Low density polyethylene, films thereof, and methods and catalysts for producing same

Abstract

The present disclosure relates to catalysts, catalyst systems, polyethylene polymers, polymerization processes for making such polyethylene polymers, and films made therefrom. In some embodiments, the catalyst compound is represented by formula (I) wherein M is Zr or Hf; r5 and R6 are each hydrogen; each of R1, R2, R3 and R4 is independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group; one pair of (1) R7 and R8, (2) R8 and R9, or (3) R9 and R10 is bonded to form a substituted or unsubstituted aromatic ring or a saturated ring fused to the indenyl ring shown in formula (I), and the remaining R7, R8, R9, and R10 are each hydrogen. In other embodiments, a process for producing a polyethylene composition is provided, comprising introducing ethylene and a C3-C40 alpha-olefin to a catalyst system in a reactor under first polymerization conditions, and forming the polyethylene composition.

Description

[0001] Cross-references to related applications

[0002] This application claims the benefit of U.S. Provisional Application 63 / 503,869, filed May 23, 2023, entitled “Low Density Polyethylenes, Films Thereof, And Methods And Catalysts For Production Thereof,” the entire contents of which are incorporated herein by reference. Technical Field

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

[0004] In many cases, low-density polyethylene (LDPE) (e.g., LDPE resin) is produced via free radical polymerization using autoclave or tubular reaction methods. Autoclave and tubular reaction methods differ significantly, at least in the distribution of reaction residence time (which can affect LDPE properties). In autoclave methods, backmixing of the reactant stream is significant, while in tubular methods, a recurrence state of the reactant stream is characteristic. Both methods require high-pressure processes (e.g., 60 MPa to 350 MPa) to produce polyethylene compositions with good processability, high melt strength, high shrinkage, and good optical properties (primarily attributed to the numerous long-chain branched LCB structures in the polyethylene composition). However, LDPE formed by high-pressure free radical polymerization typically suffers from poor mechanical properties such as low TD tear and dart impact strength. Furthermore, high-pressure methods require higher energy consumption than low-pressure methods.

[0005] Alternatively, linear low-density polyethylene (LLDPE) is a substantially linear polymer composed of ethylene monomer units and α-olefin comonomer units. LLDPE differs from conventional LDPE in several aspects, including different manufacturing methods and different rheological and mechanical properties, such as tear properties. However, LLDPE often requires higher motor power and higher extruder pressure to match the extrusion rates of LDPE.

[0006] In the past, LLDPEs have been modified in an attempt to achieve a good balance of stiffness, toughness, optical properties (e.g., haze and gloss), and processability. Such a balance can be provided by some LLDPEs with a broad orthogonal compositional distribution (called "BOCD"). These LLDPEs are typically prepared in a gas-phase reactor at pressures lower than those required for LDPEs produced by high-pressure radical polymerization, using catalysts that promote the polymerization of olefin monomers (mixed with one or more other components to form a catalyst system). Such catalyst systems often contain two or more different metallocene catalysts to obtain LLDPEs with, for example, BOCD properties. However, pairing different catalysts (within a single catalyst system) that perform optimally under similar / identical conditions is challenging.

[0007] In general, there is a need for new polyethylenes formed using low-pressure methods, employing a single catalyst to produce LCB polyethylene compositions that exhibit good extrusion processability similar to LDPE, as well as good tear properties and dart impact strength. Such new LCB polyethylene compositions would offer the benefits of improved processability versus improved tear balance, improved TD tear strength, and significantly better stretch characteristics, making the production of gauge films easier.

[0008] Some references of potential interest in this regard include: U.S. Patent Nos. 6,479,424; 7,601,666; 8,829,115; 9,068,033; 10,633,471; 11,267,917 and 11,352,386; WO2021 / 257264; WO2022 / 015094; US2006 / 0122342; US2021 / 0332169; US2021 / 0388191; US2021 / 0395404; US2022 / 0185916; US2022 / 0315680; US2022 / 0064344; KR10-2022-0009900, KR10-2022-0009782; KR10-2021-0080974; KR10-2021-0038379; KR10-2020-0089599; KR10-2018-0063669; KR10-2007-0098276; and Foster et al., Journal of Organometallic Chemistry, 571 (1998) 171. Summary of the Invention

[0009] This disclosure relates to a carrier-bonded activator, a supported catalyst system, and a method of using the same.

[0010] In some implementations, the catalyst compound is represented by formula (I):

[0011] (I)

[0012] Where M is Zr or Hf; R 5 and R 6 Each is hydrogen; R 1 R 2 R 3 and R 4 Each of the atoms in the group is independently hydrogen or a substituted or unsubstituted C1 to C2. 10 Alkyl; (1)R 7 and R 8 (2)R 8 and R 9 Or (3)R 9 and R 10 A pair of bonds in the mixture fused to form a substituted or unsubstituted aromatic ring or a saturated ring of the indenyl ring shown in formula (I), and the remaining R 7 R 8 R 9 and R 10 Each is hydrogen; T is derived from formula R a 2J、(R a )4J2 or (R a )6J3 indicates that each J is independently carbon, silicon, or germanium, and each R a Independently, it is hydrogen, halide, substituted or unsubstituted C1 to C2. 40 Hydrocarbon group, or two Rs a It can form a substituted or unsubstituted fully saturated ring, a substituted or unsubstituted partially saturated ring, or a substituted or unsubstituted aromatic ring; and each X is independently a halogen, a substituted or unsubstituted hydrocarbon, a hydride, an amide, a substituted or unsubstituted alkoxide, a sulfide, a phosphide, or a combination thereof, or two X are joined together to form a substituted or unsubstituted metal ring, or two X are joined together to form a chelate ligand, a diene ligand, or an alkylidene group.

[0013] In some embodiments, the method for producing a polyethylene composition includes introducing ethylene and C3-C into a reactor under first polymerization conditions. 40 α-olefins and a catalyst system are used to form a polyethylene copolymer, said polyethylene copolymer having ethylene monomer-derived content and C3-C4 content. 40 The content of α-olefin comonomer derivatization. The catalyst system comprises a catalyst compound. The catalyst compound is represented by formula (I):

[0014] (I)

[0015] Where M is a Group 4 metal; R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 and R 10 Each 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 are joined to form a substituted or unsubstituted fully saturated ring or a substituted or unsubstituted aromatic ring, 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 elements in the formula (I) are bonded to form a substituted or unsubstituted aromatic ring fused to the indenyl ring shown in formula (I); T is derived from formula R. a 2J、(R a )4J2 or (R a )6J3 indicates that each J is independently carbon, silicon, or germanium, and each R a Independently hydrogen, halogen, substituted or unsubstituted C1 to C2 40 Hydrocarbon group, or two Rs a It can form a substituted or unsubstituted fully saturated ring, a substituted or unsubstituted partially saturated ring, or a substituted or unsubstituted aromatic ring; and 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 X are joined together to form a substituted or unsubstituted metal ring, or two X are joined together to form a chelate ligand, a diene ligand, or an alkylidene group.

[0016] In some embodiments, this document describes a membrane comprising a polyethylene copolymer having a composition distribution width index (CDBI) of about 70% to about 80%, and about 0.914 g / cm³. 3 Approximately 0.926 g / cm³ 3The density, melt index from about 0.10 g / 10 min to about 6 g / 10 min, olefin comonomer content from about 5 wt% to about 12 wt%, high load melt index (HLMI) from about 120 g / 10 min to about 275 g / 10 min, melt index ratio (MIR) from about 60 to about 150, and molecular weight distribution (MWD) from about 8 to about 12. Attached Figure Description

[0017] To gain a more detailed understanding of the features described above, the invention, which has been briefly summarized above, can be described in more detail 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 are therefore not intended to limit its scope, as the invention allows for other equally effective embodiments.

[0018] Figure 1 This is a graph illustrating the TREFIR5 of the polyethylene copolymer synthesized by catalyst 1 compared to the polyethylene copolymer synthesized by the comparative catalyst.

[0019] Figure 2 This is a graph illustrating the complex viscosity of the polyethylene copolymer synthesized with catalyst 1 compared to that synthesized with the comparative catalyst.

[0020] Figure 3 This is a graph illustrating the shear thinning index of the polyethylene copolymer synthesized with catalyst 1 compared to the polyethylene copolymer synthesized with the comparative catalyst.

[0021] Figure 4 This is a graph illustrating the phase angle versus complex modulus of the polyethylene copolymer synthesized by catalyst 1) compared to the polyethylene copolymer synthesized by the comparative catalyst.

[0022] Figure 5 This is a graph illustrating the phase angle (at 10 kPa) of the polyethylene copolymer synthesized by catalyst 1 compared to the polyethylene copolymer synthesized by the comparative catalyst.

[0023] definition

[0024] For the purposes of this disclosure, the numbering scheme of the periodic table family as described in Chemical and Engineering News, 63(5), page 27 (1985) is used.

[0025] The following abbreviations may be used in this article: Me is methyl, Et is ethyl, Ph is phenyl, 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.

[0026] The term "alkenyl" means a straight-chain, 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 analogues.

[0027] The terms "alkoxy" and "alkoxide" refer to an alkyl or aryl group bonded to an oxygen atom, such as an alkyl ether or aryl ether group / radical bonded to an oxygen atom, and may include alkyl / aryl groups that are C1 to C2. 10 Those with hydrocarbon groups. Alkyl groups can be straight-chain, branched, or cyclic. Alkyl groups can be saturated or unsaturated. Examples of suitable alkoxy groups may include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, and phenoxy.

[0028] The terms "alkyl radical," "alkyl group," and "alkyl" are used interchangeably throughout this disclosure. For the purposes of this disclosure, an "alkyl group" is defined as a C1-C group that can be straight-chain, 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.

[0029] The term "α-olefin" refers to an olefin having a terminal carbon-carbon double bond in its structure ((R''R''')-C=CH2, where R'' and R''' can be hydrogen or any hydrocarbon group independently, such as R'' being hydrogen and R''' being an alkyl group). "Linear α-olefin" is an α-olefin as defined in this paragraph, where R'' is hydrogen and R''' is either hydrogen or a linear alkyl group.

[0030] For the purposes of this disclosure, ethylene should be considered as an α-olefin.

[0031] 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 electrically neutral ligand that donates one or more pairs of electrons to a metal ion. Examples of Lewis bases include diethyl ether, trimethylamine, pyridine, tetrahydrofuran, dimethyl sulfide, and triphenylphosphine. The term "heterocyclic Lewis base" refers to a Lewis base that is still heterocyclic. Examples of heterocyclic Lewis bases include pyridine, imidazole, thiazole, and furan.

[0032] The term "arenyl" as used in this article refers to an unsaturated cyclic hydrocarbon ligand that may consist of one ring or two or more fused or catenated rings.

[0033] The term “aryl” or “aryl group” means an aromatic ring and its substituted variants, such as phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl. Similarly, “heteroaryl” means an aryl group in which a ring carbon atom (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 (nearly planar) similar to aromatic heterocyclic ligands, but is not aromatic by definition; similarly, the term “aromatic” also refers to substituted aromatic compounds.

[0034] "Bulk polymerization" means a polymerization method in which the monomers and / or comonomers involved in the polymerization are used as solvents or diluents, and inert solvents are used in small amounts or not at all. A small portion of the inert solvent / diluent can be used as a carrier for catalysts and scavengers. The bulk polymerization system contains less than 25% by weight of inert solvent or diluent, for example, less than 10% by weight, less than 1% by weight, or 0% by weight.

