Polyethylene, catalysts for their polymerization and membranes thereof

Abstract

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

Description

[0001] Cross-references to related applications

[0002] This application claims the benefit of U.S. Provisional Application 63 / 503893, filed May 23, 2023, entitled "Polyethylene, Catalysts for Polymerization Thereof and Membranes 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] Low-density polyethylene (LDPE) is typically synthesized using high-pressure free radical polymerization to produce polyethylene compositions with good processability and other desired properties, primarily due to its extensively branched long-chain LCB structure. Other desirable properties of LDPE formed under high pressure include high melt strength, high shrinkage, and good optical properties. However, high-pressure formed LDPE generally suffers from poor mechanical properties, such as low TD tear and dart impact strength. Furthermore, high-pressure methods involve 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. Typical comonomer units used are derived from 1-butene, 1-hexene, or 1-octene. LLDPE can be distinguished from conventional LDPE in several ways, including different manufacturing methods and different rheological and mechanical properties, such as tear properties.

[0006] LLDPE formed using metallocene catalysts is called "mLLDPE". Extrusion of mLLDPE requires more motor power and higher extruder pressure to match the extrusion rate of LDPE. In practice, commercial mLLDPE exhibits flow challenges in the dies and extruders used in cast film production lines, resulting in high melt pressures, high motor loads, and suboptimal flow to the edges of the die, which can lead to encapsulation of adjacent resin layers. Regardless of these processing and rheological challenges, mLLDPE does exhibit superior physical properties compared to LDPE.

[0007] In the past, various levels of LDPE have been blended with mLLDPE to increase melt strength, improve shear sensitivity (e.g., enhance flow in extruders at commercial shear rates), and reduce the tendency for melt fracture. However, such blends typically exhibit poor mechanical properties compared to pure mLLDPE. In fact, improving the processability of mLLDPE without sacrificing physical properties remains a challenge.

[0008] In summary, there remains a need for new polyethylenes with a medium LCB polyethylene composition that offer extrusion processability similar to LDPE while maintaining good tear properties and dart impact strength to match those of mLLDPE. This new LLDPE would provide the benefits of increased processability, increased tear balance, increased TD tear strength, and significantly better drawdown characteristics, making it easier to produce stronger films without resorting to the many complexities and trade-offs associated with blending mLLDPE and LDPE.

[0009] Some references with 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.'s Journal of Organometallic Chemistry, 571(1998)171. Summary of the Invention

[0010] This disclosure relates to support-bound activators, supported catalyst systems, and methods of using them.

[0011] In some embodiments, the catalyst system includes a first catalyst compound. The first catalyst compound is represented by the following formula (I):

[0012]

[0013] in:

[0014] In formula (I), M is a Group 4 metal;

[0015] R in equation (I) 1 R 2 R 3 R 4R 5 R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 and R 14 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 1 and R 2 R 4 and R 5 R 5 and R 6 R 6 and R 7 R 9 and R 10 R 11 and R 12 R 12 and R 13 and R 13 and R 14 One or more pairs are connected to form a fully saturated ring or a substituted or unsubstituted aromatic ring;

[0016] Where R in equation (I) 4 and R 5 R 5 and R 6 or R 6 and R 7 At least one pair of rings are connected to form a first substituted or unsubstituted fully saturated ring fused with an indenyl ring, and R 11 and R 12 R 12 and R 13 or R 13 and R 14 At least one pair of rings are connected to form a second substituted or unsubstituted fully saturated ring fused with the indenyl ring; and

[0017] Each X in formula (I) is independently a halide, a substituted or unsubstituted hydrocarbon group, a hydride, an amide, a substituted or unsubstituted alkoxide, a sulfide, a phosphide, or a combination thereof, or two of X are linked together to form a substituted or unsubstituted metallocycle ring, or two of X are linked together to form a chelate ligand, a diene ligand, or an alkylidene.

[0018] The catalyst system may further include a second catalyst represented by the following formula (III):

[0019]

[0020] in:

[0021] M in formula (III) is a group 4 metal;

[0022] R in equation (III) 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 linked to form a substituted or unsubstituted fully saturated ring or a substituted or unsubstituted aromatic ring, wherein R 7 and R 8 R 8 and R 9 Or R 9 and R 10 At least one pair of the rings are connected to form a fully saturated ring, substituted or unsubstituted, fused with the indenyl ring;

[0023] The T expression in equation (III) 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, halogenated, 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 or substituted or unsubstituted aromatic rings; and

[0024] Each X in formula (III) 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 of X are linked together to form a substituted or unsubstituted metal cyclization ring, or two of X are linked together to form a chelate ligand, a diene ligand, or an alkylidene group.

[0025] In some embodiments, the polyethylene copolymer comprises ethylene-derived units and the remainder being C3-C. 20 The unit is derived from the comonomer. The polyethylene copolymer has a broad orthogonal composition distribution of approximately 0.914 g / cm³. 3 To approximately 0.925 g / cm 3 The density, melt index from about 0.6 g / 10min to about 1.3 g / 10min, olefin comonomer content from about 10 wt% to about 13 wt%, high load melt index (HLMI) from about 80 g / 10min to about 90 g / 10min, melt index ratio (MIR) from about 60 to about 98, and polydispersity index (PDI, defined as Mw / Mn) from about 8 to about 10. Attached Figure Description

[0026] To gain a more detailed understanding of the features listed above, a more specific description of the invention can be obtained by referring to some of the embodiments shown in the accompanying drawings. However, it should be noted that the drawings are merely illustrative of typical embodiments of the invention and are therefore not intended to limit the scope of the invention, as the invention can be practiced in other equally effective embodiments.

[0027] Figure 1 A diagram illustrating the GPC of polyethylene copolymers according to various embodiments is provided, which simultaneously includes the polymer chain distribution (which may be labeled on the y-axis as dwt / d(logM) or equivalently as MWD(IR)), the y-axis value reflecting the molecular weight distribution being a measure of the relative number of polymer molecules of a given molecular weight in the analyzed polymer molecular population of the polymer composition) and the g'vis value (also labeled on the y-axis) as a function of log(molecular weight) (which may be labeled on the x-axis as logM). It should be noted that... Figure 1 The MWD(IR) used in this labeling is not necessarily the same as the mathematical term MWD (defined as Mw / Mn, also known as the polydispersity index or PDI, see below); rather, it simply refers to the distribution (i.e., the relative amount) of polymer chains of different molecular weights. Figure 1 The value is displayed as a function of molecular weight.

[0028] Figure 2This is a diagram illustrating the GPC of polyethylene copolymers according to various embodiments, including molecular weight distribution (labeled as MWD(IR) on the left y-axis) and comonomer weight % as a function of log(molecular weight) (labeled as weight %C6 on the right y-axis). Figure 2 The MWD(IR) marker in the text is used to... Figure 1 Use it in the same way.

[0029] definition

[0030] As used herein, "olefin," or "alkene hydrocarbon," is a linear, branched, or cyclic compound having at least one double bond of carbon and hydrogen. For the purposes of this specification and the appended claims, when a polymer or copolymer is referred to as "containing" an olefin, the olefin present in such polymer or copolymer is the polymeric form of said olefin. For example, when a copolymer is described as having an "ethylene" content of about 35% to about 55% by weight, it should be understood that the matrix units in said copolymer are derived from ethylene in the polymerization reaction and that said derived units are present at about 35% to about 55% by weight, based on the weight of said copolymer.

[0031] As used herein, the terms “polyethylene polymer,” “polyethylene copolymer,” “polyethylene,” “ethylene polymer,” “ethylene copolymer,” and “vinyl polymer” refer to polymers or copolymers 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).

[0032] 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 with respect to monomer units indicates that the monomer units differ from each other by at least one atom or are isomerically different. Therefore, the definition of copolymer as used herein includes terpolymers and the like. Similarly, the definition of polymer as used herein includes copolymers and the like.

[0033] As used in this article, the density is greater than 0.860 to less than 0.910 g / cm³. 3 Ethylene polymers can be called ethylene plastides or ethylene plastids; their density ranges from 0.910 to less than 0.925 g / cm³. 3Ethylene polymers that are substantially linear (with little or no long-chain branching) can be called "linear low-density polyethylene" (LLDPE), as is often the case with Ziegler-Natta or metallocene-catalyzed PE, or significantly branched (with highly long-chain branching) can be called branched low-density polyethylene (LDPE), as is often the case with free-radical polymerized PE; 0.925 to 0.940 g / cm³ 3 It can be called "medium-density polyethylene" (MDPE); it has a density greater than 0.940 g / cm³. 3 Ethylene polymers with a density of [specific value] can be called "high-density polyethylene" (HDPE). Density is determined according to ASTM D792. Samples are prepared according to ASTM D4703 - Appendix 1 Procedure C, and then conditioned according to ASTM D618 - Procedure A prior to testing.

[0034] When used herein and unless otherwise specified, the term "hydrocarbon" means a class of compounds containing hydrogen atoms bonded 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.

[0035] As used herein, a composition or membrane "free of" a component means that the composition / membrane is substantially free of that component, or contains less than 0.01% by weight of that component based on the total weight of the composition.

[0036] As used herein, the term "polymerization conditions" refers to conditions that, when in contact with an activated olefin polymerization catalyst, favor the reaction of one or more olefin monomers to produce a polyolefin polymer, including selections by those 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.

[0037] For the purposes of this disclosure, the new numbering scheme for the groups of the periodic table is used as described in Chemical and Engineering News, 63(5), pg. 27, (1985).

[0038] The following abbreviations may be used in this document: 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.

[0039] As used in this article, “olefin polymerization catalyst (one or more)” refers to any catalyst capable of coordination polymerization addition, such as organometallic complexes or compounds, wherein successive monomers are added to the monomer chain at the organometallic active site.

[0040] The terms “substituent,” “base,” “group,” and “structural part” are used interchangeably.

[0041] 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; for example, R'' is hydrogen and R''' is an alkyl group). "Linear α-olefin" is the α-olefin defined in this paragraph where R'' is hydrogen and R''' is hydrogen or a linear alkyl group.

[0042] For the purposes of this disclosure, ethylene should be considered an α-olefin.

[0043] When used herein and unless otherwise specified, the term “Cn” refers to a hydrocarbon (one or more) containing n carbon atoms (one or more) per molecule, where n is a positive integer. The term “hydrocarbon” refers to a class of compounds containing hydrogen atoms bonded to carbon atoms and covers (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and / or unsaturated), including mixtures of hydrocarbon compounds with different n values. Similarly, “Cn” refers to a hydrocarbon containing one or more carbon atoms (one or more) per molecule, where n is a positive integer. m -C y "A group or compound refers to a group or compound that contains a total of carbon atoms from m to y. Therefore, C1-C..." 50 Alkyl refers to an alkyl group that contains a total of about 1 to about 50 carbon atoms.

[0044] Unless otherwise specified (e.g., the definition of "substituted hydrocarbon group", "substituted aromatic group", 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, heteroatom or heteroatom-containing group, such as a halogen group (e.g. Br, Cl, F or I) or at least one functional group, such as -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*3, -GeR*3, -SnR*3, -PbR*3, wherein each R* is independently a hydrocarbon group or a halocarbyl radical, and two or more R* may be linked 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.

[0045] The term "substituted hydrocarbon group" refers to a hydrocarbon group in which at least one hydrogen atom is replaced by at least one heteroatom (e.g., a halogen group, such as Br, Cl, F, or I) or a heteroatom-containing group (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* may be linked 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.

[0046] The term "substituted aromatic" refers to an aromatic group having one or more hydrogen groups that are replaced by a hydrocarbon group, a substituted hydrocarbon group, a heteroatom, or a heteroatom-containing group.

[0047] The terms "hydrocarbyl radical," "hydrocarbyl group," or "hydrocarbyl" are used interchangeably and are defined as meaning a group containing only hydrogen and carbon atoms. For example, a hydrocarbyl group can be C1-C. 100 A functional group, which may be linear, 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.

[0048] 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 bonded to an oxygen atom, and may include alkyl / aryl groups that are C1-C. 10 Those with hydrocarbon groups. Alkyl groups can be linear, branched, or cyclic. Alkyl groups can be saturated or unsaturated. Examples of suitable alkoxy groups can include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, and phenoxy.

[0049] The term "alkenyl" refers to a linear, branched, or cyclic hydrocarbon group having one or more double bonds. These alkenyl groups may be optionally substituted. Examples of suitable alkenyl groups may include vinyl, propenyl, allyl, 1,4-butadienyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, and their substituted analogs.

[0050] The terms "alkyl radical," "alkyl group," and "alkyl" are used interchangeably throughout this disclosure. For the purposes of this disclosure, "alkyl" is defined as a C1-C group that can be linear, branched, or cyclic. 100 Alkyl groups. Examples of these groups may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and 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.

[0051] The term "aryl" or "aryl group" refers to an aromatic ring and its substituted variants, such as phenyl, 2-methyl-phenyl, xylyl, and 4-bromo-xylyl. Similarly, "heteroaryl" refers to an aryl group in which one (or two or three) ring carbon atoms have been replaced by a heteroatom, such as N, O, or S. As used herein, the term "aromatic" also refers to pseudoaromatic heterocycles, which have similar properties and structures (almost planar) to aromatic heterocyclic ligands but are not part of the heterocyclic substituents that define an aromatic group; again, the term "aromatic" also refers to substituted aromatic compounds.

[0052] When a specified alkyl, alkenyl, alkoxy, or aryl isomer is present (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl), mentioning alkyl, alkenyl, alkoxy, or aryl without specifying a particular isomer (e.g., butyl) explicitly discloses all isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl).

[0053] The term "ring atom" refers to an atom that belongs to a cyclic ring structure. According to this definition, benzyl has 6 ring atoms and tetrahydrofuran has 5 ring atoms.

[0054] A heterocycle is a ring structure containing a heteroatom, as opposed to a ring in which hydrogen atoms on a ring atom are replaced by heteroatoms. For example, tetrahydrofuran is a heterocycle, and 4-N,N-dimethylamino-phenyl is a heteroatom-substituted ring. Other examples of heterocycles include pyridine, imidazole, and thiazole.

[0055] In this article, Mn is the number-average molecular weight, Mw is the weight-average molecular weight, Mz is the z-average molecular weight, wt% is the weight percentage, and mol% is the molar percentage. Molecular weight distribution (MWD) (also known as polydispersity index (PDI)) is defined as Mw divided by Mn. Unless otherwise stated, all molecular weight units (e.g., Mw, Mn, Mz) are in g / mol.

[0056] The terms "catalyst compound", "catalyst complex", "transition metal complex", "transition metal compound", "precatalyst compound" and "precatalyst complex" are used interchangeably.

[0057] A “catalyst system” is a combination of at least one catalyst compound, at least one activator, optional coactivator, and optional support material. When “catalyst system” is used to describe such a pairing prior to activation, it refers to the unactivated catalyst complex (pre-catalyst) together with the activator and, optionally, the coactivator. When it is used to describe such a pairing after activation, it refers to the activated complex and the activator or other charge-balanced structural components. The catalyst compound can be neutral, as in the pre-catalyst, or a charged substance with a balance ion, as in the activated catalyst system. For the purposes of this disclosure and its claims, when a catalyst system is described as comprising a neutral, stable form of a component, those skilled in the art will understand that the ionic form of said 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 structural formulas herein are intended to cover catalyst compounds and activators in both neutral and ionic forms.

