Catalyst and polymerization for improved polyolefins

Abstract

The present disclosure relates to polyethylene polymers and films made therefrom. In some embodiments, the polyethylene copolymer comprises 90 wt% or more ethylene units and the remaining balance of C3-C20 comonomer units. The polyethylene copolymer has a bimodal composition distribution, a density of from 0.914 g / cm3 to 0.925 g / cm3, a melt index of from 0.1 g / 10 min to 1 g / 10 min, a high load melt index (HLMI) of from 21 g / 10 min to 70 g / 10 min, a melt index ratio (MIR) of from 40 to 65, and a molecular weight distribution (MWD) of from 4 to 7.

Description

[0001] Cross-references to related applications

[0002] This application claims the benefit of U.S. Provisional Application 63 / 503845, filed May 23, 2023, entitled “Polyethylenes Having Improved Processability and Films Thereof,” the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure relates to polyethylene polymers and films made therefrom. 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 each other, those with a higher melt index are better for processing, and the combination of a higher melt index and lower density is particularly good for cast film applications. However, less long-chain branching can lead to reduced film properties (e.g., tear properties in films / articles made from it). In practice, finding an LLDPE with a combination of density and melt index that is still commercially processable is challenging.

[0008] Some references that may be of interest in this regard include: U.S. Patent Nos. 6,479,424; 7,601,666; 9,068,033; 10,633,471 and 11,352,386; WIPO Publication WO 2021 / 257264; US 2021 / 0395404; US 2022 / 0185916; US 2022 / 0315680 and Foster et al., Journal of Organometallic Chemistry, 571 (1998) 171.

[0009] In general, there is a need for new LLDPEs that combine desirable properties (such as density, melt index properties, and long-chain branching) to simultaneously deliver commercially viable LLDPE polymerization and extrusion. Summary of the Invention

[0010] This disclosure relates to polyethylene polymers and films made therefrom.

[0011] In some embodiments, the polyethylene copolymer comprises about 90% by weight or more ethylene units and the balance C3-C 20 Comonomer unit. The polyethylene copolymer has a bimodal composition distribution, approximately 0.914 g / cm³. 3 To approximately 0.925 g / cm 3 The density, melt index from about 0.1 g / 10 min to about 1 g / min, high load melt index (HLMI) from about 21 g / 10 min to about 70 g / 10 min, melt index ratio (MIR) from about 40 to about 65, and molecular weight distribution (MWD) from about 4 to about 7.

[0012] In some embodiments, the polyethylene copolymer comprises about 90% by weight or more ethylene units and the balance C3-C 20 Comonomer unit. The polyethylene copolymer has a bimodal composition distribution, approximately 0.92 g / cm³. 3 To approximately 0.925 g / cm 3The density, melt index of about 0.4 g / 10 min to about 0.5 g / min, high load melt index (HLMI) of about 24 g / 10 min to about 29 g / 10 min, melt index ratio (MIR) of about 50 to about 65, and molecular weight distribution (MWD) of about 4 to about 7.

[0013] In some embodiments, the polyethylene copolymer comprises about 90% by weight or more ethylene units and the balance C3-C 20 Comonomer unit. The polyethylene copolymer has a bimodal composition distribution, approximately 0.92 g / cm³. 3 To approximately 0.925 g / cm 3 The density, melt index from about 0.9 g / 10 min to about 1 g / min, high load melt index (HLMI) from about 50 g / 10 min to about 60 g / 10 min, melt index ratio (MIR) from about 55 to about 65, and molecular weight distribution (MWD) from about 6 to about 7.

[0014] In some embodiments, the membrane comprises the polyethylene copolymer of this disclosure. Attached Figure Description

[0015] To gain a more detailed understanding of the features described above, a more specific description of the invention, which has been briefly outlined above, can be obtained by referring to embodiments, some of which are illustrated in the accompanying drawings. However, it should be noted that the drawings only illustrate general embodiments of the invention and should not be considered as limiting its scope; other equally effective embodiments are permissible.

[0016] Figure 1 This is a graph showing the 4D GPC (population or mass of polymer chains as a function of the logarithm of molecular weight (LogM)) traces of polyethylene copolymers prepared according to the various embodiments described herein using a base catalyst and / or a base catalyst plus a modifier catalyst. The y-axis value of the population or mass of the polymer chains can be labeled as d(wt fraction) / d(LogM) or equivalently as MWD(IR) to reflect that the y-axis value is a molecular weight population or distribution; however, it should be noted that in this context, MWD does not mean Mw / Mn as it does in other contexts herein. Figure 1 Also shown on its y-axis are the g' values ​​of polyethylene copolymers prepared using a base catalyst and / or a base catalyst plus a modifier catalyst according to the various embodiments described herein. vis ave value.

[0017] Figure 2This is a graph showing the 4D GPC (population or mass of polymer chains as a function of the logarithm of molecular weight (LogM)) traces of polyethylene copolymers prepared according to the various embodiments described herein using a base catalyst and / or a base catalyst plus a modifier catalyst. The y-axis value of the population or mass of the polymer chains can be labeled as d(wt fraction) / d(LogM) or equivalently as MWD(IR) to reflect that the y-axis value is the molecular weight population or distribution; however, it should be noted that in this context, MWD does not mean Mw / Mn as it does in other contexts herein. Figure 2 Also shown on its y-axis are the g' values ​​of polyethylene copolymers prepared using a base catalyst and / or a base catalyst plus a modifier catalyst according to the various embodiments described herein. vis ave value.

[0018] Figure 3 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.

[0019] 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. Detailed Implementation

[0020] 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.

[0021] This disclosure relates to polyethylene polymers and membranes made therefrom. The polyethylene polymers are copolymers formed from a dual-catalyst system, particularly such systems supplied to the polymerization reactor using a “tuning” method, and the polyethylene polymers possess 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.

[0022] Compared to conventional LLDPE, the polyethylene copolymers of this disclosure exhibit increased long-chain branching (also referred to as "LCB") in the copolymer, thereby providing reduced necking and increased tensile stability. The polyethylene copolymers of this disclosure can exhibit lower zero-shear viscosity, resulting in lower motor torque and lower melt pressure and melt temperature during extrusion, thus providing increased output of extruded polyethylene copolymer products. Furthermore, since the LCB is controlled (adjustable, e.g., by adjustment methods), the advantageous tear properties can also be controlled (adjustable) for the desired polymer end-use (e.g., shrink packaging film). For example, a reduction in motor torque and melt pressure can be observed during cast film manufacturing due to the increased polymer LCB. The LCB can be demonstrated, for example, by a high melt index ratio and / or rheological characteristics (e.g., η) shown by small-angle oscillating shear (SAOS) experiments. 0.01 / η 100 This is demonstrated by the ratio of complex viscosities (recorded at shear rates of 0.01 and 100 rad / s, respectively) and by the Van Gurp Palmen plot of the phase angle versus the complex modulus (which tracks the viscosity response of the polymer to the applied shear).

[0023] Furthermore, the polyethylene copolymers of this disclosure have been found to provide excellent shear-thinning characteristics; and can also be used to produce blown films with excellent bubble stability and / or little or no melt breakage. Compared to conventional LLDPE, the polyethylene copolymers of this disclosure can further provide films formed with reduced motor loads and melt pressures (which increase production volume) due to improved flow behavior. For example, reductions in melt pressure and melt temperature can be provided during blown film manufacturing. The films of this disclosure are particularly suitable for use as shrink packaging films (improved by the presence of LCB in the polyethylene copolymers of this disclosure).

[0024] In practice, the catalyst (e.g., for adjusting the method) and the method disclosed herein can adjust (e.g., in-line adjust) the LCB catalyst onto a supported catalyst to, for example, control (adjust) the melt index ratio of the polyethylene copolymer formed in the reactor. The catalyst used for adjustment can provide different molecular weight capacities compared to, for example, an in-line supported catalyst. These different molecular weight capacities of the catalyst provide a bimodal compositional distribution of the polyethylene copolymer formed in the reactor.

[0025] definition

[0026] As used herein, "olefin," or alternatively "alkene," is a linear, branched, or cyclic compound having at least one double bond between carbon and hydrogen. For the purposes of this specification and the appended claims, when a polymer or copolymer is referred to as "containing" an olefin, the olefin present in such polymer or copolymer is a polymeric form of the olefin. For example, when a copolymer is described as having an "ethylene" content of 35% to 55% by weight, it should be understood that the monomer units in the copolymer are derived from ethylene in the polymerization reaction, and the derived units are present at 35% to 55% by weight based on the copolymer.

[0027] As used herein, the terms “polyethylene polymer,” “polyethylene copolymer,” “polyethylene,” “ethylene polymer,” “ethylene copolymer,” and “ethylene-based polymer” mean a polymer or copolymer containing 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 homopolymers).

[0028] As used herein, “polymer” can refer to homopolymers, copolymers, interpolymers, terpolymers, etc. A “polymer” has two or more identical or different monomer units. A “homogeneous polymer” is a polymer having identical monomer units. A “copolymer” is a polymer having two or more different monomer units. A “terpolymer” is a polymer having three different monomer units. The term “different” used to refer to monomer units indicates that the monomer units differ from each other by at least one atom or are isomerically different. Therefore, as used herein, the definition of a copolymer includes terpolymers, etc. Similarly, as used herein, the definition of a polymer includes copolymers, etc.

[0029] As used in this article, it has a concentration greater than 0.860 to less than 0.910 g / cm³. 3 Ethylene polymers with a density of 0.910 to 0.925 g / cm³ are called ethylene plastites or ethylene plastides; 3 The density of ethylene polymers is referred to as "linear low-density polyethylene" (LLDPE) when they are substantially linear (with little or no long-chain branching), as is commonly the case for Ziegler-Natta or metallocene-catalyzed PE, or as "branched low-density polyethylene" (LDPE) when they are significantly branched (with a high degree of long-chain branching), as is commonly the case for radical-polymerized PE; 0.925 to 0.940 g / cm³ 3 It is known as "medium-density polyethylene" (MDPE); and has a density greater than 0.940 g / cm³. 3High-density polyethylene (HDPE) is a polymer of ethylene with a density that is defined according to ASTM D792. Test specimens are prepared according to ASTM D4703 – Appendix 1 Procedure C, then conditioned according to ASTM D618 – Procedure A, and then tested.

[0030] As used herein and unless otherwise specified, 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.

[0031] As used herein, a composition or membrane that is "free of" a component means a composition / membrane that is substantially free of the component or contains a component in an amount less than about 0.01% by weight of the total composition.

[0032] As used herein, the term “polymerization conditions” refers to conditions that, when in contact with an activated olefin polymerization catalyst, favor the reaction of one or more olefin monomers to produce a polyolefin polymer, including selections by a person skilled in the art of at least one polymerization reactor for temperature, pressure, reactant concentration, optional solvent / diluent, reactant mixing / addition parameters, and other conditions.

[0033] For the sake of brevity, this document only explicitly discloses certain ranges. However, a range from any lower bound can be combined with any upper bound to enumerate ranges not explicitly enumerated, and a range from any lower bound can be combined with any other lower bound to enumerate ranges not explicitly enumerated, just as a range from any upper bound can be combined with any other upper bound to enumerate ranges not explicitly enumerated. Furthermore, "in a range" or "within a range" includes every point or single value between its endpoints, even if not explicitly stated, and includes the endpoints themselves. Therefore, each point or single value can be combined as its own lower or upper bound with any other point or single value or any other lower or upper bound to enumerate ranges not explicitly enumerated.

[0034] For the purposes of this disclosure, the numbering scheme of the periodic table families described in Chemical and Engineering News, 63(5), page 27 (1985) is used.

[0035] The following abbreviations may be used in this article: 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, and THF is tetrahydrofuran.

[0036] As used herein, one or more olefin polymerization catalysts refer to any catalyst, such as organometallic complexes or compounds capable of coordination polymerization addition (whereby a series of monomers are added to the monomer chain at the organometallic active site).

[0037] The terms “substituent,” “radical,” “group,” and “structural part” are used interchangeably.

[0038] The term "α-olefin" refers to an olefin whose structure (R... ” R ’’’ )-C=CH2, where R ” and R ’’’ It can be hydrogen or any hydrocarbon group independently; such as R ” It is hydrogen and R ’’’ An alkyl group is an alkene with a terminal carbon-carbon double bond. "Linear α-alkene" is the α-alkene as defined in this paragraph, where R... ” It is hydrogen, and R ’’’ It is hydrogen or a linear alkyl group.

[0039] For the purposes of this disclosure, ethylene should be considered an α-olefin.

[0040] As used herein, and unless otherwise stated, the term "C" is used in conjunction with other terms. n "C" refers to hydrocarbons (one or more) having n carbon atoms (one or more) per molecule, where n is a positive integer. The term "hydrocarbon" refers to a class of compounds containing hydrogen atoms bonded 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 with different values ​​of n. Similarly, "C" m -C y "A group or compound refers to a group or compound containing a total number of carbon atoms from m to y. Therefore, C1-C..." 50 Alkyl groups are alkyl groups containing a total number of carbon atoms ranging from about 1 to about 50.

