WO2024242932A1 - Polethylenes, catalysts for their polymerization, and films thereof - Google Patents

Abstract

The present disclosure relates to catalysts, polyethylene polymers, polymerization processes for making such polyethylene polymers, and films made therefrom. In some embodiments, a catalyst system includes a first catalyst compound. The first catalyst compound is represented by Formula (I). At least one of R⁴ and R⁵, R⁵ and R⁶, or R⁶ and R⁷ of Formula (I) are joined to form a first substituted or unsubstituted completely saturated ring fused to the indenyl ring and at least one of R¹¹ and R¹², R¹² and R¹³, or R¹³ and R¹⁴ are joined to form a second substituted or unsubstituted completely saturated ring fused to the indenyl ring. The catalyst system further includes a second catalyst represented by Formula (III). At least one of R⁷ and R⁸, R⁸ and R⁹, or R⁹ and R¹⁰ of Formula (III) are joined to form a substituted or unsubstituted completely saturated ring fused to the indenyl ring.

Description

POLETHYLENES, CATALYSTS FOR THEIR POLYMERIZATION, AND FILMS THEREOF

CROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit of U.S. Provisional Application 63/503893, filed May 23, 2023 and entitled “POLETHYLENES, CATALYSTS FOR THEIR POLYMERIZATION, AND FILMS THEREOF”, the entirety of which is incorporated by reference herein.

FIELD

[0001] This disclosure relates to catalysts, catalyst systems, polyethylene polymers, polymerization processes for making such polyethylene polymers, and films made therefrom.

BACKGROUND

[0002] Low density polyethylenes (LDPEs) are often synthesized using high pressure free radical polymerization processes to produce polyethylene compositions having good processability and other desirable attributes, mainly due to their extensive long chain branched LCB structure. Additional desirable attributes of LDPEs formed under high pressure include high melt strength, high shrink, and good optical properties. However, high-pressure formed LDPEs typically suffer from poor mechanical properties such as low TD tear and dart impact strength. In addition, high pressure processes involve higher energy consumption than low pressure processes. [0003] Alternatively, 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 LDPE in several ways including their different manufacturing processes and different rheological and mechanical properties, such as tear properties, as compared to LDPEs.

[0004] An LLDPE formed using a metallocene catalyst is known as an “mLLDPE”. Extrusions of mLLDPEs need more motor power and higher extruder pressures to match the extrusion rates of LDPEs. Indeed, commercial mLLDPEs exhibits flow challenges in a die and extruder used in Cast Film lines, causing high melt pressures, high motor load, and suboptimal flow to edge in the die, which can result in adjacent resin layer encapsulation. Regardless of the processing and rheological challenges, mLLDPEs do exhibit superior physical properties as compared to LDPEs.

[0005] In the past, 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 blends generally have poor mechanical properties as compared with neat mLLDPEs. Indeed, it has been a challenge to improve mLLDPEs processability without sacrificing physical properties.

[0006] Overall, there is a need for new polyethylenes having moderate LCB polyethylene compositions having extrusion processability like LDPE, while also retaining good tear properties and Dart impact strength, to match that of mLLDPEs. Such new LLDPEs would provide the benefits of increased processability with an increased tear balance, increased TD tear, and much better drawdown characteristics, making easier-to-produce, stronger films, without having to resort to much of the complexity and tradeoffs associated with blending mLLDPEs and LDPEs. [0007] Some references of potential interest in this regard include: US Patent Nos. 6,479,424;

7,601,666; 8,829,115; 9,068,033; 10,633,471; 11,267,917; and 11,352,386; WO2021/257264; W02022/015094; US2006/0122342; US2021/0332169; US2021/0388191; US2021/0395404; US2022/0185916; US2022/0315680; US2022/0064344; KR10-2022-0009900, KR10-2022- 0009782; KR10-2021-0080974; KR10-2021-0038379; KR10-2020-0089599; KR10-2018- 0063669; KR10-2007-0098276; and Foster, et al., Journal of Organometallic Chemistry, 571 (1998) 171.

SUMMARY

[0008] The present disclosure relates to support-bound activators, supported catalyst systems, and processes for use thereof.

[0009] In some embodiments, a catalyst system includes a first catalyst compound. The first catalyst compound is represented by Formula (I):

M of Formula (I) is a group 4 metal; each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ , R¹¹, R¹² , R¹³ and R¹⁴ of Formula (I) 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 R¹ and R², R⁴ and R⁵, R⁵ and R⁶, R⁶ and R⁷, R⁹ and R¹⁰, R¹¹ and R¹², R¹² and R¹³, and R¹³ and R¹⁴ are joined to form a substituted or unsubstituted completely saturated ring or a substituted or unsubstituted aromatic ring; wherein at least one of R⁴ and R⁵, R⁵ and R⁶, or R⁶ and R⁷ of Formula (I) are joined to form a first substituted or unsubstituted completely saturated ring fused to the indenyl ring and at least one of R¹¹ and R¹², R¹² and R¹³, or R¹³ and R¹⁴ are joined to form a second substituted or unsubstituted completely saturated ring fused to the indenyl ring; and each X of Formula (I) is independently a halide, a substituted or unsubstituted hydrocarbyl, hydride, amide, substituted or unsubstituted alkoxide, sulfide, phosphide, or a combinati on thereof, or two of X are j oined together to form a sub stituted or unsub stituted metallocycle ring, or two of X are joined to form a chelating ligand, a diene ligand, or an alkylidene.

[0010] The catalyst system can further include a second catalyst represented by Formula (III):

wherein:

M of Formula (III) is a group 4 metal; each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ of 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 R⁵ and R⁶, R⁷ and R⁸, R⁸ and R⁹, and R⁹ and R¹⁰ are joined to form a substituted or unsubstituted completely saturated ring or a substituted or unsubstituted aromatic ring, wherein at least one of R⁷ and R⁸, R⁸ and R⁹, or R⁹ and R¹⁰ are joined to form a substituted or unsubstituted completely saturated ring fused to the indenyl ring;

T of Formula (III) represents the formula R^a2J, (R^a) 2, or (R^a)eJ3 wherein each J is independently C, Si, or Ge, and each R^a is independently hydrogen, halide, a substituted or unsubstituted Ci to C40 hydrocarbyl, or two R^a can form a substituted or unsubstituted cyclic structure including a substituted or unsubstituted completely saturated ring or a substituted or unsubstituted aromatic ring; and each X of Formula (III) is independently a halide, a substituted or unsubstituted hydrocarbyl, hydride, amide, substituted or unsubstituted alkoxide, sulfide, 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.

[0011] In some embodiments, a polyethylene copolymer includes ethylene-derived units and a remainder balance of C3-C20 comonomer-derived units. The polyethylene copolymer has a broad orthogonal composition distribution, a density of about 0.914 g/cm³ to about 0.925 g/cm³, a melt index of about 0.6 g/10 min to about 1.3 g/10 min, an olefin comonomer content of about 10 wt% to about 13 wt%, a high load melt index (HLMI) of about 80 g/10 min to about 90 g/10 min, a melt index ratio (MIR) of about 60 to about 98, and a poly dispersity index (PDI, defined as Mw/Mn) of about 8 to about 10.

BRIEF DESCRIPTION OF THE DRAWINGS

[0012] So that the manner in which the above recited features of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.

[0013] FIG. 1 is a graph illustrating a GPC of polyethylene copolymers in accordance with various embodiments, including both polymer chain distributions (which may be labeled on the y axis as dwt d(logM) or equivalently as MWD(IR), to reflect that the y-axis value of molecular weight distribution is a measure of relative number of polymer molecules of a given molecular weight in the population of polymer molecules analyzed in the polymer composition) and g’vis values (also labeled on y-axis) as a function of log(molecular weight) (which may be labeled as logM on the x axis). Note that MWD(IR) as used in the FIG. 1 label is not necessarily the same as the mathematical term MWD (defined as Mw/Mn and also referred to as poly dispersity index or PDI, see below); instead, it is meant only to refer to distribution (that is, relative amount) of different-molecular-weight polymer chains, shown as a function of molecular weight on FIG. 1.

[0014] FIG. 2 is a graph illustrating a GPC of polyethylene copolymers in accordance with various embodiments, including both molecular weight distributions (labeled on the left y-axis as MWD(IR)) and comonomer wt% (labeled on the right y-axis as Wt% C6) as a function of log(molecular weight). The MWD(IR) label in FIG. 2 is used in the same manner as in FIG. 1.

Definitions

[0015] 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 about 35 wt % to about 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 about 35 wt % to about 55 wt %, based upon the weight of the copolymer.

[0016] 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).

[0017] As used herein, a “polymer” may refer to homopolymers, copolymers, interpolymers, terpolymers, etc. A “polymer” has two or more of the same or different monomer 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.

[0018] As used herein, an ethylene polymer having a density of greater than 0.860 to less than 0.910 g/cm³ may be referred to as an ethylene plastomer or plastomer; an ethylene polymer having a density of 0.910 to less than 0.925 g/cm³ may be 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; 0.925 to 0.940 g/cm³ may be referred to as a “medium density polyethylene” (MDPE); and an ethylene polymer having a density of greater than 0.940 g/cm³ may be 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. [0019] 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.

[0020] 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 0.01 wt %, by weight of the total composition.

[0021] 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.

[0022] 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).

[0023] The following abbreviations may be used herein: Me is methyl, Et is ethyl, Ph is phenyl, PDI is polydispersity index, MAO is methylalumoxane, SMAO is supported methylalumoxane, NMR is nuclear magnetic resonance, ppm is part per million, THF is tetrahydrofuran.

[0024] 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 where successive monomers are added in a monomer chain at the organometallic active center.

[0025] The terms “substituent,” “radical,” “group,” and “moiety” may be used interchangeably.

[0026] 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 alphaolefin” is an alpha-olefin defined in this paragraph wherein R is hydrogen, and R is hydrogen or a linear alkyl group.

[0027] For the purposes of the present disclosure, ethylene shall be considered an alpha-olefin. [0028] As used herein, and unless otherwise specified, the term “C_n” 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 “C_m-C_y” group or compound refers to a group or compound including carbon atoms at a total number thereof from m to y. Thus, a C1-C50 alkyl group refers to an alkyl group including carbon atoms at a total number thereof of about 1 to about 50.

[0029] Unless otherwise indicated, (e. ., 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.

[0030] 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.

[0031] 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.

[0032] 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 C1-C100 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, alkyl 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.

[0033] 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 alkyl 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, isobutoxy, sec-butoxy, tert-butoxy, phenoxyl.

[0034] The term "alkenyl" means a straight-chain, branched-chain, or cyclic hydrocarbon radical having one or more double bonds. These alkenyl 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.

[0035] 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 alkyls 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, cyclopentyl, cyclohexyl, cyclooctyl, including their substituted analogues. Some examples of alkyl may include 1 -methylethyl, 1 -methylpropyl, 1 -methylbutyl, 1- ethylbutyl, 1,3 -dimethylbutyl, 1 -methyl- 1 -ethylbutyl, 1,1 -di ethylbutyl, 1 -propylpentyl, 1- phenylethyl, i-propyl, 2-butyl, sec-pentyl, sec-hexyl, and the like.

[0036] The term "aryl" or "aryl group" means an aromatic ring and the substituted variants thereof, such as phenyl, 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.

[0037] 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).

[0038] 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.

[0039] 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.

[0040] As used herein, Mn is number average molecular weight, Mw is weight average molecular weight, and Mz is z average molecular weight, wt% is weight percent, and mol% is mole percent. Molecular weight distribution (MWD), also referred to as poly dispersity index (PDI), is defined to be Mw divided by Mn. Unless otherwise noted, all molecular weight units (e.g., Mw, Mn, Mz) are g/mol.

[0041] The terms “catalyst compound”, “catalyst complex”, “transition metal complex”, “transition metal compound”, “precatalyst compound”, and “precatalyst complex” are used interchangeably.

[0042] 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 chargebalancing 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.

[0043] 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 heteroyclic Lewis bases include pyridine, imidazole, thiazole, and furan.

[0044] 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 premixed with the transition metal compound to form an alkylated transition metal compound.

