Bimodal polyethylene copolymer

Abstract

Ethylene-based polymers are characterized by 0.92 to 0.955 g / cm 3 The present invention relates to ethylene polymers having a density of less than 1000 g / 10 min, a HLMI of less than 35 g / 10 min, and a ratio of the number of short chain branches (SCB) per 1000 total carbon atoms at Mz to the number of SCBs per 1000 total carbon atoms at Mn in the range of 11.5 to 22. These polymers may have a higher molecular weight (HMW) component and a lower molecular weight (LMW) component, wherein the ratio of the number of SCBs per 1000 total carbon atoms at Mn of the HMW component to the number of SCBs per 1000 total carbon atoms at Mn of the LMW component is in the range of 10.5 to 22. These ethylene polymers may be produced using a dual catalyst system comprising: an unbridged metallocene compound having an indenyl group having at least one halogen-substituted hydrocarbyl substituent having at least two halogen atoms; and a monoatom bridged metallocene compound having a fluorenyl group and a cyclopentadienyl group.

Description

[0001] Citation of Related Applications

[0002] This application is a continuation-in-part of co-pending U.S. patent application No. 16 / 593,566, filed on October 4, 2019, the disclosure of which is incorporated herein by reference in its entirety. Technical Field

[0003] The present disclosure relates generally to bimodal ethylene-based polymers and, more particularly, to polymers having a majority of the short chain branch content concentrated in the high molecular weight portion of the polymer. Background Art

[0004] Incorporating comonomer short chain branches (SCBs) into high density polyethylene (HDPE) copolymers and linear low density polyethylene (LLDPE) copolymers can be used to tailor the properties of the polymers. For example, SCBs can reduce polymer crystallinity and increase impact strength, but can also reduce polymer stiffness and polymer density.

[0005] For bimodal ethylene polymers, it is generally advantageous for the low molecular weight portion of the polymer to have a low concentration of comonomer SCB, while the high molecular weight portion has a relatively higher concentration of comonomer SCB. The present invention is generally directed to these objectives. Summary of the invention

[0006] This summary is provided to introduce a selection of concepts further described below in the detailed description in a simplified form. This summary is not intended to identify the necessary or essential features of the claimed subject matter. This summary is also not intended to be used to limit the scope of the claimed subject matter.

[0007] In one aspect, the present invention generally relates to ethylene-based polymers characterized by 0.92 to 0.955 g / cm 3 A density in the range of 1000 g / 10 min, a HLMI less than or equal to 35 g / 10 min, and a ratio of the number of short chain branches (SCB) per 1000 total carbon atoms at Mz to the number of SCB per 1000 total carbon atoms at Mn in the range of 11.5 to 22.

[0008] In another aspect, provided herein is an ethylene polymer characterized by 0.92 to 0.955 g / cm 3 A density within a range of 5 to 10 g / 10 min, a HLMI of less than or equal to 35 g / 10 min, and a higher molecular weight (HMW) component and a lower molecular weight (LMW) component, wherein the ratio of the SCB number per 1000 total carbon atoms at Mn of the HMW component to the SCB number per 1000 total carbon atoms at Mn of the LMW component is in the range of 10.5 to 22.

[0009] Polymerization methods are also included herein. For example, a representative polymerization method can include contacting a catalyst composition with ethylene and an alpha-olefin comonomer in a polymerization reactor system under polymerization conditions to produce an ethylene polymer, wherein the catalyst composition comprises: a catalyst component I comprising any unbridged metallocene compound disclosed herein, a catalyst component II comprising any bridged metallocene compound disclosed herein, any activator disclosed herein, and optionally any cocatalyst disclosed herein.

[0010] The foregoing summary of the invention and the following detailed description all provide examples and are illustrative only. Therefore, the foregoing summary of the invention and the following detailed description should not be considered as restrictive. In addition, features or variations other than those set forth herein may also be provided. For example, certain aspects and embodiments may be directed to various feature combinations and sub-combinations described in the detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Figure 1 The definitions of D85 and D15 on the molecular weight distribution curve are explained.

[0012] Figure 2 The definitions of D50 and D10 on the molecular weight distribution curve and the short chain branch content at D50 and D10 are explained.

[0013] Figure 3 A plot of the short chain branching distribution across the molecular weight distribution of the polymers of Examples 1-2 is presented.

[0014] Figure 4 A plot of the short chain branching distribution across the molecular weight distribution of the polymers of Examples 3-4 is presented.

[0015] definition

[0016] In order to more clearly define the terms used herein, the following definitions are provided. Unless otherwise indicated, the following definitions apply to the present disclosure. If the term is used in the present disclosure but is not specifically defined in this article, the definition in IUPAC Compendium of Chemical Terminology, the 2nd edition (1997) can be applied, as long as the definition does not conflict with any other disclosure or definition used herein, or does not make any technical solution used by the definition unclear or invalid. If any definition or usage provided by any file incorporated herein by reference conflicts with the definition or usage provided herein, then the definition or usage provided herein shall prevail.

[0017] Herein, features of the subject matter are described such that within a particular aspect, combinations of different features are contemplated. For each aspect and / or feature disclosed herein, all combinations that do not adversely affect the designs, compositions, and / or methods described herein are contemplated, with or without explicit description of a particular combination. Furthermore, unless otherwise expressly stated, any aspect and / or feature disclosed herein may be combined to describe inventive features consistent with the present disclosure.

[0018] Although compositions and methods are described herein as "comprising" various components or steps, unless otherwise specified, compositions and methods may also "consist essentially of" or "consist of" various components or steps. For example, a catalyst composition consistent with various aspects of the present invention may comprise catalyst component I, catalyst component II, an activator, and a co-catalyst; alternatively, may consist essentially of catalyst component I, catalyst component II, an activator, and a co-catalyst; or alternatively, may consist of catalyst component I, catalyst component II, an activator, and a co-catalyst.

[0019] Unless otherwise stated, the terms "a", "an", "the", etc. are intended to include multiple alternatives, such as at least one. For example, unless otherwise stated, disclosure of "co-catalyst" or "metallocene compound" is intended to cover one of the co-catalyst or metallocene compound, or a mixture or combination of more than one, respectively.

[0020] In general, element groups are referred to using the numbering scheme indicated in the version of the periodic table published in Chemical and Engineering News, 63(5), 27, 1985. In some cases, element groups may be referred to using the common name assigned to the group; for example, alkali metals refer to Group 1 elements, alkaline earth metals refer to Group 2 elements, transition metals refer to Groups 3-12 elements, and halogens or halide ions refer to Group 17 elements.

[0021] For any particular compound disclosed herein, unless otherwise indicated, the general structure or name presented is also intended to include all structural isomers, conformational isomers and stereoisomers that can be generated by a specific set of substituents. Therefore, unless otherwise explicitly stated, the compound generally mentioned includes all structural isomers; for example, the pentane generally mentioned includes n-pentane, 2-methyl-butane and 2,2-dimethylpropane, while the butyl generally mentioned includes n-butyl, sec-butyl, isobutyl and tert-butyl. In addition, as the context allows or requires, the general structure or name mentioned includes all enantiomers, diastereomers and other optical isomers, whether enantiomers or racemic forms, and mixtures of stereoisomers. For any specific formula or name provided, any general formula or name provided also covers all conformational isomers, regioisomers and stereoisomers that can be generated by a set of specific substituents.

[0022] The term "substituted" when used to describe a group, for example, when referring to a substituted analog of a particular group, is intended to describe any non-hydrogen moiety that formally replaces a hydrogen in the group, and is intended to be non-limiting. One or more groups may also be referred to herein as "unsubstituted," or equivalent terms such as "non-substituted," which refer to the original group in which the non-hydrogen moiety does not replace a hydrogen in the group. Unless otherwise noted, "substituted" is intended to be non-limiting and includes inorganic or organic substituents as understood by those of ordinary skill in the art.

[0023] Whenever used in this specification and claims, the term "hydrocarbon" refers to a compound containing only carbon and hydrogen. Other identifiers may be used to indicate the presence of specific groups in a hydrocarbon (e.g., a halogenated hydrocarbon indicates the presence of one or more halogen atoms that replace an equivalent amount of hydrogen atoms in the hydrocarbon). The term "hydrocarbon group" is used herein according to the definition specified by IUPAC: a monovalent group formed by removing one hydrogen atom from a hydrocarbon (i.e., a group containing only carbon and hydrogen). Non-limiting examples of hydrocarbon groups include alkyl, alkenyl, aryl, and aralkyl, etc.

[0024] The term "polymer" is generally used herein to include olefin homopolymers, copolymers, terpolymers, etc., and their alloys and blends. The term "polymer" also includes impact, block, graft, random and alternating copolymers. Copolymers are derived from olefin monomers and an olefin comonomer, while terpolymers are derived from olefin monomers and two olefin comonomers. Therefore, "polymer" covers copolymers and terpolymers derived from any olefin monomer and comonomer disclosed herein. Similarly, the scope of the term "polymerization" includes homopolymerization, copolymerization and terpolymerization. Therefore, ethylene polymers include ethylene homopolymers, ethylene copolymers (e.g., ethylene / α-olefin copolymers), ethylene terpolymers, etc., and their blends or mixtures. Therefore, ethylene polymers include polymers commonly referred to as LLDPE (linear low density polyethylene) and HDPE (high density polyethylene) in the art. For example, olefin copolymers (such as ethylene copolymers) can be derived from ethylene and comonomers, such as 1-butene, 1-hexene or 1-octene. If the monomer and comonomer are ethylene and 1-hexene, respectively, the resulting polymer can be classified as an ethylene / 1-hexene copolymer. Unless otherwise specified, the term "polymer" also includes all possible geometric configurations, and such configurations may include isotactic, isotactic, and random symmetries. In addition, unless otherwise specified, the term "polymer" is also intended to include polymers of all molecular weights, and includes lower molecular weight polymers.

[0025] The term "co-catalyst" is generally used herein to refer to compounds that, when used, may constitute a component of the catalyst composition in addition to the activator-support, for example, aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds, organoaluminum compounds, organozinc compounds, organomagnesium compounds, organolithium compounds, etc. The term "co-catalyst" is used independently of the actual function of the compound or any chemical mechanism by which the compound may work.

[0026] The term "activator-support" is used herein to refer to a solid inorganic oxide with a relatively high porosity, which may exhibit Lewis acidic or Bronsted acidic behavior, and has been treated with an electron-withdrawing component (usually an anion) and calcined. The electron-withdrawing component is usually an electron-withdrawing anion source compound. Therefore, the activator-support may include a calcined contact product of at least one solid oxide and at least one electron-withdrawing anion source compound. Typically, the activator-support includes at least one acidic solid oxide compound. The "activator-support" of the present invention can be a chemically treated solid oxide. The term "activator-support" is used to imply that these components are not inert, and these components should not be interpreted as inert components of the catalyst composition. As used herein, the term "activator" generally refers to a substance that is capable of converting a metallocene component into a catalyst that can polymerize an olefin, or converting a contact product of a metallocene component with a component into a catalyst that can polymerize an olefin, when the metallocene compound does not yet contain an activatable ligand (e.g., alkyl, hydride), the component provides such a ligand to the metallocene. This term is used regardless of the actual activation mechanism. Illustrative activators include activator-supports, aluminoxanes, organoboron or organoborate compounds, ionizing ionic compounds, and the like. If aluminoxanes, organoboron or organoborate compounds, and ionizing ionic compounds are used in a catalyst composition in the absence of an activator-support, they are generally referred to as activators. If the catalyst composition contains an activator-support, aluminoxanes, organoboron or organoborate compounds, and ionizing ionic materials are typically referred to as co-catalysts.