[0058] An "anionic ligand" is a negatively charged ligand that contributes one or more electron pairs to a metal ion. A "Lewis base" or "neutral donor ligand" is an electrically neutral ligand that donates one or more electron pairs to a metal ion. Examples of Lewis bases include diethyl ether, trimethylamine, pyridine, tetrahydrofuran, dimethyl sulfide, and triphenylphosphine. The term "heterocyclic Lewis base" refers to a Lewis base that is also heterocyclic. Examples of heterocyclic Lewis bases include pyridine, imidazole, thiazole, and furan.

[0059] Scavengers are compounds 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 (not scavengers) can also be used in combination with activators to form active catalysts. In at least one embodiment, the co-activator can be premixed with a transition metal compound to form an alkylated transition metal compound.

[0060] The term "continuous" refers to a system that operates without interruption or cessation over an extended period of time. For example, a continuous method for preparing polymers would be one in which reactants are continuously introduced into one or more reactors and polymer products are continuously removed.

[0061] Solution polymerization is a polymerization method in which the polymer is dissolved in a liquid-phase polymerization medium, such as an inert diluent or monomers (one or more) or blends thereof. Solution polymerization can be homogeneous solution polymerization. Homogeneous polymerization is polymerization in which the polymer product is dissolved in a polymerization medium. Suitable systems may not be turbid, as described in J. Vladimir Oliveira, C. Dariva and JC Pinto, Ind. Eng, Chem. Res. 2000, Vol. 29, p. 4627.

[0062] Bulk polymerization refers to a polymerization method in which the monomers and / or comonomers involved in the polymerization are used as solvents or diluents, with little or no use of inert solvents or diluents. A small amount of inert solvent / diluent may be used as a carrier for catalysts and scavengers. Bulk polymerization systems contain less than about 25% by weight of inert solvent or diluent, for example, less than 10% by weight, less than 1% by weight, or 0% by weight.

[0063] The term "single catalyst compound" refers to a catalyst compound that corresponds to a single general structural formula, but such catalyst compounds may include and be used as mixtures of isomers (e.g., stereoisomers).

[0064] A catalyst system using a single catalyst compound refers to a catalyst system prepared using only a single catalyst compound in its preparation. Therefore, this type of catalyst system differs from, for example, a "dual" catalyst system, which is prepared using two catalyst compounds with different structural formulas, such as differences in the bonding between atoms, the number of atoms, and / or the type of atoms. Thus, a catalyst compound is considered different from another catalyst compound if they differ by at least one atom (number, type, or bonding). For example, dichloro-bisindenylzirconium is different from dichloro-(indenyl)(2-methylindenyl)zirconium, which is different from dichloro-(indenyl)(2-methylindenyl)hafnium. Unless otherwise stated, catalyst compounds that differ only in that they are stereoisomers of each other are not considered different catalyst compounds. For example, racemic-dimethyl-dimethylsilyl-bis(2-methyl-4-phenyl)hafnium and meso-dimethyl-dimethylsilyl-bis(2-methyl-4-phenyl)hafnium are not considered different.

[0065] The terms “co-catalyst” and “activator” are used interchangeably herein and are defined as any compound capable of activating any of the aforementioned catalyst compounds by converting a neutral catalyst compound into a catalytically active catalyst compound cation.

[0066] In the extrusion process, "viscosity" is a measure of resistance to shear flow. Shear is the layer-by-layer movement of a fluid, like a stack of cards. When a polymer flows through a straight pipe or channel, it is sheared, and the resistance is expressed as viscosity.

[0067] "Elongation" or "elongational viscosity" is the resistance to stretching. Elongational viscosity plays a role in fiber spinning, film blowing, and other methods of stretching melt polymers. For example, for some liquids, the stretching resistance can be three times greater than the shear resistance. For some polymer liquids, elongational viscosity can increase with rate (stretch hardening) even though shear viscosity decreases.

[0068] The term "melt index" ("MI") is the number of grams extruded in 10 minutes under a standard load (2.16 kg) and is inversely proportional to viscosity. A high MI means low viscosity, and a low MI means high viscosity. Furthermore, polymers can exhibit shear-thinning behavior, meaning their flow resistance decreases with increasing shear rate. This is due, for example, to molecular alignment in the flow and disentanglement directions. As provided here, MI (I²) is determined according to ASTM D1238-E (190°C / 2.16 kg) and is sometimes also referred to as I² or I. 2.16 .

[0069] The term "High Load Melt Index" ("HLMI") refers to the number of grams extruded in 10 minutes under a standard load (21.6 kg) and is inversely proportional to viscosity. As provided here, HLMI (I 21 ) Measured according to ASTM D1238 (190℃ / 21.6kg), and sometimes also referred to as I 21 or I 21.6 .

[0070] The "melt index ratio" ("MIR") provides a quantitative indication of the shear-thinning behavior of a polymer and is a parameter that can be correlated with total polymer mixture molecular weight distribution data obtained individually using gel permeation chromatography ("GPC") and possibly in combination with other polymer analyses including TREF. MIR is I 21 The ratio of / I2 (also known as HLMI / MI).

[0071] The term "melt strength" is a measure of elongation viscosity and represents the maximum tensile force that can be applied to a melt without it breaking. Elongation viscosity is the ability of polyethylene to resist thinning at high draw rates and high draw ratios. In the melt processing of polyolefins, melt strength is defined by properties that can be quantified in both process-related and rheological terms. In extrusion blow molding and melt phase thermoforming, branched polyolefins of appropriate molecular weight can support the weight of a fully molten sheet or extruded portion before the molding stage. This behavior is sometimes referred to as sag resistance.

[0072] For simplicity, only certain numerical ranges are explicitly disclosed in this document. However, a lower limit can be combined with any other upper limit to define a range that is not explicitly stated, and similarly, a lower limit can be combined with any other lower limit to define a range that is not explicitly stated; likewise, an upper limit can be combined with any upper limit to define a range that is not explicitly stated. Furthermore, "within a range" or "within a range" includes every point or individual value between its endpoints, even if not explicitly stated, and includes the endpoints themselves. Therefore, each point or individual value itself can serve as a lower or upper limit, combined with other points or individual values ​​or other lower or upper limits to define a range that is not explicitly stated. Invention Details

[0074] Various embodiments and forms of the disclosed compounds, methods, and articles will now be described, including specific embodiments and definitions adopted herein. While specific embodiments are given in the following detailed description, those skilled in the art will understand that these embodiments are merely exemplary and that embodiments of this disclosure can be practiced in other ways. Any reference to embodiments may refer to one or more, but not necessarily all, of the compounds, methods, or articles defined by the claims. The use of headers is for convenience only and does not limit the scope of this disclosure.

[0075] 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 a dual catalyst system of a first metallocene catalyst and a second metallocene catalyst for polymerization. The catalyst ratio of the first and second metallocene catalysts can be adjusted to react at low pressures to produce polyethylene compositions with significant levels of long branching and high levels of broad orthogonal comonomer distribution characteristics in a gas-phase polymerization process.

[0076] In some implementations, the catalyst ratio of the first metallocene catalyst and the second metallocene catalyst can be adjusted by using a "trim" method.

[0077] Compared to conventional LLDPE, the polyethylene copolymers of this disclosure exhibit increased long-chain branching (also referred to as "LCB") and increased introduction of broadly orthogonal comonomers (BOCD) in the copolymer, thereby providing reduced shrinkage and increased stretch stability. The polyethylene copolymers of this disclosure can exhibit lower zero-shear viscosity, resulting in lower motor torque and lower melt pressure and melt temperature during extrusion, providing increased yield of the extruded polyethylene copolymer product. Furthermore, because LCB and BOCD are controlled (adjustable by the ratio of the first metallocene to the second metallocene), favorable tear and dart properties can also be controlled (adjustable) to the desired polymer end use (e.g., shrink wrap). For example, a reduction in motor torque and melt pressure can be observed during cast film manufacturing due to the increased polymer LCB and increased BOCD. LCB can be demonstrated, for example, by lower g' values, higher melt index ratios, and / or increased rheological properties. BOCD can be demonstrated, for example, by higher T... 75 -T 25 Values, high CBDI%, high melt index ratio and / or increased rheological properties, as demonstrated by small-angle oscillating shear (SAOS) experiments.

[0078] Furthermore, the polyethylene copolymers of this disclosure have been found to offer excellent tear properties and dart impact strength, thereby overcoming the key weaknesses of LDPE. For example, compared to conventional LLDPE, the polyethylene copolymers of this disclosure can provide films formed with reduced motor loads and melt pressures (which increase production capacity) due to improved flow behavior. For instance, reductions in melt pressure and melt temperature can be provided during film manufacturing. The films of this disclosure are particularly suitable as shrink wrap films (improved by the presence of LCB and BOCD in the polyethylene copolymers of this disclosure).

[0079] In fact, the dual catalyst and method disclosed herein can provide gas-phase polymerization to deliver LCB polyethylene products with excellent extrusion processability, as well as good tear properties and dart impact strength. Furthermore, the tear balance of the polyethylene copolymers described herein can exhibit high TD tear, which is desirable in many end-use applications. Another advantage includes improved draw characteristics, which provides easier production of thin-film materials.

[0080] Furthermore, the dual catalyst and method disclosed herein can provide trimming (e.g., in-line trimming) of a first catalyst that promotes the transfer of LCB to a supported catalyst, wherein the supported catalyst provides BOCD to control (adjust) the melt index ratio of the polyethylene copolymer formed in the reactor. The trimming catalyst can provide a different molecular weight capacity compared to, for example, an in-line supported catalyst. This different molecular weight capacity of the catalyst provides a bimodal compositional distribution of the polyethylene copolymer formed in the reactor.

[0081] In at least one embodiment, the properties and performance of polyethylene can be improved by a combination of: (1) changing reactor conditions such as reactor temperature, reactor pressure, hydrogen concentration, comonomer concentration, etc.; and (2) selecting and feeding a dual catalyst system having a first catalyst and a second catalyst, which is modified or unmodified together with the first catalyst, the second catalyst, or the third catalyst.

[0082] In at least one embodiment of the catalyst system, the first catalyst is a high molecular weight component and the second catalyst is a low molecular weight component. In other words, the first catalyst can primarily provide the high molecular weight portion of the polyethylene polymer, and the second catalyst can primarily provide the low molecular weight portion of the polyethylene polymer.

[0083] In at least one embodiment, the amount of the first or second catalyst in the feed (or the catalyst trimming ratio), the amount of the third catalyst in the feed, and / or reactor conditions (e.g., pressure, temperature, and hydrogen concentration) can be varied to provide a range of MI and MIR while maintaining the polyethylene density. Embodiments of the methods described herein can advantageously provide a wide range of MI using the same catalyst system, such as the same dual-catalyst system. For the catalyst system fed into the polymerization reactor, the polymer MI, MIR, and density can be controlled by varying the reactor conditions, which include, for example, the reactor mixture of the added additional catalyst, operating temperature, operating pressure, hydrogen concentration, and comonomer concentration in the reaction mixture.

[0084] By preparing polymer products in a single reactor rather than multiple reactors, it may be economically advantageous to use multiple pre-catalysts co-supported on a single support (e.g., methylaluminoxane (MAO)) mixed with an activator. Furthermore, using a single support facilitates homogeneous mixing of the resulting polymers, while improving the process, compared to preparing mixtures by post-reactor blending of polymers with different Mw and densities independently of multiple catalysts in a single reactor. The catalyst can be co-supported in a single operation or used in trimming operations, where one or more additional catalysts are added to the supported catalyst.

[0085] Evidence of comonomer introduction into the polymer is indicated by the density of the polyethylene copolymer, with lower densities indicating higher introduction rates. The density difference between the low molecular weight (LMW) and high molecular weight (HMW) components will preferably be greater than about 0.02, or greater than about 0.04, wherein the HMW component has a lower density than the LMW component. Satisfactory control of MWD leads to the adjustment of these factors, which can be adjusted by regulating the relative amounts of the two metallocene catalysts used in the polymerization of this disclosure. Additionally, the amount of catalyst added can be controlled using feedback from the obtained polymer property data.

[0086] Furthermore, various polymers with different MWD and LCBD can be prepared using a limited number of catalysts. In at least one embodiment, a mixed catalyst system provides a blend of beneficial properties to the polymer due to a customized combination of MWD, polymer branching, and BOCD. The ability to control MWD and polymer branching can be important in determining the processability and strength of the resulting polymer.

[0087] Other embodiments provide methods for preparing polyethylene, including: polymerizing ethylene in a reactor in the presence of a catalyst system to form polyethylene, wherein the catalyst system comprises a first catalyst and a second catalyst; and adjusting the reactor pressure, reactor temperature, reactor hydrogen concentration, and / or the amount of trimming catalyst (e.g., a first catalyst, a second catalyst, or a third catalyst) fed into the reactor to obtain a narrower range of MIR of polyethylene while maintaining, for example, the BOCD, LCB, and MI of polyethylene. At least one embodiment provides a system and method for preparing polyethylene, including: polymerizing ethylene in a reactor in the presence of a catalyst system to form polyethylene, wherein the catalyst system comprises a first catalyst and a second catalyst; and adjusting the reactor conditions and the amount of trimming catalyst (e.g., a first catalyst, a second catalyst, or a third catalyst) fed into the reactor to adjust the MI, BOCD, LCB, and MIR of the polymer product.

[0088] Aggregation methods

[0089] Polymerization methods can include gas-phase polymerization, particularly fluidized bed gas-phase polymerization. Generally, in gas fluidized bed methods for preparing polymers, a gaseous stream containing one or more monomers is continuously circulated through a fluidized bed under reactive conditions in the presence of a catalyst. In some embodiments, the reaction medium includes a condenser, typically a noncoordinate inert liquid that is converted to gas during polymerization, such as isopentane, isohexane, or isobutane. The gaseous stream is discharged from the fluidized bed and recycled back to the reactor. Simultaneously, polymer product is discharged 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. 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 for their discussions of suitable gas-phase fluidized bed polymerization systems, which are incorporated herein by reference.

[0090] In such polymerization methods, the gas-phase fluidized bed process involves continuously passing a stream containing ethylene and olefin comonomers through a fluidized bed reactor at a velocity sufficient to keep the solid particle bed suspended 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 "recirculated gas" stream) is continuously removed from the reactor, compressed, cooled, optionally partially or completely condensed, and recycled back to the reactor. The resulting polyethylene copolymer is removed from the reactor, and replacement ethylene and olefin comonomers are added to the recirculated stream. In some embodiments, a gas inert to the catalyst composition and reactants is present in the gas stream.

