Bimodal HDPE resins with improved ESCR and processability for conduit, cable, blow molding and other end-use applications

Abstract

Ethylene-based polymers having a melt index of 0.15 to 0.5 g / 10 min, a high load melt index of 15 to 50 g / 10 min, a density of 0.94 to 0.96 g / cm3, and higher and lower molecular weight components are disclosed. The higher molecular weight component has an HMW HL275 of from 3 to 8 g / 10 min and an HMW density of from 0.92 to 0.94 g / cm3. These polymers can have one or more of the following: an environmental stress crack resistance (ESCR) of at least 1,000 hours, a yield strength of 3,000 to 5,000 psi, a viscosity at 100 sec-1 of 1,000 to 1,800 Pa-sec, and / or a notched constant toughness stress (NCLS) of 80 to 1,000 hours.

Description

REFERENCE TO RELATED APPLICATIONS

[0001] This application is being filed on September 17, 2024 as a PCT International Patent Application and claims the benefit of and priority to U.S. Provisional Patent Application No. 63 / 584,237, filed September 21, 2023, the disclosure of which is incorporated by reference herein in its entirety. TECHNICAL FIELD

[0002] The present disclosure relates generally to Ziegler-Natta catalyzed bimodal ethylene polymers with excellent stress crack resistance and improved processability that can be used in various wire and cable, conduit pipe, and related applications. BACKGROUND

[0003] Polyolefins, such as high density polyethylene (HDPE) homopolymers and copolymers and linear low density polyethylene (LLDPE) copolymers can be produced using various combinations of catalyst systems and polymerization processes for wire and cable and conduit pipe (e.g., duct) applications, such as power cables and telecommunication and data transmission cables. However, polymeric resins used for these applications can be susceptible to cracking and failure under various environmental stresses. In addition, high yield strength can be required, often necessitating the use of higher density polymers. Thus, there is a need for bimodal high density ethylene-based polymers with improved environmental stress crack resistance (ESCR), particularly at densities of 0.94 g / cm3or greater, and improved processability. 3 and the polyethylene resins above. Accordingly, the present invention is generally directed to these ends. SUMMARY

[0004] This summary is provided to introduce a selection of concepts further described below in the detailed description. This summary is not intended to identify essential or necessary features of the claimed subject matter. Nor is this summary intended to be used to limit the scope of the claimed subject matter.

[0005] Disclosed herein are bimodal high density ethylene-based polymers with excellent processability, yield strength, stress crack resistance, and heat resistance. In one aspect, the ethylene polymers can have (or can be characterized by) a melt index (MI) in the range of 0.15 to 0.5 g / 10 min, a high load melt index (HLMI) in the range of 15 to 50 g / 10 min, a density in the range of 0.94 to 0.96 g / cm3, and a higher molecular weight component and a lower molecular weight component. The higher molecular weight component can have (or can be characterized by) a HMW HL275 in the range of 3 to 8 g / 10 min and a HMW density in the range of 0.92 to 0.94 g / cm3. 3 3 Disclosed herein are bimodal high density ethylene-based polymers with excellent processability, yield strength, stress crack resistance, and heat resistance. In one aspect, the ethylene polymers can have (or can be characterized by) a melt index (MI) in the range of 0.15 to 0.5 g / 10 min, a high load melt index (HLMI) in the range of 15 to 50 g / 10 min, a density in the range of 0.94 to 0.96 g / cm3, and a higher molecular weight component and a lower molecular weight component. The higher molecular weight component can have (or can be characterized by) a HMW HL275 in the range of 3 to 8 g / 10 min and a HMW density in the range of 0.92 to 0.94 g / cm3.​

[0006] These ethylene polymers can be used to produce various articles, such as for wire and cable, conduit pipe, and related end-use applications.

[0007] The foregoing summary and the following detailed description both provide examples and are explanatory only. Accordingly, the foregoing summary and the following detailed description should not be considered to be restrictive. Further, features or variations can be provided in addition to those set forth herein. For example, certain aspects can be directed to alternative BRIEF DESCRIPTION OF DRAWINGS

[0008] Figure 1 Molecular weight distribution plots for the polymers of Inventive Examples 1-4 are presented.

[0009] Figure 2 A plot of heat distortion temperature (ASTM D648, 66 psi) versus polymer density is shown.

[0010] DEFINITIONS To more clearly define the terms used herein, the following definitions are provided. Unless otherwise indicated, the following definitions are applicable to this disclosure. If a term is used in this disclosure but is not specifically defined herein, the definition from the IUPAC Compendium of Chemical Terminology (1997) can apply, to the extent that the definition does not conflict with any other disclosure or definition applied herein, or render indefinite or invalid any claim to which that definition is applied. If any definition or usage provided in any document incorporated by reference conflicts with the definition or usage provided herein, the definition or usage provided herein is to control.

[0011] In this document, features of the subject matter are described so that combinations of different features can be contemplated within a particular aspect. For each and every aspect disclosed herein, all combinations of the features of that aspect are contemplated, with or without explicit description of the combinations. Additionally, any aspect and / or feature disclosed herein can be combined with any other aspect and / or feature disclosed herein to describe an inventive feature in accordance with the present disclosure, unless otherwise explicitly stated.

[0012] Generally, the group of elements uses Chemical and Engineering NewsThe numbering scheme indicated in the version of the Periodic Table of the Elements published in CRC Handbook of Chemistry and Physics, 63(5), 27, 1985, is used to indicate groups where appropriate. In some cases, a group of elements can be indicated using a generic name assigned to the group; for example, alkali metals indicate Group 1 elements, alkaline earth metals indicate Group 2 elements, transition metals indicate Groups 3-12 elements, and halogens or halides indicate Group 17 elements.

[0013] For any particular compound disclosed herein, unless otherwise indicated, the general structure or name presented is also intended to encompass all structural isomers, conformational isomers, and stereoisomers that can result from a particular set of substituents. Thus, unless explicitly indicated otherwise, a general reference to a compound includes all structural isomers; for example, a general reference to pentane includes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane, while a general reference to a butyl group includes n-butyl, sec-butyl, iso-butyl, and t-butyl. In addition, a reference to a general structure or name encompasses all enantiomers, diastereomers, and other optical isomers (whether in enantiomeric or racemic forms) where the context allows or requires, as well as mixtures of stereoisomers. For any particular formula or name presented, any general formula or name presented also encompasses all conformational isomers, regioisomers, and stereoisomers that can result from a particular set of substituents.

[0014] The terms “a,” “an,” “the” and “said” are intended to include plural alternatives, such as “at least one,” unless otherwise indicated.

