Catalyst and polymerization for improved polyolefins

Abstract

The present disclosure relates to catalysts, polyethylene polymers, polymerization processes for making such polyethylene polymers, and films made therefrom. In various embodiments, the polymerization process includes dual catalyst polymerization, such as those performed by combining a base metallocene catalyst and a conditioned metallocene catalyst, where the base catalyst may optionally be supported in a first catalyst mixture, such as a solvent, and the conditioning catalyst may be added to the supported base catalyst at different ratios. Polymerization using a combination of a base catalyst and a conditioning catalyst, such as those described herein, can produce linear low density polyethylene copolymers having a medium degree of long chain branching, which can exhibit improved processability in the production of films. Furthermore, films made from such polymers may exhibit improved properties, such as excellent shrinkage.

Description

[0001] Cross-reference to related applications

[0002] This application claims the benefit of U.S. Provisional Application 63 / 503,810, filed May 23, 2023, entitled “Catalysts and Polymerizations for Improved Polyolefins,” the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure relates to catalysts, catalyst systems, and polymerization methods for preparing polyethylene polymers. Background Technology

[0004] Linear low-density polyethylene (LLDPE) is a substantially linear polymer composed of ethylene monomer units and α-olefin comonomer units. The commonly used comonomer units are derived from 1-butene, 1-hexene, or 1-octene. LLDPE can be distinguished from conventional low-density polyethylene (LDPE) in several ways, including their different manufacturing methods. Furthermore, LLDPE has little or no detectable long-chain branching (LCB) / 1,000 carbon atoms, while conventional LDPE contains a relatively high degree of long-chain branching. Long-chain branching provides reduced necking and increased tensile stability during the extrusion process. In addition, LLDPE typically has a narrower molecular weight distribution (MWD) relative to LDPE, especially metallocene-catalyzed LLDPE (“mLLDPE”). LLDPE also exhibits different rheological and mechanical properties compared to LDPE, such as tear properties.

[0005] Although mLLDPEs generally offer superior mechanical properties to existing LDPEs in films and other articles made from them, they are generally more difficult to process than LDPEs. For example, they have lower melt strength (which can affect the stability of membrane bubbles in a variety of film-forming methods and can also lead to melt breakage in films produced at typical commercial extrusion rates – resulting in rough or similar irregularities).

[0006] Therefore, various levels of LDPE have been blended with mLLDPE to increase melt strength, increase shear sensitivity (e.g., improve flow at commercial shear rates in extruders), and reduce the tendency for melt fracture. However, such blending often has a negative impact on the mechanical properties of films made from the polymer. In fact, improving the processability of mLLDPE without sacrificing physical properties has always been challenging.

[0007] Comparing LLDPEs to one another, LLDPEs with higher melt indices are better for processing, and the combination of higher melt index and lower density are particularly good for cast film applications. However, less long chain branching can result in decreased film properties (e.g., tear properties in films / articles made therefrom). In fact, it is challenging to find LLDPEs with a combination of density and melt index while still being commercially processable.

[0008] Some references of interest in this regard include: U.S. 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; WO2022 / 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.

[0009] Overall, there is a need for new LLDPEs with a combination of desirable properties such as density, melt index properties, long chain branching while providing commercially desirable LLDPE polymerization and extrusion. SUMMARY

[0010] The present disclosure relates to catalysts, catalyst systems, and polymerization processes for making polyethylene polymers.

[0011] In some embodiments, the catalyst compound is represented by formula (III):

[0012] (III)

[0013] wherein:

[0014] M is a Group 4 metal;

[0015] R 1 , R 2 , R 3 , R 4 , R5 6 7 8 9 10 each R is independently hydrogen, a substituted or unsubstituted hydrocarbyl group, a substituted or unsubstituted heteroatom, or a substituted or unsubstituted heteroatom-containing group, or two R 5 and R 6 are joined to form a substituted or unsubstituted fully saturated ring or a substituted or unsubstituted aromatic ring; 7 8 8 9 and R 9 and R 10 are joined to form a substituted or unsubstituted fully saturated ring or a substituted or unsubstituted aromatic ring; 5 or at least one of R 6 is independently a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group;

[0016] T is represented by the formula R a 2J, (R a )4J2, or (R a )6J3, wherein each J is independently carbon, silicon, or germanium, and each R a is independently hydrogen, a halide, a substituted or unsubstituted C1to C 40 hydrocarbyl group, and further, two R a may optionally be joined to form a substituted or unsubstituted fully saturated ring or a substituted or unsubstituted partially saturated ring; and

[0017] each X is independently a substituted or unsubstituted hydrocarbyl group, a hydride, an amide, a substituted or unsubstituted alkoxy group, a sulfide, a phosphide, or a combination thereof, or two Xs are joined together to form a substituted or unsubstituted metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene.

[0018] In some embodiments, the catalyst compound is represented by formula (IV):

[0019] (IV)

[0020] wherein:

[0021] M is a Group 4 metal;

[0022] R 1 , R 2 , R 3 , R 4 , R 5 , R​​​​​​​​6 , R 7 , R 8 , R 9 , and R 10 each independently is hydrogen, a substituted or unsubstituted hydrocarbyl, a substituted or unsubstituted heteroatom, or a substituted or unsubstituted heteroatom-containing group, or R 5 and R 6 , R 7 and R 8 , R 8 and R 9 , and R 9 and R 10 join to form a substituted or unsubstituted fully saturated ring or a substituted or unsubstituted aromatic ring, wherein (1) at least one of R 7 and R 8 , (2) at least one of R 8 and R 9 , or (3) at least one of R 9 and R 10 join to form a substituted or unsubstituted fully saturated ring fused to the indenyl ring shown in formula (IV);

[0023] T is represented by the formula R a 2J, (R a )4J2, or (R a )6J3, wherein each J is independently carbon, silicon, or germanium, and each R a is independently hydrogen, a halo group, a substituted or unsubstituted C1to C 40 hydrocarbyl group, or two R a may form a substituted or unsubstituted fully saturated ring, a substituted or unsubstituted partially saturated ring, or a substituted or unsubstituted aromatic ring; and

[0024] each X is independently a substituted or unsubstituted hydrocarbyl, hydride, amide, substituted or unsubstituted alkoxide, sulfide, phosphide, or a combination thereof, or two Xs are joined together to form a substituted or unsubstituted metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene.

[0025] In some embodiments, a method for producing a polyethylene copolymer includes contacting a first composition and a second composition in a line to form a third composition. The first composition includes a contact product of a first diluent, a first catalyst compound, a support material, and an activator. The second composition includes a contact product of a second diluent and a second catalyst compound that is a tuning catalyst of the present disclosure. The method includes introducing the third composition from the line into a gas-phase fluidized bed reactor. The method includes exposing the third composition to polymerization conditions by introducing ethylene and at least one C3-C 20an alpha-olefin is introduced into a gas phase fluidized bed reactor, with ethylene and at least one C3-C 20 polymerization of an alpha-olefin. The method includes obtaining a polyethylene copolymer. BRIEF DESCRIPTION OF DRAWINGS

[0026] In order that the above-recited features of the present application can be understood in detail, a more particular description of the application, some of which implementations will be presented in conjunction with the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this application and therefore are not to be considered limiting of its scope, as the application can admit to other equally effective embodiments.

[0027] Figure 1 is a graph showing 4D GPC (population or mass of polymer chains as a function of Log of molecular weight (Log M)) traces of polyethylene copolymers made using a base catalyst and / or a base catalyst plus tuning catalyst according to various embodiments described herein. The y-axis values of population or mass of polymer chains can be labeled d(wt fraction) / d(Log M) or equivalently MWD(IR) to reflect that the y-axis values are molecular weight population or distribution, but it should be noted that in this context, MWD does not mean Mw / Mn as in other contexts herein. Figure 1 g' values of polyethylene copolymers made using a base catalyst and / or a base catalyst plus tuning catalyst according to various embodiments described herein are also shown on the y-axis thereof. vis ave

[0028] Figure 2 is a graph showing 4D GPC (population or mass of polymer chains as a function of Log of molecular weight (Log M)) traces of polyethylene copolymers made using a base catalyst and / or a base catalyst plus tuning catalyst according to various embodiments described herein. The y-axis values of population or mass of polymer chains can be labeled d(wt fraction) / d(Log M) or equivalently MWD(IR) to reflect that the y-axis values are molecular weight population or distribution, but it should be noted that in this context, MWD does not mean Mw / Mn as in other contexts herein. Figure 2 g' values of polyethylene copolymers made using a base catalyst and / or a base catalyst plus tuning catalyst according to various embodiments described herein are also shown on the y-axis thereof. vis ave

[0029] Figure 3 is a graph showing TREF IR5 overlays of polyethylene copolymers made using a single catalyst and polyethylene copolymers made using a base catalyst plus tuning catalyst according to various embodiments described herein.

[0030] ​​Figure 4 This is a superimposed diagram showing the TREFIR5 of polyethylene copolymers prepared using a single catalyst and polyethylene copolymers prepared using a base catalyst plus a modifier catalyst according to the various embodiments described herein.

[0031] Figure 5 This is a graph showing the pull-out speed of the polymers in the examples relative to force, as well as the pull-out speed of two commercial polyethylenes, LD103.09 and Exceed, relative to force. TM 1018 MA.

[0032] Figure 6 This is a superimposed diagram showing the TREFIR5 of polyethylene copolymers prepared using a single catalyst and polyethylene copolymers prepared using a base catalyst plus a modifier catalyst according to the various embodiments described herein.

[0033] Figure 7 This is a superimposed diagram showing the TREFIR5 superposition of polyethylene copolymers prepared using a single catalyst and polyethylene copolymers prepared using a base catalyst plus a modifier catalyst according to the various embodiments described herein. Detailed Implementation

[0034] Various embodiments and variations of the disclosed compounds, methods, and articles of manufacture will now be described, including specific embodiments and definitions adopted herein. While specific embodiments are given in the following detailed description, those skilled in the art will understand that these embodiments are merely exemplary and that embodiments of this disclosure may be practiced in other ways. Any reference to embodiments may refer to one or more, but not necessarily all, of the compounds, methods, or articles of manufacture as defined in the claims. The use of headings is for convenience only and does not limit the scope of this disclosure.

[0035] This disclosure relates to catalysts, catalyst systems, and polymerization methods for preparing polyethylene polymers. The polyethylene polymers are copolymers formed from dual-catalyst systems, particularly such systems supplied to the polymerization reactor using a "tuning" method. The polyethylene polymers exhibit a combination of low density, low melt index, high melt index ratio, and controllable long-chain branching (introduced via the tuning method), while also providing commercially desirable polymerization and extrusion of polyethylene copolymers.

[0036] In comparison to conventional LLDPEs, the polyethylene copolymers of the present disclosure exhibit increased long chain branching (also referred to as "LCB") in the copolymer, thereby providing reduced neck-in and increased stretch stability. The polyethylene copolymers of the present disclosure can exhibit lower zero shear viscosity, resulting in lower motor torque and lower melt pressure and melt temperature during extrusion, thereby providing increased output of extruded polyethylene copolymer product. Moreover, since the LCB is controlled (tunable, e.g., by adjusting the process), the advantageous tear properties likewise can be controlled (tunable) for the desired polymer end use (e.g., shrink wrap film). For example, due to the increased polymer LCB, a reduction in motor torque and melt pressure can be observed during cast film manufacturing. The LCB can be evidenced by, for example, the ratio of high melt index ratio and / or rheological characteristics (e.g., the ratio of complex viscosities recorded at shear rates of 0.01 and 100 rad / s, respectively) and in Van Gurp Palmen plots (which track the viscosity response of a polymer to applied shear) of the phase angle versus complex modulus) as shown by small angle oscillatory shear (SAOS) experiments. 0.01 / η 100 (0.01 and 100 rad / s, respectively) and in Van Gurp Palmen plots (which track the viscosity response of a polymer to applied shear) of the phase angle versus complex modulus) as shown by small angle oscillatory shear (SAOS) experiments.

[0037] Moreover, it has been found that the polyethylene copolymers of the present disclosure can provide excellent shear thinning characteristics; and moreover can be used to produce blown films with excellent bubble stability and / or little or no melt fracture. In comparison to conventional LLDPEs, the polyethylene copolymers of the present disclosure can further provide films formed at reduced motor load and melt pressure (which increases production throughput) due to the improved flow behavior. For example, a reduction in melt pressure and a reduction in melt temperature can be provided during blown film manufacturing. The films of the present disclosure can be particularly useful as shrink wrap films (improved by the presence of LCB in the polyethylene copolymers of the present disclosure).

[0038] In fact, the catalysts (e.g., for tuning the process) and processes of the present disclosure can facilitate LCB catalyst tuning (e.g., in-line tuning) onto a supported catalyst to, for example, control (tune) the melt index ratio of the polyethylene copolymers formed in the reactor. The catalysts used for tuning can provide different molecular weight capabilities in comparison to, for example, in-line supported catalysts. The different molecular weight capabilities of the catalysts provide a bimodal composition distribution of the polyethylene copolymers formed in the reactor.

[0039] Definitions

[0040] As used herein, "olefin," alternatively referred to as "alkene," is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond. For the purposes of this specification and the accompanying claims, when a polymer or copolymer is referred to as "comprising" an olefin, the olefin present in such polymer or copolymer is in polymeric form. For example, when a copolymer is described as having a 35 wt% to 55 wt% "ethylene" content, it is understood that the monomer units in the copolymer are derived from ethylene in the polymerization reaction, and the derived units are present at 35 wt% to 55 wt% based on the weight of the copolymer.

[0041] 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).

[0042] As used herein, a "polymer" can refer to a homopolymer, copolymer, interpolymer, terpolymer, and the like. A "polymer" has two or more identical or different monomer units. A "homopolymer" is a polymer having identical monomer units. A "copolymer" is a polymer having two or more different monomer units from one another. A "terpolymer" is a polymer having three different monomer units from one another. The term "different" used in reference to monomer units indicates that the monomer units differ from one another by at least one atom or are isomerically different. Thus, as used herein, the definition of copolymer includes terpolymer and the like. Likewise, as used herein, the definition of polymer includes copolymer and the like.

[0043] As used herein, an ethylene polymer having a density greater than 0.860 to less than 0.910 g / cm 3 is referred to as an ethylene plastomer or plastomer; an ethylene polymer having a density of 0.910 to 0.925 g / cm 3 is referred to as a "linear low density polyethylene" (LLDPE) when substantially linear (having small or no long chain branches), as typically for Ziegler-Natta or metallocene-catalyzed PE, or a "highly branched low density polyethylene" (LDPE) when significantly branched (having a high level of long chain branching), as typically for free-radically polymerized PE; 0.925 to 0.940 g / cm 3 is referred to as a "medium density polyethylene" (MDPE); and having a density greater than 0.940 g / cm 3Ethylene polymers having a density of 0.94 g / cm3 or greater are referred to as "high density polyethylene" (HDPE). Density is determined according to ASTM D792. Test specimens are prepared according to ASTM D4703 - Appendix 1 Procedure C, followed by conditioning according to ASTM D618 - Procedure A, prior to testing.

[0044] As used herein and unless otherwise indicated, the term "hydrocarbon" means a class of compounds containing hydrogen bound to carbon, and includes (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated or unsaturated), including mixtures of hydrocarbon compounds having different n values.

[0045] As used herein, a composition or film that is "free of" a component means a composition / film that is essentially free of the component, or that contains the component in an amount less than about 0.01 wt% of the total composition by weight.

[0046] As used herein, the term "polymerization conditions" refers to conditions that favor reaction of one or more olefin monomers to produce a polyolefin polymer upon contact with an activated olefin polymerization catalyst, including the skilled artisan's selection of temperature, pressure, reactant concentrations, optional solvent / diluent, reactant mixing / addition parameters, and other conditions within at least one polymerization reactor.

[0047] For the sake of brevity, only certain ranges are explicitly disclosed herein. However, from any lower limit of a range, any and every higher limit of that range is also a lower limit of a disclosed range, and the same applies to the upper limits of the ranges. Moreover, "in a range" or "within a range" includes every point or individual value within the range, even if not explicitly stated, and includes the endpoints of the range. Thus, each point or individual value can be combined with any other point or individual value, or with any other lower limit or upper limit, to recite a range not explicitly disclosed.

[0048] For the purposes of the present disclosure, the numbering scheme of the Periodic Table Groups is used as reproduced below:

[0049] The following abbreviations can be used herein: Me is methyl, Et is ethyl, Ph is phenyl, tBu is tert-butyl, PDI is polydispersity index, MAO is methylaluminoxane, SMAO is supported methylaluminoxane, NMR is nuclear magnetic resonance, ppm is parts per million, THF is tetrahydrofuran.

[0050] As used herein, one or more olefin polymerization catalyst refers to any catalyst, such as an organometallic complex or compound capable of coordination polymerization addition, in which successive monomers are added in a monomer chain at an organometallic active center.

[0051] The terms "substituent," "radical," "group," and "moiety" are used interchangeably.

[0052] The term "alpha-olefin" refers to an olefin having a terminal carbon-carbon double bond in its structure ((R ” R ’’’ )-C=CH2, where R ” and R ’’’ can independently be hydrogen or any hydrocarbyl group; such as R ” is hydrogen and R ’’’ is an alkyl group. A "linear alpha-olefin" is an alpha-olefin as defined in this paragraph, where R ” is hydrogen and R ’’’ is hydrogen or a linear alkyl group.

[0053] For the purposes of the present disclosure, ethylene shall be considered an alpha-olefin.

[0054] As used herein, and unless otherwise specified, the term "C n " means a hydrocarbon(s) having n carbon atom(s) per molecule, where n is a positive integer. The term "hydrocarbon" means a class of compounds containing hydrogen bound to carbon, and includes (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 n values. Likewise, a "C m -C y " group or compound refers to a group or compound comprising a total number of carbon atoms from m to y. Thus, a C1-C 50 alkyl group refers to an alkyl group comprising a total number of carbon atoms from about 1 to about 50.