[0091] The circulating gas may include an induced condensate (ICA). An ICA is one or more non-reactive alkanes that are condensable during polymerization to remove the heat of reaction. In some embodiments, the non-reactive alkanes are selected from C1-C6 alkanes, such as propane, butane, isobutane, pentane, isopentane, hexane, and one or more of their isomers and derivatives. In some cases, mixtures of two or more such ICAs may be particularly useful (e.g., propane and pentane, propane and butane, butane and pentane, etc.).

[0092] The reactor pressure during polymerization can be 100 psig (680 kPag) - 500 psig (3448 kPag), for example 200 psig (1379 kPag) - 400 psig (2759 kPag), for example 250 psig (1724 kPag) - 350 psig (2414 kPag). In some embodiments, the reactor operates at temperatures from 60°C to 110°C, for example 60°C to 100°C, for example 70°C to 90°C, for example 80°C to 92°C, for example 82°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.

[0093] The mol% of ethylene (based on total monomers) can be 25-90 mol%, such as 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 in the range of 35-95 mol%, for example, from the lower limit of 35, 40, 45, 50, or 55 mol% to the upper limit of 70, 75, 80, 85, 90, or 95 mol%, and further wherein the ethylene mol% is measured based on the total number of moles of gas in the reactor (including, if present, ethylene and / or comonomer gases and inert gases, such as nitrogen, isopentane, or one or more other ICAs); as in the case of 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, from the lower limit of 0.2, 0.3, 0.4, or 0.5 mol% to the upper limit of 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95, 1.0, 1.5, or 2 mol%.

[0094] Use trimmed aggregate

[0095] The polymerization method disclosed herein can be carried out using a "trimming" method. According to such a method, the mixture containing a first catalyst (which may be referred to as a catalyst component slurry) comprises a support material suspended in a suitable carrier liquid, at least one activator, and at least one catalyst compound (optionally further comprising a second, third, or more catalyst compounds). Preferably, the catalyst component slurry comprises at least the first and second catalyst compounds.

[0096] A mixture containing a second catalyst (which may be referred to as a catalyst component solution) containing one or more catalyst compounds (e.g., a first catalyst compound and / or a second, third, fourth, etc. catalyst compound) identical to those found on a supported catalyst in the slurry can be added (i.e., "trimmed") to the slurry to achieve online and immediate adjustment of the proportion of catalyst components in the catalyst system delivered to the polymerization reactor. Adjusting the proportion of catalyst components allows for the modification of one or more properties of the polymer being formed in the reactor, as described herein. This "trimming" method is very economical because it does not require stopping polymerization to adjust polymer properties in cases where the catalyst system does not behave as desired, or in cases of desired grade changes as part of polymer production activities.

[0097] The first and second catalysts are described below, together forming a particularly useful dual-catalyst system. Therefore, these catalysts can all be used in the trimming method just described. For example, the catalyst component slurry may include the first catalyst and / or the second catalyst (preferably both) described below in a diluent, a support, and at least one activator. Therefore, the first and / or second catalysts are preferably disposed in an activated form on a support in the diluent. The catalyst component solution may include any one or both of the first and second catalysts described below suspended in a diluent (which may be the same as or different from the diluent of the slurry) (preferably, one of the second or first catalysts). Optionally, the activator may be included in solution. The trimming method will involve introducing the catalyst component solution online into the catalyst component slurry to form a modified catalyst slurry comprising the catalyst system (in desired proportions of supported, activated first and second catalysts) for delivery to a polymerization reactor.

[0098] Therefore, it should be anticipated that, for different catalysts selected, some of the second catalyst may initially be co-deposited with the first catalyst on a common support, and the remaining amount of the first or second catalyst may be added as a trimming agent to achieve the final desired ratio of the first to the second catalysts. Alternatively, the slurry may consist only of the first catalyst or only of the second catalyst, and the solution may contain only other catalysts.

[0099] In other embodiments, either the first or second catalyst described below may be combined with different catalysts in different dual-catalyst systems (in trimming methods or otherwise). For example, the first catalyst described below may be combined with an additional metallocene catalyst instead of the second catalyst described below (or in addition to being combined with the second catalyst described below); the same applies to the second catalyst described below. Examples of such additional metallocene catalysts include, for example, those described in U.S. Patent Nos. US5,278,272; US5,763,543; US6,255,426; and US7,951,873, each of which is incorporated herein by reference. For example, the catalyst may be a silica-supported metallocene catalyst prepared from a composition comprising a metallocene catalyst compound and a methylaluminoxane cocatalyst. In some embodiments, the metallocene catalyst compound is racemic-meso-dimethylbis(1-ethylindenyl)2-zirconium, dimethyl-dimethylsilylbis(tetrahydroindenyl)zirconium metallocene, dimethyl-dimethylsilylbis(tetrahydroindenyl)zirconium, dimethyl-(n-propylcyclopentadienyl)2-hafnium, or a combination thereof.

[0100] As noted, one or more diluents may be used to facilitate the combination of any two or more components of the catalyst system in the slurry or trimmed catalyst solution. Toluene is one example of a diluent, but other suitable diluents may include, but are not limited to, ethylbenzene, xylene, pentane, hexane, heptane, octane, other hydrocarbons (especially aliphatic hydrocarbons), or any combination thereof.

[0101] The diluent may be or may include mineral oil. The mineral oil may have a concentration of approximately 0.85 g / cm³ at 25°C according to ASTM D4052. 3 Approximately 0.9 g / cm³ 3 For example, approximately 0.86 g / cm³ 3 Approximately 0.88 g / cm³ 3 The mineral oil may have a kinematic viscosity at 25°C of about 150 cSt to about 200 cSt, such as about 160 cSt to about 190 cSt, such as about 170 cSt, according to ASTM D341. The mineral oil may have an average molecular weight of about 400 g / mol to about 600 g / mol, such as about 450 g / mol to about 550 g / mol, such as about 500 g / mol, according to ASTM D2502. In at least one embodiment, the mineral oil is HYDROBRITE obtained from Sonneborn, LLC. ® 380 PO white mineral oil (“HB380”).

[0102] The diluent may further include wax, which can provide increased viscosity to slurries (such as mineral oil slurries). The wax is food-grade petrolatum, also known as petroleum jelly. The wax can be paraffin wax. Paraffin wax includes SONO JELL from Sonneborn, LLC. ® Paraffin, such as SONO JELL ® 4 and SONO JELL ® 9. In at least one embodiment, the slurry contains 5% by weight or more wax, such as 10% by weight or more, 25% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more. For example, a mineral oil slurry may contain about 70% by weight mineral oil, about 10% by weight wax, and about 20% by weight supported catalyst (one or more) (e.g., a supported dual catalyst). The increased viscosity provided by the wax in the slurry (such as a mineral oil slurry) provides reduced deposition of the supported catalyst (one or more) in the trim vessel or catalyst tank (used to introduce the supported catalyst into the pipeline). Furthermore, using a mineral oil slurry with increased viscosity does not inhibit trim efficiency. In at least one embodiment, the wax has a content of about 0.7 g / cm³. 3 (at 100℃) to approximately 0.95 g / cm³ 3 (At 100℃), for example, approximately 0.75 g / cm³ 3 (at 100°C) to approximately 0.87 g / cm³ 3 Density (at 100°C). Wax can have a density of approximately 5 mm. 2 / s (at 100°C) to approximately 30 mm 2 The kinematic viscosity is 1 / s (at 100°C). Waxes can have boiling points of about 200°C or higher, such as about 225°C or higher, or about 250°C or higher. Waxes can have melting points of about 25°C to about 100°C, such as about 35°C to about 80°C.

[0103] The catalyst slurry and / or modified catalyst slurry may be further transported together with a carrier fluid, which may advantageously include fluids otherwise used in the polymerization. For example, in gas-phase polymerization, molecular nitrogen, induced condensate (ICA) (one or more), and / or circulating gas may be used to carry the catalyst slurry and / or modified catalyst slurry (the circulating gas typically includes nitrogen, ICA (one or more), and one or more gaseous monomers / comonomers). ICA may be, or may include, but is not limited to, one or more alkanes. Illustrative alkanes may be, or may include, but are not limited to, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, isohexane, n-heptane, n-octane, or any mixture thereof. Further details regarding induced condensate can be found in U.S. Patent Nos. 5,352,749; 5,405,922; 5,436,304 and 7,122,607; and International Patent Application Publication No. WO 2005 / 113615 (A2).

[0104] In some implementations, the catalyst is not limited to slurry and / or trimmed configurations, as a mixed catalyst system can be prepared on a support and dried. The dried catalyst system can then be fed to the reactor via a dry feed system.

[0105] In methods for preparing fumed polyethylene, it may be desirable to use one or more electrostatic control agents to help regulate the electrostatic level in the reactor. The electrostatic control agents used here are chemical compositions that, when introduced into a fluidized bed reactor, can influence or drive the static charge (negative, positive, or to zero) in the fluidized bed. The specific electrostatic control agent used can depend on the nature of the static charge, and the choice of electrostatic control agent can vary depending on the polymer being prepared and the unit site catalyst compound used.

[0106] Static control agents such as aluminum stearate can be used. The choice of static control agent should be based on its ability to accept static charge in the fluidized bed without adversely affecting productivity. Other suitable static control agents may include aluminum distearate, ethoxylated amines, and antistatic compositions.

[0107] First catalyst

[0108] The first catalyst can be unsupported or supported on a carrier material.

[0109] In some implementations, the first catalyst is an unbridged metallocene catalyst represented by the following formula (I):

[0110]

[0111] Where M is a Group 4 metal; R 1 R 2 R 3 R 4 R5 R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 and R 14 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 1 and R 2 R 4 and R 5 R 5 and R 6 R 6 and R 7 R 9 and R 10 R 11 and R 12 R 12 and R 13 and R 13 and R 14 One or more pairs of rings are linked to form a substituted or unsubstituted fully saturated ring, or a substituted or unsubstituted aromatic ring, wherein R 4 and R 5 R 5 and R 6 or R 6 and R 7 At least one pair of rings are connected to form a first substituted or unsubstituted fully saturated ring fused with an indenyl ring, and R 11 and R 12 R 12 and R 13 or R 13 and R 14 At least one pair of rings are connected to form a second substituted or unsubstituted fully saturated ring fused with an indenyl ring, wherein if R 12 and R 13 If linked to form a fully saturated ring, either substituted or unsubstituted, then R 9 It is neither a substituted nor an unsubstituted hydrocarbon group, wherein if R 5 and R 6 If linked to form a fully saturated ring, either substituted or unsubstituted, then R 2 Not a substituted or unsubstituted hydrocarbon group; and each X is independently a halogen group, 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 of X are linked together to form a substituted or unsubstituted metal cyclization ring, or two of X are linked together to form a chelate ligand, a diene ligand or an alkylidene group.

[0112] In some implementations, R of formula (I) 4 R 5 R 6 R 7 R 11 R 12 R 13 and R 14 Each of them is independently hydrogen or C1-C 10 Alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl), wherein (1)R 4 and R 5 (2)R 5 and R 6 Or (3)R 6 and R 7 At least one pair of the rings are connected to form a first substituted or unsubstituted fully saturated ring fused with the indenyl ring shown in formula (I), and (1)R 11 and R 12 (2)R 12 and R 13 Or (3)R 13 and R 14 At least one pair of the rings are connected to form a second substituted or unsubstituted fully saturated ring fused with the indene ring shown in formula (I).

[0113] In some implementation schemes, (1)R 4 and R 5 (2)R 5 and R 6 Or (3)R 6 and R 7 At least one pair of rings are connected to form a first substituted or unsubstituted fully saturated ring fused with the indenyl ring shown in formula (I). In some embodiments, R 4 and R 5 The rings are joined to form substituted or unsubstituted saturated C4 rings, substituted or unsubstituted saturated C5 rings, substituted or unsubstituted saturated C6 rings, or substituted or unsubstituted saturated C7 rings, wherein the C4 ring, C5 ring, C6 ring, or C7 ring is fused with the indene ring shown in formula (I). In some embodiments, R 5 and R 6 The rings are joined to form substituted or unsubstituted saturated C4 rings, substituted or unsubstituted saturated C5 rings, substituted or unsubstituted saturated C6 rings, or substituted or unsubstituted saturated C7 rings, wherein the C4 ring, C5 ring, C6 ring, or C7 ring is fused with the indene ring shown in formula (I). In some embodiments, R 6 and R 7The rings are connected to form substituted or unsubstituted saturated C4 rings, substituted or unsubstituted saturated C5 rings, substituted or unsubstituted saturated C6 rings, or substituted or unsubstituted saturated C7 rings, wherein the C4 ring, C5 ring, C6 ring, or C7 ring is fused with the indene ring shown in formula (I).

[0114] In some implementation schemes, (1)R 11 and R 12 (2)R 12 and R 13 Or (3)R 13 and R 14 At least one pair of rings are connected to form a first substituted or unsubstituted fully saturated ring fused with the indenyl ring shown in formula (I). In some embodiments, R 11 and R 12 The rings are joined to form substituted or unsubstituted saturated C4 rings, substituted or unsubstituted saturated C5 rings, substituted or unsubstituted saturated C6 rings, or substituted or unsubstituted saturated C7 rings, wherein the C4 ring, C5 ring, C6 ring, or C7 ring is fused with the indene ring shown in formula (I). In some embodiments, R 12 and R 13 The rings are joined to form substituted or unsubstituted saturated C4 rings, substituted or unsubstituted saturated C5 rings, substituted or unsubstituted saturated C6 rings, or substituted or unsubstituted saturated C7 rings, wherein the C4 ring, C5 ring, C6 ring, or C7 ring is fused with the indene ring shown in formula (I). In some embodiments, R 13 and R 14 The rings are connected to form substituted or unsubstituted saturated C4 rings, substituted or unsubstituted saturated C5 rings, substituted or unsubstituted saturated C6 rings, or substituted or unsubstituted saturated C7 rings, wherein the C4 ring, C5 ring, C6 ring, or C7 ring is fused with the indene ring shown in formula (I).

[0115] In some implementations, R of formula (I) 1 R 2 R 3 R 8 R 9 and R 10 Each of them is hydrogen or C1-C 10 Alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl). In some embodiments, R 1 R 2 R 3 R 8 R 9 and R 10 Each of these is independently hydrogen, methyl, ethyl, or propyl. In some embodiments, R 1 R 2R 3 R 8 R 9 and R 10 Each of them is hydrogen. In some implementations, R 1 R 2 R 3 R 8 R 9 and R 10 Each of these is a methyl group. In some embodiments, R 3 and R 10 At least one of them is C1-C 10 Alkyl group. In some embodiments, R 3 and R 10 Each of them is independently C1-C 10 Alkyl group. In some embodiments, R 3 and R 10 Each of them is independently C1-C 10 Alkyl (e.g., methyl), and R 1 R 2 R 4 R 5 R 6 R 7 R 8 R 9 R 11 R 12 R 13 and R 14 It is hydrogen.

[0116] In some implementations, R of formula (I) 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 and R 14 One or more of them are independently hydrogen, hydrocarbon group, silylcarbyl group, alkoxy group, halogen group or siloxyl group.

