Catalyst, polyethylene, polymerization thereof, and films thereof

Abstract

The present disclosure relates to catalysts, catalyst systems, polyethylene polymers, polymerization processes for making such polyethylene polymers, and films made therefrom. In some embodiments, the unbridged catalyst compound is represented by Formula (II). M is a Group 4 metal. Each of R1, R2, R3, R4, R7, R8, R9, R10, R11, R14, R15, R15 ', R16, R16', R17, R17 ', R18, R18', R19, R19 ', R20, R20', R21, R21 ', R22 and R22' is independently hydrogen, a substituted or unsubstituted hydrocarbyl group, a substituted or unsubstituted heteroatom, or a substituted or unsubstituted heteroatom-containing group. Each X is independently a halide group, a substituted or unsubstituted hydrocarbyl group, a hydrogen group, an amino group, a substituted or unsubstituted alkoxy group, a sulfenyl group, a phosphino group, or a combination thereof, or two of the X are linked together to form a substituted or unsubstituted metal cyclization ring, or two of the X are linked to form a chelate ligand, a diene ligand, or an alkylidene group.

Description

[0001] Cross-references to related applications

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 503915, filed May 23, 2023, entitled "Catalyst, Polyethylene, 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] Polyethylene (PE) polymers are typically labeled according to their density, most commonly as low-density PE (LDPE) (and its linear variants, linear LDPE, or LLDPE), which is generally considered to have a density of 0.940 g / cm³. 3 Those PEs with densities of 0.940 g / cm³ or lower, on the other hand, are labeled as high-density PE (HDPE) and are generally considered to have a density higher than 0.940 g / cm³. 3 Those PEs. However, medium-density PE (MDPE) is increasingly used as an additional grader for PE density, most typically referring to a density of about 0.925 to about 0.940 g / cm³. 3 Sometimes as high as 0.955 g / cm³ 3 PEs that overlap with the upper limit of the LDPE density range and the lower limit of the HDPE density range. MDPE and / or lower density HDPEs can be used in applications such as thin-layer pipes, blown breathable membranes, waterproof sheets, and pipe adhesives. To achieve high throughput rates during processing, it may be desirable for polymers to have low melt rates at the shear rates typically encountered during extrusion and melt processing. Polymers with high melt indexes (low molecular weight) typically exhibit the desired low melt viscosity within the extrusion shear rate range. However, such high melt index polymers also exhibit low melt viscosity at lower shear rates (e.g., at zero shear viscosity), which leads to poor bubble stability during processing. Metallocene-catalyzed MDPEs and other PE variants, while offering excellent mechanical properties, often still suffer from poor processability and / or poor bubble stability. Such polymers may also exhibit low melt strength, which not only affects bubble stability (as mentioned above) but also leads to melt breakage (surface roughness or similar irregularities) in films produced at typical commercial extrusion rates.

[0005] Some polymers, particularly LDPEs (typically prepared using radical polymerization), exhibit a high degree of long-chain branching (LCB), which can be beneficial for processing and membrane stability, as well as mechanical properties such as tear resistance. However, LDPEs are known to have poorer mechanical properties compared to more linear and / or metallocene-catalyzed PEs. Therefore, various levels of LDPE have been blended with metallocene PEs (e.g., mLLDPE and / or mMDPE) to increase melt strength, increase shear sensitivity (e.g., increase flow at commercial shear rates in extruders), and reduce the tendency for melt fracture. However, such blending often negatively impacts the mechanical properties of membranes made from the polymers. Indeed, improving the processing properties of mLLDPE and / or mMDPE without sacrificing physical properties is a challenge.

[0006] In summary, there remains a need for new catalysts and MDPEs and / or HDPEs that combine desired properties (such as density, melt index properties, and long-chain branching) while also providing the commercially viable polymerization and extrusion capabilities required for MDPEs and / or HDPEs. For example, there is a need for new catalysts and MDPEs and / or HDPEs that exhibit low melt rates at the shear rates typically encountered during extrusion and melt processing and high melt viscosities at lower shear rates (such as at zero shear viscosity) to improve film and bubble stability during processing.

[0007] Some references with potential interest in this area 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 / 006434 4; KR10-2022-0009900, KR10-2022-0009782; KR10-2021-0080974; KR10-2021-0038379; KR10-2020-0089599; KR10-2018-0063669; KR10-2007-0098276 and Foster et al., Journal of Organometallic Chemistry, 571(1998) 171. Summary of the Invention

[0008] This disclosure relates to catalysts, catalyst systems, polyethylene polymers, polymerization methods for preparing such polyethylene polymers, and membranes prepared therefrom.

[0009] In some embodiments, a method for preparing a polyethylene composition includes reacting ethylene and C3-C under polymerization conditions. 40 An α-olefin is introduced into the reactor along with a catalyst system. The method includes forming a polyethylene copolymer. The catalyst system comprises an unbridged catalyst compound represented by the following formula (I):

[0010]

[0011] in:

[0012] M is a Group 4 metal;

[0013] R 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 of rings are linked to form a substituted or unsubstituted fully saturated ring or a substituted or unsubstituted aromatic 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 It is neither a substituted nor an unsubstituted hydrocarbon group;

[0014] Where 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 the indenyl ring; and

[0015] Each X 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.

[0016] In some embodiments, the catalyst compound is an unbridged metallocene represented by the following formula (II):

[0017]

[0018] in:

[0019] M is a Group 4 metal;

[0020] 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 R20' 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

[0021] 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.

[0022] In some embodiments, the polyethylene copolymer comprises about 95% by weight or more ethylene units and the balance C3-C 20 Comonomer unit. The polyethylene copolymer has approximately 0.925 g / cm³. 3 To approximately 0.955 g / cm 3 The composition distribution width index (CDBI) is approximately 40% to 65%. The molecular weight is approximately 10% to 65%. Other molecular weights include: density, weight-average molecular weight (Mw) of approximately 50,000 g / mol to approximately 300,000 g / mol, number-average molecular weight (Mn) of approximately 5,000 g / mol to approximately 50,000 g / mol, Z-average molecular weight (Mz) of approximately 300,000 g / mol to approximately 2,000,000 g / mol, melt index of approximately 0.3 g / 10min to approximately 11 g / 10min, melt index ratio of approximately 20 to approximately 200, g'vis value of approximately 0.85 to approximately 0.97, and density of approximately 50% to approximately 65%. Attached Figure Description

[0023] 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.

[0024] Figure 1 It is a diagram showing the superposition of complex viscosity of ethylene-hexene copolymer using catalyst 19 in a gas-phase reactor according to various embodiments.

[0025] Figure 2 It is a graph showing the superposition of the tensile viscosity of the ethylene-hexene copolymer using catalyst 19 in a gas-phase reactor according to various embodiments.

[0026] Figure 3 The drawing is a Van Gurp Palmen diagram of ethylene-hexene copolymers from different catalysts in a gas-phase reactor according to various embodiments. Invention Details

[0028] 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.