[0045] 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.

[0046] 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 systems may be not turbid as described in J. Vladimir Oliveira, C. Dariva and J. C. Pinto, Ind. Eng. Chem. Res., 2000, Vol. 29, p. 4627.

[0047] 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 sol vent/ 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%.

[0048] 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.

[0049] 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. Unless otherwise noted, catalyst compounds that differ only in that they are stereoisomers of each other are not considered to be different catalyst compounds. For example, /Y7c-dimethylsilylbis(2-methyl 4-phenyl)hafnium dimethyl and 77?e5o-dimethylsilylbis(2-methyl 4-phenyl)hafnium dimethyl are considered to be not different.

[0050] 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.

[0051] In an extrusion process, “viscosity” is a measure of resistance to shearing flow. Shearing is the motion of a fluid, layer-by-layer, like a deck of cards. When polymers flow through straight tubes or channels, the polymers are sheared and resistance is expressed in terms of viscosity.

[0052] “Extensional” or “elongational viscosity” is the resistance to stretching. In fiber spinning, film blowing and other processes where molten polymers are stretched, the elongational viscosity plays a role. For example, for certain liquids, the resistance to stretching can be three times larger than in shearing. For some polymeric liquids, the elongational viscosity can increase (tension stiffening) with the rate, although the shear viscosity decreased.

[0053] The term “melt index” (“MI”) is the number of grams extruded in 10 minutes under the action of a standard load (2.16 kg) and is an inverse measure of viscosity. A high MI implies low viscosity and a low MI implies high viscosity. In addition, polymers can have shear thinning behavior, which means that their resistance to flow decreases as the shear rate increases. This is due to, e.g., molecular alignments in the direction of flow and disentanglements. As provided herein, MI (E) is determined according to ASTM D1238-E (190 °C/2.16 kg), also sometimes referred to as E or I2.16.

[0054] 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. 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. [0055] The “melt index ratio” (“MIR”) provides an indication of the amount of shear thinning behavior of the polymer and is a parameter that can be correlated to the overall polymer mixture molecular weight distribution data obtained separately by using Gel Permeation Chromatography (“GPC”) and possibly in combination with another polymer analysis including TREF. MIR is the ratio of I21/I2 (also referred to as HLMI/MI).

[0056] The term “melt strength” is a measure of the extensional viscosity and is representative of the maximum tension that can be applied to the melt without breaking. Extensional viscosity is the polyethylene’s ability to resist thinning at high draw rates and high draw ratios. In melt processing of polyolefins, the melt strength is defined by characteristics that can be quantified in process-related terms and in rheological terms. In extrusion blow molding and melt phase thermoforming, a branched polyolefin of the appropriate molecular weight can support the weight of the fully melted sheet or extruded portion prior to the forming stage. This behavior is sometimes referred to as sag resistance.

[0057] 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, “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 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.

DETAILED DESCRIPTION

[0058] 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. [0059] This disclosure relates to catalysts, catalyst systems, polyethylene polymers, polymerization processes for making such polyethylene polymers, and films made therefrom. Catalyst systems and processes described herein employ a dual catalyst system of a first metallocene catalyst and a second metallocene catalyst for use in polymerizations. The catalyst ratio of the first metallocene catalyst and the second metallocene catalyst can be tuned to react in low pressure to produce a polyethylene composition with a significant level of long branching and a high level of broad orthogonal comonomer distribution characteristics in a gas phase polymerization process.

[0060] In some embodiments, the catalyst ratio of the first metallocene catalyst and the second metallocene catalyst can be tuned by using “trim” processes.

[0061] As compared to conventional LLDPEs, polyethylene copolymers of the present disclosure have increased long chain branching (also referred to as “LCB”) and increased broad orthogonal comonomer incorporation (BOCD) in the copolymers providing reduced neck-in and increased draw stability. Polyethylene copolymers of the present disclosure can exhibit lower zero shear viscosity, leading to lower motor torque and lower melt pressures and melt temperatures during extrusion, providing increased output of the extruded polyethylene copolymer product. In addition, because LCB and BOCD is controlled (adjustable by ratio of first metallocene to second metallocene), advantageous tear properties and dart drop properties can be likewise controlled (adjustable) to a desired polymer end use (e. ., shrink wrap film). For example, a reduction in motor torque and melt pressure may be observed during cast film fabrication due to increased polymer LCB and increased BOCD. The LCB can be evidenced by, e.g., lower g’ values, high melt index ratio, and/or increased rheology characteristics. BOCD can be evidenced by, e.g., a high T75- T25 value, a high CBDI %, a high melt index ratio and/or increased rheology characteristics, e.g., small angle oscillatory shear (SAGS) experiments.

[0062] In addition, it has been discovered that polyethylene copolymers of the present disclosure can provide excellent tear properties and dart impact strength, overcoming key weaknesses of LDPEs. For example, polyethylene copolymers of the present disclosure can provide films formed with reduced motor load and melt pressure (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 film fabrication. Films of the present disclosure can be particularly useful as shrink wrap films (improved by the presence of LCB and BOCD in the polyethylene copolymers of the present disclosure).

[0063] Indeed, dual catalysts and processes of the present disclosure can provide gas phase polymerization to provide LCB polyethylene products with excellent extrusion processability, as well as good tear properties and Dart impact strength. Furthermore, the tear balance of the polyethylene copolymers described herein can have high TD tear, which is desirable in many end use applications. Another advantage includes improved drawdown characteristic, which provides easier production of thin gauge fdms.

[0064] Additionally, dual catalysts and processes of the present disclosure can provide trimming (e.g., in-line) of a first catalyst that promotes LCB onto a supported catalyst that provides BOCD to control (adjust) the melt index ratio of the polyethylene copolymer that is formed in the reactor. The catalysts used for trimming can provide different molecular weight capabilities as compared to, for example, the in-line supported catalyst. Different molecular weight capabilities of the catalysts provides bimodal composition distribution of the polyethylene copolymer that is formed in the reactor.

[0065] In at least one embodiment, the properties and performance of the polyethylene may be advanced by the combination of: (1) varying reactor conditions such as reactor temperature, reactor pressure, hydrogen concentration, comonomer concentration, and so on; and (2) selecting and feeding a dual catalyst system having a first catalyst and second catalyst trimmed or not with the first catalyst, the second catalyst, or a third catalyst.

[0066] With respect to at least one embodiment of the catalyst system, the first catalyst is a high molecular weight component and the second catalyst is a low molecular weight component. In other words, the first catalyst may provide primarily for a high molecular-weight portion of the polyethylene polymer and the second catalyst may provide primarily for a low molecular weight portion of the polyethylene polymer.

[0067] In at least one embodiment, the amount of first or second catalyst fed (or the catalyst trim ratio), the amount of third catalyst fed, and/or the reactor conditions (e.g., pressure, temperature, and hydrogen concentration), may be varied to give a range of MI and MIR while maintaining polyethylene density. The embodiments of the processes described herein may advantageously provide a broad range of Mi's with the same catalyst system, e.g., the same dual catalyst system. For a catalyst system fed to the polymerization reactor, the polymer MI, MIR, and density may be controlled by varying reactor conditions such as the reactor mixture including an additional catalyst added, operating temperature, operating pressure, hydrogen concentration, and comonomer concentration in the reaction mixture.

[0068] Using multiple pre-catalysts that are co-supported on a single support mixed with an activator, such as a methylaluminoxane (MAO), can be economically advantageous by making the polymer product in one reactor instead of multiple ones. Additionally, using a single support also eases intimate mixing of the polymers formed while improving the process relative to preparing a mixture by post-reactor blending of polymers of different Mw and density independently from multiple catalysts in a single reactor. The catalysts can be co-supported during a single operation, or may be used in a trim operation, in which one or more additional catalysts are added to catalysts that are supported.

[0069] Evidence of the incorporation of comonomer into a polymer is indicated by the density of a polyethylene copolymer, with lower densities indicating higher incorporation. The difference in densities of the low molecular weight (LMW) component and the high molecular weight (HMW) component would be greater than about 0.02, or greater than about 0.04, with the HMW component having a lower density than the LMW component. Satisfactory control of the MWD lead to the adjustment of these factors, which can be adjusted by tuning the relative amount of the two metallocene catalysts utilized in a polymerization of the present disclosure. Furthermore, the amount of catalyst addition can be controlled by means of feedback of polymer property data obtained.

[0070] Moreover, a variety of polymers with different MWD and LCBD may be prepared from a limited number of catalysts. In at least one embodiment, the mixed catalyst system provides a polymer with a mix of beneficial properties as a result of a tailored combination of MWD, polymer branching, and BOCD. The ability to control the MWD and polymer branching can be important in determining the processability and strength of the resultant polymer.

[0071] Other embodiments provide for a method of producing polyethylene, including: polymerizing ethylene in the presence of a catalyst system in a reactor to form polyethylene, where the catalyst system comprises a first catalyst and a second catalyst; and adjusting reactor pressure, reactor temperature reactor hydrogen concentration, and/or an amount of the trim catalyst (e.g., first catalyst, second catalyst, or third catalyst) fed to the reactor, to give a narrower range of MIR of the polyethylene while maintaining, e.g., BOCD, LCB, and MI of the polyethylene. At least one embodiment provides for a system and method of producing polyethylene, including: polymerizing ethylene in the presence of a catalyst system in a reactor to form polyethylene, wherein the catalyst system comprises a first catalyst and a second catalyst, and adjusting reactor conditions and an amount of the trim catalyst (e.g., first catalyst, second catalyst, or third catalyst) fed to the reactor, to adjust the MI, BOCD, LCB, and MIR of polymer product.

Polymerization Processes

[0072] 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 are typically noncoordinating 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 Patents 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 gasphase polymerization may be carried out in any suitable reactor system, e.g., a stirred- or paddletype 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.

[0073] 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.

[0074] The cycle gas can include induced condensing agents (ICA). An ICA is one or more non-reactive alkanes that are condensable in the polymerization process for removing the heat of reaction. In some embodiments, the non-reactive alkanes are selected from Ci-Ce alkanes, e.g., one or more of propane, butane, isobutane, pentane, isopentane, hexane, as well as isomers thereof and derivatives thereof. In some instances, mixtures of two or more such ICAs may be particularly useful (e.g., propane and pentane, propane and butane, butane and pentane, etc.).

[0075] The reactor pressure during polymerization may be 100 psig (680 kPag)-500 psig (3448 kPag), such as 200 psig (1379 kPag)-400 psig (2759 kPag), such as 250 psig (1724 kPag)-350 psig (2414 kPag). In some embodiments, the reactor is operated at a temperature of 60°C to 110°C, such as 60°C to 100°C, such as 70°C to 90°C, such as 80°C to 92°C, such as 82°C. A ratio of hydrogen gas to ethylene can be 8 to 30 ppm/mol%, such as 8 to 15 ppm/mol%, such as 9 to 11 ppm/mol%.

[0076] The mole percent of ethylene (based on total monomers) may be 25-90 mole percent, such as 50-90 mole percent, or 60.0-75.0 mole percent, and the ethylene partial pressure (in the reactor) can be 75 psia (517 kPa)-300 psia (2069 kPa), or 100-275 psia (689-1894 kPa), or 150- 265 psia (1034-1826 kPa), or 180-200 psia. Ethylene concentration in the reactor can also range from 35-95 mol%, such as within the range from a low of 35, 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 0.2-2 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, 1.0, 1.5, or 2.0 mol%.

Polymerizations Using Trim

[0077] Polymerization processes of the present disclosure can be performed using a “trim” process. According to such processes, a first catalyst-containing mixture (which may be referred to as a catalyst component slurry) includes a support material, at least one activator, and at least one catalyst compound (optionally also including second, third, or more catalyst compounds) suspended in a suitable carrier liquid. Preferably, the catalyst component slurry includes at least first and second catalyst compounds.

