TUBO, E, PROCESSO PARA PRODUZIR UM TUBO

Abstract

The present invention relates to a pipe including a multimodal high density polyethylene composition, as well as processes for making the pipe. The multimodal high density polyethylene composition includes a high molecular weight component and a low molecular weight component and can be made in a single reactor. The combination of properties of the composition deliver a desirable balance of ESCR, flexibility, and stiffness particularly suitable for pipe such as conduit and pressure-less pipe applications.

Description

41 PIPE, AND PROCESS FOR PRODUCING A PIPE Field

[001] The present invention relates to pipes including multimodal polyethylene compositions and methods for producing them. Introduction

[002] Polyethylene compositions can be formed into useful articles using molding and extrusion processes. Such items include containers, films, and pipes. When extruding polyethylene compositions, it is generally desirable that the polyethylene compositions have lower molecular weight and lower viscosity, particularly under shear conditions that occur when forming pipes, so that the polyethylene compositions can be more easily processed. However, lower molecular weight polyethylene compositions do not achieve a desirable balance of environmental stress cracking resistance (ESCR) and stiffness required for pipe applications, since a lower melt viscosity and / or higher density (e.g., greater than 0.935 g / cm3) can lead to undesirable ESCR.

[003] Attempts to achieve a desirable balance of rigidity and ESCR includes the introduction of narrow molecular weight distribution catalysts in dual reactor systems to produce multimodal polyethylene compositions. With multimodal compositions in dual reactor systems, it is possible to increase stress crack resistance by increasing the molecular weight or comonomer content of the high molecular weight fraction, which in turn decreases density. However, altering the higher molecular weight fraction can increase viscosity and decrease stiffness, and producing multimodal compositions in a dual or multiple reactor system can be cost-prohibitive and less sustainable. Consequently, a Petition 870250084107, dated 09 / 18 / 2025, page 13 / 58 / 41: need for pipes comprising multimodal compositions of high-density polyethylene that can be produced in a single reactor, that can be more easily processed, and that can provide a desirable balance of properties such as flexibility, stiffness, and ESCR. Summary

[004] The present invention provides a pipe comprising a multimodal composition of high-density polyethylene, as well as a process for producing pipes comprising the multimodal composition of high-density polyethylene. The multimodal high-density polyethylene, in some embodiments, can provide a melt index and shear thinning behavior that aids processability while maintaining a balance of physical properties desirable for pipe forming.

[005] In a first aspect, the present invention relates to a tube comprising a multimodal composition of high-density polyethylene. In some embodiments, the multimodal composition of high-density polyethylene comprises more than 40% by weight of a high molecular weight component and less than 60% by weight of a low molecular weight component, based on the total weight of the multimodal polyethylene composition, wherein the multimodal polyethylene composition has: a. a density greater than 0.950 g / cm3; b a high-charge melting index (I21) of 20.0 to 35.0 g / 10 min; c. a viscosity at 0.1 rad / s greater than 30,000 Pas; d. a shear thinning ratio of 15.0 to 25.0; e. a tensile hardening modulus greater than 30.00 MPa; f. a PENT value greater than 30 hours; and Petition 870250084107, dated 09 / 18 / 2025, page 14 / 58 / 41 e.g., an Mz / Mw ratio greater than 5.5.

[006] In a second aspect, the present invention relates to a process for producing a pipe comprising the composition according to the embodiments of the first aspect. In some embodiments, the process for producing a pipe comprises forming a multimodal high-density polyethylene composition according to the embodiments disclosed herein and extruding the multimodal high-density polyethylene composition to form a pipe, wherein the multimodal high-density polyethylene is formed by polymerizing ethylene monomer and an alpha-olefin comonomer in the presence of a bimodal catalyst system in a single gas-phase polymerization (GPP); wherein the bimodal catalyst system essentially consists of a metallocene catalyst, a single-site non-metallocene catalyst that is a bis(alkylsubstituted phenylamido)ethyl)amine catalyst, optionally a host material and optionally an activator;wherein the host material, when present, is selected from at least one of an inert hydrocarbon liquid and a solid support; wherein the metallocene catalyst is a product of the activation reaction of the contact of an activator with a metal-ligand complex of formula (R1-2Cp)((alkyl)1-3 indenyl)MX2, wherein R is hydrogen, methyl or ethyl; each alkyl is independently a (C1-C4)alkyl; M is titanium, zirconium or hafnium; and each X is independently a halide, a (C1 to C20)alkyl, a (C7 to C20)aralkyl, a (C6 to C12)aryl substituted by (C1 to C6)alkyl or a benzyl substituted by (C1 to C6)alkyl;wherein the bis((alkyl-substituted phenylamido)ethyl)amine catalyst is a contact activation reaction product of an activator with a ZrR12 of bis((alkyl-substituted phenylamido)ethyl)amine, wherein each R1 is independently selected from F, Cl, Br, I, benzyl, -CH2Si(CH3)3, a (C1-C5)alkyl, and a (C2) alkyl. Petition 870250084107, dated 09 / 18 / 2025, page 15 / 58 / 41; Csjalquenila.

[007] These and other modalities are described in detail in Detailed Description. Brief description of the drawings

[008] Figure 1 is an absolute GPC chromatogram of examples of the invention and comparisons described below. Detailed Description

[009] Unless otherwise indicated, either implied by the context or customary in the art, all parts and percentages are based on weight, all temperatures are in °C, and all test methods are current as of the filing date of this disclosure.

[0010] The term “composition”, as used in this document, refers to a mixture of materials comprising the composition, and also to reaction products and decomposition products formed from the materials of the composition.

[0011] The term “polymer” means a polymeric compound prepared by the polymerization of monomers, whether of the same type or of a different type. The generic term polymer thus encompasses the term homopolymer, as defined below, and the term interpolymer, as defined below. Trace amounts of impurities (e.g., catalyst residues) may be incorporated into and / or within the polymer. A polymer may be a single polymer, a polymer blend, or a polymer mixture, including mixtures of polymers that are formed locally during polymerization.

[0012] The term “homopolymer”, as used in this document, refers to polymers prepared from only one type of monomer with the understanding that trace amounts of impurities may be incorporated into the polymer structure.

[0013] The term “interpolymer”, as used herein, refers to Petition 870250084107, dated 09 / 18 / 2025, page 16 / 58 / 41 polymers prepared by polymerization of at least two different types of monomers. The generic term interpolymer thus includes copolymers (used to refer to polymers prepared from two different types of monomers) and polymers prepared from more than two different types of monomers.

[0014] The terms “olefin-based polymer” or “polyolefin”, as used herein, refer to a polymer comprising, in polymerized form, a major amount of olefin monomer, for example, ethylene or propylene (based on polymer weight) and optionally may comprise one or more comonomers.

[0015] The term “ethylene / α-olefin interpolymer”, as used herein, refers to an interpolymer comprising, in polymerized form, a major amount (> 50 mol%) of units derived from the ethylene monomer, and the remaining units derived from one or more α-olefins. Typical α-olefins used in the formation of ethylene / α-olefin interpolymers are C3-C10 alkenes.

[0016] The term “ethylene / α-olefin copolymer”, as used herein, refers to a copolymer comprising, in polymerized form, a major amount (> 50 mol%) of ethylene monomer and an α-olefin as the only two types of monomer.

[0017] The term “alpha-olefin” or “α-olefin”, as used herein, refers to an alkene having a double bond in the primary position or alpha (α) position.

[0018] “Polyethylene” or “ethylene-based polymer” means polymers comprising a major amount (> 50 mol%) of units derived from ethylene monomer. This includes polyethylene homopolymers or copolymers (i.e., units derived from two or more comonomers). Common forms of polyethylene known in the art include low-density polyethylene (LDPE). Petition 870250084107, dated 09 / 18 / 2025, page 17 / 58 / 41 polyethylene); linear low-density polyethylene (LLDPE); ultra-low-density polyethylene (ULDPE); linear low-density polyethylene produced with a single-site catalyst, including both linear and substantially linear low-density resins (m-LLDPE); ethylene-based plastomers (POP) and ethylene-based elastomers (POE); medium-density polyethylene (MDPE); and high-density polyethylene (HDPE).

[0019] The term “HDPE” refers to polyethylenes with densities greater than about 0.935 g / cm3 and up to about 0.980 g / cm3, which are generally prepared with Ziegler-Natta catalysts, chromium catalysts or single-site catalysts including, but not limited to, substituted mono- or bis-cyclopentadienyl catalysts (typically called metallocenes), restricted geometry catalysts, pyridylamine catalysts, phosphinimine catalysts and polyvalent aryloxyether catalysts (typically called bisphenylphenoxy).

[0020] The term “multimodal” means compositions that can be characterized by having at least two (2) polymer components or subcomponents with different molecular weights and / or different comonomer contents. In one embodiment, multimodal can be defined as having at least two distinct peaks in an absolute gel permeation chromatography (GPC) chromatogram showing the molecular weight distribution of the composition. The term “bimodal” means compositions that can be characterized by having two (2) polymer components or subcomponents with different molecular weights and / or different comonomer contents. In one embodiment, bimodal can be defined as having two distinct peaks in an absolute gel permeation chromatography (GPC) chromatogram that Petition 870250084107, dated 09 / 18 / 2025, page 18 / 58 / 41 shows the molecular weight distribution of the composition. All GPC measurement values ​​(e.g., Mw, Mn, Mz) cited herein are absolute GPC measurements provided in accordance with the test methods described below. A person skilled in the art understands the difference between absolute GPC and conventional GPC measurements.