[0029] This disclosure relates to catalysts, catalyst systems, polyethylene, polymerization methods for preparing such polyethylene, and films prepared therefrom. The polyethylene of this disclosure may be medium-density polyethylene (MDPE) or high-density polyethylene (HDPE) formed using, for example, metallocene catalysts, ethylene monomers, and comonomers. The polyethylene of this disclosure can be characterized as having a unique balance of chemical, physical, and mechanical properties relative to conventional MDPE, conventional LLDPE, and other conventional polyethylene grades. For example, the polyethylene of this disclosure exhibits densities conventionally associated with MDPE (or HDPE), while also possessing long-chain branching and a low melt index. Even though (1) the catalysts of this disclosure can provide low comonomer introgression rates and (2) the polyethylene of this disclosure, in some embodiments, does not have a broad orthogonal composition distribution (BOCD), long-chain branching and a low melt index can still be obtained. BOCD refers to the comonomer of the copolymer that is primarily incorporated into the high molecular weight chains of the copolymer composition formed during polymerization. Even though the polyethylene copolymer (1) has good film-forming processability and (2) the catalyst of this disclosure provides high molecular weight (low melt index) polyethylene, the lack of BOCD in the polyethylene copolymer of this disclosure can also provide improved film properties.

[0030] Furthermore, and compared to conventional LLDPE and other conventional polyethylene grades, the polyethylene of this disclosure can have a low melt index, higher viscosity at low shear rates (e.g., due to a generally low comonomer introduction rate and, in particular, a low comonomer content in the high molecular weight portion of the polyethylene copolymer), and improved processability, such as improved extrudability (e.g., due to long-chain branching), while maintaining good bubble stability during the manufacturing process. For example, the catalysts and polymerization of this disclosure can provide polyethylene with a low melt rate at shear rates typically encountered during extrusion and melt processing, and a high melt viscosity at lower shear rates (e.g., at zero shear viscosity) to improve bubble stability during processing. These advantages can be achieved even when the catalysts of this disclosure provide high molecular weight polyethylene copolymers. For example, the catalysts of this disclosure provide improved molecular weight capacity compared to conventional bisindenylzirconia. Such high molecular weight polyethylene copolymers (except for the lack of BOCD) can provide improved toughness of polyethylene copolymers compared to conventional MDPE.

[0031] The polyethylene described herein is a polyethylene copolymer. Compared to conventional LLDPE, the polyethylene copolymer of this disclosure has increased long-chain branching (also referred to as "LCB") in the copolymer, thereby providing reduced necking and improved draw stability. The polyethylene copolymer of this disclosure can exhibit a lower zero-shear viscosity, resulting in lower motor torque and lower melt pressure and melt temperature during extrusion, providing increased yield of extruded polyethylene copolymer products. Due to the increased polymer LCB, a reduction in motor torque and melt pressure can be observed during cast film manufacturing. LCB can be demonstrated by, for example, a high melt index ratio and / or specific rheological properties, as shown by data obtained through small-angle oscillating shear (SAOS) experiments (e.g., η). 0.01 / η 100 The ratio of the complex viscosity recorded at shear rates of 0.01 and 100 rad / s, respectively, and the Van Gurp Palmen plot of the phase angle versus the complex modulus, which tracks the viscosity response of the polymer to applied shear.

[0032] definition

[0033] As used herein, "olefin," or "olefinic 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 mer unit in said copolymer is derived from ethylene in the polymerization reaction and that said derived unit is present in about 35% to about 55% by weight, based on the weight of said copolymer.

[0034] 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).

[0035] 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.

[0036] 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. 3 Ethylene 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. 3Ethylene 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.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] 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).

[0041] 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.

[0042] 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.

[0043] The terms “substituent,” “base,” “group,” and “structural part” are used interchangeably.

[0044] 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 either hydrogen or a linear alkyl group.

[0045] For the purposes of this disclosure, ethylene should be considered as an α-olefin.

[0046] 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, a “Cm-Cy” group or compound refers to a group or compound containing a total number of carbon atoms from m to y. Therefore, C1-C 50 Alkyl refers to an alkyl group that contains a total of about 1 to about 50 carbon atoms.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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 to C2. 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.

[0052] The term "alkenyl" refers to a linear, branched, or cyclic hydrocarbon group having one or more double bonds. These alkenyl groups may optionally be substituted. Examples of suitable alkenyl groups may include vinyl, propenyl, allyl, 1,4-butadienyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, and their substituted analogs.

[0053] 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.

[0054] The term "aryl" or "aryl group" refers to an aromatic ring and its substituted variants, such as phenyl, 2-methyl-phenyl, xylyl, and 4-bromo-xylyl. Similarly, "heteroaryl" refers to an aryl group in which one of the ring carbon atoms (or two or three ring carbon atoms) has been replaced by a heteroatom, such as N, O, or S. As used herein, the term "aromatic" also refers to 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.

[0055] 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).

[0056] 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.

[0057] 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.

[0058] 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.

[0059] The terms "catalyst compound", "catalyst complex", "transition metal complex", "transition metal compound", "precatalyst compound" and "precatalyst complex" are used interchangeably.

[0060] A “catalyst system” is a combination of at least one catalyst compound, at least one activator, optional co-activator, and optional support material. When “catalyst system” is used to describe such a pairing prior to activation, it refers to the unactivated catalyst complex (pre-catalyst) together with the activator and, optionally, the co-activator. 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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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 JCPinto, Ind. Eng, Chem. Res. 2000, Vol. 29, p. 4627.

[0065] 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.

[0066] 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).

[0067] 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.

[0068] 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.

[0069] 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.

[0070] "Stretching" or "elongational viscosity" refers to 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 the shear resistance. For some polymer liquids, elongational viscosity can increase with rate (tension stiffening) despite a decrease in shear viscosity.

[0071] 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 .

[0072] 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 .

[0073] 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).

[0074] The term "melt strength" is a measure of tensile viscosity and represents the maximum tensile force that can be applied to a melt without it breaking. Tensile 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.

[0075] 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.

[0076] Catalyst compounds

[0077] The catalyst compounds disclosed herein can be unsupported or supported on a carrier material.

[0078] In some embodiments, the catalyst compound is an unbridged metallocene represented by the following formula (I):

[0079]

[0080] in:

[0081] M is a Group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf);

[0082] R 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 R14 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 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 It is neither a substituted nor an unsubstituted hydrocarbon group;

[0083] Among them (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 an indenyl ring as 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 rings in the form of a second substituted or unsubstituted fully saturated ring fused with an indenyl ring as shown in formula (I); and

[0084] 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.

[0085] 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 7At 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).

[0086] 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 7 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).

[0087] 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 12The 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).

[0088] 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 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 10Alkyl 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.

[0089] 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.

[0090] 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, 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.