[0055] Unless otherwise indicated, the term "substituted" means that at least one hydrogen atom has been replaced by at least one non-hydrogen group, such as a hydrocarbyl group, a heteroatom, or a heteroatom-containing group, such as a halo group (such as Br, CI, 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 group, and two or more R* can 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.

[0056] The term "substituted hydrocarbyl" means a hydrocarbyl group in which at least one hydrogen atom of the hydrocarbyl group has been replaced by at least one heteroatom, such as a halo group (e.g., Br, CI, F, or I) or a 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, etc., where each R* is independently a hydrocarbyl or halocarbyl group, and two or more R* can 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.

[0057] The term "substituted aromatic compound" means an aromatic group in which one or more hydrogen groups are replaced by a hydrocarbyl group, a substituted hydrocarbyl group, a heteroatom, or a heteroatom-containing group.

[0058] The terms "hydrocarbyl radical," "hydrocarbyl group," or "hydrocarbyl" can be used interchangeably and are defined to mean a group comprising only hydrogen and carbon atoms. For example, a hydrocarbyl group can be a C1-C 100 groups, which can be linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic. Examples of such groups can include, but are not limited to, alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, pentyl, i-pentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and aryl groups such as phenyl, benzyl, naphthyl.

[0059] The term "alkoxy" or "alkoxide" means an alkyl or aryl group bonded to an oxygen atom, such as an alkyl or aryl ether group / radical attached to an oxygen atom, and can include where the aryl / alkyl group is a Ci to C 10 Those of hydrocarbyl. Alkyl groups can be linear, branched, or cyclic. Alkyl groups can be saturated or unsaturated. Examples of suitable alkoxyl groups can include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, t-butoxy, phenoxy.

[0060] The term "alkenyl" means a linear, branched, or cyclic hydrocarbon group having one or more double bonds. These alkenyl groups can be optionally substituted. Examples of suitable alkenyl groups can include ethenyl, propenyl, allyl, 1,4-butadienyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, including substituted analogs thereof.

[0061] The terms "alkyl radical," "alkyl group," and "alkyl" are used interchangeably throughout this disclosure. For purposes of this disclosure, "alkyl" is defined to be a Ci-Ci2 100 alkyl groups. Examples of such groups can include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t-butyl, pentyl, iso-pentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, including substituted analogs thereof. Some examples of alkyl groups can include 1-methylethyl, 1-methylpropyl, 1-methylbutyl, 1-ethylbutyl, 1,3-dimethylbutyl, 1-methyl-1-ethylbutyl, 1,1-diethylbutyl, 1-propylpentyl, 1-phenylethyl, iso-propyl, 2-butyl, sec-pentyl, sec-hexyl, and the like.

[0062] The term "aryl" or "aryl group" means an aromatic ring and substituted variants thereof, such as phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl. Likewise, "heteroaryl" means an aryl group in which 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 heterocyclic rings, which are heterocyclic substituents that have similar properties and structure (nearly planar) to aromatic heterocyclic ligands, but by definition are not aromatic; likewise, the term aromatic also refers to substituted aromatic compounds.

[0063] In the presence of isomers of named alkyl, alkenyl, alkoxy, or aryl groups (e.g., n-butyl, iso-butyl, sec-butyl, and t-butyl), a reference to an alkyl, alkenyl, alkoxy, or aryl group without specifying a particular isomer (e.g., butyl) expressly discloses all isomers (e.g., n-butyl, iso-butyl, sec-butyl, and t-butyl).

[0064] The term "ring atom" means an atom that is part of a cyclic ring structure. In terms of this definition, a benzyl group has six ring atoms, and tetrahydrofuran has five ring atoms.

[0065] A heterocycle is a ring with heteroatoms in the ring structure, as opposed to a heteroatom-substituted ring in which a hydrogen on a ring atom is replaced by a heteroatom. For example, tetrahydrofuran is a heterocycle, while 4-N,N-dimethylamino-phenyl is a heteroatom-substituted ring. Other examples of heterocycles can include pyridine, imidazole, and thiazole.

[0066] As used herein, Mn is number average molecular weight, Mw is weight average molecular weight, and Mz is z average molecular weight, wt% is weight percent, and mol% is mole percent. Molecular weight distribution (MWD), also referred to as polydispersity (PDI), is defined to be Mw divided by Mn. Unless otherwise indicated, all molecular weight units (e.g., Mw, Mn, Mz) are g / mol.

[0067] The terms "catalyst compound," "catalyst complex," "transition metal complex," "transition metal compound," "precatalyst compound," and "precatalyst complex" are used interchangeably.

[0068] A "catalyst system" is a combination of at least one catalyst compound, optionally at least one activator, an optional co-activator, and an optional support material. When a "catalyst system" is used to describe this pairing prior to activation, it is meant to be the unactivated catalyst complex (precatalyst) together with the activator and optionally a co-activator. When it is used to describe this pairing after activation, it is meant to be the activated complex and the activator or other charge- balancing moieties. The catalyst compound can be neutral as in a precatalyst, or charged as in an activated catalyst system with a counterion. For the purposes of the present disclosure and its claims, where a catalyst system is described as including a component, it is understood that the ion form of the component is what is used as the catalyst system, e.g., as is typical for purposes of its use in polymerization reactions. A polymerization catalyst system is a catalyst system that can polymerize monomers into polymers. Furthermore, catalyst compounds and activators represented by formulas herein are intended to include both neutral and ionic forms of the catalyst compounds and activators.

[0069] An "anionic ligand" is a negatively charged ligand that donates one or more pairs of electrons to a metal ion. A "Lewis base" or "neutral donor ligand" is a charge neutral ligand that donates one or more pairs of electrons to a metal ion. Examples of Lewis bases include diethyl ether, trimethylamine, pyridine, tetrahydrofuran, dimethyl sulfide, and triphenylphosphine. The term "heterocyclic Lewis base" refers to a Lewis base that is also a heterocycle. Examples of heterocyclic Lewis bases include pyridine, imidazole, thiazole, and furan.

[0070] A scavenger is a compound that can be added to facilitate polymerization by scavenging impurities. Some scavengers can also act as activators and can be referred to as co-activators. Non- scavenger co-activators can also be used in conjunction with activators in order to form an active catalyst. In at least one embodiment, a co-activator can be pre-mixed with a transition metal compound to form an alkylated transition metal compound.

[0071] The term "continuous" means a system that operates without interruption or stoppage for an extended period of time. For example, a continuous process to produce a polymer would be one in which reactants are continuously introduced into one or more reactors and a polymer product is continuously withdrawn.

[0072] Solution polymerization means a polymerization process in which the polymer is dissolved in a liquid polymerization medium, such as an inert diluent or one or more monomers or a blend thereof. Solution polymerization can be homogeneous. Homogeneous polymerization is polymerization in which the polymer product is dissolved in the polymerization medium. Suitable systems can not be hazy, as described in J. Vladimir Oliveira, C. Dariva, and J. C. Pinto, Ind. Eng. Chem. Res., 2000, Vol. 29, p. 4627.

[0073] Bulk polymerization means a polymerization process in which the polymerized monomer and or comonomer is used as a solvent or diluent, with little or no inert solvent used as a solvent or diluent. Small fractions of inert solvent / diluent can be used as a carrier for the catalyst and scavenger. Bulk polymerization systems contain 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%.

[0074] The term "single catalyst compound" refers to a catalyst compound that corresponds to a single structural formula, although such a catalyst compound can comprise and be used as a mixture of isomers (e.g., stereoisomers).

[0075] A catalyst system utilizing a single catalyst compound means a catalyst system prepared using only a single catalyst compound in the preparation of the catalyst system. Thus, such a catalyst system is distinguished from, for example, a "dual" catalyst system, which is prepared using two catalyst compounds having different structural formulas, e.g., the connectivity between atoms, the number of atoms, and / or the type of atoms is different in the two catalyst compounds. Thus, one catalyst compound is considered different from another if it differs in at least one of the number, type, or connectivity of atoms. For example, bisindenyl zirconium dichloride is different from (indenyl)(2-methylindenyl)zirconium dichloride, which is different from (indenyl)(2-methylindenyl)hafnium dichloride. Catalyst compounds that differ only in that they are stereoisomers of one another are not considered to be different catalyst compounds. For example, rac-dimethylsilyl bis(2-methyl-4-phenyl)dimethylhafnium and meso-dimethylsilyl bis(2-methyl-4-phenyl)dimethylhafnium are not considered to be different.

[0076] The terms "cocatalyst" and "activator" are used interchangeably herein, and are defined to be any compound which can activate any of the catalyst compounds described above by converting the neutral catalyst compound into a catalytically active catalyst compound cation.

[0077] Polymerization process

[0078] The polymerization process can include a gas phase polymerization reaction, and in particular, a fluidized bed gas phase polymerization reaction. Generally, in a fluid gas bed process for producing a polymer, a gaseous stream containing one or more monomers is continuously circulated through a fluidized bed in the presence of a catalyst under reactive conditions. In some embodiments, the reaction medium includes a condensing agent, which is typically a non-coordinating, inert liquid that is converted to a gas in the polymerization process, 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 polymerized monomer. (See, for example, U.S. Patent Nos. 4,543,399; 4,588,790; 5,028,670; 5,317,036; 5,352,749; 5,405,922; 5,436,304; 5,453,471; 5,462,999; 5,616,661; and 5,668,228; all of which are incorporated herein by reference.) The gas phase polymerization can be conducted in any suitable reactor system (e.g., stirred or paddle reactor systems). For a discussion of suitable gas phase fluidized bed polymerization systems, see U.S. Patent 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, which are incorporated herein by reference.

[0079] In such polymerization processes, a gas phase fluidized bed process is conducted by continuously passing a stream containing ethylene and olefin comonomer through a fluidized bed reactor under reaction conditions and in the presence of a catalyst composition at a rate sufficient to maintain a solid particulate bed in a suspended state. A stream containing unreacted ethylene and olefin comonomer, which can be referred to as a “cycle gas” stream, is continuously withdrawn from the reactor, compressed, cooled, optionally partially or completely condensed, and recycled back to the reactor. The produced polyethylene copolymer is withdrawn from the reactor and replacement ethylene and olefin comonomer is added to the recycle stream. In some embodiments, a gas inert to the catalyst composition and reactants is present in the gas stream.

[0080] The cycle gas can include an induced condensing agent (ICA). An ICA is one or more non-reactive alkanes that are condensable in the polymerization process for removing heat of reaction. In some embodiments, the non-reactive alkanes are selected from one or more of C1-C6 alkanes, for example, propane, butane, isobutane, pentane, isopentane, hexane, and isomers thereof and derivatives thereof. In some cases, a mixture of two or more such ICAs can be particularly useful (e.g., propane and pentane, propane and butane, butane and pentane, etc.).

[0081] The reactor pressure during polymerization can be from about 100 psig (680 kPag) to about 500 psig (3448 kPag), such as from about 200 psig (1379 kPag) to about 400 psig (2759 kPag), such as from about 250 psig (1724 kPag) to about 350 psig (2414 kPag). In some embodiments, the reactor is operated at a temperature from about 60 °C to about 120 °C, such as from about 60 °C to about 115 °C, such as from about 70 °C to about 110 °C, such as from about 70 °C to about 95 °C, such as from about 80 °C to about 90 °C. The ratio of hydrogen to ethylene can be from about 10 to about 30 ppm / mol%, such as from about 15 to about 25 ppm / mol%, such as from about 16 to about 20 ppm / mol%.

[0082] The mole percent of ethylene (based on total monomer) can be from about 25 to about 90 mole percent, such as from about 50 to about 90 mole percent, or from about 70 to about 85 mole percent, and the ethylene partial pressure (in the reactor) can be from about 75 psia (517 kPa) to about 300 psia (2069 kPa), or from about 100 psia to about 275 psia (689-1894 kPa), or from about 150 psia to about 265 psia (1034-1826 kPa), or from about 180 psia to about 200 psia. The ethylene concentration in the reactor can also be from about 35 mol% to about 95 mol%, such as in a range from a low value of 35 mol%, 40 mol%, 45 mol%, 50 mol%, or 55 mol% to a high value of 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol%, or 95 mol%, and further wherein the ethylene mol% is measured based on the total moles of gas in the reactor (including ethylene and / or comonomer gas, if present, and inert gas, such as nitrogen, isopentane, or one or more of other ICAs, etc.); as with the vol-ppm hydrogen, this measurement can be made in the recycle gas outlet rather than in the reactor itself. The comonomer concentration can be from about 0.2 mol% to about 1 mol%, such as a low value of 0.2 mol%, 0.3 mol%, 0.4 mol%, or 0.5 mol% to a high value of 0.65 mol%, 0.70 mol%, 0.75 mol%, 0.80 mol%, 0.85 mol%, 0.90 mol%, 0.95 mol%, or 1.0 mol%.

[0083] Polymerization using adjustments

[0084] The polymerization processes of the present disclosure can be conducted using a “tuning” process. Tuning processes are described in, for example, U.S. Patent Publication No. 2021 / 0395404, especially in connection with the Figure 1 and at paragraphs

[0113] -

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

[0085] For delivery of catalyst slurry to a reactor, high solids concentration of the slurry generally increases the slurry viscosity. High solids concentration also increases the amount of foaming generally generated in the catalyst slurry vessel. High slurry viscosity and foaming can cause handling, storage, and reactor injection problems. A low viscosity diluent can be added to the slurry to reduce the viscosity. However, the reduced viscosity promotes settling of the slurry in solution, which can cause plugging of reactor components and accumulation of solids on the catalyst slurry vessel walls.

[0086] A second catalyst solution can be added (i.e., “tuned”) to the slurry to adjust one or more properties of the polymer formed in the reactor “in situ.” Such “tuning” processes are very economical because they do not require polymerization to stop in order to adjust polymer properties in the event that the catalyst system is not performing in the desired manner. However, the second catalyst is typically delivered to the slurry as a low viscosity solution, which can promote settling of the slurry solution and subsequent gelling and / or plugging of reactor components.

[0087] Accordingly, a process for polymerizing one or more olefins can include using a dual catalyst system (e.g., by in situ loading of a second catalyst). In particular, the process includes combining a catalyst component slurry with a catalyst component solution (to “tune”) to form a third catalyst composition, and introducing the third composition into a polymerization reactor (e.g., a gas phase reactor).

[0088] In some embodiments, the process includes contacting a first composition with a second composition in a line leading to a reactor to form a third composition. The first composition includes a first catalyst (or catalyst compound), a support, and a diluent. The first catalyst or catalyst compound can be referred to herein as a “primary catalyst” or “base catalyst.” The second composition includes a second catalyst (or catalyst compound) and a second diluent. The second catalyst or catalyst compound can be referred to as a “tuning catalyst,” particularly in the context of the processes described herein, tuning processes are preferably used to adjust the ratio of the first catalyst to the second catalyst by increasing or decreasing the relative amount of the tuning catalyst to the primary catalyst. The process includes introducing the third composition from the line into a gas phase fluidized bed reactor, and exposing the third composition to polymerization conditions. The process includes obtaining a polyolefin.

[0089] The method can include adjusting reactor conditions, such as the amount of second catalyst fed to the reactor (via a line leading to the reactor), to control one or more polymer properties of the polyolefin obtained from the reactor.

[0090] By using the metallocene catalysts of the present disclosure as the second catalyst, which is adjusted on-line to the slurry of the first catalyst in various ratios, and vice versa, as well as different reactor conditions (including temperature, reaction mixture component concentrations, etc.), beneficial polyolefin products can be formed.

[0091] Further, it is also contemplated that some of the second catalyst can be initially co-deposited with the first catalyst on a common support, and the remaining amount of either the first catalyst or the second catalyst is added as an adjuster, for the different catalysts selected.

[0092] The catalyst system can include a catalyst compound in a slurry and an added solution catalyst component added to the slurry. Typically, the first catalyst and / or the second catalyst will be supported in the initial slurry, depending on solubility. However, in at least one embodiment, the initial catalyst component slurry can not have a catalyst. In that case, two or more solution catalysts can be added to the slurry as "adjusters" to be supported.

[0093] Further, although a distinction between the "primary catalyst" or "base catalyst" and the "adjustment catalyst" as noted above, it is contemplated that the role of the primary catalyst described herein can be readily exchanged with the adjustment catalyst to achieve a similar effect (i.e., any "primary catalyst" described herein can be used as a "second catalyst" in the just described method; and any "adjustment catalyst" can be used as a "first catalyst" in the just described method, in various embodiments).

[0094] The slurry can include one or more activators and a support, as well as one or more catalyst compounds. For example, the slurry can include two or more activators (such as aluminoxane and modified aluminoxane) and a catalyst compound, or the slurry can contain a supported activator and more than one catalyst compound. In at least one embodiment, the slurry contains a support, an activator, and two catalyst compounds. In another embodiment, the slurry contains a support, an activator, and two different catalyst compounds, which can be added to the slurry individually or in combination. A slurry containing silica and aluminoxane can be contacted with a catalyst compound, reacted, and thereafter the slurry is contacted with another catalyst compound (e.g., as an "adjustment").

[0095] One or more diluents can be used to facilitate the combination of any two or more components of the catalyst system in a slurry or in conditioning the catalyst solution. For example, the single site catalyst compound and activator can be combined together in the presence of toluene or another non-reactive hydrocarbon or mixture of hydrocarbons to provide a catalyst mixture. Other suitable diluents can include, but are not limited to, ethylbenzene, xylene, pentane, hexane, heptane, octane, other hydrocarbons, or any combination thereof, in addition to toluene. The support, either dry or mixed with toluene, can then be added to the catalyst mixture, or the catalyst / activator mixture can be added to the support.