[0035] The terms “catalyst compound”, “catalyst complex”, “transition metal complex”, “transition metal compound”, “precatalyst compound”, and “precatalyst complex” are used interchangeably.

[0036] A “catalyst system” is a combination of at least one catalyst compound, at least one activator, optional co-activator, and optional support material. When “catalyst system” is used to describe such a pairing before activation, it means the unactivated catalyst complex (pre-catalyst) together with the activator and optional co-activator. When used to describe such a pairing after activation, it means the activated complex and the activator or other structural part with balanced charge. The catalyst compound can be neutral, as in the pre-catalyst, or charged as in the activated catalyst system, having a counterion. For the purposes of this disclosure and the appended claims, when the catalyst system is described as comprising a neutral, stable form of the component, it is fully understood by those skilled in the art that the ionic form of the component is the form in which it reacts with the monomer to produce a polymer. 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 the catalyst compounds and activators.

[0037] A catalyst system utilizing a single catalyst compound is a catalyst system prepared using only a single catalyst compound in its preparation. Therefore, such a catalyst system differs from, for example, a "dual" catalyst system, which is prepared using two catalyst compounds with different structural formulas, such as different atomic connections, atomic numbers, and / or atomic types. Thus, a catalyst compound is considered different from another catalyst compound if it differs in at least one atom (in number, type, or connection). For example, bis(indenyl)zirconia is different from (indenyl)(2-methylindenyl)zirconia, which is different from (indenyl)(2-methylindenyl)hafnium dichloride. 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 not considered different.

[0038] As used herein, and unless otherwise stated, the term "C" n "C" means a hydrocarbon (one or more) with n carbon atoms (one or more) per molecule, where n is a positive integer. Similarly, "C" means a hydrocarbon (one or more) with n carbon atoms (one or more) per molecule. m -C y "A group or compound refers to a group or compound containing a total of m to y carbon atoms. Therefore, C1-C..." 50 Alkyl groups are alkyl groups that contain a total of about 1 to about 50 carbon atoms.

[0039] 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.

[0040] The term "continuous" means a system that operates for an extended period of time without interruption or stoppage. For example, a continuous process for producing polymers would be one in which reactants are continuously introduced into one or more reactors and polymer products are continuously extracted.

[0041] As used herein, the term "film" refers to a continuous, flat (and in some cases flexible) polymeric structure having an average thickness of 0.1, or 1, or 5, or 10, or 15, or 20 μm to 50, or 75, or 100, or 150, or 200, or 250, or 1000, or 2000 μm, or a coating having a similar thickness adhered to a flexible, non-flexible, or solid structure. A "film" may be made of or contain a single layer or multiple layers. Each layer may be made of or contain polyethylene copolymers of the present disclosure. For example, one or more layers of a "film" may comprise a mixture of the disclosed polyethylene copolymers as well as LDPE, additional LLDPE, polypropylene, or a plastide.

[0042] As used herein, "free of" a component means that the composition / membrane is substantially free of that component or contains that component in an amount of less than about 0.01% by weight (based on the total weight of the composition).

[0043] A "heterocyclic ring" is a ring structure containing heteroatoms, as opposed to a heteroatom-substituted ring, where hydrogen atoms on the ring atoms are replaced by heteroatoms. For example, tetrahydrofuran is a heterocyclic ring and 4-N,N-dimethylamino-phenyl is a heteroatom-substituted ring. Other examples of heterocycles can include pyridine, imidazole, and thiazole.

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

[0045] The terms "hydrocarbyl radical," "hydrocarbyl group," or "hydrocarbyl group" are used interchangeably and are defined as a group containing only hydrogen and carbon atoms. For example, a hydrocarbyl group can be C1-C. 100A functional group, which may be straight-chain, branched, or cyclic, and when cyclic, may be aromatic or non-aromatic. Examples of such functional 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, cyclooctyl, and aryl groups such as phenyl, benzyl, and naphthyl.

[0046] As used herein, Mn is the number-average molecular weight, Mw is the weight-average molecular weight, and Mz is the z-average molecular weight. wt% is the weight percentage, and mole% is the mole 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, or Mz) are in g / mol.

[0047] As used herein, “olefin”, optionally referred to as “alkene”, is a straight-chain, branched, or cyclic compound of carbon and hydrogen having at least one double bond. For the purposes of this specification and its appended claims, when a polymer or copolymer is referred to as “containing” an olefin, the olefin present in such a polymer or copolymer is in the form of a polymerized 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 comonomers in the copolymer are derived from ethylene in the polymerization reaction and the derived units are present in 35% to 55% by weight, based on the weight of the copolymer.

[0048] As used herein, “olefin polymerization catalyst (one or more)” means any catalyst capable of coordinative addition polymerization (in which successive monomers are added to the monomer chain at the organometallic active site), such as organometallic complexes or compounds.

[0049] "Noncoordinate anion (NCA)" means an anion that is either not coordinated to the catalyst metal cation or is coordinated to the metal cation but only weakly coordinated. The term "NCA" is also defined as an activator comprising multiple components containing NCA, such as N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate, which contains an acidic cation group and a noncoordinate anion. The term NCA is also defined as a neutral Lewis acid, such as tris(pentafluorophenyl)boron, which can react with the catalyst to form an activator by abstracting an anionic group. The coordination of the NCA is weak enough that a neutral Lewis base, such as an alkene or alkyne unsaturated monomer, can displace it from the catalyst center. Noncoordinate anions may use or contain any metal or metalloid that can form a compatible, weakly coordinated complex. Suitable metals include, but are not limited to, aluminum, gold, and platinum. Suitable metalloids include, but are not limited to, boron, aluminum, phosphorus, and silicon. The term noncoordinate anionic activator includes neutral activators, ionic activators, and Lewis acid activators. The terms “noncoordinate anionic activator” and “ionized activator” are used interchangeably in this document.

[0050] As used herein, the term "polycyclic aromatic ligand" refers to a substituted or unsubstituted monoanionic C9 to C14 ligand. 103 Hydrocarbon ligands containing an aromatic five-membered hydrocarbon ring (also called a cyclopentadienyl ring) fused to one or two partially unsaturated or aromatic hydrocarbon ring structures, wherein the hydrocarbon ring structure may be fused to additional saturated, partially unsaturated or aromatic hydrocarbon rings.

[0051] 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).

[0052] 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 means that the monomer units are different from each other 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.

[0053] 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 A low-density polyethylene polymer (LDPE) is a polymer with a density of 0.925 to 0.940 g / cm³. When it is substantially linear (with little or no long-chain branching) (which is typically the case for Ziegler-Natta or metallocene-catalyzed PE), it is called "linear low-density polyethylene" (LLDPE), or when it is significantly branched (with a high degree of long-chain branching) (which is often the case for free-radical polymerized PE), it is called linear low-density polyethylene (LDPE). 3 Ethylene polymers with a density greater than 0.940 g / cm³ are called "medium-density polyethylene" (MDPE); and have a density greater than 0.940 g / cm³. 3 High-density polyethylene (HDPE) is a polymer of ethylene with a density that is specified in ASTM D792. The density is determined according to ASTM D4703 - Appendix 1 Procedure C, and then conditioned according to ASTM D618 - Procedure A prior to testing.

[0054] As used herein, the term “polymerization conditions” refers to conditions that favor the reaction of one or more olefin monomers when in contact with an activated olefin polymerization catalyst to produce a polyolefin polymer, including selections by a person skilled in the art for temperature, pressure, reactant concentration, optional solvent / diluent, reactant mixing / addition parameters, and other conditions within at least one polymerization reactor.

[0055] The terms "process" and "method" are used interchangeably.

[0056] The term "ring atom" refers to an atom that is part of a ring structure. According to this definition, the benzyl group has six ring atoms and tetrahydrofuran has five ring atoms.

[0057] A "scavenger" is a compound that can be added to promote polymerization by removing impurities. Some scavengers can also act as activators and can be called co-activators. Co-activators that are not scavengers can also be used in combination with activators to form an active catalyst. In at least one embodiment, the co-activator can be premixed with a transition metal compound to form an alkylated transition metal compound.

[0058] The term "single catalyst compound" refers to a catalyst compound that corresponds to a single structural formula, although such catalyst compounds may contain mixtures of isomers (e.g., stereoisomers) and may be used as mixtures of isomers (e.g., stereoisomers).

[0059] "Solution polymerization" means a polymerization method in which the polymer is dissolved in a liquid polymerization medium, such as an inert diluent or monomers (one or more) or blends thereof. Solution polymerization can be homogeneous. Homogeneous polymerization is polymerization in which the polymer product is dissolved in the 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.

[0060] The terms “substituent,” “radical,” “group,” and “structural part” are used interchangeably.

[0061] Unless otherwise stated (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 group containing a heteroatom, such as a halogen (e.g., Br, Cl, F or I) or at least one 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, wherein each R* is independently a hydrocarbon or halocarbyl group, and two or more R* may be joined together to form a substituted or unsubstituted fully saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure), or wherein at least one heteroatom has been inserted into the hydrocarbon ring.

[0062] The term "substituted aromatic compound" means an aromatic group in which one or more hydrogen groups are replaced by a hydrocarbon group, a substituted hydrocarbon group, a heteroatom, or a group containing a heteroatom.

[0063] 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 (e.g., a halogen group, such as Br, Cl, F or I) or a group containing a heteroatom (e.g., a 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 halohydrocarbon group, and two or more R* can be joined together to form a substituted or unsubstituted fully saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure), or wherein at least one heteroatom has been inserted into the hydrocarbon ring.

[0064] The term "substituted phenyl" means a phenyl group in which one or more hydrogen groups are replaced by a hydrocarbon group, a substituted hydrocarbon group, a heteroatom, or a group containing a heteroatom.

[0065] In the presence of isomers of a specified alkyl, alkenyl, alkoxy, or aryl group (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl), the reference to the alkyl, alkenyl, alkoxy, or aryl group without specifying a particular isomer (e.g., butyl) explicitly discloses all isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl).

[0066] For the sake of brevity, this document only explicitly discloses certain ranges. However, a range from any lower limit can be combined with any upper limit to describe a range not explicitly described, and a range from any lower limit can be combined with any other lower limit to describe a range not explicitly described, just as a range from any upper limit can be combined with any other upper limit to describe a range not explicitly described. Additionally, "within a range" or "within a range," even if not explicitly described, includes every point or individual value between its endpoints, and includes the endpoints themselves. Therefore, each point or individual value can serve as its own lower or upper limit, combined with any other point or individual value or any other lower or upper limit, to describe a range not explicitly described. Detailed Implementation

[0067] 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 the detailed description below provides for specific embodiments, those skilled in the art will understand that these embodiments are merely exemplary and that embodiments of this disclosure may be implemented 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 defined by the claims. The headings are used for convenience only and do not limit the scope of this disclosure.

[0068] This disclosure relates to catalysts, catalyst systems, polyethylene polymers, polymerization methods for preparing such polyethylene polymers, and membranes prepared therefrom. The catalyst systems and methods described herein employ metallocene catalyst systems for the polymerization of long-chain branched polyethylene polymers (which have a combination of a wide polydispersity index, a wide orthogonal compositional distribution, and a high compositional distribution width index). In some embodiments, the polyethylene polymer is a copolymer having a combination of low density, low melt index, high melt index ratio, and long-chain branching. Additionally, the polyethylene polymer involves the polymerization and extrusion of commercially desirable polyethylene copolymers.

