WO2022165503A1 - Copolymères de polyéthylène bimodal - Google Patents

Copolymères de polyéthylène bimodal Download PDF

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Publication number
WO2022165503A1
WO2022165503A1 PCT/US2022/070392 US2022070392W WO2022165503A1 WO 2022165503 A1 WO2022165503 A1 WO 2022165503A1 US 2022070392 W US2022070392 W US 2022070392W WO 2022165503 A1 WO2022165503 A1 WO 2022165503A1
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Prior art keywords
polymer
range
carbon atoms
total carbon
ethylene
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PCT/US2022/070392
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English (en)
Inventor
Graham R. Lief
Qing Yang
Youlu Yu
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Chevron Phillips Chemical Company Lp
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Priority claimed from US17/160,481 external-priority patent/US11667777B2/en
Application filed by Chevron Phillips Chemical Company Lp filed Critical Chevron Phillips Chemical Company Lp
Priority to CA3210180A priority Critical patent/CA3210180A1/fr
Priority to EP22704487.2A priority patent/EP4284845A1/fr
Priority to CN202280011968.7A priority patent/CN116783224A/zh
Priority to KR1020237025643A priority patent/KR20230130025A/ko
Priority to MX2023008719A priority patent/MX2023008719A/es
Publication of WO2022165503A1 publication Critical patent/WO2022165503A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/07—Catalyst support treated by an anion, e.g. Cl-, F-, SO42-
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/05—Bimodal or multimodal molecular weight distribution
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65904—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with another component of C08F4/64
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged

Definitions

  • SCBs comonomer short chain branches
  • HDPE high density polyethylene
  • LLDPE linear low density polyethylene
  • SCBs can reduce polymer crystallinity and improve impact strength, but also can decrease polymer stiffness and polymer density.
  • bimodal ethylene polymers it is often advantageous for the low molecular weight fraction of the polymer to have a low concentration of comonomer SCBs, while the high molecular weight fraction has a relatively higher concentration of comonomer SCBs. t is to these ends that the present invention is generally directed.
  • the present invention generally relates, in one aspect, to ethylene-based polymers characterized by a density in a range from 0.92 to 0.955 g/cm 3 , a HLMI of less than or equal to 35 g/10 min, and a ratio of a number of short chain branches (SCBs) per 1000otal carbon atoms at Mz to a number of SCBs per 1000 total carbon atoms at Mn in a ange from 11.5 to 22.
  • SCBs short chain branches
  • ethylene polymers characterized by a densityn a range from 0.92 to 0.955 g/cm 3 , 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, in which a ratio of a number of SCBs per 1000 total carbon atoms at Mn of the HMW component to a number of SCBs per 1000 total carbon atoms at Mn of the LMW component is in a range from 10.5 to 22.
  • Polymerization processes also are encompassed herein.
  • a epresentative polymerization process can comprise contacting a catalyst composition with ethylene and an ⁇ -olefin comonomer in a polymerization reactor system under polymerization conditions to produce an ethylene polymer, wherein the catalyst composition comprises catalyst component I comprising any unbridged metallocene compound disclosed herein, catalyst component II comprising any bridged metallocene compound disclosed herein, any activator disclosed herein, and optionally, any co-catalyst disclosed herein.
  • FIG. 1 illustrates the definitions of D85 and D15 on a molecular weight distribution curve.
  • FIG. 2 illustrates the definitions of D50 and D10 on a molecular weight distribution curve and the short chain branch content at D50 and D10.
  • FIG. 3 presents a plot of the short chain branch distributions across the molecular weight distributions of the polymers of Examples 1-2.
  • FIG. 4 presents a plot of the short chain branch distributions across the molecular weight distributions of the polymers of Examples 3-4.
  • compositions and methods are described herein in terms of “comprising” various components or steps, the compositions and methods also can “consist essentially of” or “consist of” the various components or steps, unless stated otherwise.
  • a catalyst composition consistent with aspects of the present invention can comprise; alternatively, can consist essentially of; or alternatively, can consist of; catalyst component , catalyst component II, an activator, and a co-catalyst.
  • the terms “a,” “an,” “the,” etc., are intended to include plural alternatives, e.g., ateast one, unless otherwise specified.
  • the disclosure of “a co-catalyst” or “a metallocene compound” is meant to encompass one, or mixtures or combinations of morehan one, co-catalyst or metallocene compound, respectively, unless otherwise specified.
  • groups of elements are indicated using the numbering scheme indicatedn the version of the periodic table of elements published in Chemical and Engineering News, 63(5), 27, 1985.
  • a group of elements can be indicated using a common name assigned to the group; for example, alkali metals for Group 1 elements, alkaline earth metals for Group 2 elements, transition metals for Group 3-12 elements, and halogens or halides for Group 17 elements.
  • the general structure or name presented is also intended to encompass all structural isomers, conformational isomers, and tereoisomers that can arise from a particular set of substituents, unless indicated otherwise.
  • a general reference to a compound includes all structural isomers unless explicitly indicated otherwise; e.g., a general reference to pentane includes n-pentane, 2- methyl-butane, and 2,2-dimethylpropane, while a general reference to a butyl groupncludes an n-butyl group, a sec-butyl group, an iso-butyl group, and a tert-butyl group. Additionally, the reference to a general structure or name encompasses all enantiomers, diastereomers, and other optical isomers whether in enantiomeric or racemic forms, as well as mixtures of stereoisomers, as the context permits or requires.
  • any general formula or name presented also encompasses all conformational isomers, regioisomers, and stereoisomers that can arise from a particular et of substituents.
  • substituted when used to describe a group, for example, when referringo a substituted analog of a particular group, is intended to describe any non-hydrogen moiety that formally replaces a hydrogen in that group, and is intended to be non-limiting.
  • a group or groups can also be referred to herein as “unsubstituted” or by equivalent terms uch as “non-substituted,” which refers to the original group in which a non-hydrogen moiety does not replace a hydrogen within that group.
  • hydrocarbon whenever used in this specification and claims refers to a compound containing only carbon and hydrogen. Other identifiers can be utilized tondicate the presence of particular groups in the hydrocarbon (e.g., halogenated hydrocarbon indicates the presence of one or more halogen atoms replacing an equivalent number of hydrogen atoms in the hydrocarbon).
  • hydrocarbyl group is used herein in accordance with the definition specified by IUPAC: a univalent group formed by emoving a hydrogen atom from a hydrocarbon (that is, a group containing only carbon and hydrogen).
  • hydrocarbyl groups include alkyl, alkenyl, aryl, and aralkyl groups, amongst other groups.
  • polymer is used herein generically to include olefin homopolymers, copolymers, terpolymers, and the like, as well as alloys and blends thereof.
  • polymer also includes impact, block, graft, random, and alternating copolymers.
  • a copolymer is derived from an olefin monomer and one olefin comonomer, while aerpolymer is derived from an olefin monomer and two olefin comonomers. Accordingly, “polymer” encompasses copolymers and terpolymers derived from any olefin monomer and comonomer(s) disclosed herein. Similarly, the scope of the term “polymerization”ncludes homopolymerization, copolymerization, and terpolymerization.
  • an ethylene polymer includes ethylene homopolymers, ethylene copolymers (e.g., ethylene/ ⁇ - olefin copolymers), ethylene terpolymers, and the like, as well as blends or mixtureshereof.
  • an ethylene polymer encompasses polymers often referred to in the art as LLDPE (linear low density polyethylene) and HDPE (high density polyethylene).
  • an olefin copolymer such as an ethylene copolymer, can be derived from ethylene and a comonomer, such as 1-butene, 1-hexene, or 1-octene.
  • the resulting polymer can be categorized an as ethylene/1-hexene copolymer.
  • the term “polymer” also includes all possible geometrical configurations, unless stated otherwise, and such configurations cannclude isotactic, syndiotactic, and random symmetries. Moreover, unless stated otherwise, the term “polymer” also is meant to include all molecular weight polymers, ands inclusive of lower molecular weight polymers.
  • co-catalyst is used generally herein to refer to compounds such as aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds, organoaluminum compounds, organozinc compounds, organomagnesium compounds, organolithium compounds, and the like, that can constitute one component of a catalyst composition, when used, for example, in addition to an activator-support.
  • Theerm “co-catalyst” is used regardless of the actual function of the compound or any chemical mechanism by which the compound may operate.
  • activator-support is used herein to indicate a solid, inorganic oxide of elatively high porosity, which can exhibit Lewis acidic or Br ⁇ nsted acidic behavior, and which has been treated with an electron-withdrawing component, typically an anion, and which is calcined.
  • the electron-withdrawing component is typically an electron- withdrawing anion source compound.
  • the activator-support can comprise a calcined contact product of at least one solid oxide with at least one electron-withdrawing anion ource compound.
  • the activator-support comprises at least one acidic solid oxide compound.
  • the “activator-support” of the present invention can be a chemically-reated solid oxide.
  • activator-support is used to imply that these components are not inert, and such components should not be construed as an inert component of the catalyst composition.