[0091] In some embodiments of formula (I), (1) M is Zr or Hf, (2) X is a C1-C4 alkyl group, and (3) R 1R 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 4 and R 5 R 5 and R 6 or R 6 and R 7 At least one of them is connected to form a substituted fully saturated ring fused with the indenyl ring shown in formula (I), and (6) R 11 and R 12 R 12 and R 13 or R 13 and R 14 The rings are linked to form a substituted, fully saturated ring fused with the indenyl ring shown in formula (I).

[0092] In some embodiments, the catalyst compound is an unbridged metallocene represented by the following formula (II):

[0093]

[0094] in:

[0095] M is a Group 4 metal, such as titanium (Ti), zirconium (Zr), or hafnium (Hf);

[0096] 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' R19 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

[0097] 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.

[0098] 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' R 20 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 15R 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.

[0099] 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, 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 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, R3 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.

[0100] 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.

[0101] In some embodiments of formula (II), (1) M is Zr or Hf, (2) X is a C1-C4 alkyl group, and (3) R 1 R 2 R 3 R 4 R 7 R 15 R 15' 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.

[0102] In some embodiments of formula (II), the catalyst is:

[0103]

[0104]

[0105]

[0106]

[0107] .

[0108] Aggregation methods

[0109] 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. Patent Nos. 4,543,399; 4,588,790; 5,028,670; 5,317,036; 5,352,749; 5,405,922; 5,436,304; 5,453,471; 5,462,999; 5,616,661 and 5,668,228; all of which are incorporated herein by reference.) Gas-phase polymerization can be carried out in any suitable reactor system, such as 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.

[0110] 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.

[0111] 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.).

[0112] The reactor pressure during polymerization can be from about 100 psig (680 kPag) to about 500 psig (3448 kPag), for example from about 200 psig (1379 kPag) to about 400 psig (2759 kPag), for example from about 250 psig (1724 kPag) to about 350 psig (2414 kPag). In some embodiments, the reactor is operated at temperatures from about 60°C to about 120°C, such as from about 60°C to about 115°C, such as from about 70°C to about 110°C, such as from about 70°C to about 95°C, such as from about 80°C to about 90°C. The ratio of hydrogen to ethylene can be from about 10 to about 30 ppm / mol%, such as from about 15 to about 25 ppm / mol%, such as from about 16 to about 20 ppm / mol.

[0113] The mol% of ethylene (based on total monomers) can be about 25 to about 90 mol%, for example, about 50 to about 90 mol%, or about 70 to about 85 mol%, and the partial pressure of ethylene (in the reactor) can be about 75 psia (517 kPa) to about 300 psia (2069 kPa), or about 100 psia to about 275 psia (689-1894 kPa), or about 150 psia to about 265 psia (1034-1826 kPa), or about 180 psia to about 200 psia. The ethylene concentration in the reactor can also be in the range of about 35 mol% to about 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 moles of gases in the reactor (including, if present, ethylene and / or comonomer gases and inert gases, such as nitrogen, isopentane or other ICAs (one or more), etc.); as with 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 about 0.2 to about 1 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 or 1.0 mol%.

[0114] Activator

[0115] The terms "co-catalyst" and "activator" are used interchangeably here.

[0116] 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.

[0117] In at least one embodiment, the catalyst system includes an activator, a catalyst compound as described herein, and an optional support.

[0118] Aluminoxane activator

[0119] 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. 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 a clear aluminum oxane can be decanted from the turbid solution. A useful aluminum oxane is modified methylaluminoxane (MMAO) co-catalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylaluminoxane Type 3A, as described in U.S. Patent No. 5,041,584, which is incorporated herein by reference). Another useful aluminoxane is solid polymethylaluminoxane, as described in U.S. Patent Nos. 9,340,630, 8,404,880, and 8,975,209, which are incorporated herein by reference.

[0120] 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.

[0121] 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.

[0122] Ionized / noncoordinated anion activators

[0123] 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 derived from the anion. Noncoordinate anions that may 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.

[0124] 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.

[0125] 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).

[0126] Furthermore, the catalyst system of this disclosure may include a metal hydrocarbon alkenyl chain transfer agent represented by the following formula:

[0127]

[0128] 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; v can be 0.1 to 3.

[0129] carrier material

[0130] 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.

[0131] 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.

[0132] Carrier materials, such as inorganic oxides, can have 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 3.0cm 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 Davison Chemical Division of WRGrace 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).

[0133] 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 approximately 100°C to approximately 1000°C, for example, at least approximately 600°C. When the support material is silica, it is heated to at least 200°C, for example, from approximately 200°C to approximately 850°C, for example, from approximately 600°C; and held for approximately 1 minute to approximately 100 hours, from approximately 12 hours to approximately 72 hours, or from approximately 24 hours to approximately 60 hours. The calcined support material must possess at least some reactive hydroxyl groups (OH) 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.

[0134] 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.

[0135] 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.

[0136] A suitable nonpolar diluent is a material in which all reactants used herein (e.g., activators and catalyst compounds) are at least partially soluble and are liquid at the polymerization temperature. Nonpolar diluents can be alkanes, such as isopentane, hexane, n-heptane, octane, nonane, and decane, but a variety of other materials may also be used, including cycloalkanes, such as cyclohexane, and aromatic compounds, such as benzene, toluene, and ethylbenzene.

[0137] 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).

[0138] polyethylene copolymer

[0139] This disclosure provides polyethylene copolymers with a useful combination of medium- or high-density, high molecular weight, low comonomer incorporation, high melt index ratio, low melt index, and long-chain branching. This makes these polyethylene copolymers suitable for a variety of membrane applications requiring a good balance of strength and processability; however, it also makes the catalysts and catalyst systems described herein potential candidates for dual-catalyst systems (whereby the catalysts described herein, when combined with catalyst compounds for the production of lower molecular weight polyethylene, can be used to produce high molecular weight, high-density (low comonomer incorporation) fractions of polyethylene).

[0140] Therefore, polyethylene copolymers prepared using the catalyst system of this disclosure typically exhibit one or more of the following properties:

[0141] • Approximately 0.925 to approximately 0.955 g / cm³ 3 For example, from 0.925, 0.93, 0.935, 0.94, 0.945 or 0.95 g / cm³ 3 The lower limit of any one of them is 0.93, 0.935, 0.94, 0.945, 0.95, 0.952 or 0.955 g / cm³. 3 The upper limit of any one of them, for example, approximately 0.93 g / cm³. 3 Approximately 0.940 g / cm³ 3 Or approximately 0.94 g / cm³ 3 Approximately 0.95 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 0.94 to approximately 0.955 g / cm³. 3 The density.