[0078] A second catalyst-containing mixture (which can be referred to as a catalyst component solution), containing one or more of the same catalyst compound(s) as found on the supported catalyst of the slurry (e.g., the first catalyst compound and/or a second, third, fourth, etc. catalyst compound) can be added (i.e. “trimmed”) to the slurry to enable online and on-the-fly adjustment of the ratio of catalyst components in a catalyst system delivered to a polymerization reactor. Adjusting catalyst component ratios enables one to adjust one or more properties of polymer being formed in a reactor, as described herein. 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, or in the event of a desired grade change as part of a polymer production campaign.

[0079] Below, we describe a first catalyst and second catalyst that together make a particularly useful dual catalyst system. Thus, these catalysts can both be used in a trim process as just described. For instance, the catalyst component slurry can include the below-described first catalyst and/or the below-described second catalyst (preferably both), a support, and at least one activator, in a diluent. The first and/or second catalysts are therefore preferably disposed in activated form on the support in the diluent. The catalyst component solution can include either or both of the below-described first and second catalysts (preferably, one of either the second or the first catalyst) suspended in diluent (which may be the same as or different from the diluent of the slurry). Optionally, activator can be included in the solution. The trim process would include online introduction of the catalyst component solution to the catalyst component slurry to form a modified catalyst slurry including the catalyst system (supported, activated first and second catalysts in desired ratio) for delivery to a polymerization reactor.

[0080] Thus, it should 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 to achieve final desired ratios of first to second catalyst. Alternatively, the slurry can include only first or only second catalyst, and the solution can contain only the other catalyst.

[0081] In yet other embodiments, either one of the below-described first catalyst and second catalyst can be combined with different catalysts in distinct dual catalyst systems (either in a trim process or otherwise). For example, the below-described first catalyst could be combined with an additional metallocene catalyst instead of (or in addition to) combination with the below-described second catalyst; and vice-versa with respect to the below-described second catalyst. Examples of such additional metallocene catalysts include, for example, the catalysts described in US Patent 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. For instance, the catalysts may be silica-supported metallocene catalyst compounds prepared from compositions comprising a metallocene catalyst compound and methylalumoxane cocatalyst. In some embodiments, a metallocene catalyst compound is rac- meso-bis(l -ethyl indenyl)2 zirconium dimethyl, dimethylsilylbis(tetrahydroindenyl) zirconium dimethyl metallocene, dimethylsilylbis(tetrahydroindenyl) zirconium dimethyl, (n-propyl cyclopentadienyl)2 hafnium dimethyl, or combinations thereof.

[0082] As noted, 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. Toluene is one example of a diluent, although other suitable diluents can include, but are not limited to, ethylbenzene, xylene, pentane, hexane, heptane, octane, other hydrocarbons (particularly aliphatic hydrocarbons), or any combination thereof.

[0083] The diluent can be or include mineral oil. Mineral oil can have a density of about 0.85 g/cm³ to about 0.9 g/cm³ at 25°C according to ASTM D4052, such as about 0.86 g/cm³ to 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 HYDROB RITE" 380 PO White Mineral Oil (“HB380”) from Sonnebom, LLC.

[0084] 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 slurry, provides reduced settling of supported catalyst(s) in a trim vessel or catalyst pot (for introducing supported catalyst to the line). Also, using an increased viscosity mineral oil slurry does not inhibit trim efficiency. In at least one embodiment, a wax has a density of about 0.7 g/cm³ (at 100°C) to about 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.

[0085] The catalyst slurry and/or modified catalyst slurry can further be conveyed with a carrier fluid, which can advantageously include fluids otherwise used in the polymerization. For instance, in a gas phase polymerization, molecular nitrogen, induced condensing agent(s) (ICA(s)), and/or cycle gas can be used to carry the catalyst slurry and/or modified catalyst slurry (cycle gas frequently includes one or more of nitrogen, ICA(s), and gaseous monomer/comonomer). The ICA can be or can include, but is not limited to, one or more alkanes. Illustrative alkanes can be or can include, but are not limited to, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, isohexane, n-heptane, n-octane, or any mixture thereof. Further details on induced condensing agents can be found in U.S. Patent Nos. 5,352,749; 5,405,922; 5,436, 304; and 7,122,607; and International Patent Application Publication Number WO 2005/113615(A2).

[0086] In some embodiments, the catalyst is not limited to a slurry and/or trim 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.

[0087] 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 static charge, and the choice of static control agent may vary dependent upon the polymer being produced and the single site catalyst compounds being used.

[0088] 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.

First Catalyst

[0089] A first catalyst can be unsupported or supported onto a support material. [0090] In some embodiments, a first catalyst is an unbridged metallocene catalyst represented by Formula (I):

wherein M is a group 4 metal; each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ , R¹¹, R¹² , R¹³ and R¹⁴ 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 R¹ and R², R⁴ and R⁵, R⁵ and R⁶, R⁶ and R⁷, R⁹ and R¹⁰, R¹¹ and R¹², R¹² and R¹³, and R¹³ and R¹⁴ are joined to form a substituted or unsubstituted completely saturated ring, or a substituted or unsubstituted aromatic ring, wherein at least one of R⁴ and R⁵, R⁵ and R⁶, or R⁶ and R⁷ are joined to form a first substituted or unsubstituted completely saturated ring fused to the indenyl ring and at least one of R¹¹ and R¹², R¹² and R¹³, or R¹³ and R¹⁴ are joined to form a second substituted or unsubstituted completely saturated ring fused to the indenyl ring, wherein if R¹² and R¹³ are joined to form a substituted or unsubstituted completely saturated ring, then R⁹ is not substituted or unsubstituted hydrocarbyl, wherein if R⁵ and R⁶ are joined to form a substituted or unsubstituted completely saturated ring, then R² is not substituted or unsubstituted hydrocarbyl; and each X is independently a halide, a substituted or unsubstituted hydrocarbyl, hydride, amide, substituted or unsubstituted alkoxide, sulfide, 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.

[0091] In some embodiments, each of R⁴, R⁵, R⁶, R⁷, R¹¹, R¹² , R¹³ and R¹⁴ of Formula (I) is independently hydrogen or Ci-Cio alkyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl), wherein at least one of (1) R⁴ and R⁵, (2) R³ and R⁶, or (3) R⁶ and R⁷ are joined to form a first substituted or unsubstituted completely saturated ring fused to the indenyl ring shown in Formula (I), and at least one of (1) R¹¹ and R¹², (2) R¹² and R¹³, or (3) R¹³ and R¹⁴ are joined to form a second substituted or unsubstituted completely saturated ring fused to the indenyl ring shown in Formula (I).

[0092] In some embodiments, at least one of (1) R⁴ and R⁵, (2) R⁵ and R⁶, or (3) R⁶ and R⁷ are joined to form a first substituted or unsubstituted completely saturated ring fused to the indenyl ring shown in Formula (I). In some embodiments, R⁴ and R^? are 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 (I). In some embodiments, R⁵ and R⁶ are 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 (I). In some embodiments, R⁶ and R⁷ are 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, C? ring, Ce ring, or C7 ring is fused to the indenyl ring shown in Formula (I).

[0093] In some embodiments, at least one of (1) R¹¹ and R¹², (2) R¹² and R¹³, or (3) R¹³ and R¹⁴ are joined to form a first substituted or unsubstituted completely saturated ring fused to the indenyl ring shown in Formula (I). In some embodiments, R¹¹ and R¹² are 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 (I). In some embodiments, R¹² and R¹³ are 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 (I). In some embodiments, R¹³ and R¹⁴ are 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 (I).

[0094] In some embodiments, each of R¹, R², R³, R⁸, R⁹, and R¹⁰ of Formula (I) is independently hydrogen or C1-C10 alkyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl). In some embodiments, each of R¹, R², R³, R⁸, R⁹, and R¹⁰ is independently hydrogen, methyl, ethyl, or propyl. In some embodiments, each of R¹, R², R³, R⁸, R⁹, and R¹⁰ is hydrogen. In some embodiments, each of R¹, R², R³, R⁸, R⁹, and R¹⁰ is methyl. In some embodiments, at least one of R³ and R¹⁰ is C1-C10 alkyl. In some embodiments, each of R³ and R¹⁰ is independently C1-C10 alkyl. In some embodiments, each of R³ and R¹⁰ are independently Ci- C10 alkyl (such as methyl) and R¹, R², R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹¹, R¹², R¹³ and R¹⁴ are hydrogen.

[0095] In some embodiments, one or more of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ , R¹¹, R¹² , R¹³ and R¹⁴ of Formula (I) is independently hydrogen, hydrocarbyl, silylcarbyl, alkoxyl, halide, or siloxyl.

[0096] In some embodiments of Formula (I), 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(trimethyl silyl), neopentyl, ethyl, propyl, butyl, phenyl, hydrido, chloro, fluoro, bromo, iodo, trifluoromethanesulfonate, dimethylamido, diethylamido, dipropylamido, and diisopropylamido.

[0097] In some embodiments of Formula (I), (1) M is Zr or Hf, (2) X is chloro, (3) R¹, R², R³, R⁴, R⁵, R⁶, and R⁷ is independently hydrogen or substituted or unsubstituted C1-C10 alkyl, (4) R⁸, R⁹, R¹⁰ , R¹¹, R¹² , R¹³ and R¹⁴ is independently hydrogen or substituted or unsubstituted C1-C10 alkyl, (5) at least one of R³ and R¹⁰ is C1-C10 alkyl, (6) at least one of R⁴ and R^?, R⁵ and R⁶, or R⁶ and R⁷ are joined to form a substituted completely saturated ring fused to the indenyl ring shown in Formula (I), and (7) R¹¹ and R¹², R¹² and R¹³, or R¹³ and R¹⁴ are joined to form a substituted completely saturated ring fused to the indenyl ring shown in Formula (I).

[0098] The first catalyst can, for example, be an unbridged metallocene catalyst represented by Formula (II):

wherein:

M is a group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf); each of R¹, R², R³, R⁴, R⁷, R⁸, R⁹, R¹⁰ , R¹¹, R¹⁴, R¹⁵, R¹⁵ , R¹⁶, R¹⁶ , R¹⁷, R¹⁷ , R¹⁸, R¹⁸ , R¹⁹, R¹⁹ , R²⁰, R²⁰ , R²¹, R²¹ , R²² , and R²² is 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, hydride, amide, substituted or unsubstituted alkoxide, sulfide, 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.

[0099] In some embodiments, each of R⁴, R⁷, R¹¹, R¹⁴, R¹⁵, R¹³ , R¹⁶, R¹⁶ , R¹⁷, R¹⁷ , R¹⁸, R¹⁸ , R¹⁹, R¹⁹ , R²⁰, R²⁰ , R²¹, R²¹ , R²² , and R²² of Formula (II) is independently hydrogen or C1-C10 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 R²² is independently hydrogen, methyl, ethyl, or propyl. In some embodiments, each of R¹⁵, R¹³ , R¹⁸, R¹⁸ , R¹⁹, R¹⁹ , R²², and R²² is hydrogen. In some embodiments, each of R¹⁵, R¹⁵ , R¹⁸, R¹⁸ , R¹⁹, R¹⁹ , R²², and R²² is C1-C10 alkyl (such as methyl). In some embodiments, each of R⁴, R⁷, R¹¹, R¹⁴, R¹⁶, R¹⁶ , R¹⁷, R¹⁷ , R²⁰, R²⁰ , R²¹, and R²¹ is hydrogen.

[00100] In some embodiments, each of R¹, R², R³, R⁸, R⁹, and R¹⁰ of Formula (II) 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 R¹, R², R³, R⁸, R⁹, and R¹⁰ is independently hydrogen, methyl, ethyl, or propyl. In some embodiments, each of R¹, R², R³, R⁸, R⁹, and R¹⁰ is hydrogen. In some embodiments, each of R¹, R², R³, R⁸, R⁹, and R¹⁰ is methyl. In some embodiments, at least one of R³ and R¹⁰ is C1-C10 alkyl. In some embodiments, each of R³ and R¹⁰ is independently C1-C10 alkyl. In some embodiments, R³ and R¹⁰ are C1-C10 alkyl (such as methyl), and R¹, R², R⁸, and R⁹ are hydrogen.