[0041] Unless otherwise specified (e.g., the definition of "substituted hydrocarbon group", "substituted aromatic compound", etc.), the term "substituted" means that at least one hydrogen atom has been replaced by at least one non-hydrogen group, such as a hydrocarbon group, a heteroatom, or a heteroatom-containing group, such as a halogen (such as Br, Cl, F, or I) or at least one functional group (such as -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*3, -GeR*3, -SnR*3, -PbR*3, wherein each R* is independently a hydrocarbon group or a halocarbyl group, and two or more R* may be joined together to form a substituted or unsubstituted fully saturated, partially unsaturated, or aromatic ring or polycyclic structure), or wherein at least one heteroatom has been inserted into the hydrocarbon ring.

[0042] The term "substituted hydrocarbon group" means a hydrocarbon group in which at least one hydrogen atom of the hydrocarbon group has been replaced by at least one heteroatom (such as a halogen group, e.g., Br, Cl, 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., wherein each R* is independently a hydrocarbon group or a halohydrocarbon group, and two or more R* can be joined together to form a substituted or unsubstituted fully saturated, partially unsaturated, or aromatic ring or polycyclic structure), or wherein at least one heteroatom has been inserted into the hydrocarbon ring.

[0043] The term "substituted aromatic compound" refers to an aromatic group in which one or more hydrogen groups are replaced by a hydrocarbon group, a substituted hydrocarbon group, a heteroatom, or a heteroatom-containing group.

[0044] The terms "hydrocarbyl radical," "hydrocarbyl group," or "hydrocarbyl" are used interchangeably and are defined as meaning a group containing only hydrogen and carbon atoms. For example, a hydrocarbyl group can be C1-C. 100 Groups, which can be linear, branched, or cyclic, and when cyclic, are aromatic or non-aromatic. Examples of such groups may include, but are not limited to, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl, and aryl groups such as phenyl, benzyl, and naphthyl.

[0045] The term "alkoxy" or "alkoxide" refers to an alkyl or aryl group bonded to an oxygen atom, such as an alkyl ether or aryl ether group (group / radical) attached to an oxygen atom, and may include aryl / alkyl groups where the aryl / alkyl group is C1 to C2. 10 Those with hydrocarbon groups. Alkyl groups can be linear, branched, or cyclic. Alkyl groups can be saturated or unsaturated. Suitable examples of alkoxy groups may include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, and phenoxy.

[0046] The term "alkenyl" refers to a linear, branched, or cyclic hydrocarbon group having one or more double bonds. These alkenyl groups may be optionally substituted. Examples of suitable alkenyl groups may include vinyl, propenyl, allyl, 1,4-butadienyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, and their substituted analogs.

[0047] The terms "alkyl radical," "alkyl group," and "alkyl" are used interchangeably throughout this disclosure. For the purposes of this disclosure, "alkyl" is defined as a C1-C group that can be linear, branched, or cyclic. 100 Alkyl groups. Examples of such groups may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, including their substituted analogs. Some examples of alkyl groups may include 1-methylethyl, 1-methylpropyl, 1-methylbutyl, 1-ethylbutyl, 1,3-dimethylbutyl, 1-methyl-1-ethylbutyl, 1,1-diethylbutyl, 1-propylpentyl, 1-phenylethyl, isopropyl, 2-butyl, sec-pentyl, sec-hexyl, etc.

[0048] The term "aryl" or "aryl group" refers to an aromatic ring and its substituted variants, such as phenyl, 2-methyl-phenyl, xylyl, and 4-bromo-xylyl. Similarly, "heteroaryl" refers to an aryl group in which one of the ring carbon atoms (or two or three ring carbon atoms) has been replaced by a heteroatom such as N, O, or S. As used herein, the term "aromatic" also refers to a pseudoaromatic heterocycle, which is a heterocyclic substituent having properties and structure (almost planar) similar to aromatic heterocyclic ligands, but is not an aromatic compound by definition; similarly, the term aromatic compound also refers to a substituted aromatic compound.

[0049] In the presence of the named alkyl, alkenyl, alkoxy, or aryl isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl), or in the absence of a specific isomer (e.g., butyl), a reference to alkyl, alkenyl, alkoxy, or aryl explicitly discloses all isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl).

[0050] The term "ring atom" refers to an atom that is part of a ring structure. For this definition, benzyl has six ring atoms, and tetrahydrofuran has five.

[0051] A heterocycle is a ring with a heteroatom in its ring structure, as opposed to a ring in which a hydrogen atom 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.

[0052] 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 percentage, and mol% is molar percentage. Molecular weight distribution (MWD), also known as polydispersity (PDI), is defined as Mw divided by Mn. Unless otherwise specified, all molecular weight units (e.g., Mw, Mn, Mz) are in g / mol.

[0053] The terms “catalyst compound”, “catalyst complex”, “transition metal complex”, “transition metal compound”, “precatalyst compound”, and “precatalyst complex” are used interchangeably.

[0054] A “catalyst system” is a combination of at least one catalyst compound, optionally at least one activator, optionally a co-activator, and optionally a support material. When used to describe such a pairing prior to activation, “catalyst system” means the unactivated catalyst complex (pre-catalyst) together with the activator and optionally the co-activator. When used to describe such a pairing after activation, it means the activated complex and the activator or other charge-balanced structural portion. The catalyst compound can be neutral, as in the pre-catalyst, or charged with counterions, as in the activated catalyst system. For the purposes of this disclosure and its claims, when a catalyst system is described as comprising components in a neutral, stable form, those skilled in the art will fully understand that the ionic form of the components is the form in which they react with monomers to produce polymers. A polymerization catalyst system is a catalyst system that can polymerize monomers into polymers. Furthermore, the catalyst compounds and activators represented by the formulas herein are intended to include both neutral and ionic forms of catalyst compounds and activators.

[0055] 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 an uncharged 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 heterocyclic. Examples of heterocyclic Lewis bases include pyridine, imidazole, thiazole, and furan.

[0056] Scavengers are compounds that can be added to promote polymerization by removing 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 combination with activators to form active catalysts. In at least one embodiment, the co-activator can be premixed with a transition metal compound to form an alkylated transition metal compound.

[0057] The term "continuous" refers to a system that operates continuously for an extended period of time without interruption or cessation. For example, a continuous method for producing polymers would be a method in which reactants are continuously introduced into one or more reactors and polymer products are continuously discharged.

[0058] Solution polymerization refers to a polymerization method in which the polymer is dissolved in a liquid polymerization medium (such as an inert diluent or one or more monomers or blends thereof). Solution polymerization can be homogeneous. Homogeneous polymerization is polymerization in which the polymer product is dissolved in a polymerization medium. A suitable system may not be turbid, as described in J. Vladimir Oliveira, C. Dariva and JC Pinto, Ind. Eng. Chem. Res., 2000, Vol. 29, p. 4627.

[0059] Bulk polymerization refers to a polymerization method in which the monomers and / or comonomers being polymerized are used as solvents or diluents, with little or no use of inert solvents or diluents. Small fractions of inert solvents / diluents may be used as carriers for catalysts and scavengers. Bulk polymerization systems contain less than 25% by weight of inert solvents or diluents, such as less than 10% by weight, less than 1% by weight, or 0% by weight.

[0060] The term "single catalyst compound" refers to a catalyst compound that corresponds to a single structural formula, although such catalyst compounds may contain and be used as a mixture of isomers (e.g., stereoisomers).

[0061] A catalyst system utilizing a single catalyst compound refers to a catalyst system prepared using only a single catalyst compound in its preparation. Therefore, this type of catalyst system differs from, for example, a "double" catalyst system (which is prepared using two catalyst compounds with different structural formulas), such as differences in the atomic linkages, number of atoms, and / or type of atoms in the two catalyst compounds. Thus, if they differ in at least one atom's number, type, or linkage, one catalyst compound is considered different from the other. For example, bis(indenyl)zirconia is different from (indenyl)(2-methylindenyl)zirconia, which in turn is different from (indenyl)(2-methylindenyl)hafnium dichloride. The only difference is that catalyst compounds that are stereoisomers of each other are not considered different catalyst compounds. For example, racemic-dimethylsilylbis(2-methyl-4-phenyl)dimethylhafnium and meso-dimethylsilylbis(2-methyl-4-phenyl)dimethylhafnium are considered not different.

[0062] The terms “co-catalyst” and “activator” are used interchangeably herein and are defined as any compound that can activate any of the catalyst compounds described above by converting a neutral catalyst compound into a catalytically active catalyst compound cation.

[0063] Aggregation methods

[0064] Polymerization methods can include gas-phase polymerization reactions, and particularly fluidized bed gas-phase polymerization reactions. Typically, in fluidized bed processes for producing polymers, a gaseous stream containing one or more monomers is continuously circulated through a fluidized bed under reactive conditions in the presence of a catalyst. In some embodiments, the reaction medium includes a condenser, which is typically a noncoordinate inert liquid that is converted to gas during the polymerization process, such as isopentane, isohexane, or isobutane. The gaseous stream is discharged from the fluidized bed and recycled back to the reactor. Simultaneously, the polymer product is discharged from the reactor and fresh monomers are added to replace the monomers used in polymerization. (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.) Gas-phase polymerization can be carried out in any suitable reactor system, such as a stirred or paddle reactor system. 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.

[0065] In such polymerization methods, the gas-phase fluidized bed method involves continuously passing a stream containing ethylene and olefin comonomers through a fluidized bed reactor at a rate sufficient to maintain a bed of solid particles in suspension under reaction conditions and in the presence of a catalyst composition. The stream containing unreacted ethylene and olefin comonomers (which may be referred to as the "recycled gas" stream) is continuously discharged from the reactor, compressed, cooled, optionally partially or completely condensed, and recycled back to the reactor. The resulting polyethylene copolymer is discharged from the reactor, and alternative ethylene and olefin comonomers are added to the recycled stream. In some embodiments, the gas stream contains a gas that is inert to the catalyst composition and reactants.

[0066] The circulating gas may include an induced condensate (ICA). An ICA is one or more non-reactive alkanes that are condensable in the polymerization process and are used to remove the heat of reaction. In some embodiments, the non-reactive alkanes are selected from C1-C6 alkanes, such as propane, butane, isobutane, pentane, isopentane, hexane, and one or more of their isomers and derivatives. In some cases, mixtures of two or more such ICAs may be particularly available (e.g., propane and pentane, propane and butane, butane and pentane, etc.).

[0067] 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 temperatures 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 hydrogen to ethylene ratio 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.

[0068] The molar percentage of ethylene (based on total monomers) can be about 25 to about 90 molar percentages, such as about 50 to about 90 molar percentages, or about 70 to about 85 molar percentages, and the partial pressure of ethylene (in the reactor) can be about 75 psia (517 kPa) to about 300 psia (2069 kPa), or about 100 psia to about 275 psia (689-1894 kPa), or about 150 psia to about 265 psia (1034-1826 kPa), or 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 the range of low values ​​of 35 mol%, 40 mol%, 45 mol%, 50 mol%, or 55 mol% to high values ​​of 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol%, or 95 mol%, and additionally, the ethylene mol% is measured based on the total number of moles of gases in the reactor (if present, including ethylene and / or comonomer gases and inert gases, such as nitrogen, isopentane, or one or more other ICAs); such as vol-ppm hydrogen, for convenience, this measurement can be performed at the recirculated gas outlet rather than in the reactor itself. The concentration of comonomers can be from about 0.2 mol% to about 1 mol%, such as low values ​​of 0.2 mol%, 0.3 mol%, 0.4 mol% or 0.5 mol% to high values ​​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%.

[0069] Using adjusted aggregation

[0070] The aggregation method disclosed herein can be performed using an "adjustment" method. Adjustment methods are described, for example, in U.S. Patent Publication No. 2021 / 0395404, and particularly in connection with therein... Figure 1 And in paragraphs

[0113] –

[0124] therein, this description is incorporated herein by reference. An overview of such methods specifically used in this disclosure is also provided below.

[0071] For delivering catalyst slurry to the reactor, a high solids concentration typically increases slurry viscosity. High solids concentration also increases the amount of foaming that typically occurs in the catalyst slurry vessel. High slurry viscosity and foaming can lead to handling, storage, and reactor injection problems. Low-viscosity diluents can be added to the slurry to reduce viscosity. However, reduced viscosity promotes sedimentation of the slurry in the solution, which can lead to clogging of reactor components and accumulation of solids on the walls of the catalyst slurry vessel.

[0072] A second catalyst solution can be added to the slurry (i.e., "adjusted") to modify one or more properties of the polymer formed in the reactor "in situ." Such "adjustment" methods are very economical because they do not require polymerization to be stopped in order to adjust polymer properties if the catalyst system does not behave as desired. However, the second catalyst is typically delivered to the slurry as a low-viscosity solution, which can promote sedimentation of the slurry solution and subsequent gelation and / or clogging of reactor components.

[0073] Therefore, methods for polymerizing one or more olefins may include using a dual-catalyst system (e.g., by in-situ supported second catalyst). In particular, the method includes combining a catalyst component slurry with a catalyst component solution ("adjusted") to form a third catalyst composition, and introducing the third composition into a polymerization reactor (e.g., a gas-phase reactor).

[0074] In some embodiments, the method includes contacting a first composition with a second composition in a pipeline leading to a reactor to form a third composition. The first composition comprises a first catalyst (or catalyst compound), a support, and a diluent. The first catalyst or catalyst compound may be referred to herein as a “primary catalyst” or a “base catalyst.” The second composition comprises a second catalyst (or catalyst compound) and a second diluent. The second catalyst or catalyst compound may be referred to as a “tuning catalyst,” and particularly within the scope of the methods described herein, the tuning method is 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 method includes introducing the third composition from the pipeline into a gas-phase fluidized bed reactor and exposing the third composition to polymerization conditions. The method includes obtaining a polyolefin.