[0027] As used herein, the term "metallocene" describes a metallocene comprising at least one 3 To 5 -cyclodiene-type moiety, wherein n 3 To 5 -Cycloalkadienyl moieties include cyclopentadienyl ligands, indenyl ligands, fluorenyl ligands, and the like (including partially saturated or substituted derivatives or analogs of any of these). Possible substituents on these ligands may include H, and thus the present invention includes ligands such as tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, substituted partially saturated indenyl, substituted partially saturated fluorenyl, etc. In some contexts, metallocenes are simply referred to as "catalysts," in much the same way as the term "cocatalyst" is used herein to refer to, for example, organoaluminum compounds.

[0028] The terms "catalyst composition", "catalyst mixture", "catalyst system", etc. do not depend on the actual products or compositions produced by the contact or reaction of the initial components of the disclosed or claimed catalyst composition / mixture / system, the nature of the active catalytic sites, or the fate of the cocatalyst, metallocene compound, or activator after combining these components. Thus, the terms "catalyst composition", "catalyst mixture", "catalyst system", etc. encompass the initial starting components of the composition, as well as any products that may be produced by contacting these initial starting components, and this includes heterogeneous and homogeneous catalyst systems or compositions. The terms "catalyst composition", "catalyst mixture", "catalyst system", etc. may be used interchangeably throughout this disclosure.

[0029] Unless otherwise indicated, the term "contact product" is used herein to describe a composition in which components are contacted together in any order, in any manner, and for any length of time. For example, the components may be contacted by blending or mixing. In addition, contact of any component may occur in the presence or absence of any other component of the composition described herein. Additional materials or components may be combined by any suitable method. In addition, the term "contact product" includes mixtures, blends, solutions, slurries, reaction products, etc., or combinations thereof. Although the "contact product" may include reaction products, it is not required that the individual components react with each other. Similarly, the term "contact" is used herein to refer to materials that can be blended, mixed, slurried, dissolved, reacted, processed, or otherwise combined.

[0030] Although any methods, devices, and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the typical methods, devices, and materials are described herein.

[0031] All publications and patents mentioned herein are incorporated herein by reference for the purpose of describing and disclosing, for example, the constructs and methodologies that are described in the publications, which might be used in connection with the presently described invention.

[0032] Several types of ranges are disclosed herein. When any type of range is disclosed or claimed, it is intended that every possible number that such range could reasonably encompass is disclosed or claimed individually, including the endpoints of the range and any subranges and combinations of subranges encompassed therein. For example, when a chemical moiety having a certain number of carbon atoms is disclosed or claimed, it is intended that every possible number that the range could reasonably encompass is disclosed or claimed individually. For example, as used herein, a moiety is C1 to C2. 18A hydrocarbyl group, or in other words, a hydrocarbyl group having 1 to 18 carbon atoms, refers to a moiety that can have 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms, and any range between these two numbers (e.g., C1 to C8 hydrocarbyl groups), and also includes any combination of ranges between these two numbers (e.g., C2 to C4 and C8). 12 To C 16 Hydrocarbon).

[0033] Similarly, another representative example follows the Mw / Mn ratio of ethylene polymers consistent with aspects of the present invention. By disclosing that the Mw / Mn ratio can be in the range of 6 to 25, it is intended to state that the Mw / Mn ratio can be any ratio within the range, and for example can include any range or range combination of 6 to 25, such as 7 to 20, 7 to 18, or 8 to 15, etc. Likewise, all other ranges disclosed herein should be interpreted in a manner similar to these examples.

[0034] In general, an amount, size, formulation, parameter, range, or other quantity or feature is "about" or "approximately," whether or not expressly stated as such. Whether or not modified by the term "about" or "approximately," the claims include equivalents to the quantities or features. DETAILED DESCRIPTION

[0035] The present invention generally relates to a dual metallocene catalyst system, a process for polymerizing olefins using the catalyst system, polymer resins produced using such catalyst systems, and articles produced using these polymer resins. In particular, the present invention generally relates to a bimodal ethylene copolymer having a low molecular weight fraction containing a low concentration of comonomer SCB and a high molecular weight fraction containing a relatively high concentration of comonomer SCB.

[0036] The disclosed bimodal ethylene polymers have surprisingly high short chain branching ratios between the high molecular weight and low molecular weight components. Advantageously, the low level of comonomer SCB content in the low molecular weight fraction of the polymer combined with the unexpectedly high level of SCB content in the high molecular weight fraction of the polymer can improve polymer properties such as stress crack resistance (ESCR), PENT slow crack growth resistance (ASTM F1473) and natural draw ratio (NDR), especially at equivalent total polymer density.

[0037] Ethylene polymer

[0038] Typically, the polymers disclosed herein are ethylene-based polymers or ethylene polymers, including homopolymers of ethylene and copolymers, terpolymers, and the like of ethylene and at least one olefin comonomer. Comonomers copolymerizable with ethylene may typically have 3 to 20 carbon atoms in their molecular chains. For example, typical comonomers may include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and the like, or combinations thereof. In one aspect, the olefin comonomers may include C3-C 18 olefins; alternatively, the olefin comonomer may comprise C3-C 10 olefins; alternatively, the olefin comonomer may comprise C4-C 10 olefins; alternatively, the olefin comonomer may comprise C3-C 10 α-olefins; alternatively, the olefin comonomer may comprise C4-C 10 α-olefin; alternatively, the olefin comonomer may comprise 1-butene, 1-hexene, 1-octene, or any combination thereof; or alternatively, the comonomer may comprise 1-hexene.

[0039] In one aspect, the ethylene polymer of the present invention may comprise an ethylene / α-olefin copolymer. For example, the ethylene polymer may comprise an ethylene / 1-butene copolymer, an ethylene / 1-hexene copolymer, an ethylene / 1-octene copolymer, or any combination thereof; alternatively, an ethylene / 1-butene copolymer; alternatively, an ethylene / 1-hexene copolymer; or alternatively, an ethylene / 1-octene copolymer.

[0040] If the resulting polymer produced according to the present invention is, for example, an ethylene copolymer, its properties can be characterized by various analytical techniques known and used in the polyolefin industry. Articles can be formed from and / or can include the ethylene polymers (e.g., ethylene copolymers) of the present invention, typical properties of which are provided below.

[0041] Illustrative and non-limiting examples of ethylene polymers described herein (e.g., ethylene / 1-hexene copolymers) may have a molecular weight of 0.92 to 0.955 g / cm 3 The present invention relates to a polymer having a density in the range of 0.92 to 0.955 g / cm2, a HLMI of less than or equal to 35 g / 10 min, and a ratio of the number of short chain branches (SCB) per 1000 total carbon atoms at Mz to the number of SCB per 1000 total carbon atoms at Mn of 11.5 to 22. Another illustrative and non-limiting example of the ethylene polymers described herein (e.g., ethylene / 1-hexene copolymers) may have a density in the range of 0.92 to 0.955 g / cm2. 3The present invention also provides a density within a range of 100 g / min, a HLMI of less than or equal to 35 g / 10 min, and a higher molecular weight (HMW) component and a lower molecular weight (LMW) component. The ratio of the SCB number per 1000 total carbon atoms at Mn of the HMW component to the SCB number per 1000 total carbon atoms at Mn of the LMW component can be in the range of 10.5 to 22. Unless otherwise stated, these illustrative and non-limiting examples of ethylene polymers consistent with the present invention can also have any of the polymer characteristics listed below and in any combination.

[0042] The density of ethylene-based polymers can range from 0.92 to 0.955 g / cm 3 In one aspect, the density can be in the range of 0.92 to 0.95, in another aspect, 0.92 to 0.94, in another aspect, 0.925 to 0.955, in another aspect, 0.925 to 0.95, or in another aspect, 0.925 to 0.943 g / cm 3 .

[0043] Ethylene polymers have very low melt indexes, as shown by a high load melt index (HLMI) of less than or equal to 35 g / 10 min. In some aspects, the HLMI of ethylene polymers may be less than or equal to 30 g / 10 min, or less than or equal to 25 g / 10 min. In other aspects, the HLMI of ethylene polymers may be less than or equal to 20 g / 10 min, or less than or equal to 15 g / 10 min.

[0044] Ethylene polymer can comprise high or higher molecular weight (HMW) component (or first component) and low or lower molecular weight (LMW) component (or second component).These component terms are relative, use with reference to each other, and are not limited to the actual molecular weight of each component.The molecular weight characteristics of these LMW and HMW components are determined (for example, using gel permeation chromatography to determine) by deconvoluting complex (total polymer) molecular weight distribution.By total polymer, the amount of lower molecular weight (LMW) component is not limited to any specific range.But, usually, the amount of lower molecular weight component can be in 40 to 90 weight %, 40 to 85 weight %, 45 to 90 weight %, 45 to 85 weight % or 50 to 85 weight %.

[0045] The higher molecular weight component may have an Mn in the range of 400,000 to 800,000 g / mol. For example, the Mn may be in the range of 450,000 to 750,000 g / mol, or alternatively, 500,000 to 700,000 g / mol. Additionally or alternatively, the higher molecular weight component may have an Mp in the range of 400,000 to 1,100,000 g / mol, such as 500,000 to 1,100,000 g / mol, or 550,000 to 1,000,000 g / mol. The lower molecular weight component of the ethylene polymer may have an Mz in the range of 70,000 to 200,000 g / mol (or 70,000 to 170,000, or 75,000 to 150,000, or 80,000 to 130,000 g / mol).

[0046] Typically, the unexpectedly high ratio of the number of SCBs per 1000 total carbon atoms at Mn of the HMW component to the number of SCBs per 1000 total carbon atoms at Mn of the LMW component is in the range of 10.5 to 22. Other suitable ranges for this ratio include, but are not limited to, 11 to 22, 11 to 21, 12 to 22, 12 to 20, or 13 to 19, etc. Additionally or alternatively, the ratio of the number of SCBs per 1000 total carbon atoms at Mp of the HMW component to the number of SCBs per 1000 total carbon atoms at Mp of the LMW component can be in the range of 11 to 18, and in some aspects, in the range of 11 to 14, 11.5 to 16, or 11.5 to 15. Additionally or alternatively, the ratio of the number of SCBs per 1000 total carbon atoms at Mp of the HMW component to the number of SCBs per 1000 total carbon atoms at Mz of the LMW component can be in the range of 7.5 to 18, and in some aspects, in the range of 8 to 16, 9 to 14, or 10 to 12.

[0047] In one aspect, ethylene polymers (including higher and lower molecular weight components) can have an Mw in the range of 200,000 to 800,000, 225,000 to 725,000, 250,000 to 600,000, or 275,000 to 575,000 g / mol. Additionally or alternatively, ethylene polymers can have an Mp in the range of 30,000 to 90,000 g / mol, such as 35,000 to 85,000, 40,000 to 80,000, or 45,000 to 75,000 g / mol. Additionally or alternatively, ethylene polymers can have an Mn in the range of 15,000 to 60,000 g / mol, such as 18,000 to 57,000, 22,000 to 53,000, or 25,000 to 50,000 g / mol. Additionally or alternatively, the ethylene polymer may have an Mz in the range of 1,300,000 to 3,100,000 g / mol, e.g., 1,400,000 to 3,000,000, 1,500,000 to 2,500,000, or 1,700,000 to 2,200,000 g / mol. Ethylene polymers have a relatively broad molecular weight distribution, typically with an Mw / Mn ratio in the range of 6 to 25. For example, the polymer may have an Mw / Mn ratio of 7 to 20; alternatively, 7 to 18; alternatively, 8 to 15; or alternatively, 9 to 13.