[00101] In some embodiments of Formula (II), 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, trimethyl silyl, methyl(trimethylsilyl), neopentyl, ethyl, propyl, butyl, phenyl, hydrido, chloro, fluoro, bromo, iodo, trifluoromethanesulfonate, dimethylamido, diethylamido, dipropylamido, and diisopropylamido.

[00102] In some embodiments of Formula (II), (1) M is Zr or Hf, (2) X is chloro, (3) R¹, R², R³, R⁴, R⁷, R¹⁵, R^1? , R¹⁶, R¹⁶ , R¹⁷, R¹⁷ , R¹⁸, and R¹⁸ is independently hydrogen or substituted or unsubstituted C1-C10 alkyl, (4) R⁸, R⁹, R¹⁰ , R¹¹, R¹⁴, R¹⁹, R¹⁹', R²⁰, R²⁰’, R²¹, R²¹ , R²² , and R²² is independently hydrogen or substituted or unsubstituted C1-C10 alkyl, and (5) at least one of R³ and R¹⁰ is C1-C10 alkyl.

[00103] In some embodiments of Formula (II), the catalyst is selected from:

Second Catalyst

[00104] A second catalyst of the present disclosure includes a second catalyst that can be unsupported or supported onto a support along with the first catalyst to form a dual catalyst system. The second catalyst can be unsupported or supported and the dual catalyst system can be isolated. Alternatively, the second catalyst can be provided as a “trim” catalyst onto a supported first catalyst, e.g., 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). [00105] In some embodiments, the second catalyst is a bridged metallocene catalyst represented by Formula (III):

wherein:

M is a group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf); each of R¹, R², R³, R⁴, R\ R⁶, R⁷, R⁸, R⁹, and R¹⁰ 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 R⁵ and R⁶, R⁷ and R⁸, R⁸ and R⁹, and R⁹ and R¹⁰ (preferably one of R⁷ and R⁸, R⁸ and R⁹, and R⁹ and R¹⁰) are joined to form a substituted or unsubstituted completely saturated ring, or a substituted or unsubstituted aromatic ring fused to the indenyl ring shown in Formula (III);

T represents the formula R , (R^a)4J2, or (R^a)eJ3 wherein each J is independently C, Si, or Ge, and each R^a is independently hydrogen, halide, a substituted or unsubstituted Ci to C40 hydrocarbyl, or two R^a can 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 X is independently a halide, a substituted or unsubstituted hydrocarbyl, hydride, amide, substituted or unsubstituted alkoxide, sulfide, 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 .

[00106] In some embodiments, each of R⁷, R⁸, R⁹, and R¹⁰ of Formula (III) is independently hydrogen or C1-C10 alkyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl), wherein at least one of (1) R⁷ and R⁸, (2) R⁸ and R⁹, or (3) R⁹ and R¹⁰ are joined to form a substituted or unsubstituted completely saturated ring fused to the indenyl ring shown in Formula (III). The substituted or unsubstituted ring may, for example, be a Cs, Ce, or C7 ring fused to the indenyl ring shown in Formula (III).

[00107] In some embodiments, each of R¹, R², R³, and R⁴ of Formula (III) is independently hydrogen or C1-C10 alkyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl); preferably methyl, ethyl, or propyl (and in certain embodiments, each is methyl).

[00108] In some embodiments of Formula (III), T is represented by the formula RSI (R^a)4J2, or (R^a)eJ3 where J is C, Si, or Ge, and each R^a is independently hydrogen or Ci to C20 hydrocarbyl. In some embodiments, two R^a can form a cyclic structure including unsubstituted completely saturated, partially saturated, or aromatic ring. In some embodiments, T is selected from CH2, CH2CH2, C(CH₃) 2, CPh₂, SiMe₂, SiEt₂, SiPh₂, SiMePh, SiEtPh, SiMeEt, Si(CH₂)3, Si(CH₂)₄, or Si(CH2)5. In some embodiments, T is SiMe , SiEt2, or SiMeEt.

[00109] In some embodiments, one or more of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ of Formula (III) is independently hydrogen, hydrocarbyl, silylcarbyl, alkoxyl, halide, or siloxyl.

[00110] In some embodiments of Formula (III), M is a group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (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. In some embodiments, each X is chloro.

[00111] In some embodiments of Formula (III), (1) M is Zr or Hf, (2) X is chloro, (3) T is Si(CH2)₃, Si(CH2)4, or Si(CH2)s, (4) R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ is independently hydrogen or substituted or unsubstituted C1-C10 alkyl, (5) at least one of R⁷ and R⁸, R⁸ and R⁹, or R⁹ and R¹⁰ are joined to form a substituted or unsubstituted completely saturated ring fused to the indenyl ring shown in Formula (III), and (6) R¹, R², R³, and R⁴ is independently methyl, ethyl, or propyl. [00112] In some embodiments of Formula (HI), the second catalyst is:

Alternatively, the second catalyst can be an analogue of the just-illustrated catalyst, wherein ZrCh is replaced with ZrMe2 (that is, the catalyst could be the zirconium dimethyl analogue of the just- illustrated catalyst). Also or instead, second catalysts of various embodiments can be according to the just-illustrated catalyst formula, except with any one or more of the methyls pendent on the cyclopentadienyl moiety being replaced with a C2 - C10 alkyl (preferably ethyl or propyl).

[00113] In yet further embodiments, the above description of the second catalyst of formula

(III) may be as just-described, except instead of at least one of R⁷ and R⁸, R⁸ and R⁹, or R⁹ and R¹⁰ being joined to form a substituted or unsubstituted completely saturated ring fused to the indenyl ring shown in Formula (III), in these embodiments at least one of R⁷ and R⁸, R⁸ and R⁹, or R⁹ and R¹⁰ are joined to form a substituted or unsubstituted aromatic ring fused to the indenyl ring of Formula (III). Thus, a particular example of a catalyst according to such embodiments includes:

Alternatively, any one or more of the methyls pendent on the cyclopentadienyl moiety in the just- illustrated catalyst formula can instead be a C2 - C10 alkyl (preferably ethyl or propyl). Activators

[00114] The terms “cocatalysf ’ and “activator” are used herein interchangeably. [00115] 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 activators and 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 noncoordinating or weakly coordinating anion, e.g., a non-coordinating anion.

[00116] In some embodiments, the catalyst system includes an activator and a catalyst compound of Formula (I), Formula (II), and/or Formula (III).

Alumoxane Activators

[00117] Alumoxane activators are utilized as activators in the catalyst systems described herein. Alumoxanes are generally oligomeric compounds containing -Al(R^a )-O- sub-units, where R^a is an alkyl group. Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, 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 3 A, covered under patent number US 5,041,584, which is incorporated by reference herein). Another useful alumoxane is solid polymethylaluminoxane as described in US 9,340,630, US 8,404,880, and US 8,975,209, which are incorporated by reference herein.

[00118] 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.

[00119] 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

[00120] 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. Noncoordinating 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. 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.

[00121] 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 [00119] to page 81, paragraph [00151] and W02004/046214 page 72, paragraph [00177] to page 74, paragraph [00178]). [00122] 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")V where each R' can be independently a C1-C30 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.

Support Materials

[00123] 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.

[00124] 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, silicachromium, silica-alumina, silica-titania. In at least one embodiment, the support material is selected from AI2O3, ZrC>2, SiCh, SiCh/AhCh, SiCh/TiCh, silica clay, silicon oxide/clay, or mixtures thereof.

[00125] The support material, such as an inorganic oxide, can have a surface area of about 10

2 2 m /g to about 700 m /g, pore volume of about 0.1 cm³/g to about 4.0 cm³/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 support material can be about 100 m /g to about 400 m /g, pore volume of about 0.8 cm³/g 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 2 3 a high surface area, amorphous silica (surface area=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).

[00126] 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°C to 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.

[00127] The support material, having reactive surface groups, such as hydroxyl groups, is slurried in a non-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.

[00128] 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.

[00129] 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 or gas 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.

[00130] 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 Copolymers

[00131] The present disclosure provides polyethylene copolymers having a combination of low density, high melt index, long chain branching, broad orthogonal compositional distribution (BOCD), and bimodal composition distribution. The combination of long chain branching and BOCD can be particularly advantageous for achieving a strong balance of outstanding mechanical properties and excellent ease of processability. Thus, the polyethylene copolymers and films thereof can be formed by commercially desirable polymerizations and extrusions of the polyethylene copolymers.

[00132] Thus, polyethylene copolymers of various embodiments herein in general can exhibit one or more of the following properties:

• Density within the range from about 0.910 to about 0.925 g/cm³, such as from a low of any one of 0.910, 0.912, 0.914, 0.915, 0.916, 0.917, 0.918, 0.919, or 0.92 g/cm³ to 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/cm³ to about 0.920 g/cm³, alternatively about 0.918 g/cm³ to about 0.922 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, such as about 0.918 to about 0.92 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 D1238, 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 a high 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 1.2 g/10 min, such as about 0.3 to about 1.1 g/10 min, such as about 0.7 to about 1.1, 1.2, or 1.3 g/10 min, etc.

[00133] In addition, 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, di cyclopentadiene, 4-vinylcyclohex-l-ene, methyloctadiene, 1 -methyl- 1,6- octadiene, 7-methyl-l,6-octadiene, 1,5-cyclooctadiene, norbornadiene, ethylidene norbomene, 5- vinylidene-2-norbornene, 5-vinyl-2-norbornene, 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 from ethylene (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 85 to about 93 wt%, such as about 87 to about 90 wt% ethylene-derived units and the balance olefin comonomer-derived content).

Molecular Weight Properties

[00134] The polyethylene copolymers can also have a molecular weight distribution (MWD, defined in context of polymer properties as Mw/Mn and sometimes also referred to as poly dispersity index (PDI)) of about 5 to about 15. The MWD or PDI can also range from a low of about 5, 5.1, 5.2, 5.3, 5.4, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, or 9 to a high of about 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 12, 13, 14, or 15, with ranges from any foregoing low to any foregoing high contemplated, provided the high end of the range is greater than the low end (e.g., within the range from 7 to 15, such as from 8 to 12, or 7 to 10, etc.).

[00135] Weight-average molecular weight (Mw) of polyethylene copolymers of various embodiments may be within the range from about 70,000 to about 200,000 g/mol, such as about 75,000, about 80,000, or about 90,000 g/mol to about 125,000, 130,000, 135,000, 140,000, 145,000, or 150,000 g/mol, such as about 90,000 to about 130,000 g/mol, such as about 120,000 to about 130,000 g/mol, with ranges from any foregoing low end to any foregoing high end contemplated.

[00136] Number-average molecular weight (Mn) of polyethylene copolymers of various embodiments may be within the range from about 10,000 to about 40,000 g/mol, such as about 10,000 to about 15,000 g/mol, 20,000 g/mol, 25,000 g/mol, or about 30,000 g/mol, such as about 12,000 to about 15,000 g/mol, with ranges from any foregoing low end to any foregoing high end contemplated.

[00137] Z-average molecular weight (Mz) of polyethylene copolymers of various embodiments may be within the range from about 300,000 to about 1,200,000 g/mol, such as within the range from any one of about 300,000; 400,000; 500,000; 600,000 or 650,000 to about 750,000; 800,000; 850,000; 900,000; 950,000; 1,000,000; 1,100,000; or 1,200,000 g/mol, with ranges from any foregoing low end to any foregoing high end also contemplated herein (e g., within the range from about 650,000 to about 750,000 g/mol; or from about 400,000 to about 800,000 g/mol; or from about 500,000 to about 1,000,000 g/mol; etc.).

[00138] The distributions and the moments of molecular weight (Mw, Mn, Mw/Mn, etc.), and the branching index (g'vis) 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-tri chlorobenzene (TCB) with 300 ppm antioxidant butylated hydroxytoluene (BHT) is used as the mobile phase. The TCB mixture is filtered through a 0.1-p.m 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 hour. 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(Xi„ /Xi) flpo +1 , , , log = ^ps — log M_ps a + 1 6/ I I where the variables with subscript “PS” stand for polystyrene while those without a subscript are the test samples. In this method, aps = 0.67 and Kps = 0.000175 while a and K are for ethylenehexene 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 CH3 channel calibrated with a series of PE and ethyl ene-hexene homo/copolymer standards whose nominal values are predetermined by NMR or FTIR. Here the concentrations are expressed 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. Unless stated otherwise herein, any molecular weight value should be assumed to be determined using IR.