  • activator refers generally to a substancehat is capable of converting a metallocene component into a catalyst that can polymerize olefins, or converting a contact product of a metallocene component and a component that provides an activatable ligand (e.g., an alkyl, a hydride) to the metallocene, when the metallocene compound does not already comprise such a ligand, into a catalyst that can polymerize olefins. This term is used regardless of the actual activating mechanism.
  • activators include activator-supports, aluminoxanes, organoboron or organoborate compounds, ionizing ionic compounds, and the like.
  • Aluminoxanes, organoboron or organoborate compounds, and ionizing ionic compounds generally are eferred to as activators if used in a catalyst composition in which an activator-support is not present. If the catalyst composition contains an activator-support, then the aluminoxane, organoboron or organoborate, and ionizing ionic materials are typically eferred to as co-catalysts.
  • metalocene as used herein describes compounds comprising at least one ⁇ 3 to ⁇ 5 -cycloalkadienyl-type moiety, wherein ⁇ 3 to ⁇ 5 -cycloalkadienyl moietiesnclude cyclopentadienyl ligands, indenyl ligands, fluorenyl ligands, and the like, including partially saturated or substituted derivatives or analogs of any of these.
  • Possible ubstituents on these ligands can include H, therefore this invention comprises ligands such as tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, substituted partially saturated indenyl, substituted partially aturated fluorenyl, and the like.
  • the metallocene is referred to simply ashe “catalyst,” in much the same way the term “co-catalyst” is used herein to refer to, for example, an organoaluminum compound.
  • catalyst composition do not depend upon the actual product or composition resulting from the contact or eaction of the initial components of the disclosed or claimed catalyst composition/mixture/system, the nature of the active catalytic site, or the fate of the co- catalyst, the metallocene compound(s), or the activator, after combining these components. Therefore, the terms “catalyst composition,” “catalyst mixture,” “catalyst system,” and theike, encompass the initial starting components of the composition, as well as whatever product(s) may result from contacting these initial starting components, and this isnclusive of both heterogeneous and homogenous catalyst systems or compositions.
  • compositions can be used interchangeably throughout this disclosure.
  • contact product is used herein to describe compositions wherein the components are contacted together in any order, in any manner, and for any length of time, unless otherwise specified.
  • the components can be contacted by blending or mixing.
  • contacting of any component can occur in the presence or absence of any other component of the compositions described herein. Combining additional materials or components can be done by any suitable method.
  • contact product ncludes mixtures, blends, solutions, slurries, reaction products, and the like, or combinations thereof.
  • contact product can include reaction products, it is not equired for the respective components to react with one another.
  • contacting is used herein to refer to materials which can be blended, mixed, slurried, dissolved, reacted, treated, or otherwise combined in some other manner.
  • any methods, devices, and materials similar or equivalent to those described herein can be used in the practice or testing of the invention, the typical methods, devices, and materials are herein described. All publications and patents mentioned herein are incorporated herein by reference or 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. Several types of ranges are disclosed in the present invention.
  • a moiety is a C 1 to C 18 hydrocarbyl group, or in alternative language, a hydrocarbyl group having from 1 to 18 carbon atoms, as used herein, 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, as well as any range between these two numbers (for example, a C 1 to C 8 hydrocarbyl group), and alsoncluding any combination of ranges between these two numbers (for example, a C 2 to C 4 and a C12 to C16 hydrocarbyl group).
  • another representative example follows for the ratio of Mw/Mn of an ethylene polymer consistent with aspects of this invention.
  • the ratio of Mw/Mn can be in a range from 6 to 25, the intent is to recite that the ratio of Mw/Mn can be any ratio in the range and, for example, can include any range or combination of ranges rom 6 to 25, such as from 7 to 20, from 7 to 18, or from 8 to 15, and so forth.
  • all other ranges disclosed herein should be interpreted in a manner similar to these examples.
  • an amount, size, formulation, parameter, range, or other quantity or characteristic is “about” or “approximate” whether or not expressly stated to be such. Whether or not modified by the term “about” or “approximately,” the claims include equivalents to the quantities or characteristics.
  • the present invention is directed generally to dual metallocene catalyst systems, methods for using the catalyst systems to polymerize olefins, the polymer resins produced using such catalyst systems, and articles of manufacture produced using these polymer esins.
  • the present invention generally relates to bimodal ethylene copolymers having a low molecular weight fraction with a low concentration of comonomer SCBs and a high molecular weight fraction with a relatively higher concentration of comonomer SCBs.
  • the disclosed bimodal ethylene polymers have a surprisingly high short chain branching ratio between the high molecular weight and low molecular weight components.
  • the low level of comonomer SCB content in the low molecular weight raction of the of the polymer in combination with unexpectedly high levels of SCB content in the high molecular weight fraction of the polymer can result in improved polymer properties, such as stress crack resistance (ESCR), PENT slow crack growth esistance (ASTM F1473), and natural draw ratio (NDR), and particularly at an equivalent overall polymer density.
  • ESCR stress crack resistance
  • ASTM F14 PENT slow crack growth esistance
  • NDR natural draw ratio
  • ETHYLENE POLYMERS Generally, the polymers disclosed herein are ethylene-based polymers, or ethylene polymers, encompassing homopolymers of ethylene as well as copolymers, terpolymers, etc., of ethylene and at least one olefin comonomer.
  • Comonomers that can be copolymerized with ethylene often can have from 3 to 20 carbon atoms in their molecular chain.
  • typical comonomers can include, but are not limited to, propylene, 1- butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and the like, or combinations thereof.
  • the olefin comonomer can comprise a C 3 -C 18 olefin; alternatively, the olefin comonomer can comprise a C 3 -C 10 olefin; alternatively, the olefin comonomer can comprise a C4-C10 olefin; alternatively, the olefin comonomer can comprise a C3-C10 ⁇ - olefin; alternatively, the olefin comonomer can comprise a C4-C10 ⁇ -olefin; alternatively,he olefin comonomer can comprise 1-butene, 1-hexene, 1-octene, or any combinationhereof; or alternatively, the comonomer can comprise 1-hexene.
  • the ethylene polymer of this invention can comprise an ethylene/ ⁇ - olefin copolymer.
  • the ethylene polymer can 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.
  • the resultant polymer produced in accordance with the present invention is, for example, an ethylene copolymer, its properties can be characterized by various analyticalechniques known and used in the polyolefin industry.
  • Articles of manufacture can be ormed from, and/or can comprise, the ethylene polymers (e.g., ethylene copolymers) ofhis invention, whose typical properties are provided below.
  • An illustrative and non-limiting example of an ethylene polymer (e.g., an ethylene/1-hexene copolymer) described herein can have a density in a range from 0.92 to 0.955 g/cm 3 , a HLMI of less than or equal to 35 g/10 min, and a ratio of a number of short chain branches (SCBs) per 1000 total carbon atoms at Mz to a number of SCBs per 1000otal carbon atoms at Mn in a range from 11.5 to 22.
  • SCBs short chain branches
  • an ethylene polymer e.g., an ethylene/1-hexene copolymer
  • an ethylene polymer e.g., an ethylene/1-hexene copolymer
  • a density in a range from 0.92 to 0.955 g/cm 3
  • a HLMI of less than or equal to 35 g/10 min
  • a higher molecular weight (HMW) component and a lower molecular weight LMW) component can be in a range from 10.5 to 22.
  • the density of the ethylene-based polymer can range from 0.92 to 0.955 g/cm 3 . In one aspect, the density can range from 0.92 to 0.95, from 0.92 to 0.94 in another aspect, rom 0.925 to 0.955 in another aspect, from 0.925 to 0.95 in yet another aspect, or from 0.925 to 0.943 g/cm 3 in still another aspect.
  • the ethylene polymer has a very low melt index, as indicated by the high load meltndex (HLMI) of less than or equal to 35 g/10 min.
  • the HLMI of the ethylene polymer can 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 the ethylene polymer can be less than or equal to 20 g/10 min, or less than or equal to 15 g/10 min.
  • the ethylene polymer can comprise a high or higher molecular weight (HMW) component (or a first component) and a low or lower molecular weight (LMW) component or a second component). These component terms are relative, are used in reference to each other, and are not limited to the actual molecular weights of the respective components.
  • the molecular weight characteristics of these LMW and HMW components are determined by deconvoluting the composite (overall polymer) molecular weight distribution (e.g., determined using gel permeation chromatography).
  • the amount of theower molecular weight (LMW) component, based on the total polymer, is not limited to any particular range. Generally, however, the amount of the lower molecular weight component can be in a range from 40 to 90 wt. %, from 40 to 85 wt. %, from 45 to 90 wt. %, from 45 to 85 wt. %, or from 50 to 85 wt. %.
  • the higher molecular weight component can have a Mn in a range from 400,000 to 800,000 g/mol.
  • the Mn can fall within a range from 450,000 to 750,000 g/mol, or alternatively, from 500,000 to 700,000 g/mol.
  • the higher molecular weight component can have a Mp in a range from 400,000 to 1,100,000 g/mol, such as from 500,000 to 1,100,000 g/mol, or from 550,000 to 1,000,000 g/mol.