[0048] According to a particular aspect of the present invention, ethylene polymers can have bimodal molecular weight distribution.Usually, there are two distinguishable peaks (using gel permeation chromatography (GPC) to measure) in the molecular weight distribution curve, a valley between the peaks, and the peaks can be separated or deconvoluted.On the other hand, ethylene polymers can have multimodal (e.g., trimodal) molecular weight distribution.For example, ethylene polymers can have LMW component, MMW (medium molecular weight) component and HMW component.The LMW component can be a homopolymer or a copolymer with very low comonomer content.MMW and HMW components can be copolymers, wherein the HMW component has more comonomers (and SCB) than the MMW component.

[0049] Typically, the unexpectedly high ratio of the SCB number per 1000 total carbon atoms at Mz to the SCB number per 1000 total carbon atoms at Mn is in the range of 11.5 to 22. Other suitable ranges for this ratio include, but are not limited to, 12 to 21, 12 to 18, 13 to 22, or 13 to 19, etc. Although not limited thereto, and depending on the polymer density, the SCB number per 1000 total carbon atoms of the ethylene polymer at Mz may be in the range of 10 to 30, and in some aspects, in the range of 12 to 30, 15 to 28, or 17 to 26.

[0050] Figure 1is a graphical depiction of the molecular weight distribution curve of D85 and D15 as the molecular weight increases logarithmically. D85 is the molecular weight at which 85% by weight of the polymer has a higher molecular weight, and D15 is the molecular weight at which 15% by weight of the polymer has a higher molecular weight. According to one aspect of the invention, the molecular weight of the ethylene polymers disclosed herein at D85 may be in the range of 14,000 to 50,000 g / mol, and in another aspect, in the range of 15,000 to 40,000, 16,000 to 38,000, or 17,000 to 35,000 g / mol.

[0051] Similar to Figure 1 , Figure 2 It is a graphical description of the molecular weight distribution curve D50 and D10 as the molecular weight increases logarithmically. D50 is the molecular weight when 50% by weight of the polymer has a higher molecular weight, and D10 is the molecular weight when 10% by weight of the polymer has a higher molecular weight. In one aspect, the molecular weight of the ethylene polymer disclosed herein at D10 can be in the range of 750,000 to 2,000,000 g / mol, and in the range of 800,000 to 1,750,000 g / mol on the other hand, and in the range of 850,000 to 2,000,000 g / mol on the other hand, and in the range of 900,000 to 1,750,000 g / mol on the other hand. Although not limited to this, and depending on the polymer density, the SCB number per 1000 total carbon atoms of the ethylene polymer at D10 can be in the range of 9 to 30; alternatively, in the range of 12 to 28; alternatively, in the range of 14 to 27; or alternatively, in the range of 16 to 25.

[0052] In one aspect, the ethylene polymers described herein can be reactor products (e.g., single reactor products), e.g., rather than, for example, post-reactor blends of two polymers having different molecular weight characteristics. Those skilled in the art will readily recognize that physical blends of two different polymer resins can be prepared, but this requires additional processing and complexity that is not required for reactor products.

[0053] In addition, ethylene polymers can be produced with a dual metallocene catalyst system comprising zirconium and / or hafnium, as discussed herein. Ziegler-Natta and chromium-based catalyst systems can be used, but are not required. Therefore, ethylene polymers may not contain a measurable amount (i.e., less than 0.1ppm by weight) of chromium or titanium or vanadium or magnesium (catalyst residues). In some aspects, ethylene polymers may independently contain less than 0.08ppm, less than 0.05ppm or less than 0.03ppm of chromium (or titanium, or vanadium, or magnesium).

[0054] Products

[0055] Articles can be formed by ethylene polymers of the present invention (e.g., ethylene / 1-hexene copolymers), and / or can include the ethylene polymers, and are therefore encompassed herein. For example, articles that can include polymers of the present invention can include, but are not limited to, agricultural films, auto parts, bottles, chemical containers, barrels, fibers or fabrics, food packaging films or containers, food service products, fuel tanks, geomembranes, household containers, liners, molded products, medical devices or materials, outdoor storage products (e.g., panels of outdoor shed walls), outdoor recreational equipment (e.g., kayaks, basketball goal bases), pipelines, sheets or tapes, toys or traffic barriers, etc. Various methods can be used to form these articles. Non-limiting examples of these methods include injection molding, blow molding, rotational molding, film extrusion, sheet extrusion, profile extrusion, thermoforming, etc. In addition, additives and modifiers are usually added to these polymers to provide useful polymer processing or end-use product attributes. Such methods and materials are described in Modern Plastics Encyclopedia, Mid-November 1995 Issue, Vol. 72, No. 12; and Film Extrusion Manual—Process, Materials, Properties, TAPPI Press, 1992; the disclosures of which are incorporated herein by reference in their entireties.

[0056] Catalyst system and polymerization method

[0057] According to various aspects of the present invention, ethylene polymers (e.g., ethylene copolymers) can be produced using a dual catalyst system. In these aspects, catalyst component I can include any suitable unbridged metallocene compound disclosed herein, and catalyst component II can include any suitable bridged metallocene compound disclosed herein. The catalyst system can also include any suitable activator or any activator disclosed herein, and optionally, any suitable cocatalyst or any cocatalyst disclosed herein.

[0058] First, with reference to catalyst component I, it may include an unbridged metallocene compound. In one aspect, catalyst component I may include an unbridged metallocene compound containing two indenyls or an indenyl and a cyclopentadienyl, wherein at least one indenyl has at least one halogen-substituted hydrocarbyl substituent, and the substituent has at least two halogen atoms. On the other hand, catalyst component I may include an unbridged metallocene compound containing two indenyls, wherein at least one indenyl has at least one halogen-substituted hydrocarbyl substituent, and the substituent has at least two halogen atoms. On the other hand, catalyst component I may include an unbridged metallocene compound containing an indenyl and a cyclopentadienyl, wherein the indenyl has at least one halogen-substituted hydrocarbyl substituent, and the substituent has at least two halogen atoms. Although not limited thereto, the halogen-substituted hydrocarbyl substituent may include an aryl. Independently, the halogen atom may be any halogen, but typically each halogen is fluorine. The unbridged metallocene compound may contain titanium, zirconium or hafnium, but catalyst component I is typically a zirconium-based metallocene compound.

[0059] In a particular aspect of the present invention, catalyst component I may comprise an unbridged metallocene compound having the formula: 1 )(X 2 )(X 3 )(X 4 )M 1 , where M 1 , X 1 , X 2 , X 3 and X 4 Choose from the following: a) M 1 Can be titanium, zirconium or hafnium; b) X 1 It may be a substituted indenyl ligand, wherein at least one substituent is a halogen-substituted C1-C ... 20 Hydrocarbyl; c) X 2 may be [1] a substituted or unsubstituted cyclopentadienyl ligand which does not contain a halogen-substituted hydrocarbon group, or [2] a substituted or unsubstituted indenyl ligand; wherein X 1 and X 2 is unbridged, and where X 1 and X 2 C1-C 20 Any substituent of the hydrocarbon group is independently selected from C1-C 20 alkyl; and d) X 3 and X 4 independently selected from halides, hydrides, C1-C 20 Hydrocarbon, C1-C 20 Heteroalkyl, tetrahydroborate or OBR A 2 or OSO2R A , where R AIndependently C1-C 12 Hydrocarbon.

[0060] Unexpectedly, when the metallocene indenyl ligand X1 contains at least one substituent which is a halogen-substituted C1-C1-C2-olefin, a catalyst composition comprising catalyst component I can produce low molecular weight polyethylene having unexpectedly low levels of short chain branching even in the presence of significant concentrations of α-olefin comonomers. 20 A hydrocarbon group, such as a C1-C1-C1-substituted group, substituted with at least two independently selected fluorine, chlorine or bromine substituents. 20 When [1] the metallocene contains a C1-C 20 Indenyl ligand X with hydrocarbon group as substituent 1 , and [2] when ligand X 2 When X is a cyclopentadienyl ligand, 2 When there is no halogen-substituted hydrocarbon group, a polymer having these characteristics can be produced. 2 When X is an indenyl ligand, 2 The presence of halogen-substituted hydrocarbon groups still provides the desired low level of short chain branching, but when X 2 It is not provided for cyclopentadienyl ligands.

[0061] In one aspect, the substituted indenyl ligand X containing a halo substituent 1 does not contain a halogen substituent directly bonded to the indenyl ligand. In another aspect, X 2 Ligand or X 1 and X 2 Neither contain a halogen substituent directly bonded to the indenyl ligand.

[0062] In one aspect, the M in the unbridged metallocene 1 May be Ti; alternatively, M 1 may be Zr; alternatively, M 1 May be Hf; alternatively, M 1 Can be Ti or Zr; alternatively, M 1 Can be Ti or Hf; alternatively, M 1 Can be Zr or Hf; or alternatively, M 1 It can be Ti, Zr or Hf.

[0063] According to another aspect, the group X which is not bridged to the metallocene 3 and X 4 Can be independently selected from F, Cl, Br, Cl-C 12 Alkyloxy, C1-C 12 A hydrocarbylamino or trihydrocarbylsilyl group, wherein each hydrocarbyl group is independently C1-C 12 Hydrocarbon.

[0064] Unbridged metallocene X 1 The halogen-substituted hydrocarbyl substituents may be selected from C1-C12-substituted alkyl groups substituted with at least two independently selected fluorine substituents, chlorine substituents, bromine substituents or iodine substituents or a combination thereof. 20 In some aspects, X 1 The halogen-substituted hydrocarbon substituent is selected from C1-C2-substituted hydrocarbon substituents substituted with at least two fluorine substituents, chlorine substituents or bromine substituents. 20 Hydrocarbon or C1-C 12 In one aspect, X 1 It may be a substituted indenyl ligand, wherein at least one substituent is a halogen-substituted C1-C 20 Hydrocarbyl groups containing 2, 3, 4, 5, 6, 7, 8 or more halogen atoms, such as fluorine atoms, include ranges between any of these values ​​as permitted by the size and structure of the particular hydrocarbyl group. 20 When the hydrocarbon group is phenyl, the upper limit of the number of halogen substituents is five (5) substituents, and the phenyl group may include 2, 3, 4 or 5 substituents. 20 The hydrocarbyl group may contain 2 to 8, 2 to 7, 2 to 6, 2 to 5, 2 to 4 or 2 to 3 halogen atoms.

[0065] For example, in one aspect, the unbridged metallocene X 1 The halogen-substituted hydrocarbyl substituents may be selected from C1-C1-C1-substituted hydrocarbyl substituents substituted with at least two fluorine substituents, chlorine substituents or bromine substituents. 20 Aliphatic group or C6-C 20 In another aspect, the unbridged metallocene X 1 The halogen-substituted hydrocarbon substituents may be selected from C1-C 12 Alkyl, C2-C 12 alkenyl, C3-C7 cycloalkyl, C3-C7 cycloalkenyl, C6-C 10 Aryl or C7-C 12 On the other hand, the metallocene X 1 The halogen-substituted hydrocarbyl substituent may be further substituted with at least one selected from C1-C 12 The hydrocarbon group is substituted with additional substituents.