[0015] The terms “contacting” and “combining” are used herein to describe compositions and processes / methods in which materials are brought together in any order, in any manner, and for any length of time, unless otherwise indicated. For example, materials can be blended, mixed, slurried, dissolved, reacted, treated, impregnated, compounded, or contacted or combined in some other manner or by any suitable method or technique.

[0016] The term “hydrocarbon” refers to a compound containing only carbon and hydrogen. Other designators can be used to indicate the presence of particular groups in a hydrocarbon (e.g., halogenated hydrocarbon indicates the presence of one or more halogen atoms in place of the same number of hydrogen atoms in a hydrocarbon). The term “hydrocarbyl” is used herein according to the definition specified by IUPAC: a monovalent radical formed by the removal of one hydrogen atom from a hydrocarbon (i.e., a group containing only carbon and hydrogen). Non-limiting examples of hydrocarbyl groups include alkyl, alkenyl, aryl, and aralkyl groups, among others.

[0017] The term "polymer" is generally used herein to include olefin homopolymers, copolymers, terpolymers, etc., as well as alloys and blends thereof. The term "polymer" also includes impact, block, graft, random, and alternating copolymers. Copolymers are derived from an olefin monomer and one olefin comonomer, while terpolymers are derived from an olefin monomer and two olefin comonomers. Thus, "polymer" encompasses copolymers and terpolymers derived from any olefin monomer and comonomer disclosed herein. Similarly, the scope of the term "polymerization" includes homopolymers, copolymers, and trimers. Therefore, ethylene polymers include ethylene homopolymers, ethylene copolymers (e.g., ethylene / α-olefin copolymers), ethylene terpolymers, etc., as well as blends or mixtures thereof. Thus, ethylene polymers encompass polymers commonly referred to in the art as LLDPE (linear low-density polyethylene) and HDPE (high-density polyethylene). As an example, ethylene copolymers can be derived from ethylene and comonomers such as 1-butene, 1-hexene, or 1-octene. If the monomer and comonomer are ethylene and 1-hexene, respectively, the resulting polymer can be classified as an ethylene / 1-hexene copolymer. Unless otherwise stated, the term "polymer" also includes all possible geometries, and such geometries can include isotactic, synisotactic, and random symmetries. Furthermore, unless otherwise stated, the term "polymer" is also intended to include polymers of all molecular weights, and includes polymers of lower molecular weights.

[0018] This invention discloses several types of ranges. When any type of range is disclosed or claimed, it is intended to individually disclose or claim every possible number that such range can reasonably cover, including the endpoints of the range and any sub-ranges and combinations thereof covered therein. For example, in aspects of this invention, ethylene polymers can have various Mw / Mn ratios. By disclosing that Mw / Mn ratios are in the range of 10 to 20, it is intended to state that the Mw / Mn ratio can be any ratio within that range, and can, for example, include any range or combination in the range of 10 to 20, such as 11 to 19, 12 to 20, 12 to 19, 12 to 18, 13 to 20, 13 to 19, or 13 to 18, etc. Similarly, all other ranges disclosed herein should be interpreted in a manner similar to this example.

[0019] Generally, quantities, sizes, formulas, parameters, ranges, or other quantities or features are described as “about” or “approximately”, whether or not such explicit statements are made. Claims include equivalents of quantities or features, regardless of whether they are modified by the terms “about” or “approximately”.

[0020] Although any methods and materials similar to or equivalent to those described herein may be used in the practice or testing of this invention, typical methods and materials are described herein.

[0021] All publications and patents mentioned herein are incorporated herein by reference in their entirety for the purpose of describing and disclosing, for example, the constructs and methods described in the publications and patents, which may be used in conjunction with the present invention. Detailed Implementation

[0022] This disclosure generally relates to polymer resins produced using Ziegler-Natta catalyst systems and articles formed from these polymer resins. While polymers with relatively high density and melt flow rates (to obtain improved extrusion processability) typically have poor environmental stress cracking resistance (ESCR), the bimodal ethylene polymers described herein offer an advantageous combination of high density, high ESCR, and excellent processability.

[0023] Another object of the present invention is to give the ethylene polymer a relatively high density, which in part translates into excellent mechanical properties such as high yield strength, tensile modulus and notched constant toughness stress (NCLS) and high drawing speed.

[0024] Another object of the present invention is to give ethylene polymers excellent processability to achieve high extrusion yields, typically through a relatively high melt index (and / or a high-load melt index) and 100 sec. -1 The relatively low viscosity is used for quantification. Due to improved processability (e.g., lower die back pressure), up to 15% increase in output or production can be achieved.

[0025] Another object of the present invention is to give ethylene polymers excellent processability to obtain a combination of high extrusion yield with relatively high density and heat distortion temperature (e.g., above 65°C or above 70°C) and / or thermal stability (e.g., above 240°C or above 250°C) and unexpectedly high ESCR values.

[0026] Ethylene polymer 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 typically have 3 to 20 carbon atoms in their molecular chains. For example, typical comonomers may include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, etc., or combinations thereof. In one aspect, olefin comonomers may contain C3-C... 18 Olefins; alternatively, olefin comonomers may contain C3-C 10 Olefins; alternatively, olefin comonomers may contain C4-C 10 Olefins; alternatively, olefin comonomers may contain C3-C 10 α-olefins; alternatively, olefin comonomers may contain C4-C10 α-Olefins; alternatively, the olefin comonomer may comprise 1-butene, 1-hexene, 1-octene, or any combination thereof; or alternatively, the comonomer may comprise 1-hexene. Typically, the amount of comonomer may range from 0.01 to 20 wt.%, 0.01 to 1 wt.%, 0.5 to 15 wt.%, 0.5 to 2 wt.%, or 1 to 15 wt.%, based on the total weight of the monomer (ethylene) and the comonomer.

[0027] In one aspect, the ethylene polymer of the present invention may include an ethylene / α-olefin copolymer, while in another aspect, the ethylene polymer may include an ethylene homopolymer, and in yet another aspect, the ethylene polymer of the present invention may include both an ethylene / α-olefin copolymer and an ethylene homopolymer. For example, the ethylene polymer may include an ethylene / 1-butene copolymer, an ethylene / 1-hexene copolymer, an ethylene / 1-octene copolymer, an ethylene homopolymer, or any combination thereof; alternatively, an ethylene / 1-butene copolymer, an ethylene / 1-hexene copolymer, an ethylene / 1-octene copolymer, or any combination thereof; or alternatively, an ethylene / 1-hexene copolymer.