  • Theower molecular weight component of the ethylene polymer can have a Mz in a range from 70,000 to 200,000 g/mol (or from 70,000 to 170,000, or from 75,000 to 150,000, or from 80,000 to 130,000 g/mol).
  • 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 falls within a range from 10.5 to 22.
  • Other suitable anges for this ratio include, but are not limited to, from 11 to 22, from 11 to 21, from 12 to 22, from 12 to 20, or from 13 to 19, and the like.
  • the ratio ofhe 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 range rom 11 to 18, and in some aspects, from 11 to 14, from 11.5 to 16, or from 11.5 to 15.
  • 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 range from 7.5 to 18, and in some aspects, from 8 to 16, from 9 to 14, or from 10 to 12.
  • the ethylene polymer (inclusive of the higher and lower molecular weight components) can have a Mw in a range from 200,000 to 800,000, from 225,000 to 725,000, from 250,000 to 600,000, or from 275,000 to 575,000 g/mol.
  • the ethylene polymer can have a Mp in a range from 30,000 to 90,000 g/mol, uch as from 35,000 to 85,000, from 40,000 to 80,000, or from 45,000 to 75,000 g/mol. Additionally or alternatively, the ethylene polymer can have a Mn in a range from 15,000o 60,000 g/mol, such as from 18,000 to 57,000, from 22,000 to 53,000, or from 25,000 to 50,000 g/mol. Additionally or alternatively, the ethylene polymer can have a Mz in a ange from 1,300,000 to 3,100,000 g/mol, such as from 1,400,000 to 3,000,000, from 1,500,000 to 2,500,000, or from 1,700,000 to 2,200,000 g/mol.
  • the ethylene polymer has a relatively broad molecular weight distribution, often with a ratio of Mw/Mn in a range rom 6 to 25.
  • the ratio of Mw/Mn of the polymer can be from 7 to 20; alternatively, from 7 to 18; alternatively, from 8 to 15; or alternatively, from 9 to 13.
  • the ethylene polymer can have a bimodal molecular weight distribution. Generally, there are two distinguishable peaks in the molecular weight distribution curve (as determined using gel permeation chromatography (GPC)), there is a valley between the peaks, and the peaks can be eparated or deconvoluted.
  • GPC gel permeation chromatography
  • the ethylene polymer can have a multimodal e.g., trimodal) molecular weight distribution.
  • the ethylene polymer can have a LMW component, a MMW (medium molecular weight) component, and a HMW component.
  • the LMW component can be a homopolymer or a copolymer with very low comonomer content.
  • the MMW and HMW components can be copolymers, with the HMW component having more comonomer (and SCBs) than the MMW component.
  • the unexpectedly high 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 falls within a range rom 11.5 to 22.
  • FIG.1 is a graphical depiction of D85 and D15 for a molecular weight distribution curve as a function of increasing logarithm of the molecular weight.
  • D85 is the molecular weight at which 85% of the polymer by weight has higher molecular weight
  • D15 ishe molecular weight at which 15% of the polymer by weight has higher molecular weight.
  • the ethylene polymers disclosed herein can have a molecular weight at D85 in a range from 14,000 to 50,000 g/mol, and in another aspect, from 15,000 to 40,000, from 16,000 to 38,000, or from 17,000 to 35,000 g/mol.
  • FIG.2 is a graphical depiction of D50 and D10 for a molecular weight distribution curve as a function of increasing logarithm of the molecular weight.
  • D50 is the molecular weight at which 50% of the polymer by weight has higher molecular weight
  • D10 is the molecular weight at which 10% of the polymer by weight has higher molecular weight.
  • the ethylene polymers disclosed herein can have a molecular weight at D10 in a range from 750,000 to 2,000,000 g/mol, and from 800,000 to 1,750,000 g/mol in another aspect, and from 850,000 to 2,000,000 g/mol in yet another aspect, and from 900,000 to 1,750,000 g/mol in still another aspect.
  • the number of SCBs per 1000 total carbon atoms of the ethylene polymer at D10 can range from 9 to 30; alternatively, from 12 to 28; alternatively, from 14 to 27; or alternatively, from 16 to 25.
  • the ethylene polymer described herein can be a reactor product (e.g., a ingle reactor product), for example, not a post-reactor blend of two polymers, for instance, having different molecular weight characteristics.
  • a reactor product e.g., a ingle reactor product
  • physical blends of two different polymer resins can be made, but this necessitates additional processing and complexity not required for a reactor product.
  • the ethylene polymer can be produced with dual metallocene catalyst ystems containing zirconium and/or hafnium, as discussed herein. Ziegler-Natta and chromium based catalysts systems can be used, but are not required.
  • the ethylene polymer can contain no measurable amount of chromium or titanium or vanadium or magnesium (catalyst residue), i.e., less than 0.1 ppm by weight.
  • the ethylene polymer can contain, independently, less than 0.08 ppm, less than 0.05 ppm, oress than 0.03 ppm, of chromium (or titanium, or vanadium, or magnesium).
  • ARTICLES AND PRODUCTS Articles of manufacture can be formed from, and/or can comprise, the ethylene polymers (e.g., ethylene/1-hexene copolymers) of this invention and, accordingly, are encompassed herein.
  • articles which can comprise the polymers of thisnvention can include, but are not limited to, an agricultural film, an automobile part, a bottle, a container for chemicals, a drum, a fiber or fabric, a food packaging film or container, a food service article, a fuel tank, a geomembrane, a household container, ainer, a molded product, a medical device or material, an outdoor storage product (e.g., panels for walls of an outdoor shed), outdoor play equipment (e.g., kayaks, bases for basketball goals), a pipe, a sheet or tape, a toy, or a traffic barrier, and the like.
  • Various processes can be employed to form these articles.
  • Non-limiting examples of these processes include injection molding, blow molding, rotational molding, film extrusion, heet extrusion, profile extrusion, thermoforming, and the like. Additionally, additives and modifiers often are added to these polymers in order to provide beneficial polymer processing or end-use product attributes. Such processes 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 entirety. CATALYST SYSTEMS AND POLYMERIZATION PROCESSES In accordance with aspects of the present invention, the ethylene polymer (e.g., the ethylene copolymer) can be produced using a dual catalyst system.
  • catalyst component I can comprise any suitable unbridged metallocene compound disclosed herein
  • catalyst component II can comprise any suitable bridged metallocene compound disclosed herein
  • the catalyst system also can comprise any suitable activator or any activator disclosed herein, and optionally, any suitable co-catalyst or any co-catalyst disclosed herein. Referring first to catalyst component I, which can comprise an unbridged metallocene compound.
  • catalyst component I can comprise an unbridged metallocene compound containing two indenyl groups or an indenyl group and a cyclopentadienyl group, wherein at least one indenyl group has at least one halogen- ubstituted hydrocarbyl substituent with at least two halogen atoms.
  • catalyst component I can comprise an unbridged metallocene compound containing twondenyl groups, wherein at least one indenyl group has at least one halogen-substituted hydrocarbyl substituent with at least two halogen atoms.
  • catalyst component I can comprise an unbridged metallocene compound containing an indenyl group and a cyclopentadienyl group, wherein the indenyl group has at least one halogen- ubstituted hydrocarbyl substituent with at least two halogen atoms.
  • the halogen-substituted hydrocarbyl substituent can comprise an aryl group.
  • the halogen atoms independently, can be any halogen, but often each halogen is fluorine.
  • the unbridged metallocene compound can contain titanium, zirconium, or hafnium, but catalyst component I often is a zirconium-based metallocene compound.
  • Catalyst component I can comprise, in particular aspects of this invention, an unbridged metallocene compound having the formula: (X 1 )(X 2 )(X 3 )(X 4 )M 1 , wherein M 1 , X 1 , X 2 , X 3 and X 4 are selected as follows: a) M 1 can be titanium, zirconium, or hafnium; b) X 1 can be a substituted indenyl ligand wherein at least one substituent is a halogen- ubstituted C 1 -C 20 hydrocarbyl group comprising at least two halogen atoms; c) X 2 can be 1] a substituted or unsubstituted cyclopentadienyl ligand which is absent a halogen- ubstituted hydrocarbyl group, or [2] a substituted or unsubstituted indenyl ligand; wherein X 1 and X 2 are un
  • the catalyst composition comprising catalyst component I can produce low molecular weight polyethylene with unexpectedly low levels of short chain branching, even in the presence of significant concentrations of an ⁇ -olefin co-monomer.
  • Polymers having these properties can occur when [1] the metallocene comprises onendenyl ligand X 1 which contains a halogen-disubstituted C1-C20 hydrocarbyl group as a ubstituent, and [2] when the ligand X 2 is a cyclopentadienyl ligand, X 2 is absent a halogen-substituted hydrocarbyl group.
  • the presence of a halogen-substituted hydrocarbyl group on X 2 when X 2 is an indenyl ligand still provides the desirable low levels of short chain branching, but not when X 2 is a cyclopentadienyl ligand.
  • the X 2 ligand, or both X 1 and X 2 are absent a halogen substituent which is bonded directly to the indenyl ligand.