[00139] Light-scattering MW: For any molecular weight values indicated as being determined by LS, 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

Here, 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(9) is the form factor for a monodisperse random coil, and Ko is the optical constant for the system:

where N 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 ethyl ene-hexene copolymers.

[00140] Viscosity-average molecular weight (Mv): 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, p_s, for the solution flowing through the viscometer is calculated from their outputs. The intrinsic viscosity, [p], at each point in the chromatogram is calculated from the equation [p]= p_s/c, where c is concentration and is determined from the IR5 broadband channel output. The viscosity MW at each point is calculated as M - K M^aps+1 l\ \ ps ' ^{L /} , where aps is 0.67 and Kps is 0.000175. The average intrinsic viscosity [p]_avg °f the sample is calculated by

where the summations are over the chromatographic slices, i, between the integration limits.

[00141] The branching index (g'_vjs) can be calculated using the output of the GPC-IR5-LS-VIS method as follows. First, it is noted that g’ or g’_vis can in general be considered the ratio of a polymer’s intrinsic viscosity to that of a linear polymer of the same molecular weight and composition: g’ = [T|_Poi_ymer] / [preference], where [qpoiymer] is the intrinsic viscosity of the polymer under investigation and [preference] is the intrinsic viscosity of a linear resin of the same composition with the same molecular weight. A polymer’s relative intrinsic viscosity (g’) is therefore a measure of how much the polymer enhances its solution’s viscosity relative to how much a linear polymer of the same molecular weight and composition enhances its solution’s viscosity, under the same conditions of temperature and pressure.

[00142] Following this principle, the [p_poiymer] value in the above simplified relationship may be taken as the weight-average intrinsic viscosity, [ ]_avg> °f the sample, which is calculated by:

where the summations are over the chromatographic slices, i, between the integration limits. The branching index g' _vjs is defined against the linear reference as g'_vis =

, where M_v is the

KM" viscosity-average molecular weight based on molecular weights determined by LS analysis and the K and a are for the reference linear polymer; for purposes of the present disclosure, a and K are the same as described above for linear polyethylene polymers.

[00143] The branching index g’_vis may equivalently be referred to as g’ vis ave to reflect that it is an average value of g’ determined at each of multiple discrete concentration slices. For example, with reference to FIG. 1, one can see g’ for various polyethylene copolymers plotted as a function of LogM (log of molecular weight), implying a g’ value can be calculated for a given molecular weight population of polymer chains in the polyethylene copolymer composition. The above calculations provide the g’vis ave as a weighted average of these multiple g’ values, and the g’vis ave can be taken as a good relative indicator of the presence of long chain branching when comparing such value between two different copolymer compositions, with lower g’_{vis a}ve indicating greater long chain branching.

Broad Orthogonal Composition Distribution

[00144] ‘ ‘BOCD” refers to a Broad Orthogonal Composition Distribution in which the comonomer of a copolymer is incorporated predominantly in the high molecular weight chains or species of a polyolefin polymer or composition. The distribution of the short chain branches can be measured, for example, using Temperature Raising Elution Fractionation (TREF) in connection with a Light Scattering (LS) detector to determine the weight average molecular weight of the molecules eluted from the TREF column at a given temperature. The combination of TREF and LS (TREF-LS) yields information about the breadth of the composition distribution and whether the comonomer content increases, decreases, or is uniform across the chains of different molecular weights of polymer chains. BOCD has been described, for example, in U.S. Patent Nos. 8,378,043, Col. 3, line 34, bridging Col. 4, line 19, and 8,476,392, line 43, bridging Col. 16, line 54.

[00145] The BOCD nature of the present polyethylene copolymers can be quantified in the composition distribution breadth index (CDBI). For instance, polyethylene copolymers described herein can have a very low value of composition distribution breadth index (CBDI), in which the polyethylene copolymers may have a CBDI % within a range from a low of any one of about 5, 10, 15, 20, 22, 23, 24, 25, or 26 % to a high of any one of about 30, 31, 32, 33, 34, 35, 40, 45, or 50%; with ranges from any of the foregoing lows to any of the foregoing highs contemplated herein (e.g., about 5% to about 35%, such as about 20% to about 30%).

[00146] CDBI is defined as the weight percent of the copolymer molecules having a comonomer content within +/-50% of the median comonomer mol% value, as described at pp. 18-19 of WO 1993/003093 in conjunction with FIG. 17 therein. This means that for a copolymer having median comonomer mol% value (Cmed) of 8mol% comonomer on a polymer chain, CDBI is the wt% of copolymer chains having comonomer mol% that is between (0.5 x Cmed) and (1.5 x Cmed). In this example, CDBI is the wt% of copolymer chains having comonomer mol% between (0.5 x 8) and (1.5 x 8), or comonomer content between 4 mol% and 12 mol%. WO 1993/003093 also describes the process for determining the weight fraction of polymer vs. composition curve (i.e., the composition distribution curve) using chromatography and C13 NMR, and determining the median comonomer composition Cmed therefrom, with reference to Figures 16 and 17 of that publication. The CDBI of a copolymer is readily determined utilizing a technique for isolating individual fractions of a sample of the copolymer. One such technique is generation of a solubility distribution curve using Temperature Rising Elution Fraction (TREF), as described in WO 1993003093 (which in turn references Wild, et al., J. Poly. Sci., Poly. Phys. Ed., vol. 20, p. 441 (1982) and U.S. Patent No. 5,008,204 in this regard). All three of the foregoing publications are incorporated herein by reference.

[0002] The solubility distribution curve can be first generated for the copolymer using data acquired from TREF techniques (as described, e.g., in the just-referenced publications). This solubility distribution curve is a plot of the weight fraction of the copolymer that is solubilized as a function of temperature. This can be converted to a weight fraction versus composition distribution curve. For the purpose of simplifying the correlation of composition with elution temperature the weight fractions less than 15,000 can be ignored. These low weight fractions generally represent a trivial portion of the ethylene-based polymers disclosed herein.

[0003] Alternatively or additionally, the composition distribution can be characterized by the T75- T25 value, wherein T25 is the temperature at which 25% of the eluted polymer is obtained and T75 is the temperature at which 75% of the eluted polymer is obtained, both in a TREF experiment (and plotting of eluted polymer molecular weights vs. elution temperatures) as described in US2019/0119413 (especially in paragraphs [0055] - [0058] thereof, which description is incorporated by reference herein). A narrow composition distribution is reflected in a relatively small difference in the T75 - T25 value, while a broad distribution is reflected in a relatively larger difference in the T75 - T25 value, implying greater differences in crystallinity between fractions of the polymer composition. It is also noted that, in the event of discrepancies between the actual TREF procedure as described in US2019/0119413 vs. the TREF procedure as described in WO 1993003093, US 5,382,630, and/or US 5,008,204, the TREF procedure as described in US2019/0119413 should be used. (Note further that the curves generated ancillary to the TREF procedures - solubility distribution curve for CDBI, and eluted molecular weights vs elution temperature for T75 - T25, may have appropriate differences in their generation and analysis for CDBI and T75 - T25.) Finally, the TREF curve (eluted polymer molecular weights vs elution temperatures) generated in connection with T75-T25 measurements can be further processed as follows:

1. The solvent-only response of the instrument can be generated and subtracted from the TREF curve of the sample. The solvent-only response can be 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.

2. The temperature axis of the TREF curve can be appropriately shifted to correct for the delay in the IR signal caused by the column-to-detector volume. This volume can be 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).

[00147] The curve can be baseline corrected and appropriate integration limits can be selected; and the curve can be normalized so that the area of the curve is 100 wt%.

[00148] A broad distribution, as in the present polyethylene copolymers, is reflected in the relatively large difference in the T75 - T25 value being greater than 25°C, such as within the range from a low of any one of 25, 26, 27, 28, 29, 30, 31, 32, or 33 °C to a high of any one of 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, or 50°C, with ranges from any foregoing low to any foregoing high contemplated (e.g., 25°C to 50°C, such as 25°C to 40°C or 30°C to 38°C).

Further Polyethylene Copolymer Rheology

[00149] In addition to the melt index (MI) values noted previously, 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 20, 40, 60, 65, 70, 75, 80, or 85 g/10 min to a high of about 120, 110, 100, 95, 90, 85, or 80, g/10 min; with ranges from any of the foregoing lows to any of the foregoing highs contemplated herein (e.g., about 60 to about 100 g/10 min, such as about 80 to about 90 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. 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.

[00150] 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 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 71, 72, 73, 74, or 75 to a high of any one of 80, 85, 90, 95, 96, 97, 98, 99, 100, 105, 110, 120, 130, 140, or 150, with ranges from any of the foregoing lows to any of the foregoing highs contemplated herein (e.g., 60 or 70 to 105, or 90 to 97, or 70 to 80, etc.).

[00151] As noted, polyethylene copolymers of various embodiments may also exhibit moderate long-chain branching; less than incumbent LDPE (produced in free radical polymerization with large variations in, and little control over, polymer branching directions), but more than typical metallocene LLDPE. This moderate amount of LCB can be evidenced through, e.g., a high MIR (discussed above) and/or particular rheology characteristics as shown through data obtained by SAGS experiments (such as ratio of qo.oi/r| 100, the ratio of complex viscosity recorded at shear rates or frequencies of 0.01 and 100 rad/s, respectively).

[00152] For instance, the polyethylene copolymers can have a relatively high shear thinning index (STI 0.1/100). STI 0.1/100 data measures the ratio of complex viscosities at 0.1 and 100 rad/s. STI 0.1/100 data of polyethylene copolymers of various embodiments may be greater than 5, such as greater than 6 or even higher. For instance, STI0.1/100 may be within the range from a low of any one of about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55 to a high of any one of about 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, or 10, with ranges from any foregoing low to any foregoing high also contemplated (for example, about 10 to about 50, such as about 20 to about 40, such as about 25 to about 35.

[00153] Further, LCB or branching index (referred to herein as g’vis or alternatively g'vis ave) could be less than 1, such as within the range from a low of any one of about 0.67, 0.68, 0.69, 0.70, or 0.71 to a high of any one of about 0.73, 0.74, 0.75, 0.76, 0.77, 0.78, 0.79, 0.80, 0.83, 0.85, 0.87, or 0.9, with ranges from any foregoing low end to any foregoing high end contemplated (e.g., 0.71 to 0.73 or 0.65 to 0.75).

[00154] Also or instead, the polyethylene copolymers can have a G7G”@0.1 s’¹ value (which is a ratio of shear storage modulus (Pa) to shear loss modulus (Pa) at 0.1 s-1) of about 0.5 or greater, or about 1.0 or greater, or about 1.25 or greater, such as within the range from a low of any one of 0.5, 0.75, 1.0, 1.25, or 1.5 to a high of any one of 2.0, 2.5, 3.0, 3.5, 4.0, or 4.5.

[00155] Rheological data such as “Complex shear viscosity (T|*),” reported in Pascal seconds, can be measured at 0.01 rad/sec and 100 rad/sec. Complex shear viscosity and other rheological measurements can be obtained from small angle oscillatory shear (SAGS) experiments.