[0021] The terms “comprising”, “including”, “having” and their derivatives are not intended to exclude the presence of any additional component, step or procedure, whether or not specifically disclosed. In order to avoid any doubt, all compositions claimed through the use of the term “comprising” may include any additional additive, adjuvant or compound, whether polymeric or otherwise, unless otherwise indicated. In contrast, the term “essentially consisting of” excludes from the scope of any subsequent recitation any other component, step or procedure, except those that are not essential to operability. The term “consisting of” excludes any component, step or procedure not specifically outlined or listed.

[0022] The tube disclosed herein comprises a multimodal composition of high-density polyethylene. The composition according to the embodiments disclosed herein comprises a high molecular weight (HMW) component and a low molecular weight (LMW) component. “High molecular weight” means that the HMW component is calculated to have a higher molecular weight than the LMW component, and “lower molecular weight” means that the LMW component is calculated to have a lower molecular weight than the HMW component. The composition is multimodal. In some embodiments, the composition is bimodal and consists of an HMW component and an LMW component.

[0023] Component HMW is a copolymer of ethylene and one or more alpha-olefin comonomers. Component LMW is also a Petition 870250084107, dated 09 / 18 / 2025, page 19 / 58 / 41 ethylene copolymer and one or more alpha-olefin comonomers. The alpha-olefin comonomers may have from 3 to 10 carbon atoms or from 3 to 8 carbon atoms. Exemplary alpha-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene. In some embodiments, the alpha-olefin comonomers can be selected from the group consisting of 1-butene, 1-hexene, and 1-octene, or from the group consisting of 1-butene and 1-hexene, or from the group consisting of 1-hexene or 1-octene. In some embodiments, the HMW component is a non-metallocene-catalyzed ethylene copolymer. In some embodiments, the LMW component is a metallocene-catalyzed ethylene copolymer. As discussed below, the HMW component and the LMW component can be polymerized in a single reactor in the presence of a bimodal catalyst system.

[0024] The multimodal high-density polyethylene composition comprises more than 40% by weight of a high molecular weight component and less than 60% by weight of a low molecular weight component. The multimodal high-density polyethylene composition may comprise more than 40% by weight, more than 42% by weight, more than 45% by weight, more than 46% by weight, or more than 47% by weight of the HMW component, or from 40 to 60% by weight, or from 45 to 55% by weight, or from 47 to 53% by weight of the HMW component, based on the total weight of the composition. The multimodal high-density polyethylene composition may comprise less than 60% by weight, less than 55% by weight, less than 54% by weight, or less than 53% by weight of the LMW component, or from 40 to 60% by weight, or from 45 to 55% by weight, or from 47 to 53% by weight of the LMW component, based on the total weight of the composition.Without delving into theory, it is believed that the concentration of the HMW component in the composition contributes to tenacity and helps distribute the short-chain branching that promotes entanglement. Petition 870250084107, dated 09 / 18 / 2025, p. 20 / 58 / 41 chain and improves properties, such as slow crack growth.

[0025] In some embodiments, the HMW component has an Mw of 300,000 g / mol to 400,000 g / mol, an Mn of 80,000 to 120,000 g / mol, an Mz of 900,000 to 1,000,000 g / mol or an Mw / Mn of 2.0 to 5.5, when measured according to the test methods below. In some embodiments, the LMW component has an Mw of 10,000 to 30,000 g / mol, an Mn of 3,000 to 7,000 g / mol, an Mz of 20,000 to 90,000 or an Mw / Mn of 2.5 to 5.0, when measured according to the test methods below.

[0026] The multimodal composition of high-density polyethylene has a density greater than 0.950 g / cm3. In some embodiments, the multimodal composition of high-density polyethylene may have a density greater than 0.951 g / cm3 or greater than 0.952 g / cm3 or from 0.950 g / cm3 to 0.960 g / cm3, or from 0.951 to 0.957 g / cm3, or from 0.952 to 0.955 g / cm3.

[0027] The multimodal high-density polyethylene composition has a high-load melt index (I21) of 20.0 to 35.0 g / 10 min. In some embodiments, the multimodal high-density polyethylene composition has a high-load melt index (I21) of 21.0 to 33.0 g / 10 min, 23.0 to 33.0 g / 10 min, and 27.0 to 31.0 g / 10 min.

[0028] The multimodal composition of high-density polyethylene has a complex viscosity at 190 °C and 0.1 radians per second (rad / s) greater than 30,000 Pascal-seconds (Pas). In some embodiments, the viscosity at 190 °C and 0.1 rad / s may be greater than 31,000 Pas, greater than 32,000 Pas, greater than 40,000 Pas, or from 30,000 Pas to 50,000 Pas.

[0029] The multimodal high-density polyethylene composition has a shear thinning index of 15.0 to 25.0. The term “shear thinning index” refers to a ratio between the complex viscosity of a polymer at a frequency of 0.1 rad / sec and a ratio between the complex viscosity of the polymer at a frequency of 100 rad / sec. All individual values ​​and subranges from 15.0 to 25.0 are disclosed and included. Petition 870250084107, dated 09 / 18 / 2025, page 21 / 58 / 41 here. For example, in some embodiments, the multimodal composition of high-density polyethylene has a shear thinning index of 17.0 to 24.0, 18.0 to 23.0, 19.0 to 22.0, or 20.0 to 21.0. The shear thinning index in the specified range contributes to improved processability for the manufacture of pipes with desirable properties such as toughness and stiffness.

[0030] The multimodal high-density polyethylene composition has a PENT value greater than 30 hours. In some embodiments, the multimodal high-density polyethylene has a PENT value greater than 40 hours, greater than 45 hours, greater than 50 hours, greater than 60 hours, greater than 100 hours, greater than 200 hours, greater than 300 hours, greater than 400 hours, greater than 500 hours, or greater than 600 hours.

[0031] The multimodal composition of high-density polyethylene has an Mz / Mw ratio greater than 5.5. In some embodiments, the multimodal composition of high-density polyethylene has an Mz / Mw ratio greater than 5.7 or greater than 6.0.

[0032] In some embodiments, the multimodal composition of high-density polyethylene has a molecular weight distribution based on absolute GPC, wherein the molecular weight distribution based on absolute GPC has a first peak, a local minimum, and a second peak in a Log(molecular weight) range of 3.5 to 6.0, wherein the local minimum is an inflection point between the first peak and the second peak, and the first peak corresponds to the low molecular weight component and the second peak corresponds to the high molecular weight component. Within this Log(molecular weight) range of 3.5 to 6.0, a first and then a second derivative of equally spaced data yields three inflection points for a bimodal molecular weight distribution. Two positive inflection points, derived values ​​going from positive to negative values ​​as Log(molecular weight) increases, and one negative inflection point, values Petition 870250084107, dated 09 / 18 / 2025, page 22 / 58 / 41 derivatives going from negative to positive as Log(molecular weight) increases. The local minimum is located between the first peak and the second peak. The first peak, which can be designated as the local maximum (Mmax1), is the molecular weight at the inflection point corresponding to the low molecular weight component, and the second peak, which can be designated as the local maximum (Mmax2), is the molecular weight at the inflection point corresponding to the high molecular weight component. The local minimum is the lowest molecular weight value between the first peak and the second peak and is the negative inflection point between the first peak and the second peak. One skilled in the art understands that the GPC chromatogram refers to the molecular architecture of the multimodal high-density polyethylene composition and is, in part, a result of the particular catalyst system used to form the composition.It has been found that, according to the embodiments disclosed herein, a particular type of catalyst is suitable for producing the multimodal high-density polyethylene composition in a single reactor and, relatedly, distributing a specific GPC chromatogram, whereas prior art compositions with similar characteristics or different catalyst systems cannot be produced in a single reactor system, distribute the specific GPC chromatogram, and / or distribute the desirable properties disclosed herein. In some embodiments, the absolute GPC chromatogram has a first peak, a local minimum, and a second peak in a Log(molecular weight) range of 3.5 to 5.8 or 3.5 to 5.5.

[0033] The multimodal composition of high-density polyethylene has a modulus of elongation greater than 30.00 MPa, or greater than 32.00 MPa, or greater than 34.00 MPa, or greater than 38.00 MPa, or greater than 44.00 MPa, or greater than 48.00 MPa. In some embodiments, the modulus of elongation is less than 70.00 MPa, less than 60.00 MPa, or less than 55.00 MPa. Without adhering to theory, it is believed Petition 870250084107, dated 09 / 18 / 2025, page 23 / 58 / 41, states that the elongation hardening modulus is related to the amount of chain entanglement in the composition, which in turn provides desirable mechanical properties such as PENT and ESCR.

[0034] In some embodiments, the multimodal high-density polyethylene composition has an I21 / I5 ratio of 25 to 35. All individual values ​​and subranges from 25 to 35 are disclosed and included in the present invention. For example, the multimodal high-density polyethylene composition may have an I21 / I5 ratio of 25 to 35, 25 to 33, or 25 to 31. In some embodiments, the multimodal polyethylene composition has a melt index (I5) of 0.50 to 1.50 g / 10 min, or 0.60 to 1.30 g / 10 min, or 0.70 to 1.20 g / 10 min.