  • the M 1 in the unbridged metallocene can be Ti; alternatively, M 1 can be Zr; alternatively, M 1 can 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 can be Ti, Zr, or Hf.
  • the groups X 3 and X 4 of the unbridged metallocene can be independently selected from F, Cl, Br, a C1-C12 hydrocarbyloxide group, a C1-C12 hydrocarbylamino group, or a trihydrocarbylsilyl group wherein each hydrocarbyl isndependently a C 1 -C 12 hydrocarbyl group.
  • the halogen-substituted hydrocarbyl substituent of X 1 of the unbridged metallocene can be selected from a C 1 -C 20 hydrocarbyl group substituted with at least two luoro-, chloro-, bromo-, or iodo-substituents, or a combination thereof independently elected.
  • the halogen-substituted hydrocarbyl substituent of X 1 is selected rom a C1-C20 hydrocarbyl group or a C1-C12 hydrocarbyl group substituted with at leastwo fluoro-, chloro-, or bromo-substituents.
  • the X 1 can be a substitutedndenyl ligand wherein at least one substituent is a halogen-substituted C1-C20 hydrocarbyl group comprising 2, 3, 4, 5, 6, 7, 8, or more halogen atoms such as fluorine atoms,ncluding ranges between any of these numbers, as allowed by the size and structure of a particular hydrocarbyl group.
  • halogen-substituted C 1 -C 20 hydrocarbyl group is a phenyl group
  • the upper limit of halogen substituents is five (5) ubstituents
  • the phenyl group can include 2, 3, 4, or 5 substituents.
  • the halogen-substituted C 1 -C 20 hydrocarbyl group can comprise from 2 to 8, from 2 to 7, from 2 to 6, from 2 to 5, from 2 to 4, or from 2 to 3 halogen atoms.
  • the halogen-substituted hydrocarbyl substituent of X 1 of the unbridged metallocene can be selected from C 1 -C 20 aliphatic or C 6 -C 20 aromatic group substituted with at least two fluoro-, chloro-, or bromo-substituents, or a combination thereof.
  • the halogen-substituted hydrocarbyl substituent of X 1 of the unbridged metallocene can be selected from a fluoro-disubstituted, chloro- disubstituted, or bromo-disubstituted C1-C12 alkyl, C2-C12 alkenyl, C3-C7 cycloalkyl, C3-C7 cycloalkenyl, C6-C10 aryl, or C7-C12 aralkyl.
  • the halogen- ubstituted hydrocarbyl substituent of X 1 of the metallocene can be further substituted with at least one additional substituent selected from a C1-C12 hydrocarbyl group.
  • the X 1 ligand of the unbridged metallocene can be an indenyligand which can be substituted with a halogen-substituted hydrocarbyl group selected rom: [1] -C6X 9 nH5-n or -CH2C6X 9 nH5-n, wherein n is an integer from 2 to 5; [2] - CH2)mCX 9 pH3-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 (CH 3 ) 3-q or -C(CX 9 3 ) q H 3-q , wherein q is an integer from 2 to 3; and where
  • the X 2 ligand of the unbridged metallocene can be [1] a substituted or unsubstituted cyclopentadienyl ligand which is absent a halogen- ubstituted hydrocarbyl group, or [2] a substituted or unsubstituted indenyl ligand; wherein X 1 and X 2 are unbridged, and wherein any substituent on X 1 and X 2 which is not a halogen-substituted C1-C20 hydrocarbyl group is selected independently from a C1-C20 hydrocarbyl group.
  • X 2 can be an indenyl ligand which is unsubstituted; alternatively, substituted with at least one C 1 -C 20 hydrocarbyl group; alternatively, substituted with at least one halogen-substituted C1-C20 hydrocarbyl group; alternatively, substituted with at least one C1-C12 hydrocarbyl group; or alternatively, ubstituted with at least one halogen-substituted C 1 -C 12 hydrocarbyl group.
  • the X 2 ligand of the unbridged metallocene can be an indenyligand which is unsubstituted, substituted with at least one unsubstituted C1-C20 aliphatic or C 6 -C 20 aromatic group, or substituted with at least one C 1 -C 20 aliphatic or C 6 -C 20 aromatic group substituted with at least one fluoro-, chloro-, or bromo-substituent, or a combinationhereof.
  • X 2 can be an indenyl ligand which is substituted with at least one halogen-substituted hydrocarbyl substituent selected from C 1 -C 12 aliphatic or C 6 -C 10 aromatic group substituted with at least one fluoro-, chloro-, or bromo-substituent, or a combination thereof.
  • the X 2 ligand of the unbridged metallocene can be anndenyl ligand which is substituted with at least one halogen-substituted hydrocarbyl ubstituent selected from a fluoro-substituted, chloro-substituted, or bromo-substituted C1- C12 alkyl, C2-C12 alkenyl, C3-C7 cycloalkyl, C3-C7 cycloalkenyl, C6-C10 aryl, or C7-C12 aralkyl.
  • halogen-substituted hydrocarbyl ubstituent selected from a fluoro-substituted, chloro-substituted, or bromo-substituted C1- C12 alkyl, C2-C12 alkenyl, C3-C7 cycloalkyl, C3-C7 cycloalkenyl, C6-C10
  • the X 2 ligand of the unbridged metallocene can be a cyclopentadienyl ligand which is unsubstituted.
  • the X 2 ligand of the metallocene can be a cyclopentadienyl ligand which is substituted with at least one C 1 -C 20 hydrocarbyl group; or alternatively, substituted with at least one C1-C12 hydrocarbyl group.
  • the X 2 ligand of the metallocene can be a cyclopentadienyl ligand which is substituted with at least one C 1 -C 20 aliphatic group; alternatively, substituted with at least one C 6 -C 20 aromatic group; alternatively, substituted at least one C1-C12 aliphatic group; or alternatively, substituted with at least one C6-C10 aromatic group.
  • the X 2 ligand of the unbridged metallocene can be a cyclopentadienyl ligand whichs substituted with at least one hydrocarbyl substituent selected independently from a C1- C 12 alkyl, C 2 -C 12 alkenyl, C 3 -C 7 cycloalkyl, C 3 -C 7 cycloalkenyl, C 6 -C 10 aryl, or C 7 -C 12 aralkyl.
  • the X 1 ligand of the unbridged metallocene can be a ubstituted indenyl ligand wherein at least one substituent is a halogen-substituted C 1 -C 20 hydrocarbyl group comprising at least two halogen atoms, for example, a fluoride- disubstituted indenyl ligand.
  • the halogen-substituted C 1 -C 20 hydrocarbyl group comprises at least two halogen atoms and up to 8 or more halogen atoms, depending upon the size and structure of the C 1 -C 20 hydrocarbyl group.
  • X 2 ligand of the unbridged metallocene can be a substituted or an unsubstituted indenyl ligand, for example, X 2 can be an indenyl ligand which is substituted with at least one C 1 -C 20 aliphatic or C 6 -C 20 aromatic group substituted with at least one fluoro-, chloro-, or bromo- ubstituent, or a combination thereof.
  • X 1 can be an indenyl ligand which is ubstituted with a group selected independently from F F ; and/or X 2 can be an indenyl ligand which is substituted with a group ndently from
  • suitable metallocene compounds for use as catalyst component I can nclude, but are not limited to, the following: ; or any combination thereof. For .
  • s, X 3 and X 4 can be independently selected from a halide, F, Cl, Br, a C 1 -C 12 hydrocarbyloxide group, a C 1 -C 12 hydrocarbylamino group, or a rihydrocarbylsilyl group wherein each hydrocarbyl of these groups is independently elected from a C 1 -C 12 hydrocarbyl group.
  • each hydrocarbyl of these groups can be independently selected from a C 1 -C 20 hydrocarbyl group.
  • catalyst component II which can be a bridged metallocene compound.
  • catalyst component II can comprise a bridged zirconium or hafnium based metallocene compound.
  • catalyst component II can comprise a bridged zirconium or hafnium based metallocene compound with an alkenyl substituent.
  • catalyst component II can comprise a bridged zirconium or hafnium based metallocene compound with an alkenyl substituent and a fluorenyl group.
  • catalyst component II can comprise a bridged zirconium or hafnium based metallocene compound with a cyclopentadienyl group and a fluorenyl group, and with an alkenyl substituent on the bridging group and/or on the cyclopentadienyl group.
  • catalyst component II can comprise a bridged metallocene compound having an aryl group substituent on the bridging group.
  • Catalyst component II can comprise, in particular aspects of this invention, a bridged metallocene compound having the formula (X 5 )(X 6 )(X 7 )(X 8 )M 2 , wherein M 2 , X 5 , X 6 , X 7 and X 8 are selected as follows: a) M 2 can be titanium, zirconium, or hafnium; b) X 5 can be a substituted cyclopentadienyl, indenyl, or fluorenyl ligand, wherein any non- bridging substituent, when present, is selected independently from a C1-C12 hydrocarbyl group; c) X 6 can be a substituted fluorenyl ligand, wherein any non-bridging substituent, when present, is selected independently from a C 1 -C 12 hydrocarbyl group or a
  • x is an integer from 1 to 3
  • E is selected independently from a carbon atom or a silicon atom
  • R B in each occurrence is selected independently from H or a C 1 -C 12 hydrocarbyl group, and wherein optionally, two R B moieties independently form a C 3 -C 6 cyclic group.