[0142] • Approximately 0.1 to approximately 10 g / 10 min (ASTM D1238, 190°C, 2.16 kg), for example, from the lower limit of any one of 0.01, 0.05, 0.1, 0.3, 0.5, 0.7, 0.9, 1, 1.1, 1.2, 1.5, 2, 2.1, 2.2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, or 8 g / 10 min to 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, The upper limit of any one of 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, or 11 g / 10 min, wherein this document considers the range from any lower limit to any upper limit (provided the upper limit is greater than the lower limit), for example, about 0.1 to about 1 g / 10 min, or about 1 to about 3 g / 10 min, or about 7 to about 10 g / 10 min. The melt index (MI, also referred to as I2 or I in the case of the 2.16 kg load used in the identification test) is also considered. 2.16 ).

[0143] To further elaborate, the polyethylene copolymer can be a polymerization product of ethylene monomer and one or more olefin comonomers, such as α-olefin comonomers. The α-olefin comonomer 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 / or olefins formed in situ in the polymerization medium. In some embodiments, the comonomer is selected from isoprene, styrene, butadiene, isobutene, chloroprene, acrylonitrile, and / or cycloolefins. In some embodiments, a combination of olefin comonomers is utilized. In some embodiments, the olefin comonomer is selected from 1-butene and / or 1-hexene. Based on the total weight of monomers in the polyethylene copolymer, the olefin comonomer content of the polyethylene copolymer can range from a lower limit of about 0.1, 0.3, 0.5, 0.7, 0.9, 1.1, 1.3, 1.5, 1.7, 1.9, 2.1, 2.3 or 2.5% by weight to an upper limit of about 1.5, 1.7, 1.9, 2.1, 2.3, 2.5, 2.7, 2.9, 3.1, 3.3 or 3.5% by weight. The remaining portion of the polyethylene comonomer consists of units derived from ethylene (e.g., from a lower limit of about 80, 85, 90, 95, 96, 97, 97.5, 98, 98.5, 99 or 99.5% by weight to an upper limit of about 90, 95, 97, 97.5, 98, 98.5, 99, 99.5 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 97 to about 98.5% by weight, such as about 97.5 to about 98.5% by weight of ethylene-derived units and the balance of olefin comonomer-derived content).

[0144] Molecular weight properties

[0145] The polyethylene copolymer may also have a molecular weight distribution (MWD) of about 3 to about 10. The MWD may also be in the range of a lower limit of about 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, or 7 to an upper limit of about 6.5, 7, 7.5, 8, 8.5, 9, 9.5, or 10, wherein the range from any of the aforementioned lower limits to any of the aforementioned upper limits is considered, provided that the upper limit of the range is greater than the lower limit. MWD is defined as weight-average molecular weight (Mw) divided by number-average molecular weight (Mn).

[0146] The weight-average molecular weight (Mw) of the polyethylene copolymers in various embodiments can be in the range of about 50,000 to about 300,000 g / mol, for example about 60,000 to about 150,000 g / mol, for example about 65,000 to about 100,000 g / mol, for example about 70,000 to about 90,000 g / mol, or about 120,000 to about 200,000 g / mol, for example about 150,000 to about 175,000 g / mol, wherein the range from any of the aforementioned lower limits to any of the aforementioned upper limits is taken into consideration.

[0147] The number average molecular weight (Mn) of the polyethylene copolymers in various embodiments can be in the range of about 5,000 to about 50,000 g / mol, for example about 5,000 to about 25,000 g / mol, for example about 5,000 to about 15,000 g / mol, or about 18,000 to about 30,000 g / mol, for example about 20,000 to about 25,000 g / mol, wherein the range from any of the aforementioned lower limits to any of the aforementioned upper limits is taken into consideration.

[0148] The Z-average molecular weight (Mz) of the polyethylene copolymers in various embodiments can be in the range of about 300,000 to about 2,000,000 g / mol, for example about 500,000 to about 2,000,000 g / mol, or about 800,000 to about 1,000,000 g / mol, or about 1,000,000 g / mol to about 2,000,000 g / mol, for example about 1,200,000 g / mol to about 1,800,000 g / mol, for example about 1,400,000 to about 1,600,000 g / mol, wherein the range from any of the aforementioned lower limits to any of the aforementioned upper limits is taken into consideration.

[0149] Composition and distribution

[0150] The polyethylene copolymers described herein exhibit a relatively uniform comonomer distribution, meaning that the shorter and longer polymer chains within the polymer chain clusters of the copolymer have slightly similar relative comonomer loadings (i.e., similar amounts of short-chain branching per 1000 carbon atoms), with some deviations. This relatively uniform comonomer distribution may, for example, be attributed to the medium to high density range of the polyethylene described herein (particularly from about 0.933 to about 0.950), which implies a generally lower comonomer incorporation compared to LLDPE (which has a lower density and therefore a higher overall comonomer incorporation rate). This comonomer distribution can be characterized in several ways.

[0151] For example, the polyethylene copolymers described herein can have a medium to high compositional width index (CBDI), wherein the polyethylene copolymer can have about 40% to about 70%, for example, from the lower limit of any one of 40, 42, or 44% to the upper limit of any one of 50, 55, 60, 65, or 70%, wherein the range from any of the aforementioned lower limits to any of the aforementioned upper limits is taken into consideration. CDBI is defined as the weight percentage of copolymer molecules with a comonomer content 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) having 8 mol% comonomer on the polymer chain, CDBI is the weight 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 copolymer chains with a comonomer molar percentage between (0.5 × 8) and (1.5 × 8) or a comonomer content between 4 mol% and 12 mol%. WO 1993 / 003093 also describes the use of chromatography and C2... 13 The method for determining the median comonomer composition (Cmed) by NMR determination of the polymer weight fraction relative to the composition curve (i.e., composition distribution curve) and from it, refers to Figures 16 and 17 of this disclosure. The CDBI of the copolymer can be readily determined using techniques for separating individual fractions of the copolymer sample. One such technique is to use temperature rise elution fractionation (TREF) to generate a solubility distribution curve, 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 above publications are incorporated herein by reference.

[0152] 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.

[0153] 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 the temperature described in the TREF experiment (and plotting of the elution temperature relative to the molecular weight of the eluted polymer) as described in US2019 / 0119413 (particularly in its paragraphs

[0055] -

[0058] , which are described by reference and 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 25 Significant 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 The elution molecular weight, compared to the elution temperature, is related to 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 (elution polymer molecular weight relative to elution temperature) can be further processed as follows:

[0154] 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 as for the polymer sample, typically prior to that method, but without adding any polymer to the sample vial; using the same solvent reservoir as for the polymer sample, and without replenishing with fresh solvent; and within a reasonable timeframe of the polymer sample run.

[0155] 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, fill the injection valve loop with a ~1 mg / ml HDPE resin solution; then load the loop volume to the same location in the column where the sample was loaded for TREF analysis; then use an isothermal method to allow the hot solution to flow directly to the detector at a constant flow rate of 1 ml / min; then measure the time it takes for the HDPE probe peak to appear in the IR signal after injection. Therefore, the delay volume (ml) is equivalent to the time (min).

[0156] 3. The curve can be baseline corrected and an appropriate integration limit can be selected; and the curve can be normalized such that the area of ​​the curve is 100% of the weight.