[0075] The method may include adjusting reactor conditions, such as the amount of a second catalyst fed into the reactor (via a pipeline leading to the reactor), to control one or more polymeric properties of the polyolefin obtained from the reactor.

[0076] By using the metallocene catalyst disclosed herein as a second catalyst, the second catalyst being linearly adjusted to feed the slurry of the first catalyst at various ratios and vice versa, and by different reactor conditions (including temperature, reaction mixture component concentration, etc.), beneficial polyolefin products can be formed.

[0077] Furthermore, it should be envisioned that, for different catalysts selected, some of the second catalysts may initially be co-deposited with the first catalyst on a common support, and the remaining amount of the first or second catalyst may be added as an adjuster.

[0078] The catalyst system may include a catalyst compound in a slurry and added solution catalyst components to the slurry. Typically, depending on solubility, a first catalyst and / or a second catalyst will be loaded in the initial slurry. However, in at least one embodiment, the initial catalyst component slurry may not contain a catalyst. In this case, two or more solution catalysts may be added to the slurry as "modifiers" to ensure that each is loaded.

[0079] Furthermore, despite the distinction between “primary catalyst” or “basic catalyst” and “adjusting catalyst” as noted above, it is conceivable that the role of the primary catalyst described herein can be readily interchanged with that of the adjusting catalyst to achieve similar effects (i.e., in various embodiments, any “primary catalyst” described herein can be used as a “secondary catalyst” in the method just described; and any “adjusting catalyst” can be used as a “first catalyst” in the method just described).

[0080] The slurry may include one or more activators and a support, as well as one or more catalyst compounds. For example, the slurry may include two or more activators (such as aluminoxanes and modified aluminoxanes) and catalyst compounds, or the slurry may contain a supported activator and more than one catalyst compound. In at least one embodiment, the slurry comprises a support, an activator, and two catalyst compounds. In another embodiment, the slurry comprises a support, an activator, and two different catalyst compounds, which may be added to the slurry individually or in combination. A slurry containing silica and aluminoxane may be contacted with the catalyst compounds to react, and subsequently contacted with another catalyst compound (e.g., as a "modifier").

[0081] One or more diluents can be used to facilitate the combination of any two or more components of the catalyst system in the slurry or in the modified catalyst solution. For example, a unit-point catalyst compound and an activator can be combined in the presence of toluene or other non-reactive hydrocarbons or mixtures of hydrocarbons to provide a catalyst mixture. Other suitable diluents besides toluene may include, but are not limited to, ethylbenzene, xylene, pentane, hexane, heptane, octane, other hydrocarbons, or any combination thereof. A dry or toluene-mixed support can then be added to the catalyst mixture, or a catalyst / activator mixture can be added to the support.

[0082] The diluent may be or may include mineral oil. According to ASTM D4052, mineral oil can have a concentration of approximately 0.85 g / cm³ at 25°C. 3 To approximately 0.9 g / cm 3 Such as approximately 0.86 g / cm 3 Approximately 0.88 g / cm 3 The density. According to ASTM D341, mineral oils can have a kinematic viscosity of about 150 cSt to about 200 cSt at 25°C, such as about 160 cSt to about 190 cSt, such as about 170 cSt. According to ASTM D2502, mineral oils 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. In at least one embodiment, the mineral oil is HYDROBRITE from Sonneborn, LLC. ® 380 PO White Mineral Oil ("HB380").

[0083] Diluents may additionally include waxes, which can provide increased viscosity to slurries such as mineral oil slurries. Waxes are food-grade petroleum jelly, also known as petroleum petrolatum. Waxes can be paraffin wax. Paraffin waxes include SONO JELL. ® Paraffin, such as SONO JELL from Sonneborn, LLC ® 4 and SONO JELL ®9. In at least one embodiment, the slurry contains 5% by weight or more, such as 10% by weight or more, such as 25% by weight or more, such as 40% by weight or more, such as 50% by weight or more, such as 60% by weight or more, such as 70% by weight or more, and so on. For example, a mineral oil slurry may contain about 70% by weight of mineral oil, about 10% by weight of wax, and about 20% by weight of one or more supported catalysts (e.g., a supported dual catalyst). The increased viscosity provided by the wax in the slurry (such as a mineral oil slurry) provides reduced settling of one or more supported catalysts in a conditioning vessel or catalyst tank (for introducing the supported catalyst into the pipeline); while conditioning efficiency can be suitably maintained. In at least one embodiment, the wax has about 0.7 g / cm³. 3 (at 100°C) to approximately 0.95 g / cm³ 3 (At 100°C), such as approximately 0.75 g / cm³ 3 (at 100°C) to approximately 0.87 g / cm³ 3 Density (at 100°C). Wax can have a density of approximately 5 mm. 2 / s (at 100°C) to approximately 30 mm 2 The kinematic viscosity is 600 kJ / s (at 100°C). Waxes can have boiling points of about 200°C or higher, such as about 225°C or higher, and such as about 250°C or higher. Waxes can have melting points of about 25°C to about 100°C, such as about 35°C to about 80°C.

[0084] The catalyst component solution (referred to as the "adjustment" solution) may contain only one or more catalyst compounds or may contain an activator. In at least one embodiment, the one or more catalyst compounds in the catalyst component solution are unsupported. The catalyst solution used in the adjustment method can be prepared by dissolving the catalyst compound and optionally the activator in a liquid diluent. The liquid diluent may be an alkane, such as C5 to C6. 30 Alkanes, or C5 to C6 10 Alkanes. Cyclic alkanes such as cyclohexane and aromatic compounds such as toluene may also be used. Mineral oil is used as a diluent for other alkanes such as C5 to C6. 30 Alkane substitution or supplementation. According to ASTM D4052, mineral oil can have approximately 0.85 g / cm³ at 25°C. 3 To approximately 0.9 g / cm 3 Such as approximately 0.86 g / cm 3 Approximately 0.88 g / cm 3The density. According to ASTM D341, mineral oils can have a kinematic viscosity of about 150 cSt to about 200 cSt at 25°C, such as about 160 cSt to about 190 cSt, such as about 170 cSt. According to ASTM D2502, mineral oils 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. In at least one embodiment, the mineral oil is HYDROBRITE from Sonneborn, LLC. ® 380 PO White Mineral Oil ("HB380").

[0085] The solution used should be liquid and relatively inert under polymerization conditions. In at least one embodiment, the liquid used in the catalyst compound solution is different from the diluent used in the catalyst component slurry. In another embodiment, the liquid used in the catalyst compound solution is the same as the diluent used in the catalyst component solution.

[0086] In an alternative implementation, the catalyst is not limited to a slurry arrangement, as the mixed catalyst system can be prepared and dried on a support. The dried catalyst system can then be fed into the reactor via a dry feed system.

[0087] In the production process of fumed polyethylene, it is desirable to use one or more electrostatic control agents to help regulate the electrostatic level in the reactor. As used herein, an electrostatic control agent is a chemical composition that, when introduced into a fluidized bed reactor, can influence or drive the static charge (negative, positive, or zero charge) in the fluidized bed. The specific electrostatic control agent used can depend on the nature of the static charge, and the choice of electrostatic control agent can vary depending on the polymer being produced and the single-site catalyst compound used.

[0088] Static control agents, such as aluminum stearate, can be used. The static control agent used can be selected based on its ability to receive static charge in the fluidized bed without adversely affecting productivity. Other suitable static control agents may include aluminum distearate, ethoxylated amines, and antistatic compositions.

[0089] main catalyst

[0090] The catalyst used in the polymerization of this disclosure may be a metallocene catalyst. Metallocene catalysts are well described, for example, in US2021 / 0395404 in paragraphs

[0066] –

[0083] , which is incorporated herein by reference. Any metallocene catalyst according to that description may be suitable as the primary catalyst in the systems and methods described herein. Of particular interest are metallocene catalysts having bridging or non-bridging cyclopentadienyl (Cp) and / or indene (In) ligands bonded to at least one Group 3 to Group 12 metal atom (preferably Zn, Hf, or Ti), and one or more (preferably two) leaving groups bonded to the at least one metal atom (preferably each leaving group is independently a C1 to C4 alkyl such as methyl, or a halogen such as Cl).

[0091] More specifically, the primary catalyst according to various embodiments may comprise unbridged hafnium diacene or zirconium diacene, such as the hafnium diacene described in column 3, line 62 through column 4, line 51 of U.S. Patent No. 7,078,467, which is incorporated herein by reference, and its zirconium diacene analogues; and / or the catalyst described in column 4, line 22 through column 7, line 36 of U.S. Patent No. 6,936,675, which is also incorporated herein by reference. For example, suitable primary catalysts may comprise unbridged bis-indenyl hafnium diacene or zirconium diacene, such as one or more of the following:

[0092] bis(n-ethylcyclopentadienyl)Zr(CH3)2,

[0093] bis(n-ethylcyclopentadienyl)ZrCl2,

[0094] bis(n-ethylcyclopentadienyl)Hf(CH3)2,

[0095] bis(n-ethylcyclopentadienyl)HfCl2,

[0096] (n-ethylcyclopentadienyl, pentamethylcyclopentadienyl)ZrCl2

[0097] (n-ethylcyclopentadienyl, pentamethylcyclopentadienyl)Zr(CH3)2,

[0098] (n-ethylcyclopentadienyl, pentamethylcyclopentadienyl)HfCl2

[0099] (n-ethylcyclopentadienyl, pentamethylcyclopentadienyl)Hf(CH3)2,

[0100] bis(n-propylcyclopentadienyl)Zr(CH3)2,

[0101] bis(n-propylcyclopentadienyl)ZrCl2,

[0102] bis(n-propylcyclopentadienyl)Hf(CH3)2,

[0103] bis(n-propylcyclopentadienyl)HfCl2,

[0104] (n-propylcyclopentadienyl, pentamethylcyclopentadienyl)ZrCl2

[0105] (n-propylcyclopentadienyl, pentamethylcyclopentadienyl)Zr(CH3)2

[0106] (n-propylcyclopentadienyl, pentamethylcyclopentadienyl)HfCl2

[0107] (n-propylcyclopentadienyl, pentamethylcyclopentadienyl)Hf(CH3)2

[0108] bis(n-butylcyclopentadienyl)Zr(CH3)2,

[0109] bis(n-butylcyclopentadienyl)ZrCl2,

[0110] bis(n-butylcyclopentadienyl)Hf(CH3)2,

[0111] bis(n-butylcyclopentadienyl)HfCl2,

[0112] (n-Butylcyclopentadienyl, pentamethylcyclopentadienyl)ZrCl2

[0113] (n-Butylcyclopentadienyl, pentamethylcyclopentadienyl)Zr(CH3)2

[0114] (n-Butylcyclopentadienyl, pentamethylcyclopentadienyl)HfCl2

[0115] (n-Butylcyclopentadienyl, pentamethylcyclopentadienyl)Hf(CH3)2

[0116] Or a combination thereof.

[0117] In other embodiments, the primary catalyst may be a bridged metallocene catalyst, such as those described in one or more of US 5,314,973; US 6,255,426 (particularly lines 61 through 17 of column 2, which are incorporated herein by reference) and US 5,763,543 (particularly lines 42 through 22 of column 4, which are incorporated herein by reference). Specific examples include bridged bis-indenyl catalysts, such as bridged bis-indenylzirconium or bridged bis-indenyl hafnium, particularly those in which each indenyl ligand is unsubstituted (e.g., a tetrahydroindenyl ligand), and in which the bridge is C1-C. 10Alkyl or R1R2Si, wherein R1 and R2 are each independently selected from methyl, ethyl, propyl, butyl, and pentyl. Examples of such bridging bis-indenyl hafnium eccentricum and zirconium eccentricum 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)2Zr(CH3)2, ((CH3)2Si)2(4,5,6,7-tetrahydroindenyl)2Zr(CH3)2, and ((CH3)2Si)2(4,5,6,7-tetrahydroindenyl)2Zr(CH3)2. (CH3)2ZrCl2, (CH3)2Si(4,5,6,7-tetrahydroindene)2Hf(CH3)2, (CH3)2Si(4,5,6,7-tetrahydroindene)2HfCl2, (CH2CH3)2Si(4,5,6,7-tetrahydroindene)2Hf(CH3)2, (CH2CH3)2Si(4,5,6,7-tetrahydroindene)2HfCl2, ((CH3)2Si)2(4,5,6,7-tetrahydroindene)2Hf(CH3)2, ((CH3)2Si)2(4,5,6,7-tetrahydroindene)2HfCl2, or combinations thereof.

[0118] Although catalyst compounds may be written or shown with methyl, chloro, or phenyl leaving groups attached to the central metal, it is understood that these groups can be different. For example, each of these ligands can independently be benzyl (Bn), methyl (Me), chloro (Cl), fluorine (F), or any number of other groups, including organic or heteroatom groups. Furthermore, these ligands will change during the reaction as the pre-catalyst is converted into an active catalyst for the reaction to proceed.