[0069] Compared to conventional LDPE, the polyethylene copolymers of this disclosure exhibit increased long-chain branching (also referred to as "LCB") and an increased broad orthogonal composition distribution (BOCD) in the copolymer, while still providing necking stability and tensile stability. The polyethylene copolymers of this disclosure can exhibit lower zero-shear viscosity compared to LLDPE, resulting in lower motor torque and lower melt pressure and melt temperature during extrusion, providing increased yield of extruded polyethylene copolymer products. LCB can be demonstrated, for example, by high melt index ratios and / or rheological characteristics (e.g., η) as shown by small-angle oscillating shear (SAOS) experiments. 0.01 / η 100 The ratio, η 0.01 and η 100 This was confirmed by the complex viscosity recorded at shear rates of 0.01 and 100 rad / s, respectively.

[0070] Furthermore, it has been found that the polyethylene copolymers of this disclosure can provide excellent tear properties, dart impact strength, and shear thinning greater than that of comparative PEs from both gas-phase and high-pressure methods, overcoming key drawbacks of LDPE. For example, compared to conventional LLDPE, the polyethylene copolymers of this disclosure can provide films formed with reduced motor load and melt pressure (which increases production output) due to improved flow behavior. For example, a reduction in melt pressure and a decrease in melt temperature can be provided during film manufacturing.

[0071] In at least one embodiment, the properties and performance of polyethylene can be improved by a combination of the following: (1) changing reactor conditions such as reactor temperature, reactor pressure, hydrogen concentration, comonomer concentration, etc.; and (2) selecting and feeding a catalyst system having the catalyst of this disclosure.

[0072] The implementation scheme can advantageously maintain a wide MI range using the same catalyst system. For the catalyst system fed into the polymerization reactor, the MI, MIR, and density of the polymer can be controlled by changing reactor conditions, such as the reactor mixture including additional catalyst, operating temperature, operating pressure, hydrogen concentration, and comonomer concentration in the reaction mixture.

[0073] Evidence of comonomer incorporation into the polymer is indicated by the density of the polyethylene copolymer, with lower density indicating higher incorporation. The density difference between the low molecular weight (LMW) and high molecular weight (HMW) components can be greater than approximately 0.02 g / cm³. 3 or greater than approximately 0.04 g / cm³ 3 The HMW component has a lower density than the LMW component. Satisfactory control of MWD and long-chain branched distribution (LCBD) allows for the modulation of these factors, which can be adjusted by modifying reactor conditions.

[0074] Other embodiments provide a method for producing polyethylene, comprising introducing a composition of a contact product comprising a first diluent, a first catalyst compound, a carrier material, and an activator into a gas-phase fluidized bed reactor; exposing the first composition to polymerization conditions by reacting ethylene with at least one C3-C... 20 α-olefins are introduced into a gas-phase fluidized bed reactor to polymerize ethylene and at least one C3-C 20 α-olefins; and to obtain polyethylene copolymers.

[0075] Catalyst compounds

[0076] In some implementations, the catalyst is represented by formula (I):

[0077] (I)

[0078] in:

[0079] M is a Group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf);

[0080] 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 substituted or unsubstituted fully saturated ring or a substituted or unsubstituted aromatic ring;

[0081] 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 hydrogen, halogen, substituted or unsubstituted C1 to C2 40 Hydrocarbon group, in which two R aOptionally, substituted or unsubstituted cyclic structures can be formed, including substituted or unsubstituted fully saturated rings, substituted or unsubstituted partially saturated rings, or substituted or unsubstituted aromatic rings (preferably, such ring structures contain J in the ring and have 2-10 carbon atoms in addition to the atom represented by J); and

[0082] 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 X are joined together to form a substituted or unsubstituted metal ring, or two X are joined together to form a chelate ligand, a diene ligand, or an alkylidene group.

[0083] More specifically, R in formula (I) 7 R 8 R 9 and R 10 Each of them can be independently hydrogen or C1-C. 10 Alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl), and preferably (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 (I) are bonded to form a substituted or unsubstituted ring (which may be aromatic or fully saturated) fused to the indenyl ring shown in the formula (I). In particular, it may be a C4, C5, C6 or C7 aromatic ring (e.g., cyclopentadienyl, benzyl, etc.) or a fully saturated ring (e.g., cyclopentyl, cyclobenzyl, etc.).

[0084] R in equation (I) 1 R 2 R 3 and R 4 Each of them can be independently hydrogen or C1-C. 10 Alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl), preferably methyl, ethyl, or propyl; most preferably R. 1 R 2 R 3 and R 4 Each of them is a methyl group.

[0085] Regarding the bridging group T, each R a Independently, hydrogen or C1 to C2 is the most preferred option. 20The hydrocarbon group, and J is preferably Si or C, with Si being the most preferred. For example, T can be selected from CH2, CH2CH2, C(CH3)2, CPh2, SiMe2, SiEt2, SiPh2, SiMePh, SiEtPh, SiMeEt, Si(CH2)3, Si(CH2)4 or Si(CH2)5, and preferably, T is SiMe2, SiEt2 or SiMeEt.

[0086] R in equation (I) 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 can be hydrogen, hydrocarbon, silylcarbyl, alkoxy, halogen, or silyloxy.

[0087] In some embodiments of formula (I), M is a Group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf). In some embodiments, each X is independently a halogen group, such as a chloro group. 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, chloro, fluoro, bromo, iodo, trifluoromethanesulfonate, dimethylamido, diethylamido, dipropylamido, and diisopropylamido.

[0088] In some embodiments of formula (I), (1) M is Zr or Hf, (2) X is chloro or methyl, (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 R9 and R 10 At least one pair of them are joined to form a substituted or unsubstituted ring (saturated or aromatic, preferably C5 or C6 saturated or aromatic ring) fused to the indenyl ring shown in formula (I), and (6)R 1 R 2 R 3 and R 4 Independently hydrogen or C1 to C 10 Alkyl (preferably methyl, ethyl, or propyl). Preferably, R 5 and R 6 It is hydrogen, and in addition, R 7 -R 10 The non-conjugation in R to form either a substituted or unsubstituted ring is also hydrogen (therefore, when R...). 7 and R 8 When joined to form a ring, then R 9 and R 10 Each is hydrogen; and when R 8 and R 9 When joined to form a ring, then R 7 and R 10 (Each is hydrogen). In some embodiments, the ring is an unsubstituted cyclopentyl ring fused to an indenyl ring of formula (I). In still other embodiments, the ring may be an unsubstituted benzyl ring fused to an indenyl ring of formula (I). When the ring is cyclopentyl, it is preferably composed of R 8 and R 9 Formation; when the ring is benzyl, it is preferably formed from R 7 and R 8 form.

[0089] Therefore, the catalyst according to various implementation schemes can be either (Ia) or (Ib):

[0090]

[0091] In some embodiments, the catalyst may comprise the fused benzyl ring discussed above (e.g., with respect to formula (Ib)), but said ring may be substituted. Therefore, the catalyst in some embodiments is represented by formula (II):

[0092] (II)

[0093] Among them, M, T, X and R 1 -R 10 This conforms to the above discussion on equation (I), and R of equation (II) 11 R 12 R 13 and R 14 Each of them is independently hydrogen or C1-C 10Alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl). Preferably, R 1 -R 4 T and X conform to the above discussion of equation (I), and, more specifically, R 5 -R 14 Each is hydrogen.

[0094] Aggregation methods

[0095] 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 comprises 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 withdrawn from the fluidized bed and recycled back to the reactor. Simultaneously, polymer products are withdrawn from the reactor and fresh monomers are added to replace the monomers used in polymerization. (See, for example, U.S. Patents 4,543,399; 4,588,790; 5,028,670; 5,317,036; 5,352,749; 5,405,922; 5,436,304; 5,453,471; 5,462,999; 5,616,661 and 5,668,228, all of which are incorporated herein by reference.) Gas-phase polymerization can be carried out in any suitable reactor system, such as stirred or paddle reactor systems. For a discussion of suitable gas-phase fluidized bed polymerization systems, see U.S. Patent Nos. 7,915,357; 8,129,484; 7,202,313; 6,833,417; 6,841,630; 6,989,344; 7,504,463; 7,563,851 and 8,101,691, which are incorporated herein by reference.

[0096] In such a polymerization method, the gas-phase fluidized bed process is carried out by continuously passing a stream containing ethylene and olefin comonomers through a fluidized bed reactor at a rate sufficient to keep the 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 extracted from the reactor, compressed, cooled, optionally partially or completely condensed, and recycled back to the reactor. The prepared polyethylene copolymer is extracted 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.

[0097] The circulating gas may include an induced condensate (ICA). An ICA is one or more non-reactive alkanes that can be condensed in the polymerization process to remove heat from the 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 useful (e.g., propane and pentane, propane and butane, butane and pentane, etc.).

[0098] The reactor pressure during polymerization can be 100 psig (680 kPag) to 500 psig (3448 kPag), for example 200 psig (1379 kPag) to 400 psig (2759 kPag), for example 250 psig (1724 kPag) to 350 psig (2414 kPag). In some embodiments, the reactor operates at temperatures between 60°C and 120°C, for example 60°C to 115°C, for example 70°C to 110°C, for example 70°C to 95°C, for example 80°C to 90°C. The hydrogen-to-ethylene ratio can be 8 to 30 ppm / mol%, for example 8 to 15 ppm / mol%, for example 9 to 11 ppm / mol.

[0099] The mol% of ethylene (based on total monomers) can be 25-90 mol%, for example 50-90 mol%, or 60.0-75.0 mol%, and the partial pressure of ethylene (in the reactor) can be 75 psia (517 kPa)-300 psia (2069 kPa), or 100-275 psia (689-1894 kPa), or 150-265 psia (1034-1826 kPa), or 180-200 psia. The ethylene concentration in the reactor can also be 35-95 mol%, for example, within the range of a lower limit of 35, 40, 45, 50, or 55 mol% to an upper limit of 70, 75, 80, 85, 90, or 95 mol%, and the mol% of ethylene is measured based on the total 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 of other ICAs); similar to vol-ppm hydrogen, for convenience, this measurement can be performed at the recirculated gas outlet rather than in the reactor itself. The comonomer concentration can be 0.2-2 mol%, for example, within the range of a lower limit of 0.2, 0.3, 0.4, or 0.5 mol% to an upper limit of 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95, 1.0, 1.5, or 2.0 mol%.

[0100] Activator

[0101] The terms “co-catalyst” and “activator” are used interchangeably in this document.

[0102] The catalyst systems described herein may comprise one or more of the catalyst compounds described above and an activator such as an aluminoxane or a noncoordinate anion, and may be formed by combining the catalyst compounds and activators described herein in any manner known in the literature, including combining them with a support such as silica. The catalyst systems may also be added to solution polymerization or bulk polymerization (in monomers) 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 (which may be neutral or ionic), and conventional types of co-catalysts. Suitable activators may include aluminoxane compounds, modified aluminoxane compounds, and ionized anion precursor compounds that abstract reactive, σ-bonded metal ligands, making the metal compound a cation and providing a charge-balanced noncoordinate or weakly coordinated anion, such as a noncoordinate anion.

[0103] In some embodiments, the catalyst system comprises an activator and a catalyst compound of formula (I), formula (II), formula (III) and / or formula (IV).

[0104] Aluminoxane activator

[0105] Aluminoxane activators are used as activators in the catalyst systems 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, for example, when the abstractable ligand is alkyl, halogen, alkoxy, or amino. Mixtures of different aluminum oxanes and modified aluminum oxanes can also be used. Using visually clear methylaluminoxanes can be suitable. Turbid or gelled aluminum oxanes can be filtered to produce a clear solution or the clear aluminum oxane can be decanted from the turbid solution. A useful aluminum oxane is modified methylaluminoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A [Modified Methylaluminoxane Type 3A] (protected by patent number US 5,041,584, which is incorporated herein by reference)). Other useful aluminoxanes are solid polymethylaluminoxanes, such as those described in US 9,340,630, US 8,404,880 and US 8,975,209, which are incorporated herein by reference.