[0096] The diluent can be or include a mineral oil. The mineral oil can have a density of about 0.85 g / cm3to about 0.9 g / cm3at 25 °C, such as about 0.86 g / cm3to about 0.88 g / cm3, according to ASTM D4052. The mineral oil can have a kinematic viscosity of about 150 cSt to about 200 cSt, such as about 160 cSt to about 190 cSt, such as about 170 cSt at 25 °C, according to ASTM D341. The mineral oil can have an average molecular weight of about 400 g / mol to about 600 g / mol, such as about 450 g / mol to about 550 g / mol, such as about 500 g / mol, according to ASTM D2502. In at least one embodiment, the mineral oil is HYDROBRITE® 380 PO White Mineral Oil (“HB380”) from Sonneborn, LLC. 3 3 3 3 The diluent can be or include a mineral oil. The mineral oil can have a density of about 0.85 g / cm3to about 0.9 g / cm3at 25 °C, such as about 0.86 g / cm3to about 0.88 g / cm3, according to ASTM D4052. The mineral oil can have a kinematic viscosity of about 150 cSt to about 200 cSt, such as about 160 cSt to about 190 cSt, such as about 170 cSt at 25 °C, according to ASTM D341. The mineral oil can have an average molecular weight of about 400 g / mol to about 600 g / mol, such as about 450 g / mol to about 550 g / mol, such as about 500 g / mol, according to ASTM D2502. In at least one embodiment, the mineral oil is HYDROBRITE® 380 PO White Mineral Oil (“HB380”) from Sonneborn, LLC. ® 380 PO White Mineral Oil (“HB380”) from Sonneborn, LLC.

[0097] The diluent can additionally include a wax, which can provide increased viscosity to the slurry, such as a mineral oil slurry. The wax is a food grade petrolatum, also known as petroleum jelly. The wax can be a paraffin wax. The paraffin wax includes SONO JELL® 4 and SONO JELL® 5 from Sonneborn, LLC. ® ® ® ​​​​​9. In at least one embodiment, the slurry has 5 wt% or more, such as 10 wt% or more, such as 25 wt% or more, such as 40 wt% or more, such as 50 wt% or more, such as 60 wt% or more, such as 70 wt% or more of a wax. For example, a mineral oil slurry can have about 70 wt% mineral oil, about 10 wt% wax, and about 20 wt% of one or more supported catalysts (e.g., supported dual catalysts). The increased viscosity provided by the wax in the slurry (such as a mineral oil slurry) provides for reduced settling of the one or more supported catalysts in the conditioning vessel or catalyst pot (used to introduce the supported catalyst into the line); while conditioning efficiency can be suitably maintained. In at least one embodiment, the wax has a density of about 0.7 g / cm 3 at 100°C to about 0.95 g / cm 3 at 100°C, such as about 0.75 g / cm 3 at 100°C to about 0.87 g / cm 3 at 100°C. The wax can have a kinematic viscosity of about 5 mm 2 / s at 100°C to about 30 mm 2 / s at 100°C. The wax can have a boiling point of about 200°C or more, such as about 225°C or more, such as about 250°C or more. The wax can have a melting point of about 25°C to about 100°C, such as about 35°C to about 80°C.

[0098] The catalyst component solution (referred to as a "conditioning" solution) can include only one or more catalyst compounds or can include an activator. In at least one embodiment, the one or more catalyst compounds in the catalyst component solution are non-supported. The catalyst solution used in the conditioning process can be prepared by dissolving the catalyst compound(s) and optional activator in a liquid diluent. The liquid diluent can be an alkane, such as a C5to C 30 alkane, or a C5to C 10 alkane. Cyclic alkanes such as cyclohexane and aromatic compounds such as toluene can also be used. Mineral oil is used as an alternative or in addition to other alkanes such as C5to C 30 alkanes as a diluent. The mineral oil can have a density of about 0.85 g / cm 3 to about 0.9 g / cm 3 at 25°C according to ASTM D4052, such as about 0.86 g / cm 3 to about 0.88 g / cm 3density. The mineral oil can have a kinematic viscosity at 25°C of about 150 cSt to about 200 cSt, such as about 160 cSt to about 190 cSt, such as about 170 cSt, according to ASTM D341. The mineral oil can have an average molecular weight of about 400 g / mol to about 600 g / mol, such as about 450 g / mol to about 550 g / mol, such as about 500 g / mol, according to ASTM D2502. In at least one embodiment, the mineral oil is HYDROBRITE ® 380 PO White Mineral Oil (“HB380”).

[0099] The solution used should be a liquid and relatively inert under the polymerization conditions. In at least one embodiment, the liquid utilized in the catalyst compound solution is different than the diluent used in the catalyst component slurry. In another embodiment, the liquid utilized in the catalyst compound solution is the same as the diluent used in the catalyst component solution.

[0100] In alternative embodiments, the catalyst is not limited to a slurry arrangement, as the mixed catalyst system can be prepared on a support and dried. The dried catalyst system can then be fed to the reactor through a dry feed system.

[0101] In gas phase polyethylene production processes, it can be desirable to use one or more static control agents to help regulate the level of static in the reactor. As used herein, a static control agent is a chemical composition that can influence or drive the static charge (negative, positive, or zero) in the fluidized bed when introduced into the fluidized bed reactor. The particular static control agent used can depend on the nature of the static charge, and the selection of the static control agent can vary depending on the polymer produced and the single site catalyst compound used.

[0102] A control agent such as aluminum stearate can be used. The static control agent used can be selected for its ability to receive the static charge in the fluidized bed without adversely affecting production rates. Other suitable static control agents can also include aluminum distearate, ethoxylated amines, and antistatic compositions.

[0103] Primary Catalyst

[0104] The catalyst employed in the polymerization of the present disclosure can be a metallocene catalyst. Metallocene catalysts are well described, for example, at paragraphs

[0066] -

[0083] of US2021 / 0395404, which description is incorporated herein by reference. Any metallocene catalyst according to this description can be suitable as the primary catalyst in the systems and methods described herein. Of particular interest are metallocene catalysts having bridged or unbridged, cyclopentadienyl (Cp) and / or indenyl (In) ligands bound to at least one Group 3 to Group 12 metal atom (preferably Zn, Hf, or Ti), and one or more (preferably two) leaving groups bound to the at least one metal atom (preferably wherein each leaving group is independently a Ci to C4alkyl such as methyl, or a halide such as Cl).

[0105] More particularly, the primary catalyst according to various embodiments can comprise an unbridged hafnocene or zirconocene, such as the hafnocene described at column 3, line 62 to column 4, line 51 of U.S. Patent No. 7,078,467, which description is incorporated herein by reference, and its zirconocene analog; and / or the catalyst described at column 4, line 22 to column 7, line 36 of U.S. Patent No. 6,936,675, which description is also incorporated herein by reference. For example, suitable primary catalysts can include unbridged bis-indenyl hafnium or zirconium complexes, such as one or more of:

[0106] bis(n-ethylcyclopentadienyl)Zr(CH3)2,

[0107] bis(n-ethylcyclopentadienyl)ZrCl2,

[0108] bis(n-ethylcyclopentadienyl)Hf(CH3)2,

[0109] bis(n-ethylcyclopentadienyl)HfCl2,

[0110] (n-ethylcyclopentadienyl, pentamethylcyclopentadienyl)ZrCl2,

[0111] (n-ethylcyclopentadienyl, pentamethylcyclopentadienyl)Zr(CH3)2,

[0112] (n-ethylcyclopentadienyl, pentamethylcyclopentadienyl)HfCl2,

[0113] (n-ethylcyclopentadienyl, pentamethylcyclopentadienyl)Hf(CH3)2,

[0114] bis(n-propylcyclopentadienyl)Zr(CH3)2,

[0115] bis(n-propylcyclopentadienyl)ZrCl2,

[0116] bis(n-propylcyclopentadienyl)Hf(CH3)2,

[0117] bis(n-propylcyclopentadienyl)HfCl2,

[0118] (n-propylcyclopentadienyl, pentamethylcyclopentadienyl)ZrCl2,

[0119] (n-propylcyclopentadienyl, pentamethylcyclopentadienyl)Zr(CH3)2,

[0120] (n-propylcyclopentadienyl, pentamethylcyclopentadienyl)HfCl2,

[0121] (n-propylcyclopentadienyl, pentamethylcyclopentadienyl)Hf(CH3)2,

[0122] bis(n-butylcyclopentadienyl)Zr(CH3)2,

[0123] bis(n-butylcyclopentadienyl)ZrCl2,

[0124] bis(n-butylcyclopentadienyl)Hf(CH3)2,

[0125] bis(n-butylcyclopentadienyl)HfCl2,

[0126] (n-butylcyclopentadienyl, pentamethylcyclopentadienyl)ZrCl2,

[0127] (n-butylcyclopentadienyl, pentamethylcyclopentadienyl)Zr(CH3)2,

[0128] (n-butylcyclopentadienyl, pentamethylcyclopentadienyl)HfCl2,

[0129] (n-butylcyclopentadienyl, pentamethylcyclopentadienyl)Hf(CH3)2,

[0130] or combinations thereof.

[0131] In yet other embodiments, the primary catalyst can be a bridged metallocene catalyst, such as those described in one or more of US 5,314,973; US 6,255,426 (especially at col. 2, line 61 to col. 3, line 17, which description is incorporated herein by reference); and US 5,763,543 (especially at col. 2, line 42 to col. 4, line 22, which description is incorporated herein by reference). Specific examples include bridged bis-indenyl catalysts, such as bridged bis-indenyl zirconocene or bridged bis-indenyl hafniumocene, particularly those in which each indenyl ligand is unsubstituted (e.g., is a tetrahydroindenyl ligand), and in which the bridge is a C1 - C 10alkyl or R1R2Si, where each of R1and R2is independently selected from the group consisting of methyl, ethyl, propyl, butyl, and pentyl. Examples of such bridged bisindenyl hafnium and zirconium complexes can include (CH3)2Si(4,5,6,7-tetrahydroindenyl)2Zr(CH3)2, (CH3)2Si(4,5,6,7-tetrahydroindenyl)2ZrCl2, (CH2CH3)2Si(4,5,6,7-tetrahydroindenyl)2Zr(CH3)2, (CH2CH3)2Si(4,5,6,7-tetrahydroindenyl)2ZrCl2, ((CH3)2Si)2(4,5,6,7-tetrahydroindenyl)2Zr(CH3)2, ((CH3)2Si)2(4,5,6,7-tetrahydroindenyl)2ZrCl2, (CH3)2Si(4,5,6,7-tetrahydroindenyl)2Hf(CH3)2, (CH3)2Si(4,5,6,7-tetrahydroindenyl)2HfCl2, (CH2CH3)2Si(4,5,6,7-tetrahydroindenyl)2Hf(CH3)2, (CH2CH3)2Si(4,5,6,7-tetrahydroindenyl)2HfCl2, ((CH3)2Si)2(4,5,6,7-tetrahydroindenyl)2Hf(CH3)2, ((CH3)2Si)2(4,5,6,7-tetrahydroindenyl)2HfCl2, or combinations thereof.

[0132] While the catalyst compounds can be written or shown with methyl-, chloro-, or phenyl- leaving groups attached to the central metal, it can be understood that these groups can be different. For example, each of these ligands can independently be a benzyl (Bn), methyl (Me), chloro group (Cl), fluoro group (F), or any number of other groups, including organic groups, or heteroatom groups. Further, these ligands will change during the reaction as the precatalyst is converted to the active catalyst to carry out the reaction.

[0133] Second catalyst (e.g., “tune” catalyst)

[0134] The second catalyst of the present disclosure includes a second catalyst that is loaded onto a support along with the first catalyst to form a dual catalyst system. The second catalyst can be loaded and the dual catalyst system can be isolated. Alternatively, the second catalyst can be loaded as a “tune” catalyst on the supported first catalyst on-line in its way to the reactor. The dual catalyst system (e.g., also with an activator) is introduced into a reactor (e.g., a gas phase reactor).

[0135] In some embodiments, the second catalyst is represented by formula (III):

[0136] (III)

[0137] wherein:

[0138] M is a Group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf);

[0139] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 each independently is hydrogen, a substituted or unsubstituted hydrocarbyl, a substituted or unsubstituted heteroatom, or a substituted or unsubstituted heteroatom-containing group; optionally, one or more pairs of R 5 and R 6 , R 7 and R 8 , R 8 and R 9 , and R 9 and R 10 may join to form a substituted or unsubstituted fully saturated ring or a substituted or unsubstituted aromatic ring, and further at least one pair of R 5 and R 6 independently is a substituted or unsubstituted aryl or a substituted or unsubstituted heteroaryl;

[0140] T represents the formula R a 2J, (R a )4J2, or (R a )6J3, wherein each J independently is C, Si, or Ge, and each R a independently is hydrogen, a halo group, a substituted or unsubstituted C1to C 40 hydrocarbyl group, and wherein two R a groups optionally can join to form a substituted or unsubstituted cyclic structure, including a substituted or unsubstituted fully saturated ring, or a substituted or unsubstituted partially saturated ring (preferably, such ring structure has 2 - 10 carbon atoms in addition to the J atoms, and further the ring structure is preferably saturated); and

[0141] each X independently is a halo group, a substituted or unsubstituted hydrocarbyl group, a hydride group, an amide group, a substituted or unsubstituted alkoxy group, a sulfide group, a phosphide group, or a combination thereof, or two Xs join together to form a substituted or unsubstituted metallocycle ring, or two Xs join to form a chelating ligand, a diene ligand, or an alkylidene;

[0142] wherein at least one of R 5 or R 6 independently is a substituted or unsubstituted aryl or a substituted or unsubstituted heteroaryl.

[0143] In some embodiments, R 5 or R 6 is hydrogen, and the other of R 5 or R 6 is independently substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl. The aryl or heteroaryl can be represented by the following formula:

[0144] where each of R 11 , R 12 , R 13 , R 14 , and R 15 is independently hydrogen, a hydrocarbyl group, a heteroatom, or a heteroatom-containing group, or one or more pairs of R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , and R 14 and R 15 join to form a completely saturated, partially saturated, or aromatic ring. In some embodiments, each of R 11 , R 12 , R 13 , R 14 , and R 15 is independently hydrogen or a C1-C 10 alkyl group (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl). In some embodiments, each of R 11 , R 12 , R 13 , R 14 , and R 15 is hydrogen.

[0145] In some embodiments, each of R 1 , R 2 , R 3 , and R 4 of formula (III) is independently hydrogen or a C1-C 10 alkyl group (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl). In some embodiments, each of R 1 , R 2 , R 3 , and R 4 is independently methyl, ethyl, or propyl. In some embodiments, each of R 1 , R 2 , R 3 , and R 4 is methyl.

[0146] In some embodiments, each of R 7 , R 8 , R 9 , and R 10 in formula (III) is independently hydrogen or a C1-C 10 alkyl group (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl). In some embodiments, each of R 7 , R 8 , R 9 , and R 10 is hydrogen.

[0147] In some embodiments of formula (III), T is represented by formula R a 2J, (R a )4J2, or (R a )6J3, where J is C, Si, or Ge, and each R a is independently hydrogen or a C1 to C 20 hydrocarbyl group. In some embodiments, two R a may form a cyclic structure, including an unsubstituted fully saturated, partially saturated, or aromatic ring. In some embodiments, T is selected from CH2, CH2CH2, C(CH3)2, CPh2, SiMe2, SiEt2, SiMeEt, SiPr2, SiBu2, SiPh2, SiMePh, Si(CH2)3, Si(CH2)4, or Si(CH2)5. In some embodiments, T is SiMe2, SiEt2, SiPr2, SiBu2, or, more preferably, T is a cyclic structure such as Si(CH2)3(silacyclobutyl), Si(CH2)4(silacyclopentyl), or Si(CH2)5(silacyclohexyl).

[0148] In some embodiments, each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 in formula (III) (and each of R 11 , R 12 , R 13 , R 14 , and R 15 ) is independently hydrogen, a hydrocarbyl group, a silylcarbyl group, an alkoxy group, a halide group, or a silyloxy group.

[0149] In some embodiments of formula (III), M is a Group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf). In some embodiments, M is Zr or Hf. In some embodiments, each X is independently a halide, such as chlorine. In yet other embodiments, each X is independently a Ci-C4alkyl, such as methyl. In some embodiments, each X is independently selected from the group consisting of substituted or unsubstituted hydrocarbyl, a heteroatom, or a substituted or unsubstituted heteroatom-containing group, such as methyl, benzyl, trimethylsilyl, methyl(trimethylsilyl), neopentyl, ethyl, propyl, butyl, phenyl, hydrido, chlorine, fluorine, bromine, iodine, triflate, dimethylamido, diethylamido, dipropylamido, and diisopropylamido.

[0150] In some embodiments of formula (III), (1) M is Zr or Hf, (2) X is Ci-C5alkyl, (3) T is Si(CH2)3, Si(CH2)4, or Si(CH2)5, (4) R 5 , R 7 , R 8 , R 9 , and R 10 are independently hydrogen or substituted or unsubstituted Ci-C 10 alkyl, (5) R 1 , R 2 , R 3 , and R 4 are independently methyl, ethyl, or propyl, and (6) R 6 is substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl. In some embodiments, R 6 is aryl represented by the following formula:

[0151] wherein each of R 11 , R 12 , R 13 , R 14 , and R 15 is independently hydrogen, a hydrocarbyl group, a heteroatom, or a heteroatom-containing group, or R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , and R 14 and R 15one or more of R 11 , R 12 , R 13 , R 14 , and R 15 are independently hydrogen or a Ci-C 10 alkyl group (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl). In some embodiments, each of R 11 , R 12 , R 13 , R 14 , and R 15 is hydrogen.