[0028] Illustrative and non-limiting examples of ethylene polymers (e.g., including ethylene copolymers) consistent with the present invention may have (or may be characterized by) a melt index (MI) in the range of 0.15 to 0.5 g / 10 min, a high load melt index (HLMI) in the range of 15 to 50 g / 10 min, and a melt index in the range of 0.94 to 0.96 g / cm³. 3 The density ranges from 3 to 8 g / 10 min, and the higher and lower molecular weight components are also considered. The higher molecular weight components may have (or may be characterized by) an HMW HL275 in the range of 0.92 to 0.94 g / cm³. 3 HMW density within the range. Unless otherwise stated, this illustrative and non-limiting example of an ethylene polymer consistent with the present invention may also have any polymer properties listed below and in any combination thereof.

[0029] In some respects, the melt index (MI or I2) of the ethylene polymers covered herein can be in the range of 0.15 to 0.45 g / 10 min, 0.15 to 0.4 g / 10 min, 0.2 to 0.5 g / 10 min, 0.2 to 0.4 g / 10 min, 0.2 to 0.35 g / 10 min, 0.25 to 0.5 g / 10 min, 0.25 to 0.45 g / 10 min, 0.25 to 0.4 g / 10 min, 0.27 to 0.5 g / 10 min, 0.27 to 0.45 g / 10 min, 0.27 to 0.4 g / 10 min, or 0.3 to 0.4 g / 10 min. Additionally or alternatively, the high-load melt index (HLMI or I2) of these ethylene polymers... 21 It is usually within the range of 15 to 45 g / 10 min or 20 to 50 g / 10 min, such as 15 to 40 g / 10 min, 20 to 45 g / 10 min, 20 to 40 g / 10 min, 25 to 50 g / 10 min, 25 to 45 g / 10 min, 25 to 40 g / 10 min, 27 to 45 g / 10 min or 27 to 40 g / 10 min. Alternatively, the I5 of these ethylene polymers is typically in the range of 0.8 to 2.4 g / 10 min, 1 to 2.2 g / 10 min, 1 to 2 g / 10 min, or 1 to 1.8 g / 10 min in one aspect, and in the range of 1.1 to 2.2 g / 10 min, 1.1 to 2 g / 10 min, or 1.1 to 1.9 g / 10 min in another aspect, and in yet another aspect, and in the range of 1.2 to 2 g / 10 min, 1.2 to 1.9 g / 10 min, or 1.2 to 1.8 g / 10 min in yet another aspect, and in yet another aspect, and in the range of 1.3 to 2.2 g / 10 min, 1.3 to 2 g / 10 min, 1.3 to 1.9 g / 10 min, or 1.3 to 1.8 g / 10 min.

[0030] The HLMI / MI ratio of ethylene polymers can in some respects range from 80 to 130, 85 to 125, 85 to 120, 85 to 115 or 90 to 130, while in other respects the HLMI / MI ratio of these polymers can range from 90 to 125; alternatively, 90 to 120; alternatively, 90 to 115; alternatively, 95 to 125; alternatively, 95 to 120; or alternatively, 95 to 115.

[0031] These ethylene-based polymers have a density greater than or equal to 0.94 g / cm³. 3And less than or equal to 0.96 g / cm³ 3 The density of these polymers can range from 0.94 to 0.958 g / cm³. 3 0.94 to 0.954 g / cm³ 3 0.945 to 0.96 g / cm 3 0.945 to 0.958 g / cm³ 3 0.945 to 0.954 g / cm³ 3 0.947 to 0.958 g / cm³ 3 0.947 to 0.954 g / cm³ 3 0.949 to 0.958 g / cm³ 3 0.949 to 0.955 g / cm³ 3 Or 0.949 to 0.953 g / cm³ 3 wait.

[0032] In one respect, these ethylene polymers can have a number-average molecular weight (Mn) in the range of 7,000 to 16,000 g / mol, such as 8,000 to 15,000 g / mol, 9,000 to 15,000 g / mol, 9,000 to 14,000 g / mol, or 10,000 to 14,000 g / mol. Although not limited thereto, these ethylene polymers may have a weight-average molecular weight (Mw) in the range of 150,000 to 280,000 g / mol, 150,000 to 250,000 g / mol, 150,000 to 225,000 g / mol, 160,000 to 260,000 g / mol, 160,000 to 240,000 g / mol, 160,000 to 220,000 g / mol, 170,000 to 260,000 g / mol, 170,000 to 220,000 g / mol, 180,000 to 250,000 g / mol, 180,000 to 225,000 g / mol, or 180,000 to 205,000 g / mol. Alternatively or concurrently, these ethylene polymers may have a z-average molecular weight (Mz) in the range of 700,000 to 1,900,000 g / mol, 800,000 to 1,800,000 g / mol, 850,000 to 1,750,000 g / mol, 900,000 to 1,700,000 g / mol, 950,000 to 1,650,000 g / mol, or 1,000,000 to 1,600,000 g / mol.

[0033] In one aspect, the ethylene polymer may have a Mw / Mn ratio or polydispersity index in the range of 10 to 20, such as 11 to 20, 11 to 19, 12 to 20, 12 to 19, 12 to 18, 13 to 20, 13 to 19, or 13 to 18. Alternatively or additionally, these ethylene polymers may have an Mz / Mw ratio in the range of 4 to 10, 4 to 9, 4 to 8, 4.5 to 10, 4.5 to 9, 4.5 to 8.5, 4.5 to 8, 5 to 10, 5 to 9, 5 to 8, 5.25 to 9, 5.25 to 8, 5.5 to 9, or 5.5 to 8.

[0034] According to certain aspects of the invention, the IB parameter derived from the molecular weight distribution curve (a graph of dW / d(Log M) against Log M; normalized for the area equal to 1) can be an important characteristic of the ethylene polymers described herein. The IB parameter is commonly referred to as the integral width and is defined as 1 / [dW / d(Log M)]. MAX This parameter can be used to describe the shape of the maximum peak in a bimodal MWD: as the IB parameter increases, the maximum peak becomes smaller / wider. Typically, in one aspect, the IB parameter of the ethylene polymer consistent with this invention can be in the range of 1.7 to 2.4. In another aspect, the ethylene polymer can be characterized by an IB parameter in the range of 1.7 to 2.3 or 1.7 to 2.2, and in yet another aspect, the IB parameter can be in the range of 1.8 to 2.3 or 1.8 to 2.2, and in yet another aspect, the IB parameter can be in the range of 1.8 to 2.1 or 1.9 to 2.3, and in yet another aspect, the IB parameter can be in the range of 1.9 to 2.2 or 2 to 2.4, and in yet another aspect, the IB parameter can be in the range of 2 to 2.3 or 2 to 2.2, and in yet another aspect, the IB parameter can be in the range of 2 to 2.1.