[0066] In some aspects, the unbridged metallocene X 1 The ligand may be an indenyl ligand which may be substituted with a halogen-substituted hydrocarbon group selected from: [1] -C6X 9 n H 5-n or -CH2C6X 9 n H5-n , wherein n is an integer from 2 to 5; [2] -(CH2) m CX 9 p H 3-p , wherein m is an integer from 0 to 3 and wherein p is an integer from 2 to 3; or [3] -C(CX 9 3) q (CH3) 3-q or -C(CX 9 3) q H 3-q , wherein q is an integer from 2 to 3; and wherein X 9 is independently selected at each occurrence from fluoro, chloro or bromo.

[0067] As disclosed herein, in one aspect, the unbridged metallocene X 2 The ligand may be [1] a substituted or unsubstituted cyclopentadienyl ligand which does not contain a halogen-substituted hydrocarbon group, or [2] a substituted or unsubstituted indenyl ligand; wherein X 1 and X 2 is unbridged, and where X 1 and X 2 C1-C 20 Any substituent of the hydrocarbon group is independently selected from C1-C 20 For example, in one aspect, X 2 may be an indenyl ligand, which is unsubstituted; alternatively, substituted by at least one C1-C 20 Alternatively, a C1-C 20 Alternatively, at least one C1-C 12 or alternatively, a C1-C 12 Hydrocarbyl substitution.

[0068] On the other hand, the unbridged metallocene X 2 The ligand may be an indenyl ligand, which is unsubstituted and is replaced by at least one unsubstituted C1-C 20 Aliphatic group or C6-C 20 The aromatic group is substituted or substituted with at least one C1-C2-substituted with at least one fluorine substituent, chlorine substituent or bromine substituent or a combination thereof. 20 Aliphatic group or C6-C 20 In addition, X 2 The indenyl ligand may be substituted with at least one halogen-substituted hydrocarbyl substituent selected from C1-C2-substituted hydrocarbyl substituents substituted with at least one fluorine substituent, chlorine substituent or bromine substituent or a combination thereof. 12 Aliphatic group or C6-C 10 Aromatic groups.

[0069] For example, in some aspects, the unbridged metallocene X 2 The ligand may be an indenyl ligand substituted with at least one halogen-substituted hydrocarbyl substituent selected from fluorine-substituted, chlorine-substituted or bromine-substituted C1-C 12 Alkyl, C2-C 12 alkenyl, C3-C7 cycloalkyl, C3-C7 cycloalkenyl, C6-C 10 Aryl or C7-C 12 Aralkyl.

[0070] In another aspect, the unbridged metallocene X 2 The ligand may be an unsubstituted cyclopentadienyl ligand. 2 The ligand may be a cyclopentadienyl ligand which is bound by at least one C1-C 20 or, alternatively, at least one C1-C 12 Hydrocarbon substitution. Metallocene X 2 The ligand may be a cyclopentadienyl ligand which is bound by at least one C1-C 20 aliphatic group; alternatively, at least one C6-C 20 aromatic group; alternatively, at least one C1-C 12 or, alternatively, at least one C6-C 10 For example, in one aspect, the unbridged metallocene X 2 The ligand may be a cyclopentadienyl ligand substituted with at least one hydrocarbyl substituent independently selected from C1-C 12 Alkyl, C2-C 12 alkenyl, C3-C7 cycloalkyl, C3-C7 cycloalkenyl, C6-C 10 Aryl or C7-C 12 Aralkyl.

[0071] As disclosed herein, the unbridged metallocene X 1 The ligand may be a substituted indenyl ligand, wherein at least one substituent is a halogen-substituted C1-C ... 20 In one aspect, depending on the C1-C 20 Size and structure of hydrocarbon groups, halogen-substituted C1-C 20 The hydrocarbon group contains at least two halogen atoms and up to 8 or more halogen atoms. 2 The ligand may be a substituted or unsubstituted indenyl ligand, such as X 2 It may be a C1-C1-C1-substituted group substituted with at least one fluorine substituent, chlorine substituent or bromine substituent or a combination thereof.20 Aliphatic group or C6-C 20 Aromatic group substituted indenyl ligand. For example, X 1 may be an indenyl ligand substituted by groups independently selected from the following

[0072] and / or X 2 may be an indenyl ligand substituted by groups independently selected from the following

[0073]

[0074] Examples of metallocene compounds used as catalyst component I may include, but are not limited to, the following:

[0075]

[0076] Or any combination thereof. For example, in one aspect, the catalyst component I may be:

[0077]

[0078] In some respects, X 3 and X 4 Can be independently selected from halogen, F, Cl, Br, C1-C 12 Alkyloxy, C1-C 12 Hydrocarbylamino or trihydrocarbylsilyl, wherein each hydrocarbon group of these groups is independently selected from C1-C 12 In some aspects, each hydrocarbon group of these groups can be independently selected from C1-C 20 Hydrocarbon.

[0079] Reference is now made to catalyst component II, which may be a bridged metallocene compound. In one aspect, for example, catalyst component II may comprise a bridged zirconium or hafnium-based metallocene compound. In another aspect, catalyst component II may comprise a bridged zirconium or hafnium-based metallocene compound having an alkenyl substituent. In another aspect, catalyst component II may comprise a bridged zirconium or hafnium-based metallocene compound having an alkenyl substituent and a fluorenyl group. In another aspect, catalyst component II may comprise a bridged zirconium or hafnium-based metallocene compound having a cyclopentadienyl group and a fluorenyl group and having an alkenyl substituent on the bridging group and / or the cyclopentadienyl group. In addition, catalyst component II may comprise a bridged metallocene compound having an aryl substituent on the bridging group.

[0080] In a particular aspect of the present invention, catalyst component II may comprise 5 )(X 6 )(X 7)(X 8 )M 2 A bridged metallocene compound, wherein M 2 , X 5 , X 6 , X 7 and X 8 Choose from the following: a) M 2 Can be titanium, zirconium or hafnium; b) X 5 may be a substituted cyclopentadienyl, indenyl or fluorenyl ligand, wherein any non-bridging substituents, when present, are independently selected from C1-C 12 c) X6 may be a substituted fluorenyl ligand, wherein any non-bridging substituent, when present, is independently selected from C1-C 12 Hydrocarbon or C1-C 12 Heteroalkyl; wherein X 5 and X6 can each be selected from (>ER B 2) x or>BRB bridging group substitution, wherein x is an integer from 1 to 3, E is independently selected from carbon atoms or silicon atoms at each occurrence, R B is independently selected at each occurrence from H or C1-C 12 A hydrocarbon group, and wherein optionally, two R B The parts independently form a C3-C6 cyclic group; and d) X 7 and X 8 Can be independently selected from halides, hydrides, C1-C 20 Hydrocarbon, C1-C 20 Heteroalkyl, tetrahydroborate or OBR A 2 or OSO2R A , where R A Independently C1-C 12 Hydrocarbon.

[0081] In the bridging group (>ER B 2) x or >BR B In which x is an integer from 1 to 3, in (>ERB2) x In each occurrence, E is independently selected from a carbon atom or a silicon atom, and R B is independently selected at each occurrence from H or C1-C 12 alkyl, and wherein optionally, two RB moieties independently form a C3-C6 cyclic group. In another aspect, (>ER B 2) x Can be (-CR B 2CRB2-), (-SiR B 2SiR B 2-), (-CR B 2SiR B2-), (-CR B 2CR B 2CRB2-), (-SiRB2CR B 2CR B 2-), (-CR B 2SiR B 2CR B 2-), (-SiR B 2CR B 2SiR B 2-), (-SiR B 2SiR B 2CR B 2-) or (-SiR B 2SiR B 2SiR B 2-). Bridging group (>ERB2) x or >BR B Examples include, but are not limited to, >CMe2, >CPh2, >CHMe, >CHPh, >CH(tolyl), >CMeEt, >CMe(CH2CH2CH3), >CMe(CH2CH2CH2CH3), >CH(CH2CH2CH=CH2), >CMe(CH2CH2CH=CH2), >CEt(CH2CH2CH=CH2), >CPh(CH2CH2CH=CH2), >SiMe2, >SiPh2, >SiEt2, >Si(tolyl)2, (-CH2CH2-), (-CMe2CMe2-), (-CH2CH2CH2-), (-CH2SiMe2CH2-), (-CH2SiPh2CH2-), (-SiMe2SiMe2-), >BMe, >BEt, >BPh, >B(tolyl), etc. (Me is methyl, Et is ethyl, and Ph is phenyl), etc.

[0082] In one aspect, in addition to comprising a bridging substituent, X 5 It may also [1] be unsubstituted or [2] be C1-C 12 In some aspects, X 5 It may be a cyclopentadienyl ligand which, in addition to comprising a bridging substituent, is [1] otherwise unsubstituted or [2] substituted by C1-C6 alkyl or C2-C8 alkenyl.

[0083] In one aspect, in addition to the bridging substituent, X 6 It can be two independently selected from C1-C 12 In one aspect, X 6 may be a fluorenyl ligand, and wherein R B Independently selected from C1-C6 alkyl or C2-C8 alkenyl.

[0084] According to one aspect, catalyst component II may comprise, consist essentially of, consist of, or be selected from a metallocene compound having the formula:

[0085] in:

[0086] M 4 is zirconium or hafnium;

[0087] X 5 is independently at each occurrence F, Cl, Br, I, H, methyl, benzyl, phenyl or methoxy;

[0088] R D independently selected at each occurrence from H, C1-C 12 Alkyl, C2-C 12 Alkenyl, C6-C 10 Aryl, C7-C 12 Arylalkyl or C1-C 12 Alkyloxy;

[0089] E is C or Si;

[0090] R E independently selected at each occurrence from H, C1-C 12 Alkyl, C2-C 12 Alkenyl, C6-C 10 Aryl or C7-C 12 Aralkyl; and

[0091] R F Independently selected from H, C1-C 12 Alkyl, C2-C 12 Alkenyl, C6-C 10 Aryl or C7-C 12 Aralkyl.

[0092] In some aspects, catalyst component II can comprise, consist essentially of, consist of, or be selected from a metallocene compound having the formula:

[0093]

[0094]

[0095] Illustrative and non-limiting examples of bridged metallocene compounds suitable for use as catalyst component II may include the following compounds (Me = methyl, Ph = phenyl; t-Bu = tert-butyl):

[0096]

[0097]

[0098] etc., and combinations thereof.

[0099] Catalyst component II is not limited to the bridged metallocene compounds described above. Other suitable bridged metallocene compounds are disclosed in U.S. Pat. Nos. 7,026,494, 7,041,617, 7,226,886, 7,312,283, 7,517,939, 7,619,047, 7,763,561, 8,268,944, 8,507,621, 8,703,886, and 10,239,975, which are incorporated herein by reference in their entirety.

[0100] According to one aspect of the present invention, the weight ratio of catalyst component I to catalyst component II in the catalyst composition may be in the range of 10:1 to 1:10, 8:1 to 1:8, 5:1 to 1:5, 4:1 to 1:4, 3:1 to 1:3, 2:1 to 1:2, 1.5:1 to 1:1.5, 1.25:1 to 1:1.25, or 1.1:1 to 1:1.1. In another aspect, catalyst component II is the major component of the catalyst composition, and in such aspects, the weight ratio of catalyst component I to catalyst component II in the catalyst composition may be in the range of 1:1 to 1:10, 1:1 to 1:5, or 1:1 to 1:3.

[0101] In addition, the dual catalyst system contains an activator. For example, the catalyst system may contain an activator-support, an aluminoxane compound, an organic boron or organic borate compound, an ionizing ionic compound, or the like, or any combination thereof. The catalyst system may contain one or more than one activator.