[0157] Narrow distribution is reflected in T below 10℃ 75 -T 25 Smaller differences in values, for example, in the range of 2 to 10°C, such as from the lower limit of any one of about 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5 or 6°C to the upper limit of any one of about 10, 9.5, 9, 8.5, 8, 7.5, 7, 6.5, 6, 5.5, 5, 4.5 or 4°C, where any combination of the lower limit to any upper limit is considered (provided that the upper limit is greater than the lower limit), for example, from about 2°C to about 8°C.

[0158] 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:

[0159]

[0160] 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 The molecular weight is expressed in g / mol, and the intrinsic viscosity (and therefore K in the Mark-Houwink equation) is expressed in dL / g.

[0161] The molecular weight (M) of LS at each point in the chromatogram was determined by analyzing the LS output using the Zimm model of static light scattering.

[0162]

[0163] 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.

[0164]

[0165] 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.

[0166] 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 αps is 0.67 and Kps is 0.000175. The average intrinsic viscosity of the sample is [η].平均 The calculation is as follows (where [η]). avg Represents [η] 平均 ):

[0167]

[0168] The sum is taken from all chromatogram slices i between the integration limits.

[0169] 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, [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.

[0170] 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 Represents [η] 平均 ):

[0171]

[0172] The sum is taken from all chromatographic slices i between the integration limits. The branching index g'vis is defined for linear reference samples as follows: Where Mv is the viscosity-average molecular weight based on the molecular weight determined by LS analysis, and K and α are for a reference linear polymer; for the purposes of this disclosure, α and K are the same as those described above for linear polyethylene polymers.

[0173] The branching index g'vis can be equivalently called 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 1 The 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.

[0174] Other polyethylene copolymer rheology

[0175] 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 5, 25, 50, 75, 100, 125, 150, 175, 200 or 225 g / 10min to an upper limit of about 20, 50, 100, 150, 200, 225, 250, 275, 300 or 325 g / 10min (the 21.6 kg load used in the identification test, also known as I...). 21 or I 21.6 ); wherein this document considers the range from any of the aforementioned lower limits to any of the aforementioned upper limits (e.g., about 5 to about 20 g / 10 min, or about 25 to about 50 g / 10 min, or about 200 to about 300 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 .

[0176] Therefore, the polyethylene copolymer may also have a melt index ratio (MIR, defined as I) in the range from the lower limit of any one of about 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140 or 150 to the upper limit of any one of about 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200. 21.6 / I 2.16 The proportions), where this article considers the range from any of the aforementioned lower limits to any of the aforementioned upper limits (e.g., about 20 to about 40, or about 120 to about 180).

[0177] The polyethylene copolymers of 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 proportion of complex viscosity recorded at shear rates or frequencies of 0.01 and 100 rad / s, respectively, is used to demonstrate this. Another useful parameter indicating the presence of LCB is shown in... Figure 3 Plot by Van Gurp Palmen (VGP). Specifically, polyethylene copolymers (even LLDPEs) with some to moderate levels of LCB can have VGP curves that typically have a negative slope, but also include portions referred to herein as "inflection points" (where such points can constitute a significant decrease in the magnitude of the negative slope, a flattening of the slope, or even a change in the direction of the slope, before resuming the negative sloping trend in the aforementioned portion of the curve), while LLDPEs with little or no LCB do not follow this characteristic pattern. See also Figure 3 Comparative Example 1 (without inflection point) compared to Examples 1, 2 and 3.

[0178] In addition, the LCB index (g' or alternatively g'vis) may be less than 1, for example in the range of about 0.7 to about 0.99, for example about 0.85 to about 0.97, for example about 0.87 to about 0.96, for example about 0.89 to about 0.92, or about 0.92 to about 0.96, wherein the range from any of the aforementioned lower limits to any of the aforementioned upper limits is taken into account.

[0179] Therefore, extending the foregoing, polyethylene copolymers can have a complex shear viscosity (η*) @ 0.01 rad / sec and 190 °C within the range of 1,000 to 700,000 Pa·s, for example, from the lower limit of any one of 1,000, 15,000, 30,000, 45,000, 60,000, 75,000, 90,000 or 105,000 Pa·s to the upper limit of any one of 700,000, 685,000, 670,000, 655,000, 640,000, 625,000, 610,000, 595,000, 580,000 or 565,000 Pa·s. Pa·s or 30,000 to 60,000 Pa·s).

[0180] Complex shear viscosity (η*) @ 100 rad / sec and 190 °C can be in the range of 300 to 3,000 Pa·s, for example from the lower limit of any one of 300, 500, 700, 900, 1,100, 1,300 or 1,500 Pa·s to the upper limit of any one of 3,000, 2,800, 2,600, 2,400, 2,200, 2,000 or 1,800 Pa·s, wherein the range from any of the aforementioned lower limit to any of the aforementioned upper limit (e.g., 300 to 700 Pa·s or 700 to 1,100 Pa·s) is also taken into consideration.

[0181] Therefore, polyethylene copolymers can also exhibit 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 can be greater than 5, for example, greater than 6 or even higher. For example, the STI 0.1 / 100 can 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 5 to 10, 30, 40, or 50; or about 20 to 65; or 5 to 65, etc.).

[0182] Compared to typical metallocene PE, polyethylene copolymers can also exhibit lower phase angles at a complex modulus of 10 kPa. Phase angle data measures the viscous and elastic properties of the material. The phase angle data for the polyethylene copolymers of various embodiments can be in the range of about 35 to about 65 degrees, for example about 40 to about 65 degrees, for example about 40 to about 50 degrees, or about 55 to about 65 degrees at 10 kPa.

[0183] In some embodiments, the polyethylene copolymer has a G' / G''@0.1s ratio of about 0.2 to about 2, for example about 0.5 to about 2, for example about 0.5 to about 1, or about 1 to about 2, for example about 1 to about 1.5. -1 Value (which is in 0.1s) -1 The ratio of shear storage modulus (Pa) to shear loss modulus (Pa).

[0184] 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.

[0185] 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 at 190 °C without affecting the measured viscoelastic property. 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. The nitrogen stream 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 purely elastic materials, 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:

[0186]

[0187] 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.

[0188] 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 linearity versus long-chain branching, 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).

[0189] 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.