[0119] Second catalyst (e.g., "tuned" catalyst)

[0120] The second catalyst disclosed herein comprises a second catalyst supported together with the first catalyst on a support to form a dual-catalyst system. The second catalyst can be supported and the dual-catalyst system can be separated. Alternatively, the second catalyst can be loaded online onto the supported first catalyst as a "tuning" catalyst in its path to the reactor. The dual-catalyst system (e.g., also having an activator) is introduced into the reactor (e.g., a gas-phase reactor).

[0121] In some implementations, the second catalyst is represented by formula (III):

[0122] (III)

[0123] in:

[0124] M is a Group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf);

[0125] R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 and R 10 Each of these is independently hydrogen, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted heteroatom, or a substituted or unsubstituted heteroatom-containing group; optionally, R 5 and R 6 R 7 and R 8 R 8 and R 9 and R 9 and R 10 One or more pairs of rings can join to form a fully saturated ring, substituted or unsubstituted, or a substituted or unsubstituted aromatic ring, and furthermore, R 5 and R 6 At least one pair of them is independently a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group;

[0126] T represents R a 2J、(R a )4J2, or (R a )6J3, where each J is independently C, Si, or Ge, and each R a Independently, it is hydrogen, halogenated, substituted or unsubstituted C1 to C2. 40 Hydrocarbon group, and two of the R groups are... a Optionally, they can be joined to form substituted or unsubstituted cyclic structures, including fully saturated substituted or unsubstituted rings, or partially saturated substituted or unsubstituted rings (preferably, such ring structures have 2-10 carbon atoms in addition to the J atom, and the ring structure is preferably saturated); and

[0127] Each X is independently a halogen, a substituted or unsubstituted hydrocarbon, a hydrogen, an amino, a substituted or unsubstituted alkoxy, a thio, a phosphorus, or a combination thereof, or two Xs are joined together to form a substituted or unsubstituted metal ring, or two Xs are joined together to form a chelate ligand, a diene ligand, or an alkylene.

[0128] Where R 5 Or R 6 At least one of them is independently a substituted or unsubstituted aryl or a substituted or unsubstituted heteroaryl.

[0129] In some implementation schemes, R 5 Or R 6 At least one of them is hydrogen, and R 5 Or R 6 Another independent element is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. An aryl or heteroaryl group can be represented by the following formula:

[0130] , where R 11 R 12 R 13 R 14 and R 15 Each of these is independently a hydrogen, hydrocarbon group, heteroatom, or heteroatom-containing group, or R 11 and R 12 R 12 and R 13 R 13 and R 14 and R 14 and R 15 One or more pairs of rings in R combine to form fully saturated, partially saturated, or aromatic rings. In some embodiments, R 11 R 12 R 13 R 14 and R 15 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 11 R 12 R 13 R 14 and R 15 Each of them is hydrogen.

[0131] In some implementations, R of formula (III) 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.

[0132] In some implementations, R of formula (III) 7 R 8 R 9 and R 10 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 7 R 8 R 9 and R 10 Each of them is hydrogen.

[0133] In some implementations of equation (III), T is derived from equation 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... a A cyclic structure 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, 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 (siliconehexacyclobutyl), Si(CH2)4 (siliconehexapentyl), or Si(CH2)5 (siliconehexacyclohexyl).

[0134] In some implementations, R of formula (III) 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 and R 10 (and R) 11 R 12 R 13 R 14 and R 15 Each of the following is independently hydrogen, hydrocarbon, silylcarbyl, alkoxy, halogen, or silylalkoxy.

[0135] 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 group, such as chlorine. In still other embodiments, each X is independently a C1-C4 alkyl group, such as methyl. In some embodiments, each X is independently selected from substituted or unsubstituted hydrocarbon groups, heteroatoms, or substituted or unsubstituted heteroatom-containing groups, such as methyl, benzyl, trimethylsilyl, methyl(trimethylsilyl), neopentyl, ethyl, propyl, butyl, phenyl, hydrido, chlorine, fluorine, bromine, iodine, trifluoromethanesulfonate, dimethylamido, diethylamido, dipropylamido, and diisopropylamido.

[0136] In some embodiments of formula (III), (1) M is Zr or Hf, (2) X is a C1-C5 alkyl group, (3) T is Si(CH2)3, Si(CH2)4, or Si(CH2)5, and (4) R 5 R 7 R 8 R 9 and R 10 Independently hydrogen or substituted or unsubstituted C1-C 10 Alkyl, (5) R 1 R 2 R 3 and R 4 It is independently methyl, ethyl, or propyl, and (6) R 6 It is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. In some embodiments, R 6 An aryl group is represented by the following formula:

[0137] , where R 11 R 12 R 13 R 14 and R 15 Each of these is independently a hydrogen, hydrocarbon group, heteroatom, or 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 pairs of rings in R combine to form fully saturated, partially saturated, or aromatic rings. In some embodiments, R 11 R 12 R 13 R 14 and R 15 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 11 R 12 R 13 R 14 and R 15 Each of them is hydrogen.

[0138] In some embodiments of formula (III), the catalyst is selected from:

[0139] In some implementations, the second catalyst is represented by formula (IV):

[0140] (IV)

[0141] in:

[0142] M is a Group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf);

[0143] R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 and R 10 Each of these is independently hydrogen, a substituted or unsubstituted hydrocarbon 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 One or more pairs of rings join to form a fully saturated ring, substituted or unsubstituted, or a substituted or unsubstituted aromatic ring;

[0144] T represents R a 2J、(R a )4J2, or (Ra )6J3, where each J is independently C, Si, or Ge, and each R a Independently, it is hydrogen, halogenated, substituted or unsubstituted C1 to C2. 40 Hydrocarbon group, or two Rs a It can form substituted or unsubstituted cyclic structures, including fully saturated substituted or unsubstituted rings, partially saturated substituted or unsubstituted rings, or substituted or unsubstituted aromatic rings; and

[0145] Each X is independently a halogen, a substituted or unsubstituted hydrocarbon, a hydrogen, an amino, a substituted or unsubstituted alkoxy, a thio, a phosphorus, or a combination thereof, or two Xs are joined together to form a substituted or unsubstituted metal ring, or two Xs are joined together to form a chelate ligand, a diene ligand, or an alkylene.

[0146] Among them (1) R 7 and R 8 (2) R 8 and R 9 、or (3) R 9 and R 10 At least one pair of the rings are joined to form a fully saturated ring fused to the indene ring shown in formula (IV), whether substituted or unsubstituted.

[0147] In some implementations, R of formula (IV) 7 R 8 R 9 and R 10 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), wherein (1) R 7 and R 8 (2)R 8 and R 9 、or (3) R 9 and R 10 At least one pair of the rings are joined to form a fully saturated ring fused to the indene ring shown in formula (IV), whether substituted or unsubstituted.

[0148] In some implementation schemes, (1) R 7 and R 8 (2) R 8 and R 9 、or (3) R 9 and R 10 At least one pair of rings in the formula (IV) are joined to form a fully saturated ring, either substituted or unsubstituted, of 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).

[0149] 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.

[0150] 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... aIt can form cyclic structures, 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.

[0151] In some implementations, R of formula (IV) 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 and R 10 One or more of them are independently hydrogen, hydrocarbon, silyl hydrocarbon, alkoxy, halogen, or siloxy.

[0152] 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 group, such as chlorine. In still other embodiments, each X is independently a C1-C4 alkyl group, such as methyl. In some embodiments, each X is independently selected from substituted or unsubstituted hydrocarbon groups, heteroatoms, or substituted or unsubstituted heteroatom-containing groups, such as methyl, benzyl, trimethylsilyl, methyl(trimethylsilyl), neopentyl, ethyl, propyl, butyl, phenyl, hydrazine, chlorine, fluorine, bromine, iodine, trifluoromethanesulfonate, dimethylamino, diethylamino, dipropylamino, and diisopropylamino.

[0153] In some embodiments of formula (IV), (1) M is Zr or Hf, (2) X is a C1-C5 alkyl group, (3) T is Si(CH2)3, Si(CH2)4, or Si(CH2)5, and (4) R 5 R 6 R 7 R 8 R 9 and R 10 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 links are connected to form a fully saturated ring, either substituted or unsubstituted, of the indenyl ring shown in formula (IV), and (6) R 1 R 2 R 3 and R 4 It can be methyl, ethyl, or propyl on its own.

[0154] In some embodiments of formula (IV), the catalyst is selected from:

[0155] Activator

[0156] The terms “co-catalyst” and “activator” are used interchangeably in this document.

[0157] The catalyst systems described herein may include one or more catalyst compounds as described above and activators such as aluminoxanes or noncoordinate anions, and may be formed by combining the catalyst compounds described herein with activators in any manner known from the literature (including combining them with a support such as silica). The catalyst systems may also be added to or generated in solution polymerization or bulk polymerization (in monomers). The catalyst systems disclosed herein may have one or more activators and one, two, or more catalyst components. An activator is defined as any compound that can activate any of the catalyst compounds described above by converting a neutral metal compound into a catalytically active metal compound cation. Non-limiting activators may include, for example, aluminoxanes, alkylaluminum, ionized activators that may be neutral or ionic, and conventional types of co-catalysts. Suitable activators may include aluminoxane compounds, modified aluminoxane compounds, and ionized anionic precursor compounds that acquire reactive σ-bound metal ligands, making the metal compound a cation and providing a charge-balanced noncoordinate or weakly coordinated anion, for example, a noncoordinate anion.

[0158] 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.

[0159] Aluminoxane activator

[0160] Aluminoxane activators are used as activators in the catalyst system described herein. Aluminoxanes typically contain -Al(R...) a’’’ Oligomeric compounds with )-O- subunits, wherein R a’’’It is an alkyl group. Examples of aluminum oxanes include methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, and isobutylaluminoxane. Alkylaluminoxanes and modified alkylaluminoxanes are suitable as catalyst activators, such as when the entrained ligand is alkyl, halogen, alkoxy, or amino (amide). Mixtures of different aluminum oxanes and modified aluminum oxanes can also be used. It may be suitable to use visually clear methylaluminoxane. Turbid or gelled aluminum oxanes can be filtered to produce a clear solution or clear aluminum oxane can be decanted from a turbid solution. The available aluminum oxane is modified methylaluminoxane (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 available aluminoxane is solid polymethylaluminoxane as described in U.S. Patent Nos. 9,340,630, 8,404,880 and 8,975,209 (which are incorporated herein by reference).

[0161] When the activator is an aluminoxane (modified or unmodified), and in at least one embodiment, an activator in an amount with an Al / M excess of up to 5,000 times (by metal catalytic site) relative to the catalyst compound (by metal catalytic site) can be used. The minimum activator-to-catalyst compound molar ratio can be 1:1. 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.

[0162] In alternative embodiments, little or no aluminum oxane is used in the polymerization method described herein. For example, the aluminum oxane may be present at zero mol%, or alternatively, the aluminum oxane may be present at a molar ratio of aluminum to the transition metal of the catalyst compound of less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1.

[0163] Ionized / noncoordinated anion activators

[0164] The term "noncoordinate anion" (NCA) refers to an anion that does not coordinate with a cation or only weakly coordinates with a cation, thus remaining sufficiently unstable to be replaced by a Lewis base. "Compatible" noncoordinate anions are those that do not degrade to neutral when the initially formed complex decomposes. Furthermore, the anion will not transfer anionic substituents or fragments to the cation, thereby preventing the formation of neutral transition metal compounds and neutral byproducts from the anion. Noncoordinate anions available according to this disclosure are those that are compatible, stabilize the transition metal cation in the sense of balancing their ionic charge at +1, and still maintain sufficient instability to allow replacement during polymerization. Suitable ionizing activators may include NCAs, such as compatible NCAs.

[0165] The use of neutral or ionic ionizing activators is within the scope of this disclosure. The use of neutral or ionic activators, alone or in combination with aluminoxane or modified aluminoxane activators, is also within the scope of this disclosure. For a description of suitable activators and combinations of activators, the 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 herein by reference); and US Patent Publication 2021 / 0179650, and in particular paragraphs

[0084] –

[0135] of WIPO Patent Publication No. WO2021 / 257264, which is incorporated herein by reference (including various descriptions incorporated herein by reference, such as paragraphs

[00119] on page 72 to paragraph

[00151] on page 81 of WO2004 / 026921 and paragraphs

[00177] on page 72 to paragraph

[00178] on page 74 of WO2004 / 046214).

[0166] Furthermore, the catalyst system disclosed herein may include a metal hydrocarbon alkenyl chain transfer agent represented by the following formula:

[0167] Al(R') 3-v (R'') v

[0168] Each R' can be independently C1-C 30 The hydrocarbon group, and / or each R'' can independently be a C4-C group with a terminal vinyl group. 20 Hydrocarbenyl; and v can be from 0.1 to 3.

[0169] carrier material

[0170] In the embodiments described herein, the catalyst system may include an inert support material. The support material may be a porous support material, such as talc and inorganic oxides. Other support materials include zeolites, clay, organoclay, or another organic or inorganic support material, or mixtures thereof.