[0035] In some embodiments, the multimodal high-density polyethylene composition has a residual metallic catalyst of at least 0.2 ppm by combined weight of at least zirconium, titanium and / or hafnium per million parts of the composition. In some embodiments, the multimodal high-density polyethylene composition has a residual metallic catalyst of at least 0.2 ppm of zirconium per million parts of the composition.

[0036] In some embodiments, the multimodal high-density polyethylene composition has a weight-average molecular weight (Mw) greater than 175,000 g / mol, or greater than 180,000 g / mol, or greater than 190,000 g / mol, or greater than 200,000 g / mol. In some embodiments, the multimodal high-density polyethylene composition has a melt index (I2) of 0.20 to 0.40 g / 10 min, or 0.22 to 0.38 g / 10 min, or 0.24 to 0.36 g / 10 min, or 0.26 to 0.34 g / 10 min. In some embodiments, the multimodal composition of high-density polyethylene has an I21 / I2 ratio of 90 to 110 or 95 to 105. In some embodiments, the multimodal composition of high-density polyethylene has a molecular weight distribution (Mw / Mn) greater than 20.0, or from 10.0 to 30.0, or from 15.0 to 25.0, or from 20.0 to Petition 870250084107, dated 09 / 18 / 2025, p. 24 / 58 / 41 25.0, or from 20.0 to 30.0.

[0037] In some embodiments, the multimodal high-density polyethylene composition has a 2% secant modulus greater than 130 ksi (896 MPa). In some embodiments, the multimodal high-density polyethylene composition has an ESCR value greater than 1,000 hours.

[0038] The multimodal high-density polyethylene composition of the present invention is suitable for the manufacture of pipes. In some embodiments, the pipe is a conduit pipe or a non-pressurized pipe. The conduit pipes must meet or exceed the PE224420C / E classification of D3350 cells. The characteristics of the multimodal high-density polyethylene composition, including its density and melt index properties, contribute to making it particularly suitable for conduits or non-pressurized pipes. The pipe can be extruded by methods known to those skilled in the art. The pipe can be a monolayer pipe and may comprise suitable additives used for pipe applications. Such additives include colorants and materials suitable for protecting the composition from adverse environmental effects, for example, oxidation during extrusion or degradation under service conditions.Suitable additives include process stabilizers, antioxidants, pigments, metal deactivators, and additives to improve chlorine and UV resistance. In some embodiments, the pipe may be a multi-layer composite pipe including metal / plastic composite pipes and pipes comprising one or more (e.g., one or two) layers, wherein at least one layer comprises the composition according to the present invention. The pipe according to the embodiments of the present invention may meet the hydrostatic test requirements known in the industry and by those skilled in the art. For example, in some embodiments, the pipe may exhibit hydrostatic performance of 1,600 psi at 23 °C according to ASTM D1598 greater than 1,000 hours. Petition 870250084107, dated 09 / 18 / 2025, p. 25 / 58 / 41

[0039] The process for producing a tube comprises forming a multimodal high-density polyethylene composition according to the embodiments disclosed herein and extruding the multimodal high-density polyethylene composition to form a tube, wherein the multimodal high-density polyethylene is formed by polymerization of ethylene monomer and an alpha-olefin comonomer in the presence of a bimodal catalyst system in a single gas-phase polymerization (GPP); wherein the bimodal catalyst system essentially consists of a metallocene catalyst, a single-site non-metallocene catalyst that is a bis(alkyl-substituted phenylamido)ethyl)amine catalyst, optionally a host material and optionally an activator; wherein the host material, when present, is selected from at least one of an inert hydrocarbon liquid and a solid support;wherein the metallocene catalyst is a product of the activation reaction of the contact of an activator with a metal-ligand complex of formula (R1-2Cp)((alkyl)1-3 indenyl)MX2, wherein R is hydrogen, methyl or ethyl; each alkyl is independently a (C1-C4)alkyl; M is titanium, zirconium or hafnium; and each X is independently a halide, a (C1 to C20)alkyl, a (C7 to C20)aralkyl, a (C1 to C12)aryl substituted by (C1 to C6)alkyl or a benzyl substituted by (C1 to C1)alkyl; wherein the bis((alkyl-substituted phenylamido)ethyl)amine catalyst is a contact activation reaction product of an activator with a ZrR'2 of bis((alkyl-substituted phenylamido)ethyl)amine, wherein each R1 is independently selected from F, Cl, Br, I, benzyl, -CH2Si(CH3)3, a (C1—Cs)alkyl, and a (C2Cs)alkenyl. In some embodiments, the metal-ligand complex of formula (I) is a compound in which M is zirconium (Zr); R is H, alternatively methyl, alternatively ethyl;and each X is Cl, methyl or benzyl; and bis((alkyl-substituted phenylamido)ethyl)amine MR12 is a bis(2(pentamethylphenylamido)ethyl)-amine zirconium complex of formula (II):; Petition 870250084107, dated 09 / 18 / 2025, p. 26 / 58 15 / 41 Formula (1) (II), wherein M is Zr and each R1 independently is Cl, Br, a (C1 to C20)alkyl, a (C1-C1n)alkyl substituted by (C1 to C2)alkyl, benzyl or a benzyl substituted by (C1 to C2)alkyl. In some embodiments, the compound of formula (II) is bis(2-(pentamethylphenylamido)ethyl)-amino zirconium dibenzyl. In some embodiments, each X and RI is independently Cl, methyl, 2,2-dimethylpropyl, -CFES^CFEh or benzyl. In some embodiments, the metal-ligand complex of formula (I) is dimethyl (cyclopentadienyl)(I,5-dimethylindenyl)zirconium. (methylcyclopentadienyl)(I,3-dimethyl-4,5,6,7-tetrahydroindenyl)zirconium Process for producing the composition multimodal.

[0040] In some embodiments, the composition is produced by polymerization of ethylene and an alpha-olefin in the presence of a bimodal catalyst system in a single gas-phase polymerization (GPP); wherein the bimodal catalyst system essentially consists of a metallocene catalyst, a single-site non-metallocene catalyst that is a bis(alkyl-substituted phenylalanine)ethyl)amine catalyst, optionally a host material and optionally an activator; wherein the host material, when present, is selected from at least one of an inert hydrocarbon liquid and a solid support; wherein the metallocene catalyst is a product of the contact activation reaction of an activator Petition 870250084107, dated 09 / 18 / 2025, p. 27 / 58 / 41 with a metal-ligand complex of formula (Ri-2Cp)((alkyl)i-3 Indenyl)MX2, where R is hydrogen, methyl or ethyl; each alkyl is independently a (C1-C4)alkyl; M is titanium, zirconium or hafnium; and each X is independently a halide, a (C1 to C20)alkyl, a (C7 to C20)aralkyl, a (C6 to Cn)aryl substituted by (C1 to C6)alkyl or a benzyl substituted by (C1 to C6)alkyl; wherein the bis((alkyl-substituted phenylamido)ethyl)amine catalyst is a contact activation reaction product of an activator with a ZrR12 of bis((alkyl-substituted phenylamido)ethyl)amine, wherein each R1 is independently selected from F, Cl, Br, I, benzyl, -CH2Si(CH3)3, a (C1-C5)alkyl, and a (C2C5)alkenyl.

[0041] In some embodiments, the high-density multimodal polyethylene composition may be a polymerized reaction product of an ethylene monomer and at least one C3-C12 alpha-olefin comonomer. For example, embodiments of the composition may be a polymerized reaction product of an ethylene monomer and 1-butene, 1-hexene, or both. Alternatively, embodiments of the bimodal polyethylene composition may be a polymerized reaction product of an ethylene monomer and 1-butene, 1-octene, or both. Embodiments of the bimodal polyethylene may also be a polymerized reaction product of an ethylene monomer and 1-hexene, 1-octene, or both. In some embodiments, the C3-C12 α-olefin comonomer may not be propylene.

[0042] In some embodiments, bimodal polyethylene can be produced with a catalyst system in a single reactor. As used herein, a “catalyst system” may comprise a main catalyst, a compensating catalyst and, optionally, at least one activator. Catalyst systems may also include other components, such as supports, and are not limited to a main catalyst, a compensating catalyst and, optionally, at least one activator. Petition 870250084107, dated 09 / 18 / 2025, page 28 / 58 / 41 activator. Catalyst system embodiments may comprise a main catalyst and a metallocene compensation catalyst. Catalyst system embodiments may also comprise one or more additives commonly used in the olefin polymerization technique. For example, catalyst system embodiments may comprise one or more continuity additives, flow aids, and antistatic aids. In embodiments, the reactor may be a gas-phase reactor, although fluid paste phase reactors may also be used.

[0043] Embodiments of the catalyst system may comprise at least one catalyst for producing a high molecular weight fraction of bimodal polyethylene through polymerization (sometimes referred to herein as an “HMW catalyst”), and at least one catalyst compound for producing a low molecular weight fraction of bimodal polyethylene through polymerization (sometimes referred to herein as an “LMW catalyst”).