[0106] When the activator is an aluminoxane (modified or unmodified), and in at least one embodiment, an activator in an amount with a molar excess of up to 5000 times Al / M relative to the catalyst compound (per metal catalytic site) can be used. The minimum activator-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.

[0107] In alternative embodiments, a small amount of aluminum oxane or no aluminum oxane is used in the polymerization method described herein. For example, the aluminum oxane may be present at zero molar %, 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, for example less than 300:1, for example less than 100:1, for example less than 1:1.

[0108] Ionized / noncoordinated anion activators

[0109] The term "noncoordinate anion" (NCA) means an anion that either does not coordinate to a cation or coordinates to a cation but only weakly, thus maintaining sufficient instability to be replaced by a Lewis base. "Compatible" noncoordinate anions are those that do not degrade to neutrality when the initially formed complex decomposes. Furthermore, the anion does not transfer anionic substituents or fragments to the cation, resulting in 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 transition metal cations (in the sense of balancing their ionic charge with +), and also maintain sufficient instability to allow substitution during polymerization. Suitable ionizing activators may include NCAs, such as compatible NCAs.

[0110] 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.

[0111] 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, which are incorporated herein by reference; and US Patent Publication 2021 / 0179650, and in particular WIPO Patent Publication No. WO2021 / 257264, paragraphs

[0084] -

[0135] , which are incorporated herein by reference (including descriptions incorporated herein by reference, such as WO2004 / 026921, page 72, paragraphs

[00119] through 81, paragraph

[00151] , and WO2004 / 046214, page 72, paragraphs

[00177] through 74, paragraph

[00178] ).

[0112] Furthermore, the catalyst system disclosed herein may comprise a metal hydrocarbon alkenyl chain transfer agent represented by the following formula:

[0113]

[0114] 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 alkenyl group. 20 Hydrocarbon alkenyl group; and v can be from 0.1 to 3.

[0115] carrier material

[0116] In the embodiments described herein, the catalyst system may comprise an inert support material. The support material may be a porous support material, such as talc and inorganic oxides. Other support materials include zeolites, clays, organoclays, or other organic or inorganic support materials, or mixtures thereof.

[0117] The support material can be an inorganic oxide. The inorganic oxide can be in a finely divided form. Suitable inorganic oxide materials for the catalyst system described herein may 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 may include magnesium oxide, titanium oxide, and zirconium oxide. However, other suitable support materials may be used, such as finely divided functionalized polyolefins, such as finely divided polyethylene. Examples of suitable supports may include magnesium oxide, titanium oxide, zirconium oxide, montmorillonite, layered silicates, zeolites, talc, and clay. Furthermore, combinations of these support materials may be used, such as silica-chromium, silica-alumina, and silica-titanium oxide. In at least one embodiment, the support material is selected from Al₂O₃, ZrO₂, SiO₂, SiO₂ / Al₂O₃, SiO₂ / TiO₂, silica clay, silicon oxide / clay, or mixtures thereof.

[0118] Support 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. The surface area of ​​the support material can be approximately 50 m². 2 / g to approximately 500 m 2 / g, with 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, with approximately 0.8 cm 3 / g to approximately 3.0 cm 3 The pore volume and average particle size per g can be from about 5 μm to about 100 μm. The average pore size of the support material available in this disclosure can be from about 10 Å to about 1000 Å, for example from about 50 Å to about 500 Å, and for example from about 75 Å to about 350 Å. In at least one embodiment, the support material is high surface area amorphous silica (surface area = 300 m² / g). 2 / gm; pore volume is 1.65 cm³. 3 / gm). For example, suitable silica can be silica commercially available from 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, calcined (e.g., at 875°C) ES-70™ silica (PQ Corporation, Malvern, Pennsylvania).

[0119] 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 about 100°C to about 1000°C, for example at least about 600°C. When the support material is silica, it is heated to at least 200°C, for example about 200°C to about 850°C, and for example about 600°C; and maintained for about 1 minute to about 100 hours, about 12 hours to about 72 hours, or about 24 hours to about 60 hours. The calcined support material must have at least some reactive hydroxyl (OH) groups to produce the supported catalyst system of this disclosure. The calcined support material is then contacted with at least one polymerization catalyst comprising at least one catalyst compound and an activator.

[0120] 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.

[0121] The mixture of catalyst (one or more), activator (one or more), and support is heated to about 0°C to about 70°C, for example, about 23°C to about 60°C, for example, room temperature. The contact time can be about 0.5 hours to about 24 hours, for example, about 2 hours to about 16 hours, or about 4 hours to about 8 hours.

[0122] A suitable nonpolar diluent is a material in which all reactants (e.g., activators and catalyst compounds) used herein are at least partially soluble and are liquid or gaseous at the reaction temperature. Nonpolar diluents can be alkanes, such as isopentane, hexane, n-heptane, octane, nonane, and decane, but a variety of other materials can also be used, including cycloalkanes, such as cyclohexane, and aromatic compounds, such as benzene, toluene, and ethylbenzene.

[0123] In at least one embodiment, the carrier material is a supported methylaluminoxane (SMAO), which is a MAO activator treated with silica (e.g., ES-70-875 silica).

[0124] polyethylene copolymer

[0125] This disclosure provides polyethylene copolymers having a combination of low density, high melt index, long-chain branching, broad orthogonal compositional distribution, and bimodal compositional distribution. Furthermore, the polyethylene copolymers and their films can be formed through commercially desirable polymerization and extrusion of the polyethylene copolymers.

[0126] Therefore, the polyethylene copolymers of the various embodiments described herein can exhibit one or more of the following properties:

[0127] • 0.914 to 0.926 g / cm³ 3 Densities within the range of, for example, 0.914, 0.915, 0.916, 0.917, 0.918, 0.919, or 0.92 g / cm³. 3 The lower limit of any of them is up to 0.926, 0.925, 0.924, 0.923, 0.922, 0.921, 0.920 or 0.919 g / cm³. 3 The upper limit of any one of them, for example 0.915 g / cm³. 3 Up to 0.920 g / cm 3 0.918 g / cm³ is available as an option. 3 Up to 0.922 g / cm 3 This covers any combination of lower and upper limits (as long as the lower limit is greater than the upper limit), for example, 0.916 to 0.921 g / cm³. 3 .

[0128] • Melt index (MI, also known as I2 or I) of approximately 0.1 g / 10 min or greater 2.16According to the 2.16 kg load used in the test (ASTM D1238, 190℃, 2.16 kg), for example, the lower limit of any one of 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4 or 1.5 g / 10 min to 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, 5 or 6 g / 10 min. The upper limit of any of the min values, and this document covers any combination of lower and upper limits (as long as the lower limit is greater than the upper limit), such as about 0.1 to about 1.2 g / 10 min, alternatively about 1.4 to about 2.5 g / 10 min, alternatively about 4 to about 5.9 g / 10 min, etc.

[0129] 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 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 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, ethyleneide-norbornene, 5-vinylidene-2-norbornene, 5-vinyl-2-norbornene, and olefins formed in situ in a polymerization medium. In some embodiments, the comonomer is selected from isoprene, styrene, butadiene, isobutene, chloroprene, acrylonitrile, and cyclic olefins. In some embodiments, a combination of olefin comonomers is used. In some embodiments, the olefin comonomer is selected from 1-butene and 1-hexene. The olefin comonomer content of the polyethylene copolymer can be from a lower limit of about 0.1, 5, 5.5, 6, 6.5, 7, 7.5, 8 or 8.5% by weight to an upper limit of about 20, 15, 13, 12.5, 12, 11.5, 11, 10.5, 10, 9.5 or 9% by weight, based on the total weight of the monomers in the polyethylene copolymer. The balance of the polyethylene comonomer consists of units derived from ethylene (e.g., from a lower limit of 80, 85, 88, 90, 91, 92, 92.5, 93, 93.5 or 94% by weight to an upper limit of 90, 91, 92, 92.5, 93, 93.5, 94, 94.5, 95, 95.5, 96, 97, 99 or 99.9% by weight). This document covers the range of any of the aforementioned lower limits to any of the aforementioned upper limits (e.g., about 88 to about 93% by weight, or about 91 to about 93% by weight of ethylene-derived units and the balance being olefin comonomer-derived content).

[0130] Polyethylene copolymers may also have a high load melt index (HLMI) (also known as I) in the range of lower limits of about 30, 35, 40, 45, 50 or 55 g / 10 min to about 275, 270, 260, 250, 240, 230, 220, 210, 200, 190, 180, 170, 160, 150, 140, 130, 120, 110, 100, 90, 80, 70 or g / 10 min. 21 or I 21.6(based on the 21.6 kg load used in the test); this document covers any range from the aforementioned lower limit to any of the aforementioned upper limit (e.g., about 90 to about 275 g / 10 min, for example about 110 to about 140 g / 10 min, alternatively about 270 to about 275 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 the inverse measure of viscosity. As provided herein, HLMI (I 21 It is determined according to ASTM D1238 (190 °C / 21.6 kg) and is sometimes referred to as I. 21 or I 21.6 .

[0131] The polyethylene copolymer may also have a melt index ratio (MIR, defined as I) within the range of a lower limit of about 20, 25, 30, 35, 40, 45, 50 or 55 and an upper limit of about 150, 140, 130, 120, 110, 100, 90, 80, 70, 60, 50 or 40. 21.6 / I 2.16 The ratio), this document covers the range of any of the aforementioned lower limits to any of the aforementioned upper limits (e.g., about 40 to about 70, or alternatively about 140 to about 150).

[0132] The polyethylene copolymer may also have a molecular weight distribution (MWD) of about 2 to about 15, for example, about 9 to about 13. The MWD may also be a lower limit of about 2, 2.5, 3, 3.5, 4, 4.2, 4.4, 4.6, 4.8, 5, 5.1, 5.2, 5.3, 5.4, 5.5, or 6, and an upper limit 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, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, or 12, covering the range from any of the aforementioned lower limits to any of the aforementioned upper limits, provided that the upper limit of the range is greater than the lower limit. The MWD is defined as the weight-average molecular weight (Mw) divided by the number-average molecular weight (Mn).

[0133] The weight-average molecular weight (Mw) of the polyethylene copolymers in various embodiments can be in the range of about 70,000 to about 300,000 g / mol, for example about 75,000 to about 150,000 g / mol, for example about 90,000 to about 130,000 g / mol, and optionally about 200,000 to about 250,000 g / mol, covering any of the aforementioned lower limits to any of the aforementioned upper limits.

[0134] 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, for example about 10,000 to about 30,000 g / mol, for example about 12,000 to about 15,000 g / mol, optionally about 10,000 to about 12,000 g / mol, covering any of the aforementioned lower limits to any of the aforementioned upper limits.

[0135] The Z-average molecular weight (Mz) of the polyethylene copolymers in various embodiments can range from about 400,000 to about 950,000 g / mol, for example from about 400,000 to about 650,000 g / mol, or from about 775,000 to about 930,000 g / mol, or from about 400,000 to about 550,000 g / mol, covering any of the aforementioned lower limits to any of the aforementioned upper limits.