[0171] The support material can be an inorganic oxide. The inorganic oxide can be in a finely crushed form. Suitable inorganic oxide materials for the catalyst system used herein can include Group 2, 4, 13, and 14 metal oxides, such as silica, alumina, and mixtures thereof. Other inorganic oxides that can be used alone or in combination with silica or alumina can be magnesium oxide, titanium dioxide, or zirconium oxide. However, other suitable support materials can be used, for example, finely crushed functionalized polyolefins, such as finely crushed polyethylene. Examples of suitable supports can include magnesium oxide, titanium dioxide, zirconium oxide, montmorillonite, phyllosilicates, zeolite, talc, and clay. Additionally, combinations of these support materials can be used, such as silica-chromium, silica-alumina, and silica-titanium dioxide. In at least one embodiment, the support material is selected from Al2O3, ZrO2, SiO2, SiO2 / Al2O3, SiO2 / TiO2, silica-clay, silica / clay, or mixtures thereof.

[0172] Carrier materials, such as inorganic oxides, can have a thickness of approximately 10 μm. 2 / g to approximately 700 m 2 / g surface area, approximately 0.1cm 3 / g to approximately 4.0 cm 3 The pore volume is approximately 5 μm / g, and the average particle size is approximately 500 μm to approximately 500 μm. The surface area of ​​the support material can be approximately 50 m². 2 / g to approximately 500 m 2 / g, approximately 0.5 cm 3 / g to approximately 3.5 cm 3 The pore volume is approximately 10 μm to approximately 200 μm, and the average particle size is approximately 10 μm to approximately 200 μm. For example, the surface area of ​​the support material can be approximately 100 m². 2 / g to approximately 400 m 2 / g, approximately 0.8 cm 3 / g to approximately 3.0cm 3 The pore volume is approximately 5 μm to approximately 100 μm, and the average particle size can be approximately 5 μm to approximately 100 μm. The average pore size of the support material used in this disclosure can be approximately 10 Å to approximately 1000 Å, such as approximately 50 Å to approximately 500 Å, and such as approximately 75 Å to approximately 350 Å. In at least one embodiment, the support material is amorphous silica with a high surface area (surface area = 300 m² / g). 2 / gm; 1.65cm 3(pore volume / gm). For example, suitable silica can be silica sold by the Davison Chemical Division of WR Grace and Company under the trade names Davison™ 952 or Davison™ 955. In other embodiments, DAVISON™ 948 is used. Alternatively, the silica can be, for example, ES-70™ silica (PQ Corporation, Malvern, Pennsylvania) that has been calcined (e.g., at 875°C).

[0173] The support material should be dry, i.e., free from or substantially free from absorbed water. Drying of the support material can be achieved by heating or calcining at a temperature of about 100°C to about 1000°C, such as at least about 600°C. When the support material is silica, it is heated to at least 200°C, such as about 200°C to about 850°C, and such as at about 600°C; and sustained for a period 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 possess at least some reactive hydroxyl groups (OH) to produce the supported catalyst system of this disclosure. The calcined support material is then contacted with at least one polymerization catalyst comprising at least one catalyst compound and an activator.

[0174] A support material having reactive surface groups such as hydroxyl groups is slurried in a nonpolar 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 about 0.5 h to about 24 h, about 2 h to about 16 h, or about 4 h to about 8 h. Then, the solution of the catalyst compound is contacted with the separated support / activator. In at least one embodiment, the supported catalyst system is generated in situ. In an alternative embodiment, the slurry of the support material is first contacted with the catalyst compound for a period of about 0.5 h to about 24 h, about 2 h to about 16 h, or about 4 h to about 8 h. Then, the slurry of the supported catalyst compound is contacted with the activator solution.

[0175] A mixture of one or more catalysts, one or more activators, and a 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.

[0176] A suitable nonpolar diluent is a material in which all reactants used herein (e.g., activators and catalyst compounds) are at least partially soluble and are liquid at the polymerization temperature. Nonpolar diluents can be alkanes such as isopentane, hexane, n-heptane, octane, nonane, and decane, but a variety of other materials may also be used, including cycloalkanes such as cyclohexane, and aromatic compounds such as benzene, toluene, and ethylbenzene.

[0177] In at least one embodiment, the carrier material is supported methylaluminoxane (SMAO), which is a MAO activator treated with silica (e.g., ES-70-875 silica).

[0178] polyethylene copolymer

[0179] This disclosure provides a polyethylene copolymer having a combination of low density, high melt index, long-chain branching, and bimodal composition distribution. Furthermore, the polyethylene copolymer and its film can be formed by polymerization and extrusion of commercially desirable polyethylene copolymers.

[0180] Therefore, the polyethylene copolymers of the various embodiments described herein may exhibit one or more of the following properties:

[0181] Approximately 0.914 to approximately 0.925 g / cm³ 3 The density, such as from 0.914, 0.915, 0.916, 0.917, 0.918, 0.919, or 0.92 g / cm³. 3 The lowest value of any one of them is 0.925, 0.924, 0.923, 0.922, 0.921, 0.920, or 0.919 g / cm³. 3 A high value for any of the following, such as approximately 0.915 g / cm³ 3 To approximately 0.920 g / cm 3 The replaceable amount is approximately 0.918 g / cm³. 3 To approximately 0.922 g / cm 3 Any combination of values ​​from low to high is envisioned (provided that the high end is greater than the low end), for example, from about 0.916 to about 0.921 g / cm³. 3 .

[0182] • A melt index (MI) of approximately 0.1 g / 10 min or greater, also known as I2 or I2, based on the 2.16 kg load used in the test. 2.16(ASTM D1238, 190°C, 2.16 kg), such as from the low 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 the high 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, wherein any range from the low end to any high end is contemplated herein (provided the high end is greater than the low end), such as about 0.1 to about 1 g / 10 min. 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.

[0183] Polyethylene copolymers can be polymerization products of ethylene monomers and one or more olefin comonomers, such as α-olefin comonomers. α-olefin comonomers can have 3 to 12 carbon atoms, or 4 to 10 carbon atoms, or 4 to 8 carbon atoms. Olefin comonomers can be selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methylpent-1-ene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-hexadecene, and any combination thereof, such as 1-butene, 1-hexene, and / or 1-octene. In some embodiments, polyenes are used as comonomers. In some embodiments, the polyene 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, norbornene, ethylidene norbornene, 5-vinyl-2-norbornene, 5-vinyl-2-norbornene, and olefins formed in situ in a polymerization medium. In some embodiments, the comonomer is selected from the group consisting of isoprene, styrene, butadiene, isobutene, chloroprene, acrylonitrile, and cycloolefins. In some embodiments, a combination of olefin comonomers is used. In some embodiments, the olefin comonomer is selected from the group consisting of 1-butene and 1-hexene. Based on the total weight of monomers in the polyethylene copolymer, the olefin comonomer content of the polyethylene copolymer can range from a low value 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 value 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%. The balance of the polyethylene comonomer consists of ethylene-derived units (e.g., from 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%). A range from any of the aforementioned low to any of the aforementioned high values ​​is contemplated herein (e.g., from about 88 wt% to about 93 wt%, such as about 91 wt% to about 93 wt% of ethylene-derived units and the balance of olefin comonomer derivatives).

[0184] Polyethylene copolymers may also have high load melt index (HLMI) ranging from low values ​​of about 15, 20, 25, 30, 35, 40, 45, 50, or 55 g / 10 min to high values ​​of about 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, or 25 g / 10 min (also known as I based on the 21.6 kg load used in the test). 21 or I 21.6 ); where any of the aforementioned low values ​​to any of the aforementioned high values ​​are contemplated herein (e.g., about 45 to about 70 g / 10 min, such as about 50 to about 60 g / 10 min, alternatively about 20 to about 30 g / 10 min). The term “high load melt index” (“HLMI”) is the number of grams extruded in 10 minutes under a standard load (21.6 kg) and is an inverse measure of viscosity. As provided herein, HLMI (I 21 Determined according to ASTM D1238 (190 °C / 21.6 kg), and sometimes also referred to as I. 21 or I 21.6 .

[0185] The polyethylene copolymer may also have a melt index ratio (MIR, defined as I) in the range of a low value from about 20, 25, 30, 35, 40, 45, 50, or 55 to a high value from about 70, 65, 60, 55, 50, 45, or 40. 21.6 / I 2.16 The ratio), wherein any of the aforementioned low values ​​to any of the aforementioned high values ​​are contemplated herein (e.g., about 40 to about 50, or alternatively about 50 to about 60).

[0186] Polyethylene copolymers 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 and 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, wherein any of the aforementioned low values ​​to any of the aforementioned high values ​​are 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).

[0187] The weight-average molecular weight (Mw) of the polyethylene copolymers in various embodiments can be in the range of about 70,000 to about 200,000 g / mol, such as about 75,000 to about 150,000 g / mol, such as about 90,000 to about 130,000 g / mol, such as about 100,000 to about 120,000 g / mol, wherein any of the aforementioned lower end to any of the aforementioned higher end is contemplated.

[0188] The number-average molecular weight (Mn) of the polyethylene copolymers in various embodiments can be in the range of about 10,000 to about 40,000 g / mol, such as about 10,000 to about 30,000 g / mol, such as about 15,000 to about 25,000 g / mol, wherein any of the aforementioned lower end to any of the aforementioned higher end is contemplated.

[0189] The Z-average molecular weight (Mz) of the polyethylene copolymers in various embodiments can be in the range of about 150,000 to about 400,000 g / mol, such as about 200,000 to about 350,000 g / mol, or about 200,000 to about 275,000 g / mol, such as about 220,000 to about 260,000 g / mol, wherein any of the aforementioned lower end to any of the aforementioned higher end is contemplated.

[0190] Polyethylene copolymers from various embodiments can also exhibit long-chain branching. As previously noted, this can be observed, for example, through SAOS viscosity data (especially η). 0.01 / η 100 ) and / or MIR to prove it. In addition, LCB or branching index (referred to as g' in this paper) vis ave Or alternatively g' vis The value can be less than 1, such as in the low values ​​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, and in the low values ​​of about 0.80, 0.85, 0.86, 0.87, 0.88, 0.89, 0.90, 0. The range of any of the higher values ​​of 0.91, 0.92, 0.93, or 0.94, wherein any of the aforementioned lower end to any of the aforementioned higher end is envisioned, provided that the higher end is greater than the lower end (e.g., 0.65 to 0.87, or 0.90, or 0.95, such as 0.72 to 0.87, or 0.82 to 0.92, or 0.86 to 0.92, or 0.72 to 0.92, or 0.70 to 0.87, 0.88, 0.89, or 0.90, etc.).

[0191] The molecular weight distribution and moments (Mw, Mn, Mw / Mn, etc.) and branching index (g'vis) were determined by high-temperature gel permeation chromatography (Polymer Char GPC-IR) using an infrared detector IR5 based on a multi-channel bandpass filter, an 18-angle Wyatt Dawn Heleos light scattering detector, and a 4-capillary viscometer with a Wheatstone bridge configuration. Polymer separation was achieved using three Agilent PLgel 10-μm Mixed-B LS columns. Aldrich reagent-grade 1,2,4-trichlorobenzene (TCB) with 300 ppm of the 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 was 1.0 ml / min, and the nominal injection volume was 200 μL. The entire system, including the delivery lines, column, and viscometer detector, is contained in an oven maintained at 145°C. The polymer sample is weighed and sealed in a standard vial containing 80 μL of a flow marker (heptane). After loading the vial into the autosampler, the polymer is automatically dissolved in the instrument by adding 8 ml of TCB solvent. The polymer is dissolved at 160°C with continuous shaking for approximately 2 hours. The concentration (c) at each point in the chromatogram is calculated using the following equation: c = βI, where β is a mass constant. The mass recovery is calculated as the ratio of the integral area of ​​the concentration chromatography within the elution volume to the injection mass equal to the predetermined concentration multiplied by the injection loop volume. The conventional molecular weight (IR MW) is determined by combining a universal calibration relationship with column calibration using a series of monodisperse polystyrene (PS) standards ranging from 700 to 10 million g / mol. The MW per elution volume is calculated using the following equation:

[0192]

[0193] Variables with the subscript "PS" represent polystyrene, while variables without subscripts represent the test sample. In this method, α... PS = 0.67 and K PS= 0.000175, while for ethylene-hexene copolymers, α and K are calculated by empirical equations (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 the hexene comonomer. It should be noted that the comonomer composition is determined by the ratio of the IR5 detector intensities corresponding to the CH2 and CH3 channels, calibrated using a series of PE and ethylene-hexene homopolymer / copolymer standards pre-determined by NMR or FTIR with their nominal values. Concentrations here are expressed in g / cm³. 3 The molecular weight is expressed in g / mol, and the intrinsic viscosity (and therefore K in the Mark-Hovink equation) is expressed in dL / g.

[0194] The LS molecular weight (M) at each point in the chromatogram was determined by analyzing the LS output using a Zimm model for static light scattering.

[0195] .

[0196] Here, ΔR(θ) is the excess Rayleigh scattering intensity measured at scattering angle θ, c is the polymer concentration determined by IR5 analysis, A2 is the second virial coefficient, P(θ) is the shape factor of the monodisperse random coil, and Ko is the optical constant of the system.

[0197]

[0198] Where N A is the Avogadro number, and (dn / dc) is the refractive index increment of the system. At 145 °C and λ = 665 nm, the refractive index of TCB is n = 1.500. For the purposes of this disclosure and its claims, for ethylene-hexene copolymers, (dn / dc) = 0.1048.

[0199] Unless otherwise stated, when molecular weight values ​​are mentioned herein, it should be assumed that they are determined by light scattering (LS) techniques.