[0102] In one aspect, the catalyst system may include an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or a combination thereof. Examples of such activators are disclosed in, for example, U.S. Patents Nos. 3,242,099, 4,794,096, 4,808,561, 5,576,259, 5,807,938, 5,919,983, and 8,114,946, the disclosures of which are incorporated herein by reference in their entirety. In another aspect, the catalyst system may include an aluminoxane compound. In another aspect, the catalyst system may include an organoboron or organoborate compound. In another aspect, the catalyst system may include an ionizing ionic compound.

[0103] In other aspects, the catalyst system can comprise an activator-support, for example, an activator-support comprising a solid oxide treated with an electron-withdrawing anion. Examples of such materials are disclosed, for example, in U.S. Pat. Nos. 7,294,599, 7,601,665, 7,884,163, 8,309,485, 8,623,973, and 9,023,959, which are incorporated herein by reference in their entirety. For example, the activator-support can comprise fluorided alumina, chlorided alumina, brominated alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, brominated silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided-chlorided silica-coated alumina, fluorided silica-coated alumina, sulfated silica-coated alumina, or phosphated silica-coated alumina, and the like, and any combination thereof. In some aspects, the activator-support can comprise a fluorided solid oxide and / or a sulfated solid oxide.

[0104] Various methods can be used to form the activator-support useful in the present invention. Methods for contacting the solid oxide with an electron-withdrawing component, suitable electron-withdrawing components and addition amounts, impregnation with metals or metal ions (e.g., zinc, nickel, vanadium, titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium, etc., or combinations thereof), and various calcination procedures and conditions are disclosed, for example, in U.S. Pat. Nos. 6,107,230, 6,165,929, 6,294,494, 6,300,271, 6,316,553, 6,355,594, 6,376,415, 6,388,017, Nos. 6,391,816, 6,395,666, 6,524,987, 6,548,441, 6,548,442, 6,576,583, 6,613,712, 6,632,894, 6,667,274, 6,750,302, 7,294,599, 7,601,665, 7,884,163, and 8,309,485, which are incorporated herein by reference in their entirety. Other suitable methods and procedures for preparing activator-supports (e.g., fluorided solid oxides and sulfated solid oxides) are well known to those skilled in the art.

[0105] The present invention can use the catalyst composition containing catalyst component I, catalyst component II, activator (one or more than one) and optional co-catalyst.When present, co-catalyst can include but is not limited to metal alkyl or organometallic co-catalyst, wherein the metal covers boron, aluminum, zinc, etc. Optionally, the catalyst system provided herein can include a combination of co-catalyst or co-catalyst.For example, alkyl boron, alkyl aluminum and alkyl zinc compounds can be used as co-catalysts in such catalyst systems.Representative boron compounds can include but are not limited to tri-n-butyl borane, tripropyl borane, triethyl borane, etc., and this includes two or more combinations of these materials.Although not limited to this, representative aluminum compounds (such as organoaluminum compounds) can include trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, tri-n-butyl aluminum, tri-isobutyl aluminum, tri-n-hexyl aluminum, tri-n-octylaluminum, diisobutyl aluminum hydride, diethyl ethoxy aluminum, diethyl aluminum chloride, etc., and any combination thereof. Exemplary zinc compounds (e.g., organozinc compounds) that can be used as co-catalysts may include, but are not limited to, dimethyl zinc, diethyl zinc, dipropyl zinc, dibutyl zinc, dineopentyl zinc, bis(trimethylsilyl) zinc, bis(triethylsilyl) zinc, bis(triisopropylsilyl) zinc, bis(triphenylsilyl) zinc, bis(allyldimethylsilyl) zinc, bis(trimethylsilylmethyl) zinc, and the like, or combinations thereof. Thus, in one aspect of the present invention, the dual catalyst composition may include catalyst component I, catalyst component II, an activator-support, and an organoaluminum compound (and / or an organozinc compound).

[0106] In another aspect of the present invention, a catalyst composition is provided, the catalyst composition comprising catalyst component I, catalyst component II, an activator-support and an organoaluminum compound, wherein this catalyst composition is substantially free of aluminoxane, organoboron or organoborate compounds, ionizing ionic compounds and / or other similar materials; alternatively, substantially free of aluminoxane; alternatively, substantially free of or organoboron or organoborate compounds; or alternatively, substantially free of ionizing ionic compounds. In these aspects, the catalyst composition has the catalytic activity discussed herein in the absence of these additional materials. For example, the catalyst composition of the present invention may be essentially composed of catalyst component I, catalyst component II, an activator-support and an organoaluminum compound, wherein no other materials are present in the catalyst composition, and the other materials will increase / decrease the activity of the catalyst composition by more than 10% compared to the catalyst activity of the catalyst composition in the absence of the materials.

[0107] The present invention also includes methods of preparing these catalyst compositions, such as contacting the individual catalyst components in any order or sequence. In one aspect, for example, the catalyst composition can be produced by a method comprising contacting catalyst component I, catalyst component II, and an activator in any order, while in another aspect, the catalyst composition can be produced by a method comprising contacting catalyst component I, catalyst component II, an activator, and a co-catalyst in any order.

[0108] Ethylene polymers (e.g., ethylene / α-olefin copolymers) can be produced by the disclosed catalyst system using any suitable polymerization process, using various types of polymerization reactors, polymerization reactor systems, and polymerization reaction conditions. One such polymerization process for polymerizing olefins in the presence of the catalyst composition of the present invention may include: contacting the catalyst composition with ethylene and α-olefin comonomers (one or more) in a polymerization reactor system under polymerization conditions to produce an ethylene polymer, wherein the catalyst composition may include catalyst component I, catalyst component II, an activator, and optional cocatalysts as disclosed herein. The present invention also encompasses any ethylene polymer produced by any polymerization process disclosed herein.

[0109] As used herein, "polymerization reactor" includes any polymerization reactor capable of polymerizing (including oligomerizing) olefin monomers and comonomers (one or more than one comonomer) to produce homopolymers, copolymers, terpolymers, etc. Various types of polymerization reactors include those that may be referred to as batch reactors, slurry reactors, gas phase reactors, solution reactors, high pressure reactors, tubular reactors, autoclave reactors, etc., or combinations thereof; or alternatively, the polymerization reactor system may include a slurry reactor, a gas phase reactor, a solution reactor, or a combination thereof. The polymerization conditions of various reactor types are well known to those skilled in the art. The gas phase reactor may include a fluidized bed reactor or a graded horizontal reactor. The slurry reactor may include a vertical or horizontal loop. The high pressure reactor may include an autoclave or a tubular reactor. The reactor type may include an intermittent or continuous process. The continuous process may use intermittent or continuous product discharge. The polymerization reactor system and method may also include partial or complete direct recycling of unreacted monomers, unreacted comonomers, and / or diluents.

[0110] The polymerization reactor system may include a single reactor or multiple reactors (2 reactors, more than 2 reactors) of the same or different types. For example, the polymerization reactor system may include a slurry reactor, a gas phase reactor, a solution reactor or a combination of two or more of these reactors. Producing polymers in multiple reactors may include several stages in at least two separate polymerization reactors interconnected by a transfer device, and the transfer device makes it possible to transfer the polymer produced by the first polymerization reactor to the second reactor. The polymerization conditions required in one reactor may be different from the operating conditions of other reactors. Alternatively, the polymerization in multiple reactors may include manually transferring the polymer from one reactor to a subsequent reactor to continue polymerization. The multi-reactor system may include any combination, including but not limited to a combination of multiple loop reactors, multiple gas phase reactors, a combination of loop reactors and gas phase reactors, multiple high-pressure reactors, or a combination of high-pressure reactors and loop reactors and / or gas phase reactors. Multiple reactors can be connected in series, in parallel, or in series and in parallel. Therefore, the present invention encompasses a polymerization reactor system including a single reactor, including two reactors, and including more than two reactors. In certain aspects of the present invention, the polymerization reactor system may include a slurry reactor, a gas phase reactor, a solution reactor, and a combination of multiple reactors thereof.

[0111] According to one aspect, the polymerization reactor system may include at least one loop slurry reactor including a vertical or horizontal loop. Monomer, diluent, catalyst and comonomer can be continuously fed into the loop reactor where polymerization occurs. In general, a continuous process may include continuously introducing monomer / comonomer, catalyst and diluent into the polymerization reactor, and continuously removing a suspension comprising polymer particles and diluent from this reactor. The reactor effluent may be flashed to remove solid polymers from a liquid comprising diluent, monomer and / or comonomer. Various techniques may be used for this separation step, including but not limited to flashing that may include any combination of heating and decompression, separation by cyclone action in a cyclone separator or hydrocyclone separator, or separation by centrifugation.

[0112] Typical slurry polymerization processes (also referred to as particle form processes) are disclosed, for example, in U.S. Pat. Nos. 3,248,179, 4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191, 6,833,415, and 8,822,608; each of which is incorporated herein by reference in its entirety.

[0113] Diluents suitable for use in slurry polymerization include, but are not limited to, the monomers being polymerized and hydrocarbons that are liquid under the reaction conditions. Examples of suitable diluents include, but are not limited to, hydrocarbons such as propane, cyclohexane, isobutane, normal butane, normal pentane, isopentane, neopentane, and normal hexane. Some loop polymerization reactions can occur under bulk conditions without the use of a diluent.

[0114] According to another aspect, the polymerization reactor system may include at least one gas phase reactor (e.g., fluidized bed reactor). Such reactor systems may employ a continuous recycle stream containing one or more monomers, which is continuously circulated through a fluidized bed in the presence of a catalyst under polymerization conditions. The recycle stream may be discharged from the fluidized bed and recycled back into the reactor. At the same time, the polymer product may be discharged from the reactor, and fresh monomers may be added to replace the polymerized monomers. Such gas phase reactors may include a multi-step gas phase polymerization process for olefins, wherein olefins are polymerized in a gas phase in at least two independent gas phase polymerization zones, while the catalyst-containing polymer formed in the first polymerization zone is fed to the second polymerization zone. Representative gas phase reactors are disclosed in U.S. Patents Nos. 5,352,749, 4,588,790, 5,436,304, 7,531,606, and 7,598,327, each of which is incorporated herein by reference in its entirety.

[0115] According to another aspect, the polymerization reactor system may include a high pressure polymerization reactor, for example, a tubular reactor or an autoclave reactor. The tubular reactor may have several zones in which fresh monomers, initiators or catalysts are added. The monomers may be entrained in an inert gas stream and introduced in one zone of the reactor. Initiators, catalysts and / or catalyst components may be entrained in a gas stream and introduced in another zone of the reactor. The gas streams may be mixed to perform polymerization. Heat and pressure may be used appropriately to obtain optimal polymerization reaction conditions.

[0116] According to another aspect, the polymerization reactor system may include a solution polymerization reactor in which monomer / comonomer is contacted with the catalyst composition by suitable stirring or other means. A carrier comprising an inert organic diluent or excess monomer may be used. If necessary, the monomer / comonomer may be contacted with the catalytic reaction product in the gas phase in the presence or absence of a liquid material. The polymerization zone may be maintained at a temperature and pressure that will form a polymer solution in the reaction medium. Stirring may be used to obtain better temperature control and maintain a uniform polymerization mixture throughout the polymerization zone. Use appropriate means to dissipate the exothermic heat of polymerization.

[0117] The polymerization reactor system may also include any combination of at least one feed system, at least one feed system for catalyst or catalyst components, and / or at least one polymer recovery system. Suitable reactor systems may also include systems for raw material purification, catalyst storage and preparation, extrusion, reactor cooling, polymer recovery, fractionation, recycling, storage, loading, laboratory analysis, and process control. Depending on the desired properties of the ethylene polymer, hydrogen may be added to the polymerization reactor (e.g., continuously or in pulses) as desired.