[0190] Tensile viscosity can be measured at 190°C using the SER2-P testing platform, available from Xpansion Instruments LLC, Tallmadge, Ohio, USA. Samples can be prepared by placing the polymer in a mold measuring approximately 50 mm × 50 mm with a thickness of ~0.5 mm. The mold can be pressed in a Carver laboratory press at 190°C using a three-stage pressure program: the material can be preheated at 0 psi for 2 minutes, pressed at 5 kpsi for 2 minutes, and then held at 0 psi while still in the mold for 15 minutes. Samples can be cut into test strips, for example, with a width between 13 and 13.4 mm, a length of ~18 mm, and an average thickness between 0.5 mm and 0.6 mm. It should be noted that dimensional variations exist due to sample type. Samples can be tested on an MCR 501 rheometer with SER test fixtures. Sample temperature can be equilibrated for 10–15 minutes before testing. The SER testing platform can be used on an MCR501 rheometer available from Anton Paar. The SER testing platform is described in US 6,578,413 and US 6,691,569, which are incorporated herein by reference. A general description of transient uniaxial tensile viscosity measurements is provided, for example, in "Measuring the transient extensional rheology of polyethylene melts using the SER universal testing platform", The Society of Rheology, Inc., J. Rheol. 49(3), 585-606 (2005). When a polymer is subjected to elongational flow, strain hardening occurs, and the transient tensile viscosity increases relative to the linear viscoelastic envelope (LVE). Strain hardening is observed as a sharp increase in tensile viscosity in a transient tensile viscosity versus time plot. The strain hardening ratio (SHR) is used to characterize the increase in tensile viscosity and is defined as the ratio of the maximum transient tensile viscosity at a given strain rate to the corresponding value of the LVE. When this ratio is greater than 1, strain hardening is present in the material.

[0191] Blends and Additives

[0192] 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, or other differentiated polyethylenes.

[0193] In some embodiments, the formulated blends may contain additives, which are determined based on the end use of the formulated blends. In some embodiments, the additives are selected from 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, nucleating agents, or any combination thereof. In some embodiments, the additives are present in an amount from about 0.1 ppm to about 5% by weight.

[0194] 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).

[0195] Products

[0196] The polyethylene copolymers disclosed herein are particularly suitable for manufacturing end-use articles, 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 by cast film extrusion, blown film extrusion, rotational molding, or injection molding processes. In some embodiments, the polyethylene copolymers can be used in the form of blends.

[0197] The polyethylene copolymers disclosed herein can provide excellent shear-thinning properties and almost no melt breakage of extrudate at high die shear rates. Furthermore, compared to other LLDPEs, the polyethylene copolymers of this disclosure can provide films formed with reduced motor loads and melt pressures (which increase input volume) due to their improved flow behavior.

[0198] 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 roll forming. 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 provide improved shrink wrapping capabilities due to their long-chain branched 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, troughs, large hollow articles, rigid food containers, and toys.

[0199] 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.

[0200] 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).

[0201] 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.

[0202] Shrink film

[0203] 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 U.S. Patent No. 7,235,607, which is incorporated herein by reference.

[0204] 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.

[0205] Retail films can be used for packaging and / or bundling products for consumer use, such as for supermarket goods. These films are typically formed to a thickness of approximately 35 μm to 80 μm in a single bubble blown extrusion process.

[0206] 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.

[0207] experiment

[0208] General Considerations and Reagents

[0209] Unless otherwise noted, all manipulations were carried out under an inert atmosphere using glovebox techniques. Prior to 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.

[0210] Relaxation Time and Cross Equation Constants: In addition to SAOS and other parameters described elsewhere herein, relaxation time τ and / or Cross equation values (notably viscosity, time, and power law constants) can help indicate the presence of polydispersity / MWD and / or long chain branching in the polymer composition (or the behavior of the polymer composition in a manner simulating a long chain branched polymer). The relaxation time τ can be determined from the Cross equation used to model viscosity data collected over a frequency range. Viscosity data collected over a certain frequency range can be fit using the Cross equation in general form (J.M Dealy and K.F Wissbrun, Melt Rheology and Its Role in Plastics Processing Theory and Applications; Van Nostrand Reinhold: New York, p. 162 (1990)):

[0211] <000098​​​​​​​​​​​​This expression gives the relaxation time when tested under constant strain and temperature. As noted, the relaxation time τ in the Cross Model can be correlated with polydispersity and / or long-chain branching in the polymer. For increased levels of branching (and / or simulating polymer compositions with increased branching levels), τ is expected to be higher compared to linear polymers of the same molecular weight. The three Cross parameters—viscosity (η0), time (τ), and power-law (n) constants—can also be labeled as Cross equation constants A1, A2, and A3, respectively.

[0215] Catalyst synthesis of catalyst 19:

[0216] (Catalyst 19)

[0217] Synthesis of (5,5,8,8-tetramethyl-6,7-dihydro-1H-cyclopentadieno[b]naphthalen-1-yl)lithium(1):

[0218] 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).

[0219] Synthesis of dichlorobis(5,5,8,8-tetramethyl-6,7-dihydro-1H-cyclopentadien[b]naphth-1-yl)zirconium(2):

[0220] (5,5,8,8-tetramethyl-6,7-dihydro-1H-cyclopentadieno[b]naphthyl)lithium (1) (9.97 g, 42.9 mmol, 2.00 equivalent) was added to a white suspension of zirconium tetrachloride (5.00 g, 21.5 mmol, 1.00 equivalent) in diethyl ether (200 mL) under vigorous stirring at -40 °C. The reaction was warmed to room temperature and stirred overnight, then concentrated under vacuum. The solid was extracted with dichloromethane and the extract was filtered and then dried under vacuum. The resulting solid was washed with cold pentane and dried under vacuum to give a yellow solid (12.9 g, 98%). 1 H NMR(C6D6) 7.52(s,4H),6.15(dt,2H),5.82(dt,4H),1.58(m,8H),1.37(s,12H),1.23(s,12H).

[0221] Synthesis of dimethylbis(5,5,8,8-tetramethyl-6,7-dihydro-1H-cyclopentadieno[b]naphth-1-yl)zirconium (catalyst 19):

[0222] Adding 3 M MeMgBr (39.7 mL, 0.119 mol, 5.0 equivalent) in Et₂O to a bright yellow suspension of dichloro-(5,5,8,8-tetramethyl-6,7-dihydro-1H-cyclopentadieno[b]naphth-1-yl)zirconium(2) (14.6 g, 0.024 mol, 1.0 equivalent) in diethyl ether (100 mL) at -35 °C yielded a cold, turbid, yellow mixture. The reaction mixture was stirred overnight at room temperature. The solvent was removed under vacuum. The product was extracted with pentane and a dark brown solid was filtered off. Removal of pentane under vacuum resulted in the formation of a pale yellow solid (yield 12.5 g, 91.6%). 1 H NMR(C6D6) 7.37(s,4H),5.82(dt,4H),5.70(dt,2H),1.59(m,8H),1.27(s,24H),-0.83(s,6H).

[0223] Catalyst synthesis of catalyst 1:

[0224]

[0225] Synthesis of (5,5,8,8-tetramethyl-6,7-dihydro-1H-cyclopentadieno[b]naphth-1-yl)lithium(1):

[0226] 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).

[0227] Synthesis of 3,5,5,8,8-pentamethyl-6,7-dihydro-3H-cyclopentadien[b]naphthalene(2):

[0228] (5,5,8,8-tetramethyl-6,7-dihydro-1H-cyclopentadieno[b]naphthyl)lithium (1) (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) at -35 °C, 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 to give 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 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).