[0044] Catalyst system modalities may be referred to as a “bimodal catalyst system.” Such a catalyst system produces a bimodal polyethylene composition having separate and identifiable high molecular weight and low molecular weight distributions. The term “bimodal catalyst system” may encompass any formulation, mixture, or system comprising at least two different catalyst compounds, each having the same or different metal group, but generally different catalyst linkers or structure, including a “double catalyst.” Alternatively, each different catalyst compound of the bimodal catalyst system resides on a single support particle, and in this case, a double catalyst is considered a supported catalyst.However, the term "bimodal catalyst system" also broadly encompasses a system or mixture in which one catalyst is in one collection of support particles, and another catalyst is in a different collection. Petition 870250084107, dated 09 / 18 / 2025, page 29 / 58 / 41 supporting particles. In such embodiments, the two supported catalysts are introduced into a single reactor, either simultaneously or sequentially, and polymerization is conducted in the presence of the two collections of supported catalysts. Alternatively, the bimodal catalyst system may comprise a mixture of unsupported catalysts in the form of a fluid paste.

[0045] The single gas-phase polymerization reactor may be a fluidized bed gas-phase polymerization (FB-GPP) reactor and the effective polymerization conditions may comprise conditions (a) to (e): (a) the FB-GPP reactor having a fluidized resin bed at a bed temperature of 80 to 110 degrees Celsius (°C), alternatively 85 to 108 °C, alternatively 90 to 108 °C, alternatively 94 to 107 °C, alternatively 103 °C to 106 °C;(b) the FB-GPP reactor receiving feed streams of independently controlled respective amounts of ethylene, 1-alkene characterized by a molar ratio between 1-alkene and ethylene (CX / C2), the bimodal catalyst system, optionally a compensating catalyst comprising a solution in an inert hydrocarbon liquid of an unsupported dissolved amount of the metallocene catalyst produced from the metal-ligand complex of formula (I) and activator, optionally hydrogen gas (H2) characterized by a molar ratio between hydrogen and ethylene (H2 / C2) or by a parts by weight per million ratio between H2 and molar percentage of C2 (ppm H2 / mol% C2) and, optionally, an induced condensing agent (ICA) comprising a (C5-C10)alkane or (C5-C10)alkanes, for example, isopentane; where the molar ratio (C6 / C2) is from 0.0001 to 0.1, or from 0.001 to 0.01;whereby when H2 is fed, the molar ratio H2 / C2 is from 0.0001 to 2.0, alternatively from 0.0030 to 0.0060, or the ratio in ppm of H2 / % mol of C2 is from 1 to 20,000, alternatively from 30.0 to 60.0; and whereby, when ICA is fed, the concentration of ICA in the reactor is from 1 to 20; Petition 870250084107, dated 09 / 18 / 2025, p. 30 / 58 / 41 mol percent (% mol), alternatively from 7 to 16% mol, based on the total moles of ethylene, 1-alkene and ICA in the reactor. The average residence time of the copolymer in the reactor can be from 1 to 6 hours, alternatively from 2 to 4 hours. A continuity additive can be used in the FB-GPP reactor during polymerization.

[0046] The bimodal catalyst system can be characterized by an inverse response to bed temperature such that, when the bed temperature is increased, the viscoelastic property value of the resulting composition is decreased, and when the bed temperature is decreased, the viscoelastic property value of the resulting bimodal poly(ethylene-co-1-alkene) copolymer is increased. The bimodal catalyst system can also be characterized by an inverse response to the H2 / C2 ratio such that, when the H2 / C2 ratio is increased, the viscoelastic property value of the resulting bimodal poly(ethylene-co-1-alkene) copolymer is decreased, and when the H2 / C2 ratio is decreased, the viscoelastic property value of the resulting composition is increased.

[0047] The composition comprises the higher molecular weight component (HMW component) and the lower molecular weight component (LMW component). In an illustrative pilot plant process for producing bimodal polyethylene polymer, a gas-phase, fluidized bed polymerization reactor (“FB-GPP reactor”) having a reaction zone dimensioned as 304.8 mm (twelve inches) internal diameter and 2.4384 meters (8 feet) straight side height and containing a fluidized bed of composition granules. Configure the FB-GPP reactor with a recycle gas line to flow a recycle gas stream. Fit the FB-GPP reactor with gas feed inlets and polymer product outlet. Introduce gaseous feed streams of ethylene and hydrogen along with 1-alkene comonomer (e.g., 1-hexene) below the FB-GPP reactor bed into the recycle gas line. Measure the total concentration. Petition 870250084107, dated 09 / 18 / 2025, page 31 / 58 / 41 of (C5-C2o)alkane(s) in the gas / vapor effluent, sampling the gas / vapor effluent in the recycle gas line. Return the gas / vapor effluent (excluding a small portion removed for sampling) to the FB-GPP reactor via the recycle gas line.

[0048] Polymerization operating conditions are any variable or combination of variables that can affect a polymerization reaction in the GPP reactor or a composition or property of a bimodal polyethylene copolymer made in this way. Variables may include reactor design and size, catalyst composition and composition; reactant composition and quantity; molar ratio of two different reactants; presence or absence of feed gases such as H2 and / or O2, molar ratio of feed gases versus reactants, absence or concentration of interfering materials (e.g., H2O), average residence time of polymer in the reactor, partial pressures of constituents, monomer feed rates, reactor bed temperature (e.g., fluidized bed temperature), nature or sequence of process steps, time periods for transition between steps.Variables other than the one(s) being described or altered by the method or usage may be held constant.

[0049] When operating the method, control the individual flow rates of ethylene (“C2”), 1-alkene (“Cx”, e.g., 1-hexene or “C6” or “Cx”, where x is 6) and any hydrogen (“H2”) to maintain a fixed molar ratio between comonomer and ethylene monomer gas (Cx / C2, e.g., C6 / C2) equal to a described value, a constant molar ratio between hydrogen gas and ethylene (“H2 / C2”) equal to a described value, and a constant partial pressure of ethylene (“C2”) equal to a described value (e.g., 1,000 kPa). Measure gas concentrations by an in-line gas chromatograph to understand and maintain a composition in the recycle gas stream. Maintain a reaction bed of growing polymer particles in a fluidized state by the continuous flow of a replacement feed and recycle gas through Petition 870250084107, dated 09 / 18 / 2025, p. 32 / 58 / 41 of the reaction zone. Use a superficial gas velocity of 0.49 to 0.67 meters per second (m / s) (1.6 to 2.2 feet per second (ft / s)). Operate the FB-GPP reactor at a total pressure of approximately 2344 to approximately 2413 kilopascals (kPa) (approximately 340 to approximately 350 pounds per square inch gauge (psig)) and at a described reactor bed temperature RBT. Maintaining the fluidized bed at a constant height by removing a portion of the bed at a rate equal to the production rate of the particulate form of the bimodal polyethylene polymer, which can be 10 to 20 kilograms per hour (kg / h), or alternatively 13 to 18 kg / h.The semi-continuously produced bimodal poly(ethylene-co-1-alkene) copolymer is removed via a series of valves in a fixed-volume chamber, and the removed composition is purged with a stream of humidified nitrogen gas (N2) to remove entrained hydrocarbons and deactivate any trace amounts of residual catalysts.

[0050] The bimodal catalyst system can feed the polymerization reactor (or polymerization reactors) in “dry mode” or “wet mode”, alternatively, in dry mode, alternatively, in wet mode. The dry mode is a dry powder or dry granules. The wet mode is a suspension in an inert liquid, such as mineral oil or the alkane(s) (C5C20). In some respects, the composition is produced by contacting the metal-ligand complex of formula (I) and the single-site non-metallocene catalyst with at least one local activator in the GPP reactor in the presence of olefin monomer and comonomer (e.g., ethylene and 1-alkene) and growing polymer chains. These embodiments may be referred to herein as local contact embodiments.In other respects, the metal-ligand complex of formula (I), the single-site non-metallocene catalyst and at least one activator are premixed together for a period of time to generate an activated bimodal catalyst system and then the activated bimodal catalyst system is injected into the GPP reactor where it enters. Petition 870250084107, dated 09 / 18 / 2025, page 33 / 58 / 41 contact with the olefin monomer and with the growing polymer chains. These latter embodiments come into prior contact with the metal-ligand complex of formula (I), the single-site non-metallocene catalyst and at least one activator together in the absence of olefin monomer (e.g., in the absence of ethylene and alpha-olefin) and growing polymer chains, i.e., in an inert environment, and are referred to herein as pre-contact embodiments. The pre-mixing time of the pre-contact embodiments may be from 1 second to 10 minutes, alternatively from 30 seconds to 5 minutes, alternatively from 30 seconds to 2 minutes. The ICA may be fed separately into the FB-GPP reactor or as part of a mixture also containing the bimodal catalyst system.The ICA can be a (C11-C20)alkane, alternatively a (C5-C10)alkane, alternatively a (C5)alkane, for example, pentane or 2-methylbutane; a hexane; a heptane; an octane; a nonane; a decane; or a combination of two or more of these. Aspects of the polymerization method that use the ICA can be referred to as an induced condensation mode (ICMO) operation. The ICMO is described in US documents 4,453,399; US 4,588,790; US 4,994,534; US 5,352,749; US 5,462,999; and US 6,489,408. The concentration of ICA in the reactor is measured indirectly as the total concentration of vented ICA in the recycle line using gas chromatography by calibrating peak area percentage to mole percentage (% mol) with a gas mixture standard of known concentrations of ad rem gas phase components.