[0136] Polyethylene copolymers in 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 This can be confirmed using ) and / or MIR. SAOS viscosity data for polyethylene copolymers of various embodiments can be found in the range of 10-60, for example 10-20, 20-30, or 40-55 η. 0.01 / η 100 Within the range. Furthermore, the LCB, or branching index (referred to as g' in this paper), vis Or the alternative g' vis ave The value can be less than 1, for example, in the range of about 0.6 to about 0.99, about 0.7 to about 0.8, for example, about 0.71 to about 0.73, and optionally in the range of about 0.6 to about 0.7, covering the range from any of the aforementioned lower limits to any of the aforementioned upper limits. Furthermore, polyethylene copolymers (even LLDPEs) with some LCB will show an inflection point in their VanGurp Palmen curves, while LLDPEs without any LCB will not show such an inflection point.

[0137] The polyethylene copolymers of various embodiments can also exhibit lower phase angles at 10 kPa. Phase angle data measures the viscous and elastic properties of the material. The phase angle data of the polyethylene copolymers of various embodiments at 10 kPa can range from about 40 to about 55 degrees.

[0138] The polyethylene copolymers of various embodiments may also exhibit a high shear thinning index (STI 0.1 / 100). The STI 0.1 / 100 data measures the ratio of complex viscosity at 0.1 to 100 rad / s. The STI 0.1 / 100 data for the polyethylene copolymers of various embodiments can range from about 10 to about 55 rad / s.

[0139] Rheological data, such as "complex shear viscosity (η*)", reported in Pa·s, can be measured at 0.01 rad / sec and 100 rad / sec. Complex shear viscosity and other rheological measurements can be obtained by small-angle oscillating shear (SAOS) experiments.

[0140] For example, complex shear viscosity can be measured in dynamic mode under a nitrogen atmosphere using a rotational rheometer such as the Advanced Rheometrics Expansion System (ARES-G2) or the Discovery Hybrid Rheometer (DHR-3) with parallel plates (diameter = 25 mm). The rheometer can be thermally stabilized at 190 °C for at least 20 minutes, after which the compressed specimen is inserted onto the parallel plates. To determine the viscoelastic behavior of the specimen, frequency sweeps ranging from 0.01 to 628 rad / s can be performed at a constant strain without affecting the measured viscoelastic properties at 190 °C. The sweep frequencies are equidistantly distributed on a logarithmic scale so that 5 frequencies are probed every decade. Depending on the molecular weight and temperature, 3% strain can be used, and the linearity of the response has been verified. During the experiment, the nitrogen feed stream is circulated through the oven to minimize chain elongation or crosslinking. The specimen can be compressed at 190 °C without a stabilizer. Sinusoidal shear strain can be applied. The shear-thinning slope (STS) can be measured using a plot of the logarithm (base 10) of dynamic viscosity against the logarithm (base 10) of frequency. The slope is 100 s². -1 The log(dynamic viscosity) at the frequency and 0.01 s -1 The difference in log(dynamic viscosity) at each frequency is divided by 4. The complex shear viscosity (η*) versus frequency (ω) curve can be fitted using the Carreau-Yasuda model:

[0141]

[0142] The five parameters in this model are: zero shear viscosity Relaxation time λ; power-law exponent n; infinite-rate viscosity The zero-shear viscosity is the value at the plateau in the Newtonian region of the flow curve at low frequencies, where the dynamic viscosity is independent of frequency. The relaxation time corresponds to the reciprocal of the frequency at which shear thinning begins. The power-law exponent describes the degree of shear thinning; on the log(η*)-log(ω) plot, the slope of the flow curve at high frequencies is approximately n-1. For Newtonian fluids, n=1 and the dynamic complex viscosity is independent of frequency.

[0143] In addition to dynamic and complex viscosity (each in Pa·s), various other parameters were collected at different frequency scans in the SAOS experiment, including storage modulus (Pa), loss modulus (Pa), complex modulus (Pa), tan(δ), and phase angle. The phase angle versus complex shear modulus plot generated by rheological experiments produces a Van Gurp Palmen plot, which can be used to extract some information about molecular characteristics, such as linear versus long-chain branching, the type of long-chain branching, and polydispersity (Dealy, MJ, Larson, RG, “Structure and Rheology of Molten Polymers”, Carl HanserVerlag, Munich 182-183 (2006)). It has been proposed that the Van Gurp Palmen plot can be used to indicate the presence of long-chain branching in polymers. See Trinkle, S., Walter, P., Friedrich, C. “Van Gurp-Palmenplot II—Classification of long chain branched polymers by their topology,” 41Rheol. Acta 103-113 (2002).

[0144] The "shear thinning ratio," reported as a unitless value, is characterized as the decrease in complex viscosity with increasing shear rate. In this paper, shear thinning can be defined as the ratio of the complex viscosity at a frequency of 0.01 rad / s to that at a frequency of 100 rad / s.

[0145] 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 with a multi-channel bandpass filter, an 18-angle Wyatt Dawn Heleos light scattering detector, and a 4-capillary viscometer configured with a Wheatstone bridge. Polymer separation was provided using three Agilent PLgel 10-µm Mixed-B LS columns. Aldrich reagent-grade 1,2,4-trichlorobenzene (TCB) containing 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 using an in-line 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 transfer lines, columns, and viscometer detector, was contained in an oven maintained at 145 °C. The polymer sample was weighed and sealed in a standard vial containing 80 μL of a flow marker (heptane). After the vial was loaded into the autosampler, the polymer was automatically dissolved in the instrument containing 8 mL of added TCB solvent. The polymer was dissolved at 160 °C with continuous shaking for approximately 2 hours. The concentration (c) at each point in the chromatogram was calculated by subtracting the baseline IR5 broadband signal intensity (I) using the following equation: c = βI, where β is the mass constant. The mass recovery was calculated by the ratio of the integral area of ​​the concentration chromatogram within the elution volume to the injection mass (which is equal to the predetermined concentration multiplied by the injection loop volume). The conventional molecular weight (IR MW) was determined by combining a universal calibration relationship with column calibration (using a range of monodisperse polystyrene (PS) standards ranging from 700 to 10,000,000 g / mol). The MW at each elution volume was calculated using the following equation:

[0146]

[0147] Variables with the subscript "PS" represent polystyrene, while those 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 corresponding to the IR5 detector intensity of the CH2 and CH3 channels calibrated using a series of PE and ethylene-hexene homopolymer / copolymer standards (whose nominal values ​​are predetermined by NMR or FTIR). Here, concentrations are expressed in g / cm³. 3 The molecular weight is expressed in g / mol, and the intrinsic viscosity (and therefore K in the Mark-Houwink equation) is expressed in dL / g.

[0148] The LS molecular weight (M) at each point in the chromatogram was determined by analyzing the LS output using the Zimm model for static light scattering.

[0149] .

[0150] 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 K o These are the optical constants of the system:

[0151]

[0152] Where N A is Avogadro's constant, and (dn / dc) is the refractive index increment of the system. The refractive index of TCB at 145 °C and λ = 665 nm is n = 1.500. For the purposes of this disclosure and its claims, (dn / dc) = 0.1048 for ethylene-hexene copolymers. Unless otherwise stated, the MW values ​​reported herein should be considered as determined using the LS methodology.

[0153] Viscosity-average molecular weight (M) V The intrinsic viscosity is determined using a high-temperature Polymer Char viscometer, which has four capillaries arranged in a Wheatstone bridge configuration and two pressure sensors. One sensor measures the total pressure drop across the detector, and the other, located between the two sides of the bridge, measures the pressure difference. The specific viscosity η of the solution flowing through the viscometer is calculated from their outputs. S The intrinsic viscosity [η] at each point in the chromatogram is 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 is calculated according to... Calculate, where α psIt is 0.67 and K ps It is 0.000175. The average intrinsic viscosity of the sample [η] avg Calculated using the following formula:

[0154]

[0155] The sum is taken from all chromatographic slices i between the integration limits.

[0156] Branching index (g') vis The output of the GPC-IR5-LS-VIS method can be used to calculate as follows. First, g' or g' should be specified. 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 composition and molecular weight. Therefore, the relative intrinsic viscosity (g') of a polymer is a measure of the degree to which it 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.

[0157] According to this principle, in the simplified relation above, [η] 聚合物 The value [η] can be considered as the weight-average intrinsic viscosity of the sample. avg It is calculated using the following formula:

[0158]

[0159] The sum is taken from all chromatographic slices i between the integration limits. Branching index g' vis Relative linear reference is defined as M V It is based on the viscosity-average 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.

[0160] Branching index g' vis It can be called g' vis ave This reflects the average value of g' measured at each of multiple discrete concentration slices. For example, g' for individual polyethylene copolymers can be plotted as a function of molecular weight (or the logarithm of molecular weight, as is commonly done in GPC plots), meaning that the g' value for a given molecular weight group of polymer chains in a polyethylene copolymer composition can be calculated. The calculation above provides g'. vis aveAs the weight average of these multiple g' values, and when comparing the g' values ​​of two different copolymer compositions vis ave When the value is g' vis ave This can be seen as a good relative indicator of the existence of long-chain branching, with a lower g' vis ave It indicates a higher degree of long-chain branching.

[0161] Composition and distribution

[0162] "BOCD" refers to a broad orthogonal compositional distribution, in which the comonomers of a copolymer are predominantly incorporated into the high molecular weight chains or substances of the polyolefin or composition. Conversely, a more uniform comonomer or compositional distribution is observed when polymer chains of different lengths have similar amounts of comonomer (short chain) incorporation. The distribution of short chain branches can be measured, for example, using a temperature-elution fractionation (TREF) coupled 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 (or similarly, narrowness) of the compositional distribution and whether the comonomer content increases, decreases, or is moderately or highly uniform across different molecular weight chains of the polymer. BOCD and other compositional distribution concepts have been described, for example, in U.S. Patent Nos. 8,378,043, column 3, line 34, spanning column 4, line 19, and 8,476,392, line 43, spanning column 16, line 54.

[0163] The polyethylene copolymers of the present invention have a comonomer distribution that reflects a similar degree of comonomer incorporation across polymer chains of different lengths, quantified as a compositional distribution width index (CDBI). For example, the polyethylene copolymer can have a high compositional distribution width index (CBDI), wherein the polyethylene copolymer can have a CBDI of about 50%, 55%, 60%, 65%, or 70% to about 75%, 80%, or 85%, with the range (e.g., 50% to 80%, or 70% to 75% or 80%) covered herein, encompassing any of the aforementioned lower limits to any of the aforementioned upper limits. CDBI is defined as the weight percentage of copolymer molecules having a comonomer content within 50% of the median total molar comonomer content (i.e., within + / - 25% of the median), and is mentioned, for example, in U.S. Patent 5,382,630. Generally, copolymers with a wider distribution produce a lower CDBI, while a theoretical copolymer with exactly the same relative comonomer content across all polymer chains of different lengths would have a 100% CDBI. The CDBI of the copolymer is readily determined using techniques for separating individual fractions of a sample of the copolymer. One such technique involves using heated rinsing fractionation (TREF) to generate solubility distribution profiles, as described in WO 1993003093 (which in this regard cites Wild et al., J. Poly. Sci., Poly. Phys. Ed., Vol. 20, p. 441 (1982) and U.S. Patent No. 5,008,204). All three of the foregoing disclosures are incorporated herein by reference.

[0164] Blends and Additives

[0165] In some embodiments, the polyethylene copolymer may be formulated (e.g., blended) with one or more other polymer components. In some embodiments, these other polymer components are α-olefin polymers such as polypropylene or polyethylene homopolymers and copolymer compositions. In some embodiments, these other polyethylene polymers are selected from linear low-density polyethylene, high-density polyethylene, medium-density polyethylene, low-density polyethylene, and other differentiated polyethylenes.