[0152] In some embodiments of formula (III), the catalyst is selected from:

[0153] In some embodiments, the second catalyst is represented by formula (IV):

[0154] (IV)

[0155] wherein:

[0156] M is a Group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf);

[0157] one or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are independently hydrogen, a substituted or unsubstituted hydrocarbyl group, a substituted or unsubstituted heteroatom, or a substituted or unsubstituted heteroatom-containing group, or R 5 and R 6 , R 7 and R 8 , R 8 and R 9 , and R 9 and R 10 are taken together to form a substituted or unsubstituted fully saturated ring or a substituted or unsubstituted aromatic ring;

[0158] T represents the formula R a 2J, (R a )4J2, or (Ra )6J3, where each J is independently C, Si, or Ge, and each R a is independently hydrogen, halo, substituted or unsubstituted Ci to C 40 hydrocarbyl, or two R a may 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

[0159] each X is independently halo, substituted or unsubstituted hydrocarbyl, hydrido, amino, substituted or unsubstituted alkoxy, sulfido, phosphido, or a combination thereof, or two Xs are joined together to form a substituted or unsubstituted metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene;

[0160] wherein (1) R 7 and R 8 , (2) R 8 and R 9 , or (3) R 9 and R 10 are joined to form a substituted or unsubstituted completely saturated ring fused to the indenyl ring shown in formula (IV).

[0161] In some embodiments, each of R 7 , R 8 , R 9 , and R 10 is independently hydrogen or Ci-C 10 alkyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl), wherein (1) R 7 and R 8 , (2) R 8 and R 9 , or (3) R 9 and R 10 are joined to form a substituted or unsubstituted completely saturated ring fused to the indenyl ring shown in formula (IV).

[0162] In some embodiments, (1) R 7 and R 8 , (2) R 8 and R 9 , or (3) R 9 and R 10 are joined to form a substituted or unsubstituted completely saturated ring fused to the indenyl ring shown in formula (IV). In some embodiments, R 7 and R 8The rings are joined to form a substituted or unsubstituted saturated C4 ring, a substituted or unsubstituted saturated C5 ring, a substituted or unsubstituted saturated C6 ring, or a substituted or unsubstituted saturated C7 ring, wherein the C4 ring, C5 ring, C6 ring, or C7 ring is fused to the indenyl ring shown in formula (IV). In some embodiments, R 8 and R 9 The rings are joined to form a substituted or unsubstituted saturated C4 ring, a substituted or unsubstituted saturated C5 ring, a substituted or unsubstituted saturated C6 ring, or a substituted or unsubstituted saturated C7 ring, wherein the C4 ring, C5 ring, C6 ring, or C7 ring is fused to the indenyl ring shown in formula (IV). In some embodiments, R 9 and R 10 Joined to form a substituted or unsubstituted saturated C4 ring, a substituted or unsubstituted saturated C5 ring, a substituted or unsubstituted saturated C6 ring, or a substituted or unsubstituted saturated C7 ring, wherein the C4 ring, C5 ring, C6 ring, or C7 ring is fused to the indene ring shown in formula (IV).

[0163] In some implementations, R of formula (IV) 1 R 2 R 3 and R 4 Each of them is independently hydrogen or C1-C 10 Alkyl groups (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl). In some embodiments, R 1 R 2 R 3 and R 4 Each of these is independently methyl, ethyl, or propyl. In some embodiments, R 1 R 2 R 3 and R 4 Each of them is a methyl group.

[0164] In some implementations of formula (IV), T is derived from formula R. a 2J、(R a )4J2, or (R a )6J3 represents, where J is C, Si, or Ge, and each R a Independently hydrogen or C1 to C 20 Hydrocarbon group. In some implementations, the two R groups... aRings structures can be formed, including unsubstituted fully saturated, partially saturated, or aromatic rings. 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 SiMe2, SiEt2, or SiMeEt.

[0165] In some embodiments of formula (IV), one or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are independently hydrogen, hydrocarbyl, silylhydrocarbyl, alkoxy, halide, or siloxy.

[0166] In some embodiments of formula (IV), M is a Group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf). In some embodiments, M is Zr or Hf. In some embodiments, each X is independently a halide, such as chlorine. 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, heteroatom, or substituted or unsubstituted heteroatom-containing groups, such as methyl, benzyl, trimethylsilyl, methyl(trimethylsilyl), neopentyl, ethyl, propyl, butyl, phenyl, hydride, chloride, fluoride, bromide, iodide, triflate, dimethylamino, diethylamino, dipropylamino, and diisopropylamino.

[0167] In some embodiments of formula (IV), (1) M is Zr or Hf, (2) X is C1-C5 alkyl, (3) T is Si(CH2)3, Si(CH2)4, or Si(CH2)5, (4) R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are independently hydrogen or substituted or unsubstituted C1-C 10 alkyl, (5) R 7 and R 8 , R 8 and R 9 , or R 9 and R 10at least one pair of the R 1 , R 2 , R 3 , and R 4 are independently methyl, ethyl, or propyl.

[0168] In some embodiments of formula (IV), the catalyst is selected from:

[0169] activator

[0170] The terms "cocatalyst" and "activator" are used interchangeably herein.

[0171] The catalyst systems described herein can include one or more catalyst compounds as described above and an activator such as an aluminoxane or a non-coordinating anion, and can be formed by combining the catalyst compounds described herein with an activator in any manner known from the literature, including combining them with a support such as silica. The catalyst systems can also be added to or generated in solution or bulk polymerization (in monomer). The catalyst systems of the present disclosure can have one or more activators and one, two or more catalyst components. An activator is defined as any compound which can activate any of the catalyst compounds described above by converting a neutral metal compound to a catalytically active metal compound cation. Non-limiting activators can include aluminoxanes, alkylaluminums, ionizing activators which can be neutral or ionic, and conventional types of cocatalysts. Suitable activators can include alumoxane compounds, modified alumoxane compounds, and ionized anion precursor compounds which snatch a reactive s-bonded metal ligand, make the metal compound cationic and provide a charge-balancing non-coordinating or weakly coordinating anion, for example, a non-coordinating anion.

[0172] In at least one embodiment, the catalyst system comprises an activator, a catalyst compound of formula (I), formula (II), formula (III), and / or formula (IV), and a support.

[0173] Aluminoxane activators

[0174] Aluminoxanes are utilized as activators in the catalyst systems described herein. Aluminoxanes are generally oligomeric compounds containing -Al(R a’’’ )-O- subunits, where R a’’’is an alkyl group. Examples of aluminoxanes include methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, and isobutylaluminoxane. Alkylaluminoxanes and modified alkylaluminoxanes are suitable as catalyst activators, such as when the available ligand is an alkyl, halo, alkoxy, or amide group. Mixtures of different aluminoxanes and modified aluminoxanes can also be used. It can be suitable to use visually clear methylaluminoxane. Cloudy or gelled aluminoxanes can be filtered to yield a clear solution or the clear aluminoxane can be decanted from a cloudy solution. A useful aluminoxane is modified methylalumoxane (MMAO) cocatalyst type 3A (commercially available under the trade name Modified Methylalumoxane type 3A from Akzo Chemicals, Inc., as described in U.S. Patent No. 5,041,584, which is incorporated herein by reference). Another useful aluminoxane is a solid polymethylaluminoxane as described in U.S. Patent Nos. 9,340,630, US 8,404,880, and US 8,975,209, which are incorporated herein by reference.

[0175] When the activator is an aluminoxane (modified or unmodified), and in at least one embodiment, the activator can be used in amounts of up to 5,000-fold molar excess of Al / M relative to the catalyst compound (by metal catalytic sites). The minimum activator to catalyst compound can be a 1 : 1 molar ratio. Alternative ranges can include about 1 : 1 to about 500: 1, alternatively about 1 : 1 to about 200: 1, alternatively about 1 : 1 to about 100: 1, or alternatively about 1 : 1 to about 50: 1.

[0176] In alternative embodiments, little or no aluminoxane is used in the polymerization processes described herein. For example, the aluminoxane can be present at zero mol%, alternatively the aluminoxane can be present in a molar ratio of aluminum to catalyst compound transition metal of less than 500: 1, such as less than 300: 1, such as less than 100: 1, such as less than 1 : 1.

[0177] Ionizing / Non-coordinating Anion Activators

[0178] The term "non-coordinating anion" (NCA) means an anion which does not coordinate to the cation or coordinates only weakly, so as to remain sufficiently destabilizing as to be displaced by a Lewis base. "Compatible" non-coordinating anions are those which do not degrade upon initial complex formation when the complex decomposes to neutral species. Additionally, the anion will not transfer an anionic substituent or fragment to the cation so as to cause it to form a neutral complex and a neutral byproduct. Non-coordinating anions useful in accordance with the present disclosure are those which are compatible, stabilize the transition metal cation in the sense of the equilibrium of its ionic charge, and still remain sufficiently destabilized to allow displacement during polymerization. Suitable ionizing activators can include NCAs, such as compatible NCAs.

[0179] Ionic ionizing activators, either neutral or ionic, are within the scope of the present disclosure. Neutral or ionic activators used alone or in combination with aluminoxane or modified aluminoxane activators are also within the scope of the present disclosure. For a description 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, see US 8,658,556 and US 6,211,105 (incorporated by reference herein); and US Patent Publication 2021 / 0179650, and in particular paragraphs

[0084] -

[0135] of WIPO Patent Publication No. WO 2021 / 257264, which descriptions are incorporated by reference herein (including the various descriptions incorporated by reference therein, such as WO 2004 / 026921 pp. 72 para

[00119] to pp. 81 para

[00151] and WO 2004 / 046214 pp. 72 para

[00177] to pp. 74 para

[00178] ).

[0180] Further, the catalyst systems of the present disclosure can include a metal hydrocarbenyl chain transfer agent represented by the following formula:

[0181] Al(R') 3-v (R'') v

[0182] where each R' can independently be a C1-C 30 hydrocarbyl group, and or each R" can independently be a C4-C 20 hydrocarbenyl group having a terminal vinyl group; and v can be 0.1 to 3.

[0183] Support material

[0184] In embodiments herein, the catalyst system can 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.

[0185] 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 the catalyst system herein can include Group 2, 4, 13, and 14 metal oxides, such as silicon dioxide, aluminum oxide, and mixtures thereof. Other inorganic oxides that can be employed, either alone or in combination with silicon dioxide or aluminum oxide, can be magnesium oxide, titanium dioxide, zirconium oxide. However, other suitable support materials can be employed, for example, finely divided functionalized polyolefins, such as finely divided polyethylene. Examples of suitable supports can include magnesium oxide, titanium dioxide, zirconium oxide, montmorillonite, phyllosilicates, zeolites, talc, clays. Additionally, combinations of these support materials can be used, for example, silica-chromium, silica-alumina, silica-titania. In at least one embodiment, the support material is selected from the group consisting of AI2O3, ZrO2, SiO2, SiO2 / AI2O3, SiO2 / TiO2, silica clay, silica / clay, or mixtures thereof.

[0186] The support material, such as the inorganic oxide, can have a surface area of about 10 m 2 / g to about 700 m 2 / g, a pore volume of about 0.1 cm 3 / g to about 4.0 cm 3 / g, and an average particle size of about 5 μm to about 500 μm. The surface area of the support material can be about 50 m 2 / g to about 500 m 2 / g, a pore volume of about 0.5 cm 3 / g to about 3.5 cm 3 / g, and an average particle size of about 10 μm to about 200 μm. For example, the surface area of the support material can be about 100 m 2 / g to about 400 m 2 / g, a pore volume of about 0.8 cm 3 / g to about 3.0 cm 3 / g, and the average particle size can be about 5 μm to about 100 μm. The average pore diameter of the support material useful in the present disclosure can be about 10 A to about 1000 A, such as about 50 A to about 500 A, and such as about 75 A to about 350 A. In at least one embodiment, the support material is a high surface area amorphous silica (surface area = 300 m 2 / gm; 1.65 cm 3(gm of pore volume). For example, a suitable silica can be the silica sold under the trade designation DAVISON™ 952 or DAVISON™ 955 by the Davison Chemical Division of W. R. Grace and Company. In other embodiments, DAVISON™ 948 is used. Alternatively, the silica can be ES-70™ silica (PQ Corporation, Malvern, Pennsylvania) that has been calcined, such as at 875 °C.

[0187] The support material should be dry, i.e., free or substantially free of absorbed water. Drying of the support material can be achieved 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; for a period of 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 the supported catalyst system of the present disclosure. The calcined support material is then contacted with at least one polymerization catalyst comprising at least one catalyst compound and an activator.

[0188] 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 separate support / activator. In at least one embodiment, the supported catalyst system is generated in situ. In alternative 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.

[0189] The mixture of one or more catalysts, one or more activators, and support is heated at about 0 °C to about 70 °C, such as about 23 °C to about 60 °C, such as at room temperature. The contact time 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.

[0190] Suitable non-polar diluents are materials in which all of the reactants used herein (e.g., activators and catalyst compounds) are at least partially soluble and are liquid at the polymerization temperature. Non-polar diluents can be alkanes such as isopentane, hexane, n-heptane, octane, nonane, and decane, although a variety of other materials can also be employed, including cycloalkanes such as cyclohexane, aromatic compounds such as benzene, toluene, and ethylbenzene.

[0191] In at least one embodiment, the support material is a supported methylaluminoxane (SMAO) which is a MAO activator treated with silica (e.g., ES-70-875 silica).

[0192] Polyethylene copolymer

[0193] The present disclosure provides polyethylene copolymers having a combination of low density, high melt index, long chain branching, and bimodal composition distribution. In addition, the polyethylene copolymers and films thereof can be formed by polymerization and extrusion of commercially desirable polyethylene copolymers.

[0194] Accordingly, the polyethylene copolymers of the various embodiments herein can exhibit one or more of the following properties:

[0195] a density of from about 0.914 to about 0.925 g / cm 3 such as from any of the low values of 0.914, 0.915, 0.916, 0.917, 0.918, 0.919, or 0.92 g / cm 3 to any of the high values of 0.925, 0.924, 0.923, 0.922, 0.921, 0.920, or 0.919 g / cm 3 such as about 0.915 g / cm 3 to about 0.920 g / cm 3 alternatively about 0.918 g / cm 3 to about 0.922 g / cm 3 where any combination of a low value to a high value is contemplated (provided the high end is greater than the low end), for example, from about 0.916 to about 0.921 g / cm 3 .

[0196] a melt index (MI, also referred to as I2or I 2.16(ASTM D1238, 190 °C, 2.16 kg), such as a low value of any 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 value of any 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 any low end to any high end range contemplated herein (provided the high end is greater than the low end), such as about 0.1 to about 1 g / 10 min, such as about 0.3 to about 0.8 g / 10 min, such as about 0.4 to about 0.6 g / 10 min.

[0197] The polyethylene copolymer can be a polymerization product of ethylene monomer and one or more olefin comonomers, such as alpha-olefin comonomers. The alpha-olefin comonomers can have 3 to 12 carbon atoms, or 4 to 10 carbon atoms, or 4 to 8 carbon atoms. The olefin comonomer can be selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methylpent-1-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 multiolefin is used as a comonomer. In some embodiments, the multiolefin is selected from the group consisting of 1,3-hexadiene, 1,4-hexadiene, cyclopentadiene, dicyclopentadiene, 4-vinylcyclohex-1-ene, methyloctadiene, 1-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 1,5-cyclooctadiene, norbornadiene, ethylidenenorbornene, 5-vinylidene-2-norbornene, 5-vinyl-2-norbornene, and olefins formed in situ in the polymerization medium. In some embodiments, the comonomer is selected from the group consisting of isoprene, styrene, butadiene, isobutylene, chlorobutadiene, acrylonitrile, and cyclic olefins. In some embodiments, a combination of olefin comonomers is utilized. In some embodiments, the olefin comonomer is selected from the group consisting of 1-butene and 1-hexene. The polyethylene copolymer can have an olefin comonomer content ranging from a low of about 0.1 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, or 8.5 wt% to a high of about 20 wt%, 15 wt%, 13 wt%, 12.5 wt%, 12 wt%, 11.5 wt%, 11 wt%, 10.5 wt%, 10 wt%, 9.5 wt%, or 9 wt%, based on the total weight of monomers in the polyethylene copolymer. The balance of the polyethylene copolymer is made up of units derived from ethylene (e.g., a low of about 80 wt%, 85 wt%, 88 wt%, 90 wt%, 91 wt%, 92 wt%, 92.5 wt%, 93 wt%, 93.5 wt%, or 94 wt% to a high of about 90 wt%, 91 wt%, 92 wt%, 92.5 wt%, 93 wt%, 93.5 wt%, 94 wt%, 94.5 wt%, 95 wt%, 95.5 wt%, 96 wt%, 97 wt%, 99 wt%, or 99.9 wt%). Any range from a foregoing low to a foregoing high is contemplated herein (e.g., about 88 wt% to about 93 wt%, such as about 91 wt% to about 93 wt% of ethylene-derived units and the balance of the olefin comonomer-derived content).

[0198] The polyethylene copolymer can also have a high load melt index (HLMI) (also referred to as I 21 or I 21.6 ) in a range from a low value of any of about 15, 20, 25, 30, 35, 40, 45, 50, or 55 g / 10 min to a high value of any of about 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, or 25 g / 10 min (per Test 1 below using a 21.6 kg load). 21 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, the HLMI (I 21 or I 21.6 .

[0199] The polyethylene copolymer can also have a melt index ratio (MIR, defined as the ratio of I 21.6 / I 2.16 ) in a range from a low value of any of about 20, 25, 30, 35, 40, 45, 50, or 55 to a high value of any of about 75, 70, 65, 60, 55, 50, 45, or 40.

[0200] The polyethylene copolymer can also have a molecular weight distribution (MWD) of about 2 to about 10. The MWD can be a low value of about 2, 2.5, 3, 3.5, 4, 4.2, 4.4, 4.5, 4.6, 4.8, 5, 5.1, 5.2, 5.3, 5.4, 5.5, or 6 to a high value of about 3.5, 4, 4.5, 5, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6, 6.5, 7, 7.1, 7.2, 7.3, 7.4, 7.5, 8.0, 8.5, 9.0, 9.5, or 10.0, with any range from a foregoing low value to a foregoing high value being contemplated, provided that the high end of the range is greater than the low end. The MWD is defined as the weight average molecular weight (Mw) divided by the number average molecular weight (Mn) and can be referred to as the polydispersity index (PDI).