[0051] The method uses a gas-phase polymerization (GPP) reactor, such as a stirred-bed gas-phase polymerization reactor (SB-GPP reactor) or a fluidized-bed gas-phase polymerization reactor (FB-GPP reactor), to produce the composition disclosed herein. Such reactors and gas-phase polymerization methods are generally well known in the art. For example, the FB-GPP reactor / method can be Petition 870250084107, dated 09 / 18 / 2025, pp. 34 / 58 / 41 as described in documents US 3,709,853; US 4,003,712; US 4,011,382; US 4,302,566; US 4,543,399; US 4,882,400; US 5,352,749; US 5,541,270; EP-A-0,802,202 and Belgian patent no. 839,380. These SB-GPP and FB-GPP polymerization processes and reactors can either mechanically stir or fluidize the polymerization medium within the reactor by continuous flow of gaseous monomer and diluent, respectively. Other useful reactors / processes considered include serial or multi-stage polymerization processes as described in documents US 5,627,242; US 5,665,818; US 5,677,375; EP-A-0,794,200 EP-B1-0,649,992 EP-A0,802,202 and EP-B-634421.

[0052] Polymerization conditions may also include one or more additives, such as a chain transfer agent or a promoter. Chain transfer agents are well known and may be alkylmetals, such as diethylzinc. Promoters are known as per US 4,988,783 and may include chloroform, CFCE, trichloroethane, and difluorotetrachloroethane. Before reactor startup, a scavenging agent may be used to react with moisture, and during reactor transitions, a scavenging agent may be used to react with excess activator. Scavenging agents may be a trialkylaluminum. Gas-phase polymerizations may be operated without (not deliberately added) scavenging agents.The polymerization conditions for the gas-phase polymerization reactor / method may additionally include an amount (e.g., from 0.5 to 200 ppm based on all feed flows into the reactor) of static control agent and / or continuity additive, such as aluminum stearate or polyethyleneimine. The static control agent may be added to the FB-GPP reactor to inhibit the formation or accumulation of static charge within it.

[0053] The method may use a pilot-scale fluidized bed gas phase polymerization reactor (Pilot Reactor) comprising a vessel Petition 870250084107, dated 09 / 18 / 2025, page 35 / 58 / 41, describes a reactor containing a fluidized bed of a bimodal polymer powder and a distributor plate disposed above a lower head, defining a bottom gas inlet and having an expanded section, or a cyclone system, at the top of the reactor vessel to reduce the amount of resin fines that may escape from the fluidized bed. The expanded section defines a gas outlet. The pilot reactor further comprises a compressor blower with sufficient power to circulate gas in a closed circuit or continuous cycle around the gas outlet in the expanded section at the top of the reactor vessel to the lower gas inlet of the pilot reactor and through the distributor plate and fluidized bed. The pilot reactor further comprises a cooling system to remove the heat of polymerization and maintain the fluidized bed at a target temperature.Gas compositions, such as ethylene, 1-alkene (e.g., 1-hexene), and hydrogen, fed into the Pilot Reactor are monitored by an in-line gas chromatograph in the closed-loop cycle to maintain specific concentrations that define and allow control of polymer properties. The bimodal catalyst system can be fed as a fluid paste or a dry powder into the Pilot Reactor from high-pressure devices; the paste is fed via a syringe pump, and the dry powder is fed via a metering disc. The bimodal catalyst system typically enters the fluidized bed in the lower 1 / 3 of its bed height.The Pilot Reactor further comprises a means of weighing the fluidized bed and isolation orifices (Product Discharge System) to discharge the bimodal polyethylene polymer powder from the reactor vessel in response to an increase in fluidized bed weight as the polymerization reaction proceeds.

[0054] In some embodiments, the FB-GPP reactor is a commercial-scale reactor, such as a UNIPOL™ reactor, which is available from Univation Technologies, LLC, a subsidiary of The Dow Chemical. Petition 870250084107, dated 09 / 18 / 2025, pages 36 / 58 / 41 Company, Midland, Michigan, USA. In some embodiments, the bimodal catalyst system used in the method consists essentially of the metallocene catalyst and the bis(alkyl-substituted phenylamido)ethyl)amine ZrR12 catalyst and, optionally, the host material; wherein the host material, when present, is selected from at least one of the inert hydrocarbon liquid and the solid support; wherein the metallocene catalyst is a contact activation reaction product of an activator with a metal-ligand complex of formula (I) described; and wherein the bis(alkyl-substituted phenylamido)ethyl)amine catalyst is a contact activation reaction product of an activator with the bis(alkyl-substituted phenylamido)ethyl)amine ZrR12 catalyst described above.The phrase essentially means that the bimodal catalyst system and method used is free of a third simple site catalyst (e.g., a different metallocene, a different amine catalyst, or a biphenylphenolic catalyst) and free of non-simple site catalysts (e.g., free of Ziegler-Natta or chromium catalysts). The bimodal catalyst system may also essentially consist of the host material and / or at least one activator species, which is a reaction byproduct of the metallocene catalyst or non-metallocene molecular catalyst with the activator(s).

[0055] Without adhering to theory, it is believed that the bis((alkyl substituted phenylamido)ethyl)amine catalyst (e.g., bis(2(pentamethylphenylamido)ethyl)amine zirconium dibenzyl) is a substantially simple site non-metallocene catalyst effective for producing the HMW component of the bimodal poly(ethylene-co-1-alkene) copolymer and the metallocene catalyst (produced from the metal-ligand complex of formula (I)) is a substantially simple site catalyst that is independently effective for producing the LMW component of the composition. The molar ratio of the two catalysts in the bimodal catalyst system may Petition 870250084107, dated 09 / 18 / 2025, pp. 37 / 58 / 41, should be based on the molar ratio of their respective contents of catalytic metal atom (M, for example, Zr), which can be calculated from the weights of the ingredients or can be measured analytically. The molar ratio of the two catalysts can be varied in the polymerization method by using a different bimodal catalyst system formulation having a different molar ratio or by using the same bimodal catalyst system and the compensating catalyst. The variation of the molar ratio of the two catalysts during the polymerization method can be used to vary the particular properties of the bimodal poly(ethyleneco-1-alkene) copolymer within the limits of its described characteristics.

[0056] The catalysts in the bimodal catalyst system may be unsupported when they come into contact with an activator, which may be the same or different for the different catalysts. Alternatively, the catalysts may be spray-dried onto a solid support material before coming into contact with the activator(s). The solid support material may be uncalcined or calcined before coming into contact with the catalysts. The solid support material may be a hydrophobic fumed silica (e.g., a fumed silica treated with dimethyldichlorosilane). The bimodal catalyst system (unsupported or supported) may be in the form of a free-flowing particulate powder solid. Support material. The support material may be an inorganic oxide material. The terms “support” and “support material” are the same as used in this document and refer to a porous inorganic substance or an organic substance.In some embodiments, the desirable support materials may be inorganic oxides that include oxides of Group 2, 3, 4, 5, 13, or 14 atoms, or alternatively Group 13 or 14 atoms. Examples of inorganic oxide-type support materials are silica, alumina, titania, zirconia, thorium, and mixtures of any two or more of these. Petition 870250084107, dated 09 / 18 / 2025, page 38 / 58 / 41 inorganic oxides. Examples of such mixtures are silica-chromium, silica-alumina, and silica-titania.

[0057] The inorganic oxide support material is porous and has variable surface area, pore volume, and average particle size. In some embodiments, the surface area is 50 to 1,000 square meters per gram (m² / g) and the average particle size is 20 to 300 micrometers (μιιι). Alternatively, the pore volume is 0.5 to 6.0 cubic centimeters per gram (cm³ / g) and the surface area is 200 to 600 m² / g. Alternatively, the pore volume is 1.1 to 1.8 cm³ / g and the surface area is 245 to 375 m² / g. Alternatively, the pore volume is 2.4 to 3.7 cm³ / g and the surface area is 410 to 620 m² / g. Alternatively, the pore volume is 0.9 to 1.4 cm³ / g and the surface area is 390 to 590 m² / g. Each of the above properties is measured using conventional techniques known in the art.

[0058] The support material may comprise silica, alternatively amorphous silica (not quartz), or alternatively an amorphous silica with a large surface area (e.g., 500 to 1,000 m² / g). These silicas are commercially available from various sources, including the Davison Chemical Division of W.R. Grace and Company (e.g., Davison 952 and Davison 955 products) and PQ Corporation (e.g., ES70 product). The silica may be in the form of spherical particles, which are obtained by a spray-drying process. Alternatively, the MS3050 product is a silica from PQ Corporation that is not spray-dried. As purchased, these silicas are not calcined (i.e., not dehydrated). Silica that is calcined before purchase may also be used as support material.

[0059] Before coming into contact with a catalyst, the support material can be pretreated by heating the support material in air to provide a calcined support material. The pretreatment comprises Petition 870250084107, dated 09 / 18 / 2025, page 39 / 58 / 41 heating the support material to a peak temperature of 350 to 850 °C, alternatively 400 to 800 °C, alternatively 400 to 700 °C, alternatively 500 to 650 °C, and for a period of time of 2 to 24 hours, alternatively 4 to 16 hours, alternatively 8 to 12 hours, alternatively 1 to 4 hours, thus producing a calcined support material. The support material may be a calcined support material.