[0117] In some embodiments of formula (I), M is a Group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf), for example, Zr or Hf. In some embodiments, each X is independently a halide group, such as chlorine. In 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, hydrogen, chlorine, fluorine, bromine, iodine, trifluoromethanesulfonate, dimethylamido, diethylamido, dipropylamido, and diisopropylamido.

[0118] In some embodiments of formula (I), (1) M is Zr or Hf, (2) X is chlorine, and (3) R 1 R 2 R 3 R 4 R 5 R 6 and R 7 Independently hydrogen or substituted or unsubstituted C1-C 10 Alkyl, (4)R 8 R 9 R 10 R 11 R 12 R 13 and R 14 Independently hydrogen or substituted or unsubstituted C1-C 10 Alkyl, (5)R 3 and R 10 At least one of them is C1-C 10 Alkyl, (6)R 4 and R 5 R 5 and R 6 or R 6 and R 7 At least one pair of rings in the form of a fully saturated substituted ring fused with the indenyl ring shown in formula (I), and (7)R 11 and R 12 R 12 and R 13 or R 13 and R 14 The rings are connected to form a substituted, fully saturated ring that is fused with the indene ring shown in formula (I).

[0119] The first catalyst can be, for example, an unbridged metallocene catalyst represented by formula (II):

[0120]

[0121] in:

[0122] M is a Group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf);

[0123] R 1 R 2 R 3 R 4 R 7 R 8 R 9 R 10 R 11 R 14 R 15 R 15' R 16 R 16' R 17 R 17' R 18 R 18' R 19 R 19' R 20 R 20' R 21 R 21' R 22 and R 22' 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; and

[0124] 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 of X are linked together to form a substituted or unsubstituted metal cyclization ring, or two of X are linked together to form a chelate ligand, a diene ligand, or an alkylidene group.

[0125] In some implementations, R of formula (II) 4 R 7 R 11 R 14 R 15 R 15' R 16 R 16' R 17 R 17' R 18 R 18' R 19 R 19' R20 R 20' R 21 R 21' R 22 and R 22' Each of them is independently hydrogen or C1-C 10 Alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl). In some embodiments, R 15 R 15' R 18 R 18' R 19 R 19' R 22 and R 22' Each of these is independently hydrogen, methyl, ethyl, or propyl. In some embodiments, R 15 R 15' R 18 R 18' R 19 R 19' R 22 and R 22' Each of them is hydrogen. In some implementations, R 15 R 15' R 18 R 18' R 19 R 19' R 22 and R 22' Each of them is C1-C 10 Alkyl (e.g., methyl). In some embodiments, R 4 R 7 R 11 R 14 R 16 R 16' R 17 R 17' R 20 R 20' R 21 and R 21' Each of them is hydrogen.

[0126] In some implementations, R of formula (II) 1 R 2 R 3 R 8 R 9 and R 10 Each of them is hydrogen or C1-C 10 Alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl). In some embodiments, R1 R 2 R 3 R 8 R 9 and R 10 Each of these is independently hydrogen, methyl, ethyl, or propyl. In some embodiments, R 1 R 2 R 3 R 8 R 9 and R 10 Each of them is hydrogen. In some implementations, R 1 R 2 R 3 R 8 R 9 and R 10 Each of these is a methyl group. In some embodiments, R 3 and R 10 At least one of them is C1-C 10 Alkyl group. In some embodiments, R 3 and R 10 Each of them is independently C1-C 10 Alkyl group. In some embodiments, R 3 and R 10 It is C1-C 10 Alkyl (e.g., methyl), and R 1 R 2 R 8 and R 9 It is hydrogen.

[0127] In some embodiments of formula (II), M is a Group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf), for example, Zr or Hf. In some embodiments, each X is independently a halogen group, such as chlorine. In 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, hydrogen, chlorine, fluorine, bromine, iodine, trifluoromethanesulfonate, dimethylamino, diethylamino, dipropylamino, and diisopropylamino.

[0128] In some embodiments of formula (II), (1) M is Zr or Hf, (2) X is chlorine, and (3) R 1 R 2 R 3 R 4 R 7 R 15 R15' R 16 R 16' R 17 R 17' R 18 and R 18' Independently hydrogen or substituted or unsubstituted C1-C 10 Alkyl, (4)R 8 R 9 R 10 R 11 R 14 R 19 R 19' R 20 R 20' R 21 R 21' R 22 and R 22' Independently hydrogen or substituted or unsubstituted C1-C 10 Alkyl groups, and (5)R 3 and R 10 At least one of them is C1-C 10 alkyl.

[0129] In some embodiments of formula (II), the catalyst is selected from:

[0130]

[0131]

[0132]

[0133]

[0134] Second catalyst

[0135] The second catalyst disclosed herein includes a second catalyst, which may be unsupported or supported on a support together with the first catalyst to form a dual catalyst system. The second catalyst may be unsupported or supported, and the dual catalyst system may be segregated. Alternatively, the second catalyst may be provided as a "trimming" catalyst onto the supported first catalyst, for example, provided online en route to the reactor. The dual catalyst system (e.g., also along with an activator) is introduced into the reactor (e.g., a gas-phase reactor).

[0136] In some embodiments, the second catalyst is a bridged metallocene catalyst represented by the following formula (III):

[0137]

[0138] in:

[0139] M is a Group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf);

[0140] 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 (preferably R) 7 and R 8 R 8 and R 9 and R 9 and R 10 (a pair of them) are connected to form a substituted or unsubstituted fully saturated ring or a substituted or unsubstituted aromatic ring fused with the indene ring shown in formula (III);

[0141] 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, halogenated, 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

[0142] 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 of X are linked together to form a substituted or unsubstituted metal cyclization ring, or two of X are linked together to form a chelate ligand, a diene ligand, or an alkylidene group.

[0143] In some implementations, R of formula (III) 7 R 8 R 9 and R 10Each of them is independently hydrogen or C1-C 10 Alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl), wherein (1)R 7 and R 8 (2)R 8 and R 9 Or (3)R 9 and R 10 At least one pair of rings are connected to form a substituted or unsubstituted fully saturated ring fused with the indenyl ring shown in Formula (III). The substituted or unsubstituted ring may be, for example, a C5, C6, or C7 ring fused with the indenyl ring shown in Formula (III).

[0144] In some implementations, R of formula (III) 1 R 2 R 3 and R 4 Each of them is independently hydrogen or C1-C 10 Alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl); preferably methyl, ethyl, or propyl (and in some embodiments, each is methyl).

[0145] In some implementations of formula (III), T is derived from formula R. a 2J、(R a )4J2 or (R a )6J3 represents, where J is C, Si, or Ge, and each R a Independently hydrogen or C1 to C 20 Hydrocarbon group. In some implementations, the two R groups... a It can form cyclic structures including unsubstituted fully saturated, partially saturated, or aromatic rings. In some embodiments, T is selected from CH2, CH2CH2, C(CH3)2, CPh2, SiMe2, SiEt2, SiPh2, SiMePh, SiEtPh, SiMeEt, Si(CH2)3, Si(CH2)4, or Si(CH2)5. In some embodiments, T is SiMe2, SiEt2, or SiMeEt.

[0146] In some implementations, R of formula (III) 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 and R 10One or more of them are independently hydrogen, hydrocarbon, silyl hydrocarbon, alkoxy, halogen or siloxy.

[0147] In some embodiments of formula (III), M is a Group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf). In some embodiments, each X is independently a halogen group, such as chlorine. In 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, hydrogen, chlorine, fluorine, bromine, iodine, trifluoromethanesulfonate, dimethylamino, diethylamino, dipropylamino, and diisopropylamino. In some embodiments, each X is chlorine.

[0148] In some embodiments of formula (III), (1) M is Zr or Hf, (2) X is chlorine, (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 It is independently hydrogen or substituted or unsubstituted C1-C 10 Alkyl, (5)R 7 and R 8 R 8 and R 9 or R 9 and R 10 At least one pair of the rings are connected to form a substituted or unsubstituted fully saturated ring fused with the indenyl ring shown in formula (III), and (6)R 1 R 2 R 3 and R 4 It is methyl, ethyl, or propyl, on its own.

[0149] In some embodiments of formula (III), the second catalyst is: .

[0150] Alternatively, the second catalyst may be an analogue of the catalyst just shown, wherein ZrCl2 is replaced by ZrMe2 (i.e., the catalyst may be a dimethylzirconium analogue of the catalyst just shown). Additionally or alternatively, the second catalyst in various embodiments may be based on the catalyst formula just shown, except that any one or more methyl side chains on the cyclopentadienyl structural moiety are C2-C... 10 Alkyl (preferably ethyl or propyl) substitution.

[0151] In other embodiments, the second catalyst of formula (III) can be described as above, except that in these embodiments, R 7 and R 8 R 8 and R 9 or R 9 and R 10 At least one pair of substituted or unsubstituted aromatic rings in formula (III) are connected to form fused to the indenyl ring, rather than R. 7 and R 8 R 8 and R 9 or R 9 and R 10 At least one pair of the rings are connected to form a substituted or unsubstituted fully saturated ring fused with the indenyl ring shown in formula (III). Therefore, specific examples of catalysts according to such embodiments include:

[0152]

[0153] Alternatively, any one or more methyl side groups on the cyclopentadienyl structural moiety in the catalyst formula just shown can be C2-C. 10 Alkyl (preferably ethyl or propyl).

[0154] Activator

[0155] The terms "co-catalyst" and "activator" are used interchangeably here.

[0156] The catalyst systems described herein may include one or more catalyst compounds as described above and activators such as aluminoxanes or noncoordinate anions, and may be formed by combining the catalyst compounds described herein with activators in any manner known in the literature, including combining them with a support such as silica. The catalyst systems may also be added to or generated in solution polymerization or bulk polymerization (in monomers). The catalyst systems disclosed herein may have one or more activators and one, two, or more catalyst components. An activator is defined as any compound that can activate any of the above-described catalyst compounds 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 type co-catalysts. Suitable activators may include aluminoxane compounds, modified aluminoxane compounds, and ionized anion precursor compounds that abstract reactive, σ-bonded metal ligands, thereby cationizing the metal compound and providing a noncoordinated or weakly coordinated anion, such as a noncoordinated anion, to balance the charge.

[0157] In some embodiments, the catalyst system includes an activator and a catalyst compound of formula (I), formula (II) and / or formula (III).

[0158] Aluminoxane activator

[0159] Aluminoxane activators are used as activators in the catalyst system described herein. Aluminoxanes typically contain -Al(R...) a’’’ Oligomeric compounds with )-O- subunits, wherein R a’’’ It is an alkyl group. Examples of aluminum oxanes include methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, and isobutylaluminoxane. Alkylaluminoxanes and modified alkylaluminoxanes are suitable as catalyst activators, for example, when the ligand that can be abstracted is alkyl, halogen, alkoxy, or amino (amide). Mixtures of different aluminum oxanes and modified aluminum oxanes can also be used. Visually transparent methylaluminoxanes can be used. Turbid or gelled aluminum oxanes can be filtered to prepare a clear solution or 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 Methylaluminoxane Type 3A, covered by U.S. Patent No. 5,041,584, which is incorporated herein by reference). Another useful aluminoxane is solid polymethylaluminoxane, as described in US 9,340,630, US 8,404,880 and US 8,975,209, which are incorporated herein by reference.

[0160] When the activator is an aluminoxane (modified or unmodified), and in at least one embodiment, an activating dose of up to 5,000 molar excess Al / M relative to the catalyst compound (per metal catalytic site) can be used. The minimum activator-to-catalyst compound ratio can be 1:1 molar ratio. Optional ranges may include about 1:1 to about 500:1, or about 1:1 to about 200:1, or about 1:1 to about 100:1, or about 1:1 to about 50:1.

[0161] In an alternative embodiment, the polymerization method described herein uses little or no aluminum oxane. For example, the aluminum oxane may be present at zero molar percentage, or alternatively, the aluminum oxane may be present at a molar ratio of aluminum to the catalyst compound transition metal of less than 500:1, for example less than 300:1, for example less than 100:1, for example less than 1:1.

[0162] Ionized / noncoordinated anion activators

[0163] The term "noncoordinate anion" (NCA) refers to an anion that is not coordinated to the cation or is only weakly coordinated to the cation, thus remaining sufficiently unstable 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, this anion does not transfer anionic substituents or fragments to the cation, causing it to form neutral transition metal compounds and neutral byproducts from the anion. Noncoordinate anions that can be used according to this disclosure are anions that are compatible, stabilize the transition metal cation at +1 in the sense of balancing its ionic charge, and still retain sufficient instability to allow displacement during polymerization. Suitable ionizing activators may include NCAs, such as compatible NCAs. The use of ionizing activators (neutral or ionic) 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.

[0164] For a description of suitable activators and combinations of activators, as well as activator and catalyst compounds, and the relative amounts of optional chain transfer agents used 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] , the description of which is incorporated herein by reference (including various descriptions incorporated herein by reference, such as paragraphs

[00119] on page 72 to paragraph

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

[00177] on page 72 to paragraph

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

[0165] Furthermore, the catalyst system of this disclosure may include a metal hydrocarbon alkenyl chain transfer agent represented by the following formula:

[0166]

[0167] Each R' can be independently C1-C 30 The hydrocarbon group, and / or each R'' can independently be a C4-C group with a terminal vinyl group. 20 Hydrocarbon alkenyl; and v can be from 0.1 to 3.

[0168] carrier material

[0169] In the embodiments described herein, the catalyst system may include an inert support material. The support material may be a porous support material, such as talc, and inorganic oxides. Other support materials include zeolites, clay, organoclay, or another organic or inorganic support material, or mixtures thereof.

[0170] The support material can be an inorganic oxide. The inorganic oxide can be in a finely fragmented form. Suitable inorganic oxide materials for the catalyst system used herein can include Group 2, 4, 13, and 14 metal oxides such as silica, alumina, and mixtures thereof. Other inorganic oxides that can be used alone or in combination with silica or alumina can be magnesium oxide, titanium oxide, or zirconium oxide. However, other suitable support materials can be used, for example, finely fragmented functionalized polyolefins such as finely fragmented polyethylene. Examples of suitable supports can include magnesium oxide, titanium oxide, zirconium oxide, montmorillonite, layered silicates, zeolite, talc, and clay. Furthermore, combinations of these support materials can 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, silica / clay, or mixtures thereof.

[0171] Carrier materials, such as inorganic oxides, can have a thickness of approximately 10 μm. 2 / g to approximately 700m 2 / g surface area, approximately 0.1cm 3 / g to approximately 4.0cm 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 / g. 2 / g to approximately 500m 2 / g, pore volume approximately 0.5cm³ 3 / g to approximately 3.5cm 3 / g, with an average particle size of 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 400m 2 / g, pore volume is approximately 0.8cm³ 3 / g to approximately 3cm 3 / g and the average particle size can be from about 5 μm to about 100 μm. The average pore size of the support material that can be used in this disclosure can be from about 10 Å to about 1000 Å, for example from about 50 Å to about 500 Å, for example from about 75 Å to about 350 Å. In at least one embodiment, the support material is amorphous silica with high surface area (surface area = 300 m² / g). 2 / gm; pore volume is 1.65 cm³. 3 / gm). For example, suitable silica can be produced by the Davison Chemical Division of WR Grace and Company under the trade name Davison. TM 952 or Davison TM955 brand silica. In other embodiments, DAVISON is used. TM 948. Alternatively, the silica can be, for example, ES-70 that has been calcined (e.g., calcined at 875°C). TM Silica (PQ Corporation, Malvern, Pennsylvania).