[0201] The weight average molecular weight (Mw) of the polyethylene copolymers of various embodiments (e.g., when the base catalyst is a bridged bis-indenyl hafnium or zirconium complex) can range from about 70,000 to about 400,000 g / mol, such as from about 75,000 to about 150,000 g / mol, such as from about 90,000 to about 130,000 g / mol, such as from about 100,000 to about 120,000 or 125,000 g / mol, alternatively (e.g., when the base catalyst is a non-bridged bis-indenyl hafnium or zirconium complex) can range from about 100,000 to about 300,000 g / mol, such as from about 150,000 to about 250,000 g / mol, such as from about 150,000 to about 210,000 g / mol, alternatively from about 128,000 to about 150,000 g / mol, with any range from any of the foregoing low end to any of the foregoing high end being contemplated.

[0202] The number average molecular weight (Mn) of the polyethylene copolymers of various embodiments can range from about 10,000 to about 45,000 g / mol, such as from about 10,000 to about 30,000 g / mol, such as from about 15,000 to about 25,000 g / mol, with any range from any of the foregoing low end to any of the foregoing high end being contemplated.

[0203] The Z-average molecular weight (Mz) of the polyethylene copolymers of various embodiments (e.g., when the base catalyst is a bridged bis-indenyl hafnium or zirconium complex) can range from about 150,000 to about 400,000 g / mol, such as from about 200,000 to about 350,000 g / mol, or from about 200,000 to about 275,000 g / mol, such as from about 220,000 to about 260,000 g / mol, alternatively (e.g., when the base catalyst is a non-bridged bis-indenyl hafnium or zirconium complex) can range from about 150,000 to about 1,000,000 g / mol, such as from about 300,000 to about 900,000 g / mol, or from about 300,000 to about 400,000 g / mol, alternatively from about 400,000 g / mol to about 500,000 g / mol, alternatively from about 500,000 g / mol to about 600,000 g / mol, alternatively from about 600,000 g / mol to about 700,000 g / mol, alternatively from about 700,000 g / mol to about 800,000 g / mol, alternatively from about 800,000 g / mol to about 900,000 g / mol, with any range from any of the foregoing low end to any of the foregoing high end being contemplated.

[0204] The polyethylene copolymers of the various embodiments can also exhibit long chain branching. As previously noted, this can be evidenced by, for example, SAOS viscosity data (especially η 0.01 / η 100 ) and / or MIR. Further, the LCB or branching index (referred to herein as g' vis ave or alternatively g' vis ) can be less than 1, such as in a range from a low of about 0.65, 0.66, 0.67, 0.68, 0.69, 0.70, 0.71, 0.72, 0.73, 0.74, 0.75, 0.76, 0.77, 0.78, 0.79, 0.80, 0.81, 0.82, 0.83, 0.84, 0.85, or 0.86 to a high of about 0.80, 0.85, 0.86, 0.87, 0.88, 0.89, 0.90, 0.91, 0.92, 0.93, or 0.94, with any range from any of the foregoing low ends to any of the foregoing high ends being contemplated, provided the high end is greater than the low end (e.g., 0.65 to 0.95, such as 0.72 to 0.87, or 0.82 to 0.92, or 0.86 to 0.92, etc.).

[0205] The distribution and moments of molecular weight (Mw, Mn, Mw / Mn, etc.) and branching index (g'vis) were determined by using a high temperature Gel Permeation Chromatography (Polymer Char GPC-IR) equipped with an infrared detector based on a multi-channel band filter IR5, an 18-angle Wyatt Dawn Heleos light scattering detector and a 4-capillary viscometer with Wheaton bridge configuration. Three Agilent PLgel 10-μm Mixed-B LS columns were used to provide polymer separation. Aldrich reagent grade 1,2,4-trichlorobenzene (TCB) with 300 ppm antioxidant butylated hydroxytoluene (BHT) was used as the mobile phase. The TCB mixture was filtered through a 0.1-μm Teflon filter and degassed with an online degasser before entering the GPC instrument. The nominal flow rate of the at 25 °C under continuous shaking for about 2 hours. The concentration (c) at each point in the chromatogram was calculated from the IR5 broadband signal intensity (I) minus the baseline using the equation: c = βI, where β is the mass constant. Mass recovery was calculated from the integrated area of the concentration chromatogram over the elution volume divided by the injection mass equal to the pre-determined concentration multiplied by the injection loop volume. The conventional molecular weight (IR MW) was determined by combining a universal calibration relationship with column calibration performed with a series of monodisperse polystyrene (PS) standards ranging from 700 to 10 million g / mol. The MW at each elution volume was calculated using the equation:

[0206]

[0207] where variables with subscript “PS” refer to polystyrene, and variables without a subscript are the test sample. In this method, a PS = 0.67 and K PS = 0.000175, while for ethylene-hexene copolymers a and K are calculated from an empirical equation (Sun, T. et al. Macromolecules 2001, 34, 6812) where a = 0.695 and K = 0.000579(1-0.75Wt), where Wt is the weight fraction of hexene comonomer. It should be noted that the comonomer composition is determined from the ratio of IR5 detector intensities corresponding to CH2and CH3channels, which is calibrated with a series of PE and ethylene-hexene homopolymer / copolymer standards whose nominal values are pre-determined by NMR or FTIR. Concentration is expressed here in g / cm 3 , molecular weight in g / mol, and intrinsic viscosity (hence, K in the Mark-Houwink equation) in dL / g.

[0208] The LS molecular weight (M) at each point in the chromatogram was determined by analyzing the LS output using the Zimm model for static light scattering

[0209] .

[0210] Here, AR(0) is the excess Rayleigh scattering intensity measured at scattering angle 0, c is the polymer concentration determined from the IR5 analysis, A2 is the second virial coefficient, P(0) is the form factor for a monodisperse random coil, and Ko is the optical constant of the system:

[0211]

[0212] where N Ais Avogadro's number, and (dn / dc) is the refractive index increment of the system. The refractive index of TCB, n = 1.500 at 145°C and λ = 665 nm. For the purposes of the present disclosure and its claims, (dn / dc) = 0.1048 for ethylene-hexene copolymers.

[0213] Unless otherwise indicated, when reference is made herein to molecular weight values, it is assumed that they are determined via light scattering (LS) techniques.

[0214] Viscosity-average molecular weight (M V ): Specific viscosity is determined using a high temperature Polymer Char viscometer with four capillaries arranged in a Wheatstone bridge configuration and two pressure sensors. One sensor measures the total pressure drop through the detector, while the other sensor, located between these two sides of the bridge, measures the pressure difference. From their outputs, the specific viscosity of the solution flowing through the viscometer, ηs, is calculated. The intrinsic viscosity [η] at each point in the chromatogram is calculated by the equation [η] = ηs / c, where c is the concentration and determined from the IR5 broadband channel output. The viscosity-average molecular weight Mw at each point is calculated as , where αpsis 0.67 and Kpsis 0.000175. The average intrinsic viscosity [η] avg is calculated by:

[0215]

[0216] where the sum is taken over the chromatographic slices i between the integration limits.

[0217] The branching index (g' vis ) can be calculated using the output of the GPC-IR5-LS-VIS method as follows. First, it should be noted that g’ or g’ vis can generally be considered as the ratio of the intrinsic viscosity of a polymer to that of a linear polymer of the same molecular weight and composition: g’ = [η 聚合物 ] / [η 参考 ], where [η 聚合物 ] is the intrinsic viscosity of the polymer under study, and [η 参考 ] is the intrinsic viscosity of a linear resin of the same molecular weight and same composition. Thus, the relative intrinsic viscosity of a polymer (g’) is a measure of the extent to which the polymer enhances the viscosity of its solution relative to a linear polymer of the same molecular weight and composition under the same temperature and pressure conditions.

[0218] Following this rationale, the [η 聚合物 ] value in the above simplified relationship can be considered as the weight-average intrinsic viscosity [η avg ] of the sample, which is calculated by:

[0219]

[0220] where the sum is taken over all chromatographic slices i between the integration limits. Branching index g' vis defined relative to a linear reference as where Mv is the viscosity average molecular weight based on the molecular weight determined by LS analysis, and K and a are for a reference linear polymer; a and K are the same as described above for linear polyethylene polymers for the purposes of the present disclosure.

[0221] Branching index g' vis may be referred to equivalently as g' vis ave to reflect that it is an average value of g' determined at each of a plurality of discrete concentration slices. For example, with reference to Figure 1 , it can be seen that g' for various polyethylene copolymers is plotted as a function of Log M (logarithm of molecular weight), meaning that the g' value for a given population of polymer chains in a polyethylene copolymer composition can be calculated. The above calculation provides g' vis ave , and when comparing such values between two different copolymer compositions, g' vis ave can be considered a good relative indicator of the presence of long chain branching, where a lower g' vis ave indicates greater long chain branching.

[0222] broad orthogonal composition distribution

[0223] “BOCD” refers to a broad orthogonal composition distribution, in which the comonomer of the copolymer is incorporated primarily into the high molecular weight chains or species of the polyolefin polymer or composition. For example, the distribution of non-short chain branches can be measured as follows: using temperature rising elution fractionation (TREF) in combination with a light scattering (LS) detector to determine the weight average molecular weight of molecules eluted from the TREF column at a given temperature. The combination of TREF and LS (TREF-LS) gives information about the breadth of the composition distribution and whether the comonomer content is increasing, decreasing, or uniform across the different molecular weight chains of the polymer. BOCD has been described, for example, in U.S. Patent Nos. 8,378,043 at column 3, line 34 through column 4, line 19 and 8,476,392 at line 43 through column 16, line 54.

[0224] The BOCD properties of the inventive polyethylene copolymers can be quantified in terms of composition distribution breadth index (CDBI). For example, the polyethylene copolymers described herein can have a low value of composition distribution breadth index (CBDI) where the polyethylene copolymer can have a CBDI% in a range from a low value of any one of about 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, or 80% to a high value of any one of about 99%, 95%, 90%, 85%, 80%, 75%, 70%, 65%, or 60%; where any range of any preceding low value to any preceding high value is contemplated herein (e.g., about 50% to about 85%, such as about 55% to about 75%, alternatively about 70% to about 85%, alternatively about 75% to about 85%). In some embodiments, the polyethylene copolymers described herein can have a low value of composition distribution breadth index (CBDI) where the polyethylene copolymer can have a CBDI% in a range from a low value of any one of about 30%, 35%, 40%, 45%, 50%, or 55% to a high value of any one of about 70%, 65%, 60%, 55%, 50%, or 45%; where any range of any preceding low value to any preceding high value is contemplated herein (e.g., about 35% to about 65%, such as about 40% to about 50%, alternatively about 50% to about 65%, such as about 50% to about 60%).

[0225] CDBI is defined as the weight percent of copolymer molecules having a comonomer content within + / - 50% of the median comonomer mol% value, as described in WO 1993 / 003093 at pages 18-19 in conjunction with Figure 17 therein. This means that for a copolymer having a median comonomer mol% value (Cmed) of 8 mol% comonomer on the polymer chain, the CDBI is the weight % of copolymer chains having a comonomer mol% of (0.5 x Cmed) to (1.5 x Cmed). In this example, the CDBI is the weight % of copolymer chains having a comonomer mol% of (0.5 x 8) to (1.5 x 8) or a comonomer content of 4 mol% to 12 mol%. WO 1993 / 003093 also describes methods for using chromatography and C 13The method of NMR to determine the weight fraction of the polymer versus the composition curve (i.e., the composition distribution curve) and from it the median comonomer composition, Cmed, is referenced to Figures 16 and 17 of that publication. The CDBI of the copolymer is readily determined using techniques for separating individual fractions of a sample of the copolymer. One such technique is to use temperature rising elution fractionation (TREF) to generate a solubility distribution curve 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). All three of the foregoing publications are incorporated herein by reference.

[0226] The solubility distribution curve of the copolymer can first be generated using data obtained from the TREF technique (as described in the just cited publications, for example). This is a plot of the weight fraction of the dissolved copolymer 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, weight fractions less than 15,000 can be ignored. These low weight fractions generally represent an insignificant portion of the ethylene-based polymers disclosed herein.

[0227] Alternatively or additionally, the composition distribution can be characterized by the T 75 - T 25 values, where T 25 is the temperature at which 25% of the eluted polymer is obtained and T 75 is the temperature at which 75% of the eluted polymer is obtained, both in a TREF experiment (and plot of eluted polymer molecular weight versus elution temperature) as described in US 2019 / 0119413 (especially in paragraphs

[0055] -

[0058] thereof, which description is incorporated herein by reference). A narrow composition distribution is reflected in a relatively small difference in the T 75 - T 25 values, while a broad distribution is reflected in a relatively larger difference in the T 75 - T 25 values (meaning a larger difference in crystallinity between fractions of the polymer composition). It is also noted that in the event there is a difference between the actual TREF procedure as described in US 2019 / 0119413 versus the TREF procedure as described in WO 1993003093, US 5,382,630, and / or US 5,008,204, the TREF procedure as described in US 2019 / 0119413 should be used. (It is further noted that the TREF procedure assists in generating the curve - the solubility distribution curve of the CDBI and the T 75- T 25 of eluted molecular weight versus elution temperature, CDBI and T 75 - T 25 may have appropriate differences in their generation and analysis. Finally, in conjunction with T 75 - T 25 The generated TREF curve (eluted polymer molecular weight versus elution temperature) can be further processed as follows:

[0228] 1. The instrument's solvent-only response can be generated and subtracted from the TREF curve of the sample. The solvent-only response can be generated by running the same method before running the method for the polymer sample, but without adding any polymer to the sample vial; using the same solvent reservoir as for the polymer sample and not replenishing fresh solvent; and within a reasonable time from the run of the polymer sample.

[0229] 2. The temperature axis of the TREF curve can be appropriately shifted to correct for the delay of 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 HDPE resin; then loading the loop volume at the same location within the column as the sample is loaded for TREF analysis; then using the isothermal method to flow the hot solution directly to the detector at a constant flow rate of 1 ml / min; and then measuring the time after injection at which the HDPE probe peak appears in the IR signal. Thus, the delay volume (ml) equals the time (min).

[0230] The curve can be baseline corrected and appropriate integration limits can be chosen; and the curve can be normalized so that the area of the curve is 100 wt%.

[0231] As in some embodiments of the polyethylene copolymers of the present disclosure, the narrow distribution is reflected in a T 75 - T 25 of less than 15°C, such as in a range from a low value of 1°C, 2°C, 3°C, 4°C, 5°C, 6°C, 7°C, 8°C, or 9°C to a high value of 10°C, 11°C, 12°C, 13°C, 14°C, or 15°C, with any range from any preceding low value to any preceding high value being contemplated (e.g., about 1°C to about 10°C, such as about 5°C to about 8°C, alternatively about 7°C to about 11°C). In yet other embodiments, the polyethylene copolymers of the present disclosure can exhibit a bimodal composition distribution, such as a BOCD (broad orthogonal composition distribution, meaning that the comonomer preferentially incorporates onto longer polymer chains compared to shorter chains), and have a relatively high T 75 - T 25values, such as 15 °C or greater, such as a low value of 15 °C, 16 °C, 17 °C, or 18 °C to a high value of 21 °C, 22 °C, 23 °C, 24 °C, 25 °C, 26 °C, 27 °C, 28 °C, 29 °C, 30 °C, or 35 °C, wherein any foregoing low value to any foregoing high value range is contemplated (e.g., about 15 °C to about 30 °C, such as 18 °C to 28 °C, alternatively about 18 °C to about 25 °C, such as about 19 °C to about 22 °C or 23 °C).

[0232] Blends and additives

[0233] In some embodiments, the polyethylene copolymer can be formulated (e.g., blended) with one or more other polymeric components. In some embodiments, those other polymeric 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 polyethylene.

[0234] In some embodiments, the formulated blend can contain additives, which are determined based on the end use of the formulated blend. In some embodiments, the additives are selected from the group consisting of fillers, antioxidants, phosphites, anti-block additives, tackifiers, ultraviolet stabilizers, heat stabilizers, anti-cling agents, mold release agents, anti-static agents, pigments, colorants, dyes, waxes, silica, processing aids, neutralizing agents, lubricants, surfactants, and nucleating agents. In some embodiments, the additives are present in an amount of about 0.1 ppm to about 5 wt%.

[0235] The polyethylene copolymers of the present disclosure can optionally be blended with one or more processing aids to form a polyethylene blend. Due to the improved properties of the polyethylene copolymers of the present disclosure, such processing aids can advantageously be omitted even in blown films (e.g., the films of some embodiments and particularly blown films can be free or substantially free of polymeric processing aids, and particularly polymeric processing aids comprising fluorine; wherein “substantially free” means free of any intentionally added components, but allowing up to 100 ppm of one or more such components as impurities).

[0236] Articles

[0237] The polyethylene copolymers of the present disclosure can be particularly suitable for use in the manufacture of end-use articles, such as films (e.g., as can be formed by lamination, extrusion, co-extrusion, casting, and / or blowing); and other articles as can be formed, for example, by rotational molding or injection molding. The polyethylene copolymers can form articles by cast film extrusion, blown film extrusion, rotational molding, or injection molding processes. In some embodiments, the polyethylene copolymers can be used in a blend.

[0238] It has been found that the polyethylene copolymers of the present disclosure can provide excellent shear thinning characteristics with little or no melt fracture of the extrudate at high die shear rates. In addition, the polyethylene copolymers of the present disclosure can provide films formed at reduced motor load and melt pressure due to improved flow behavior compared to other LLDPEs.

[0239] The polyethylene copolymers of the present disclosure (or blends thereof) can be used in such forming operations as film, sheet, and fiber extrusion and co-extrusion, and blown, injection, and rotational molding. Films include blown or cast films formed by co-extrusion or lamination, which films are useful as shrink film, cling film, stretch film, sealing films, oriented films, snack packaging, heavy duty bags, grocery bags, bakery and frozen food packaging, medical packaging, industrial liners, membranes, and the like in food-contact and non-food contact applications. For example, the polyethylene copolymers of the present disclosure provide improved shrink packaging capabilities due to long chain branching properties. Fibers include melt spinning, solution spinning, and melt blown fiber operations for making filters, diaper fabrics, medical garments, geotextiles, and the like in woven or non-woven form. Extruded articles include medical tubing, wire and cable coatings, pipe, geomembranes, and pond liners. Molded articles include single and multi-layer constructions in the form of bottles, tanks, large hollow articles, rigid food containers, and toys.