[0060] The method may also employ a compensating catalyst. The compensating catalyst may be any of the metallocene catalysts mentioned above produced from the metal-ligand complex of formula (I) and activator. For convenience, the compensating catalyst is fed in solution in a hydrocarbon solvent (e.g., mineral oil or heptane). The hydrocarbon solvent may be ICA. The compensating catalyst may be produced from the same metal-ligand complex of formula (I) as that used to produce the metallocene catalyst of the bimodal catalyst system; alternatively, the compensating catalyst may be composed of a different metal-ligand complex of formula (I) than that used to produce the metallocene catalyst of the bimodal catalyst system.A compensating catalyst can be used to vary, within limits, the amount of metallocene catalyst used in the method relative to the amount of single-site non-metallocene catalyst in the bimodal catalyst system. Each catalyst in the bimodal catalyst system is activated upon contact with an activator. The activators may be the same or different from one another and, independently, may be a Lewis acid, a non-coordinating ionic activator, or an ionizing activator, or a Lewis base, an alkylaluminum or an alkylaluminoxane. The alkylaluminum may be a trialkylaluminum, alkylaluminum halide, or alkylaluminum alkoxide (diethylaluminum ethoxide). The trialkylaluminum may be trimethylaluminum, triethylaluminum (“TEAI”). Petition 870250084107, dated 09 / 18 / 2025, p. 40 / 58 / 41 tripropylaluminum or tris(2-methylpropyl)aluminum. The alkylaluminum halide may be diethylaluminum chloride. The alkylaluminum alkoxide may be diethylaluminum ethoxide. The alkylaluminoxane may be a methylaluminoxane (MAO), ethylaluminoxane, 2-methylpropylaluminoxane, or a modified methylaluminoxane (MMAO). Each alkyl group of the alkylaluminum or alkylaluminoxane may independently be a (C1-C7)alkyl group, alternatively a (C1-C6)alkyl group, or alternatively a (C1-C4)alkyl group. The molar ratio between the activator metal (Al) and the metal of a specific catalytic compound (catalytic metal, for example, Zr) can be from 1.000:1 to 0.5:1, alternatively from 300:1 to 1:1, or alternatively from 150:1 to 1:1. Suitable activators are commercially available.

[0061] Once the activator and the bimodal catalyst system come into contact with each other, the catalysts of the bimodal catalyst system are activated and activator species can be produced locally. The activator species may have a structure or composition different from the catalyst and the activator from which it is derived and may be a byproduct of catalyst activation or may be a derivative of the byproduct. The corresponding activator species may be a Lewis acid derivative, non-coordinating ionic activator, ionization activator, Lewis base, alkylaluminum, or alkylaluminoxane, respectively. An example of a byproduct derivative is a methylaluminoxane species that is formed by devolatilization during spray drying of a bimodal catalyst system produced with methylaluminoxane.

[0062] Each contact step between activator and catalyst can be done independently either in a separate vessel outside the GPP reactor (e.g., outside the FB-GPP reactor) or in a feed line to the GPP reactor. In option (a), the bimodal catalyst system, once its catalysts are activated, can be fed into the GPP reactor with a dry powder, alternatively with a flowable paste in a non-polar solvent, Petition 870250084107, dated 09 / 18 / 2025, page 41 / 58 / 41 aprotic (hydrocarbon). The activator (or activators) can be fed into the polymerization reactor in "wet mode" and in the form of a solution of the same in an inert liquid, such as mineral oil or toluene, in flowable paste mode, as a suspension, or in dry mode, as a powder. Each contact step can be done simultaneously or at different times. Test methods

[0063] Density - Density measurements are in accordance with ASTM D792, Method B. Density is reported in grams per cubic centimeter (g / cc or g / cm3).

[0064] Melting Index (I2, I5, I21) - Melting indices are measured according to ASTM D1238, Method B, at 190 °C. Data are reported as g / 10 min or dg / min. Samples can be run with loads of 21.6 kg, 5.0 kg, or 2.16 kg (i.e., i21, i5, or I2, respectively).

[0065] Absolute GPC (molecular weight distribution) - The chromatographic system consisted of a PolymerChar GPC-IR high-temperature GPC chromatograph (Valencia, Spain) equipped with an internal IR5 infrared detector and a 4-capillary viscometer (DV) coupled to precision detectors (now Agilent Technologies), 2-angle laser light scattering (LS) detector, model 2040. For all absolute light scattering measurements, a 15-degree angle is used for measurement. The autosampler oven compartment was set to 160° Celsius and the column and detector compartments were set to 150° Celsius. The columns used were 4 Agilent “Mixed A” 30 cm, 20 micron linear mixed-bed columns. The chromatographic solvent used was 1,2,4-trichlorobenzene and contained 200 ppm butylated hydroxytoluene (BHT). The solvent source was sprayed with nitrogen.The injection volume used was 200 microliters and the flow rate was 1.0 milliliter / minute.

[0066] The total plate count of the GPC column set was Petition 870250084107, dated 09 / 18 / 2025, pp. 42 / 58 / 41, performed with decane that was introduced into the blank sample by means of a micropump controlled with the PolymerChar GPC-IR system. The plate count for the chromatographic system must be greater than 18,000 for the 4 Agilent “Mixed A” 30 cm, 20 micron, linear mixed-bed columns.

[0067] Samples were prepared semi-automatically using PolymerChar Instrument Control software, with samples weight-directed to 2 mg / mL and solvent (containing 200 ppm BHT) added to a septum-capped flask pre-sprayed with nitrogen via the PolymerChar high-temperature autosampler. Samples were dissolved for 2 hours at 160° Celsius under low-speed stirring.

[0068] In order to monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled with the PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate (Flow rate(nominal)) of each sample by aligning the flow rate (RV) of the respective decane peak in the sample (RV(FM sample)) with that of the decane peak from the narrow standard calibration (RV(FM calibrated)). Any changes in the decane marker peak over time were then assumed to be related to a linear shift in the flow rate (flow rate(effective)) for the entire round. After calibrating the system based on a flow marker peak, the effective flow rate (relative to the narrow standard calibration) is calculated as Equation 1. Flow marker peak processing was performed via PolymerChar GPCOne™ software.The acceptable flow correction is such that the effective flow rate should be within + / - 0.5% of the nominal flow rate. Petition 870250084107, dated 09 / 18 / 2025, page 43 / 58 / 41 Effective flow rate = Nominal flow rate * (RV(calibrated FM) / RV(sample FM)) (Equation 1)

[0069] For the determination of the viscometer and light scattering detector shifts of the IV5 detector, the systematic approach for multidetector shift determination is done in a manner consistent with that published by Balke, Mourey, et al. (Mourey and Balke, Chromatography Polym. Chapter 12, (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym. Chapter 13, (1992)), optimizing the triple detector log (MW and IV) resulting from a linear homopolymer polyethylene standard (3.5 > Mw / Mn > 2.2) with molecular weight in the range of 115,000 to 125,000 g / mol up to the narrow standard column calibration resulting from the narrow standard calibration curve using the PolymerChar GPCOne™ software.

[0070] Absolute molecular weight data were obtained in a manner consistent with that published by Zimm (Zimm, BH, J. Chem. Phys., 16, 1099 (1948)) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987)) using PolymerChar GPCOne™ software. The total injected concentration, used in the molecular weight determination, was obtained from the mass detector area and the mass detector constant, derived from a suitable linear polyethylene homopolymer, or from one of the polyethylene standards of known weight-average molecular weight. The calculated molecular weights (using GPCOne™) were obtained using a light scattering constant, derived from one or more of the polyethylene standards mentioned below, and a concentration coefficient per refractive index, dn / dc, of 0.104.In general, the mass detector response (IR5) and the light scattering constant (determined using GPCOne™) should be determined from a linear standard with a molecular weight above approximately 50,000 g / mol. The viscometer calibration (determined using GPCOne™) is also required. Petition 870250084107, dated 09 / 18 / 2025, pp. 44 / 58 33 / 41 can be performed using the methods described by the manufacturer or, alternatively, using published values ​​of suitable linear standards, for example, Standard Reference Materials (SRM) 1475a (available from the National Institute of Standards and Technology (NIST)). A viscometer constant (obtained using GPCOne™) is calculated that relates the specific viscosity area (DV) and the injected mass of the calibration standard to its intrinsic viscosity. Chromatographic concentrations are assumed to be low enough to eliminate / treat viral coefficient effects (concentration effects on molecular weight).