[0035] In one aspect, these ethylene polymers may have a CY-a parameter in the range of 0.18 to 0.33. Other suitable ranges for the CY-a parameter include, but are not limited to, 0.2 to 0.32, 0.2 to 0.3, 0.22 to 0.3, 0.24 to 0.3, 0.24 to 0.28, or 0.25 to 0.28. Additionally or alternatively, these ethylene polymers may have a relaxation time (Tau(eta) or τ(η)) in the range of 0.1 to 0.8 seconds. Other suitable ranges for relaxation time include, but are not limited to, 0.2 to 0.7, 0.2 to 0.6, 0.3 to 0.7, 0.3 to 0.6, or 0.3 to 0.5 seconds. The polymer relaxation time generally refers to the time required for the polymer chains to return to equilibrium after being disturbed. Non-Newtonian fluids have a characteristic memory timescale called relaxation time. These materials relax within their characteristic relaxation time when the applied rate of deformation decreases to zero. A low τ(η) value is desirable because it corresponds to minimized stress during polymer orientation processes, such as in cable or pipe fabrication. Typically, τ(η) increases with increasing molecular weight; however, polymer entanglement, long-chain branching, molecular weight, and molecular weight distribution all affect relaxation behavior. While not limited to this, ethylene polymers can typically have zero-shear viscosity (η0) in the range of 40,000 to 140,000 Pa-sec, and other illustrative ranges include 50,000 to 130,000 Pa-sec, 50,000 to 110,000 Pa-sec, 50,000 to 100,000 Pa-sec, 60,000 to 120,000 Pa-sec, 60,000 to 100,000 Pa-sec, 60,000 to 90,000 Pa-sec, or 70,000 to 85,000 Pa-sec. The CY-a, relaxation time, and zero-shear viscosity parameters were determined from viscosity data measured at 190 °C using the Carreau-Yasuda (CY) empirical model described herein.

[0036] While not limited to this, ethylene polymers can have a temperature range of 1.8 to 3.2 degrees within 0.1 sec. -1 The tan δ (tan d or tangent δ) is given below. At 0.1 sec -1 Other suitable ranges for tan δ include, but are not limited to, 2 to 3, 2.1 to 2.8, 2.1 to 2.7, 2.2 to 2.7, 2.3 to 2.7, or 2.3 to 2.6 degrees. Values ​​greater than 1, rather than less than 1, are within 0.1 sec. -1The (low-frequency) tanδ indicates a polymer with relatively low elasticity under low shear, which can be beneficial for certain end-use applications such as cable and conduit applications. Alternatively or additionally, these ethylene polymers may have a tanδ value in the range of 0.5 to 1 degree, and more often in the ranges of 0.5 to 0.9, 0.6 to 1, 0.6 to 0.9, 0.6 to 0.8, 0.65 to 0.9, 0.65 to 0.8, 0.7 to 0.9, or 0.7 to 0.8 degrees at 100 sec. -1 The rheological parameter tanδ (tan d or tangent δ) is used, but is not limited to. The tanδ rheological parameter is determined by viscosity data measured at 190 °C and using the Carreau-Yasuda (CY) empirical model described herein.

[0037] Alternatively or concurrently, these ethylene polymers may have a range of 1,000 to 1,800 Pa-sec, such as 1,100 to 1,700 Pa-sec or 1,200 to 1,800 Pa-sec, with a 100 sec [unclear text - possibly related to a pressure range]. -1 The viscosity at 100 sec (eta @ 100 or η @ 100). In some respects, the viscosity of ethylene polymers at 100 sec -1 The viscosity can be in the range of 1,100 to 1,600; alternatively, 1,100 to 1,500; alternatively, 1,200 to 1,700; alternatively, 1,200 to 1,600; alternatively, 1,200 to 1,500; alternatively, 1,300 to 1,700; alternatively, 1,300 to 1,600; or alternatively, 1,300 to 1,500 Pa-sec. Furthermore, the ethylene polymer can have a ratio of η @ 0.1 / η @ 100 at 190°C in the range of 14 to 24; alternatively, 15 to 22; alternatively, 16 to 21; alternatively, 17 to 20; or alternatively, 18 to 19 (in 0.1 sec). -1 The viscosity at 100 sec -1 (The ratio of viscosity to viscosity). Both viscosity and ratio were determined using the CY model at 190°C.

[0038] Advantageously, ethylene polymers exhibit excellent resistance to stress cracking, which is particularly surprising given their relatively high polymer density. In one aspect of this disclosure, these polymers can have an environmental stress cracking resistance (ESCR) of at least 1,000 hours (ASTM D1693, Condition B, 10% Igepal) and more typically, at least 1,500 hours or at least 2,000 hours. Surprisingly, these polymers can typically have an ESCR of at least 2,500 hours, at least 2,800 hours, at least 3,000 hours, or at least 3,500 hours (under Condition B, 10% Igepal). ESCR testing typically stops after a certain number of hours, and given the long duration of the tests, the upper limit of ESCR (in hours) is generally uncertain.

[0039] As disclosed herein, ethylene polymers may have a high or higher molecular weight (HMW) component (or first component) and a low or lower molecular weight (LMW) component (or second component). These component terms are relative, used with reference to each other, and are not limited to the actual molecular weight of each component. Generally, the higher molecular weight component (HMW) may have (or may be characterized by) an HMW HL275 in the range of 3 to 8 g / 10 min and an HMW in the range of 0.92 to 0.94 g / cm³. 3 The HMW density is within the range specified. In this context, the HMW component is produced in the first reactor, and the LMW component is produced in the second reactor. The polymer properties of the HMW components discharged from the first reactor and introduced into the second reactor can be readily tested. The HMW HL275 of the higher molecular weight components is typically in the range of 3 to 7 g / 10 min or 4.2 to 8 g / 10 min. Other representative and non-limiting ranges for HL275 include 3 to 6.5 g / 10 min, 3.5 to 7.5 g / 10 min, 3.5 to 7 g / 10 min, 3.5 to 6.5 g / 10 min, 4 to 7.5 g / 10 min, 4 to 7 g / 10 min, 4.2 to 7.5 g / 10 min, 4.2 to 7 g / 10 min, 4.2 to 6.5 g / 10 min, 4.5 to 8 g / 10 min, 4.5 to 7.5 g / 10 min, 4.5 to 7 g / 10 min, 4.5 to 6.5 g / 10 min, or 4.9 to 6.1 g / 10 min, etc. Additionally, the HMW density (the density of the HMW component discharged from the first reactor) is greater than or equal to 0.92 g / cm³. 3 And less than or equal to 0.94 g / cm³ 3 Representative and non-limiting ranges for HMW density can include 0.92 to 0.935 g / cm³. 30.925 to 0.94 g / cm³ 3 0.925 to 0.938 g / cm³ 3 0.925 to 0.935 g / cm³ 3 0.928 to 0.94 g / cm 3 0.928 to 0.938 g / cm³ 3 0.928 to 0.935 g / cm³ 3 0.93 to 0.94 g / cm³ 3 0.93 to 0.938 g / cm³ 3 Or 0.93 to 0.935 g / cm³ 3 wait.