[0240] The polyethylene copolymers (or blends thereof) can be formed into monolayer or multilayer films. These films can be formed by any conventional technique, including extrusion, co-extrusion, extrusion coating, lamination, blowing, and casting. The films can be obtained by flat film or tubular processes, which can then be oriented in the plane of the film in a single axial direction or in two perpendicular directions to each other. One or more of the layers of the film can be oriented in the transverse and / or longitudinal direction to the same or different extent. The orientation can be carried out before bringing the individual layers together or after. For example, the polyethylene copolymers (or blends thereof) can be extrusion coated or laminated onto oriented polypropylene layers, or the polyethylene copolymers (or blends thereof) and polypropylene can be co-extruded into a film together, which is then oriented. Likewise, oriented polypropylene can be laminated to oriented polyethylene copolymers (or blends thereof), or oriented polyethylene copolymers (or blends thereof) can be coated onto polypropylene, which combination can then optionally be oriented even further.

[0241] The films include monolayer films or multilayer films. Specific end-use films include, for example, blown films, cast films, stretched films, stretch / cast films, stretch cling films, stretch hand wrap films, machine stretch wrap, shrink films, shrink wrap films, greenhouse films, laminates, and laminated films. Exemplary films are prepared by any conventional technique known to one skilled in the art, such as, for example, techniques for making blown, extruded, and / or cast stretch and / or shrink films, including shrink-on-shrink applications.

[0242] In at least one embodiment, multilayer films (multiple-layer films) can be formed by any suitable method. The overall thickness of the multilayer film can vary depending on the desired application. An overall film thickness of 5-100 pm, such as 10-50 pm, is suitable for most applications. One skilled in the art will appreciate that the thickness of individual layers of the multilayer film can be adjusted based on the desired end-use performance, the polymer(s) employed, equipment capabilities, and other factors. The materials forming each layer can be co-extruded through a co-extrusion feedblock and die assembly to result in a film having two or more layers that are adhered together but differ in composition. Co-extrusion 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 film is composed of five to ten layers.

[0243] In at least one embodiment, the films of the present disclosure have an average 1% secant modulus (M) of about 30,000 psi to about 40,000 psi, such as about 31,000 psi to about 40,000 psi, such as about 33,000 to about 38,000 psi, such as about 34,000 psi to about 36,000 psi, according to ASTM D882-18 at 23 o C.

[0244] The films of the present disclosure can have an Elmendorf tear value according to ASTM D-1922. In at least one embodiment, the films have an Elmendorf tear (MD) of at least 30 g / mil, such as at least 50 g / mil, such as about 60 g / mil to about 100 g / mil, such as about 80 g / mil to about 100 g / mil.

[0245] The films of the present disclosure can have a dart drop impact (or impact failure or Dart F50 or dart impact strength (DIS)) reported in grams (g) or grams per mil (g / mil) according to ASTM D-1709 Method A. The films of the present disclosure can have a dart drop impact of about 5 g / mil to about 600 g / mil. In at least one embodiment, the films have 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.

[0246] Shrinkage of the films (reported in percent) can be measured by cutting a circular specimen from the film using a 100 mm die. The samples can be marked in their respective directions, dusted with talc, and placed on a preheated talc-covered brick. The samples can then be heated using a hot air gun (e.g., Model HG-501A) for about 10 to 45 seconds, or until any dimensional change stops. Values are the average of three specimens. Negative shrinkage values indicate expansion of the dimensions after heating when compared to their pre-heated dimensions. The films of the present disclosure can have a % shrinkage (machine direction) of about 40% to about 90%, such as about 60% to about 80%, such as about 65% to about 75%. The films of the present disclosure can have a % shrinkage (cross direction) of about 0% to about 5%, such as about 0.5% to about 4%, such as about 1% to about 3%.

[0247] In certain embodiments, the films can have a break puncture energy of at least about 25 in-lbs / mil, such as at least about 30 in-lbs / mil, such as at least about 35 in-lbs / mil, such as about 25 in-lbs / mil to about 40 in-lbs / mil, such as about 30 in-lbs / mil to about 40 in-lbs / mil, such as about 30 in-lbs / mil to about 35 in-lbs / mil according to modified ASTM D5748 (using ASTM probe with two 0.25 mil HDPE sliding sheets. Machine model: United SFM-1. Test speed: 10 in / min).

[0248] In at least one embodiment, the films of the present disclosure have 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.

[0249] In at least one embodiment, the films of the present disclosure have a transparency (defined as the regular transmittance of incident light through a film sample block of less than 0.1) of about 80% or greater, about 85% or greater, about 90% or greater, about 95% or greater, about 97% or greater, as determined by ASTM D1746.

[0250] In at least one embodiment, the films of the present disclosure have a gloss (where a light source is illuminated onto a film surface at a 45° angle and the amount of reflected light is measured) of about 30% or greater, about 35% or greater, about 40% or greater, about 45% or greater, about 50% or greater, as determined by ASTM D-2457.

[0251] Shrink film

[0252] The compositions of the present disclosure can be used to make shrink film. Shrink film, also known as heat-shrinkable film, is widely used in both industrial and retail bundling and packaging applications. Such films are capable of shrinking upon the application of heat to release stresses imparted to the film during or after extrusion. The shrinkage can occur in one direction or in both the machine and transverse directions. Conventional shrink film is described, for example, in U.S. Patent No. 7,235,607, which is incorporated herein by reference.

[0253] Industrial shrink film can be used to bundle articles on a pallet. Typical industrial shrink film is formed in a single bubble blown extrusion process to a thickness of about 80 to 200 pm and provides shrinkage in both directions.

[0254] Retail film can be used to package and / or bundle articles for consumer use, such as, for example, in supermarket merchandise. Such films are typically formed in a single bubble blown extrusion process to a thickness of about 35 pm to about 80 pm.

[0255] The films can be used in “layer-by-layer shrink” applications. As used herein, “layer-by-layer shrink” refers to a process of applying an outer shrink wrap layer around one or more articles that have already been individually shrink wrapped (herein, the “inner layer” of the package). In these processes, it can be desirable for the film used to package the individual articles to have a higher melting point (or shrink point) than the film used for the outer layer. When using such a configuration, a desired level of shrinkage can be achieved in the outer layer while preventing the inner layer from melting, further shrinking, or otherwise deforming during shrinkage of the outer layer. Some of the films described herein can have a sharp shrink point when subjected to heat from a heat gun in a high heat environment, which suggests that they can be particularly suitable for use as an inner layer in a variety of layer-by-layer shrink applications.

[0256] Experiments

[0257] General Considerations and Reagents: Unless otherwise noted, all operations were performed using glovebox techniques under an inert atmosphere. Toluene and pentane were purchased from Sigma Aldrich and were degassed and dried over 3 A molecular sieves overnight prior to use. Methylaluminoxane was purchased from Grace and used as received.

[0258] Synthesis:

[0259] General Considerations and Reagents. Unless otherwise noted, all operations were performed using glovebox techniques under an inert atmosphere. Ethyl ether and dichloromethane (Sigma Aldrich) were degassed and dried over 3 A molecular sieves overnight prior to use. ZrCl4was purchased from Strem Chemicals, Inc. and used as received.

[0260] Synthesis of Catalyst 2 and Catalyst 1:

[0261]

[0262] 1-Chloro-1-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silacyclobutane

[0263] To a colorless solution of 1,1-dichlorosilacyclobutane (11.00 g, 78.0 mmol, 2.00 equiv) in tetrahydrofuran (50 mL) was added (tetramethylcyclopentadiene)lithium (5.00 g, 39.0 mmol, 1.00 equiv) at -35 o C for 1 h. The reaction was stirred for 3 h, then evaporated under vacuum to give a thick white mixture. The mixture was extracted with pentane (50 mL, then 4 x 5 mL) and the extracts were filtered to give a colorless solution. The solution was evaporated under vacuum to give an amber oil. Yield 8.79 g (99%). 1 H NMR (C6D6) δ 3.11 (br s, 1H), 1.98 (br m, 1H), 1.90 (s, 6H), 1.68-1.79 (overlapping multiplets and singlet, 7H), 1.21-1.40 (m, 4H).

[0264]

[0265] (3-Phenylindenyl)lithium

[0266] To a colorless solution of 3-phenylindene (26.20 g, 136 mmol, 1.00 equiv) in pentane (250 mL) was added 2.73 M butyllithium (50.0 mL, 136 mmol, 1.00 equiv) to give a hazy yellow solution. The reaction was stirred for 69 h to give a hazy yellow mixture. The mixture was then filtered to give a light yellow solid. The solid was washed with pentane (100 mL) and dried under vacuum. Yield 25.71 g (95%). 1 H NMR (THF-d8) δ 7.72 (dm, 1H), 7.55(dm, 2H), 7.19 (dm, 1H), 7.02 (tm, 2H), 6.86 (d, 1H), 6.51 (tm, 1H), 6.47(tm, 1H), 6.37 (tm, 1H), 5.93 (dd, 1H).

[0267]

[0268] 1-(3-phenyl-1H-inden-1-yl)-1-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silole

[0269] At -35 o To a colorless solution of 1-chloro-1-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1- yl)silole (5.14 g, 22.7 mmol, 1.00 equiv) in ether (25 mL) was added (3-phenylindene)lithium (4.81 g, 24.3 mmol, 1.07 equiv) to give a hazy yellow-orange mixture. The reaction was allowed to warm to room temperature and stirred for 24 h to give a hazy green-white mixture. The reaction was then evaporated under vacuum leaving a green semi-solid. The residue was extracted with pentane (3 x 30 mL then 3 x 5 mL) and the extracts were filtered to give a yellow solution. The solution was evaporated under vacuum leaving a Manila-colored solid. Yield 8.41 g (97%). 1H NMR (C6D6) δ 7.73 (m, 1H), 7.66 (m, 1H),7.64. (m, 1H), 7.46 (m, 1H), 7.27 (m, 2H), 7.22 (m, 2H), 7.17 (m, 2H), 6.49(d, 1H), 3.36 (d, 1H), 2.98 (br s, 1H), 1.95 (m, 1H), 1.91 (s, 3H), 1.88 (s,3H), 1.78 (s, 3H), 1.75 (s, 6H), 1.54 (m, 1H), 1.13-1.26 (m, 2H), 1.02 (m,1H), 0.81 (m, 1H)..

[0270]

[0271] [Tetramethylcyclopentadienylsilolyl(3-phenylindenyl)] lithium (diethylether) complex

[0272] To a turbid amber solution of 1-(3-phenyl-1H-inden-1-yl)-1-(2,3,4,5- tetramethylcyclopenta-2,4-dien-1-yl)silolane (8.27 g, 21.6 mmol, 1.00 equiv) in ether (40 mL) was added 2.74 M butyllithium in hexanes (16.4 mL, 44.9 mmol, 2.08 equiv) at -35 o C to give a turbid yellow mixture. The reaction was allowed to warm to room temperature and stirred for 17 hours. To the reaction was added pentane (40 mL) and the mixture was filtered to give a yellow solid. The solid was washed with pentane and dried under vacuum. Yield 9.11 g (90%) as a yellow powder. 1 H NMR (THF-d8) δ 7.71 (d, 1H), 7.61 (d, 1H), 7.57 (dd, 2H), 7.18 (s, 1H), 7.02 (t, 1H), 6.55(t, 1H), 6.50 (t, 1H), 6.41 (t, 1H), 3.40 (q, 4H), 2.27 (br m, 2H), 2.19 (s,6H), 1.95 (s, 6H), 1.46 (br m, 4H), 1.13 (t, 6H).

[0273]

[0274] [Tetramethylcyclopentadienylsilolyl(3-phenylindenyl)] zirconium dichloride, catalyst 2

[0275] at -35 o C, to a vigorously stirred white suspension of zirconium tetrachloride bis(etherate) (3.25 g, 8.54 mmol, 1.00 equiv) in ether (50 mL) was added [tetramethylcyclopentadienyl silolato(3-phenylindenyl)] lithium (diethylether) (4.00 g, 8.54 mmol, 1.00 equiv) to give a hazy yellow mixture. The reaction was allowed to warm to room temperature and stirred for 18 hours. The hazy bright yellow mixture was then evaporated under vacuum leaving a yellow solid. The solid was extracted with dichloromethane (50 ml, then 4 x 5 mL) and the extracts filtered to give a yellow solution. The solution was evaporated under vacuum leaving a yellow solid. The solid was washed with pentane and dried under vacuum to give a bright yellow powder comprising catalyst 2. Yield 4.26 g (92%).1H NMR (CD2Cl2) δ 7.91 (dt, 1H), 7.61 (m, 1H), 7.59 (m, 1H), 7.47-7.52 (m, 3H) 7.39-7.41 (m, 1H) 7.34-7.38 (m, 1H), 7.06-7.10 (m, 1H), 6.01 (s, 1H), 2.64-2.81 (m, 2H), 2.04-2.18 (m, 2H), 1.93-1.99 (m, 2H), 1.95 (s, 3H), 1.91 (s, 3H), 1.90 (s, 3H), 1.85 (s, 3H).

[0276]

[0277] [tetramethylcyclopentadienyl silolato(3-phenylindenyl)] zirconium dimethyl, (catalyst 1)

[0278] Catalyst 1 was obtained by successive synthesis as follows: at -35 o C, to a vigorously stirred white suspension of zirconium tetrachloride bis(etherate) (3.25 g, 8.54 mmol, 1.00 equiv) in ether (50 mL) was added [tetramethylcyclopentadienyl silolato(3-phenylindenyl)] lithium (diethylether) (4.00 g, 8.54 mmol, 1.00 equiv) to give a hazy yellow mixture. The reaction was allowed to warm to room temperature and stirred for 18 hours. The hazy bright yellow mixture was then evaporated under vacuum leaving a yellow solid. The solid was extracted with dichloromethane (50 ml, then 4 x 5 mL) and the extracts filtered to give a yellow solution. The solution was evaporated under vacuum leaving a yellow solid. The solid was washed with pentane and dried under vacuum to give a bright yellow powder comprising catalyst 2. Yield 4.26 g (92%).1H NMR (CD2Cl2) δ 7.91 (dt, 1H), 7.61 (m, 1H), 7.59 (m, 1H), 7.47-7.52 (m, 3H) 7.39-7.41 (m, 1H) 7.34-7.38 (m, 1H), 7.06-7.10 (m, 1H), 6.01 (s, 1H), 2.64-2.81 (m, 2H), 2.04-2.18 (m, 2H), 1.93-1.99 (m, 2H), 1.95 (s, 3H), 1.91 (s, 3H), 1.90 (s, 3H), 1.85 (s, 3H). 1H NMR (C6D6) δ 8.07 (dt, 1H), 7.69 (m, 2H), 7.28-7.35 (m, 3H), 7.21 (m, 1H), 7.13-7.18 (overlapping multiplets, 3H), 6.86 (m, 1H), 5.93 (s, 1H), 2.40-2.57 (m, 2H), 1.80 (s, 3H), 1.77 (s, 3H), 1.74 (s, 3H), 1.64-1.72 (m, 2H), 1.58 (m, 2H), 1.55 (s, 3H), -0.46 (s, 3H), -1.25 (s, 3H).

[0279] Synthesis of Preparation 2, additional catalyst 2:

[0280] At -35 o To a vigorously stirred white suspension of zirconium tetrachloride bis(etherate) (2.00 g, 5.25 mmol, 1.00 equiv) in ether (30 mL) was added [tetramethylcyclopentadienyl)(3-phenylindenyl)silanide] lithium (2.46 g, 5.25 mmol, 1.00 equiv) to give a cold, hazy, light yellow mixture. After stirring for 20 minutes, the reaction became hazy, bright yellow. The reaction was stirred for 18 hours, then evaporated under vacuum, leaving a bright yellow solid. The solid was extracted with dichloromethane (30 mL, then 3 x 5 mL), and the extracts were filtered to give a bright yellow solution and a dark yellow solid. The solution was evaporated under vacuum, leaving a yellow solid. The solid was washed with pentane (20 mL) and dried under vacuum. The yield was 2.61 g (92%) of a bright yellow powder.1H NMR (CD2Cl2) δ 7.91 (dt, 1H), 7.60-7.58 (m, 2H), 7.53-7.47 (m, 3H), 7.43-7.34 (m, 2H), 7.10-7.06 (m, 1H), 6.01 (s, 1H), 2.80-2.65 (m, 2H), 2.15-2.06 (m, 2H), 1.97-1.93 (m, 1H), 1.94 (s, 3H), 1.92, (s, 3H), 1.90 (s, 3H), 1.85 (s, 3H).

[0281] Synthesis of Preparation 2, additional catalyst 1:

[0282] At -35 oC, to a yellow suspension of [tetramethylcyclopentadienylsilyl(3-phenylindenyl)]zirconium dichloride (catalyst 2) (2.00 g, 3.69 mmol, 1.00 equiv) in toluene (20 mL) was added 3.28 M methylmagnesium bromide in ether (2.35 mL, 7.71 mmol, 2.09 equiv) to give a cool, cloudy, yellow mixture. After stirring for 30 min, the reaction turned cloudy, amber-yellow. The reaction was stirred for 18 h to give a cloudy, dark amber-yellow mixture. The reaction was evaporated under vacuum, leaving a yellow-brown solid. The solid was extracted with toluene (30 mL, then 3 x 5 mL), and the extracts were filtered to give a yellow solution and a brown solid. The solution was evaporated under vacuum, leaving a yellow solid. Yield was 1.77 g (96%).1H NMR (CD2Cl2) δ 8.07 (dt, 1H), 7.70-7.68 (m, 2H), 7.35-7.28 (m, 3H), 7.23-7.13 (m, 2H), 6.89-6.84 (m, 1H), 5.93 (s, 1H), 2.53-2.42 (m, 2H), 1.80 (s, 3H), 1.77 (s, 3H), 1.75-1.66 (m, 2H), 1.74 (s, 3H), 1.61-1.56 (m, 2H), 1.55 (s, 3H), -0.46 (s, 3H), -1.25 (s, 3H).