[0200] Viscosity-average molecular weight (M V Specific viscosity was determined using a high-temperature Polymer Char viscometer with four capillaries arranged in a Wheatstone bridge configuration and two pressure sensors. One sensor measured the total pressure drop across the detector, while the other sensor, located between these two sides of the bridge, measured the pressure difference. The specific viscosity ηs of the solution flowing through the viscometer was calculated from their outputs. The intrinsic viscosity [η] at each point in the chromatogram was calculated using the equation [η] = ηs / c, where c is the concentration and is determined by the IR5 broadband channel output. The viscosity MW at each point was calculated as follows: , where αps is 0.67 and Kps is 0.000175. The average intrinsic viscosity of the sample [η] avg Through the following calculations:

[0201]

[0202] The sum is taken from chromatographic slice i between the integration limits.

[0203] Branching index (g') vis The output of the GPC-IR5-LS-VIS method can be calculated as follows. First, it should be noted that g' or g' vis This can generally be considered as the ratio of the intrinsic viscosity of a polymer to the intrinsic viscosity of a linear polymer with 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 The relative intrinsic viscosity (g') is the intrinsic viscosity of a linear resin with the same molecular weight and composition. Therefore, the relative intrinsic viscosity of a polymer (g') is a measure of the degree to which a polymer increases the viscosity of its solution relative to a linear polymer with the same molecular weight and composition under the same temperature and pressure conditions.

[0204] Following this principle, the [η] in the simplified relation above 聚合物 The value [η] can be considered as the weight-average intrinsic viscosity of the sample. avg It is calculated as follows:

[0205]

[0206] The sum is taken from all chromatographic slices i between the integration limits. Branching index g' vis Relative to a linear reference, it is defined as Where Mv is the viscosity-average molecular weight based on the molecular weight determined by LS analysis, and K and α are for a reference linear polymer; for the purposes of this disclosure, α and K are the same as those described above for linear polyethylene polymers.

[0207] Branching index g' vis It can be equivalently referred to as g' vis ave This reflects the average value of g' determined at each of multiple discrete concentration slices. For example, refer to Figure 1 As can be seen, the g' values ​​of various polyethylene copolymers can be plotted as a function of LogM (logarithm of molecular weight), meaning that the g' value for a given molecular weight group of polymer chains in a polyethylene copolymer composition can be calculated. The above calculation provides g' as a weighted average of these multiple g' values. vis aveAnd when comparing this value between two different copolymer compositions, g' vis ave This can be considered a good relative indicator of the presence of long chain branching, where a lower g' vis ave It indicates greater long-chain branching.

[0208] Wide orthogonal composition distribution

[0209] "BOCD" refers to a broad orthogonal compositional distribution, in which the comonomers of a copolymer are predominantly incorporated into the high molecular weight chains of the polyolefin polymer or composition. For example, the distribution of non-short chain branches can be measured using heated elution fractionation (TREF) combined with a light scattering (LS) detector to determine the weight-average molecular weight of molecules eluted from a TREF column at a given temperature. The combination of TREF and LS (TREF-LS) provides information about the width of the compositional distribution and whether the comonomer content increases, decreases, or becomes uniform across different molecular weight chains of the polymer. BOCD has been described, for example, in U.S. Patent No. 8,378,043, column 3, line 34 spanning column 4, line 19, and in U.S. Patent No. 8,476,392, column 43 spanning column 16, line 54.

[0210] The BOCD properties of the polyethylene copolymers of the present invention can be quantified by the composition distribution width index (CDBI). For example, the polyethylene copolymers described herein may have low composition distribution width index (CBDI), wherein the polyethylene copolymers may have a CBDI in the range of low values ​​from any one of about 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, or 80% to high values ​​from any one of about 99%, 95%, 90%, 85%, 80%, 75%, 70%, 65%, or 60%; wherein any of the aforementioned low values ​​to any of the aforementioned high values ​​are 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 may have a low compositional width index (CBDI), wherein the polyethylene copolymers may have a CBDI in the range of 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%; wherein any of the aforementioned low values ​​to any of the aforementioned high values ​​are 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%).

[0211] CDBI is defined as the weight percentage of copolymer molecules having a comonomer content within + / - 50% of the median comonomer mol% value, as described in conjunction with Figure 17 on pages 18-19 of WO 1993 / 003093. This means that for a copolymer with a median comonomer mol% value (Cmed) of 8 mol% comonomer on the polymer chain, CDBI is the weight percentage of the copolymer chain having a comonomer mol% content of (0.5 × Cmed) to (1.5 × Cmed). In this example, CDBI is the weight percentage of the copolymer chain having a comonomer mol% content of (0.5 × 8) to (1.5 × 8) or a comonomer content of 4 mol% to 12 mol%. WO 1993 / 003093 also describes the use of chromatography and C... 13 NMR is used to determine the weight fraction of the polymer relative to the composition profile (i.e., the composition distribution profile) and the median comonomer composition Cmed from it, as described in Figures 16 and 17 of that publication. The CDBI of the copolymer is readily determined using techniques for separating samples of the copolymer. One such technique is to generate a solubility distribution profile using temperature elution fractionation (TREF), as described in WO 1993003093 (in this respect, it refers instead to 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 aforementioned publications are incorporated herein by reference.

[0212] A solubility profile of the copolymer can first be generated using data obtained from the TREF technique (as described, for example, in the publication just cited). This solubility profile is a graph of the weight fraction of the dissolved copolymer as a function of temperature. This can be converted into a weight fraction versus composition profile. For the purpose of simplifying the correlation between composition and elution temperature, weight fractions less than 15,000 can be ignored. These low weight fractions typically represent a negligible portion of the ethylene-based polymers disclosed herein.

[0213] Alternatively or otherwise, the composition distribution can be obtained through T 75 - T 25 The value is used to represent, where T 25 The temperature at which 25% of the eluted polymer is obtained and T 75 The temperature at which 75% of the eluted polymer was obtained is the same as the TREF experiment (and the plotting of the eluted polymer molecular weight versus elution temperature) described in US2019 / 0119413 (particularly in its paragraphs

[0055] –

[0058] , which are incorporated herein by reference). A narrow component distribution is reflected in T...75 - T 25 The values ​​show relatively small differences, while the wide distribution is reflected in T. 75 – T 25 A relatively larger difference in values ​​(meaning a greater difference in crystallinity between fractions of polymer composition). It should also be noted that in cases where there are differences between the actual TREF procedure described in US2019 / 0119413 and those described in WO 1993003093, US 5,382,630, and / or US 5,008,204, the TREF procedure described in US2019 / 0119413 should be used. (It should be further noted that the TREF procedure assists in generating curves – the solubility distribution curve of CDBI and the T...) 75 – T 25 The elution molecular weight relative to the elution temperature, in CDBI and T 75 – T 25 Appropriate differences can exist in the generation and analysis of [the data]. Finally, combining [the data] with T... 75 -T 25 The generated TREF curve (eluting polymer molecular weight relative to elution temperature) can be further processed as follows:

[0214] 1. The instrument's solvent-only response can be generated and subtracted from the sample's TREF curve. The solvent-only response can be generated by running the same method before running the polymer sample, but without adding any polymer to the sample vial; using the same solvent reservoir as for the polymer sample and without replenishing with fresh solvent; and within a reasonable time interval from the polymer sample run.

[0215] 2. The temperature axis of the TREF curve can be appropriately shifted to correct for the IR signal delay caused by the column-to-detector volume. This volume can be obtained by: first, filling the injection valve loop with a ~1 mg / ml HDPE resin solution; then, loading the loop volume at the same location within the column used for TREF analysis; then, using an isothermal method, allowing the hot solution to flow directly to the detector at a constant flow rate of 1 ml / min; and then measuring the time it takes for the HDPE probe peak to appear in the IR signal after injection. Therefore, the delay volume (ml) equals the time (min).

[0216] 3. It can perform baseline correction on the curve and select an appropriate integration limit; it can also normalize the curve so that the area of ​​the curve is 100% of the weight.

[0217] As in some embodiments of the polyethylene copolymer of the present invention, the narrow distribution is reflected in a T0 temperature of less than 15°C. 75 -T 25The values ​​vary relatively small, such as from a low value of any one 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 any one of 10°C, 11°C, 12°C, 13°C, 14°C, or 15°C, wherein any of the aforementioned low values ​​to any of the aforementioned high values ​​are 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 another embodiment, the polyethylene copolymer of this disclosure may exhibit a bimodal compositional distribution, such as BOCD (broadly orthogonal compositional distribution, meaning that comonomers preferentially incorporate into longer polymer chains compared to shorter chains), and have a relatively high T 75 - T 25 Values, such as 15°C or greater, such as the range from the low of any one of 15°C, 16°C, 17°C, or 18°C ​​to the high of any one 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 of the aforementioned low values ​​to any of the aforementioned high values ​​are 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).

[0218] Blends and Additives

[0219] In some embodiments, the polyethylene copolymer may be formulated (e.g., blended) with one or more other polymer components. In some embodiments, those other polymer components are α-olefin polymers, such as polypropylene or polyethylene homopolymers and copolymer compositions. In some embodiments, those other polyethylene polymers are selected from the group consisting of linear low-density polyethylene, high-density polyethylene, medium-density polyethylene, low-density polyethylene, and other differentiated polyethylenes.

[0220] In some embodiments, the formulated blends may contain additives, which are determined based on the end use of the formulated blends. In some embodiments, the additives are selected from the group consisting of fillers, antioxidants, phosphites, anti-adhesion additives, tackifiers, UV stabilizers, heat stabilizers, anti-blocking agents, release agents, antistatic agents, pigments, colorants, dyes, waxes, silica, processing aids, neutralizers, lubricants, surfactants, and nucleating agents. In some embodiments, the additives are present in an amount from about 0.1 ppm to about 5% by weight.

[0221] The polyethylene copolymers of this disclosure can optionally be blended with one or more processing aids to form polyethylene blends. Due to the improved properties of the polyethylene copolymers of this disclosure, it is advantageous that such processing aids can be omitted even in blown films (e.g., some embodiments of the film, and especially blown films, may be free of or substantially free of polymer processing aids, and particularly fluorinated polymer processing aids; wherein “substantially free” means free of any intentionally added components, but allows up to 100 ppm of one or more such components as impurities).

[0222] Products

[0223] The polyethylene copolymers disclosed herein are particularly suitable for manufacturing end-use articles, such as films (e.g., which may be formed by lamination, extrusion, co-extrusion, casting, and / or blow molding); and other articles, such as those that may be formed by rotational molding or injection molding. The polyethylene copolymers can be used to form articles by cast film extrusion, blown film extrusion, rotational molding, or injection molding methods. In some embodiments, the polyethylene copolymers may be used as blends.

[0224] It has been found that the polyethylene copolymers of this disclosure can provide excellent shear-thinning characteristics, with little or no melt fracture in the extrudate at high die shear rates. Furthermore, compared to other LLDPEs, the polyethylene copolymers of this disclosure can provide films formed with reduced motor loads and melt pressures due to their improved flow behavior.

[0225] The polyethylene copolymers (or blends thereof) disclosed herein can be used in forming operations such as film, sheet, and fiber extrusion and co-extrusion, as well as blow molding, injection molding, and rotational molding. Films include blow-molded or cast films formed by co-extrusion or lamination, which can be used in food contact and non-food contact applications as shrink films, cling films, stretch films, sealing films, oriented films, snack packaging, heavy-duty bags, grocery bags, baked and frozen food packaging, medical packaging, industrial linings, and membranes. For example, the polyethylene copolymers of this disclosure provide improved shrink packaging capabilities due to their long-chain branched properties. Fibers include melt spinning, solution spinning, and meltblown fiber operations for manufacturing filters, diaper fabrics, medical clothing, geotextiles, etc., in woven or nonwoven forms. Extruded articles include medical catheters, wire and cable sheaths, pipes, geomembranes, and pond liners. Molded articles include single-layer and multi-layer constructions in the form of bottles, cans, large hollow articles, rigid food containers, and toys.

[0226] Polyethylene copolymers (or blends thereof) can be formed into single-layer or multi-layer films. These films can be formed using any conventional technique, including extrusion, co-extrusion, extrusion coating, lamination, blow molding, and casting. Films can be obtained through flat-film or tubular processes, which can then be oriented in a uniaxial direction or in two mutually perpendicular directions within the plane of the film. One or more of these layers of the film can be oriented to the same or different degrees in the transverse and / or longitudinal directions. This orientation can be performed before or after bringing the individual layers together. For example, a layer of polyethylene copolymer (or blends thereof) can be extruded, coated, or laminated onto an oriented polypropylene layer, or a polyethylene copolymer (or blends thereof) and polypropylene can be co-extruded together into a film and then oriented. Similarly, an oriented polypropylene can be laminated onto an oriented polyethylene copolymer (or blends thereof), or an oriented polyethylene copolymer (or blends thereof) can be coated onto polypropylene, and then optionally, even further, the combined orientation can be achieved.

[0227] The film includes single-layer or multi-layer films. Specific end-use films include, for example, blown films, cast films, stretch films, stretch / cast films, stretch adhesive films, stretch hand packaging films, machine stretch packaging, shrink films, shrink packaging films, greenhouse films, laminates, and laminated films. Exemplary films are prepared using any conventional techniques known to those skilled in the art, such as, for example, techniques for preparing blown, extruded, and / or cast stretch and / or shrink films (including shrink-on-shrink applications).