[0118] The polymerization conditions that can be controlled to improve efficiency and provide desired polymer properties may include temperature, pressure and the concentration of various reactants. The polymerization temperature may affect catalyst productivity, polymer molecular weight and molecular weight distribution. For example, in order to produce a specific grade of olefin polymer (or ethylene polymer), various polymerization conditions can be kept substantially constant. According to the Gibbs free energy equation (Gibbs Free energy equation), a suitable polymerization temperature can be any temperature below the depolymerization temperature. Typically, depending on the type of polymerization reactor, this includes, for example, 60°C to 280°C, or 60°C to 120°C. In some reactor systems, the polymerization temperature can be generally in the range of 70°C to 105°C, or 75°C to about 100°C.

[0119] Suitable pressures will also vary depending on the reactor and polymerization type. The pressure of liquid phase polymerization in a loop reactor is typically less than 1000 psig (6.9 MPa). The pressure of gas phase polymerization is usually 200 to 500 psig (1.4 MPa to 3.4 MPa). High pressure polymerization in a tubular or autoclave reactor is generally carried out at 20,000 to 75,000 psig (138 to 517 MPa). Polymerization reactors may also be operated in supercritical regions, which generally occur at higher temperatures and pressures. Operations above the critical point (supercritical phase) of the pressure / temperature diagram may provide advantages for the polymerization process.

[0120] The olefin comonomers useful in the ethylene monomer and catalyst compositions and polymerization processes of the present invention typically may include olefin compounds having 3 to 30 carbon atoms per molecule and having at least one olefinic double bond. In one aspect, the olefin comonomers may include C3-C 20 Olefins; alternatively, C3-C 20 α-olefins; alternatively, C3-C 10 Olefin; or alternatively, C3-C 10α-Olefins. In another aspect, the α-olefin comonomer may comprise 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, styrene, or any combination thereof; alternatively, the comonomer may comprise 1-butene, 1-hexene, 1-octene, or any combination thereof; alternatively, the comonomer may comprise 1-butene; alternatively, the comonomer may comprise 1-hexene; or alternatively, the comonomer may comprise 1-octene.

[0121] Example

[0122] The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the present invention in any way. After reading the description herein, it will be appreciated by those of ordinary skill in the art that various other aspects, embodiments, modifications and equivalents do not deviate from the spirit of the present invention or the scope of the appended claims.

[0123] Melt index (MI, g / 10min) can be measured according to ASTM D1238 at 190°C with a weight of 2,160 grams, and high load melt index (HLMI, g / 10min) is measured according to ASTM D1238 at 190°C with a weight of 21,600 grams. Density is measured in grams per cubic centimeter (g / cm3) on compression molded specimens cooled at 15°C per minute and conditioned at room temperature for 40 hours according to ASTM D1505 and ASTM D4703. 3 ).

[0124] Molecular weights and molecular weight distributions were obtained using a PL-GPC 220 (Polymer Labs, Agilent Company) system equipped with an IR4 detector (Polymer Char, Spain) and three Styragel HMW-6E GPC columns (Waters, MA) operated at 145°C. The flow rate of the mobile phase 1,2,4-trichlorobenzene (TCB) containing 0.5 g / L 2,6-di-tert-butyl-4-methylphenol (BHT) was set to 1 mL / min, and the polymer solution concentration was in the range of 1.0-1.5 mg / mL depending on the molecular weight. Sample preparation was performed at 150°C, typically for 4 hours, with occasional gentle stirring, before the solution was transferred to a sample vial for injection. An injection volume of 200 μL was used. HDPE polyethylene resin from Chevron Phillips Chemical Company was used. BHB5003 was used as a broad standard and the molecular weight and molecular weight distribution were derived using an integral calibration method. The integral table for the broad standard was predetermined in a separate SEC-MALS experiment. Mn is the number average molecular weight, Mw is the weight average molecular weight, Mz is the z average molecular weight, Mv is the viscosity average molecular weight, and Mp is the peak molecular weight (the molecular weight position of the highest point of the molecular weight distribution curve).

[0125] The individual LMW and HMW component characteristics were determined by deconvoluting the molecular weight distribution of each polymer (see e.g. Figure 3-4 ). The relative amounts (weight percent) of the LMW and HMW components in the polymer were determined using a commercial software program (Systat Software, Inc., PEAK FIT v.4.05). Other molecular weight parameters of the LMW and HMW components (e.g., Mn, Mw, Mz, etc. of each component) were determined by using the deconvoluted data from the PEAK FIT program and applying the PEAK FIT chromatogram / lognormal 4-parameter (area) function and two peaks without any constraints in the deconvolution as follows (where a0=area; a1=center; a2=width (>0); and a3=shape (>0, ≠1)):

[0126]

[0127] The short chain branch content and short chain branch distribution (SCBD) in the entire molecular weight distribution are determined by a GPC system (IR5-GPC) detected by IR5 using a method established by Yu (Y Yu, Macro molecular Symposium, 2020, 390, 1900014), wherein the GPC system is a PL220 GPC / SEC system (Polymer Labs, Agilent company) equipped with three Styragel HMW-6E columns (Waters, MA) for polymer separation. The thermoelectrically cooled IR5 MCT detector (IR5) (Polymer Characterisation SA, Spain) is connected to the GPC column via a heat transfer line. Chromatographic data are obtained from the two output ports of the IR5 detector. First, the analog signal enters the digitizer from the analog output port and is then connected to computer "A" to be digitized by Cirrus software (Polymer Labs, now Agilent Company) and using HDPE Marlex TMThe molecular weight determination was performed by the integral calibration method using BHB5003 resin (Chevron Phillips Chemical) as the molecular weight standard. On the other hand, the digital signal was directly entered into computer "B" via a USB cable, where the signal was collected by LabView data collection software provided by Polymer Char. The chromatographic conditions were set as follows: column oven temperature of 145°C; flow rate of 1 mL / min; injection volume of 0.4 mL; and polymer concentration of about 2 mg / mL, depending on the sample molecular weight. The temperature of the heat transfer line and the IR5 detector sample cell were both set to 150°C, while the temperature of the IR5 detector electronics was set to 60°C. CH3(I CH3 ) and CH2(I CH2 ) and combined with a calibration curve to determine the short chain branch content. The calibration curve is the SCB content (x SCB ) with I CH3 / I cH2 In order to obtain the calibration curve, a group (no less than 5) of polyethylene resins with SCB levels ranging from zero to about 32 SCB / 1,000 total carbons (SCB standards) are used. All of these SCB standards have known SCB levels and flat SCBD profiles predetermined by NMR and solvent gradient fractionation-NMR coupling (SGF-NMR) methods, respectively. Using the SCB calibration curve thus established, a short chain branch distribution profile in the entire molecular weight distribution of the resin fractionated by the IR5-GPC system under the same chromatographic conditions as these SCB standards is obtained. Using the predetermined SCB calibration curve (i.e., I CH3 / I CH2 The relationship between the intensity ratio and elution volume is converted into the SCB distribution that varies with MWD by using the MW calibration curve (i.e., intensity ratio versus SCB content) and the MW calibration curve (i.e., molecular weight versus elution time), thereby converting I CH3 / I CH2 The intensity ratio and elution time were converted into SCB content and molecular weight.

[0128] Metal content, e.g. catalyst residues in ethylene polymers or films / articles can be determined by ICP analysis on a PerkinElmer Optima 8300 instrument. Polymer samples can be ashed with sulfuric acid in a Thermolyne furnace overnight and then acid digested with HCl and HNO3 (3:1 v:v) in a HotBlock.

[0129] Examples 1-4

[0130] The fluorinated silica-coated alumina activator-support used in Examples 1-4 was prepared as follows. 400 mL of water and 100 g of silica-coated alumina were mixed to form a slurry (40 wt% alumina, surface area 450 m 2 / g, pore volume of 1.3mL / g, and average particle size of 35 microns). Concentrated hydrofluoric acid solution (5g HF) was mixed into the slurry, and the resulting slurry was then spray dried into a dry flowable powder. Calcination was performed at 600°C by fluidizing the fluorinated silica-coated alumina in dry nitrogen for 3 hours, then cooled to room temperature while still fluidizing under nitrogen. Thereafter, the fluorinated silica-coated alumina (FSCA) was collected and stored under dry nitrogen and used without exposure to the atmosphere.

[0131] The structures of the metallocene compounds used in Examples 1-4 are shown below:

[0132]

[0133] Table I summarizes certain polymerization conditions for Examples 1-4, and the following polymerization procedures are used for Examples 1-4. In a glove box, a syringe was loaded with the following reagents in the following order: 250 mg FSCA, about 2 mL hexane, 0.5 mL TIBA (triisobutylaluminum, 1 M in hexane), and a total of 2 mg metallocene (1 mg / mL slurry in hexane). The mixture was contacted for 2-5 minutes before being injected into a 1-gallon autoclave reactor purged with isobutane. The reactor was sealed and charged with 2 L of isobutane. The mixture was heated to the desired temperature over 5-7 minutes under stirring (about 1000 rpm). When the mixture reached 8°C lower than the specified temperature target, the required amount of 1-hexene (3 mg hydrogen was used in Example 3, and 2 mg hydrogen was used in Example 4) was added as ethylene was charged to the target pressure. The reaction was allowed to continue for 30 minutes while maintaining the specified temperature and pressure with pressurized ethylene as needed. After 30 minutes, the reactor was vented and flushed with nitrogen. Prior to testing, reactor solids were removed and dried under vacuum for a minimum of 3 hours.

[0134] Tables II-V summarize the polymer properties of the ethylene copolymers of Examples 1-4, and Figure 3-4The bimodal molecular weight distribution (logarithm of the amount of polymer relative to the molecular weight) and short chain branch distribution (SCBD) of these polymers are described. The bimodal molecular weight distribution from each of these polymers was deconvoluted into their respective high molecular weight and low molecular weight components (LMW and HMW) as described herein. The molecular weight parameters of the LMW and HMW components of each example (e.g., Mn, Mw and Mz of each component) were determined using the deconvoluted data from the PEAK FIT program and are listed in Table III, along with the overall polymer molecular weight properties.

[0135] Tables II and IV summarize the number of short chain branches (SCBs) per 1000 total carbon atoms for each polymer at different positions along the bimodal molecular weight distribution. As shown in Table V, and surprisingly, the polymers of Examples 2-4 have much higher relative SCB content in the high molecular weight portion of the polymer relative to the low molecular weight portion of the polymer than Example 1. The ratio of the number of SCBs per 1000 total carbon atoms at Mz to the number of SCBs per 1000 total carbon atoms at Mn for Examples 2-4 ranges from 14 to 17, and is 38-57% higher than the same ratio (10.7) for Example 1. Also in Table V, the ratio of the number of SCBs per 1000 total carbon atoms at Mn for the HMW component of Examples 2-4 to the number of SCBs per 1000 total carbon atoms at Mn for the LMW component ranges from 14 to 19, and is 46-89% higher than the same ratio (9.7) for Example 1.

[0136] Similarly, Table V also shows that for Examples 2-4, the ratio of the number of SCBs per 1000 total carbon atoms at the Mp of the HMW component to the number of SCBs per 1000 total carbon atoms at the Mp of the LMW component is unexpectedly high, ranging from 12 to 13, and is 13-17% higher than the same ratio (10.9) for Example 1. Finally, for Examples 2-4, the ratio of the number of SCBs per 1000 total carbon atoms at the Mp of the HMW component to the number of SCBs per 1000 total carbon atoms at the Mz of the LMW component ranges from 10 to 12, and is 57-67% higher than the same ratio (6.9) for Example 1.