[00156] For instance, complex shear viscosity can be measured with a rotational rheometer such as an Advanced Rheometrics Expansion System (ARES-G2 model) or Discovery Hybrid Rheometer (DHR-3 Model) using parallel plates (diameter=25 mm) in a dynamic mode under nitrogen atmosphere. The rheometer can be thermally stable at 190°C for at least 20 minutes before inserting compression-molded specimen onto the parallel plates. To determine the specimen’s viscoelastic behavior, a frequency sweep in the range from 0.01 to 628 rad/s can be carried out at a temperature of 190°C under constant strain that does not affect the measured viscoelastic properties. The sweep frequencies are equally spaced on a logarithmic scale, so that 5 frequencies are probed per decade. Depending on the molecular weight and temperature, strains of 3% can be used and linearity of the response is verified. A nitrogen stream is circulated through the oven to minimize chain extension or cross-linking during the experiments. The specimens can be compression molded at 190°C, without stabilizers. A sinusoidal shear strain can be applied. If the strain amplitude is sufficiently small the material behaves linearly. As those of ordinary skill in the art will be aware, the resulting steady-state stress will also oscillate sinusoidally at the same frequency but will be shifted by a phase angle 5 with respect to the strain wave. The stress leads the strain by 5. For purely elastic materials 8=0° (stress is in phase with strain) and for purely viscous materials, 5=90° (stress leads the strain by 90° although the stress is in phase with the strain rate). For viscoleastic materials, 0< 8 <90. Complex viscosity, loss modulus (G") and storage modulus (G¹) as function of frequency are provided by the small amplitude oscillatory shear test. Dynamic viscosity is also referred to as complex viscosity or dynamic shear viscosity. The phase or the loss angle 8, is the inverse tangent of the ratio of G" (shear loss modulus) to G (shear storage modulus). The shear thinning slope (STS) can be measured using plots of the logarithm (base ten) of the dynamic viscosity versus logarithm (base ten) of the frequency. The slope is the difference in the log(dynamic viscosity) at a frequency of 100 s ¹ and the log(dynamic viscosity) at a frequency of 0.01 s ' divided by 4. The complex shear viscosity (r|*) versus frequency (co) curves can be fitted using the Carreau -Yasuda model:

[00157] The five parameters in this model are: r]o, the zero-shear viscosity; , the relaxation time; and n, the power-law index; qco the infinite rate viscosity; and a, the transition index. The zero-shear viscosity is the value at a plateau in the Newtonian region of the flow curve at a low frequency, where the dynamic viscosity is independent of frequency. The relaxation time corresponds to the inverse of the frequency at which shear-thinning starts. The power-law exponent describes the extent of shear-thinning, in that the magnitude of the slope of the flow curve at high frequencies approaches n-1 on a log

-log((o) plot. For Newtonian fluids, n=l and the dynamic complex viscosity is independent of frequency.

[00158] In addition to dynamic and complex viscosity (each in Pascal seconds), at each frequency sweep in the SAGS experiment, various other parameters are collected, including storage modulus (Pa), Loss modulus (Pa), Complex Modulus (Pa), tan(delta), and phase angle. Charting the phase angle versus the complex shear modulus from the rheological experiment yields Van Gurp Palmen plots useful to extract some information on the molecular characteristics, for example, linear vs. long chain branched chains, type of long chain branching, poly dispersity (Dealy, M. J., Larson, R. G., “Structure and Rheology of Molten Polymers”, Carl Hanser Verlag, Munich 182-183 (2006). It has been also suggested that Van Gurp Palmen plots can be used to reveal the presence of long chain branching in polyethylene. See Trinkle, S., Walter, P., Friedrich, C. “Van Gurp-Palmen plot II — Classification of long chain branched polymers by their topology”, in 41 Rheol. Acta 103-113 (2002). [00159] “Shear Thinning Index”, which is reported as a unitless number, is characterized by the decrease of the complex viscosity with increasing shear rate. Herein, shear thinning can be determined as a ratio of complex viscosity at a frequency of 0.01 rad/s to the complex viscosity at a frequency of 100 rad/s.

Blends and additives

[00160] In some embodiments, the polyethylene copolymers can be formulated (e. ., 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.

[00161] In some embodiments, the formulated blends can contain additives, which are determined based upon the end use of the formulated blend. In some embodiments, the additives 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 0.1 ppm to 5.0 wt %.

[00162] 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” means free of any intentionally added components, but allowing for up to 100 ppm of such component(s) as impurities).

ARTICLES OF MANUFACTURE

[00163] 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 inj ection molding processes. In some embodiments, the polyethylene copolymer can be used in a blend.

[00164] In addition, it has been discovered that polyethylene copolymers of the present disclosure can provide excellent tear properties and dart impact strength, overcoming key weaknesses of LDPEs. In addition, polyethylene copolymers of the present disclosure can provide films formed with reduced motor load and melt pressure (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 film fabrication. Films of the present disclosure can be particularly useful as shrink wrap films (improved by the presence of LCB and BOCD in the polyethylene copolymers of the present disclosure).

[00165] 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 coextrusion or by lamination useful as shrink film, cling film, stretch film, sealing films, oriented films, snack packaging, heavy duty bags, grocery sacks, baked and frozen food packaging, medical packaging, industrial liners, membranes, etc., in food-contact and non-food contact applications. For example, polyethylene copolymers of the present disclosure provide improved shrink wrap capability due to broad orthogonal composition distributions and long chain branching properties. 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.

[00166] 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 fdm 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.

[00167] 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).

[00168] 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 qm, 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 cast film 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.

[00169] In at least one embodiment, a film of the present disclosure has an averaged 1% Secant Modulus (M), at 23°C according to a ASTM D882-18 of about 25,000 psi to about 40,000 psi, such as about 27,000 psi to about 40,000 psi, such as about 28,000 to about 38,000 psi, such as about 28,000 psi to about 30,000 psi.

[00170] A film of the present disclosure can have an Elmendorf Tear value, in accordance with ASTM D-1922. In at least one embodiment, a film has an Elmendorf Tear (MD) of at least 30 g/mil, such as at least 50 g/mil to about 200 g/mil, such as about 100 g/mil to about 180 g/mil, such as about 160 g/mil to about 180 g/mil. In at least another embodiment, a film has an Elmendorf Tear (TD) of at least 300 g/mil, such as about 400 g/mil to about 600 g/mil, such as about 410 g/mil to about 460 g/mil, such as about 440 g/mil to about 470 g/mil.

[00171] 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-1709, method A. A film of the present disclosure can have a Dart Drop Impact of from about 5 g/mil to about 600 g/mil. In at least one embodiment, the film has a Dart Drop Impact of at least about 100 g/mil, such as at least about 120 g/mil, such as at least about 130 g/mil. For example, the Dart Drop Impact can be about 100 g/mil to about 200 g/mil, such as about 120 g/mil to about 170 g/mil, such as about 130 g/mil to about 160 g/mil.

[00172] Shrink of a film, reported as a percentage, can be measured by cutting circular specimens from a film using a 100 mm die. The samples can be marked in their respective directions, dusted with talc, and placed on a pre-heated, talc covered tile. The samples can then heated using a heat gun (e.g., model HG-501 A) for approximately 10 to 45 seconds, or until any dimensional change ceases. Values are the average of three specimens. A negative shrinkage number indicates expansion of a dimension after heating when compared to its pre-heating dimension. A film of the present disclosure can have a % shrink (Machine Direction) of about 40% to about 90%, such as about 60% to about 80%, such as about 60% to about 70%. A film of the present disclosure can have a % shrink (Transverse Direction) of about 0 % to about 6%, such as about 0.5 % to about 5%, such as about 2% to about 5%.

[00173] In certain embodiments, the film may have a puncture energy at break (also known as puncture break energy), in accordance with a modified BSI CEN 14477, of at least about 5 in- Ibs/mil, such as at least about 10 in-lbs/mil, such as at least about 15 in-lbs/mil, such as within the range from about 10, 11, 12, or 13 to about 20 or 25 in-lbs/mil.

[00174] In at least one embodiment, a film of the present disclosure has a haze value of about 45% or less, about 40% or less, about 35% or less, about 30% or less, about 25% or less, about 20% or less, about 15% or less, or about 10% or less, as determined by ASTM D-1003.

[00175] In at least one embodiment, a film of the present disclosure has a clarity (defined as regular transmitted light that is deflected less than 0.1 from the axis of incident light through the bulk of the film sample) of about 80% or greater, about 85% or greater, or about 90% or greater, as determined by ASTM DI 746.

[00176] In at least one embodiment, a film of the present disclosure has a gloss (MD) of about 10 GU or about 15 GU or greater, such as within the range from 10, 15, 16, 17, 18, or 19 GU to about 25, 26, 27, 28, 29, 30, 35, or 40 GU, as determined by ASTM D-2457, where a light source is beamed onto the film surface at an angle of 45° and the amount of light reflected is measured. Shrink Films

[00177] Compositions of the present disclosure may be utilized to prepare shrink films. Shrink films, also referred to as heat-shrinkable films, are widely used in both industrial and retail bundling and packaging applications. Such films are capable of shrinking upon application of heat to release stress imparted to the film during or subsequent to extrusion. The shrinkage can occur in one direction or in both longitudinal and transverse directions. Conventional shrink films are described, for example, in U.S. 7,235,607, incorporated herein by reference.

[00178] Industrial shrink films can be used for bundling articles on pallets. Typical industrial shrink films are formed in a single bubble blown extrusion process to a thickness of about 80 to 200 pm, and provide shrinkage in two directions.

[00179] Retail films can be used for packaging and/or bundling articles for consumer use, such as, for example, in supermarket goods. Such films are typically formed in a single bubble blown extrusion process to a thickness of about 35 pm to 80 pm.

[00180] Films may be used in “shrink-on-shrink” applications. “Shrink-on-shrink,” as used herein, refers to the process of applying an outer shrink wrap layer around one or more items that have already been individually shrink wrapped (herein, the “inner layer” of wrapping). In these processes, it may be desired that the films used for wrapping the individual items have a higher melting (or shrinking) point than the film used for the outside layer. When such a configuration is used, it is possible to achieve the desired level of shrinking in the outer layer, while preventing the inner layer from melting, further shrinking, or otherwise distorting during shrinking of the outer layer. Some films described herein may have a sharp shrinking point when subjected to heat from a heat gun at a high heat setting, which indicates that they may be especially suited for use as the inner layer in a variety of shrink-on-shrink applications.

EXPERIMENTAL

[00181] Relaxation Time and Cross Equation Constants: In addition to SAGS and other parameters described elsewhere herein, the relaxation time r and/or Cross equation values (esp viscosity, time, and power law constants) may help indicate polydispersity/MWD and/or the presence of long chain branching in a polymer composition (or behavior of a polymer composition in a manner that emulates long chain branched polymers). Relaxation time T may be determined from the Cross Equation as used to model viscosity data collected over a range of frequencies. The viscosity data collected over a range of frequency can be fitted (e.g., via the least squares method) using the general form of the Cross Equation (J.M Dealy and K.F Wissbrun, Melt Rheology and Its Role in Plastics Processing Theory and Applications; Van Nostrand Reinhold: New York, p. 162 (1990):

where r| is the dynamic viscosity, T|o is the limiting zero shear viscosity, ry is the infinite shear viscosity, T is the relaxation time at the given input shear frequency y, and n is the power law exponent, which can describe the extent of shear thinning. For Newtonian fluid, n=l and the dynamic complex viscosity is independent of frequency. For polymer of interest here, n<l, so that the enhanced shear thinning behavior is indicated by a decrease in n (increase in (1-n)), and. The term q / is 0 from the curve fit, with the result the expression reduces to three parameters:

[00182] This expression gives the relaxation time when testing is conducted at constant strain and constant temperature. As noted, the relaxation time, T in the Cross Model can be associated to the polydispersity and/or long chain branching in the polymer. For increased levels of branching (and/or polymer compositions emulating increased levels of branching), it is expected that r would be higher compared to a linear polymer of the same molecular weight. These three Cross parameters viscosity (r|o), time (r), and power law (n) constants can also be labeled as Cross equation constants Al, A2, and A3, respectively.

General Considerations and Reagents:

[00183] All manipulations were performed under an inert atmosphere using glove box techniques unless otherwise stated. Diethyl ether, pentane, hexane 1,2-dimethoxy ethane and dichlormethane (Sigma Aldrich) were degassed and dried over 3 molecular sieves overnight prior to use. n-Butyl Lithium in hexane, iodomethane were purchased from Sigma Aldrich and used as received. ZrCL was purchased from Strem chemicals and used as received. Methylaluminoxane was purchased from Grace and used as received.