[0040] The calculated HLMI of the HMW component can be determined based on the HL275 value. The HLMI can be calculated from HL275 based on Equation 1: HLMI = HL275 / 3.2 (Equation 1). Although not limited thereto, the calculated HLMI of the HMW component can be in some respects within the range of 0.9 to 2.5 g / 10 min, 1 to 2.4 g / 10 min, 1.1 to 2.3 g / 10 min, 1.3 to 2.2 g / 10 min, or 1.3 to 2 g / 10 min, and in other respects within the range of 1.4 to 2.2 g / 10 min, 1.4 to 2 g / 10 min, 1.5 to 2.2 g / 10 min, or 1.5 to 2 g / 10 min.

[0041] As determined by comparing the ethylene consumption in the first reactor with the total ethylene consumption, the amount of the higher molecular weight (HMW) component in the total ethylene polymer can vary from 40 wt.% to 60 wt.% in one aspect, from 42 wt.% to 58 wt.% in another aspect, from 42 wt.% to 55 wt.% in yet another aspect, from 42 wt.% to 52 wt.% in yet another aspect, and from 45 wt.% to 55 wt.% in yet another aspect.

[0042] The density of the lower molecular weight component (LMW) can be calculated from the density of the total polymer and the density of the HMW component. The calculated density of the LMW component is based on Equation 2: d = wt.% HMW *d HMW +wt.% LMW *d LMW (Equation 2). In this equation, d is the final density of the polyethylene fluff, wt.%. HMW It is the weight fraction of the HMW component, d HMW This is the density of the HMW component, wt.%. LMWIt is the weight fraction of the LMW component, and d LMW This is the density of the LMW component. The calculated density of the LMW component is typically very high, usually ranging from 0.96 to 0.975 g / cm³. 3 The calculated density of the LMW component falls within the range of [specific range missing]. Other non-limiting ranges for the calculated density include 0.96 to 0.973 g / cm³. 3 0.962 to 0.975 g / cm³ 3 0.962 to 0.973 g / cm³ 3 0.965 to 0.975 g / cm³ 3 Or 0.965 to 0.973 g / cm³ 3 As will be readily apparent, the precise polymeric properties of the LMW component cannot be directly measured because this LMW component cannot be separated from the total bimodal polymer (ethylene polymer).

[0043] Similarly, the HLMI of the lower molecular weight component (LMW) can be calculated from the HLMI of the total polymer and the HLMI of the HMW component. The calculated HLMI of the LMW component is based on Equation 3: Log(HLMI) = wt.% HMW *Log(HLMI HMW )+wt.% LMW *Log(HLMI LMW (Equation 3). In this equation, Log(HLMI) is the final Log HLMI of the polyethylene fluff, wt.%. HMW It is the weight fraction of the HMW component, HLMI HMW It is the HLMI of the HMW component, wt.% LMW It is the weight fraction of the LMW component, and HLMI LMW This refers to the HLMI of the LMW component. LMW has a very high (calculated) melt index, typically ranging from 800 to 3,000 g / 10 min. Other non-limiting ranges for the calculated HLMI of the LMW component include 800 to 2,500 g / 10 min, 1,000 to 3,000 g / 10 min, 1,000 to 2,800 g / 10 min, 1,000 to 2,500 g / 10 min, 1,200 to 2,600 g / 10 min, or 1,400 to 2,400 g / 10 min, etc.

[0044] Ethylene polymers consistent with certain aspects of this invention may have a bimodal molecular weight distribution (as determined using gel permeation chromatography (GPC) or other relevant analytical techniques). Typically (but not required) in a bimodal molecular weight distribution, there are valleys between the peaks, and the peaks can be separated or deconvoluted. Typically, a bimodal molecular weight distribution can be characterized as having an identifiable high molecular weight component (or distribution) and an identifiable low molecular weight component (or distribution).

[0045] Therefore, in various aspects of the invention, the ethylene polymer may 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, used with reference to each other, and are not limited to the actual molecular weight of each component. Unlike the HMW and LMW components determined from the first reactor and calculated for the second reactor, the molecular weight characteristics of the LMW and HMW components can be determined by deconvolving the molecular weight distribution of the complex (total polymer), for example, using gel permeation chromatography. In this context, the Mw (HMW) of these ethylene polymers may be in the range of 200,000 to 500,000 g / mol, 250,000 to 450,000 g / mol, 300,000 to 400,000 g / mol, or 320,000 to 380,000 g / mol, etc. Alternatively or alternatively, the Mn(HMW) of these ethylene polymers may be in the range of 25,000 to 55,000 g / mol, 30,000 to 50,000 g / mol, 33,000 to 47,000 g / mol, or 35,000 to 45,000 g / mol or 37,000 to 43,000 g / mol, etc.

[0046] The molecular weight distribution of HMW components is now referenced, such as the molecular weight distribution quantified by the Mw / Mn (HMW) ratio, which is usually in the range of 6 to 11, such as 6 to 10, 6 to 9, 7 to 11, 7 to 10, 7 to 9, 8 to 11, 8 to 10, or 8 to 9, etc.

[0047] Referring now to the molecular weight distribution of LMW components, such as the molecular weight distribution quantified by the Mw / Mn (LMW) ratio, it is generally narrower than that of HMW components. In one aspect, the lower molecular weight components have an Mw / Mn ratio of 4 to 8, while in another aspect, the Mw / Mn ratio is 4.5 to 7.5 or 4.5 to 7, and in yet another aspect, the Mw / Mw ratio is 5 to 7.5 or 5 to 7; and in yet another aspect, the Mw / Mn ratio is 5.5 to 7.5 or 5.5 to 7, and in yet another aspect, the Mw / Mn ratio is 5.5 to 6.5 or 5.8 to 6.2.

[0048] Although not limited thereto, the Mw (LMW) of these ethylene polymers can be in the range of 25,000 to 50,000 g / mol, 30,000 to 45,000 g / mol, 30,000 to 40,000 g / mol, 35,000 to 45,000 g / mol, or 35,000 to 40,000 g / mol, etc.