[0228] In at least one embodiment, multilayer films (multi-layer films) can be formed by any suitable method. The total thickness of the multilayer film can be varied depending on the required application. A total film thickness of 5-100 µm, such as 10-50 µm, is suitable for most applications. Those skilled in the art will understand that the thickness of the individual layers of the multilayer film can be adjusted based on the required end-use performance, one or more polymers used, equipment capabilities, and other factors. The material forming each layer can be co-extruded through a co-extrusion feed head and die assembly to obtain a film having two or more layers adhered together but with different compositions. Co-extrusion can be adapted for both cast film and blown film methods. Exemplary multilayer films have at least two, at least three, or at least four layers. In one embodiment, the multilayer film consists of five to ten layers.

[0229] In at least one embodiment, according to ASTM D882-18, at 23°C, the membrane of this disclosure has 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 psi to about 38,000 psi, such as about 34,000 psi to about 36,000 psi.

[0230] According to ASTM D-1922, the membranes of this disclosure may have an Elmendorf tear value. In at least one embodiment, the membrane has 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.

[0231] According to ASTM D-1709 Method A, the membranes of this disclosure may have dart impact (or impact failure, or Dart F50, or Dart Impact Strength (DIS)) reported in grams (g) or grams per mil (g / mil). The membranes of this disclosure may have a dart impact of about 5 g / mil to about 600 g / mil. In at least one embodiment, the membrane has a dart 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 impact may 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.

[0232] Membrane shrinkage (reported as a percentage) can be measured by cutting circular specimens from the membrane using a 100 mm die. The specimens can be marked in their respective directions, sprinkled with talcum powder, and placed on a preheated talcum-covered brick. The specimens can then be heated using a heat gun (e.g., HG-501A type) for approximately 10 to 45 seconds, or until any dimensional change ceases. The value is the average of three specimens. A negative shrinkage value indicates the expansion of the dimension after heating compared to its pre-heating dimension. The membranes of this disclosure can have a % shrinkage of approximately 40% to approximately 90%, such as approximately 60% to approximately 80%, such as approximately 65% ​​to approximately 75% (machine direction). The membranes of this disclosure can have a % shrinkage of approximately 0% to approximately 5%, such as approximately 0.5% to approximately 4%, such as approximately 1% to approximately 3% (transverse direction).

[0233] In some implementations, according to a modified ASTM D5748 (using an ASTM probe with two 0.25 mil HDPE sliding plates. Machine model: United SFM-1. Test speed: 10 in / min), the membrane can have a breaking puncture energy (also known as puncture breaking energy) of at least about 25 in-lbs / mil, such as at least about 30 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.

[0234] In at least one embodiment, as determined by ASTM D-1003, the membrane of this disclosure has a haze value of about 45% or less, about 40% or less, about 35% or less, about 30% or less, about 25% or less, about 20% or less, about 15% or less, or about 10% or less.

[0235] In at least one embodiment, as determined by ASTM D1746, the membrane of this disclosure has a transparency of about 80% or greater, about 85% or greater, about 90% or greater, about 95% or greater, or about 97% or greater (defined as conventional transmitted light deviating less than 0.1 from the axis of incident light passing through the membrane sample block).

[0236] In at least one embodiment, as determined by ASTM D-2457, the film of this disclosure has a gloss of about 30% or greater, about 35% or greater, about 40% or greater, about 45% or greater, or about 50% or greater, wherein a light source is irradiated onto the film surface at a 45° angle and the amount of reflected light is measured.

[0237] Shrink film

[0238] The compositions disclosed herein can be used to prepare shrink films. Shrink films, also known as heat-shrinkable films, are widely used in both industrial and retail bundling and packaging applications. Such films are capable of shrinking upon the application of heat to release the stress imposed on the film during or after extrusion. Shrinkage can occur in one direction or in both longitudinal and transverse directions. Conventional shrink films are described, for example, in U.S. Patent No. 7,235,607, which is incorporated herein by reference.

[0239] Industrial shrink film can be used to secure products to pallets. Typical industrial shrink film is formed in a single-bubble blow extrusion process to a thickness of approximately 80 to 200 µm and provides shrinkage in both directions.

[0240] Retail films can be used for packaging and / or bundling products intended for consumer use, such as, for example, supermarket goods. These films are typically formed in a single-bubble blow extrusion process to a thickness of approximately 35 μm to approximately 80 μm.

[0241] Films can be used in “layer-by-layer shrink wrap” applications. As used herein, “layer-by-layer shrink wrap” refers to a method of applying an outer shrink wrap layer around one or more articles that have already been individually shrink-wrapped (in this context, the “inner layer” of the wrap). In these methods, it may be desirable for the film used to wrap the individual articles to have a higher melting point (or shrinkage point) than the film used for the outer layer. When using this 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 the outer layer’s shrinkage. Some of the films described herein can have sharp shrinkage points when subjected to heat from a heat gun in a high-temperature environment, suggesting that they may be particularly suitable for use as inner layers in a variety of layer-by-layer shrink wrap applications.

[0242] experiment

[0243] General considerations and reagents: Unless otherwise specified, all operations were performed under an inert atmosphere using the glove box technique. Toluene and pentane were purchased from Sigma Aldrich and degassed and dried overnight over a 3 Å molecular sieve before use. Methylaluminoxane was purchased from Grace and used as received.

[0244] synthesis:

[0245] General considerations and reagents. Unless otherwise specified, all operations are performed under an inert atmosphere using the glove box technique. Before use, degas the diethyl ether and dichloromethane (Sigma Aldrich) and dry them overnight using a 3 Å molecular sieve. ZrCl4 was purchased from Strem Chemicals, Inc. and used as received.

[0246] Synthesis of Catalyst 2 and Catalyst 1:

[0247]

[0248] 1-Chloro-1-(2,3,4,5-tetramethylcyclopentan-2,4-dien-1-yl)silane-butane

[0249] At -35 °C, lithium (tetramethylcyclopentadiene) (5.00 g, 39.0 mmol, 1.00 equivalent) was added to a colorless solution of 1,1-dichlorosilane (11.00 g, 78.0 mmol, 2.00 equivalent) in tetrahydrofuran (50 mL) to give a turbid white mixture that slowly became clear over one hour. The reaction was stirred for 3 hours and then evaporated under vacuum to give a thick white mixture. The mixture was extracted with pentane (50 mL, then 4 × 5 mL) and the extract was filtered to give a colorless solution. The solution was evaporated under vacuum to give an amber oil. Yield: 8.79 g (99%). 1 ¹H NMR (C6D6) δ 3.11 (br s, 1H), 1.98 (br m, 1H), 1.90 (s, 6H), 1.68–1.79 (overlapping multiplets and singlets, 7H), 1.21–1.40 (m, 4H).

[0250]

[0251] (3-Phenylenol)Lithium

[0252] 2.73 M butyllithium (50.0 mL, 136 mmol, 1.00 equivalent) was added to a colorless solution of 3-phenylindene (26.20 g, 136 mmol, 1.00 equivalent) in pentane (250 mL) to give a turbid yellow solution. The reaction was stirred for 69 hours to give a turbid yellow mixture. The mixture was then filtered to give a pale 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).

[0253]

[0254] 1-(3-Phenyl-1H-inden-1-yl)-1-(2,3,4,5-Tetramethylcyclopentan-2,4-dien-1-yl)silane-butane

[0255] At -35 °C, lithium (3-phenylindene) (4.81 g, 24.3 mmol, 1.07 equivalent) was added to an amber solution of 1-chloro-1-(2,3,4,5-tetramethylcyclopentan-2,4-dien-1-yl)silane (5.14 g, 22.7 mmol, 1.00 equivalent) in ether (25 mL) to give a turbid yellow-orange mixture. The reaction was warmed to room temperature and stirred for 24 hours to give a turbid greenish-white mixture. The reaction was then evaporated under vacuum, leaving a green semi-solid. The residue was extracted with pentane (3 × 30 mL, then 3 × 5 mL), and the extract was filtered to give a yellow solution. The solution was evaporated under vacuum, leaving a Manila-colored solid. Yield: 8.41 g (97%). 1 H NMR (C6D6) δ 7.73 (m, 1H), 7.66 (m, 1H), 7.64. 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).

[0256]

[0257] [Tetramethylcyclopentadienylsilane-heterobutyl(3-phenylindenyl)](ethyl ether)dilithium

[0258] At -35 °C, 2.74 M butyllithium (16.4 mL, 44.9 mmol, 2.08 equivalent) in hexane was added to a turbid amber solution of 1-(3-phenyl-1H-inden-1-yl)-1-(2,3,4,5-tetramethylcyclopentan-2,4-dien-1-yl)silane (8.27 g, 21.6 mmol, 1.00 equivalent) in ether (40 mL) to give a turbid yellow mixture. The reaction was warmed to room temperature and stirred for 17 hours. Pentane (40 mL) was added to the reaction mixture 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%), yellow powder. 1H 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).

[0259]

[0260] [Tetramethylcyclopentadienylsilane-heterobutyl(3-phenylindenyl)]zirconium dichloride, catalyst 2

[0261] At -35 °C, dilithium [tetramethylcyclopentadiene-silyrocyclobutyl(3-phenylindene)](diethyl ether) (4.00 g, 8.54 mmol, 1.00 equivalent) was added to a vigorously stirred white suspension of zirconium tetrachloride bis(ether compound) (3.25 g, 8.54 mmol, 1.00 equivalent) in ether (50 mL) to give a turbid yellow mixture. The reaction was warmed to room temperature and stirred for 18 hours. The turbid bright yellow mixture was then evaporated under vacuum, leaving a yellow solid. The solid was extracted with dichloromethane (50 mL, then 4 × 5 mL), and the extract was 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. Yield: 4.26 g (92%). HNMR (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).

[0262]

[0263] [Tetramethylcyclopentadienylsilanecyclobutyl(3-phenylindenyl)]dimethylzirconium, (catalyst 1)

[0264] Catalyst 1 was obtained by the following sequential synthesis: 3.28M methyl magnesium bromide (2.35 mL, 7.71 mmol, 2.09 equivalent) in ether was added to a bright yellow suspension of [tetramethylcyclopentadienylsiloxane-butyl(3-phenylindenyl)]zirconium dichloride (2.00 g, 3.69 mmol, 1.00 equivalent) in toluene (20 mL) at -35 °C to give a turbid yellow mixture. The reaction was warmed to room temperature and stirred for 18 hours. The turbid, deep amber solution was then evaporated under vacuum, leaving a yellow-brown solid. The solid was extracted with toluene (30 mL, then 3 × 5 mL), and the extract was filtered to give a yellow solution. The solution was evaporated under vacuum, leaving a yellow solid. Yield: 1.77 g (96%). 1 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).

[0265] Synthesizing and preparing another catalyst 2:

[0266] At -35°C, [tetramethylcyclopentadiene)siloxane(3-phenylindene)](ethyl ether)dilithium (2.46 g, 5.25 mmol, 1.00 equivalent) was added to a white suspension of zirconium tetrachloride bis(ether compound) (2.00 g, 5.25 mmol, 1.00 equivalent) in ether (30 mL) under vigorous stirring to give a cold, turbid, pale yellow mixture. After stirring for 20 minutes, the reaction turned turbid and bright yellow. The reaction was stirred for 18 hours and then evaporated under vacuum, leaving a bright yellow solid. The solid was extracted with dichloromethane (30 mL, then 3 × 5 mL), and the extract was 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%), 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).

[0267] Synthesis and preparation of 2 additional catalysts 1:

[0268] At -35 °C, 3.28 M methyl magnesium bromide in ether (2.35 mL, 7.71 mmol, 2.09 equivalents) was added to a yellow suspension of [tetramethylcyclopentadienylsilanecyclobutyl(3-phenylindenyl)]zirconium dichloride (5806) (catalyst 2) (2.00 g, 3.69 mmol, 1.00 equivalents) in toluene (20 mL) to give a cold, turbid yellow mixture. After stirring for 30 min, the reaction turned turbid amber-yellow. The reaction was stirred for 18 h to give a turbid, 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 × 5 mL), and the extract was filtered to give a yellow solution and a brown solid. The solution was evaporated under vacuum, leaving a yellow solid. The 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).

[0269] Synthesis of Catalyst 13 and Catalyst 14:

[0270]

[0271] Dimethyl(2,3,4,5-tetramethylcyclopentan-2,4-dien-1-yl)silyltrifluoromethanesulfonate

[0272] Silver trifluoromethanesulfonate (38.00 g, 148 mmol, 1.06 equivalent) was added to a pale amber solution of dimethylchloro(2,3,4,5-tetramethylcyclopentan-2,4-dien-1-yl)silane (30.00 g, 140 mmol, 1.00 equivalent) in toluene (100 mL) to give a warm, turbid white mixture that slowly turns grayish-purple. The reaction was stirred for 4 hours and then evaporated under vacuum, leaving a dark mixture. The mixture was extracted with pentane (100 mL, then 3 × 20 mL), and the extract was 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).

[0273]

[0274] Four-hydrogen fuel cell lithium

[0275] At -35 °C, 2.71 M butyllithium (30.0 mL, 81.3 mmol, 1.00 equivalent) was added to a yellow solution of 1,2,3,5-tetrahydro-s-indane (12.70 g, 81.3 mmol, 1.00 equivalent) in ether (100 mL) to give a turbid Manila-colored mixture. The reaction was warmed to room temperature and stirred for 30 min. Pentane (80 mL) was added to the reaction mixture and the mixture was filtered to give a Manila-colored 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).