[0166] In some embodiments, the formulated blends may contain additives, the composition of which is determined based on the end use of the formulated blend. In some embodiments, the additives are selected from fillers, antioxidants, phosphites / salts, anti-cling additives, tackifiers, UV stabilizers, heat stabilizers, antiblocking agents, mold 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 amounts from 0.1 ppm to 5.0% by weight.

[0167] 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, advantageously, such processing aids can be omitted even in blown films (for example, some embodiments of films, particularly blown films, may be free of or substantially free of polymer processing aids, particularly fluorinated polymer processing aids; wherein “substantially free” means free of any intentionally added components, but allows up to 100 ppm of such components (one or more) as impurities).

[0168] Manufactured products

[0169] The polyethylene copolymers disclosed herein are particularly suitable for making end-use manufactured articles, such as films (e.g., which can be formed by lamination, extrusion, co-extrusion, casting, and / or blow molding); and other manufactured articles that can be formed, for example, by rotational molding or injection molding. The polyethylene copolymers can be used to form manufactured articles by cast film extrusion, blown film extrusion, rotational molding, or injection molding methods. In some embodiments, the polyethylene copolymers can be used in blends.

[0170] Furthermore, it has been found that the polyethylene copolymers of this disclosure can provide stronger shear thinning and better extrusion processability than comparative PEs derived from both gas-phase and high-pressure methods, overcoming key drawbacks of LDPE and LLDPE. For example, compared to conventional LLDPE, the polyethylene copolymers of this disclosure can provide films formed with reduced motor load and melt pressure (which increases production output) due to improved flow behavior. For example, reduced melt pressure and lower melt temperature can be provided during film manufacturing. Films of the polyethylene copolymers of this invention formed using low-pressure methods can provide better tear properties and dart impact strength (compared to LDPE), as well as improved processability, much better drawdown characteristics, and reduced overall energy consumption costs (compared to LLDPE).

[0171] The polyethylene copolymers (or blends thereof) disclosed herein can be used in molding operations such as film, sheet, and fiber extrusion and co-extrusion, as well as blow molding, injection molding, and rotational molding. Films include blown or cast films formed by co-extrusion or lamination, which can be used as shrink films, cling films, stretch films, sealing films, oriented films, snack packaging, heavy-duty bags, grocery bags, baked and frozen food packaging, pharmaceutical packaging, industrial linings, membranes, etc., in both food contact and non-food contact applications. For example, the polyethylene copolymers of this disclosure offer improved shrink wrapping capabilities due to their broad orthogonal compositional distribution and long-chain branching properties. Fibers include melt spinning, solution spinning, and meltblown fiber operations for use in woven or nonwoven forms to produce filter materials, diaper fabrics, medical clothing, geotextiles, etc. Extruded articles include medical tubing, wire and cable coatings, pipes, geomembranes, and pond liners. Molded articles include single-layer and multi-layer structures in the form of bottles, cans, large hollow articles, rigid food containers, and toys.

[0172] 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 using a flat-die or tubular method, and then oriented in a uniaxial direction or two mutually perpendicular directions in the plane of the film. One or more 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 the individual layers are combined. For example, a layer of polyethylene copolymer (or blend thereof) can be extruded, coated, or laminated onto an oriented polypropylene layer, or polyethylene copolymer (or blend thereof) and polypropylene can be co-extruded together into a film and then oriented. Similarly, oriented polypropylene can be laminated onto an oriented polyethylene copolymer (or blend thereof), or an oriented polyethylene copolymer (or blend thereof) can be coated onto polypropylene, and then optionally the combination can be further oriented.

[0173] 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 self-adhesive films, stretch hand-wound films, machine stretch-wound films, shrink films, shrink wrap films, canopy films, laminates, and laminated films. Exemplary films are prepared using any conventional techniques known to those skilled in the art, such as techniques used to prepare blown, extruded, and / or cast stretch and / or shrink films (including shrink-on-shrink applications).

[0174] In at least one embodiment, the multilayer film can be formed by any suitable method. The total thickness of the multilayer film can be varied based on the desired application. For most applications, a total film thickness of 5-100 μm, such as 10-50 μm, is suitable. Those skilled in the art will understand that the thickness of the individual layers of the multilayer film can be adjusted based on the desired end-use performance, the polymer(s) used, equipment capabilities, and other factors. The materials forming the layers can be co-extruded using a co-extrusion feed block and die assembly to obtain a film having two or more layers bonded together but with different compositions. Co-extrusion can be adapted for use in 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.

[0175] In at least one embodiment, the membrane of this disclosure has an average 1% secant modulus (M) of about 30,000 psi to about 40,000 psi, for example about 31,000 psi to about 40,000 psi, for example about 33,000 psi to about 38,000 psi, for example about 34,000 psi to about 36,000 psi at 23°C according to ASTM D882-18.

[0176] The membranes disclosed herein may have an Elmendorf tear value according to ASTM D-1922. In at least one embodiment, the membrane has an Elmendorf tear (MD) of at least 30 g / mil, for example at least 50 g / mil to about 200 g / mil, for example about 60 g / mil to about 100 g / mil, for example about 100 g / mil to about 180 g / mil. In at least another embodiment, the membrane has an Elmendorf tear (TD) of at least 400 g / mil, for example at least 400 g / mil to about 500 g / mil, for example about 410 g / mil to about 460 g / mil, for example about 440 g / mil to about 470 g / mil.

[0177] The membranes of this disclosure may have a dart impact (or impact failure, dart F50, or dart impact strength (DIS)) reported in grams (g) or grams per mil (g / mil) according to ASTM D-1709 Method A. The 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, for example, at least about 120 g / mil, for example, at least about 130 g / mil. For example, the dart impact may be about 100 g / mil to about 200 g / mil, for example, about 120 g / mil to about 170 g / mil, for example, about 130 g / mil to about 160 g / mil.

[0178] In some embodiments, the membrane may have a rupture puncture energy (also referred to as puncture rupture energy) of at least about 25 in-lbs / mil, for example at least about 30 in-lbs / mil, for example at least about 35 in-lbs / mil, for example about 25 in-lbs / mil to about 40 in-lbs / mil, for example about 30 in-lbs / mil to about 40 in-lbs / mil, for example about 30 in-lbs / mil to about 35 in-lbs / mil, according to modified BSI CEN 14477.

[0179] In at least one embodiment, 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, as determined by ASTM D-1003.

[0180] In at least one embodiment, the membrane of this disclosure has a transparency of about 80% or higher, about 85% or higher, about 90% or higher, about 95% or higher, or about 97% or higher (defined as conventional transmitted light passing through the bulk of the membrane sample with a deflection of less than 0.1 from the axis of the incident light), as measured by ASTM D1746.

[0181] In at least one embodiment, the film of this disclosure has a gloss of about 30% or higher, about 35% or higher, about 40% or higher, about 45% or higher, or about 50% or higher, as determined by ASTM D-2457, wherein a light source is irradiated on the film surface at a 45° angle and the amount of reflected light is measured.

[0182] experiment

[0183] synthesis:

[0184] General considerations and reagents: Unless otherwise stated, all operations were performed using the glove box technique under an inert atmosphere. Toluene and pentane were purchased from Sigma Aldrich and degassed and dried overnight on 3 Å molecular sieves prior to use. 1 Methylaluminoxane was purchased from Grace and used as is.

[0185] Synthesis of Catalyst 1:

[0186] Synthesis of (benzo[e]indene)lithium:

[0187] A solution of 2.74 M butyllithium in hexane (25.0 mL, 68.5 mmol, 1.00 equivalent) was added to a colorless solution of benzo[e]indene (11.40 g, 68.5 mmol, 1.00 equivalent) in ether (100 mL) at -35 °C to give an amber-yellow solution. The solution was stirred for 30 min and then evaporated under vacuum, leaving a light Manila-colored solid. The solid was washed with pentane (40 mL) and dried under vacuum. The yield was 11.72 g (99%) of white powder. 1 H NMR (THF-d8)δ8.05 (dm, 1H), 7.50 (dm, 1H), 7.46 (dd, 1H), 7.10 (m, 1H), 6.92 (m, 1H), 6.79 (d, 1H), 6.61 (m, 1H), 6.47 (t, 1H), 6.11 (m, 1H).

[0188] Synthesis of dimethyl (tetramethylcyclopentadienyl)silyl trifluoromethanesulfonate:

[0189] Silver trifluoromethanesulfonate (38.00 g, 140 mmol, 1.00 equivalent) was added fractionally to a pale amber solution of dimethylchloro(tetramethylcyclopentadienyl)silane (30.00 g, 140 mmol, 1.00 equivalent) in toluene (100 mL) to give a turbid, grayish-pink mixture. The reaction was heated and turned grayish-purple. The reaction was stirred for 4 hours and then evaporated under vacuum, leaving a dark, sopy mixture. The mixture was extracted with pentane (100 mL, then 3 x 20 mL) and the extract was filtered to give a pale yellow solution and a dark solid. The solution was evaporated under vacuum, leaving a pale amber liquid. The yield was 44.93 g (98%). 1 H NMR (C6D6) δ2.76 (br s 1H), 1.74 (s, 6H), 1.60 (d, 6H), -0.04 (s, 6H).

[0190] Synthesis of (3-benzo[e]indenyl)dimethyl(tetramethylcyclopentadienyl)silane:

[0191] A green solution of dimethyl(tetramethylcyclopentadienyl)silyl trifluoromethanesulfonate (20.00 g, 60.9 mmol, 1.00 equivalent) in ether (100 mL) at -35 °C was fractionally added with lithium benzo[e]indene (11.10 g, 64.5 mmol, 1.06 equivalent) to give a turbid amber-orange mixture. The mixture was stirred for 18 hours and then evaporated under vacuum, leaving an orange solid. The solid was extracted with pentane (200 mL, then 3 x 20 mL) and the extract was filtered to give an amber-orange solution and a pink solid. The solution was evaporated under vacuum to give a thick amber-orange oil. The yield was 21.29 g (101%). 1 H NMR (C6D6) δ8.15 (dt, 1H), 7.83 (dt, 1H), 7.59 (q, 2H), 7.49 (dt,1H), 7.31-7.41 (m, 2H), 6.68 (dd, 1H), 3.82 (br s, 1H), 2.91 (br s, 1H), 1.92 (s, 6H), 1.82 (s, 6H), -0.14 (s, 6H).

[0192] Synthesis of [tetramethylcyclopentadiene dimethylsilyl(3-benzo[e]indene)](ether)dilithium:

[0193] 2.74 M butyllithium (46.5 mL, 127 mmol, 2.06 equivalents) was added to an amber-orange solution of (3-benzo[e]indenyl)dimethyl(tetramethylcyclopentadienyl)silane (21.29 g, 61.8 mmol, 1.00 equivalents) in ether (100 mL) at -35 °C to give a warm, turbid mixture that rapidly turned turbid light brown. The reaction was stirred for 17 hours, and then pentane (100 mL) was added. The mixture was filtered to give a light brown solid and a dark solution. The solid was washed with pentane (40 mL) and dried under vacuum. The yield was 25.54 g (96%). 1 H NMR (THF-d8) δ8.02 (d, 1H),7.75 (d, 1H), 7.48 (d, 1H), 7.08 (t, 1H), 6.92 (t, 1H), 6.79 (d, 1H), 6.70(t, 2H), 3.39 (q, 4H), 2.12 (s, 6H), 1.12 (t, 6H), 0.62 (s, 6H).