[0229] Synthesis of (3,5,5,8,8-pentamethyl-6,7-dihydro-1H-cyclopentadieno[b]naphth-1-yl)lithium(3):

[0230] 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 (2) (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).

[0231] Synthesis of dichlorobis(3,5,5,8,8-pentamethyl-6,7-dihydro-1H-cyclopentadien[b]naphth-1-yl)zirconium(4):

[0232] Lithium (3), (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 to 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 16.01 g (97%) of bright yellow powder. 1 H NMR(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).

[0233] Synthesis of dimethylbis(3,5,5,8,8-pentamethyl-6,7-dihydro-1H-cyclopentadieno[b]naphth-1-yl)zirconium (catalyst 1):

[0234] Adding 3.28 M MeMgBr (10.7 mL, 0.032 mol, 5.0 equivalent) in Et₂O to a bright yellow suspension of dichlorobis(3,5,5,8,8-pentamethyl-6,7-dihydro-1H-cyclopentadieno[b]naphth-1-yl)zirconium(4) (4.11 g, 0.006 mol, 1.0 equivalent) in 100 mL diethyl ether at -35 °C yielded a cold, turbid, yellow mixture. The reaction mixture was stirred overnight at room temperature. The solvent was removed under vacuum. The product was extracted with pentane and a dark brown solid was filtered off. Removal of pentane under vacuum resulted in the formation of a pale yellow solid, 3.67 g, 87.2%. 1 H NMR(C6D6)7.50(S,1H),7.48(S,1H),7.28(dt,1H),7.22(dt,1H),5.49(dt,1H),5.44(m,3H),2.26(s,3H),2.26(s,3H),1.62(m ,8H),1.35(s,3H),1.32(s,6H),1.31(s,3H),1.30(s,3H),1.29(s,6H),1.28(s,3H),-0.32(s,1H),-0.89(s,3H),-1.50(s,1H).

[0235] Catalyst support:

[0236] Catalyst supported by ES70 875 C silica and MAO.

[0237] Catalyst 19 loading program:

[0238] 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 19 (1.1 g) 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 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 in a sonojell.

[0239] Catalyst 1 loading program:

[0240] 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 catalyst (1.15 g) was dissolved in 20 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.

[0241] Table 1

[0242]

[0243] The polyethylene (PE) resin used as a comparative example and in the embodiments of the present invention was produced in a small gas-phase reactor with a diameter of 12" in continuous operation. Table 1 lists the polymerization conditions used. The "EtInd" comparative catalyst in Table 1 refers to racemic-meso-dimethylbis(1-ethylindenyl)2-zirconium.

[0244] The granular PE resin from the gas-phase reactor was dry-blended in a drum mixer with the following additive: 500 ppm Irganox. TM -1076, 1,000 ppm of Irgafos TM Dynamar 168 and 600ppm TM FX5920A was then used, and subsequently compounded under typical PE compounding conditions on a laboratory-scale twin-screw extruder (Leistritz 27 or Leistritz 18). The QC properties and compositional characteristics of the resulting stabilized PE pellets were characterized. Table 2 lists the product characterization results.

[0245] Density testing was performed 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.

[0246] Melt index (MI) or high load melt index (HLMI or FI) shall conform to ASTM D-1238, at 2.16 kg or 21.6 kg at 190°C.

[0247] Rheological characterization was performed using small-amplitude oscillatory shear tests on an ARES-G2 instrument at 190°C with strains ranging from 4% to 6%, in a frequency range from 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 text abruptly ends here, so the translation stops as well.)-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.

[0248] Table 2 Product Characteristics

[0249]

[0250] Figure 1 It is a graph showing the superposition of complex viscosities of the ethylene-hexene copolymer using catalyst 19 in a gas-phase reactor.

[0251] Figure 2 This is a graph showing the superimposed tensile viscosity of the ethylene-hexene copolymer using catalyst 19 in a gas-phase reactor. The sharp increase in the tensile viscosity line of the polymer of the present invention over a long period of time indicates long-chain branching.

[0252] Figure 3 This is a Van Gurp Palmen plot of ethylene-hexene copolymers from different catalysts in a gas-phase reactor. As mentioned above, the inflection points in the curves where the polymers of the present invention typically exhibit negative slopes indicate long-chain branching.

[0253] In summary, the polyethylene of this disclosure can be characterized as having a unique balance of chemical, physical, and mechanical properties relative to conventional MDPE, conventional LLDPE, and other conventional polyethylene grades. For example, the polyethylene of this disclosure exhibits a density conventionally associated with MDPE (or HDPE), while also possessing long-chain branching and a low melt index. Even though (1) the catalyst of this disclosure provides a low comonomer introduction rate and (2) the polyethylene of this disclosure, in some embodiments, does not have BOCD, long-chain branching and a low melt index can still be obtained. Even though the polyethylene copolymer (1) has good film-forming processability and (2) the catalyst of this disclosure provides high molecular weight polyethylene, the polyethylene copolymer of this disclosure can surprisingly provide improved film properties. Furthermore, and compared to conventional LLDPE and other conventional polyethylene grades, the polyethylene of this disclosure can have a low melt index, higher viscosity at low shear rates (e.g., due to a generally low comonomer introduction rate and, in particular, a low comonomer content in the high molecular weight portion of the polyethylene copolymer), and improved processability, such as improved extrudability (e.g., due to long-chain branching), while maintaining good bubble stability during the manufacturing process. For example, the catalysts and polymerization of this disclosure can provide MDPE (or HDPE) with low melt rates at shear rates typically encountered during extrusion and melt processing, and high melt viscosity at lower shear rates (e.g., at zero shear viscosity) to improve bubble stability during processing. These advantages can be achieved even when the catalysts of this disclosure provide high molecular weight polyethylene copolymers. For example, the catalysts of this disclosure provide improved molecular weight capacity compared to conventional bisindenylzirconia. This high molecular weight of the polyethylene copolymer (except for the lack of BOCD) compared to conventional MDPE (or HDPE) can provide improved toughness properties of the polyethylene copolymer.

[0254] Certain embodiments and features have been described using a set of upper and lower limits for numerical values. It is self-evident that ranges including combinations of any two values, such as any lower limit value combined with any upper limit value, any two lower limit values, and / or any two upper limit values, are considered, unless otherwise stated. Certain lower limits, upper limits, and ranges appear in one or more of the following claims. All numerical values ​​are "approximately" or "roughly" indicating values, and experimental errors and deviations that a person skilled in the art would expect are taken into account.

[0255] For all purposes and to the full extent permitted by such incorporation, all priority documents are incorporated herein by reference in their entirety, to the extent that such specification is consistent with this disclosure. Furthermore, all references and bibliographies cited herein (including experimental procedures, publications, patents, journal articles, etc.) are incorporated herein by reference in their entirety, provided that their disclosure does not contradict this disclosure.