[0049] In the context of MWD deconvolution, there are no particular restrictions on the relative amounts of LMW and HMW components, but typically the amount of LMW component is in the range of 40 wt.% to 60 wt.% based on the total polymer (HMW plus LMW). Other typical amounts of LMW component based on the total polymer can be in the range of 40 wt.% to 55 wt.%, 42 wt.% to 55 wt.%, 45 wt.% to 55 wt.%, or 47 wt.% to 54 wt.%, etc.

[0050] The ethylene polymers disclosed herein possess a beneficial combination of stiffness and strength properties. For example, the ethylene polymers may be characterized by yield strengths (ASTM D638 tensile) in the ranges of 3,000 to 5,000 psi, 3,300 to 4,700 psi, 3,500 to 4,500 psi, 3,500 to 4,200 psi, 3,700 to 4,500 psi, or 3,700 to 4,100 psi. Alternatively or additionally, the ethylene polymers may have elongations at break (ASTM D638 tensile) in the ranges of 700% to 1,000%, 700% to 950%, 750% to 950%, 800% to 1,000%, 800% to 950%, or 800% to 900%. Alternatively or alternatively, these ethylene polymers may have a tensile modulus (ASTM D638 tensile) in the range of 200,000 to 300,000 psi, such as 200,000 to 280,000 psi, 220,000 to 300,000 psi, or 220,000 to 280,000 psi.

[0051] Using the ASTM D790 flexural test, ethylene polymers can be characterized by tangential modulus in the range of 150,000 to 250,000 psi, 170,000 to 230,000 psi, 180,000 to 220,000 psi, or 190,000 to 210,000 psi. Alternatively or additionally, ethylene polymers can have a flexural modulus (2% secant modulus) in the range of 100,000 to 180,000 psi. In some aspects, the flexural modulus (2% secant modulus) can be in the range of 125,000 to 175,000 psi; alternatively, 140,000 to 160,000 psi; or alternatively, 145,000 to 155,000 psi.

[0052] The notched constant toughness stress (NCLS) of the disclosed ethylene polymers, as determined according to ASTM F2136, is unexpectedly high, particularly considering the relatively high polymer density. In one aspect of this disclosure, these polymers may have an NCLS of 80 to 1,000 hours, and more typically 80 to 800 hours or 100 to 1,000 hours. Other typical ranges include 100 to 800 hours, 150 to 1,000 hours, 150 to 800 hours, or 150 to 700 hours, etc. Additionally or alternatively, the ethylene polymers may have a strain hardening modulus (SHM) typically in the range of 20 to 40 MPa, such as 25 to 40 MPa, 25 to 38 MPa, 25 to 35 MPa, 28 to 40 MPa, 28 to 35 MPa, 30 to 40 MPa, 30 to 38 MPa, or 30 to 35 MPa, as determined according to ISO 18488.

[0053] Alternatively or additionally, the fully notched creep test (FNCT) of the disclosed ethylene polymers, determined according to ISO 16770 (using Arkopal N 100, 2% aqueous solution as the test liquid), is also unexpectedly high. Independently, the test temperature can be any one of 50°C, 60°C, 80°C, or 90°C, and the test force or pressure can be any one of 2, 4, 6, 8, 9, or 12 MPa (e.g., a test temperature of 50°C and a test force or pressure of 9 MPa, or a test temperature of 80°C and a test force or pressure of 6 MPa). Under any of these test conditions, these ethylene polymers can have FNCT values ​​of at least 100 hours, and more typically at least 200 hours, at least 500 hours, at least 1000 hours, at least 5,000 hours, at least 10,000 hours, or at least 25,000 hours. FNCT trials are typically stopped after a certain number of hours, and given the long duration of the trials, the upper limit of FNCT (in hours) is usually uncertain.

[0054] For certain end-use applications, a high heat distortion temperature (HDT), such as at least 60°C or at least 70°C, as measured according to ASTM D648, may be advantageous. HDT is the measure of a polymer's ability to remain rigid or "hard" under constant load and high temperature. Therefore, it indicates the temperature at which the polymer begins to "soften" under a fixed load. While not limited to this, the HDT of the disclosed ethylene polymers can be in the range of 60°C to 90°C, such as 60°C to 85°C, 65°C to 90°C, 65°C to 85°C, 70°C to 90°C, or 70°C to 85°C. Similarly, high thermal stability, such as at least 240°C or at least 250°C, as measured according to ASTM D3350, may be advantageous. While not limited to this, the thermal stability of the disclosed ethylene polymers can be in the range of 240°C to 270°C, such as 240°C to 260°C, 240°C to 255°C, 245°C to 265°C, 245°C to 255°C, or 250°C to 255°C. Another indicator of thermal stability and resistance to oxidative decomposition is the oxidation induction time (OIT) measured according to ASTM D3895. While not limited to this, the OIT of the disclosed ethylene polymers can be in the range of 50 to 90 minutes, such as 50 to 75 minutes, 55 to 85 minutes, 55 to 75 minutes, or 55 to 70 minutes.

[0055] A particularly advantageous combination of properties of ethylene polymers includes the aforementioned key characteristics (melt index of 0.15 to 0.5 g / 10 min, high-load melt index of 15 to 50 g / 10 min, and 0.94 to 0.96 g / cm³). 3 The density, HMW HL275 of 3 to 8 g / 10 min, and 0.92 to 0.94 g / cm³ 3 The HMW density) combined with an ESCR of at least 1,000 hours (or at least 2,800 hours, or any other range disclosed herein), or with a yield strength of 3,000 to 5,000 psi (or 3,700 to 4,500 psi, or any other range disclosed herein), or with a 1,000 to 1,800 Pa-sec (or 1,200 to 1,600 Pa-sec, or any other range disclosed herein) in 100 seconds -1 The combination of viscosities below, or with NCLS of 80 to 1,000 hours (or 150 to 800 hours, or any other range disclosed herein), or with ESCR, yield strength, and at 100 sec, as disclosed herein. -1 The viscosity and / or NCLS properties of any two or more of the following combinations.

[0056] Furthermore, these ethylene polymers can be produced using a magnesium and titanium-containing Ziegler-Natta catalyst system, as discussed further below. Metallocene and chromium-based catalyst systems are not required. Therefore, the ethylene polymers may be free of measurable amounts of Hf, Zr, and / or Cr (catalyst residues), i.e., less than 0.1 ppm by weight. In some aspects, the ethylene polymers may independently contain less than 0.08 ppm, less than 0.05 ppm, or less than 0.03 ppm of Hf, Zr, and / or Cr.