[0071] The absolute weight-average molecular weight (Mw(Abs)) is obtained (using GPCOne™) from the integrated light scattering (DL) chromatogram area (factored by the light scattering constant) divided by the recovered mass from the mass constant and the mass detector area (IR5). The molecular weight and intrinsic viscosity responses are linearly extrapolated at the chromatographic ends where the noise signal becomes low (using GPCOne™). Other respective moments, Mn(Abs) and Mz(Abs), are calculated according to the following equations: Σ!Σ'( ·M, , , )mabsolute u í λ k 5 Σ Mw(AlJS) =----, ,, , Σ (tt?(X Λ / absolute^ ) MÁAbs) = _.-T„-------L— Σ'(^(x Mabsoh,toi) Equation (2)

[0072] Complex viscosity - Complex viscosities (q*) are calculated using Dynamic Mechanical Spectroscopy and are reported in pascal-seconds (Pa-s). Samples are compression molded in a Petition 870250084107, dated 09 / 18 / 2025, page 45 / 58 / 41 A rectangular plate measuring 9.75 inches x 10.25 inches x 1.85 mm thick is pressed at 190 °C for 6.5 minutes under a pressure of 25,000 psi in air. The sample is then removed from the press and allowed to cool. The resulting plate is subjected to a 25 mm diameter die cutter to extract disc-shaped samples for rheological testing. A constant temperature frequency scan is performed using an Advanced Rheometric Expansion System (ARES), TA Instruments, equipped with 25 mm (diameter) parallel plates under a nitrogen purge. Samples are placed on the plate and allowed to melt for five minutes at 190 °C. The plates are then closed to a gap of 1.8 mm, the samples are trimmed (any extra sample extending beyond the circumference of the 25 mm diameter plate is removed), and then the test is started.The method had an additional predefined delay of five minutes to allow for temperature equilibration. Tests are performed at 190 °C in a frequency range of 0.1 radians per second (rad / s) to 100 rad / s with a constant stretching amplitude of 10%.

[0073] Elongation hardening modulus - The elongation hardening modulus in MPa is measured using samples prepared by compression molding of pellets according to ISO 18488:2015 (sample thickness 0.3 mm, tensile speed 20 mm / min, test temperature 80 °C).

[0074] Pennsylvania Notch Test (PENT) - The Pennsylvania Notch Test (PENT) is performed following the procedure described in ASTM F-1473, Standard Test Method for Notch Tensile Test to Measure the Resistance to Slow Crack Growth of Polyethylene Pipes and Resins. The test is conducted in an air environment with a controlled temperature of 80 °C and using a tension of Petition 870250084107, dated 09 / 18 / 2025, pages 46 / 58 / 41 2.4 MPa in compression-molded plates that are notched on three sides. The compression-molded plates are produced using ASTM D4703 and include the additional preparation steps as required in F-1473. The compression-molded plates are cooled as detailed in the ASTM F-1473 procedure. The specimens are notched on the top and both sides at a speed less than 0.25 mm / min and “perpendicular to the tensile axis of the specimen,” as required in F-1473. The notch depth is approximately 35% of the sample thickness. The blade used to make the notch is 0.2 mm thick.

[0075] 2% Secant Modulus - The 2% secant modulus is measured according to ASTM D790 using a sample 0.5” wide, 5” long, and 0.125” thick. The measurement is performed at a test speed of 0.5 inch / min. Samples used for bending property measurement are molded according to ASTM D4706 Annex A.1 Procedure C (controlled cooling at 15 °C / min). Values ​​are reported in kilopound-force per square inch (ksi). (1 Megapascal (MPa) = 0.145 ksi).

[0076] Environmental stress cracking resistance (ESCR) All ESCR values ​​disclosed herein correspond to F50 failure times, reported in hours, and are measured in accordance with ASTM D1693, Method B, on compression-molded samples with a thickness of 1.90 mm, in a 10% Igepal solution at 50 °C.

[0077] Deconvolution of the GPC Chromatogram - The suitability of a chromatogram into a high molecular weight (HMW) component fraction and a low molecular weight (LMW) component fraction using a Flory distribution that was augmented with a normal distribution function as set out below: For the log M axis, 601 equally spaced Log(M) points, spaced by 0.01, were established between 2 and 8, Petition 870250084107, dated 09 / 18 / 2025, pp. 47 / 58 36 / 41 representing the molecular weight range between 100 and 100,000,000, where Log is the base-10 logarithm function. For any given Log(M), the population of the Flory distribution is in the form of the following equation 6: dWf= \ (-2M. ) ------------------- M1&· 0.868588961964 / £ junction 3 where Mw is the weighted average molecular weight of the Flory distribution and M is the specific molecular weight point on the x-axis, (10Λ[Log(M)]). The weight fraction of the Flory distribution was enlarged at each equally spaced log(M) index of 0.01, according to a normal distribution function, with width expressed as Log(M), σ; and the current M index expressed as Log(M), μ. (LagM— k)3e Ξσ2f(LagM4t,a) ~ r=~ EtfUílfòO 4 CJ Y il Jí·

[0078] It should be noted that before and after the scattering function has been applied, the area of ​​the distribution (dWf / dLogM) as a function of Log(M) is normalized to unity. Two weight fraction distributions, dWf i and dWf 2, for BPM and APM components or components 1 and 2 were expressed with two unique target values ​​Mw, Mwi and Mw2, and with global component compositions Ai and A2. Both distributions were expanded with the same width, s. The two distributions were summed as follows: dWf = dtVfi + Á2dWfZEquation 5 where: A1+A2 = 1

[0079] The weight fraction result of the molecular weight distribution measured by GPC (from absolute GPC) was interpolated across the 601 log M indices using a 2nd-order polynomial. Microsoft Excel™ 2010 Solver was used to minimize the sum of squared residuals for the equally spaced range of 601 LogM points between the interpolated molecular weight distribution determined by chromatography and the three extended Flory distribution components (51 and S2), weighted Petition 870250084107, dated 09 / 18 / 2025, pages 48 / 58 / 41 with its respective component compositions, Ai and A2. The iteration starting values ​​for the components are as follows: Component 1: Mwi = 15,000, 5 = 0.300, and Ai = 0.475 Component 2: Mw2 = 250,000, 5 = 0.300 and A2 = 1 - Ai (Note 51 = 5 2 and A1 + A2 = 1)

[0080] The limits for components 1 and 2 are such that 5 is restricted, so that 5 > 0.001, producing an Mw / Mn ratio of approximately 2.00 and 5 < 0.450, producing an Mw / Mn ratio of approximately 5.71. The composition, A1, is restricted between 0.000 and 1.000. Mw1 is restricted between 2.500 and 2,000,000. The composition, A2, is restricted between 0.000 and 1.000. Mw2 is restricted between 2.500 and 2,000,000. The “Nonlinear GRG” mechanism was selected in Excel Solver™ and the precision was set to 0.00001 and the convergence was set to 0.0001. The solutions were obtained after convergence (in all cases shown, the solution converged within 60 iterations). EXAMPLES

[0081] DOW™ TCP-2495 NT is a commercially available high-density polyethylene composition from Dow Chemical Company and has a density of 0.946 g / cm3 and properties as specified in the tables below. This is Comparative Example 1 (EC1).

[0082] CONTINUUM™ DGDA-2488 NT is a commercially available bimodal polyethylene composition from Dow Chemical Company and is produced in a dual reactor system using UNIPOL™ II process technology. This is Comparative Example 2 (CE2)._________ EI1 EI2 EC3 Reactor Type S,CM, FB GPP* S,CM, FB GPP* S,CM, FB GPP* Reactor Purge Gas Anhydrous N2 Anhydrous N2 Anhydrous N2 Bed Temp. (°C) 95.0 105.0 86.0 Rx Pressure (psig)A 349.4 349.1 349.6 Partial Pressure of C2 (psig) 219.4 217.3 220.0 Molar Ratio H2 / C2 0.0050 0.0047 0.0004 Petition 870250084107, dated 09 / 18 / 2025, pages 49 / 58 / 41 Molar Ratio C6 / C2 0.0072 0.0048 0.0004 Superficial Gas Velocity (ft / s) 1.84 1.87 1.90 Bimodal Catalyst System BMC1 BMC2 BMC2 Equilibrium Catalyst TC1 TC2 TC2 Starting Seeder = Granular HDPE Resin Precharged Precharged Precharged Fluidized Bed Weight (lb) 86.1 82.7 100.3 Copolymer Compound Production Rate (lb / hour) 40.1 36.3 31.7 Copolymer Compound Residence Time (hours) 2.1 2.3 3.2 Apparent Fluid Density of Copolymer Compound (lb / ft3) 14.6 13.7 18.2 *S,CM, FB, GPP: gas-phase polymerization in a simple fluidized bed, continuous mode. The pilot plant reactor did not operate in condensation mode. PressureARx (kPa): total reactor pressure in kilopascals. Table (1)

[0083] Bimodal Catalyst System 1 (BMC1): a spray-dried catalyst formulation prepared from Cabosil™ TS-610, methylalumoxane, dibenzyl bis(2-(pentamethylphenylamido)ethyl)-amine zirconium and dimethyl (methylcyclopentadienyl)(1,3-dimethyl-4,5,6,7tetrahydroindenyl)zirconium.

[0084] Bimodal Catalyst System 2 (BMC2): a spray-dried catalyst formulation prepared from Cabosil™ TS-610, methylalumoxane, dibenzyl bis(2-(pentamethylphenylamido)ethyl)-amine zirconium and dimethyl (cyclopentadienyl)(1,5-dimethylindenyl)zirconium.

[0085] Equilibrium catalyst 1 (TC1): a 0.04 wt% solution of dimethyl (methylcyclopentadienyl)(1,3-dimethyl-4,5,6,7-tetrahydroindenyl)zirconium in isopentane. Equilibrium catalyst 2 (TC2): a 0.04 wt% solution of dimethyl (cyclopentadienyl)(1,5-dimethylindenyl)zirconium in isopentane.