[0256] Similarly, 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 listed composition, element, or element, and vice versa, is also considered. Unless otherwise specified, the phrase "consistently composed of" does not exclude the presence of other steps, elements, or materials (whether or not specifically mentioned in this specification), provided that such steps, elements, or materials do not affect the fundamental and novel characteristics of the invention. Furthermore, the phrase does not exclude impurities and variations typically associated with the elements and materials used.

[0257] Although the invention has been described with respect to 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. Unbridged catalyst compounds represented by formula (I): in: M is a Group 4 metal; R 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 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 substituted or unsubstituted hydrocarbon groups; 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.

2. The unbridged catalyst compound of claim 1, wherein the unbridged catalyst compound 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, wherein R 2 or R 9 At least one of them is not a substituted or unsubstituted hydrocarbon 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 unbridged catalyst compound of claim 2, wherein each X of formula (II) is a halogen group, and R of formula (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.

4. The unbridged catalyst compound of claim 3, wherein 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.

5. The unbridged catalyst compound of claim 2, wherein each X of formula (II) is independently a C1-C4 alkyl or halogen group, and R 1 R 2 R 3 R 8 R 9 and R 10 Each of them is hydrogen; 5. The unbridged catalyst compound of claim 2, wherein (i) each X of formula (II) is independently a C1-C4 alkyl group, and (ii) R of formula (II) is hydrogen. 1 R 2 and R 3 One of them is C1-C 10 Alkyl groups, the rest of the R 1 R 2 and R 3 Each is hydrogen; and R in (iii) of formula (II) 8 R 9 and R 10 One of them is C1-C 10 Alkyl groups, and the remaining R 8 R 9 and R 10 Each is hydrogen.

6. The unbridged catalyst compound of claim 5, wherein R 3 and R 10 Each of them is either methyl or ethyl.

7. The unbridged catalyst compound of claim 5 or claim 6, wherein R of 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 groups and / or R of 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.

8. The unbridged catalyst compound of any one of claims 2 to 7, wherein M in formula (II) is zirconium.

9. The unbridged catalyst compound of claim 2, wherein the unbridged catalyst compound of formula (II) is selected from: 。 10. The unbridged catalyst compound of claim 9, wherein the unbridged catalyst compound is: or 。 11. The unbridged catalyst of claim 3 or claim 4, wherein the unbridged catalyst compound is selected from: 。 12. Catalyst system, comprising: Carrier material; Optionally, activator; and The unbridged catalyst compound of any one of claims 1 to 11.

13. A method for preparing a polyethylene composition, comprising: Under polymerization conditions, ethylene and C3-C 40 α-olefins are introduced into a reactor together with the catalyst system of claim 12 to form a polyethylene copolymer, wherein the polyethylene copolymer has: Approximately 95% by weight or more of ethylene-derived units and the balance C3-C 20 The total mass of units derived from comonomers, based on the combined mass of ethylene-derived and comonomer-derived units; Approximately 0.925 g / cm³ 3 To approximately 0.955 g / cm 3 density, Weight-average molecular weight (Mw) of approximately 60,000 g / mol to approximately 300,000 g / mol. Number-average molecular weight (Mn) from approximately 7,500 g / mol to approximately 50,000 g / mol. Z-average molecular weight (Mz) of approximately 700,000 g / mol to approximately 2,000,000 g / mol. Melt index (MI, 190℃, 2.16kg) of approximately 0.3 g / 10 min to approximately 11 g / 10 min. The melt index ratio (MIR, the ratio of high-load melt index to melt index (HLMI / MI)) is approximately 20 to approximately 200. A shear thinning index greater than 5 (STI 0.1 / 100).

14. The method of claim 13, wherein the polyethylene copolymer has a composition distribution width index (CDBI) of about 40% to about 65%.

15. The method of claim 13 or claim 14, wherein the polyethylene copolymer is characterized by having long-chain branching.

16. The method of claim 15, wherein the long-chain branching of said polyethylene copolymer exhibits one or more of the following properties: (a) g'vis values ​​of approximately 0.85 to approximately 0.97; (b) The inflection point in the Van Gurp Palmen plot of the phase angle relative to the complex modulus; (c) MIR of 25 to 200; and (d) Shear thinning index of 6 to 65 (STI 0.1 / 100).

17. A polyethylene copolymer, comprising: Approximately 95% by weight or more of ethylene-derived units and the balance C3-C 20 The total mass of units derived from comonomers, based on the combined mass of ethylene-derived and comonomer-derived units; The polyethylene copolymer has the following characteristics: Approximately 0.925 g / cm³ 3 To approximately 0.955 g / cm 3 density, Weight-average molecular weight (Mw) of approximately 50,000 g / mol to approximately 300,000 g / mol. Number-average molecular weight (Mn) of approximately 5,000 g / mol to approximately 50,000 g / mol. Z-average molecular weight (Mz) of approximately 300,000 g / mol to approximately 2,000,000 g / mol. The melt index ranges from approximately 0.3 g / 10 min to approximately 11 g / 10 min. The melt index ratio of approximately 20 to approximately 200, and A shear thinning index greater than 5 (STI 0.1 / 100).

18. The polyethylene copolymer of claim 17, further comprising about 40% to about 65% CDBI.

19. The polyethylene copolymer of claim 17 or claim 18, wherein the polyethylene copolymer is characterized by having long-chain branching.

20. The polyethylene copolymer of claim 19, wherein the long-chain branching of said polyethylene copolymer exhibits one or more of the following properties: (i) g'vis values ​​of approximately 0.85 to approximately 0.97; (ii) The inflection point in the Van Gurp Palmen plot of the phase angle relative to the complex modulus; (iii) MIR of 25 to 200; and (iv) Shear thinning index of 6 to 65 (STI 0.1 / 100).

21. The polyethylene copolymer of any one of claims 17-20, having one or more of the following properties: (a) Approximately 0.94 g / cm³ 3 To approximately 0.955 g / cm 3 The density; (b) Approximately 97% by weight to approximately 98.5% by weight of ethylene-derived units; (c) MIR of approximately 120 to approximately 180; (d) Molecular weight distribution (Mw / Mn) from approximately 6 to approximately 7.5; (e) Mw of about 120,000 to about 200,000 g / mol; (f) Mz of about 800,000 to about 1,000,000 g / mol; or (g) Shear thinning index of about 5 to about 65 (ST10.1 / 100).

22. The polyethylene copolymer of claim 21, wherein the polyethylene copolymer has a shear thinning index (STI 0.1 / 100) of about 25 to about 35.

23. The polyethylene copolymer of claim 21, wherein the polyethylene copolymer has a shear thinning index (STI 0.1 / 100) of about 55 to about 65.

24. The polyethylene copolymer of any one of claims 17 to 23, wherein the copolymer is prepared using the catalyst system of claim 12.

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