[0283] Synthesis of catalyst 13 and catalyst 14:

[0284]

[0285] Dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silyl trifluoromethanesulfonate

[0286] To a pale amber solution of chlorodimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1- yl)silane (30.00 g, 140 mmol, 1.00 equiv) in toluene (100 mL) was added silver trifluoromethanesulfonate (38.00 g, 148 mmol, 1.06 equiv) to give a warm, cloudy, white mixture which slowly turned to a greyish purple. The reaction was stirred for 4 h, and then evaporated under vacuum, leaving a dark mixture. The mixture was extracted with pentane (100 mL, then 3 x 20 mL), and the extracts were filtered to give a yellow solution. The solution was evaporated under vacuum, leaving a yellow liquid. Yield 44.56 g (97%). 1H NMR (C6D6) δ 2.77 (br s, 1H), 1.74 (s, 6H), 1.60 (s, 6H), 0.042 (s, 6H).

[0287]

[0288] Tetrahydroindacene and lithium

[0289] at -35 o C to a yellow solution of 1,2,3,5-tetrahydro-s-indacene (12.70 g, 81.3 mmol, 1.00 equiv) in ether (100 mL) was added 2.71 M butyllithium (30.0 mL, 81.3 mmol, 1.00 equiv) to give a turbid Manila color mixture. The reaction was allowed to warm to room temperature and stirred for 30 minutes. To the reaction was added pentane (80 mL) and the mixture was filtered to give a Manila color solid. The solid was washed with pentane (40 mL) and dried under vacuum. Yield 13.05 g (99%). 1 H NMR (THF-d8) δ 7.16 (d, 2H), 6.42 (t, 1H), 5.81 (m, 2H), 2.84 (m, 4H), 1.97 (m, 2H).

[0290]

[0291] Dimethyl(1,5,6,7-tetrahydro-s-indacen-1-yl)(2,3,4,5-tetramethylcyclopenta-2,4- dien-1-yl)silane

[0292] at -35 o C to a light yellow solution of dimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1- yl)silyl trifluoromethanesulfonate (5.00 g, 15.2 mmol, 1.00 equiv) in ether (20 mL) was added tetrahydroindacene and lithium (2.65 g, 16.2 mmol, 1.07 equiv) to give a turbid amber-orange mixture. The reaction was allowed to warm to room temperature and stirred for 16 hours to give a clear orange solution. The reaction was then evaporated under vacuum leaving an orange solid. The solid was extracted with pentane (50 mL, then 3 x 20 mL) and the extracts were filtered to give an amber solution. The solution was evaporated under vacuum leaving an orange oil. Yield 5.04 g (99%). 1H NMR (C6D6) δ 7.40 (s, 1H), 7.34 (s, 1H), 6.91 (dm, 1H), 6.50 (dd, 1H), 3.64 (s, 1H), 2.97 (br s, 1H), 2.85 (q, 4H), 1.90-1.96 (m, 8H), 1.83 (d, 6H), -0.09 (s, 3H), -0.35 (s, 3H).

[0293]

[0294] [Tetramethylcyclopentadiene dimethylsilyl(tetrahydrodimethylsilyl)](diethyl ether)dilithium

[0295] At -35 o At C, 2.74M butyllithium (11.3 mL, 31.0 mmol, 2.07 equivalents) in hexane was added to an amber solution of dimethyl(1,5,6,7-tetrahydro-S-indarsen-1-yl)(2,3,4,5-tetramethylcyclopentan-2,4-dien-1-yl)silane (5.00 g, 14.9 mmol, 1.00 equivalent) in ether (20 mL) to give a turbid Manila-orange mixture. The reaction was warmed to room temperature and stirred for 24 hours. Pentane (20 mL) was added to the reaction mixture and the mixture was filtered to give a Manila-colored solid. The solid was washed with pentane and dried under vacuum. Yield: 5.86 g (93%). 1 H NMR (THF-d8) δ 7.46 (s, 1H), 7.16 (s, 1H), 6.65 (d, 1H), 5.91 (d, 1H), 3.40 (q, 4H), 2.82 (m, 4H), 2.10 (s, 6H), 1.95 (m, 2H), 1.87 (s, 6H), 1.13 (t, 6H), 0.59 (br s, 6H).

[0296]

[0297] [Tetramethylcyclopentadienyldimethylsilyl(tetrahydroindah)]zirconium dichloride (catalyst 14)

[0298] At -35 oC, to a white suspension of zirconium tetrachloride bis(etherate) (2.00 g, 5.25 mmol, 1.00 equiv) in ether (30 mL) was added [tetramethylcyclopentadienyl dimethylsilyl(tetrahydroindenyl)] lithium (2.21 g, 5.25 mmol, 1.00 equiv) in ether to give a hazy Manila colored mixture. The reaction was allowed to warm to room temperature and stirred for 18 hours. The hazy bright yellow mixture was then evaporated under vacuum leaving a yellow solid. The solid was extracted with dichloromethane (30 mL, then 4 x 5 mL) and the extracts were filtered to give an orange solution. The solution was evaporated under vacuum leaving a yellow solid. The solid was washed with pentane and dried under vacuum to give a bright yellow powder (Catalyst 14). Yield 2.22 g (86%). 1 H NMR (CD2Cl2) δ 7.47 (d, 1H), 7.30 (s, 1H), 7.07 (m, 1H),5.87 (d, 1H), 2.90-3.10 (dm, 2H), 2.83 (m, 2H), 2.05 (m, 2H), 1.924 (s, 3H),1.920 (s, 3H), 1.895 (s, 3H), 1.888 (s,3H), 1.15 (s, 3H), 0.94 (s, 3H).

[0299]

[0300] [ Tetramethylcyclopentadienyl dimethylsilyl(tetrahydroindenyl)] dimethylzirconium (Catalyst 13)

[0301] at -35 o C, to a white suspension of zirconium tetrachloride bis(etherate) (2.00 g, 5.25 mmol, 1.00 equiv) in ether (30 mL) was added [tetramethylcyclopentadienyl dimethylsilyl(tetrahydroindenyl)] lithium (2.21 g, 5.25 mmol, 1.00 equiv) in ether to give a hazy Manila colored mixture. The reaction was allowed to warm to room temperature and stirred for 18 hours. The hazy bright yellow mixture was then evaporated under vacuum leaving a yellow solid. The solid was extracted with dichloromethane (30 mL, then 4 x 5 mL) and the extracts were filtered to give an orange solution. The solution was evaporated under vacuum leaving a yellow solid. The solid was washed with pentane and dried under vacuum to give a bright yellow powder (Catalyst 14). Yield 2.22 g (86%). 1H NMR (C6D6) δ 7.47 (s, 1H), 7.25 (s, 1H),7.04 (d, 1H), 5.55 (d, 1H), 2.89 (m, 1H), 2.78 (m, 1H), 2.70 (t, 2H), 1.87 (multiple peaks overlapping and singlet, 8H), 1.79 (s, 3H), 1.65 (s, 3H), 0.73 (s, 3H), 0.52 (s,3H), -0.14 (s, 3H), -1.34 (s, 3H).

[0302] Example: Adjustment on base catalyst B1

[0303] The base or primary catalyst B1 (dimethylsilylbis(tetrahydroindenyl)zirconium dimethyl metallocene) to be adjusted was synthesized as described in US 5,314,973, followed by methylation with 2 equivalents of methylmagnesium bromide.

[0304] Adjustment procedure for catalyst 1:

[0305] The iC6 adjustment solution was prepared by adding pure catalyst 1 (0.04 wt%) to an empty tank and then filling the tank with iC6 diluent to the required total mass (6 kg).

[0306] Adjustment procedure for catalyst 13:

[0307] The iC6 adjustment solution was prepared by adding pure catalyst 13 (0.04 wt%) to an empty tank and then filling the tank with iC6 solvent / diluent to the required total mass (6 kg).

[0308] Polymerization

[0309] Gas phase fluid bed polymerizations were conducted using the same reactor conditions (bed temperature ~185°F, pressure ~290 psig, same ethylene, hydrogen, and hexene comonomer flow rates, and using ~10 mol% iC5 as an induced condensing agent, with ~25 mol% N2 present), except for using unadjusted catalyst B1 (Example 1) and catalyst 13 adjusted in iC6 solution in increased relative amounts into supported catalyst B1 slurry (Examples 2 and 3), as shown in Table 1, where the MI, HLMI, MIR, and density of each produced PE are also shown in Table 1. The same conditions were repeated for polymerization with base catalyst B1 (Example 4) and catalyst 13 adjusted in iC6 solution in similar relative amounts into supported base catalyst B1 slurry as Example 3 (Example 5), as shown in Table 2 below.

[0310] Table 3 below lists the molecular weight and g' data obtained from the GPC of Examples 1-5; it also shows the Figure 1 (for Examples 1-3) and Figure 2 (for Examples 4-5). Table 3, as well as Figure 1 and 2 indicate that as the relative amount of the tuning catalyst is increased, the PE copolymer shows lower g' values (indicating increasing long chain branching), as well as some very slight flattening and broadening of the molecular weight distribution as relatively more of the tuning catalyst is used. This generally indicates that copolymers made using the tuning catalyst would be expected to show improved processability (as shown by the decrease in g' and broadening of the molecular weight distribution).

[0311] Table 4 lists the CDBI and T75-T25 values (derived from the TREF-IR5 distribution) of the PE copolymers, where the TREF-IR5 distributions are also shown in Figure 3 (showing the TREF-IR5 distribution of Examples 4 and 5) and Figure 4 (showing the TREF-IR5 distribution of Examples 1-3). As can be seen in Table 4, the CDBI T75-T25 values remain approximately similar with Examples 1 (no tuning) to Examples 2-3 (with tuning catalyst 13), indicating that this catalyst is increasing long chain branching while maintaining similar comonomer distribution between polymer chains of different lengths.

[0312] In another aspect, with tuning catalyst 1, according to Table 4 and Figure 3 we see that a certain broad orthogonal composition distribution (BOCD) is obtained: the CDBI is appropriately decreased, consistent with a more uneven distribution of comonomer between polymer chains of different lengths; and the T75-T25 values derived from TREF-IR5 are increased. Consistently, Figure 3 showing a clear bimodal crystallinity in the Example 5 PE (as shown by the two distinct peaks of the TREF trace of Example 5) compared to the PE copolymer of Example 4 made without tuning. This can be explained by the different distribution of comonomer on polymer chains of different lengths, resulting in different regions of higher and lower crystallinity in the PE copolymer, respectively. In addition, the greater T75-T25 value of Example 5 indicates that the comonomer distribution of this PE has BOCD properties, meaning that the comonomer is preferentially incorporated on the longer polymer chains, and this is generally associated with superior processability without sacrificing strength properties in films made from such polyethylenes.

[0313] Table 1: Base Catalyst B1 Example Polymerization

[0314]

[0315] Table 2: Polymerization of Examples Using Another Basic Catalyst B1

[0316]

[0317] Table 3: GPC data, processability improvement as measured by g' using modified metallocene catalyst 13 and catalyst 1 together with base catalyst B1.

[0318]

[0319] Gel permeation chromatography via 4D GPC

[0320] Table 4: TREF Data

[0321]

[0322] Membranes were produced using Examples 1-5.

[0323] Under typical PE compounding conditions, the PE copolymer resins of Examples 1-3 and 5 were compounded with stabilizers to form granular resins by simple melt blending on a laboratory-scale twin-screw extruder (such as a Coperion W&P57). Prior to melt blending, the granular polyethylene resins were dry-blended in a drum mixer with the following additives: 500 ppm of Irganox™-1076, 1,000 ppm of Irgafos™ 168, and 600 ppm of Dynamar™ FX5920A.

[0324] The pellets obtained in Examples 1-3 and 5 above were combined with commercially available Enable 2005HH (Commercial C1) and converted into monolayer films on a 2.5" Battenfeld Gloucester production line equipped with a 6" oscillating die and a Future Design air ring with a 30:1 L:D ratio. The die gap was 60 mils and the blow-up ratio (BUR) was 2.5. Table 5 shows the film properties (and the repetition of MI, HLMI, and MIR for the base polymers used).

[0325] Table 5: Membrane data of the polymer obtained using basic catalyst B1

[0326]

[0327] Example: Adjustment on base catalyst B2

[0328] Similar to the preparation in US 6,936,675, synthesize / support the basic catalyst B2 ((n-propylcyclopentadienyl)2-hafnium dichloride).

[0329] Adjustment procedure for Catalyst 1 :

[0330] The iC6 adjustment solution was prepared by adding neat Catalyst 1 (0.04 wt%) to an empty tank and then filling the tank with solvent to the desired total mass (6 kg).

[0331] Adjustment procedure for Catalyst 13:

[0332] The iC6 adjustment solution was prepared by adding neat Catalyst 13 (0.04 wt%) to an empty tank and then filling the tank with solvent to the desired total mass (6 kg).

[0333] Polymerization of Example B2

[0334] Gas phase fluid bed polymerizations were conducted using the same reactor conditions (bed temperature ~ 170°F, pressure ~ 290 psig, same ethylene, hydrogen, and hexene comonomer flow rates, and using ~ 10 mol% iC5 as an induced condensing agent, with ~ 25 mol% N2 present), with the difference being the use of unadjusted Catalyst B2 (Example C2) and Catalyst 13 adjusted into supported Catalyst B2 slurry in an iC6 solution in increasing relative amounts (Examples 6 and 7), as shown in Table 6; and the additional difference being, for Example 8, the use of significantly less hydrogen in the reaction (about 30% of that used in Examples 6 and 7) to test production of PE copolymer with significantly less short polymer chains (higher Mn). The MI, HLMI, MIR, and density of each produced PE are also shown in Table 6. Polymerization under the same conditions as Examples 6 and 7 were repeated for Catalyst 1 (in an iC6 solution) adjusted into supported Catalyst B2 slurry in relatively high (Example 9) and low (Example 10) amounts, respectively, as shown in Table 7 below.

[0335] As can be seen, Example 8 indicates that too high of a Mn (e.g., greater than 35,000 g / mol) can decrease long chain branching production by the adjusted catalyst process; but all other examples consistently indicate that when B2 + adjustment is used, the adjusted catalyst results in increased presence of long chain branching (lower g’ values, see Table 8) while maintaining very similar comonomer distribution curves (which indicate moderate levels of BOCD) (as shown in CDBI and T75-T25 values, see Table 9) compared to B2 alone (as can be seen, the produced BOCD polyethylene copolymer has no appreciable LCB, see Tables 8 and 9). Figure 6 TREF-IR5 curves of Examples C2, 9, and 10) and Figure 7The TREF-IR5 curves of Examples C2 and 6-8 (Figure 6), where a clear crystallization peak can be seen for the crystalline bimodality. Thus, it is seen that the B2 + tuning catalysts provide a unique combination of moderate LCB and BOCD in the LLDPE copolymer.

[0336] Table 6: Base Catalyst B2 Example Polymerization Data

[0337]

[0338] The MI of Example 8 was not obtained because it was too low to flow adequately in standard test equipment

[0339] Table 7: Additional Base Catalyst B2 Example Polymerization Data

[0340]

[0341] Table 8: 4D GPC data, with processability improvement as measured by g’ using tuning metallocenes 1 and 13 along with catalyst B2.

[0342]

[0343] Table 9: TREF Data

[0344]

[0345] Film Production with Examples C2 and 6-9

[0346] Examples C2 and 6-9 PE copolymer resins were compounded into pellet resins by simple melt blending on a lab scale twin-screw extruder (such as a Coperion W&P57) under typical PE compounding conditions. Prior to melt mixing, the polyethylene resins in pellet form were dry blended with the following additives in a tumble mixer: 500 ppm of Irganox™-1076, 1,000 ppm of Irgafos™ 168, and 600 ppm of Dynamar™ FX5920A.

[0347] The pellets obtained above were converted into monolayer films on a 2.5" Battenfeld Gloucester line with an L:D of 30:1, equipped with a 6" oscillating die and a Future Design air ring. The die gap was 60 mil die gap and the blow up ratio (BUR) was 2.5. Table 10 shows the film properties (as well as the repeat of the MI, HLMI, and MIR of the base polymer used therein). The BOCD + LCB PE copolymers all show significantly improved shrink properties compared to the film made from the C2 PE copolymer, while also showing improved processability.

[0348] Table 10: Membrane data of polyethylene prepared by basic catalyst B2

[0349]

[0350] also, Figure 5 This is a graph showing the pull-out speed versus force for the PE copolymers of Examples C2, 6-7, and 9-10; and also the pull-out speed versus force for the following two commercial polyethylenes: LD103.09, a free radical polymerized LDPE with significantly long-chain branching (0.919 g / cm). 3 Density; I 1.1 g / 10 min 2.16 ), and Exceed TM 1018 MA, unbranched mLLDPE (0.918 g / cm³) 3 Density; I 1.0 g / 10 min 2.16 Both were available from ExxonMobil Product Solutions Company, Spring, Texas. As can be seen, the PE copolymers of Examples 6-7 and 9-10 achieved pull-out force versus speed profiles similar to LD103 LDPE, significantly better than the more standard mLLDPEs of C2 and Exceed1018 MA (lacking LCB).

[0351] Certain embodiments and features have been described using a set of upper and lower numerical limits. It should be understood that, unless otherwise stated, ranges are contemplated that include any combination of any two values ​​(e.g., any lower limit value combined with any upper limit value, any combination of two lower limits, and / or any combination of two upper limits). Some lower limits, upper limits, and ranges appear in one or more of the following claims. All numerical values ​​are indicated values ​​of “about” or “approximately” and take into account experimental errors and biases that would be expected by one of ordinary skill in the art.