[0086] As supported by the above and below, the composition according to the embodiments disclosed herein can be produced in a single reactor, can be easily processed due to its viscosity profiles and melt index, and can provide a desirable balance of properties such as flexibility, stiffness, and ESCR compared to the examples. Petition 870250084107, dated 09 / 18 / 2025, pp. 50 / 58 / 41 comparative. Although Comparative Example 2 exhibits comparable PENT and ESCR properties, it has a significantly different molecular weight profile and cannot be produced in a single reactor system due to its catalyst system, among other things. Figure 1 shows the absolute GPC curve of the comparative examples and the invention. The Mmax1 and Mmax2 values ​​in Table 1 for EI1 and EI2 refer to the peaks in the absolute GPC curve. Mmax1 is for the lower M peak and Mmax2 is for the higher M peak. Table 2 - Properties of compositions 1 and 2___________________________ EI 1 EI 2 Bimodal Modality Bimodal Density (g / cm3) 0.953 0.953 I2 (g / 10min) 0.23 0.32 I5 (g / 10min) 0.85 1.12 I21 (g / 10min) 22.4 32.7 MFR - I21 / I2 96 102 MFR - I21 / I5 26 29 Mn (g / mol) 8,672 7,377 Mw (g / mol) 188,802 186,487 Mz (g / mol) 1,152,708 1,176,636 Mw / Mn 21.8 25.3 Mz / Mw 6.1 6.3 Mmax1 (g / mol) 13,182 13,804 Mmax2 (g / mol) 218.791 204.186 Viscosity - V.01 (Pas) 38.576 32.140 Viscosity - V100 (Pas) 1.868 1.583 Shear thinning ratio 20.7 20.3 2% Secant modulus (ksi) 132 140 Deformation hardening modulus (MPa) 49.06 35.69 PENT (hours) 660.2 51.6 ESCR (hours) >1000 >1000 HMW component, % by weight 49% 43% LMW component, % by weight 51% 57% Mw per HMW (g / mol) 356.726 374.064 Mn per HMW (g / mol) 98,276 107,933 Mz per HMW (g / mol) 957,353 961,388 Mw per LMW (g / mol) 15,830 20,642 Petition 870250084107, dated 09 / 18 / 2025, pp. 51 / 58 / 41 Mn per LMW (g / mol) 5,214 4,510 Mz per LMW (g / mol) 37,162 74,703 Table 3: Properties of comparative composition EC 1 EC 2 EC 3 Modality Unimodal Bimodal Bimodal Density (g / cm3) 0.946 0.955 0.958 I2 (g / 10min) 0.18 0.27 0.18 I5 (g / 10min) 0.99 1.08 1.28 I21 (g / 10min) 21.8 26.7 29.9 MFR - I21 / I2 121 99 166 MFR - I21 / I5 22 25 23.3 Mn (g / mol) 12,019 10,251 22,733 Mw (g / mol) 174,207 182,727 266,554 Mz (g / mol) 1,072,418 865,000 2,088,078 Mw / Mn 14.5 17.8 11.7 Mz / Mw 6.2 4.7 7.8 Viscosity - V.01 (Pas) 47.533 36.234 75.636 Viscosity - V100 (Pas) 1.557 1.680 1.364 Shear thinning ratio 30.5 21.6 55.5 2% Secant modulus (ksi) 125 155 165 Deformation hardening modulus (MPa) 29.94 37.3 15.9 PENT (hours) 21.5 60.2 Not measured ESCR (hours) 893 >1000 165 HMW component, % by weight - - 22% LMW component, % by weight - - 78% Extrusion and pipe testing

[0087] The tubes are formed from EI2, EC1, and EC2. The tubes are tested for hydrostatic burst testing. The tubes are 1” IPS (Iron Pipe Size) SDR11 (Standard Diameter Ratio). To form the tubes, pellets are added to the feed hopper of the American Maplan 60 mm groove feed pipe extrusion line (L / D=30 / 1). The tube specimens are extruded to an outside diameter (OD), and the wall thickness tolerances are in accordance with ASTM D 3035. The tube dimensions are measured in accordance with ASTM D 2122. The outside diameter is measured using a calibrated pi tape. Petition 870250084107, dated 09 / 18 / 2025, pp. 52-58 41 / 41 of the wall thickness is measured using a calibrated micrometer. The hydrostatic test is conducted according to ASTM D1598 at 73°F (23°C). The tube extrusion conditions and final dimensions are in Table 3 below. Table 4 - Tube extrusion conditions and final dimensions Resin EI2 EC1 EC2 Modality Bimodal Unimodal Bimodal Zone Temperatures (F) Matrix 1 390 390 390 2 390 390 390 3 390 390 390 4 390 390 390 5 390 390 390 6 390 390 390 7 390 390 390 8 390 390 390 Cylinder 1 370 370 370 2 380 380 380 3 390 390 390 4 390 390 390 Melting (probe) (F) 284 301 293 Barrel Press. (MPa (psi)) 1608 1665 1703 Screw RPM 49.5 51.4 47.8 Motor Amps (%) 81 87 86 Wire Drawer Speed ​​(ft / min) 28.1 27.65 27.65 Rate (lbs / h) 302.4 301.9 302.1 Specific Rate (lb / h / rpm) 6.11 5.87 6.32 Specific Power Input (J / g) 548 570 530 Molten Material Temperature at Die Exit (°F) 422 428 428 Tube Outside Diameter (in) 1.304 1.312 1.306 Tube Wall Thickness Range (in) 0.123-0.128 0.124-0.129 0.126-0.129 Petition 870250084107, dated 09 / 18 / 2025, pages 53 / 58

Claims

1 / 3 CLAIMS 1. A pipe, characterized in that it comprises a multimodal composition of high-density polyethylene, wherein the multimodal composition of high-density polyethylene comprises more than 40% by weight of a high molecular weight component and less than 60% by weight of a low molecular weight component, based on the total weight of the multimodal composition of high-density polyethylene, wherein the multimodal composition of high-density polyethylene has: a. a density greater than 0.950 g / cm3; b. a high-load melt index (I21) of 20.0 to 35.0 g / 10 min; c. a viscosity at 0.1 rad / s greater than 30,000 Pas; d. a shear thinning ratio of 15.0 to 25.0; e. a PENT value greater than 30 hours; f. an elongation hardening modulus greater than 30.00 MPa; and g. an Mz / Mw ratio greater than 5.

5.

2. Tube according to claim 1, characterized in that the composition has a molecular weight distribution from absolute GPC, wherein the absolute GPC molecular weight distribution has a first peak, a local minimum and a second peak in a Log(molecular weight) range of 3.5 to 6.0, wherein the local minimum is an inflection point between the first peak and the second peak, and the first peak corresponds to the low molecular weight component and the second peak corresponds to the high molecular weight component.

3. Tube according to any of the preceding claims, characterized in that the composition has an I21 / I5 ratio of 25 to 35. Petition 870250084107, dated 09 / 18 / 2025, page 54 / 58 2 / 3 4. Tube according to any of the preceding claims, characterized in that the composition has an Mw / Mn ratio of 20 to 30.

5. Tube according to any of the preceding claims, characterized in that the composition has a weight-average molecular weight (Mw) greater than 175,000 g / mol.

6. Tube according to any of the preceding claims, characterized in that the composition has a melting index (I2) of 0.20 to 0.40 g / 10 min.

7. Tube according to any of the preceding claims, characterized in that the composition has an I21 / I2 ratio of 90 to 110.

8. A tube according to any of the preceding claims, characterized in that the composition has a secant modulus 2% greater than 130 ksi.

9. Tube according to any of the preceding claims, characterized in that the composition has an ESCR value greater than 1,000 hours.

10. A tube according to any of the preceding claims, characterized in that the composition is produced by the polymerization process of ethylene and an alpha-olefin in the presence of a bimodal catalyst system in a single gas-phase polymerization (GPP).

11. Process for producing a pipe, characterized in that it comprises forming the multimodal high-density polyethylene composition according to claim 1, and extruding the multimodal high-density polyethylene composition to form a pipe, wherein the multimodal high-density polyethylene is formed by polymerization of ethylene monomer and an alpha-olefin comonomer in the presence of a bimodal catalyst system in a single gas-phase polymerization (GPP); wherein the bimodal catalyst system essentially consists of a metallocene catalyst, a single-site non-metallocene catalyst that is a bis(alkyl-substituted phenylamido)ethyl)amine catalyst, optionally a host material and optionally an activator; The host material, when present, is selected from at least one of an inert hydrocarbon liquid and a solid support;wherein the metallocene catalyst is a product of the activation reaction of the contact of an activator with a metal-ligand complex of formula (Ri— 2Cp)((alkyl)1-3 Indenyl)MX2, wherein R is hydrogen, methyl or ethyl; each alkyl is independently a (C1-C4)alkyl; M is titanium, zirconium or hafnium; and each X is independently a halide, a (C1 to C20)alkyl, a (C7 to C20)aralkyl, a (C6 to Cn)aryl substituted by (C1 to C6)alkyl or a benzyl substituted by (C1 to C6)alkyl; The bis((alkyl-substituted phenylamido)ethyl)amine catalyst is a contact activation reaction product of an activator with a ZrR12 bis((alkyl-substituted phenylamido)ethyl)amine, wherein each R1 is independently selected from F, Cl, Br, I, benzyl, -CH2Si(CH3)3, a (C1-Cs)alkyl, and a (C2Cs)alkenyl. Petition 870250084107, dated 09 / 18 / 2025, pp. 56 / 58;

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