[0194]

[0195] Synthesis of [tetramethylcyclopentadienyldimethylsilyl(3-benzo[e]indenyl)]zirconium dichloride:

[0196] A suspension of zirconium tetrachloride bis(ether) compound (6.00 g, 15.74 mmol, 1.00 equivalent) in ether (100 mL) under vigorous stirring at -35 °C was partially supplemented with [tetramethylcyclopentadiene dimethylsilyl(3-benzo[e]indene)](ether)dilithium (6.78 g, 15.75 mmol, 1.00 equivalent) to give a turbid Manila-colored mixture that quickly turned yellow. The mixture was stirred for 21 hours and then evaporated under vacuum, leaving a yellow solid. The solid was extracted with dichloromethane (5 x 200 mL) and the mixture was filtered to give a yellow solution and a brown solid. The solution was evaporated under vacuum to give a yellow solid. The solid was washed with pentane (20 mL) and dried under vacuum. The yield was 7.28 g (92%). 1 H NMR(CD2Cl2) δ8.17 (dt, 1H), 7.79 (dd, 1H), 7.69 (dd, 1H), 7.62 (td, 1H), 7.54(td, 1H), 7.4 (m, 2H), 6.05 (d, 1H), 2.00 (s, 3H), 1.94 (s, 3H), 1.93 (s, 3H), 1.85 (s, 3H), 1.19 (s, 3H), 0.99 (s, 3H).

[0197] Compare the synthesis of catalyst (catalyst 2):

[0198] Synthesis of (1-phenylindenyl)lithium:

[0199] A solution of 2.63 M butyllithium in hexane (50.0 mL, 132 mmol, 1.00 equivalent) was added to a pale yellow solution of 1-phenylindene (25.25 g, 131 mmol, 1.00 equivalent) in pentane (150 mL) to give a turbid yellow solution. The mixture turned turbid and pale yellow with a precipitate after stirring for 2 hours. The reaction was stirred for 42 hours and then filtered to give a pale yellow solid and a yellow solution. The solid was washed with pentane (2 x 40 mL) and dried under vacuum. The yield was 24.07 g (92%) of pale yellow powder. 1H NMR (THF-d8) δ7.72 (d, 1H), 7.55 (d, 2H), 7.19 (d, 1H),7.01 (m, 2H), 6.85 (d, 1H), 6.51 (t, 1H), 6.46 (t, 1H), 6.36 (t, 1H), 5.93(d,1H).

[0200] Synthesis of dimethyl(3-phenylindenyl)(tetramethylcyclopentadienyl)silane:

[0201] A yellow-green solution of dimethylchloro(tetramethylcyclopentadienyl)silane (5.00 g, 23.3 mmol, 1.00 equivalent) in ether (25 mL) at -35 °C was supplemented with lithium (1-phenylindenyl)silane (4.85 g, 24.5 mmol, 1.05 equivalent) to give a yellow solution. The reaction rapidly turned into a turbid bluish-white solution. The mixture was warmed to room temperature and stirred for 23 hours. The reaction was then evaporated under vacuum, leaving a viscous residue. The residue was extracted with pentane (40 mL) and filtered to give an amber solution and a bluish-white solid. The solution was evaporated under vacuum to give a viscous amber oil. The yield was 7.07 g (82%). 1 HNMR (C6D6) δ7.73 (d, 1H), 7.64 (d, 2H), 7.48 (d, 1H), 7.31-7.19 (m, 5H), 6.59(s, 1H), 3.69 (d, 1H), 2.92 (br s, 1H), 1.93 (s, 3H), 1.90 (s, 3H), 1.82 (s, 3H), 1.81 (s, 3H), -0.09 (s, 3H), -0.39 (s, 3H).

[0202] Synthesis of [tetramethylcyclopentadiene dimethylsilyl(3-phenylindene)](ether)dilithium:

[0203] A solution of 2.63 M butyllithium in hexane (14.8 mL, 38.9 mmol, 2.05 equivalents) was added to a yellow solution of dimethyl(3-phenylindenyl)(tetramethylcyclopentadienyl)silane (7.03 g, 19.0 mmol, 1.00 equivalents) in ether (25 mL) at -35 °C to give a warm, yellow solution that rapidly turned turbid yellow with a precipitate. The mixture was warmed to room temperature and stirred for 20 hours. The reaction was filtered to give a yellow solid and a yellow solution. The solid was washed with pentane (2 x 40 mL) and dried under vacuum. The yield was 8.51 g (97%) of yellow powder. 1H NMR (THF-d8) δ7.70 (d, 1H), 7.53 (m, 3H), 7.12 (s, 1H), 7.03 (t, 2H), 6.57 (t, 1H), 6.48(t, 1H), 6.41 (t, 1H), 3.39 (q, 4.36H), 2.20, (s, 6H), 1.91 (s, 6H), 1.13 (t, 6.51H), 0.64 (br s, 6H).

[0204] Synthesis of [tetramethylcyclopentadienyldimethylsilyl(3-phenylindenyl)]zirconium dichloride:

[0205] To a white suspension of zirconium tetrachloride bis(ether) compound (2.00 g, 5.25 mmol, 1.00 equivalent) in ether (35 mL) under vigorous stirring at -35 °C, 2.43 g, 5.24 mmol, 1.00 equivalent) of [tetramethylcyclopentadiene dimethylsilyl(3-phenylindene)](ether) dilithium (2.43 g, 5.24 mmol, 1.00 equivalent) was added to give a turbid Manila-colored yellow mixture. The reaction rapidly turned bright yellow and thickened with a precipitate. The mixture was stirred for 16 hours and then evaporated under vacuum, leaving a yellow solid. The solid was extracted with dichloromethane (50 mL, then 3 x 10 mL) and the extract was filtered to give a bright yellow solution and a yellowish-white solid. The solution was evaporated under vacuum, leaving an orange-yellow solid. The resulting solid was washed with pentane (2 x 20 mL) and dried under vacuum. The yield was 2.53 g (91%) of bright yellow powder. 1 H NMR (CD2Cl2) δ7.90 (d, 1H), 7.60 (m, 3H),7.49 (m, 2H), 7.42-7.36 (m, 2H), 7.10 (m, 1H), 6.00 (s,1H), 2.00 (s, 3H),1.96 (s, 3H), 1.92 (s, 3H), 1.89 (s, 3H), 1.23 (s, 3H), 1.00 (s, 3H).

[0206] Procedure for loading catalyst 1:

[0207] Add MAO (0.84 g, 30% by weight in toluene) to celestir with 50 ml of toluene. Stir the solution for two minutes. Dissolve the catalyst in 15 ml of toluene and slowly add it dropwise to the MAO solution. Stir the reaction mixture at room temperature for one hour. Then add ES70 875 silica (0.76 g) to the mixture and stir for another hour. Filter the solid support and wash with 50 ml of pentane. Then allow the supported catalyst to dry under vacuum for 3 hours to yield one gram of support.

[0208] polymerization:

[0209] Polymerization was carried out in a 7-foot-high gas-phase fluidized bed reactor with a 4-foot-high, 6''-diameter main body and a 3-foot-high, 10''-diameter extension section. Circulating and feed gases were fed into the reactor main body via perforated distributor plates, and the reactor was controlled at 300 psi and 70 mol% ethylene. The reactor temperature was maintained by heating the circulating gas. The supported catalyst was fed as a 10 wt% slurry from Sonneborn (Parsippany, NJ)'s Sono Jell®. Supported catalyst 1 (Examples 1-3) or catalyst 2 (Comparative Examples 1-2) was fed as a slurry into the reactor via nitrogen and isopentane feed through a 1 / 8" diameter catalyst probe. Polymer was collected from the reactor as needed to maintain the required bed weight. The average method conditions for polymer collection are shown in Table 1.

[0210] Table 1

[0211]

[0212] Production performance:

[0213] Resin, rheological, and processing properties are provided in Tables 2a and 2b. Molecular weight data were obtained from GPC-4D. The compositional distribution width index (CDBI), defined as the percentage of polymers whose composition comprises within 50% of the median comonomer composition, was obtained from a CryoTREFIR5 instrument. Rheological data were obtained from SAOS experiments, and the shear thinning index 0.1 / 100 was obtained from SAOS experiments, defined as the ratio of 0.1 to the complex viscosity at 100 rad / s. Comparative Example 3 is an Exceeding... TM 1018 (a metallocene-catalyzed LLDPE that is essentially LCB-free), which is available from ExxonMobil TM Product Solutions Company of Spring, TX. Comparative Example 4 is LDPE LD103.09, which is available from ExxonMobil. TMProduct Solutions Company of Spring, TX. Comparative Example 5 is LDPE LD105.30, which is available from ExxonMobil. TM Product Solutions Company of Spring, TX. Comparative Example 6 is LDPE LD 051, which is available from ExxonMobil. TM Product Solutions Company of Spring, TX. Each LDPE is a polyethylene homopolymer produced by high-pressure free radical polymerization, a method known for producing highly branched, nonlinear polymers.

[0214] Extrusion tests were also conducted on a small laboratory extruder with a 2'' screw and a 30 L / D ratio. Table 3 shows the methods used for analysis.

[0215] Table 2a

[0216]

[0217] Table 2b

[0218]

[0219]

[0220] Table 3

[0221]

[0222]

[0223] Table 4

[0224]

[0225]

[0226]

[0227] Membrane production

[0228] Evaluation of the blown films prepared and described above by the polymers was carried out on a 2'' extruder equipped with a 2'' spiral mandrel die, operating at a die production rate of 8 lbs / hr / die inch, using a melt temperature of 370°F–380°F and a BUR of 3.0. The properties of the 1.0 mil thick film are summarized in Table 4 above.

[0229] TDA is the total defect area. It is a measure of defects in a membrane sample and is expressed as the detected membrane area (in square meters (m²)). 2The cumulative area of ​​defects normalized to square millimeters (mm²) 2 The report is in units of mm, therefore it has (mm) 2 / m 2 The unit is either ppm or ppm. In Table 6, only defects with a size greater than 200 micrometers are reported.

[0230] TDA is obtained through an optical control system (OCS). This system consists of a small extruder (ME20 2800), a cast film die, a cold roll unit (CR-9 type), a winding system with good film tension control, and an in-line camera system (FSA-100 type) (used to detect optical defects in the produced cast film). Typical test conditions for the cast film are: extruder temperature settings (°C): feed throat / zone 1 / zone 2 / zone 3 / zone 4 / die: 70 / 190 / 200 / 210 / 215 / 215; extruder speed: 50 rpm; cold roll temperature: 30°C; cold roll speed: 3.5 m / min.

[0231] The system produces cast films approximately 4-5 inches wide and 1 mil in nominal thickness. The melt temperature varies depending on the material and can be approximately 215°C.

[0232] The polyethylene composition has a wide MIR (e.g., 46.6 to about 150); 0.64 to 0.73 g' vis ave This indicates significantly more long-chain branching in LLDPEs than in metallocene-catalyzed LLDPEs, although still less than in conventional LDPEs (which often have a g-value of ~0.36 to 0.49). ’vis ave Less branching; CDBI of 71 to 73.9, higher than Comparative Examples 1 and 2 (indicating a more uniform distribution of comonomers across polymer chains of varying lengths); and very strong shear-thinning characteristics compared to vapor-phase LLDPE Comparative Examples 1-3 and high-pressure LDPE Comparative Examples 4-6 (as shown by the relatively high STI of Examples 1-2). 0.1 / 100 (See values). Furthermore, Examples 1-3 exhibit better rheological characteristics (Van Gurp plots) than Comparative Examples 1-3 and High Pressure Comparative Examples 4-6, lower phase angles (at 10 kPa complex modulus), and significantly lower die pressures and motor loads compared to Comparative Examples mLLDPE 1 and 3, indicating significantly better processing.