  • (>ER B 2 ) x can be (-CR B 2 CR B 2 -), (-SiR B 2 SiR B 2 -), (-CR B 2 SiR B 2 -), (- CR B 2CR B 2CR B 2-), (-SiR B 2CR B 2CR B 2-), (-CR B 2SiR B 2CR B 2-), (- SiR B 2SiR B 2CR B 2-), or (-SiR B 2SiR B 2SiR B 2-).
  • X 5 in addition to comprising the bridging substituent, can be [1] otherwise unsubstituted or [2] substituted with a C 1 -C 12 hydrocarbyl group.
  • X 5 can be a cyclopentadienyl ligand which, in addition to comprising the bridging substituent, s [1] otherwise unsubstituted or [2] substituted with a C 1 -C 6 alkyl or C 2 -C 8 alkenyl group.
  • X 6 can be a fluorenyl ligand substituted with two substituents elected independently from a C1-C12 hydrocarbyl group, in addition to the bridging ubstituent.
  • X 6 can be a fluorenyl ligand and wherein R B is selected ndependently from a C 1 -C 6 alkyl or C 2 -C 8 alkenyl group.
  • the catalyst component II can comprise, consist essentially of, consist of, or is selected from a metallocene compound having the formula: ; wherein: m; X 5 in each occurrence is independently F, Cl, Br, I, H, methyl, benzyl, phenyl, or methoxy; R D in each occurrence is selected independently from H, C 1 -C 12 alkyl, C 2 -C 12 alkenyl, C6-C10 aryl, C7-C12 aralkyl, or C1-C12 hydrocarbyloxide; E is C or Si; R E in each occurrence is selected independently from H, C 1 -C 12 alkyl, C 2 -C 12 alkenyl, C6-C10 aryl, or C7-C12
  • Catalyst component II is not limited solely to the bridged metallocene compounds uch as described above.
  • Other suitable bridged metallocene compounds are disclosed in U.S. Patent 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.
  • the weight ratio of catalyst component I to catalyst component II in the catalyst composition can be in a range from 10:1 to 1:10, from 8:1 to 1:8, from 5:1 to 1:5, from 4:1 to 1:4, from 3:1 to 1:3; from 2:1 to 1:2, from 1.5:1 to 1:1.5, from 1.25:1 to 1:1.25, or from 1.1:1 to 1:1.1.
  • catalyst component I 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 can be in a ange from 1:1 to 1:10, from 1:1 to 1:5, or from 1:1 to 1:3.
  • the dual catalyst system contains an activator.
  • the catalyst system can contain an activator-support, an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, and the like, or any combination thereof.
  • the catalyst system can contain one or more than one activator.
  • the catalyst system can comprise an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, and the like, or a combination thereof. Examples of such activators are disclosed in, for instance, U.S. Patent Nos.
  • the catalyst system can comprise an aluminoxane compound.
  • the catalyst system can comprise an organoboron or organoborate compound.
  • the catalyst system can comprise an ionizing ionic compound.
  • 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 in, for instance, U.S. Patent Nos.
  • the activator-support can comprise fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, luorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica- alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, ulfated silica-zirconia, fluorided silica-titania, fluorided-chlorided silica-coated alumina, luorided silica-coated alumina, sulfated silica-coated alumina, or phosphated silic
  • the activator- upport can comprise a fluorided solid oxide and/or a sulfated solid oxide.
  • Various processes can be used to form activator-supports useful in the presentnvention. Methods of contacting the solid oxide with the electron-withdrawing component, suitable electron withdrawing components and addition amounts,mpregnation with metals or metal ions (e.g., zinc, nickel, vanadium, titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium, and the like, or combinationshereof), and various calcining procedures and conditions are disclosed in, for example, U.S. Patent Nos.
  • the present invention can employ catalyst compositions containing catalyst component I, catalyst component II, an activator (one or more than one), and optionally, a co-catalyst.
  • the co-catalyst can include, but is not limited to, metal alkyl, or organometal, co-catalysts, with the metal encompassing boron, aluminum, zinc, and the ike.
  • the catalyst systems provided herein can comprise a co-catalyst, or a combination of co-catalysts.
  • alkyl boron, alkyl aluminum, and alkyl zinc compounds often can be used as co-catalysts in such catalyst systems.
  • Representative boron compounds can include, but are not limited to, tri-n-butyl borane, tripropylborane,riethylborane, and the like, and this include combinations of two or more of these materials.
  • representative aluminum compounds e.g., organoaluminum compounds
  • Exemplary zinc compounds e.g., organozinc compounds) that can be used as co-catalysts can include, but are notimited to, dimethylzinc, diethylzinc, dipropylzinc, dibutylzinc, dineopentylzinc, di(trimethylsilyl)zinc, di(triethylsilyl)zinc, di(triisoproplysilyl)zinc, di(triphenylsilyl)zinc, di(allyldimethylsilyl)zinc, di(trimethylsilylmethyl)zinc, and the like, or combinationshereof.
  • the dual catalyst composition can comprise catalyst component I, catalyst component II, an activator-support, and an organoaluminum compound (and/or an organozinc compound).
  • a catalyst composition which comprises catalyst component I, catalyst component II, an activator-support, and an organoaluminum compound, wherein this catalyst composition is substantially free of aluminoxanes, organoboron or organoborate compounds, ionizing ionic compounds, and/or other similar materials; alternatively, substantially free of aluminoxanes; alternatively, ubstantially free or organoboron or organoborate compounds; or alternatively, ubstantially free of ionizing ionic compounds.
  • the catalyst composition has catalyst activity, discussed herein, in the absence of these additional materials.
  • a catalyst composition of the present invention can consist essentially of catalyst component I, catalyst component II, an activator-support, and an organoaluminum compound, wherein no other materials are present in the catalyst composition which wouldncrease/decrease the activity of the catalyst composition by more than 10% from the catalyst activity of the catalyst composition in the absence of said materials.
  • This invention further encompasses methods of making these catalyst compositions, such as, for example, contacting the respective catalyst components in any order or sequence.
  • the catalyst composition can be produced by a process comprising contacting, in any order, catalyst component I, catalyst component I, and the activator, while in another aspect, the catalyst composition can be produced by a process comprising contacting, in any order, catalyst component I, catalyst component II,he activator, and the co-catalyst.
  • Ethylene polymers e.g., ethylene/ ⁇ -olefin copolymers
  • One such polymerization process for polymerizing olefins in the presence of a catalyst composition of the present invention can comprise contacting the catalyst composition with ethylene and an ⁇ -olefin comonomer (one or more) in a polymerization eactor system under polymerization conditions to produce an ethylene polymer, whereinhe catalyst composition can comprise, as disclosed herein, catalyst component I, catalyst component II, an activator, and an optional co-catalyst.
  • This invention also encompasses any ethylene polymers produced by any of the polymerization processes disclosed herein.
  • a “polymerization reactor” includes any polymerization reactor capable of polymerizing (inclusive of oligomerizing) olefin monomers and comonomers one or more than one comonomer) to produce homopolymers, copolymers, terpolymers, and the like.
  • the various types of polymerization reactors include those that can be eferred to as a batch reactor, slurry reactor, gas-phase reactor, solution reactor, high pressure reactor, tubular reactor, autoclave reactor, and the like, or combinations thereof; or alternatively, the polymerization reactor system can comprise a slurry reactor, a gas- phase reactor, a solution reactor, or a combination thereof.
  • Gas phase reactors can comprise fluidized bed reactors or staged horizontal reactors.
  • Slurry reactors can comprise vertical or horizontal loops.
  • High pressure reactors can comprise autoclave orubular reactors.
  • Reactor types can include batch or continuous processes. Continuous processes can use intermittent or continuous product discharge.
  • Polymerization reactor ystems and processes also can include partial or full direct recycle of unreacted monomer, unreacted comonomer, and/or diluent.
  • a polymerization reactor system can comprise a single reactor or multiple reactors 2 reactors, more than 2 reactors) of the same or different type.
  • the polymerization reactor system can comprise a slurry reactor, a gas-phase reactor, a solution eactor, or a combination of two or more of these reactors.
  • Production of polymers in multiple reactors can include several stages in at least two separate polymerization reactorsnterconnected by a transfer device making it possible to transfer the polymers resulting rom the first polymerization reactor into the second reactor.
  • the desired polymerization conditions in one of the reactors can be different from the operating conditions of the other eactor(s).
  • polymerization in multiple reactors can include the manualransfer of polymer from one reactor to subsequent reactors for continued polymerization.
  • Multiple reactor systems can include any combination including, but not limited to, multiple loop reactors, multiple gas phase reactors, a combination of loop and gas phase eactors, multiple high pressure reactors, or a combination of high pressure with loop and/or gas phase reactors.
  • the multiple reactors can be operated in series, in parallel, or both.