[00184] Catalyst 1 and Catalyst 2a were synthesized as described below, for use in creating a dual metallocene catalyst system for polymerizations in accordance with various embodiments described herein. Catalyst 1 was also used as the sole catalyst compound in comparative examples as indicated in Tables IB and 2B. Catalyst 2b was also obtained, and used as a single catalyst for comparative examples as indicated in Tables IB and 2B.

Synthesis:

Synthesis of Catalyst 1:

Synthesis of (5,5,8,8-tetramethyl-6,7-dihydro-3H-cyclopenta[b]naphthalen-3-yl)lithium

[00185] To a vigorously stirred white suspension of 5,5,8,8-tetramethyl-6,7-dihydro-lH- cyclopenta[b]naphthalene (20.18 g, 89.2 mmol, 1.00 equiv.) in di ethylether (250 mb) at -35°C was added //-Butyl Lithium in hexane (36 ml, 90.0 mmol, 1.01 equiv.) to give a cold, cloudy light yellow mixture. The reaction became cloudy bright yellow after stirring 20 minutes. The reaction was stirred overnight, then was evaporated under vacuum, leaving dirty white solid. The solid was washed with pentane (100 mb) and the solid was filtered to give a bright white solid. The yield was 18.8 g (91%) bright white powder. 'H NMR (THF-Ds) 7.46 (s, 2H), 6.50 (t, 1H), 5.81 (dt, 1H), 1.72 (S, 4H), 1.34 (S, 12H).

Synthesis of 3,5,5,8,8-pentamethyl-6,7-dihydro-3H-cyclopenta[b]naphthalene:

[00186] To the colorless solution of iodomethane (7.47 g, 52.6 mmol, 2.0 equiv.) in Diethyl ether (200 ml) at -35°C was added (5,5,8,8-tetramethyl-6,7-dihydro-3H-cyclopenta[b]naphthalen- 3-yl)lithium (6.12 g, 26.3 mmol, 1.0 equiv.) to give a cloudy white mixture. The reaction mixture was allowed stir at room temperature overnight. 1,2-dimethoxy ethane (6g) was added to the clear yellow reaction mixture results in the formation of white precipitate. The solvent was removed under vacuum, leaving white solid. The product was extracted with pentane (100 ml) and filtered results in the amber solution and white precipitate. The amber solution was dried under vacuum yields yellow viscous oil. The yield was 18.8 g (91%) bright white powder. ^JH NMR (CeDe) 7.34 (dt, 2H), 6.71 (dt, 1H), 6.23 (dt, 1H), 3.29, (m, 1H), 1.65 (S, 4H), 1.30, (dt of dt, 12H), 1.15 (dt, 3H).

Synthesis of (3,5,5,8,8-pentamethyl-6,7-dihydro-lH-cyclopenta[b]naphthalen-l-yl)lithium: [00187] To a vigorously stirred white suspension of 3,5,5,8,8-pentamethyl-6,7-dihydro-3H- cyclopenta[b]naphthalene (6.48 g, 27.0 mmol, 1.00 equiv.) in diethylether (250 mL) at -35°C was added //-Butyl Lithium in hexane (10.9 ml, 27.2 mmol, 1.01 equiv.) to give a cold, cloudy light yellow mixture. The reaction became cloudy bright yellow after stirring 20 minutes. The reaction was stirred overnight, then was evaporated under vacuum, leaving dirty white solid. The solid was washed with pentane (100 mL) and the solid was filtered to give a bright white solid. The yield was 6.30 g (95%) bright white powder. 'H NMR (THF-D§) 7.28 (dt, 2H), 6.30 (dt, 1H), 5.61 (dt, 1H), 2.43 (S, 3H), 1.72 (S, 4H), 1.35 (dt, 12H).

Synthesis of bis(3, 5,5,8, 8-pentamethyl-6,7-dihydro-lH-cyclopenta[b]naphthalen-l-yl)

Zirconium dichloride:

[00188] To a vigorously stirred white suspension of zirconium tetrachloride (2.98 g, 12.8 mmol, 1.00 equiv.) in diethylether (200 mL) at -35°C was added (3,5,5,8,8-pentamethyl-6,7-dihydro-lH- cyclopenta[b]naphthalen-l-yl)lithium (6.30 g, 25.6 mmol, 2.00 equiv.) to give a cold, cloudy light yellow mixture. The reaction became cloudy bright yellow after stirring 20 minutes. The reaction was stirred overnight, then was evaporated under vacuum, leaving bright yellow solid. The solid was extracted with di chloromethane ( 100 mL) and the extracts were fdtered to give a bright yellow solid. The solid was washed with cold pentane (50 mL) and dried under vacuum. The yield was 16.01 g (97%) bright yellow powder. 'H NMR (CD2C12) 7.57 (S, 1H), 7.50 (D, 2H), 7.42 (s, 1H), 6.15 (dt, 1H), 5.89 (dt, 1H), 5.71 (dt, 1H), 5.50 (dt, 1H), 2.42(s, 3H), 2.34(s, 3H), 1.43 (m, 8H), 1.36 (m, 24H). Synthesis of Catalyst 2a:

Synthesis of (l,5,6,7-tetrahydro-s-indacen-l-yl)lithium:

[00189] To a vigorously stirred white suspension of 1,2,3,5-tetrahydro-s-indacene (9.70 g, 62.1 mmol, 1.00 equiv.) in diethyl ether (250 mL) at -35°C was added //-Butyl Lithium in hexane (36 ml, 90.0 mmol, 1.01 equiv.) to give a pink precipitate. The reaction was stirred overnight, then was evaporated under vacuum, leaving pink solid. The solid was washed with pentane (100 mL) and the solid was fdtered to give a bright white solid. The yield was 8.85 g (88%) pink powder. 'HNMR (THF-Ds) 7.15 (s, 2H), 6.42 (t, 1H), 5.81 (dt, 1H), 2.83 (m, 4H), 1.95 (m, 2H).

Synthesis of dimethyl (2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl) silyl trifluoromethanesulfonate:

[00190] To a pale amber solution of Me4CpSiMe2Cl (30.0 g, 140mmol, 1.0 equiv.) in 100 mL toluene was added AgOTf (38.00 g, 148 mmol, 1.06 equiv.) in portions. Reaction mixture turned cloudy white and warmed on adding AgOTf. The reaction mixture quickly turned gray-pink precipitate and allowed to stir at room temperature for 4 hours. The solvents were removed in vacuum, leaving dark grey mixture. The product was extracted with pentane (100 ml) and fdtered yellow with solution and brown solid. Pentane was removed from the yellow solution leaving pale yellow solid with the yield was 8.85 g (88%).

(CeDe) 1.72 (s, 6H), 1.60 (s, 6H), 0.43 (s, 6H).

Synthesis of Dimethyl(l,5,6,7-tetrahydro-s-indacen-l-yl)(2,3,4,5-tetramethylcyclopenta-2,4- dien-l-yl)silane:

[00191] To an amber-yellow solution of (2,3,4,5-tetramethylcyclopenta-2,4-dien-l-yl) silyl trifluoromethanesulfonate (5.00g, 15.2 mmol, 1.0 equiv.) in diethyl ether (50 ml) at -35°C was added (l,5,6,7-tetrahydro-s-indacen-l-yl)lithium (2.65g, 16.2 mmol, 1.07 equiv.) to give a hazy yellow-orange mixture. The reaction mixture was allowed to stir at room temperature overnight. The solvent was removed under vacuum, leaving pink-orange solid. The product was extracted with pentane (100 ml) and filtered amber solution. Then pentane was removed under vacuum. Yield is 5.04 g (99%). 'H NMR (C₆D₆) 7.51 (S, 1H), 7.34 (S, 1H), 6.90 (t, 1H), 6.489 (t, 1H), 3.64(s, 1H), 2.86 (m, 5H), 1.95 (m, 8H), 1.92 (s, 6H), 0.09 (s, 3H), 0.03 (s, 3H).

Synthesis of Dimethyl(l,5,6,7-tetrahydro-s-indacen-l-yl)(2,3,4,5-tetramethylcyclopenta-2,4 dien-l-yl)silyl)Lithium :

[00192] To the orange solution of Dimethyl(l, 5,6, 7-tetrahydro-s-indacen-l-yl)(2, 3,4,5- tetramethylcyclopenta-2,4-dien-l-yl)silane (5.0 g, 14.9 mmol, 1.0 equiv.) in diethyl ether (50 ml) at -35°C was added n-Butyllithium (11.3 ml, 31.0 mmol, 2.07 equiv.) to give amber colored solution. The reaction mixture was stirred at room temperature overnight. The solvent was removed under vacuum and the product was washed with pentane (100 ml) and filtered yields a pale yellow solid 5.86g (93%).

NMR (THF-Ds) 7.46 (s, 1H), 7.16 (s, 1H), 6.65 (dt, 1H), 5.91 (dt, 1H), 2.81 (m, 5H), 2.10 (s, 6H), 1.95 (m, 3H), 1.92 (s, 6H), 0.59 (s, 6H).

Synthesis of Dimethyl(l, 5,6, 7-tetrahydro-s-indacen-l-yl)(2, 3,4,5- tetramethylcyclopentadienyl)silyl)Zirconium dichloride (Catalyst 2a):

[00193] To a vigorously stirred white suspension of zirconium tetrachloride (3.17 g, 8.31 mmol, 1.00 equiv.) in diethyl ether (200 mb) at -35°C was added (1,5,6,7-tetrahydro-s-indacen-l- yl)(2,3,4,5-tetramethylcyclopenta-2,4 dien-l-yl)silyl)lithium (3.50 g, 8.32 mmol, 1.00 equiv.) to give a cold, cloudy light yellow mixture. The reaction became cloudy bright yellow after stirring 20 minutes. The reaction was stirred overnight, then was evaporated under vacuum, leaving bright yellow solid. The solid was extracted with dichloromethane (100 mb) and the extracts were filtered to give a bright yellow solid. The solid was washed with cold pentane (50 mb) and dried under vacuum. The yield was 3.68 g (90%) bright yellow powder. ^JH NMR (CD2C12) 7.57 (S, 1H), 7.3 (S, 1H), 7.0 (s, 1H), 5.87 (s, 1H), 3.0-2.8 (m, 5H), 2.65 (m, 3H), 1.9 (d, 12H), 1.1 (s, 3H), 0.9 (s, 3H).

Procedure of supportation:

[00194] MAO (42.5 g in 30 Wt% in toluene) was added to the celestir along with 200 ml of toluene. The solution was allowed to stir for two minutes. Catalyst 1 (949 mg) was dissolved in 50 ml of toluene and added slowly drop by drop to the MAO solution. The reaction mixture was allowed to stir for an hour at room temperature. Then ES70 875 silica (35.2 g) was added to the above mixture and stir for another hour. The solid support was filtered and washed with 200 ml of pentane. Then the supported catalyst was dried under vacuum for 8 hours yield dry support. The supported catalyst was slurried with 10% SonoJell wax.

Procedure of cosupportation of (3,5,5.8,8-pentamethyl-6.7-dihydro-lH-cyclopentalb1naphthalen- 1-yl) Zirconium dichloride (Catalyst 1) and Dimethyl(E5,6,7-tetrahydro-s-indacen-l-yl)(2,3,4,5- tetramethylcyclopentadienyl)silyl)Zirconium dichloride (Catalyst 2a):

[00195] MAO (42.5 g in 30 Wt% in toluene) was added to the celestir along with 200 ml of toluene. The solution was allowed to stir for two minutes. The catalysts, Catalyst 1 (492 mg) and Catalyst 2 (569) were dissolved in 50 ml of toluene and added slowly drop by drop to the MAO solution. The reaction mixture was allowed to stir for an hour at room temperature. Then ES70 875 silica (35.2 g) was added to the above mixture and stir for another hour. The solid support was filtered and washed with 200 ml of pentane. Then the supported catalyst was dried under vacuum for 8 hours yield dry support.