[0137] In summary, Examples 2-4 demonstrate bimodal ethylene-based copolymers having unexpectedly low levels of SCB content in the low molecular weight fraction of the polymer and unexpectedly high levels of SCB content in the high molecular weight fraction of the polymer. Such polymers may be particularly suitable for a variety of end-use applications, such as injection molding or blow molding, where improved environmental stress crack resistance (ESCR), PENT slow crack growth resistance (ASTM F1473), or natural draw ratio (NDR) is desired.

[0138]

[0139]

[0140]

[0141] The present invention has been described above with reference to a number of aspects and specific embodiments. A person skilled in the art will appreciate many variations based on the foregoing specific embodiments. All such obvious variations are within the full intended scope of the appended claims. Other aspects of the present invention may include, but are not limited to, the following (each aspect is described as "comprising / including...", but alternatively, may be "essentially composed of..." or "consisting of..."):

[0142] Aspect 1. An ethylene polymer having (or characterized by):

[0143] 0.92 to 0.955 g / cm 3 Density within range;

[0144] HLMI less than or equal to 35 g / 10 min; and

[0145] The ratio of the number of short chain branches (SCBs) per 1000 total carbon atoms at Mz to the number of SCBs per 1000 total carbon atoms at Mn in the range of 11.5 to 22.

[0146] Aspect 2. An ethylene polymer having (or characterized by):

[0147] 0.92 to 0.955 g / cm 3 Density within range;

[0148] HLMI less than or equal to 35 g / 10 min; and

[0149] A higher molecular weight component (HMW) and a lower molecular weight (LMW) component, wherein:

[0150] The ratio of the number of short chain branches (SCB) per 1000 total carbon atoms at Mn of the HMW component to the number of SCB per 1000 total carbon atoms at Mn of the LMW component is in the range of 10.5 to 22.

[0151] Aspect 3. A polymer as defined in Aspect 1 or 2, wherein the ethylene polymer has a molecular weight at D10 in any range disclosed herein, for example, 750,000 to 2,000,000, 800,000 to 1,750,000, 850,000 to 2,000,000, or 900,000 to 1,750,000 g / mol.

[0152] Aspect 4. A polymer as defined in any of the preceding aspects, wherein the ethylene polymer has a molecular weight at D85 in any range disclosed herein, such as 14,000 to 50,000, 15,000 to 40,000, 16,000 to 38,000, or 17,000 to 35,000 g / mol.

[0153] Aspect 5. A polymer as defined in any of the preceding aspects, wherein the ethylene polymer has an SCB number per 1000 total carbon atoms at D10 in any range disclosed herein, such as from 9 to 30, 12 to 28, 14 to 27, or 16 to 25.

[0154] Aspect 6. A polymer as defined in any of the preceding aspects, wherein the density is within any range disclosed herein, for example, 0.92 to 0.95, 0.92 to 0.94, 0.925 to 0.955, 0.925 to 0.95, or 0.925 to 0.943 g / cm 3 .

[0155] Aspect 7. A polymer as defined in any of the preceding aspects, wherein the HLMI is within any range disclosed herein, such as less than or equal to 30 g / 10 min, less than or equal to 25 g / 10 min, less than or equal to 20 g / 10 min, or less than or equal to 15 g / 10 min.

[0156] Aspect 8. A polymer as defined in any of the preceding aspects, wherein the ratio of the number of SCBs per 1000 total carbon atoms at Mz to the number of SCBs per 1000 total carbon atoms at Mn is within any range disclosed herein, for example, 11.5 to 22, 12 to 21, 12 to 18, 13 to 22, or 13 to 19.

[0157] Aspect 9. The polymer as defined in any of the preceding aspects, wherein the ethylene polymer has an Mw in any range disclosed herein, such as from 200,000 to 800,000, 225,000 to 725,000, 250,000 to 600,000, or 275,000 to 575,000 g / mol.

[0158] Aspect 10. The polymer as defined in any of the preceding aspects, wherein the ethylene polymer has an Mp in any range disclosed herein, such as from 30,000 to 90,000, 35,000 to 85,000, 40,000 to 80,000, or 45,000 to 75,000 g / mol.

[0159] Aspect 11. A polymer as defined in any of the preceding aspects, wherein the ethylene polymer has an Mn in any range disclosed herein, such as from 15,000 to 60,000, 18,000 to 57,000, 22,000 to 53,000, or 25,000 to 50,000 g / mol.

[0160] Aspect 12. A polymer as defined in any of the preceding aspects, wherein the ethylene polymer has an Mz in any range disclosed herein, such as from 1,300,000 to 3,100,000, 1,400,000 to 3,000,000, 1,500,000 to 2,500,000, or 1,700,000 to 2,200,000 g / mol.

[0161] Aspect 13. A polymer as defined in any of the preceding aspects, wherein the ethylene polymer has a Mw / Mn ratio within any range disclosed herein, such as from 6 to 25, 7 to 20, 7 to 18, 8 to 15, or 9 to 13.

[0162] Aspect 14. The polymer as defined in any of the preceding aspects, wherein the ethylene polymer has less than 0.008 long chain branches (LCBs) per 1000 total carbon atoms, such as less than 0.005 LCBs, or less than 0.003 LCBs.

[0163] Aspect 15. A polymer as defined in any of the preceding aspects, wherein the ethylene polymer has a higher molecular weight component (HMW) and a lower molecular weight (LMW) component, wherein the amount of the LMW component, based on the total polymer, is in any weight percentage range disclosed herein, such as 40 to 90 wt%, 40 to 85 wt%, 45 to 90 wt%, 45 to 85 wt%, or 50 to 85 wt%.

[0164] Aspect 16. A polymer as defined in any of the preceding aspects, wherein the HMW component has an Mn in any range disclosed herein, such as from 400,000 to 800,000, from 450,000 to 750,000, or from 500,000 to 700,000 g / mol.

[0165] Aspect 17. A polymer as defined in any of the preceding aspects, wherein the LMW component has an Mz in any range disclosed herein, such as from 70,000 to 200,000, from 70,000 to 170,000, from 75,000 to 150,000, or from 80,000 to 130,000 g / mol.

[0166] Aspect 18. A polymer as defined in any of the preceding aspects, wherein the HMW component has an Mp within any range disclosed herein, such as from 400,000 to 1,100,000, from 500,000 to 1,100,000, or from 550,000 to 1,000,000 g / mol.

[0167] Aspect 19. A polymer as defined in any of the preceding aspects, wherein the ratio of the SCB number per 1000 total carbon atoms at Mn of the HMW component to the SCB number per 1000 total carbon atoms at Mn of the LMW component is in any range disclosed herein, e.g., 10.5 to 22, 11 to 22, 11 to 21, 12 to 22, 12 to 20, or 13 to 19.

[0168] Aspect 20. A polymer as defined in any of the preceding aspects, wherein the ratio of the SCB number per 1000 total carbon atoms at Mp of the HMW component to the SCB number per 1000 total carbon atoms at Mp of the LMW component is in any range disclosed herein, e.g., 11 to 18, 11 to 14, 11.5 to 16, or 11.5 to 15.

[0169] Aspect 21. A polymer as defined in any of the preceding aspects, wherein the ratio of the SCB number per 1000 total carbon atoms at Mp of the HMW component to the SCB number per 1000 total carbon atoms at Mz of the LMW component is in any range disclosed herein, e.g., 7.5 to 18, 8 to 16, 9 to 14, or 10 to 12.

[0170] Aspect 22. A polymer as defined in any of the preceding aspects, wherein the ethylene polymer has an SCB number per 1000 total carbon atoms at Mz in any range disclosed herein, such as from 10 to 30, 12 to 30, 15 to 28, or 17 to 26.

[0171] Aspect 23. A polymer as defined in any one of the preceding aspects, wherein the ethylene polymer has a bimodal molecular weight distribution.

[0172] Aspect 24. A polymer as defined in any one of the preceding aspects, wherein the ethylene polymer is a single reactor product, for example, not a post-reactor blend of two polymers having different molecular weight characteristics.

[0173] Aspect 25. The polymer as defined in any one of the preceding aspects, wherein the ethylene polymer comprises an ethylene / α-olefin copolymer.

[0174] Aspect 26. A polymer as defined in any one of the preceding aspects, wherein the ethylene polymer comprises an ethylene / 1-butene copolymer, an ethylene / 1-hexene copolymer and / or an ethylene / 1-octene copolymer.

[0175] Aspect 27. A polymer as defined in any one of the preceding aspects, wherein the ethylene polymer comprises an ethylene / 1-hexene copolymer.

[0176] Aspect 28. A polymer as defined in any one of the preceding aspects, wherein the ethylene polymer independently contains less than 0.1 ppm (by weight), less than 0.08 ppm, less than 0.05 ppm, or less than 0.03 ppm of Mg, V, Ti, or Cr.

[0177] Aspect 29. An article comprising an ethylene polymer as defined in any one of the preceding aspects.

[0178] Aspect 30. An article comprising an ethylene polymer as defined in any one of Aspects 1 to 28, wherein the article is an agricultural film, an automotive part, a bottle, a chemical container, a barrel, a fiber or fabric, a food packaging film or container, a food service article, a fuel tank, a geomembrane, a household container, a liner, a molded product, a medical device or material, an outdoor storage product, an outdoor play equipment, a pipe, a sheet or tape, a toy, or a traffic barrier.

[0179] Aspect 31. A polymerization method comprising contacting a catalyst composition with ethylene and an α-olefin comonomer in a polymerization reactor system under polymerization conditions to produce an ethylene polymer, wherein the ethylene polymer is as defined in any of Aspects 1-28, and wherein the catalyst composition comprises: a catalyst component I comprising any unbridged metallocene compound disclosed herein, a catalyst component II comprising any bridged metallocene compound disclosed herein, any activator disclosed herein, and optionally any cocatalyst disclosed herein.

[0180] Aspect 32. The method as defined in aspect 31, wherein the catalyst component II comprises a bridged zirconium or hafnium based metallocene compound.

[0181] Aspect 33. The method as defined in aspect 31, wherein catalyst component II comprises a bridged zirconium or hafnium-based metallocene compound having an alkenyl substituent.

[0182] Aspect 34. The method as defined in aspect 31, wherein catalyst component II comprises a bridged zirconium or hafnium-based metallocene compound having an alkenyl substituent and a fluorenyl group.

[0183] Aspect 35. The method as defined in aspect 31, wherein catalyst component II comprises a bridged zirconium or hafnium-based metallocene compound having a cyclopentadienyl group and a fluorenyl group and having an alkenyl substituent on the bridging group and / or the cyclopentadienyl group.

[0184] Aspect 36. A method as defined in any one of aspects 31 to 35, wherein catalyst component II comprises a bridged metallocene compound having an aryl substituent on the bridging group.

[0185] Aspect 37. A method as defined in any one of Aspects 31-36, wherein catalyst component I comprises an unbridged metallocene compound containing two indenyl groups or one indenyl group and one cyclopentadienyl group, wherein at least one indenyl group has at least one halogen-substituted hydrocarbon substituent having at least two halogen atoms.

[0186] Aspect 38. A method as defined in any one of aspects 31 to 36, wherein catalyst component I comprises an unbridged metallocene compound containing two indenyl groups, wherein at least one indenyl group has at least one halogen-substituted hydrocarbyl substituent having at least two halogen atoms.