[0057] Due to their excellent ESCR and mechanical properties (e.g., yield strength), post-consumer recycled (PCR) and / or post-industrial recycled (PIR) resins are expected to be combined with ethylene polymers without significantly adverse effects on performance and processability (e.g., within + / - 10% or + / - 5%). Therefore, polymer compositions considered herein may comprise an ethylene polymer and 2 to 50 wt.%, 2 to 20 wt.%, 5 to 40 wt.%, 5 to 25 wt.%, 5 to 15 wt.%, or 10 to 30 wt.% of any suitable post-consumer recycled (PCR) and / or post-industrial recycled (PIR) resin. Typically, PIR is present in the polymer composition in an amount up to and including 40 wt.%, and PCR is present in the polymer composition in an amount up to and including 30 wt.%.

[0058] Products and products Articles may be formed from the ethylene polymers of the present invention and / or may contain the ethylene polymers (or polymer compositions) of the present invention, and are therefore covered herein. For example, articles that may contain the polymers (or compositions) of the present invention may include, but are not limited to, agricultural films, automotive parts, bottles, chemical containers, cylinders, inflatable bags, fibers or fabrics, food packaging films or containers, food service products, fuel tanks, geomembranes, household containers, liners, molded products, medical devices or materials, outdoor storage products, outdoor recreational equipment, pipes, sheets or tapes, toys or traffic barriers, etc. Various processes can be used to form these articles. Non-limiting examples of these processes include injection molding, blow molding, rotational molding, film extrusion, sheet extrusion, profile extrusion, thermoforming, etc.

[0059] In addition, additives and modifiers are typically added to these polymers (or compositions) to provide beneficial polymer processing or end-use product properties. Suitable additives that can be used in polymers (or compositions) and resulting articles include, but are not limited to, antioxidants, deacidifiers, anti-blocking additives, slip additives, colorants (e.g., carbon black), fillers, polymer processing aids, UV inhibitors (e.g., light stabilizers), etc., and this includes any combination of two or more of these additives at any suitable loading / amount. Such methods and materials are described in Modern Plastics Encyclopedia Mid-November 1995, Volume 72, Issue No. 12; and Film Extrusion Manual - Process, Materials, Properties According to TAPPI Press, 1992. In some aspects of the invention, the article may comprise any ethylene polymer (or composition) described herein, and the article may be or may comprise wires, cables, or conduits. Cables may be power cables, including low-voltage, medium-voltage, and high-voltage power cables. In other aspects, the article may comprise any ethylene polymer (or composition) described herein, and the article may be or may comprise blow-molded products, including bottles and other containers for household industrial chemicals, etc.

[0060] Depending on the end use of the ethylene polymer (or composition) or articles formed therefrom, a lower coefficient of static friction and / or coefficient of kinetic friction (COF) may be beneficial. COF is an indicator of a material's ability to slide against itself or another surface, and the higher the COF, the less likely it is to slide or move (greater viscosity). For example, in conduit applications, a lower COF means easier installation. Typically, ethylene polymers (or compositions) and / or articles formed therefrom can have a kinetic COF of less than or equal to 0.5, less than or equal to 0.4, less than or equal to 0.3, less than or equal to 0.2, or less than or equal to 0.1, with illustrative ranges including 0.05 to 0.3, 0.05 to 0.2, 0.1 to 0.3, or 0.1 to 0.2. COF can be determined according to ASTM D1894.

[0061] Catalysts and polymerization processes According to aspects of the invention, ethylene polymers can be produced using a Ziegler-Natta catalyst system in a two-reactor polymerization reactor system. Ziegler-Natta catalyst systems are well known to those skilled in the art, and any suitable Ziegler-Natta catalyst system can be used herein. The same or different Ziegler-Natta catalyst systems can be used in each reactor of the two-reactor polymerization reactor system.

[0062] As described above, the HMW and LMW components are produced in different reactors. Any suitable reactor can be used in a dual-reactor system, such as one or two slurry reactors, one or two gas-phase reactors, one or two solution reactors, or a combination of two different reactor types, and can be operated in series or parallel. In one particular aspect, the reactor system contains two slurry reactors, such as two circulating slurry reactors operating in series. While not limited to this, typically the HMW component is produced in the first circulating slurry reactor, while the LMW component and the subsequent final polymer are produced in the second circulating slurry reactor.

[0063] After the HMW component is produced in the first reactor, the polymerization reactor system can be configured to have a conveying device or pipeline for transferring the contents of the first reactor to the second reactor. The polymerization conditions in the first reactor may differ from those in the second reactor.

[0064] When the polymerization reactor system contains at least one circulating slurry reactor, the circulating slurry reactor may have a vertical or horizontal loop. Monomers, diluents, catalysts, and comonomers may be continuously fed into the circulating reactor where polymerization occurs. Typically, a continuous circulating slurry process may include the continuous introduction of monomers / comonomers, catalysts, and diluents into the reactor, and the continuous removal of a suspension containing polymer particles and diluents from the reactor. The reactor effluent may be flashed to remove solid polymers from the liquid containing diluents, monomers, and / or comonomers. Various techniques may be used for this separation step, including but not limited to flashing, which may include any combination of heating and depressurization, separation by cyclone action in a cyclone separator or hydrocyclone, or separation by centrifugation. Typical slurry polymerization processes (also known as particle-forming processes) are 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. Suitable diluents used in slurry polymerization include, but are not limited to, the monomers being polymerized and hydrocarbons that are liquid under the reaction conditions. Examples of suitable diluents include, but are not limited to, hydrocarbons such as propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, and n-hexane. Some cyclic polymerization reactions can occur under bulk conditions without the use of diluents.

[0065] Polymerization conditions that can be controlled to improve efficiency and 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. For example, to produce a specific grade of ethylene polymer, various polymerization conditions can be kept substantially constant. According to the Gibbs free energy equation, a suitable polymerization temperature can be any temperature below the depolymerization temperature. Typically, this includes, for example, 60°C to 280°C, or 60°C to 120°C, depending on the type of polymerization reactor. In some reactor systems with circulating slurry reactors, polymerization temperatures can typically range from 70°C to 105°C or 75°C to 100°C.

[0066] The appropriate pressure will also vary depending on the reactor and type of polymerization. Liquid-phase polymerization in a circulating reactor typically operates at pressures less than 1000 psi (6.9 MPa). Gas-phase polymerization typically operates at pressures of 200 to 500 psi (1.4 MPa to 3.4 MPa). High-pressure polymerization in tubular or autoclave reactors generally operates at 20,000 to 75,000 psi (138 to 517 MPa). Polymerization reactors can also be operated in the supercritical region, which generally occurs at higher temperatures and pressures. Operation above the critical point (supercritical phase) of the pressure / temperature diagram can provide advantages for the polymerization process.