  • the present invention encompasses polymerization reactor systems comprising a single reactor, comprising two reactors, and comprising more than two eactors.
  • the polymerization reactor system can comprise a slurry reactor, a gas-phase eactor, a solution reactor, in certain aspects of this invention, as well as multi-reactor combinations thereof.
  • the polymerization reactor system can comprise at least one loop slurry reactor comprising vertical or horizontal loops.
  • Monomer, diluent, catalyst, and comonomer can be continuously fed to a loop reactor where polymerization occurs.
  • continuous processes can comprise the continuous introduction of monomer/comonomer, a catalyst, and a diluent into a polymerization reactor and the continuous removal from this reactor of a suspension comprising polymer particles and the diluent.
  • Reactor effluent can be flashed to remove the solid polymer from the liquids that comprise the diluent, monomer and/or comonomer.
  • Various technologies can be used forhis separation step including, but not limited to, flashing that can include any combination of heat addition and pressure reduction, separation by cyclonic action in either a cyclone or hydrocyclone, or separation by centrifugation.
  • flashing that can include any combination of heat addition and pressure reduction, separation by cyclonic action in either a cyclone or hydrocyclone, or separation by centrifugation.
  • a typical slurry polymerization process (also known as the particle form process) is disclosed, for example, in U.S. Patent 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 eference in its entirety.
  • Suitable diluents used in slurry polymerization include, but are not limited to, the monomer being polymerized and hydrocarbons that are liquids under reaction conditions.
  • suitable diluents include, but are not limited to, hydrocarbons such as propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, and n- hexane.
  • Some loop polymerization reactions can occur under bulk conditions where no diluent is used.
  • the polymerization reactor system can comprise ateast one gas phase reactor (e.g., a fluidized bed reactor).
  • Such reactor systems can employ a continuous recycle stream containing one or more monomers continuously cycled through a fluidized bed in the presence of the catalyst under polymerization conditions.
  • a recycle stream can be withdrawn from the fluidized bed and recycled backnto the reactor.
  • polymer product can be withdrawn from the reactor and new or fresh monomer can be added to replace the polymerized monomer.
  • Such gas phase eactors can comprise a process for multi-step gas-phase polymerization of olefins, in which olefins are polymerized in the gaseous phase in at least two independent gas-phase polymerization zones while feeding a catalyst-containing polymer formed in a first polymerization zone to a second polymerization zone.
  • the polymerization reactor system can comprise a high pressure polymerization reactor, e.g., can comprise a tubular reactor or an autoclave eactor.
  • Tubular reactors can have several zones where fresh monomer, initiators, or catalysts are added.
  • Monomer can be entrained in an inert gaseous stream and introduced at one zone of the reactor.
  • Initiators, catalysts, and/or catalyst components can be entrained in a gaseous stream and introduced at another zone of the reactor.
  • the gas treams can be intermixed for polymerization. Heat and pressure can be employed appropriately to obtain optimal polymerization reaction conditions.
  • the polymerization reactor system can comprise a olution polymerization reactor wherein the monomer/comonomer are contacted with the catalyst composition by suitable stirring or other means.
  • a carrier comprising an inert organic diluent or excess monomer can be employed. If desired, the monomer/comonomer can be brought in the vapor phase into contact with the catalytic reaction product, in the presence or absence of liquid material.
  • the polymerization zone can be maintained atemperatures and pressures that will result in the formation of a solution of the polymer in a reaction medium.
  • the polymerization reactor system can further comprise any combination of at least one raw material feed system, at least one feed system for catalyst or catalyst components, and/or at least one polymer recovery system. Suitable reactor systems can further comprise systems for feedstock purification, catalyst storage and preparation, extrusion, eactor cooling, polymer recovery, fractionation, recycle, storage, loadout, laboratory analysis, and process control. Depending upon the desired properties of the ethylene polymer, hydrogen can be added to the polymerization reactor as needed (e.g., continuously or pulsed).
  • Polymerization conditions that can be controlled for efficiency and to provide desired polymer properties can include temperature, pressure, and the concentrations of various reactants.
  • Polymerization temperature can affect catalyst productivity, polymer molecular weight, and molecular weight distribution.
  • Various polymerization conditions can be held substantially constant, for example, for the production of a particular grade ofhe olefin polymer (or ethylene polymer).
  • a suitable polymerization temperature can be any temperature below the de-polymerization temperature according to the Gibbs Free energy equation. Typically, this includes from 60 ⁇ C to 280 ⁇ C, for example, or from 60 C to 120 ⁇ C, depending upon the type of polymerization reactor(s).
  • the polymerization temperature generally can be within a range from 70 ⁇ C to 105 C, or from 75 ⁇ C to 100 ⁇ C. Suitable pressures will also vary according to the reactor and polymerization type.
  • the pressure for liquid phase polymerizations in a loop reactor is typically less than 1000 psig (6.9 MPa). Pressure for gas phase polymerization is usually at 200 to 500 psig (1.4 MPa to 3.4 MPa).
  • High pressure polymerization in tubular or autoclave reactors is generally run at 20,000 to 75,000 psig (138 to 517 MPa). Polymerization reactors can also be operated in a supercritical region occurring at generally higher temperatures and pressures.
  • Olefin comonomers that can be employed with ethylene monomer and the catalyst compositions and polymerization processes of this invention typically can include olefin compounds having from 3 to 30 carbon atoms per molecule and having at least one olefinic double bond.
  • the olefin comonomer can comprise a C 3 -C 20 olefin; alternatively, a C3-C20 alpha-olefin; alternatively, a C3-C10 olefin; or alternatively, a C3-C10 alpha-olefin.
  • the alpha-olefin comonomer can comprise 1-butene, 1- pentene, 1-hexene, 1-octene, 1-decene, styrene, or any combination thereof; alternatively,he comonomer can comprise 1-butene, 1-hexene, 1-octene, or any combination thereof; alternatively, the comonomer can comprise 1-butene; alternatively, the comonomer can comprise 1-hexene; or alternatively, the comonomer can comprise 1-octene.
  • EXAMPLES The invention is further illustrated by the following examples, which are not to be construed in any way as imposing limitations to the scope of this invention.
  • MI Melt index
  • HLMI high load melt index
  • Density was determined in grams per cubic centimeter (g/cm 3 ) on a compression molded ample, cooled at 15 oC per minute, and conditioned for 40 hours at room temperature in accordance with ASTM D1505 and ASTM D4703.
  • Molecular weights and molecular weight distributions were obtained using a PL- GPC 220 (Polymer Labs, an Agilent Company) system equipped with a IR4 detector Polymer Char, Spain) and three Styragel HMW-6E GPC columns (Waters, MA) running at 145 °C.
  • the flow rate of the mobile phase 1,2,4-trichlorobenzene (TCB) containing 0.5 g/L 2,6-di-t-butyl-4-methylphenol (BHT) was set at 1 mL/min, and polymer solution concentrations were in the range of 1.0-1.5 mg/mL, depending on the molecular weight.
  • Sample preparation was conducted at 150 °C for nominally 4 hr with occasional and gentle agitation, before the solutions were transferred to sample vials for injection. An injection volume of 200 ⁇ L was used.
  • the integral calibration method was used to deduce molecular weights and molecular weight distributions using a Chevron Phillips Chemical Company’s HDPE polyethylene resin, MARLEX ® BHB5003, as the broad standard.
  • Mn is the number-average molecular weight
  • Mw is the weight-average molecular weight
  • Mz is the z-average molecular weight
  • Mv is viscosity-average molecular weight
  • Mp is the peak molecular weight (location, in molecular weight, of the highest point of he molecular weight distribution curve).
  • the respective LMW component and HMW component properties were determined by deconvoluting the molecular weight distribution (see e.g., FIGS. 3-4) of each polymer.
  • the relative amounts of the LMW and HMW components (weight percentages) in the polymer were determined using a commercial software program (Systat Software, Inc., PEAK FIT v.4.05).
  • the other molecular weight parameters for the LMW and HMW components e.g., Mn, Mw, Mz, etc., of each component
  • Short chain branch content and short chain branching distribution (SCBD) across he molecular weight distribution were determined via an IR5-detected GPC system (IR5- GPC) using the method established by Yu (Y. Yu, Macromolecular Symposium, 2020, 390, 1900014), wherein the GPC system was a PL220 GPC/SEC system (Polymer Labs, an Agilent company) equipped with three Styragel HMW-6E columns (Waters, MA) for polymer separation.
  • a thermoelectric-cooled IR5 MCT detector (IR5) Polymer Characterisation SA, Spain
  • Chromatographic data was obtained from two output ports of the IR5 detector.
  • the analog signal goes from the analog output port to a digitizer before connecting to Computer “A” for molecular weight determinations via the Cirrus software (Polymer Labs, now an Agilent Company) and the integral calibration method using a HDPE MarlexTM BHB5003 resin (Chevron Phillips Chemical) as the molecular weight standard.
  • the digital ignals go via a USB cable directly to Computer “B” where they are collected by a LabView data collection software provided by Polymer Char. Chromatographic conditions were set as follows: column oven temperature of 145 °C; lowrate of 1 mL/min; injection volume of 0.4 mL; and polymer concentration of about 2 mg/mL, depending on sample molecular weight.