[0172] The support material should be dry, i.e., free of or substantially free of adsorbed 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, for example, about 600°C; and held 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 possess at least some reactive hydroxyl (OH) groups to prepare 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.

[0173] A support material with reactive surface groups (e.g., 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 segregated support / activator. In at least one embodiment, a 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.

[0174] 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, or for example, heated at 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.

[0175] A suitable nonpolar diluent is a material in which all reactants used herein (e.g., activators and catalyst compounds) are at least partially soluble and are liquid 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 may also be used, including cycloalkanes, such as cyclohexane, and aromatic compounds, such as benzene, toluene, and ethylbenzene.

[0176] 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).

[0177] polyethylene copolymer

[0178] This disclosure provides polyethylene copolymers having a combination of low density, high melt index, long-chain branching, broad orthogonal composition distribution (BOCD), and bimodal composition distribution. The combination of long-chain branching and BOCD can be particularly advantageous for achieving a strong balance between excellent mechanical properties and excellent processability. Therefore, polyethylene copolymers and their films can be formed through the commercially desirable polymerization and extrusion of polyethylene copolymers.

[0179] Therefore, the polyethylene copolymers of the various embodiments described herein generally exhibit one or more of the following properties:

[0180] • Density is between approximately 0.910 and approximately 0.925 g / cm³ 3 Within the range, for example from 0.910, 0.912, 0.914, 0.915, 0.916, 0.917, 0.918, 0.919 or 0.92 g / cm³ 3 The lower limit of any one of them is 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, approximately 0.915 g / cm³. 3 Approximately 0.920 g / cm³ 3 Or approximately 0.918 g / cm³ 3 Approximately 0.922 g / cm³ 3 This considers any combination of lower and upper limits (provided the upper limit is greater than the lower limit), for example, approximately 0.916 to approximately 0.921 g / cm³. 3 For example, approximately 0.918 to approximately 0.92 g / cm³ 3 .

[0181] • Melt index (MI, also known as I² or I², taking into account the 2.16 kg load used in the test) 2.16(Approximately 0.1 g / 10 min (ASTM D1238, 190°C, 2.16 kg), for example from 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) The range from the lower limit of any of the following values ​​to the upper limit of any of the following values: 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 4, or 5 g / 10 min. This paper considers the range from any lower limit to any upper limit (provided that the upper limit is greater than the lower limit), for example, about 0.1 to about 1.2 g / 10 min, about 0.3 to about 1.1 g / 10 min, about 0.7 to about 1.1, 1.2, or 1.3 g / 10 min, etc.

[0182] Alternatively, the polyethylene copolymer can be a polymerization product of ethylene monomer and one or more olefin comonomers, such as α-olefin comonomers. α-olefin comonomers may contain 3 to 12 carbon atoms, or 4 to 10 carbon atoms, or 4 to 8 carbon atoms. The olefin comonomer may 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-vinylide-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 cycloolefins. In some embodiments, a combination of olefin comonomers is utilized. In some embodiments, the olefin comonomer is selected from 1-butene and 1-hexene. The olefin comonomer content of the polyethylene copolymer can range 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 about 80, 85, 88, 90, 91, 92, 92.5, 93, 93.5 or 94% by weight to an upper limit of about 90, 91, 92, 92.5, 93, 93.5, 94, 94.5, 95, 95.5, 96, 97, 99 or 99.9% by weight). This article considers a range from any of the aforementioned lower limits to any of the aforementioned upper limits (e.g., about 85 to about 93% by weight, such as about 87 to about 90% by weight of ethylene-derived units and the balance of olefin comonomer-derived content).

[0183] Molecular weight properties

[0184] Polyethylene copolymers may also have a molecular weight distribution (MWD, defined in the context of polymer properties as Mw / Mn, sometimes also called polydispersity index (PDI)) of about 5 to about 15. MWD or PDI may also be in the range of a lower limit of about 5, 5.1, 5.2, 5.3, 5.4, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, or 9 to an upper limit of about 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 12, 13, 14, or 15, wherein any of the aforementioned lower limits to any of the aforementioned upper limits are considered, provided that the upper limit of the range is greater than the lower limit (e.g., in the range of 7 to 15, such as 8 to 12 or 7 to 10, etc.).

[0185] The weight-average molecular weight (Mw) of the polyethylene copolymers in various embodiments can be in the range of about 70,000 to about 200,000 g / mol, for example about 75,000, about 80,000 or about 90,000 g / mol to about 125,000, 130,000, 135,000, 140,000, 145,000 or 150,000 g / mol, for example about 90,000 to about 130,000 g / mol, for example about 120,000 to about 130,000 g / mol, wherein the range from any of the foregoing lower limit to any of the foregoing upper limit is taken into consideration.

[0186] 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 15,000 g / mol, 20,000 g / mol, 25,000 g / mol or about 30,000 g / mol, for example about 12,000 to about 15,000 g / mol, wherein the range from any of the aforementioned lower limits to any of the aforementioned upper limits is taken into consideration.

[0187] The Z-average molecular weight (Mz) of the polyethylene copolymers in various embodiments can be in the range of about 300,000 to about 1,200,000 g / mol, for example, any one of about 300,000; 400,000; 500,000; 600,000 or 650,000 to about 750,000; 800,000; 850,000; 900,000; 950,000; 1 The range is 1,000,000; 1,100,000; or 1,200,000 g / mol, wherein this document also considers the range from any of the aforementioned lower limits to any of the aforementioned upper limits (e.g., in the range of about 650,000 to about 750,000 g / mol, or about 400,000 to about 800,000 g / mol, or about 500,000 to about 1,000,000 g / mol, etc.).

[0188] The distribution and fractions of molecular weight (Mw, Mn, Mw / Mn, etc.) and branching index (g'vis) were determined using high-temperature gel permeation chromatography (Polymer Char GPC-IR) equipped with an IR5 infrared detector based on a multi-channel bandpass filter, an 18-angle Wyatt Dawn Heleos light scattering detector, and a 4-capillary viscometer with a Wheatstone bridge configuration. Three Agilent PLgel 10 μm mixed-B LS columns were used to provide polymer separation. 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 with 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 delivery lines, columns, and viscometer detector, was loaded into an oven maintained at 145 °C. Weigh the polymer sample and seal it in a standard finger tube, adding 80 μL of flow marker (heptane). After inserting the finger tube into the autosampler, the polymer automatically dissolves in the instrument with 8 mL of added TCB solvent. Dissolve the polymer at 160 °C with continuous vibration for approximately 2 hours. The concentration (c) at each point in the chromatogram is calculated using the following equation from the baseline IR5 broadband signal intensity (I): c = βI, where β is the mass constant. Mass recovery is calculated by the ratio of the integral area of ​​the concentration chromatography to the elution volume, and the injection mass is equal to the predicted concentration multiplied by the injection loop volume. Conventional molecular weight (IR MW) is determined by combining a universal calibration relationship with column calibration using a series of monodisperse polystyrene (PS) standards ranging from 700 to 10 million g / mol. MW is calculated for each elution volume using the following equation:

[0189]

[0190] Variables with the subscript "PS" represent polystyrene, while those without subscripts are the test samples. In this method, α... PS =0.67 and K PS=0.000175, while α and K are for ethylene-hexene copolymers, calculated as by empirical formulas (Sun, T. et al. Macromolecules 2001, 34, 6812), where α = 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 was determined by the ratio of the intensity of an IR5 detector corresponding to the CH2 and CH3 channels, which were calibrated using a series of PE and ethylene-hexene homopolymer / copolymer standards, the nominal values ​​of which were predetermined by NMR or FTIR. Here, concentrations are expressed in g / cm³. 3 Molecular weight is expressed in g / mol, and intrinsic viscosity (and therefore K in the Mark-Houwink equation) is expressed in dL / g. Unless otherwise stated herein, any molecular weight value should be assumed to have been determined using IR.

[0191] Light scattering MW: For any molecular weight value indicated by LS determination, the LS molecular weight (M) at each point in the chromatogram is determined by analyzing the LS output using a Zimm model for static light scattering.

[0192] .

[0193] Here, ΔR(θ) is the excess Rayleigh scattering intensity measured at scattering angle θ, c is the polymer concentration determined by IR5 analysis, A2 is the second virial coefficient, P(θ) is the shape factor of the monodisperse random coil, and Ko is the optical constant of the system.

[0194] ,

[0195] Where N A is Avogadro's constant, and (dn / dc) is the refractive index increment of the system. The refractive index n of TCB at 145°C and λ=665nm is 1.500. For the purposes of this disclosure and the appended claims, the (dn / dc) of the ethylene-hexene copolymer is 0.1048.

[0196] Viscosity-average molecular weight (M) V Specific 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 sensor, located between the two sides of the bridge, measures the pressure difference. The specific viscosity η of the solution flowing through the viscometer is... s Calculated from their outputs. The intrinsic viscosity [η] at each point in the chromatogram is given by the equation [η] = η s / c is calculated, where c is the concentration and is determined by the IR5 broadband channel output. The viscosity (MW) at each point is calculated as follows: , where α ps The value is 0.67 and Kps is 0.000175. The average intrinsic viscosity of the sample is [η]. 平均 Calculated using the following formula:

[0197]

[0198] The sum is taken from all chromatogram slices i between the integration limits.

[0199] The branching index (g'vis) can be calculated using the output of the GPC-IR5-LS-VIS method as follows. First, it should be noted that g' or g'vis can generally be considered as the ratio of the intrinsic viscosity of the polymer to the intrinsic viscosity of a linear polymer of the same molecular weight and composition: g' = [η 聚合物 ] / [η 基准 ], where [η 聚合物 ] is the intrinsic viscosity of the polymer under study, and [η] 基准 The 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 a polymer increases the viscosity of its solution relative to a linear polymer of the same molecular weight and composition under the same temperature and pressure conditions.

[0200] Based on this principle, [η] in the simplified relation above 聚合物 The value [η] can be considered as the weight-average intrinsic viscosity of the sample. 平均 It is calculated using the following formula (where [η]). avg [η] 平均 ):

[0201]

[0202] The sum is taken from all chromatographic slices i between the integration limits. The branching index g'vis is defined for linear reference materials as follows: Where Mv is the viscosity-average molecular weight based on the molecular weight determined by LS analysis, and K and This is for a reference linear polymer; for the purposes of this disclosure, K is the same as described above for linear polyethylene polymers.

[0203] The branching index g'vis can be equivalently referred to as g' vis平均 This reflects that it is the average of g' measured at each of multiple discrete concentration slices. For example, refer to Figure 1The graph shows g' values ​​for various polyethylene copolymers plotted as a function of logM (log of molecular weight). This means that g' values ​​can be calculated for a given molecular weight group of polymer chains in a polyethylene copolymer composition. The calculation above provides g' as a weighted average of these multiple g' values. vis平均 And when comparing this value between two different copolymer compositions, g' vis平均 This can be considered a good relative indicator of the existence of long-chain branching, where g' vis平均 The lower the value, the greater the branching of the long chain.

[0204] Wide orthogonal composition distribution

[0205] "BOCD" refers to a broad orthogonal compositional distribution, in which the comonomers of a copolymer are primarily bound within the high molecular weight chains of the polyolefin polymer or composition. For example, the distribution of short-chain branches can be measured using a temperature rise elution fractionation (TREF) combined with a light scattering (LS) detector to determine the weight-average molecular weight of molecules eluted from a TREF column at a given temperature. A combination of TREF and LS (TREF-LS) provides information about the breadth of the compositional distribution and whether the comonomer content increases, decreases, or becomes uniform along different molecular weight chains of the polymer. BOCD has been described, for example, in U.S. Patent No. 8,378,043, column 3, lines 34 through 4, lines 19; and in U.S. Patent No. 8,476,392, lines 43 through 16, lines 54.

[0206] The BOCD properties of the polyethylene copolymers of the present invention can be quantified by the composition distribution width index (CDBI). For example, the polyethylene copolymers described herein may have very low composition distribution width index (CBDI) values, wherein the polyethylene copolymers may have CBDI values ​​in the range of a lower limit of any one of about 5%, 10%, 15%, 20%, 22%, 23%, 24%, 25%, or 26% to an upper limit of any one of about 30%, 31%, 32%, 33%, 34%, 35%, 40%, 45%, or 50%; wherein the range from any of the aforementioned lower limits to any of the aforementioned upper limits is considered herein (e.g., about 5% to about 35%, for example, about 20% to about 30%).

[0207] CDBI is defined as the weight percentage of copolymer molecules whose comonomer content is within + / - 50% of the median comonomer mol% value, as described on pages 18-19 of WO 1993 / 003093 in conjunction with Figure 17 therein. This means that for a copolymer with a median comonomer mol% value (Cmed) of 8 mol% comonomer on the polymer chain, CDBI is the weight percentage of the copolymer chain having a comonomer mol% between (0.5 × Cmed) and (1.5 × Cmed). In this example, CDBI is the weight percentage of the copolymer chain with a comonomer mol% between (0.5 × 8) and (1.5 × 8) or a comonomer content between 4 mol% and 12 mol%. WO 1993 / 003093 also describes a method for determining the weight fraction vs. composition curve (i.e., composition distribution curve) of the polymer using chromatography and C13 NMR and determining the median comonomer composition Cmed from it, referring to Figures 16 and 17 of that disclosure. The CDBI of copolymers can be readily determined using techniques for separating individual fractions of copolymer samples. One such technique is to use temperature rise elution fractionation (TREF) to generate solubility distribution profiles, as described in WO 1993003093 (in this respect, it also refers to Wild et al., J. Poly. Sci., Poly. Phys. Ed., Vol. 20, p. 441 (1982) and U.S. Patent No. 5,008,204). All three of the aforementioned publications are incorporated herein by reference.

[0208] Solubility profiles of the copolymer can be generated first using data obtained from TREF techniques (such as those described, for example, in the publication just cited). These solubility profiles are graphs showing the weight fraction of the dissolved copolymer as a function of temperature. This graph can be converted into a weight fraction versus composition profile. To simplify the correlation between composition and elution temperature, weight fractions smaller than 15,000 can be ignored. These low weight fractions typically represent a negligible portion of the ethylene polymers disclosed herein.