[0187] Aspect 39. A method as defined in any one of Aspects 31-36, wherein catalyst component I comprises an unbridged metallocene compound containing one indenyl group and one cyclopentadienyl group, wherein the indenyl group has at least one halogen-substituted hydrocarbyl substituent having at least two halogen atoms.

[0188] Aspect 40. A method as defined in any one of aspects 37 to 39, wherein the halogen-substituted hydrocarbyl substituent comprises an aryl group.

[0189] Aspect 41. A method as defined in any one of aspects 37-40, wherein each halogen is fluorine.

[0190] Aspect 42. A method as defined in any one of aspects 37 to 41, wherein the unbridged metallocene compound contains zirconium.

[0191] Aspect 43. The method as defined in any one of aspects 31-42, wherein the activator comprises an activator-support, an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof.

[0192] Aspect 44. The method as defined in any one of aspects 31 to 43, wherein the activator comprises an aluminoxane compound.

[0193] Aspect 45. A method as defined in any one of aspects 31 to 43, wherein the activator comprises an organoboron or organoborate compound.

[0194] Aspect 46. A method as defined in any one of aspects 31-43, wherein the activator comprises an ionizing ionic compound.

[0195] Aspect 47. The method as defined in any of aspects 31-43, wherein the activator comprises an activator-support comprising any solid oxide treated with any electron-withdrawing anion disclosed herein.

[0196] Aspect 48. A method as defined in any one of Aspects 31-43, wherein the activator comprises fluorided alumina, chlorided alumina, brominated alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, brominated silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided-chlorided silica-coated alumina, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or any combination thereof.

[0197] Aspect 49. The method as defined in any one of aspects 31 to 43, wherein the activator comprises a fluorided solid oxide and / or a sulfated solid oxide.

[0198] Aspect 50. The method as defined in any one of aspects 31-49, wherein the catalyst composition comprises a co-catalyst, such as any co-catalyst disclosed herein.

[0199] Aspect 51. The method as defined in any one of aspects 31 to 50, wherein the co-catalyst comprises any organoaluminum compound disclosed herein.

[0200] Aspect 52. The method as defined in aspect 51, wherein the organoaluminum compound comprises trimethylaluminum, triethylaluminum, triisobutylaluminum, or a combination thereof.

[0201] Aspect 53. The method as defined in any one of aspects 47-52, wherein the catalyst composition comprises catalyst component I, catalyst component II, a solid oxide treated with an electron-withdrawing anion, and an organoaluminum compound.

[0202] Aspect 54. The method as defined in any one of aspects 47-53, wherein the catalyst composition is substantially free of aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds, or combinations thereof.

[0203] Aspect 55. A method as defined in any of Aspects 31-54, wherein the weight ratio of catalyst component I to catalyst component II in the catalyst composition is within any range disclosed herein, for example, 10:1 to 1:10, 5:1 to 1:5, or 2:1 to 1:2.

[0204] Aspect 56. A method as defined in any one of Aspects 31-55, wherein the catalyst composition is prepared by a method comprising contacting catalyst component I, catalyst component II, and an activator in any order, or contacting catalyst component I, catalyst component II, an activator, and a co-catalyst in any order.

[0205] Aspect 57. The method as defined in any one of aspects 31-56, wherein the α-olefin comonomer comprises C3-C 20 α-olefins, or alternatively, C3-C 10 α-Olefins.

[0206] Aspect 58. The method as defined in any one of aspects 31 to 57, wherein the α-olefin comonomer comprises 1-butene, 1-hexene, 1-octene, or a mixture thereof.

[0207] Aspect 59. The method as defined in any one of aspects 31-58, wherein the polymerization reactor system comprises a batch reactor, a slurry reactor, a gas phase reactor, a solution reactor, a high pressure reactor, a tubular reactor, an autoclave reactor, or a combination thereof.

[0208] Aspect 60. The method as defined in any one of aspects 31 to 59, wherein the polymerization reactor system comprises a slurry reactor, a gas phase reactor, a solution reactor, or a combination thereof.

[0209] Aspect 61. The method as defined in any one of aspects 31-60, wherein the polymerization reactor system comprises a loop slurry reactor.

[0210] Aspect 62. The method as defined in any one of aspects 31 to 61, wherein the polymerization reactor system comprises a single reactor.

[0211] Aspect 63. The method as defined in any one of aspects 31-61, wherein the polymerization reactor system comprises 2 reactors.

[0212] Aspect 64. The method as defined in any one of aspects 31-61, wherein the polymerization reactor system comprises more than 2 reactors.

[0213] Aspect 65. The method as defined in any one of aspects 31 to 64, wherein the polymerization conditions comprise a polymerization reaction temperature in the range of 60°C to 120°C and a reaction pressure in the range of 200 to 1000 psig (1.4 to 6.9 MPa).

[0214] Aspect 66. A method as defined in any one of aspects 31 to 65, wherein the polymerization conditions are substantially constant, for example for a specific polymer grade.

[0215] Aspect 67. The method as defined in any one of aspects 31 to 66, wherein no hydrogen is added to the polymerization reactor system.

[0216] Aspect 68. The method as defined in any one of aspects 31 to 66, wherein hydrogen is added to the polymerization reactor system.

[0217] Aspect 69. The method as defined in any one of aspects 31-68, wherein the ethylene polymer produced is as defined in any one of aspects 1-28.

[0218] Aspect 70. An ethylene polymer produced by the olefin polymerization process defined in any one of aspects 31-68.

[0219] Aspect 71. An ethylene polymer as defined in any one of aspects 1 to 28, produced by the method as defined in any one of aspects 31 to 68.

[0220] Aspect 72. An article comprising a polymer as defined in aspect 70 or 71.

Claims

1. An ethylene polymer, comprising: 0.92 to 0.955 g / cm 3 Density within range; HLMI less than or equal to 35 g / 10 min; and The ratio of the number of short chain branches (SCB) per 1000 total carbon atoms at Mz in the range of 11.5 to 22 to the number of SCBs per 1000 total carbon atoms at Mn, wherein the ethylene polymer is prepared by a polymerization process comprising contacting a catalyst composition with ethylene and an α-olefin comonomer under polymerization conditions in a polymerization reactor system to produce the ethylene polymer, The catalyst composition comprises: Unbridged metallocene compounds; Bridged metallocene compounds; activator; and Optionally, a co-catalyst; and Wherein hydrogen is added to the polymerization reactor system.

2. An article comprising the ethylene polymer of claim 1.

3. The article of claim 2, wherein the ethylene polymer comprises an ethylene / 1-butene copolymer, an ethylene / 1-hexene copolymer and / or an ethylene / 1-octene copolymer.

4. The polymer of claim 1, wherein: The density is between 0.92 and 0.95 g / cm 3 within the scope; The HLMI is less than or equal to 20 g / 10 min; and The ratio of the number of SCBs per 1000 total carbon atoms at the Mz to the number of SCBs per 1000 total carbon atoms at the Mn is in the range of 12 to 21.

5. The polymer of claim 4, wherein the ethylene polymer has: a molecular weight at D10 ranging from 750,000 to 2,000,000 g / mol; a molecular weight at D85 in the range of 14,000 to 50,000; and The SCB number per 1000 total carbon atoms at D10 ranges from 9 to 30.

6. The polymer of claim 4, wherein the ethylene polymer has a SCB number per 1000 total carbon atoms at Mz in the range of 10 to 30.

7. The polymer of claim 1, wherein: The ethylene polymer has a bimodal molecular weight distribution; and The ethylene polymer independently contains less than 0.1 ppm by weight of Mg, V, Ti and Cr.

8. The polymer of claim 1, wherein the ethylene polymer has: Mw in the range of 200,000 to 800,000 g / mol; and Mn in the range of 15,000 to 60,000 g / mol.

9. An article comprising the ethylene polymer of claim 8, wherein the ratio of the SCB number per 1000 total carbon atoms at the Mz to the SCB number per 1000 total carbon atoms at the Mn is in the range of 13 to 19.

10. An ethylene polymer, comprising: 0.92 to 0.955 g / cm 3 Density within range; HLMI less than or equal to 35 g / 10 min; and A higher molecular weight component (HMW) and a lower molecular weight (LMW) component, wherein: the ratio of the number of SCBs per 1000 total carbon atoms at Mn of the HMW component to the number of SCBs per 1000 total carbon atoms at Mn of the LMW component is in the range of 10.5 to 22, wherein the ethylene polymer is prepared by a polymerization process comprising contacting a catalyst composition with ethylene and an α-olefin comonomer under polymerization conditions in a polymerization reactor system to produce the ethylene polymer, The catalyst composition comprises: Unbridged metallocene compounds; Bridged metallocene compounds; activator; and Optionally, a co-catalyst; and Wherein hydrogen is added to the polymerization reactor system.

11. An article comprising the ethylene polymer of claim 10.

12. The polymer of claim 10, wherein: The density is between 0.92 and 0.95 g / cm 3 within the scope; The HLMI is less than or equal to 20 g / 10 min; and The ratio of the SCB number per 1000 total carbon atoms at Mn of the HMW component to the SCB number per 1000 total carbon atoms at Mn of the LMW component is in the range of 11-21.

13. The polymer of claim 12, wherein: The ratio of the number of SCBs per 1000 total carbon atoms at Mp of the HMW component to the number of SCBs per 1000 total carbon atoms at Mp of the LMW component is in the range of 11 to 18; and The ratio of the number of SCBs per 1000 total carbon atoms at Mp of the HMW component to the number of SCBs per 1000 total carbon atoms at Mz of the LMW component is in the range of 7.5 to 18.

14. The polymer of claim 10, wherein: The ratio of the number of SCBs per 1000 total carbon atoms at Mp of the HMW component to the number of SCBs per 1000 total carbon atoms at Mp of the LMW component is in the range of 11.5 to 16; and The ratio of the number of SCBs per 1000 total carbon atoms at Mp of the HMW component to the number of SCBs per 1000 total carbon atoms at Mz of the LMW component is in the range of 8 to 16.

15. The polymer of claim 14, wherein the ethylene polymer comprises an ethylene / 1-butene copolymer, an ethylene / 1-hexene copolymer and / or an ethylene / 1-octene copolymer.

16. The polymer of claim 10, wherein: The HMW component has a Mn in the range of 400,000 to 800,000 g / mol; and The LMW component has an Mz in the range of 70,000 to 200,000 g / mol.

17. The polymer of claim 16, wherein the amount of the LMW component is in the range of 45 to 85 wt% based on the total polymer.

18. A polymerization process comprising contacting a catalyst composition with ethylene and an α-olefin comonomer in a polymerization reactor system under polymerization conditions to produce an ethylene polymer, wherein the ethylene polymer has: 0.92 to 0.955 g / cm 3 Density within range; HLMI less than or equal to 35 g / 10 min; and The ratio of the number of short chain branches (SCB) per 1000 total carbon atoms at Mz to the number of SCB per 1000 total carbon atoms at Mn in the range of 11.5 to 22; and The catalyst composition comprises: An unbridged metallocene compound containing two indenyl groups or one indenyl group and one cyclopentadienyl group, wherein at least one indenyl group has at least one halogen-substituted hydrocarbyl substituent having at least two halogen atoms; A bridged metallocene compound having a cyclopentadienyl group and a fluorenyl group and having an alkenyl substituent on the cyclopentadienyl group and / or the bridging group; activator; and Optionally, a co-catalyst, Wherein hydrogen is added to the polymerization reactor system.

19. The method of claim 18, wherein the activator comprises a fluorided solid oxide and / or a sulfated solid oxide.

20. The method of claim 18, wherein the polymerization reactor system comprises a slurry reactor, a gas phase reactor, a solution reactor, or a combination thereof.

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