic ligand, a diene ligand, an alkylidene ligand, or X1and X2are joined to form a metallocyclic ring.

16. The method of claim 15, wherein the first catalyst is bi(n- propylcyclopentadienyl)Zr(CH3)2.

17. The method of claim 1, wh erein the second catalyst is represented by the Formula (III).

18. The method of claim 17, wherein R5and R6of Formula (III) are joined to form a substituted or unsubstituted completely saturated ring or a substituted or unsubstituted aromatic ring.

19. The method of claim 17, wherein R12and R13of Formula (III) are joined to form a substituted or unsubstituted completely saturated ring or a substituted or unsubstituted aromatic ring.

20. The method of claim 17, wherein each of R1, R2, R3, R4, R7, R8, R9, R10Rn, R14, and R15of Formula (HI) is independently hydrogen or a Ci-Cio alkyl.

21. The method of claim 20, wherein each of R1, R2, R3, R4, R7, R8, R9, R10R11, R14, and R15of Formula (III) is hydrogen.

22. The method of claim 17, wherein T of Formula (III) is selected from the group consisting of Si(CH2)3, Si(CH2)4, and Si(CH2)5.

23. The method of claim 17, wherein:M of Formula (HI) is zirconium or hafnium, andeach X of Formula (HI) is independently a C1-C5 alkyl.

24. The method of 17, wherein the catalyst compound of Formula (III) is represented by25. The method of claim 15, wherein the second catalyst is represented by the Formula (V).

26. The method of claim 25, wherein each of R7, R8, R9, R10, R7, R8, R9. and R10of Formula (V) is independently hydrogen or Ci-Cio alkyl.

27. The method of claim 26, wherein each of R1, R2, R3, and R4of Formula (V) is independently hydrogen or a Ci-Cio alkyl.

28. The method of claim 27, wherein each of R1, R2, R3, and R4of Formula (V) is methyl.

29. The method of claim 28, wherein T of Formula (V) is selected from the group consisting of SiMe2, SiEt2, and SiMeEt.

30. The method of claim 29, wherein:M is zirconium or hafnium, andeach X is independently a C1-C5 alkyd.

31. The method of claim 30. wherein the catalyst compound of Formula (V) is represented byMe2Si32. The method of claim 15, wherein the polymerization conditions comprise:a reactor pressure of about 250 psig to about 350 psig; anda reactor temperature of about 85°C to about 110°C.

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