[0209] Optionally or additionally, the composition distribution can be determined by T. 75 -T 25 Value representation, where T 25 It is the temperature at which 25% of the eluted polymer is obtained, T 75 The temperature at which 75% of the eluted polymer is obtained is described in the TREF experiments (and plotting of eluted polymer molecular weight vs. elution temperature) as described in US2019 / 0119413 (particularly in its first paragraph, which is incorporated herein by reference). A narrow compositional distribution is reflected in the T... 75 -T 25 The smaller differences in values, while the wider distribution is reflected in T. 75 -T 25Significant differences in values ​​indicate substantial differences in crystallinity between fractions of the polymer composition. It should also be noted that in cases where there are differences between the actual TREF procedure described in US2019 / 0119413 and the TREF procedures described in WO 1993003093, US 5,382,630, and / or US 5,008,204, the TREF procedure described in US2019 / 0119413 should be used. (It should be noted that the solubility distribution curve of the CDBI curve and the T curve generated by the auxiliary TREF procedure are...) 75 -T 25 Eluted molecular weight vs. elution temperature, in their generation and CDBI and T 75 -T 25 (There may be appropriate differences in the analysis.) Finally, combining T... 75 -T 25 The resulting TREF curve (eluted polymer molecular weight vs. elution temperature) can be further processed as follows:

[0210] 1. The instrument's solvent-only response can be generated and subtracted from the sample's TREF curve. The solvent-only response can be generated by running the same method used for the polymer sample, typically prior to that method, but without adding any polymer to the sample vial; using the same solvent reservoir as the polymer sample, and without replenishing with fresh solvent; and within a reasonable timeframe of the polymer sample run.

[0211] 2. The temperature axis of the TREF curve can be appropriately shifted to correct for the IR signal delay caused by the column-to-detector volume. This volume can be obtained as follows: first, the injection valve loop is filled with a ~1 mg / ml HDPE resin solution; then, the loop volume is loaded into the same position within the column where the sample was loaded for TREF analysis; then, the hot solution is allowed to flow directly to the detector at a constant flow rate of 1 ml / min using an isothermal method; finally, the time it takes for the HDPE probe peak to appear in the IR signal after injection is measured. Therefore, the delay volume (ml) is equivalent to the time (min).

[0212] The curve can be baseline corrected and an appropriate integration limit can be selected; and the curve can be normalized so that the area of ​​the curve is 100 weight.

[0213] For example, in the polyethylene copolymer of the present invention, the broad distribution is reflected in T 75 -T 25The value is significantly different from 25°C, for example, within the range from the lower limit of any one of 25, 26, 27, 28, 29, 30, 31, 32 or 33°C to the upper limit of any one of 36, 37, 38, 39, 40, 41, 42, 43, 44, 45 or 50°C, where the range from any of the aforementioned lower limits to any of the aforementioned upper limits is taken into consideration (e.g., 25°C to 50°C, such as 25°C to 40°C or 30°C to 38°C).

[0214] Other polyethylene copolymer rheology

[0215] In addition to the melt index (MI) values ​​mentioned earlier, polyethylene copolymers can also have high load melt index (HLMI) ranging from a lower limit of about 20, 40, 60, 65, 70, 75, 80 or 85 g / 10 min to an upper limit of about 120, 110, 100, 95, 90, 85 or 80 g / 10 min (the 21.6 kg load used in the identification test, also known as I...). 21 or I 21.6 This document considers the range from any of the aforementioned lower limits to any of the aforementioned upper limits (e.g., about 60 to about 100 g / 10 min, or about 80 to about 90 g / 10 min). The term "high load melt index" ("HLMI") is the number of grams extruded in 10 minutes under a standard load (21.6 kg) and is inversely proportional to viscosity. As provided herein, HLMI (I 21 ) Measured according to ASTM D1238 (190℃ / 21.6kg), and sometimes also referred to as I 21 or I 21.6 .

[0216] The polyethylene copolymer may also have a melt index ratio (MIR, defined as I) ranging from the lower limit of any one of 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 71, 72, 73, 74 or 75 to the upper limit of any one of 80, 85, 90, 95, 96, 97, 98, 99, 100, 105, 110, 120, 130, 140 or 150. 21.6 / I 2.16 (ratio), this article considers the range from any of the aforementioned lower limits to any of the aforementioned upper limits (e.g., 60 or 70 to 105, or 90 to 97 or 70 to 80, etc.).

[0217] As noted, the polyethylene copolymers of the various embodiments also exhibit moderately long-chain branching; less than existing LDPEs (produced in free radical polymerization, with large variations in polymer branching direction and little control over it), but greater than typical metallocene LLDPEs. This moderate amount of LCB can be achieved through, for example, high MIR (as described above) and / or specific rheological properties (e.g., η) as shown by data obtained through SAOS experiments. 0.01 / η 100 The proportions of complex viscosities recorded at shear rates or frequencies of 0.01 and 100 rad / s, respectively, are used to demonstrate this.

[0218] For example, polyethylene copolymers may have a high shear thinning index (STI 0.1 / 100). The STI 0.1 / 100 data measures the ratio of complex viscosities at 0.1 and 100 rad / s. The STI 0.1 / 100 data for the polyethylene copolymers of various embodiments may be greater than 5, for example greater than 6 or even higher. For example, STI 0.1 / 100 may be in the range from the lower limit of any one of about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55 to the upper limit of any one of about 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, or 10, wherein the range from any of the aforementioned lower limits to any of the aforementioned upper limits is also considered (e.g., about 10 to about 50, for example about 20 to about 40, for example about 25 to about 35).

[0219] In addition, LCB, or branching index (referred to as g' in this paper), vis Or it can also be called g' vis平均 The value can be less than 1, for example, in the range from the lower limit of any one of about 0.67, 0.68, 0.69, 0.70 or 0.71 to the upper limit of any one of about 0.73, 0.74, 0.75, 0.76, 0.77, 0.78, 0.79, 0.80, 0.83, 0.85, 0.87 or 0.9, where the range from any of the aforementioned lower limits to any of the aforementioned upper limits is taken into account (e.g., 0.71 to 0.73 or 0.65 to 0.75).

[0220] Alternatively, the polyethylene copolymer may have a G' / G''@0.1s ratio of about 0.5 or greater, or about 1.0 or greater, or about 1.25 or greater, for example, within the range of the lower limit of any one of 0.5, 0.75, 1.0, 1.25 or 1.5 to the upper limit of any one of 2.0, 2.5, 3.0, 3.5, 4.0 or 4.5. -1 Value (which is in 0.1s) -1 The ratio of shear storage modulus (Pa) to shear loss modulus (Pa).

[0221] Rheological data, such as "complex shear viscosity (η*)", reported in Pascals seconds, 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.

[0222] 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 before the compression-molded specimen is inserted onto the parallel plates. To determine the viscoelastic behavior of the sample, frequency scans ranging from 0.01 to 628 rad / s can be performed at a constant strain without affecting the measured viscoelastic property at 190 °C. The scan frequencies are equally spaced on a logarithmic scale, such that 5 frequencies are probed every decimal. Depending on the molecular weight and temperature, a strain of 3% can be used to verify the linearity of the response. A nitrogen gas flow is circulated through the oven to minimize chain extension or crosslinking during the experiment. The sample can be compression-molded at 190 °C without a stabilizer. Sinusoidal shear strain can be applied. If the strain amplitude is sufficiently small, the material exhibits linear behavior. As those skilled in the art will appreciate, the resulting steady-state stress will also oscillate sinusoidally at the same frequency, but with a phase shift δ relative to the strain wave. Stress leads strain δ. For a purely elastic material, δ = 0. o (Stress and strain are in phase), and for purely viscous materials, δ=90 o (Stress leads strain 90) o (Although stress and strain rate are in phase). For viscoelastic materials, 0 < δ < 90°. Complex viscosity, loss modulus (G"), and storage modulus (G') as functions of frequency are provided by small-amplitude oscillatory shear tests. Dynamic viscosity is also called complex viscosity or dynamic shear viscosity. The phase angle or loss angle δ is the arctangent of the ratio of G" (shear loss modulus) to G' (shear storage modulus). The shear thinning slope (STS) can be measured by plotting the logarithm (base 10) of dynamic viscosity against the logarithm (base 10) of frequency. The slope is 100 s. -1 The log (dynamic viscosity) at the frequency and 0.01s -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:

[0223] .

[0224] The five parameters in this model are: η0, zero-shear viscosity; λ, relaxation time; n, power-law exponent; η∞, infinite-rate viscosity; and a, transition exponent. Zero-shear viscosity, when the dynamic viscosity is frequency-independent, is the value at a plateau in the Newtonian region of the flow curve at low frequencies. 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 because, on a 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 frequency-independent.

[0225] In addition to dynamic viscosity and complex viscosity (each in Pascal-seconds), various other parameters were collected at each frequency scan in the SAOS experiments, including storage modulus (Pa), loss modulus (Pa), complex modulus (Pa), tan(δ), and phase angle. Plotting the phase angle against the complex shear modulus using rheological experiments yielded Van Gurp Palmen plots, which can be used to extract information about molecular characteristics, such as linear vs. long-chain branched chains, type of long-chain branching, and polydispersity (Dealy, MJ, Larson, RG, "Structure and Rheology of Melted Polymers", Carl Hanser Verlag, Munich 182-183 (2006)). It has also been suggested that Van Gurp Palmen plots can be used to reveal the presence of long-chain branching in polyethylene. See Trinkle, S., Walter, P., Friedrich, C. "Van Gurp-Palmen Plot II-Classification of long chain branched polymers by their topology", in 41 Rheol. Acta 103-113 (2002).

[0226] The "shear thinning index" (reported as a unitless number) is characterized by a decrease in complex viscosity with increasing shear rate. In this paper, shear thinning can be determined as the ratio of complex viscosity at a frequency of 0.01 rad / s to complex viscosity at a frequency of 100 rad / s.

[0227] Blends and Additives

[0228] In some embodiments, the polyethylene copolymer may be formulated (e.g., blended) with one or more other polymer components. In some embodiments, those other polymer components are α-olefin polymers, such as polypropylene or polyethylene homopolymers and copolymer compositions. In some embodiments, those other polyethylene polymers are selected from linear low-density polyethylene, high-density polyethylene, medium-density polyethylene, low-density polyethylene, and other differentiated polyethylenes.

[0229] In some embodiments, the formulated blends may contain additives, the composition of which is determined based on the end use of the formulated blends. In some embodiments, the additives are selected from fillers, antioxidants, phosphites, anti-adhesion additives, tackifiers, UV stabilizers, heat stabilizers, antiblocking agents, release agents, antistatic agents, pigments, colorants, dyes, waxes, silica, processing aids, neutralizers, lubricants, surfactants, and nucleating agents. In some embodiments, the additives are present in amounts from 0.1 ppm to 5.0% by weight.

[0230] The polyethylene copolymers of this disclosure may 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 (e.g., some embodiments of films, particularly blown films, may be free of or substantially free of polymer processing aids, particularly fluorinated polymer processing aids, where "substantially free of" means free of any intentionally added components, but allows up to 100 ppm of such components (one or more) as impurities).

[0231] manufactured products

[0232] The polyethylene copolymers disclosed herein are particularly suitable for manufacturing articles for end-use, such as films (e.g., formed by lamination, extrusion, co-extrusion, casting, and / or blow molding); and other articles that can be formed, for example, by rotational molding or injection molding. The polyethylene copolymers can be formed into articles through cast film extrusion, blown film extrusion, rotational molding, or injection molding processes. In some embodiments, the polyethylene copolymers can be used in blend form.

[0233] Furthermore, the polyethylene copolymers of this disclosure have been found to provide excellent tear properties and dart impact strength, thereby overcoming the key weaknesses of LDPE. Additionally, compared to conventional LLDPE, the polyethylene copolymers of this disclosure can provide films formed with reduced motor loads and melt pressures (which increase production capacity) due to improved flow behavior. For example, reductions in melt pressure and melt temperature can be provided during film manufacturing. The films of this disclosure are particularly suitable as shrink wrap films (improved by the presence of LCB and BOCD in the polyethylene copolymers of this disclosure).

[0234] The polyethylene copolymers (or blends thereof) disclosed herein can be used in forming operations such as film, sheet, and fiber extrusion and co-extrusion, as well as blow molding, injection molding, and rotational molding. Films include blow-molded or cast films formed by co-extrusion or lamination, which can be used as shrink films, attachment films, stretch films, sealing films, oriented films, fast food packaging, heavy-duty bags, grocery bags, baked and frozen food packaging, pharmaceutical packaging, industrial liners, diaphragms, etc., in 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 in the manufacture of filters, diaper fabrics, medical clothing, geotextiles, etc. Extruded articles include medical tubing, wire and cable coatings, pipes, geomembranes, and pond liners. Molded articles include single and multi-layer structures in the form of bottles, tanks, large hollow articles, rigid food containers, and toys.

[0235] 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 by planar or tubular film methods, followed by orientation in a uniaxial direction or two mutually perpendicular directions in the plane of the film. One or more of the film layers can be oriented laterally and / or longitudinally to the same or different degrees. This orientation can be performed before or after the individual layers are assembled. For example, a layer of polyethylene copolymer (or blend thereof) can be extruded-coated or laminated onto an oriented polypropylene layer, or the 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, even further oriented, the combination.

[0236] The membrane includes single-layer or multi-layer membranes. Specific end-use membranes include, for example, blown films, cast films, stretched films, stretched / cast films, stretched adhesive films, stretched hand-rolled films, mechanically stretched wraps, shrink films, shrink wrap films, greenhouse films, laminates, and laminated films. Exemplary membranes can be prepared by any conventional method known to those skilled in the art, such as by techniques used to prepare blown, extruded, and / or cast stretched and / or shrink films (including shrink-on-shrink applications).

[0237] In at least one embodiment, the multilayer film (or multilayer membrane) can be formed by a suitable method. The total thickness of the multilayer film can be varied based on the desired application. A total film thickness of 5-100 μm, for example 10-50 μm, is suitable for most applications. Those skilled in the art will appreciate that the thickness of the individual layers of the multilayer film can be adjusted according to the desired end-use performance, the polymer(s) used, the equipment production capacity, and other factors. The material forming each layer can be co-extruded through a co-extrusion feed section and a die assembly to produce a film having two or more layers adhered together but comprising different components. Co-extrusion can be suitable 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.

[0238] In at least one embodiment, the membrane of this disclosure has an average 1% secant modulus (M) at 23°C of about 25,000 psi to about 40,000 psi, such as about 27,000 psi to about 40,000 psi, such as about 28,000 psi to about 38,000 psi, such as about 28,000 psi to about 30,000 psi according to ASTM D882-18.

[0239] The membrane of this disclosure may have an Elmendorf Tear value according to ASTM D-1922. In at least one embodiment, the membrane has an Elmendorf Tear (MD) value of at least 30 g / mil, for example at least 50 g / mil to about 200 g / mil, for example about 100 g / mil to about 180 g / mil, for example about 160 g / mil to about 180 g / mil. In at least another embodiment, the membrane has an Elmendorf Tear (TD) value of at least 300 g / mil, for example about 400 g / mil to about 600 g / mil, for example about 410 g / mil to about 460 g / mil, for example about 440 g / mil to about 470 g / mil.

[0240] The membranes of this disclosure may have 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.