  • the temperatures for both the hot- ransfer line and IR5 detector sample cell were set at 150 °C, while the temperature of the electronics of the IR5 detector was set at 60 °C.
  • Short chain branching content was determined via an in-house method using the intensity ratio of CH 3 (I CH3 ) to CH 2 (I CH2 ) coupled with a calibration curve.
  • the calibration curve was a plot of SCB content (xSCB) as a function of the intensity ratio of ICH3/ICH2.
  • SCB Standards a group of polyethylene resins (no less than 5) of SCB level ranging from zero to ca. 32 SCB/1,000 otal carbons (SCB Standards) were used.
  • SCB Standards have known SCB evels and flat SCBD profiles pre-determined separately by NMR and the solvent-gradient ractionation coupled with NMR (SGF-NMR) methods.
  • SGF-NMR solvent-gradient ractionation coupled with NMR
  • a slurry was made by mixing 400 mL of water and 100 g of silica- coated alumina (40 wt. % alumina, a surface area of 450 m 2 /g, a pore volume of 1.3 mL/g, and an average particle size of 35 microns).
  • a solution of concentrated hydrofluoric acid 5 g HF) was mixed into the slurry, and the resulting slurry was then spray dried to a dry lowable powder.
  • Calcining was performed at 600 °C by fluidizing the fluorided silica- coated alumina in dry nitrogen for 3 hr, followed by cooling to room temperature while till being fluidized under nitrogen. Afterward, the fluorided silica-coated alumina (FSCA) was collected and stored under dry nitrogen, and was used without exposure to the atmosphere.
  • FSCA fluorided silica-coated alumina
  • Examples 1-4 Structures of the metallocene compounds used in Examples 1-4 are shown below: s 1-4, and the following polymerization procedure was used for Examples 1-4.
  • a yringe was charged with the following reagents in the following order: 250 mg FSCA, ⁇ 2 mL hexanes, 0.5 mL TIBA (triisobutylaluminum, 1 M in hexanes), and a total of 2 mg of metallocenes (1 mg/mL slurry in hexanes).
  • the mixture was contacted for 2-5 min prior to being injected into an isobutane purged 1-gallon autoclave reactor.
  • the reactor was sealed and charged with 2 L of isobutane.
  • LMW and HMW high molecular weight and low molecular weight components
  • the number of short chain branches (SCBs) per 1000 total carbon atoms of each polymer at various positions along the bimodal molecular weight distribution are ummarized in Table II and Table IV. As shown in Table V, and unexpectedly, the polymers of Examples 2-4 had much higher relative SCB content in the high molecular weight fraction of the polymer versus the low molecular weight fraction of the polymer, as compared to Example 1.
  • the ratios of the number of SCBs per 1000 total carbon atoms at Mz to the number of SCBs per 1000 total carbon atoms at Mn ranged from 14 to 17 for Examples 2-4, and were 38-57% greater than the same ratio of 10.7 for Example 1.
  • the ratios 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 ranged from 14 to 19 for Examples 2-4, and were 46-89% greater than the ame ratio of 9.7 for Example 1.
  • Table V also shows unexpectedly higher ratios 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, which ranged from 12 to 13 for Examples 2-4, and were 13-17% greater than the same ratio of 10.9 for Example 1.
  • Examples 2-4 demonstrate bimodal ethylene-based copolymers with urprisingly low levels of SCB content in the low molecular weight fraction of the of the polymer in combination with unexpectedly high levels of SCB content in the high molecular weight fraction of the polymer.
  • Such polymers can be particularly useful in a variety of end-use applications, such as injection molding or blow molding, in which mprovements in environmental stress crack resistance (ESCR), PENT slow crack growthesistance (ASTM F1473), or natural draw ratio (NDR) are desired.
  • ESCR environmental stress crack resistance
  • ASTM F1413 PENT slow crack growthesistance
  • NDR natural draw ratio
  • An ethylene polymer having (or characterized by): a density in a range from 0.92 to 0.955 g/cm 3 ; a HLMI of less than or equal to 35 g/10 min; and a ratio of a number of short chain branches (SCBs) per 1000 total carbon atoms at Mz to a number of SCBs per 1000 total carbon atoms at Mn in a range from 11.5 to 22.
  • SCBs short chain branches
  • An ethylene polymer having (or characterized by): a density in a range from 0.92 to 0.955 g/cm 3 ; a HLMI of less than or equal to 35 g/10 min; and a higher molecular weight component (HMW) and a lower molecular weight (LMW) component, wherein: a ratio of a number of short chain branches (SCBs) per 1000 total carbon atoms at Mn of the HMW component to a number of SCBs per 1000 total carbon atoms at Mn of the LMW component is in a range from 10.5 to 22.
  • Aspect 3 Aspect 3.
  • Aspect 4 The polymer defined in any one of the preceding aspects, wherein the ethylene polymer has a molecular weight at D85 in any range disclosed herein, e.g., from 14,000 to 50,000, from 15,000 to 40,000, from 16,000 to 38,000, or from 17,000 to 35,000 g/mol.
  • Aspect 5 The polymer defined in aspect 1 or 2, wherein the ethylene polymer has a molecular weight at D10 in any range disclosed herein, e.g., from 750,000 to 2,000,000, from 800,000 to 1,750,000, from 850,000 to 2,000,000, or from 900,000 to 1,750,000 g/mol.
  • Aspect 4 The polymer defined in any one of the preced
  • Aspect 6 The polymer defined in any one of the preceding aspects, wherein the density is in any range disclosed herein, e.g., from 0.92 to 0.95, from 0.92 to 0.94, from 0.925 to 0.955, from 0.925 to 0.95, or from 0.925 to 0.943 g/cm 3 .
  • Aspect 8 The polymer defined in any one 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 in any range disclosed herein, e.g., from 11.5 to 22, from 12 to 21, from 12 to 18, from 13 to 22, or from 13 to 19.
  • Aspect 10 The polymer defined in any one of the preceding aspects, wherein the ethylene polymer has a Mp in any range disclosed herein, e.g., from 30,000 to 90,000, from 35,000 to 85,000, from 40,000 to 80,000, or from 45,000 to 75,000 g/mol.
  • Aspect 12 The polymer defined in any one of the preceding aspects, wherein the ethylene polymer has a Mz in any range disclosed herein, e.g., from 1,300,000 to 3,100,000, from 1,400,000 to 3,000,000, from 1,500,000 to 2,500,000, or from 1,700,000 to 2,200,000 g/mol.
  • Aspect 14 The polymer defined in any one of the preceding aspects, wherein the ethylene polymer has less than 0.008 long chain branches (LCBs) per 1000 total carbon atoms, e.g., less than 0.005 LCBs, or less than 0.003 LCBs.
  • LCBs long chain branches
  • the ethylene polymer has a higher molecular weight component (HMW) and a lower molecular weight (LMW) component, wherein an amount of the LMW component, based on the total polymer, is in any range of weight percentages disclosed herein, e.g., from 40 to 90 wt. %, from 40 to 85 wt. %, from 45 to 90 wt. %, from 45 to 85 wt. %, or from 50 to 85 wt. %.
  • HMW molecular weight component
  • LMW lower molecular weight
  • the HMW component has a Mn in any range disclosed herein, e.g., from 400,000 to 800,000, from 450,000 to 750,000, or from 500,000 to 700,000 g/mol.
  • Aspect 17 The polymer defined in any one of the preceding aspects, wherein the LMW component has a Mz in any range disclosed herein, e.g., 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.
  • Aspect 19 The polymer defined in any one of the preceding aspects, 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 any range disclosed herein, e.g., from 10.5 to 22, from 11 to 22, from 11 to 21, from 12 to 22, from 12 to 20, or from 13 to 19.
  • Aspect 20 is in any range disclosed herein, e.g., from 10.5 to 22, from 11 to 22, from 11 to 21, from 12 to 22, from 12 to 20, or from 13 to 19.
  • a ratio of a number of SCBs per 1000 total carbon atoms at Mp of the HMW component to a number of SCBs per 1000 total carbon atoms at Mp of the LMW component is in any range disclosed herein, e.g., from 11 to 18, from 11 to 14, from 11.5 to 16, or from 11.5 to 15.
  • Aspect 21 a ratio of a number of SCBs per 1000 total carbon atoms at Mp of the HMW component to a number of SCBs per 1000 total carbon atoms at Mp of the LMW component is in any range disclosed herein, e.g., from 11 to 18, from 11 to 14, from 11.5 to 16, or from 11.5 to 15.
  • a ratio of a number of SCBs per 1000 total carbon atoms at Mp of the HMW component to a number of SCBs per 1000 total carbon atoms at Mz of the LMW component is in any range disclosed herein, e.g., from 7.5 to 18, from 8 to 16, from 9 to 14, or from 10 to 12.
  • Aspect 22 The polymer defined in any one of the preceding aspects, wherein the ethylene polymer has a number of SCBs per 1000 total carbon atoms at Mz in any range disclosed herein, e.g., from 10 to 30, from 12 to 30, from 15 to 28, or from 17 to 26.