[0233] The membrane exhibits good shrinkage values, as shown in Table 4 above.

[0234] Figure 1 This is a graph illustrating the TREFIR5 of the polyethylene copolymer synthesized by catalyst 1 compared to the polyethylene copolymer synthesized by the comparative catalyst.

[0235] Figure 2This is a graph illustrating the complex viscosity of the polyethylene copolymer synthesized with catalyst 1 compared to that synthesized with the comparative catalyst.

[0236] Figure 3 This is a graph illustrating the shear thinning index of the polyethylene copolymer synthesized with catalyst 1 compared to the polyethylene copolymer synthesized with the comparative catalyst.

[0237] Figure 4 This is a graph illustrating the phase angle versus complex modulus of the polyethylene copolymer synthesized by catalyst 1 compared to the polyethylene copolymer synthesized by the comparative catalyst.

[0238] Figure 5 This is a graph illustrating the phase angle (at 10 kPa) of the polyethylene copolymer synthesized by catalyst 1 compared to the polyethylene copolymer synthesized by the comparative catalyst.

[0239] In summary, the methods, catalysts, and membranes of this disclosure can provide polyethylene polymers with BOCD, which are formed in a low-pressure (gas-phase) reactor by a single-supported catalyst. The low pressure provides a reduced energy input to the reactor during the formation of the polyethylene polymer. Compared to conventional LDPE and / or LLDPE, the low-pressure single-catalyst method produces LCB, CDBI, strong shear thinning, and STI. 0.1 / 100 It features rheological characteristics, low phase angle, and very low die pressure and motor load.

[0240] Unless otherwise stated, the phrases “consistently composed of” and “consistently composed of” do not exclude the presence of other steps, elements or materials, whether or not they are expressly mentioned in this specification, provided that such steps, elements or materials do not affect the basis and novel features of this disclosure. In addition, they do not exclude impurities and differences that are generally associated with the elements and materials used.

[0241] For the sake of brevity, this document only explicitly discloses certain ranges. However, a range from any lower limit can be combined with any upper limit to describe a range not explicitly described, and a range from any lower limit can be combined with any other lower limit to describe a range not explicitly described, just as a range from any upper limit can be combined with any other upper limit to describe a range not explicitly described. Additionally, a range includes every point or individual value between its endpoints, even if not explicitly described. Thus, each point or individual value can serve as its own lower or upper limit, which can be combined with any other point or individual value or any other lower or upper limit to describe a range not explicitly described.

[0242] All documents described herein are incorporated herein by reference, including any priority documents and / or test procedures, provided they are not inconsistent with this text. As will be apparent from the foregoing general description and specific embodiments, various modifications may be made without departing from the spirit and scope of this disclosure, despite the fact that the form of this disclosure has been described and illustrated. Therefore, it is not intended to limit this disclosure. Similarly, the term “comprising” is considered synonymous with the term “including.” Likewise, whenever a composition, element, or group of elements is preceded by the transitional phrase “comprising,” it should be understood that we also consider the same composition or group of elements preceded by the transitional phrases “substantially constitutes,” “consisting of,” “selected from the group of,” or “is,” and vice versa.

[0243] Although this disclosure has been described with respect to several 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 catalyst compound, represented by formula (I): (I) in: M is Zr or Hf; R 5 and R 6 Each is hydrogen; R 1 R 2 R 3 and R 4 Each of the atoms in the series is independently hydrogen or a substituted or unsubstituted C1 to C2. 10 Alkyl; (1)R 7 and R 8 (2)R 8 and R 9 Or (3)R 9 and R 10 A pair of bonds in the mixture fused to the substituted or unsubstituted aromatic ring or saturated ring of the indenyl ring shown in formula (I), and the remaining R 7 R 8 R 9 and R 10 Each is hydrogen; T is derived from formula R a 2J、(R a )4J2 or (R a )6J3 indicates that each J is independently carbon, silicon, or germanium, and each R a Independently hydrogen, halogen, substituted or unsubstituted C1 to C2 40 Hydrocarbon group, in which two R a Optionally, substituted or unsubstituted fully saturated rings, substituted or unsubstituted partially saturated rings, or substituted or unsubstituted aromatic rings may be formed; and 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 X are joined together to form a substituted or unsubstituted metal ring, or two X are joined together to form a chelate ligand, a diene ligand, or an alkylidene group.

2. The catalyst compound according to claim 1, wherein M is Zr or Hf; X is a C1-C4 alkyl group; and T is SiMe2, SiEt2, or SiMeEt.

3. The catalyst compound according to claim 2, wherein: (i) R 9 and R 8 The substituted or unsubstituted cyclopentyl rings are joined to form fused to the indenyl ring of formula (I); (ii) R 7 and R 10 Each is hydrogen; and (iii) R 1 R 2 R 3 and R 4 Each is independently a C1-C4 alkyl group.

4. The catalyst compound according to claim 2, wherein the catalyst compound is: 。 5. The catalyst compound according to claim 1, wherein the catalyst compound is represented by formula (II): (II) in: In formula (II), M represents zirconium; R 5 -R 14 Each is hydrogen; R 1 R 2 R 3 and R 4 Each of the atoms in the series is independently hydrogen or a substituted or unsubstituted C1 to C2. 10 Alkyl; T of formula (II) is derived from formula R a 2J、(R a )4J2 or (R a )6J3 indicates that each J is independently C, Si, or Ge, and each R a Independently hydrogen, halogen, substituted or unsubstituted C1 to C2 40 Hydrocarbon group, or two Rs a It can form substituted or unsubstituted cyclic structures, including substituted or unsubstituted fully saturated rings, substituted or unsubstituted partially saturated rings, or substituted or unsubstituted aromatic rings; and each X in formula (II) is independently a halogroup, a substituted or unsubstituted hydrocarbon group, a hydrogen group, an amino group, a substituted or unsubstituted alkoxy group, a thio group, a phosphorus group, or a combination thereof, or two X groups are joined together to form a substituted or unsubstituted metal ring, or two X groups are joined together to form a chelate ligand, a diene ligand, or an alkylidene group.

6. The catalyst according to claim 5, wherein X is a halogen group; T is SiMe2, SiEt2, or SiMeEt; and R 1 R 2 R 3 and R 4 Each of them is a C1 to C4 alkyl group.

7. The catalyst compound according to claim 6, wherein the catalyst compound is represented by the following structure: 。 8. A method for producing a polyethylene composition, comprising: Ethylene and C3-C are introduced into the reactor under the first polymerization conditions. 40 α-olefins and catalyst systems form polyethylene copolymers, which have ethylene monomer-derived content and C3-C... 40 The α-olefin comonomer content, wherein the catalyst system comprises: Catalyst compounds, wherein the catalyst compound is represented by formula (I): (I) in: M is a Group 4 metal; R 6 It is hydrogen; 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 are joined to form a substituted or unsubstituted fully saturated ring or a substituted or unsubstituted aromatic ring, 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 them are joined to form a fused to the substituted or unsubstituted aromatic ring of the indenyl ring shown in formula (I); T is derived from formula R a 2J、(R a )4J2 or (R a )6J3 indicates that each J is independently carbon, silicon, or germanium, and each R a Independently hydrogen, halogen, substituted or unsubstituted C1 to C2 40 Hydrocarbon group, or two Rs a It can form substituted or unsubstituted fully saturated rings, substituted or unsubstituted partially saturated rings, or substituted or unsubstituted aromatic rings; and 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 X are joined together to form a substituted or unsubstituted metal ring, or two X are joined together to form a chelate ligand, a diene ligand, or an alkylidene group.

9. The method according to claim 8, wherein in the catalyst compound, (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 fused to the substituted or unsubstituted aromatic ring or saturated ring of the indenyl ring shown in formula (I).

10. The method according to claim 8 or claim 9, wherein in the catalyst compound: T is selected from SiMe2, SiEt2, and SiMeEt; R in equation (I) 1 R 2 R 3 and R 4 Each of them is a methyl group; M is zirconium; and Each X is independently a methyl or halo group.

11. The method according to claim 10, wherein the catalyst compound is represented by the structure (Ia) or (Ic), or by an analogue of which ZrMe2 replaces ZrCl2: 。 12. The method according to claim 8 or any one of claims 9 to 11, wherein the polymerization conditions include: Reactor pressure from approximately 250 psig to approximately 350 psig; Reactor temperature from approximately 60°C to approximately 110°C; and Optionally, an H2 / C2 ratio greater than 10.

13. The method according to claim 8 or any one of claims 9 to 12, wherein the polyethylene copolymer has an olefin comonomer derivatization content of about 7% to about 12% by weight, based on the total mass of the olefin comonomer derivatization content and the ethylene monomer derivatization content, and further has one or more of the following properties: (a) Approximately 0.914 g / cm³ 3 Approximately 0.926 g / cm³ 3 density, (b) Melt index from about 0.10 g / 10 min to about 6 g / min; (c) High load melt index (HLMI) of approximately 120 g / 10 min to approximately 275 g / 10 min; (d) Melt index ratio (MIR) of approximately 60 to approximately 150; and (e) Molecular weight distribution from about 9 to about 15 (MWD, Mw / Mn).

14. The method according to claim 13, wherein the polyethylene copolymer has all of the properties (a)-(e).

15. The method of claim 13 or claim 14, wherein the polyethylene copolymer further has a composition width index (CDBI) of about 70% to about 80%.

16. The method according to claim 8 or any one of claims 9 to 15, wherein the polyethylene copolymer is characterized by having long-chain branching (LCB).

17. The method of claim 16, wherein the LCB of the polyethylene copolymer is characterized by one or more of the following: (a) g'vis values ​​of polyethylene copolymers from about 0.6 to about 0.8; (b) A phase angle of approximately 40 to approximately 55 degrees at 10 kPa in the molecular weight range of approximately 100,000 to approximately 250,000 Daltons; or (c) Zero-shear rate viscosity of about 100,000 to about 1,000,000 Pa in the molecular weight range of about 100,000 to about 250,000 Daltons, and shear thinning index STI of about 10 to about 60 (0.1 / 100).

18. A membrane comprising a polyethylene copolymer, said polyethylene copolymer comprising: 90% by weight or higher ethylene units; and Balance C3-C 20 Comonomer unit; The polyethylene copolymer has the following characteristics: Approximately 70% to 80% of CDBI, Approximately 0.914 g / cm³ 3 Approximately 0.926 g / cm³ 3 density, The melt index ranges from approximately 0.10 g / 10 min to approximately 6 g / 10 min. The content of olefin comonomers is from about 7% by weight to about 12% by weight. High load melt index (HLMI) of approximately 120 g / 10 min to approximately 275 g / 10 min, Melt index ratio (MIR) of approximately 60 to approximately 150, and Molecular weight distribution (MWD) of approximately 9 to approximately 13.

19. The membrane according to claim 18, wherein the polyethylene copolymer has one or more of the following: (i) g'vis values ​​of approximately 0.6 to approximately 0.8; (ii) A phase angle of approximately 40 to approximately 55 degrees at 10 kPa in the molecular weight range of approximately 100,000 to approximately 250,000 Daltons; or (iii) Zero shear rate viscosity of about 100,000 to about 1,000,000 Pa in the molecular weight range of about 100,000 to about 250,000 Daltons, and shear thinning index STI of about 10 to about 60 (0.1 / 100).

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