[0241] The shrinkage rate of the membrane (reported as a percentage) can be measured by cutting circular specimens from the membrane using a 100 mm die. The specimens can be marked along their respective orientations, dusted with talcum powder, and placed on preheated talcum-coated ceramic tiles. The specimens can then be heated using a heat gun (e.g., HG-501A type) for approximately 10 to 45 seconds, or until any dimensional change ceases. The value is the average of three specimens. A negative shrinkage value indicates dimensional expansion after heating compared to its preheated size. The membranes of this disclosure may have a shrinkage % (longitudinal) of about 40% to about 90%, for example about 60% to about 80%, for example about 60% to about 70%. The membranes of this disclosure may have a shrinkage % (transverse) of about 0% to about 6%, for example about 0.5% to about 5%, for example about 2% to about 5%.

[0242] In some embodiments, according to modified BSI CEN 14477, the membrane may have a rupture puncture energy (also known as puncture rupture energy) of at least about 5 in-lbs / mil, for example at least about 10 in-lbs / mil, for example at least about 15 in-lbs / mil, for example in the range of about 10, 11, 12 or 13 to about 20 or 25 in-lbs / mil.

[0243] 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.

[0244] In at least one embodiment, the membrane of this disclosure has a clarity of about 80% or more, about 85% or more, or about 90% or more as determined by ASTM D1746 (defined as regular transmitted light with an axis deflection of less than 0.1 from incident light passing through the membrane sample body).

[0245] In at least one embodiment, the film of this disclosure has a gloss (MD) measured by ASTM D-2457 in the range of about 10 GU or about 15 GU or greater, for example, in the range of 10, 15, 16, 17, 18 or 19 GU to about 25, 26, 27, 28, 29, 30, 35 or 40 GU, wherein a light source is irradiated onto the film surface at an angle of 45° and the amount of reflected light is measured.

[0246] Shrink film

[0247] The compositions disclosed herein can be used to prepare shrink films. Shrink films (also known as heat-shrinkable films) are widely used in industrial and retail bundling and packaging applications. Such films are capable of shrinking when heat is applied to release the stress imposed on the film during or after extrusion. Shrinkage can occur in one direction or simultaneously in both the longitudinal and transverse directions. Conventional shrink films are described, for example, in US7,235,607, which is incorporated herein by reference.

[0248] Industrial shrink film can be used to bundle products on pallets. Typical industrial shrink film is formed to a thickness of approximately 80 to 200 μm in a single-bubble blow extrusion process and provides shrinkage in both directions.

[0249] Retail films can be used for packaging and / or bundling products for consumer use, such as for supermarket goods. These films are typically formed in a single-bubble blow extrusion process to a thickness of approximately 35 μm to 80 μm.

[0250] Films can be used in “shrink-on-shrink” applications. As used herein, “shrink-on-shrink” refers to a method of applying an outer shrink wrap layer around one or more articles that have already been individually shrink-wrapped (here, the “inner layer” of the wrap). In these methods, it may be desirable for the film used to wrap the individual articles to have a higher melting point (or shrinkage point) than the film used for the outer layer. When using this configuration, the desired level of shrinkage can be achieved in the outer layer while preventing the inner layer from melting, shrinking further, or twisting during the outer layer’s shrinkage. Some of the films described herein exhibit sharp shrinkage points when subjected to heat from a heating gun under high-temperature heat setting, suggesting they may be particularly suitable as inner layers in a variety of shrink-on-shrink applications.

[0251] experiment

[0252] Relaxation time and Cross Equation constants: In addition to the SAOS and other parameters described elsewhere in this paper, relaxation time τ and / or Cross Equation values ​​(particularly viscosity, time, and power-law constants) can help indicate the presence of long-chain branching in the polydispersity / MWD and / or the polymer composition (or the polymer composition behaving in a manner that mimics long-chain branched polymers). Relaxation time τ can be determined by the Cross Equation used to model viscosity data collected over a frequency range. Viscosity data collected over a certain frequency range can be fitted using the general form of the Cross Equation (JM Dealy and KF Wissbrun, Melt Rheology and Its Role in Plastics Processing Theory and Applications; Van Nostrand Reinhold: New York, p. 162 (1990)).

[0253]

[0254] where η is the dynamic viscosity, η0 is the finite zero-shear viscosity, η ∞ is the infinite-shear viscosity, τ is the relaxation time at a given input shear frequency γ, and n is the power-law exponent, which can describe the degree of shear thinning. For Newtonian fluids, n = 1 and the dynamic complex viscosity is independent of frequency. For the polymers of interest here, n < 1, such that the enhanced shear thinning behavior is represented by a decrease in n (an increase in (1 - n)). The term η ∞ is 0 from curve fitting, and as a result, the expression reduces to three parameters:

[0255]

[0256] This expression gives the relaxation time when tested at constant strain and constant temperature. As noted, the relaxation time τ in the Cross Model can be associated with the polydispersity and / or long-chain branching in the polymer. For increasing levels of branching (and / or polymer compositions that mimic increasing levels of branching), τ is expected to be higher compared to linear polymers of the same molecular weight. These three Cross parameters - viscosity (η0), time (τ), and power-law (n) constant - can also be labeled as Cross equation constants A1, A2, and A3, respectively.

[0257] General considerations and reagents:

[0258] Unless otherwise noted, all operations were carried out under an inert atmosphere using glovebox techniques. Before use, diethyl ether, pentane, hexane, 1,2-dimethoxyethane, and dichloromethane (Sigma Aldrich) were degassed and dried over 3 Å molecular sieves overnight. n-Butyllithium and methyl iodide in hexane were purchased from Sigma Aldrich and used as received. ZrCl4 was purchased from Strem Chemicals and used as received. Methylaluminoxane was purchased from Grace and used as received.

[0259] Catalyst 1 and Catalyst 2a were synthesized as described below to produce dual metallocene catalyst systems for use in polymerization according to the various embodiments described herein. Catalyst 1 was also used as the sole catalyst compound in the comparative examples, as shown in Tables 1B and 2B. Catalyst 2b was also obtained and used as the single catalyst in the comparative examples shown in Tables 1B and 2B.

[0260] Synthesis:

[0261] Synthesis of Catalyst 1:

[0262] \

[0263] Synthesis of (5,5,8,8-tetramethyl-6,7-dihydro-3H-cyclopentadieno[b]naphthalen-3-yl)lithium

[0264] Adding n-butyllithium (36 mL, 90.0 mmol, 1.01 equivalent) in hexane to a vigorously stirred white suspension of 5,5,8,8-tetramethyl-6,7-dihydro-1H-cyclopentadieno[b]naphthalene (20.18 g, 89.2 mmol, 1.00 equivalent) in diethyl ether (250 mL) at -35 °C yielded a cold, turbid, pale yellow mixture. After stirring for 20 minutes, the reaction turned turbid and bright yellow. The reaction was stirred overnight and then evaporated under vacuum, leaving a dirty white solid. The solid was washed with pentane (100 mL) and filtered to give a bright white solid. The yield was 18.8 g (91%) of bright white powder. 1 H NMR(THF-D8)7.46(s,2H),6.50(t,1H),5.81(dt,1H),1.72(S,4H),1.34(S,12H).

[0265] Synthesis of 3,5,5,8,8-pentamethyl-6,7-dihydro-3H-cyclopentadien[b]naphthalene:

[0266] At -35 °C, lithium (5,5,8,8-tetramethyl-6,7-dihydro-3H-cyclopentadieno[b]naphthyl-3-yl) (6.12 g, 26.3 mmol, 1.0 equivalent) was added to a colorless solution of iodomethane (7.47 g, 52.6 mmol, 2.0 equivalent) in diethyl ether (200 mL), yielding a turbid white mixture. The reaction mixture was stirred overnight at room temperature. 1,2-Dimethoxyethane (6 g) was added to the clear yellow reaction mixture, resulting in the formation of a white precipitate. The solvent was removed under vacuum, leaving a white solid. The product was extracted with pentane (100 mL) and filtered, yielding an amber solution and a white precipitate. The amber solution was dried under vacuum to give a yellow viscous oil. The yield was 18.8 g (91%) of a bright white powder. 1 H NMR(C6D6)7.34(dt,2H),6.71(dt,1H),6.23(dt,1H),3.29,(m,1H),1.65(S,4H),1.30,(dt of dt,12H),1.15(dt,3H).

[0267] Synthesis of (3,5,5,8,8-pentamethyl-6,7-dihydro-1H-cyclopentadieno[b]naphthyl)lithium:

[0268] Adding n-butyllithium (10.9 mL, 27.2 mmol, 1.01 equivalent) in hexane to a vigorously stirred white suspension of 3,5,5,8,8-pentamethyl-6,7-dihydro-3H-cyclopentadieno[b]naphthalene (6.48 g, 27.0 mmol, 1.00 equivalent) in diethyl ether (250 mL) at -35 °C yielded a cold, turbid, pale yellow mixture. After stirring for 20 minutes, the reaction turned turbid and bright yellow. The reaction was stirred overnight and then evaporated under vacuum, leaving a dirty white solid. The solid was washed with pentane (100 mL) and filtered to give a bright white solid. The yield was 6.30 g (95%) of bright white powder. 1 H NMR(THF-D8)7.28(dt,2H),6.30(dt,1H),5.61(dt,1H),2.43(S,3H),1.72(S,4H),1.35(dt,12H).

[0269]

[0270] Synthesis of dichlorobis(3,5,5,8,8-pentamethyl-6,7-dihydro-1H-cyclopentadien[b]naphth-1-yl)zirconium:

[0271] Lithium (3,5,5,8,8-pentamethyl-6,7-dihydro-1H-cyclopentadieno[b]naphthyl) (6.30 g, 25.6 mmol, 2.00 equivalent) was added to a vigorously stirred white suspension of zirconium tetrachloride (2.98 g, 12.8 mmol, 1.00 equivalent) in diethyl ether (200 mL) at -35 °C, yielding a cold, turbid, pale yellow mixture. After stirring for 20 minutes, the reaction turned turbid and bright yellow. The reaction was stirred overnight and then evaporated under vacuum, leaving a bright yellow solid. The solid was extracted with dichloromethane (100 mL), and the extract was filtered to give a bright yellow solid. The solid was washed with cold pentane (50 mL) and dried under vacuum. The yield was 16.01 g (97%) of bright yellow powder. 1 HNMR(CD2Cl2)7.57(S,1H),7.50(D,2H),7.42(s,1H),6.15(dt,1H),5.89(dt,1H), 5.71(dt,1H),5.50(dt,1H),2.42(s,3H),2.34(s,3H),1.43(m,8H),1.36(m,24H).

[0272] Synthesis of catalyst 2a:

[0273]

[0274] Synthesis of (1,5,6,7-tetrahydro-s-indacen-1-yl)lithium:

[0275] To a vigorously stirred white suspension of 1,2,3,5-tetrahydro-s-indarin (9.70 g, 62.1 mmol, 1.00 equivalent) in diethyl ether (250 mL) at -35 °C, n-butyllithium in hexane (36 mL, 90.0 mmol, 1.01 equivalent) was added, yielding a pink precipitate. The reaction was stirred overnight and then evaporated under vacuum, leaving a pink solid. The solid was washed with pentane (100 mL) and filtered to give a bright white solid. The yield was 8.85 g (88%) of pink powder. 1 H NMR(THF-D8)7.15(s,2H),6.42(t,1H),5.81(dt,1H),2.83(m,4H),1.95(m,2H).

[0276] Synthesis of dimethyl(2,3,4,5-tetramethylcyclopentan-2,4-dien-1-yl)silyl trifluoromethanesulfonate:

[0277] AgOTf (38.00 g, 148 mmol, 1.0 equivalent) was added fractionally to a light amber solution of Me4CpSiMe2Cl (30.0 g, 140 mmol, 1.0 equivalent) in 100 mL of toluene. The reaction mixture turned cloudy white and was warmed upon addition of AgOTf. The reaction mixture rapidly formed a gray-pink precipitate and was stirred at room temperature for 4 hours. The solvent was removed under vacuum, leaving a dark gray mixture. The product was extracted with pentane (100 mL) and filtered through a yellow solution to give a brown solid. The pentane was removed from the yellow solution, leaving a pale yellow solid in a yield of 8.85 g (88%). 1 H NMR(C6D6)1.72(s,6H),1.60(s,6H),0.43(s,6H).

[0278] Synthesis of dimethyl(1,5,6,7-tetrahydro-s-indarsen-1-yl)(2,3,4,5-tetramethylcyclopentan-2,4-dien-1-yl)silane:

[0279] At -35 °C, (1,5,6,7-tetramethylcyclopentan-2,4-dien-1-yl)silyl trifluoromethanesulfonate (5.00 g, 15.2 mmol, 1.0 equivalent) was added to an amber-yellow solution of (2,3,4,5-tetramethylcyclopentan-2,4-dien-1-yl)silyl trifluoromethanesulfonate (50 ml) in diethyl ether, yielding a turbid yellow-orange mixture. The reaction mixture was stirred overnight at room temperature. The solvent was removed under vacuum, leaving a pink-orange solid. The product was extracted with pentane (100 ml) and the amber solution was filtered. The pentane was then removed under vacuum. The yield was 5.04 g (99%). 1 HNMR(C6D6)7.51(S,1H),7.34(S,1H),6.90(t,1H),6.489(t,1H),3.64( s,1H),2.86(m,5H),1.95(m,8H),1.92(s,6H),0.09(s,3H),0.03(s,3H).

[0280] Synthesis of lithium dimethyl(1,5,6,7-tetrahydro-s-indarsen-1-yl)(2,3,4,5-tetramethylcyclopentan-2,4-dien-1-yl)silyl):

[0281] To an orange solution of dimethyl(1,5,6,7-tetrahydrosymmetricindar-1-yl)(2,3,4,5-tetramethylcyclopentan-2,4-dien-1-yl)silane (5.0 g, 14.9 mmol, 1.0 equivalent) in diethyl ether (50 mL), n-butyllithium (11.3 mL, 31.0 mmol, 2.07 equivalent) was added at -35 °C to give an amber solution. The reaction mixture was stirred overnight at room temperature. The solvent was removed under vacuum, and the product was washed with pentane (100 mL) and filtered to give 5.86 g (93%) of a pale yellow solid. 1 HNMR(THFD8)7.46(s,1H),7.16(s,1H),6.65(dt,1H),5.91(dt,1H),2.81(m,5H),2.10(s,6H),1.95(m,3H),1.92(s,6H),0.59(s,6H).

[0282] Synthesis of dichlorodimethyl(1,5,6,7-tetrahydro-s-indarsen-1-yl)(2,3,4,5-tetramethylcyclopentadienyl)silyl)zirconium (catalyst 2a):

[0283] At -35 °C, a white suspension of zirconium tetrachloride (3.17 g, 8.31 mmol, 1.00 equivalent) in diethyl ether (200 mL) under vigorous stirring was supplemented with (1,5,6,7-tetrahydro-S-indarsen-1-yl)(2,3,4,5-tetramethylcyclopentan-2,4-dien-1-yl)silyl)lithium (3.50 g, 8.32 mmol, 1.00 equivalent), yielding a cold, turbid, pale yellow mixture. After stirring for 20 minutes, the reaction turned into a turbid, bright yellow. The reaction was stirred overnight and then evaporated under vacuum, leaving a bright yellow solid. The solid was extracted with dichloromethane (100 mL), and the extract was filtered to give a bright yellow solid. The solid was washed with cold pentane (50 mL) and dried under vacuum. The yield was 3.68 g (90%) of bright yellow powder. 1 HNMR(CD2Cl2)7.57(S,1H),7.3(S,1H),7.0(s,1H),5.87(s,1H),3.0-2.8(m,5H),2.65(m,3H),1.9(d,12H),1.1(s,3H),0.9(s,3H).