[0352] For all purposes and in all jurisdictions where such inclusion is permitted, and to the extent that this description is consistent with this disclosure, all priority documents are incorporated herein by reference in their entirety. Furthermore, for all jurisdictions where such inclusion is permitted, and to the extent that this description is consistent with this disclosure, all documents and references cited herein, including test procedures, publications, patents, journal articles, etc., are incorporated herein by reference in their entirety.

[0353] Likewise, whenever a composition, an element, or a group of elements is described as having, comprising, or consisting essentially of, unless otherwise specified, it is understood that we also contemplate the same composition or group of elements with the proviso that they do not exclude an additional step, element, or material, whether or not specifically mentioned in the specification, as long as such step, element, or material does not affect the basic and novel characteristics of the claimed application, and additionally, the phraseology "consisting essentially of" does not exclude impurities or other minor elements customary in the art that do not affect the basic and novel characteristics of the claimed application.

[0354] While the claimed application has been described with reference to various embodiments and examples, a person of ordinary skill in the art having benefit of the present disclosure should understand that other embodiments can be devised without departing from the scope and spirit of the disclosure.

Claims

1. A process for producing a polyethylene copolymer, comprising: contacting a first composition with a second composition in a line to form a third composition, wherein: the first composition comprises a contact product of a first diluent, a first catalyst compound, a support material, and an activator, the second composition comprises a contact product of a second diluent and a second catalyst compound; introducing the third composition from the line into a gas-phase fluidized bed reactor; exposing the third composition to polymerization conditions by combining ethylene and at least one C3-C 20 α-olefin into the gas phase fluidized bed reactor, polymerizing the ethylene and the at least one C3-C 20 α-olefin; and obtaining the polyethylene copolymer, wherein the second catalyst compound is represented by Formula (III) or Formula (IV): (III) wherein: M of Formula (III) is a Group 4 metal; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 each independently is hydrogen, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted heteroatom, or a substituted or unsubstituted heteroatom-containing group, optionally wherein one or more pairs of R 5 and R 6 , R 7 and R 8 , R 8 and R 9 , and R 9 and R 10 join to form a substituted or unsubstituted fully saturated ring or a substituted or unsubstituted aromatic ring, and further wherein at least one of R 5 or R 6 independently is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group; T of formula (III) is represented by the formula R a 2J, (R a )4J2, or (R a )6J3, wherein each J is independently carbon, silicon, or germanium, and each R a is independently hydrogen, a halide, a substituted or unsubstituted C1to C 40 hydrocarbyl group, and wherein two R a groups optionally can be joined to form a substituted or unsubstituted fully saturated ring or a substituted or unsubstituted partially saturated ring; and each X of Formula (III) is independently a halo group, a substituted or unsubstituted hydrocarbyl group, a hydride group, an amide group, a substituted or unsubstituted alkoxy group, a sulfide group, a phosphide group, or a combination thereof, or two Xs are joined together to form a substituted or unsubstituted metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene; (IV) wherein: M of Formula (IV) is a Group 4 metal; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 each independently are hydrogen, a substituted or unsubstituted hydrocarbyl, a substituted or unsubstituted heteroatom, or a substituted or unsubstituted heteroatom-containing group, optionally wherein one or more of R 5 and R 6 , R 7 and R 8 , R 8 and R 9 , and R 9 and R 10 join to form a substituted or unsubstituted fully saturated ring or a substituted or unsubstituted aromatic ring, wherein (1) at least one of R 7 and R 8 , (2) at least one of R 8 and R 9 , or (3) at least one of R 9 and R 10 join to form a substituted or unsubstituted fully saturated ring fused to the indenyl ring shown in formula (IV); T of formula (IV) is represented by the formula R a 2J, (R a )4J2, or (R a )6J3, wherein each J is independently carbon, silicon, or germanium, and each R a is independently hydrogen, a halide, a substituted or unsubstituted C1to C 40 hydrocarbyl group, or two R a groups can form a substituted or unsubstituted completely saturated ring, a substituted or unsubstituted partially saturated ring, or a substituted or unsubstituted aromatic ring; and each X of Formula (IV) is independently a halo group, a substituted or unsubstituted hydrocarbyl group, a hydride group, an amide group, a substituted or unsubstituted alkoxy group, a sulfide group, a phosphide group, or a combination thereof, or two Xs are joined together to form a substituted or unsubstituted metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene.

2. The method of claim 1, wherein, the second catalyst is represented by Formula (III).

3. The method of claim 2, wherein, R of formula (III) 5 or at least one of R 6 is hydrogen.

4. The method of claim 3, wherein, R of formula (III) 5 or R 6 is an aryl group represented by the following formula: wherein each of R 11 , R 12 , R 13 , R 14 , and R 15 is independently hydrogen, a hydrocarbyl group, a heteroatom, or a heteroatom-containing group, or one or more pairs of R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , and R 14 and R 15 join to form a completely saturated, partially saturated, or aromatic ring.

5. The method of claim 4, wherein, each of R 11 , R 12 , R 13 , R 14 , and R 15 in Formula (III) is independently hydrogen or C1-C 10 alkyl.

6. The method of claim 5, wherein, each of R 11 , R 12 , R 13 , R 14 , and R 15 in formula (III) is hydrogen.

7. The method of any one of claims 2 to 5, wherein, each of R 1 , R 2 , R 3 , and R 4 in Formula (III) is C1-C 10 alkyl.

8. The method of claim 7, wherein, each of R in formula (III) 1 , R 2 , R 3 , and R 4 is methyl.

9. The method of any one of claims 2 to 8, wherein, each of R 7 , R 8 , R 9 , and R 10 in formula (III) is hydrogen.

10. The method of any one of claims 2 to 9, wherein, T of Formula (III) is selected from the group consisting of Si(CH2)3, Si(CH2)4, and Si(CH2)5.

11. The catalyst compound of any one of claims 2-10, wherein: M of Formula (III) is zirconium or hafnium, and each X of Formula (III) is independently a halo group or a C1-C5 alkyl group.

12. The method of claim 2, wherein, the catalyst compound is selected from the group consisting of: 。 13. The method of claim 12, wherein, the catalyst compound of Formula (III) is selected from the group consisting of: 。 14. The method of claim 1, wherein, the second catalyst is represented by Formula (IV).

15. The method of claim 14, wherein, each of R 7 , R 8 , R 9 , and R 10 is independently hydrogen or C1-C 10 alkyl, provided that (1) R 7 and R 8 , (2) R 8 and R 9 , or (3) at least one pair of R 9 and R 10 join to form a substituted or unsubstituted fully saturated ring fused to the indenyl ring shown in formula (IV).

16. The method of claim 14 or 15, wherein, (1) R 7 and R 8 , (2) R 8 and R 9 , or (3) R 9 and R 10 are joined to form a substituted or unsubstituted fully saturated ring fused to the indenyl ring shown in formula (IV).

17. The method of any one of claims 14-16, wherein, R 7 and R 8 to form a substituted or unsubstituted saturated C4ring, a substituted or unsubstituted saturated C5ring, a substituted or unsubstituted saturated C6ring, or a substituted or unsubstituted saturated C7ring, wherein the C4ring, C5ring, C6ring, or C7ring is fused to the indenyl ring shown in formula (IV).

18. The method of any one of claims 14-16, wherein, R 8 and R 9 are joined to form a substituted or unsubstituted saturated C4ring, a substituted or unsubstituted saturated C5ring, a substituted or unsubstituted saturated C6ring, or a substituted or unsubstituted saturated C7ring, wherein the C4ring, C5ring, C6ring, or C7ring is fused to the indenyl ring shown in formula (IV).

19. The method of any one of claims 14 to 16, wherein, R 9 and R 10 are joined to form a substituted or unsubstituted saturated C4ring, a substituted or unsubstituted saturated C5ring, a substituted or unsubstituted saturated C6ring, or a substituted or unsubstituted saturated C7ring, wherein the C4ring, C5ring, C6ring, or C7ring is fused to the indenyl ring shown in formula (IV).

20. The method of any one of claims 14 to 19, wherein, each of R 1 , R 2 , R 3 , and R 4 independently is hydrogen or C1-C 10 alkyl.

21. The method of claim 20, wherein, each of R in formula (IV) 1 , R 2 , R 3 , and R 4 is methyl.

22. The method of any one of claims 14 to 21, wherein, T is selected from the group consisting of SiMe2, SiEt2, and SiMeEt.

23. The process of any one of claims 14-22, wherein: M is zirconium or hafnium, and each X is independently a halo group or a C1-C5 alkyl group.

24. The method of claim 14, wherein, the catalyst compound of Formula (IV) is selected from the group consisting of: 。 25. The method of any one of claims 1 to 24, wherein, the polymerization conditions comprise: a reactor pressure of about 250 psig to about 350 psig; and a reactor temperature of about 70 °C to about 110 °C.

26. The method of any one of claims 1 to 25, wherein, at least one of the first diluent or the second diluent comprises a mineral oil having: about 0.85 g / cm3at 25 °C 3 about 0.9 g / cm3at 25 °C 3 density, a kinematic viscosity of about 150 cSt to about 200 cSt at 25 °C, and an average molecular weight of about 400 g / mol to about 600 g / mol.

27. The method of claim 26, wherein, at least one of the first diluent or the second diluent further comprises a wax having: about 0.7 g / cm 3 a density of from about 0.7 g / cm 3 at 100°C to about 0.95 g / cm about 5 mm 2 about 30 mm 2 a kinematic viscosity at 100 °C of from about 5 mm2 / s to about 30 mm2 / s, and a boiling point of about 200 °C or greater.

28. The method of any one of claims 25-27, wherein, the first catalyst compound is represented by Formula (II): Cp A (A)Cp B MX n (II), wherein: M is titanium, zirconium, or hafnium; n is 0 or an integer from 1 to 4; Cp A and Cp B is independently selected from the group consisting of substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, substituted or unsubstituted tetrahydroindenyl, and substituted or unsubstituted fluorenyl; each X is independently selected from the group consisting of halogen, hydrido, Ci to C 12 alkyl, C2to C 12 alkenyl, C6to C 12 aryl, C7to C 20 alkylaryl, Ci to C 12 alkoxy, C6to C 16 aryloxy, C7to C8alkylaryloxy, Ci to C 12 fluoroalkyl, C6to C 12 fluoroaryl and heteroatom-containing Ci to C 12 hydrocarbons, amines, phosphines, ethers, carboxylates, dienes, and substituted derivatives thereof; and A is a divalent bridging group containing at least one Group 13 to Group 16 atom.

29. The method of claim 28, wherein, A is selected from the group consisting of methylene, ethylene, dimethylsilyl, diethylsilyl, methyl-ethylsilyl, trifluoromethylbutylsilyl, bis(trifluoromethyl)silyl, di(n-butyl)silyl, di(n-propyl)silyl, di(i-propyl)silyl, di(n-hexyl)silyl, dicyclohexylsilyl, diphenylsilyl, cyclohexylphenylsilyl, t-butylcyclohexylsilyl, di(t-butylphenyl)silyl, and di(p-tolyl)silyl.

30. The method of any one of claims 28 or 29, wherein, The first catalyst compound is selected from the group consisting of (CH3)2Si(4,5,6,7-tetrahydroindenyl)2Zr(CH3)2, (CH3)2Si(4,5,6,7-tetrahydroindenyl)2ZrCl2, (CH2CH3)2Si(4,5,6,7-tetrahydroindenyl)2Zr(CH3)2, (CH2CH3)2Si(4,5,6,7-tetrahydroindenyl)2ZrCl2, ((CH3)2Si)2(4,5,6,7-tetrahydroindenyl)2Zr(CH3)2, ((CH3)2Si)2(4,5,6,7-tetrahydroindenyl)2ZrCl2, (CH3)2Si(4,5,6,7-tetrahydroindenyl)2Hf(CH3)2, (CH3)2Si(4,5,6,7-tetrahydroindenyl)2HfCl2, (CH2CH3)2Si(4,5,6,7-tetrahydroindenyl)2Hf(CH3)2, (CH2CH3)2Si(4,5,6,7-tetrahydroindenyl)2HfCl2, ((CH3)2Si)2(4,5,6,7-tetrahydroindenyl)2Hf(CH3)2, ((CH3)2Si)2(4,5,6,7-tetrahydroindenyl)2HfCl2, and combinations thereof.

31. The method of claim 30, wherein, The first catalyst compound is (CH3)2Si(4,5,6,7-tetrahydroindenyl)2Zr(CH3)2.

32. The method of any one of claims 24 to 31, wherein, The polyethylene copolymer has: a bimodal composition distribution, about 0.914 g / cm 3 a density of about 0.925 g / cm 3 and a melt index of about 0.1 g / 10 min to about 1 g / min.

33. The method of claim 32, wherein, The polyethylene copolymer has a melt index of about 0.3 g / 10 min to about 0.8 g / 10 min.

34. The method of any one of claims 32 or 33, wherein, The polyethylene copolymer has an olefin comonomer content of about 5 wt% to about 10 wt%.

35. The method of any one of claims 32-34, wherein, The polyethylene copolymer has a high load melt index (HLMI) of about 45 g / 10 min to about 70 g / 10 min.

36. The method of any one of claims 32 to 35, wherein, The polyethylene copolymer has a melt index ratio (MIR) of about 40 to about 60.

37. The method of any one of claims 32 to 36, wherein, The polyethylene copolymer has a molecular weight distribution (MWD) of about 4 to about 7.

38. The method of any one of claims 32 to 37, wherein, The polyethylene copolymer has a g'vis value of about 0.7 to about 0.

94.

39. The method of any one of claims 25-27, wherein, The first catalyst compound is represented by formula (I): Cp A Cp B MX n (I) wherein: M of formula (I) is titanium, zirconium, or hafnium; n of formula (I) is an integer from 0 to 4; each Cp of formula (I) A and Cp B is independently selected from the group consisting of substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, substituted or unsubstituted tetrahydroindenyl, and substituted or unsubstituted fluorenyl; and Each X in formula (I) is independently chosen from halogen, hydrogen, C1 to C2. 12 Alkyl, C2 to C 12 alkenyl, C6 to C 12 Aryl, C7 to C 20 alkylaryl, C1 to C 12 Alkoxy, C6 to C 16 Aryloxy, C7 to C8 alkylaryloxy, C1 to C 12 Fluoroalkyl, C6 to C 12 Fluoroaryl, heteroatom-containing C1 to C 12 The group consisting of hydrocarbons, amino groups, amines, phosphine, ethers, carboxyl groups, dienes, and their substituted derivatives.

40. The method of claim 39, wherein, The first catalyst compound is selected from the group consisting of: bis(ethylcyclopentadienyl)Zr(CH3)2, bis(ethylcyclopentadienyl)ZrCl2, bis(ethylcyclopentadienyl)Hf(CH3)2, bis(ethylcyclopentadienyl)HfCl2, (ethylcyclopentadienyl)(pentamethylcyclopentadienyl)ZrCl2, (ethylcyclopentadienyl)(pentamethylcyclopentadienyl)Zr(CH3)2, (ethylcyclopentadienyl)(pentamethylcyclopentadienyl)HfCl2, (ethylcyclopentadienyl)(pentamethylcyclopentadienyl)Hf(CH3)2, bis(n-propylcyclopentadienyl)Zr(CH3)2, bis(n-propylcyclopentadienyl)ZrCl2, bis(n-propylcyclopentadienyl)Hf(CH3)2, bis(n-propylcyclopentadienyl)HfCl2, (n-propylcyclopentadienyl, pentamethylcyclopentadienyl)ZrCl2, (n-propylcyclopentadienyl, pentamethylcyclopentadienyl)Zr(CH3)2, (n-propylcyclopentadienyl, pentamethylcyclopentadienyl)HfCl2, (n-propylcyclopentadienyl, pentamethylcyclopentadienyl)Hf(CH3)2, bis(n-butylcyclopentadienyl)Zr(CH3)2, bis(n-butylcyclopentadienyl)ZrCl2, bis(n-butylcyclopentadienyl)Hf(CH3)2, bis(n-butylcyclopentadienyl)HfCl2, (n-butylcyclopentadienyl, pentamethylcyclopentadienyl)ZrCl2, (n-butylcyclopentadienyl, pentamethylcyclopentadienyl)Zr(CH3)2, (n-butylcyclopentadienyl, pentamethylcyclopentadienyl)HfCl2, (n-butylcyclopentadienyl, pentamethylcyclopentadienyl)Hf(CH3)2, and combinations thereof.

41. The method of claim 40, wherein, The first catalyst compound is bis(n-propylcyclopentadienyl)Hf(CH3)2 or bis(n-propylcyclopentadienyl)Hf(Cl)2.

42. The method of any one of claims 39-41, wherein, The polyethylene copolymer has: a bimodal composition distribution, about 0.914 g / cm 3 a density of about 0.925 g / cm 3 and a melt index of about 0.1 g / 10 min to about 1 g / min.

43. The method of claim 42, wherein, The polyethylene copolymer has a melt index of about 0.3 g / 10 min to about 0.8 g / 10 min.

44. The method of any one of claims 39-43, wherein, The polyethylene copolymer has an olefin comonomer content of about 5 wt% to about 10 wt%.

45. The method of any one of claims 39-44, wherein, The polyethylene copolymer has a high load melt index (HLMI) of about 1 g / 10 min to about 25 g / 10 min.

46. The method of any one of claims 39 to 45, wherein, The polyethylene copolymer has a melt index ratio (MIR) of about 40 to about 60.

47. The method of any one of claims 39 to 46, wherein, The polyethylene copolymer has a molecular weight distribution (MWD) of about 4 to about 7.

48. The method of any one of claims 39 to 47, wherein, The polyethylene copolymer has a g'vis value of about 0.7 to about 0.

9.

49. The method according to any one of claims 39 to 47, wherein, The polyethylene copolymer has a g'vis value of about 0.9 to about 0.97.

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