Catalyst 2b: Tetramethylcyclopentadienyldimethylsilyl(3-Benz[e]indenyl)]zirconium dichloride

[00196] Catalyst 2b was synthesized in a manner analogous to the synthesis of Catalyst 2a, with the following resulting compound obtained for use as indicated in Tables IB and 2B below:

Polymerizations:

[00197] PE resins (Examples 1 and 2, as well as Comparative Examples 1-4) were generated in a 6” diameter small gas phase fluidized bed reactor in continuous operation. Tables 1 A and IB list the catalyst or catalyst system used as well as the polymerization conditions employed for examples 1-2, and comparatives 1-4. Table 1A

Table IB

[00198] The PE resins, in granular forms from the gas phase reactor, were dry blended in a tumble mixer with the following additive: 500 ppm of Irganox™-1076, 1,000 ppm of Irgafos™ 168 and 600 ppm of Dynamar™ FX5920A, then compounded on lab scale twin screw extruders (Leistritz 27 or Leistritz 18) under typical PE compounding conditions. The resulting stabilized PE pellets were characterized for QC properties and composition characteristics. Tables 2A and 2B list the product characterization results of examples 1-2 and comparatives 1-5. Comparative Example 5 was obtained as LD103.09, a high-pressure, free-radical LDPE available from ExxonMobil.

Table 2A

Table 2B

[00199] Density testing followed ASTM D1505, column density. Samples were molded under ASTM D4703-10a, Procedure C, then conditioned under ASTM D618-08 (23° ± 2°C and 50±10% Relative Humidity) for 40 hours before testing.

[00200] Melt Index (MI) and High Load Melt Index (HLMI or FI) followed ASTM D-1238 at 190°C under 2.16 kg and 21.6 kg, respectively.

[00201] Rheology characterization employed Small Amplitude Oscillatory Shear testing on a RAS-G2 instrument at 190C at 4 to 6% strain over 0.01 to 626 rad/s frequency range. The resulting data were fitted by Cross equation to obtain viscosity, time and power law constants, Al, A2 and A3. G7G” at 0.1 s'¹ is the ratio of storage to loss modulus at 0.1 s'¹ frequency. Shear Thinning Index STI0.1/100 is the ratio of complex viscosity at 0.1 s'¹ over that at 100 s'¹.

[00202] All comparative and inventive PE samples were fabricated into nominal 1 and/or 2 mil films on a Little Giant blown film line by Cyber Plastic Machinery. It has a 2” general purpose screw with an L/D ratio of 30. There were a total of nine heating zones: four on the extruder, two on the die and one each for the screen changer, adapter and the block zone before the die. Typical temperature (°F) settings were as follows, 300, 350, 355, 340, 350, 355, 360, 370, and 370 for Barrel 1, Barrel 2, Barrel 3, Barrel 4, Screen Changer, Adaptor, Block Zone, Die Zone 1, Die Zone 2, respectively.

Table 3A: Film Fabrication Conditions and Performance Properties of Examples 1-2.

Table 3B; Film Fabrication Conditions and Performance Properties of Comparatives 1-5.

[00203] FIG. 1 is a graph illustrating a GPC of polyethylene copolymers in accordance with various embodiments, including both polymer chain distributions and g’vis values as a function of log(molecular weight).

[00204] FIG. 2 is a graph illustrating a GPC of polyethylene copolymers in accordance with various embodiments, including both molecular weight distributions and comonomer wt% as a function of log(molecular weight). Overall, the processes, catalysts, and films of the present disclosure provide a polyethylene composition formed in a low pressure process to generate LCB polyethylene compositions having extrusion processability like LDPE, but also with good tear properties and Dart impact strength, to match that of mLLDPEs. Such new LLDPEs achieve increased processability with an increased tear balance, increased TD tear, and much better drawdown characteristics, making easier to produce thin gauge films.

[00205] 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.

[00206] 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.

[00207] 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”. 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. [00208] 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 What is claimed is:

1. A catalyst system, comprising: a first catalyst compound, wherein the first catalyst compound is represented by

Formula (I):

M of Formula (I) is a group 4 metal; each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ , R¹¹, R¹² , R¹³ and R¹⁴ of Formula

(I) 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 R¹ and R², R⁴ and R⁵, R⁵ and R⁶, R⁶ and R⁷, R⁹ and R¹⁰, R¹¹ and R¹², R¹² and R¹³, and R¹³ and R¹⁴ are joined to form a substituted or unsubstituted completely saturated ring or a substituted or unsubstituted aromatic ring; wherein at least one of R⁴ and R⁵, R⁵ and R⁶, or R⁶ and R⁷ of Formula (I) are joined to form a first substituted or unsubstituted completely saturated ring fused to the indenyl ring and at least one of R¹¹ and R¹², R¹² and R¹³, or R¹³ and R¹⁴ are joined to form a second substituted or unsubstituted completely saturated ring fused to the indenyl ring; and each X of Formula (I) is independently a halide, a substituted or unsubstituted hydrocarbyl, hydride, amide, substituted or unsubstituted alkoxide, sulfide, 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; and a second catalyst represented by Formula (III):

wherein:

M of Formula (III) is a group 4 metal; each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ of 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 R⁵ and R⁶, R⁷ and R⁸, R⁸ and R⁹, and R⁹ and R¹⁰ are joined to form a substituted or unsubstituted completely saturated ring or a substituted or unsubstituted aromatic ring, wherein at least one of R⁷ and R⁸, R⁸ and R⁹, or R⁹ and R¹⁰ are joined to form a substituted or unsubstituted completely saturated ring fused to the indenyl ring;

T of Formula (III) represents the formula R^a2J, (R^a)4J2, or (R^a)eJ3 wherein each J is independently C, Si, or Ge, and each R^a is independently hydrogen, halide, a substituted or unsubstituted Ci to C40 hydrocarbyl, or two R^a can form a substituted or unsubstituted cyclic structure including a substituted or unsubstituted completely saturated ring or a substituted or unsubstituted aromatic ring; and each X of Formula (III) is independently a halide, a substituted or unsubstituted hydrocarbyl, hydride, amide, substituted or unsubstituted alkoxide, sulfide, 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.

2. The catalyst system of claim 1, wherein the first catalyst compound of Formula (I) is represented by Formula (II):

wherein:

M is a group 4 metal; each of R¹, R², R³, R⁴, R⁷, R⁸, R⁹, R¹⁰ , R¹¹, R¹⁴, R¹⁵, R¹⁵ , R¹⁶, R¹⁶ , R¹⁷, R¹⁷ , R¹⁸, R¹⁸ , R¹⁹, R¹⁹ , R²⁰, R²⁰ , R²¹, R²¹ , R²² , and R²² is independently hydrogen, 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, hydride, amide, substituted or unsubstituted alkoxide, sulfide, phosphide, or a combination thereof, or two of X are joined together to form a substituted or un substituted metallocycle ring, or two of X are joined to form a chelating ligand, a diene ligand, or an alkylidene.

3. The catalyst system of claim 2, wherein Formula (II) is further characterized by one of the following (i), (ii), or (iii):

(i) each X of Formula (II) is halide; each of R³, R¹⁰, R¹⁵, R¹⁵ , R¹⁸, R¹⁸’, R¹⁹, R¹⁹’, R²², and R²² of Formula (II) is independently Ci-Cio alkyl; and each of R¹, R², R⁴, R⁷, R⁸, R⁹, R¹¹, R¹⁴, R¹⁶, R¹⁶ , R¹⁷, R¹⁷ , R²⁰, R²⁰ , R²¹, and R²¹ in Formula (II) is hydrogen;

(ii) each X of Formula (II) is independently Ci - C4 alkyl or halide; each of R¹⁵, R¹³ , R¹⁸, R¹⁸ , R¹⁹, R¹⁹ , R²², and R²² of Formula (II) is independently C1-C10 alkyl; and each of R¹, R², R³, R⁴, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹⁴, R¹⁶, R¹⁶ , R¹⁷, R¹⁷’, R²⁰, R²⁰’, R²¹, and R²¹ ’in Formula (II) is hydrogen; or

(iii) each X of Formula (II) is independently Ci - C4 alkyl; one of R¹, R², and R³ of Formula (II) is C1-C10 alkyl and the remainder of R¹, R², and R³ are each hydrogen; one of R⁸, R⁹, and R¹⁰ of Formula (II) is C1-C10 alkyl and the remainder of R⁸, R⁹, and R¹⁰ are each hydrogen; each of R¹⁵, R¹⁵ , R¹⁸, R¹⁸ , R¹⁹, R¹⁹ , R²², and R²² of Formula (II) is independently C1-C10 alkyl; and each of R⁴, R⁷, R¹¹, R¹⁴, R¹⁶, R¹⁶ , R¹⁷, R¹⁷ , R²⁰, R²⁰ , R²¹, and R²¹ in Formula (II) is hydrogen.

4. The catalyst system of claim 2 or claim 3, wherein each of R¹⁵, R¹⁵ , R¹⁸, R¹⁸ , R¹⁹, R¹⁹ , R²², and R²² in Formula (II) is methyl.

5. The catalyst system of claim 2 or any one of claims 3-4, wherein the first catalyst compound is represented by one of the following structures (Il-a), (Il-b), or (II-c):

(II-c)

6. The catalyst system of any one of the foregoing claims, wherein the second catalyst compound is represented by either of the following structures (Ill-a) or (Ill-b):

7. The catalyst system of claims 5 or 6, further comprising a support material and, optionally, an activator.

8. A process for producing a polyethylene composition, comprising: introducing, under first polymerization conditions, ethylene and a C3-C40 alpha-olefin with the catalyst system of any one of claims 1-7 to a reactor and forming a polyethylene copolymer.:

9. The process of claim 8, wherein the polymerization conditions comprise a reactor pressure within the range from 250 to 350 psig and a reactor temperature within the range from 60°C to 110°C.

10. The process of claim 8 or claim 9, wherein the polyethylene copolymer has a broad orthogonal composition distribution, and furthermore has one or more of the following properties:

(a) a density of about 0.914 g/cm³ to about 0.925 g/cm³;

(b) a melt index of about 0.5 g/lOmin to about 1.5 g/min (190°C, 2.16 kg);

(c) a high load melt index (HLMI) of about 80 g/10 min to about 90 g/10 min (190°C, 21.6 kg);

(d) a melt index ratio (MIR, the ratio of HLMI/MI) of about 60 to about 98;

(e) a molecular weight distribution (MWD) of about 8 to about 10.

11. The process of claim 10, wherein the polyethylene copolymer has all of the properties (a) - (e)-

12. The process of claim 10 or claim 11, wherein the broad orthogonal composition distribution of the polyethylene copolymer is characterized by the polyethylene copolymer having a composition distribution breadth index (CDBI) of about 5 % to about 40 % and/or a T75-T25 value of about 30 to about 40.

13. The process of any one of claims 10-12, wherein the polyethylene copolymer further has a g vis ave value of about 0.7 to about 0.8.

14. The process of any one of claims 10-13, wherein the polyethylene copolymer has an olefin comonomer-derived content of about 10 wt% to about 13 wt%, on the basis of combined mass of olefin comonomer-derived content and ethylene-derived content.

15. The process of any one of claims 10-14, wherein the polyethylene copolymer has a melt index of about 0.8 g/10 min to about 1.1 g/10 min.

16. A polyethylene copolymer, comprising: ethylene-derived units; and a remainder balance of C3-C20 comonomer-derived units; the polyethylene copolymer having: a broad orthogonal composition distribution, a density of about 0.914 g/cm³ to about 0.925 g/cm³, a melt index of about 0.6 g/10 min to about 1.3 g/10 min, an olefin comonomer content of about 10 wt% to about 13 wt%, a high load melt index (HLMI) of about 80 g/10 min to about 90 g/10 min, a melt index ratio (MIR) of about 60 to about 98, and a molecular weight distribution (MWD) of about 8 to about 10.

17. The polyethylene copolymer of claim 15, wherein the polyethylene copolymer has a melt index of about 0.8 g/10 min to about 1.1 g/10 min.

18. The polyethylene copolymer of claims 28 or 29, wherein the polyethylene copolymer has 2- g vis ave value of about 0.7 to about 0.8.

19. A film comprising the polyethylene copolymer of any one of claims 16-18, wherein the film has: an Elmendorf Tear value (MD) of about 150 g/mil to about 180 g/mil, and a Dart Drop Impact of about 140 g/mil to about 160 g/mil.