[0284] Load program:

[0285] MAO (42.5 g, 30 wt% in toluene) was added to Celestir along with 200 ml of toluene. The solution was stirred for two minutes. Catalyst 1 (949 mg) was dissolved in 50 ml of toluene and slowly added dropwise to the MAO solution. The reaction mixture was stirred at room temperature for one hour. Then, ES70 875 silica (35.2 g) was added to the above mixture and stirred for another hour. The solid support was filtered and washed with 200 ml of pentane. The supported catalyst was then dried under vacuum for 8 hours to produce a dry support. The supported catalyst was slurried with 10% SonoJell wax.

[0286] Co-loading process of dichloro-(3,5,5,8,8-pentamethyl-6,7-dihydro-1H-cyclopentadienyl[b]naphthyl-1-yl)zirconium (catalyst 1) and dichloro-dimethyl(1,5,6,7-tetrahydro-s-indarsen-1-yl)(2,3,4,5-tetramethylcyclopentadienyl)silyl)zirconium (catalyst 2a):

[0287] MAO (42.5 g, 30 wt% in toluene) was added to Celestir along with 200 ml of toluene. The solution was stirred for two minutes. The catalysts (catalyst 1 (492 mg) and catalyst 2 (569 mg)) were dissolved in 50 ml of toluene and slowly added dropwise to the MAO solution. The reaction mixture was stirred at room temperature for one hour. Then, ES70 875 silica (35.2 g) was added to the mixture and stirred for another hour. The solid support was filtered and washed with 200 ml of pentane. The supported catalyst was then dried under vacuum for 8 hours to produce a dry support.

[0288] Catalyst 2b: dichloro-tetramethylcyclopentadienyldimethylsilyl(3-benzo[e]indenyl)zirconium

[0289] Catalyst 2b was synthesized in a manner similar to that used for catalyst 2a, yielding the following compounds for use as shown in Tables 1B and 2B below:

[0290]

[0291] polymerization:

[0292] PE resin (Examples 1 and 2, and Comparative Examples 1-4) was produced in a small gas-phase fluidized bed reactor with a diameter of 6" in a continuous operation. Tables 1A and 1B list the catalysts or catalyst systems used in Examples 1-2 and Comparative Examples 1-4, as well as the polymerization conditions used.

[0293] Table 1A

[0294]

[0295] Table 1B

[0296]

[0297] The granular PE resin from the gas-phase reactor was dry-blended in a rotary mixer with the following additive: 500 ppm Irganox. TM -1076, 1,000 ppm of Irgafos TM Dynamar 168 and 600ppm TM FX5920A was then compounded on a laboratory-scale twin-screw extruder (Leistritz 27 or Leistritz 18) under typical PE compounding conditions. The QC properties and compositional characteristics of the resulting stabilized PE pellets were characterized. Tables 2A and 2B list the product characterization results for Examples 1-2 and Comparative Examples 1-5. Comparative Example 5 was obtained as LD103.09 (a high-pressure free radical LDPE available from ExxonMobil).

[0298] Table 2A

[0299]

[0300] Table 2B

[0301]

[0302] Density testing was conducted according to ASTM D1505, column density. Samples were molded under ASTM D4703-10a, procedure C, and then tested prior to the test according to ASTM D618-08(23). o Condition for 40 hours at ±2℃ and 50±10% relative humidity.

[0303] Melt index (MI) and high load melt index (HLMI or FI) follow ASTM D-1238, at 2.16 kg and 21.6 kg at 190°C, respectively.

[0304] Rheological characterization was performed using small-amplitude oscillatory shear tests on a RAS-G2 instrument at 190°C with strains ranging from 4% to 6%, within a frequency range of 0.01 rad / s to 626 rad / s. Viscosity, time, and power-law constants A1, A2, and A3 were obtained by fitting the data to the Cross equation. (The last sentence appears to be incomplete and requires further context.) -1 The G' / G" value is 0.1s. -1 The ratio of storage modulus to loss modulus at a given frequency. The shear thinning index STI0.1 / 100 is 0.1 s². -1 Complex viscosity at 100s -1 The proportion of complex viscosity.

[0305] All comparative examples and PE samples of the present invention were produced into films nominally 1 mil and / or 2 mils on the Little Giant blown film production line of Cyber ​​Plastic Machinery. It features a 2" general-purpose screw with an L / D ratio of 30. There are a total of nine heating zones: four on the extruder, two on the die, and one each in the block area before the screen changer, adapter, and die. Typical temperatures ( o F) The settings are as follows: for barrel 1, barrel 2, barrel 3, barrel 4, filter changer, adapter, block area, die head area 1, and die head area 2, the values ​​are 300, 350, 355, 340, 350, 355, 360, 370, and 370, respectively.

[0306] Table 3A: Membrane manufacturing conditions and performance properties of Examples 1-2

[0307]

[0308] Table 3B: Membrane manufacturing conditions and performance properties of Comparative Examples 1-5

[0309]

[0310] Figure 1 It is a diagram showing the GPC of polyethylene copolymers according to various embodiments, including both polymer chain distribution as a function of log (molecular weight) and g'vis value.

[0311] Figure 2 This is a diagram showing the GPC of polyethylene copolymers according to various embodiments, including both molecular weight distribution as a function of log (molecular weight) and comonomer weight % . Overall, the methods, catalysts, and membranes of the present invention provide polyethylene compositions formed in a low-pressure process to produce LCB polyethylene compositions that have extrusion processability similar to LDPE, but also possess good tear properties and dart impact strength to match the tear properties and dart impact strength of mLLDPE. This new LLDPE achieves increased processability, with increased tear balance, increased TD tear, and much better draw characteristics, making it easier to produce films of thin thickness.

[0312] Unless otherwise specified, the phrase “consistently of…” does not exclude the presence of other steps, elements or materials (whether or not specifically mentioned in the specification), provided that such steps, elements or materials do not affect the fundamental and novel characteristics of this disclosure, and furthermore, they do not exclude impurities and variations generally associated with the elements and materials used.

[0313] For simplicity, only certain numerical ranges are explicitly disclosed in this document. However, a lower limit can be combined with any other upper limit to define a range that is not explicitly stated, and similarly, a lower limit can be combined with any other lower limit to define a range that is not explicitly stated; likewise, an upper limit can be combined with any upper limit to define a range that is not explicitly stated. Furthermore, even if not explicitly stated, every point or individual value between the two endpoints is included within the range. Therefore, each point or individual value itself can serve as a lower or upper limit, combined with other points or individual values ​​or other lower or upper limits to define a range that is not explicitly stated.

[0314] All literature described herein, including any priority documents and / or experimental procedures, is incorporated by reference to all rights reserved not construed herein. It will be apparent from the foregoing overview and specific embodiments that, while the form of this disclosure has been illustrated and described, various modifications may be made without departing from the spirit and scope of this disclosure. Therefore, it is not intended that this disclosure be limited thereto. Similarly, the term “comprising” is considered synonymous with the term “including.” Likewise, whenever a composition, element, or group of elements precedes the transitional term “comprising,” it should be understood that the same composition or group of elements preceding the enumerated composition, element, or elements, and vice versa, is also considered with the transitional terms “consistently composed of,” “composed of,” “selected from,” or “is” preceding the enumerated composition, element, or elements.

[0315] Although this disclosure has been described in accordance with many embodiments and examples, those skilled in the art will understand after reading this disclosure that other embodiments may be devised without departing from the scope and spirit of this disclosure.

Claims

1. Catalyst system, comprising: A first catalyst compound, wherein the first catalyst compound is represented by the following formula (I): in: In formula (I), M is a Group 4 metal; R in equation (I) 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 and R 14 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 1 and R 2 R 4 and R 5 R 5 and R 6 R 6 and R 7 R 9 and R 10 R 11 and R 12 R 12 and R 13 and R 13 and R 14 One or more pairs are connected to form a fully saturated ring or a substituted or unsubstituted aromatic ring; Where R in equation (I) 4 and R 5 R 5 and R 6 or R 6 and R 7 At least one pair of rings are connected to form a first substituted or unsubstituted fully saturated ring fused with an indenyl ring, and R 11 and R 12 R 12 and R 13 or R 13 and R 14 At least one pair of the rings are connected to form a second substituted or unsubstituted fully saturated ring fused with the indenyl ring; and Each X in formula (I) 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 of X are linked together to form a substituted or unsubstituted metal cyclic ring, or two of X are linked together to form a chelate ligand, a diene ligand, or an alkylidene group; and The second catalyst represented by formula (III): in: M in formula (III) is a group 4 metal; R in equation (III) 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 linked to form a substituted or unsubstituted fully saturated ring or a substituted or unsubstituted aromatic ring, wherein R 7 and R 8 R 8 and R 9 Or R 9 and R 10 At least one pair of the rings are connected to form a fully saturated ring, substituted or unsubstituted, fused with the indenyl ring; The T expression in equation (III) 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, halogenated, 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 or substituted or unsubstituted aromatic rings; and Each X in formula (III) 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 of X are linked together to form a substituted or unsubstituted metal cyclization ring, or two of X are linked together to form a chelate ligand, a diene ligand, or an alkylidene group.

2. The catalyst system of claim 1, wherein the first catalyst compound of formula (I) is represented by formula (II): in: M is a Group 4 metal; R 1 R 2 R 3 R 4 R 7 R 8 R 9 R 10 R 11 R 14 R 15 R 15' R 16 R 16' R 17 R 17' R 18 R 18' R 19 R 19' R 20 R 20' R 21 R 21' R 22 and R 22' 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; 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 of X are linked together to form a substituted or unsubstituted metal cyclization ring, or two of X are linked together to form a chelate ligand, a diene ligand, or an alkylidene group.

3. The catalyst system of claim 2, wherein formula (II) is further characterized by one of the following (i), (ii) or (iii): (i) Each X in equation (II) is a halogen group; R in equation (II) 3 R 10 R 15 R 15' R 18 R 18' R 19 R 19' R 22 and R 22' Each of them is independently C1-C 10 Alkyl group; and R in formula (II) 1 R 2 R 4 R 7 R 8 R 9 R 11 R 14 R 16 R 16' R 17 R 17' R 20 R 20' R 21 and R 21' Each of them is hydrogen; (ii) Each X in formula (II) is independently a C1-C4 alkyl or halogroup; R in formula (II) 15 R 15' R 18 R 18' R 19 R 19' R 22 and R 22' Each of them is independently C1-C 10 Alkyl group; and R in formula (II) 1 R 2 R 3 R 4 R 7 R 8 R 9 R 10 R 11 R 14 R 16 R 16' R 17 R 17' R 20 R 20' R 21 and R 21' Each of them is hydrogen; or (iii) Each X in formula (II) is independently a C1-C4 alkyl group; R in formula (II) 1 R 2 and R 3 One of them is C1-C 10 Alkyl, and R 1 R 2 and R 3 The remaining parts are each hydrogen; R in formula (II) 8 R 9 and R 10 One of them is C1-C 10 Alkyl, and R 8 R 9 and R 10 The remaining parts are each hydrogen; R in formula (II) 15 R 15' R 18 R 18' R 19 R 19' R 22 and R 22' Each of them is independently C1-C 10 Alkyl group; and R in formula (II) 4 R 7 R 11 R 14 R 16 R 16' R 17 R 17' R 20 R 20' R 21 and R 21' Each of them is hydrogen.

4. The catalyst system of claim 2 or claim 3, wherein R in formula (II) 15 R 15' R 18 R 18' R 19 R 19' R 22 and R 22' Each of them is a methyl group.

5. The catalyst system of claim 2 or any one of claims 3-4, wherein the first catalyst compound is represented by one of the following structures (II-a), (II-b), or (II-c): 。 6. The catalyst system of any one of the preceding claims, wherein the second catalyst compound is represented by any one of the following structures (III-a) or (III-b): 。 7. The catalyst system of claim 5 or 6 further comprises a support material and, optionally, an activator.

8. A method for preparing a polyethylene composition, comprising: Under the first polymerization conditions, ethylene and C3-C 40 The α-olefin is introduced into the reactor together with the catalyst system of any one of claims 1-7 to form a polyethylene copolymer.

9. The method of claim 8, wherein the polymerization conditions include a reactor pressure of 250 to 350 psig and a reactor temperature of 60°C to 110°C.

10. The method of claim 8 or claim 9, wherein the polyethylene copolymer has a broad orthogonal compositional distribution and additionally has one or more of the following properties: (a) Approximately 0.914 g / cm³ 3 To approximately 0.925 g / cm 3 The density; (b) Melt index of about 0.5 g / 10 min to about 1.5 g / min (190 °C, 2.16 kg); (c) High load melt index (HLMI) of approximately 80 g / 10 min to approximately 90 g / 10 min (190 °C, 21.6 kg); (d) Melt index ratio (MIR, HLMI / MI ratio) of approximately 60 to approximately 98; (e) Molecular weight distribution (MWD) from about 8 to about 10.

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

12. The method of claim 10 or claim 11, wherein the broad orthogonal compositional distribution of the polyethylene copolymer is characterized by the polyethylene copolymer having a compositional distribution width index (CDBI) of about 5% to about 40% and / or a T of about 30 to about 40. 75 -T 25 value.

13. The method of any one of claims 10-12, wherein the polyethylene copolymer further has a g'vis of about 0.7 to about 0.

8. 平均 value.

14. The method of any one of claims 10-13, wherein the polyethylene copolymer has an olefin comonomer-derived content of about 10% to about 13% by weight, based on the total mass of the olefin comonomer-derived content and the ethylene-derived content.

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

16. A polyethylene copolymer, comprising: Ethylene-derived units; and The remaining part is C3-C 20 Units derived from comonomers; The polyethylene copolymer has the following characteristics: Wide orthogonal composition distribution Approximately 0.914 g / cm³ 3 To approximately 0.925 g / cm 3 density, Melt index from approximately 0.6 g / 10 min to approximately 1.3 g / 10 min. The content of olefin comonomers is from about 10% by weight to about 13% by weight. High load melt index (HLMI) of approximately 80 g / 10 min to approximately 90 g / 10 min. Melt index ratio (MIR) of approximately 60 to approximately 98, and Molecular weight distribution (MWD) of approximately 8 to approximately 10.

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

18. The polyethylene copolymer of claim 28 or 29, wherein the polyethylene copolymer has a g'vis of about 0.7 to about 0.

8. 平均 value.

19. A film comprising the polyethylene copolymer of any one of claims 16-18, wherein the film has: Elmandorf tear value (MD) of approximately 150 g / mil to approximately 180 g / mil, and Dart impact of approximately 140 g / mil to approximately 160 g / mil.

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