  • Aspect 23 The polymer defined in any one of the preceding aspects, wherein a ratio of a number of SCBs per 1000 total carbon atoms at Mp of the HMW component to a number of SCBs per 1000 total carbon atoms at Mz of the LMW component is in any range disclosed herein, e.g., from 7.5 to 18, from 8 to 16, from 9 to 14, or from 10
  • the ethylene polymer comprises an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, and/or an ethylene/1-octene copolymer.
  • Aspect 27 The polymer defined in any one of the preceding aspects, wherein the ethylene polymer comprises an ethylene/1-hexene copolymer.
  • Aspect 28 The polymer defined in any one of the preceding aspects, wherein the ethylene polymer contains, independently, 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.
  • Aspect 29 The polymer 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.
  • Aspect 30 An article comprising the ethylene polymer defined in any one of the preceding aspects.
  • Aspect 30 An article comprising the ethylene polymer defined in any one of aspects 1-28, wherein the article is an agricultural film, an automobile part, a bottle, a container for chemicals, a drum, 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, outdoor play equipment, a pipe, a sheet or tape, a toy, or a traffic barrier.
  • Aspect 31 An agricultural film, an automobile part, a bottle, a container for chemicals, a drum, 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, outdoor play equipment, a pipe,
  • a polymerization process comprising contacting a catalyst composition with ethylene and an ⁇ -olefin comonomer in a polymerization reactor system under polymerization conditions to produce an ethylene polymer, wherein the ethylene polymer is defined in any one of aspects 1-28, and wherein the catalyst composition comprises catalyst component I comprising any unbridged metallocene compound disclosed herein, catalyst component II comprising any bridged metallocene compound disclosed herein, any activator disclosed herein, and optionally, any co-catalyst disclosed herein.
  • Aspect 32 The process defined in aspect 31, wherein catalyst component II comprises a bridged zirconium or hafnium based metallocene compound.
  • catalyst component II comprises a bridged zirconium or hafnium based metallocene compound with an alkenyl substituent.
  • Aspect 34 The process defined in aspect 31, wherein catalyst component II comprises a bridged zirconium or hafnium based metallocene compound with an alkenyl substituent and a fluorenyl group.
  • Aspect 35 The process defined in aspect 31, wherein catalyst component II comprises a bridged zirconium or hafnium based metallocene compound with a cyclopentadienyl group and a fluorenyl group, and with an alkenyl substituent on the bridging group and/or on the cyclopentadienyl group.
  • Aspect 36 The process defined in aspect 31, wherein catalyst component II comprises a bridged zirconium or hafnium based metallocene compound with an alkenyl substituent.
  • catalyst component II comprises a bridged metallocene compound having an aryl group substituent on the bridging group.
  • Aspect 37 The process defined in any one of aspects 31-36, wherein catalyst component I comprises an unbridged metallocene compound containing two indenyl groups or an indenyl group and a cyclopentadienyl group, wherein at least one indenyl group has at least one halogen-substituted hydrocarbyl substituent with at least two halogen atoms.
  • 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 with at least two halogen atoms.
  • Aspect 39 The process defined in any one of aspects 31-36, wherein catalyst component I comprises an unbridged metallocene compound containing an indenyl group and a cyclopentadienyl group, wherein the indenyl group has at least one halogen-substituted hydrocarbyl substituent with at least two halogen atoms.
  • Aspect 40 is
  • the activator comprises an aluminoxane compound.
  • Aspect 45 The process defined in any one of aspects 31-43, wherein the activator comprises an organoboron or organoborate compound.
  • Aspect 46 The process defined in any one of aspects 31-43, wherein the activator comprises an ionizing ionic compound.
  • Aspect 47 The process defined in any one of aspects 31-43, wherein the activator comprises an activator-support, the activator-support comprising any solid oxide treated with any electron-withdrawing anion disclosed herein.
  • Aspect 48 The process defined in any one of aspects 31-43, wherein the activator comprises an aluminoxane compound.
  • the activator comprises fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided 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.
  • Aspect 49 The process defined in any one of aspects 31-43, wherein the activator comprises a fluorided solid oxide and/or a sulfated solid oxide.
  • Aspect 50 The process defined in any one of aspects 31-49, wherein the catalyst composition comprises a co-catalyst, e.g., any co-catalyst disclosed herein.
  • Aspect 51 The process defined in any one of aspects 31-50, wherein the co- catalyst comprises any organoaluminum compound disclosed herein.
  • Aspect 52 The process defined in aspect 51, wherein the organoaluminum compound comprises trimethylaluminum, triethylaluminum, triisobutylaluminum, or a combination thereof.
  • Aspect 53 The process defined in aspect 51, wherein the organoaluminum compound comprises trimethylaluminum, triethylaluminum, triisobutylaluminum, or a combination thereof.
  • the catalyst composition comprises catalyst component I, catalyst component II, a solid oxide treated with an electron-withdrawing anion, and an organoaluminum compound.
  • Aspect 54 The process 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.
  • Aspect 55 The process defined in any one of aspects 31-54, wherein a weight ratio of catalyst component I to catalyst component II in the catalyst composition is in any range disclosed herein, e.g., from 10:1 to 1:10, from 5:1 to 1:5, or from 2:1 to 1:2.
  • Aspect 56 The process 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.
  • the catalyst composition is produced by a process comprising contacting, in any order, catalyst component I, catalyst component II, and the activator, or contacting, in any order, catalyst component I, catalyst component II, the activator, and the co-catalyst.
  • Aspect 57 The process defined in any one of aspects 31-56, wherein the ⁇ - olefin comonomer comprises a C3-C20 ⁇ -olefin, or alternatively, a C3-C10 ⁇ -olefin.
  • any one of aspects 31-57 wherein the ⁇ - olefin comonomer comprises 1-butene, 1-hexene, 1-octene, or a mixture thereof.
  • Aspect 59 The process 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.
  • Aspect 60 The process defined in any one of aspects 31-59, wherein the polymerization reactor system comprises a slurry reactor, a gas-phase reactor, a solution reactor, or a combination thereof.
  • Aspect 61 The process defined in any one of aspects 31-57, wherein the ⁇ - olefin comonomer comprises 1-butene, 1-hexene, 1-octene, or a mixture thereof.
  • the polymerization reactor system comprises a batch reactor, a slurry reactor, a
  • the polymerization reactor system comprises a loop slurry reactor.
  • Aspect 62 The process defined in any one of aspects 31-61, wherein the polymerization reactor system comprises a single reactor.
  • Aspect 63 The process defined in any one of aspects 31-61, wherein the polymerization reactor system comprises 2 reactors.
  • Aspect 64 The process defined in any one of aspects 31-61, wherein the polymerization reactor system comprises more than 2 reactors.
  • Aspect 65 The process defined in any one of aspects 31-64, wherein the polymerization conditions comprise a polymerization reaction temperature in a range from 60 ⁇ C to 120 ⁇ C and a reaction pressure in a range from 200 to 1000 psig (1.4 to 6.9 MPa).
  • Aspect 66 The process defined in any one of aspects 31-65, wherein the polymerization conditions are substantially constant, e.g., for a particular polymer grade.
  • Aspect 67 The process defined in any one of aspects 31-66, wherein no hydrogen is added to the polymerization reactor system.
  • Aspect 68 The process defined in any one of aspects 31-66, wherein hydrogen is added to the polymerization reactor system.
  • Aspect 69 The process defined in any one of aspects 31-68, wherein the ethylene polymer produced is defined in any one of aspects 1-28.
  • Aspect 70 An ethylene polymer produced by the polymerization process defined in any one of aspects 31-68.
  • Aspect 71 An ethylene polymer defined in any one of aspects 1-28 produced by the process defined in any one of aspects 31-68.
  • Aspect 72 An article of manufacture comprising the polymer defined in aspect 70 or 71.

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Abstract

Les polymères à base d'éthylène sont caractérisés par une densité de 0,92 à 0,955 g/cm3, un HLMI inférieur à 35 g/10 min et un rapport d'un certain nombre de ramifications à chaîne courte (SCB) pour 1000 atomes de carbone totaux à Mz à un nombre de SCB pour 1000 atomes de carbone totaux à Mn dans une plage de 11,5 à 22. Ces polymères peuvent avoir un constituant de poids moléculaire plus élevé (HMW) et un constituant de poids moléculaire inférieur (LMW), dans lequel un rapport d'un nombre de SCB pour 1000 atomes de carbone totaux à Mn du constituant HMW à un nombre de SCB pour 1000 atomes de carbone totaux à Mn du constituant LMW se situe dans une plage de 10,5 à 22. Ces polymères d'éthylène peuvent être produits à l'aide d'un système catalyseur double contenant un composé métallocène non ponté avec un groupe indényle comprenant au moins un substituant hydrocarbyle substitué par un halogène avec au moins deux atomes d'halogène, et un composé métallocène ponté à un seul atome comprenant un groupe fluorényle et un groupe cyclopentadiényle.
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