[0276]

[0277] Dimethyl(1,5,6,7-tetrahydro-s-indarsen-1-yl)(2,3,4,5-tetramethylcyclopentan-2,4-dien-1-yl)silane

[0278] At -35 °C, tetrahydroindole lithium (2.65 g, 16.2 mmol, 1.07 equivalent) was added to a pale yellow solution of dimethyl(2,3,4,5-tetramethylcyclopentan-2,4-dien-1-yl)silyltrifluoromethanesulfonate (5.00 g, 15.2 mmol, 1.00 equivalent) in ether (20 mL) to give a turbid amber-orange mixture. The reaction was warmed 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 × 20 mL), and the extract was 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).

[0279]

[0280] [Tetramethylcyclopentadiene dimethylsilyl(tetrahydrodimethylsilyl)](diethyl ether)dilithium

[0281] At -35 °C, 2.74 M 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).

[0282]

[0283] [Tetramethylcyclopentadienyldimethylsilyl(tetrahydroindah)]zirconium dichloride (catalyst 14)

[0284] At -35°C, dilithium [tetramethylcyclopentadiene dimethylsilyl(tetrahydroindahedral)](ethyl ether) (2.21 g, 5.25 mmol, 1.00 equivalent) was added to a white suspension of zirconium tetrachloride bis(ether) (2.00 g, 5.25 mmol, 1.00 equivalent) in ether (30 mL) under vigorous stirring to give a turbid Manila-colored mixture. The reaction was warmed to room temperature and stirred for 18 hours. The turbid bright yellow mixture was then evaporated under vacuum, leaving a yellow solid. The solid was extracted with dichloromethane (30 mL, then 4 × 5 mL), and the extract was 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. 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).

[0285]

[0286] [Tetramethylcyclopentadienyldimethylsilyl(tetrahydroindah)]dimethylzirconium (catalyst 13)

[0287] At -35 °C, 3.28 M methyl magnesium bromide (1.30 mL, 4.26 mmol, 2.11 equivalents) in ether was added to a bright yellow suspension of [tetramethylcyclopentadienyldimethylsilyl(tetrahydroindalkonyl)]zirconium dichloride (catalyst 14) (1.00 g, 2.02 mmol, 1.00 equivalents) in toluene (10 mL) to give a turbid yellow mixture. The reaction was warmed to room temperature and stirred for 18 hours. The turbid brown mixture was then evaporated under vacuum, leaving a brownish-yellow solid. The solid was extracted with toluene (25 mL, then 3 × 5 mL), and the extract was filtered to give a yellow solution. The solution was evaporated under vacuum, leaving a yellow solid. Yield: 0.95 g (103%). 1¹H 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 (overlapping multiplets and singlets, 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).

[0288] Adjustment on base catalyst B1

[0289] As described in US 5,314,973, the base or main catalyst B1 (dimethylsilylbis(tetrahydroindenyl)dimethylzirconium metallocene) was then synthesized by methylation with 2 equivalents of magnesium methyl bromide.

[0290] Adjustment procedure for catalyst 1:

[0291] The iC6 conditioning solution is 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).

[0292] Adjustment procedure for catalyst 13:

[0293] The iC6 conditioning solution is 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).

[0294] polymerization

[0295] Gas-phase fluidized bed polymerization was carried out using the same reactor conditions (bed temperature ~185℉, pressure ~290 psig, same ethylene, hydrogen, and hexene comonomer flow ratios, and ~10 mol% iC5 as an inducing condenser, with ~25 mol% N2 present), except that catalyst B1 (Example 1) was used without adjustment and catalyst 13 (Examples 2 and 3) was used in an iC6 solution adjusted to a supported catalyst B1 slurry in increased relative amounts, as shown in Table 1, where the MI, HLMI, MIR, and density of each produced PE are also shown in Table 1. As shown in Table 2 below, polymerization under the same conditions was repeated again for base catalyst B1 (Example 4) and for catalyst 13 (Example 5) in an iC6 solution adjusted to a supported base catalyst B1 slurry in a similar relative amount to Example 3.

[0296] Table 3 below lists the molecular weight and g' data obtained from GPC in Examples 1-5; it is also shown in Figure 1 (For Examples 1-3) and Figure 2 (For Examples 4-5). Table 3 and Figure 1 and 2 The results show that, with increasing relative amounts of modulating catalyst, the PE copolymer exhibits lower g' values ​​(indicating increasingly greater long-chain branching), and some very slight flattening and broadening of the molecular weight distribution with the use of relatively more modulating catalyst. This generally suggests that copolymers prepared using modulating catalyst will exhibit improved processability (as shown by the reduction in g' and the broadening of the molecular weight distribution).

[0297] Table 4 lists the CDBI and T75-T25 values ​​of PE copolymers (derived from the TREF-IR5 distribution), where the TREF-IR5 distribution is also shown in... Figure 3 (The TREF-IR5 distributions of Examples 4 and 5 are shown) and Figure 4 (The TREF-IR5 distribution of Examples 1-3 is shown in Table 4. As can be seen in Table 4, with the catalyst 13 adjusted, the CDBI T75-T25 values ​​remain roughly similar to those of Examples 1 (without adjustment) to Examples 2-3 (with the catalyst 13 adjusted), indicating that the catalyst is effective in increasing long-chain branching while maintaining a similar comonomer distribution between polymer chains of different lengths.

[0298] On the other hand, with catalyst 1 adjusted, according to Table 4 and Figure 3 We observed a broadly orthogonal compositional distribution (BOCD) with a moderately decreased CDBI, consistent with a more uneven distribution of comonomers among polymer chains of different lengths; and an increase in the T75-T25 values ​​derived from TREF-IR5. Consistently, Figure 3 The PE copolymer of Example 5, prepared without adjustment, exhibits a distinct bimodal crystallinity (as shown by the two distinctly different peaks in the TREF trace of Example 5). This can be explained by the different distribution of comonomers along polymer chains of varying lengths, resulting in distinct regions of higher and lower crystallinity in the PE copolymer. Furthermore, the larger T75-T25 values ​​of Example 5 indicate that the comonomer distribution of this PE has BOCD characteristics, meaning that comonomers preferentially incorporate into longer polymer chains, and this is generally associated with excellent processability without sacrificing the strength properties in films made from such polyethylene.

[0299] Table 1: Polymerization Examples Based on Catalyst B1

[0300] Table 2: Polymerization of Examples Using Another Basic Catalyst B1

[0301] Table 3: GPC data, processability improvement as measured by g' using modified metallocene catalyst 13 and catalyst 1 together with base catalyst B1.

[0302] Gel permeation chromatography via 4D GPC

[0303] Table 4: TREF Data

[0304] Membranes were produced using Examples 1-5.

[0305] 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.

[0306] 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).

[0307] Table 5: Membrane data of the polymer obtained using basic catalyst B1

[0308] In general, the catalyst, catalyst system, polyethylene polymer, and polymerization method for producing such polyethylene copolymer can provide a polyethylene polymer formed by a “tuning” method, and said polyethylene polymer can have a combination of low density, low melt index, high melt index ratio, and controllable long chain branching (introduced by the tuning method), while also providing the polymerization and extrusion of commercially desirable polyethylene copolymers.

[0309] 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.

[0310] 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.

[0311] Similarly, whenever the transitional phrase "comprising" precedes a composition, element, or group of elements, it should be understood that we also contemplate the same composition or group of elements preceding the description of a composition or one or more elements with the transitional phrases "consisting essentially of," "consisting of," "selected from the group of consisting of," or "is," and vice versa. Unless otherwise stated, the phrases "consists essentially of" and "consisting essentially of" do not exclude the presence of other steps, elements, or materials, whether or not specifically mentioned in this specification, provided that such steps, elements, or materials do not affect the essential and novel features of the claimed invention. Furthermore, the phrases do not exclude impurities and differences generally associated with the elements and materials used.

[0312] While the claimed invention has been described with reference to various embodiments and examples, those skilled in the art who benefit from this disclosure will understand that other embodiments can be designed without departing from the scope and spirit of this disclosure.

Claims

1. A polyethylene copolymer comprising: Approximately 90% by weight or more of ethylene units; and Remaining balance C3-C 20 Comonomer unit, The polyethylene copolymer has the following characteristics: Bimodal composition distribution Approximately 0.914 g / cm³ 3 To approximately 0.925 g / cm 3 density, Melt index (MI) of approximately 0.1 g / 10 min to approximately 1 g / min High load melt index (HLMI) of approximately 21 g / 10 min to approximately 70 g / 10 min, A melt index ratio (MIR) of approximately 40 to approximately 65, and Molecular weight distribution (MWD) of approximately 4 to approximately 7.

2. The polyethylene copolymer of claim 1, wherein the polyethylene copolymer has about 5% to about 10% by weight of C3-C 20 Comonomer content.

3. The polyethylene copolymer according to claim 1 or 2, wherein the high-load melt index (HLMI) is from about 45 g / 10 min to about 70 g / 10 min.

4. The polyethylene copolymer according to any one of claims 1 or 3, wherein the polyethylene copolymer has a melt index of about 0.3 g / 10 min to about 0.8 g / 10 min.

5. The polyethylene copolymer according to any one of claims 1 to 4, wherein the polyethylene copolymer has a g'vis value of about 0.8 to about 0.95 or about 0.82 to about 0.

92.

6. A membrane comprising the polyethylene copolymer according to claim 1.

7. The membrane according to claim 6, wherein the polyethylene copolymer has about 5% to about 10% by weight C3-C 20 Comonomer content.

8. The membrane according to claim 6 or 7, wherein the polyethylene copolymer has a melt index of about 0.3 g / 10 min to about 0.8 g / 10 min.

9. The membrane according to any one of claims 6 to 8, wherein the polyethylene copolymer has a g'vis value of about 0.8 to about 0.95, or about 0.82 to about 0.

92.

10. The membrane according to any one of claims 6 to 9, wherein the membrane comprises: Average 1% secant modulus (M) at 23°C at approximately 30,000 psi to approximately 40,000 psi. Elmendorf tear value (MD) of approximately 30 g / mil to approximately 75 g / mil. Dart impacts of approximately 150 g / mil to approximately 600 g / mil, and Fracture puncture energy of approximately 25 in-lbs / mil to approximately 40 in-lbs / mil.

11. The membrane according to any one of claims 6 to 10, wherein the membrane comprises: A haze value of approximately 35% or less, and Transparency of approximately 85% or more.

12. A polyethylene copolymer comprising: Approximately 90% by weight or more of ethylene units; and Remaining balance C3-C 20 Comonomer unit, The polyethylene copolymer has the following characteristics: Bimodal composition distribution Approximately 0.92 g / cm³ 3 To approximately 0.925 g / cm 3 density, Melt index (MI) of approximately 0.4 g / 10 min to approximately 0.5 g / min. High load melt index (HLMI) of approximately 24 g / 10 min to approximately 29 g / 10 min, A melt index ratio (MIR) of approximately 50 to approximately 65, and Molecular weight distribution (MWD) of approximately 4 to approximately 7.

13. The polyethylene copolymer of claim 12, wherein the polyethylene copolymer has about 5% to about 10% by weight of C3-C 20 Comonomer content.

14. The polyethylene copolymer of claim 12 or 13, wherein the polyethylene copolymer has a melt index of about 0.46 g / 10 min to about 0.48 g / 10 min.

15. The polyethylene copolymer according to any one of claims 12 to 14, wherein the polyethylene copolymer has a g'vis value of about 0.86 to about 0.

92.

16. The polyethylene copolymer according to any one of claims 12 to 15, wherein the polyethylene copolymer has a z-average molecular weight (Mz) of about 250,000 g / mol to about 350,000 g / mol.

17. A membrane comprising a polyethylene copolymer according to any one of claims 12 to 16.

18. A polyethylene copolymer comprising: Approximately 90% by weight or more of ethylene units; and Remaining balance C3-C 20 Comonomer unit, The polyethylene copolymer has the following characteristics: Bimodal composition distribution Approximately 0.92 g / cm³ 3 To approximately 0.925 g / cm 3 density, The melt index ranges from approximately 0.9 g / 10 min to approximately 1 g / min. High load melt index (HLMI) of approximately 50 g / 10 min to approximately 60 g / 10 min, A melt index ratio (MIR) of approximately 55 to approximately 65, and Molecular weight distribution (MWD) of approximately 6 to approximately 7.

19. The polyethylene copolymer of claim 18, wherein the polyethylene copolymer has about 5% to about 10% by weight of C3-C 20 Comonomer content.

20. The polyethylene copolymer of claim 18 or 19, wherein the polyethylene copolymer has a melt index of about 0.9 g / 10 min to about 0.95 g / 10 min.

21. The polyethylene copolymer according to any one of claims 18 to 20, wherein the polyethylene copolymer has a g'vis value of about 0.8 to about 0.

85.

22. The polyethylene copolymer according to any one of claims 18 to 21, wherein the polyethylene copolymer has a z-average molecular weight (Mz) of about 260,000 g / mol to about 300,000 g / mol.

23. A membrane comprising a polyethylene copolymer according to any one of claims 18 to 22.

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