[0067] Consistent with aspects of the present invention, a process for producing ethylene polymers may include a first step of introducing ethylene, a hydrocarbon diluent, a Ziegler-Natta catalyst system, optional hydrogen, and optional olefin comonomers into a first circulating slurry reactor, and then forming an HMW component of the ethylene polymer in the first circulating slurry reactor. The HMW component may be fed into a second circulating slurry reactor, wherein ethylene, optional hydrogen, and optional olefin comonomers are polymerized in the presence of the HMW component to produce an LMW component and subsequently a bimodal ethylene polymer.

[0068] The polymerization reactor system may also include any combination of at least one feed system, at least one feed system for catalyst or catalyst components, and / or at least one polymer recovery system. Suitable reactor systems may also include systems for feedstock purification, catalyst storage and preparation, extrusion, reactor cooling, polymer recovery, fractionation, recycling, storage, loading, laboratory analysis, and process control. Depending on the desired properties of the olefin polymer, hydrogen may be added to each polymerization reactor as needed (e.g., continuously or pulsedly).

[0069] When a copolymer is required, ethylene can be copolymerized with a comonomer (e.g., C2-C). 20α-olefins or C3-C 20 (α-olefin) copolymerization. According to one aspect of the invention, the comonomer may contain C3-C... 10 α-olefin; alternatively, the comonomer may include 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, styrene, or any combination thereof; alternatively, the comonomer may include 1-butene, 1-hexene, 1-octene, or any combination thereof; alternatively, the comonomer may include 1-butene; alternatively, the comonomer may include 1-hexene; or alternatively, the comonomer may include 1-octene.

[0070] Example The present invention is further illustrated by the following embodiments, which should not be construed as limiting the scope of the invention in any way. After reading this specification, those skilled in the art will conceive of various other aspects, modifications, and equivalents without departing from the spirit of the invention or the scope of the appended claims.

[0071] Melt flow index (MI, g / 10 min) was determined according to ASTM D1238 at 190°C with a weight of 2.16 kg. I5 was determined according to ASTM D1238 at 190°C with a weight of 5 kg. High load melt flow index (HLMI, g / 10 min) was determined according to ASTM D1238 at 190°C with a weight of 21.6 kg. HL275 was determined according to ASTM D1238 at 190°C with a weight of 21.6 kg, similar to HLMI, except that a die with a 2.75 mm diameter orifice was used, as described in U.S. Patent No. 10,053,563.

[0072] According to ASTM D1505 and ASTM D4703, on compression-molded samples cooled at 15°C per minute and conditioned at room temperature for 40 hours, the g / cm³ (g / cm³) is used. 3 Density is measured in units of 1 / 2.

[0073] Environmental stress cracking resistance (ESCR) was determined according to ASTM D1693, Condition B, using 10% Igepal. The measured failure time (in hours) is the result of the ESCR test.

[0074] Molecular weights and molecular weight distributions were obtained using a PL-GPC 220 system (Polymer Labs, Agilent Company) equipped with an IR4 detector (Polymer Char, Spain) and three Styragel HMW-6E GPC columns (Waters, MA) operating at 145 °C. The mobile phase of 1,2,4-trichlorobenzene (TCB) containing 0.5 g / L 2,6-di-tert-butyl-4-methylphenol (BHT) was flowed at a rate of 1 mL / min, and the polymer solution concentration ranged from 1.0 to 1.5 mg / mL, depending on the molecular weight. Sample preparation was performed at 150 °C, typically for 4 hours with occasional gentle stirring, followed by transfer of the solution to sample vials for injection. Injection volumes of approximately 400 μL were used. The HDPE polyethylene resin MARLEX from Chevron Phillips Chemical Company was used. ® BHB5003 serves as a broad standard, using an integral calibration method to derive molecular weight and molecular weight distribution. The integral table for the broad standard is pre-determined in a separate experiment using SEC-MALS. Mn is the number-average molecular weight, Mw is the weight-average molecular weight, Mz is the z-average molecular weight, Mv is the viscosity-average molecular weight, and Mp is the peak molecular weight (the position of the highest point on the molecular weight distribution curve). The IB parameter is determined by the molecular weight distribution curve (the area under the curve, normalized to 1, plotted as dW / d(Log M)) and defined as 1 / [dW / d(Log M)]. MAX IVc is the intrinsic viscosity [η], which is calculated based on Equation 4: [η] = K Mv a (Equation 4).

[0075] In Equation 4, Mv is the viscosity-average molecular weight, and K and α are the Mark-Houwink constants for the target polymer. For polyethylene, K and α are 3.95E-04 (dL / g) and 0.726 (unitless), respectively. Mv is calculated based on Equation 5, where... and These are the weight fraction and molecular weight of slice i, respectively: By analyzing the molecular weight distribution of each polymer (see...) Figure 1Deconvolution was performed to determine the properties of the corresponding LMW and HMW components. Five Shulz-Flory distributions (SFDs) were fitted to each component (five for LMW and five for HMW) using an Excel-based spreadsheet program, and the relative amounts (weight percentages) of the LMW and HMW components in the polymer were determined. The LMW and HMW could then be fractionally separated to fit the total MWD, thus providing deconvolution. The properties of each of the LMW and HMW components were then calculated.

[0076] Melt rheological characterization was performed as follows. Small strain (less than 10%) oscillatory shear measurements were performed on an Anton Paar MCR rheometer using a parallel plate geometry. All rheological tests were performed at 190 °C. The complex viscosity was then characterized using a modified three-parameter Carreau-Yasuda (CY) empirical model. η* |With frequency ( ω Curve fitting was performed on the changing data to obtain the zero-shear viscosity. η 0. Characteristic viscous relaxation time τ η and width parameter a (CY-a parameter). The simplified Carreau-Yasuda (CY) empirical model is shown in Equation 6: (Equation 6), where: | η* ( ω | = The numerical value of complex shear viscosity; η 0 = zero shear viscosity; τ η =Viscous relaxation time (τ(η)); a = "Width" parameter (CY-a parameter); n =The final power-law slope is fixed at 2 / 11; and ω = Angular frequency of oscillatory shear deformation.

[0077] Detailed information on the meaning and interpretation of the CY model and its derived parameters can be found at: CA Hieber and HHChiang. Rheol. Acta , 28, 321 (1989); CA Hieber and HH Chiang, Polym. Eng. Sci. ,32, 931 (1992); and RB Bird, RC Armstrong and O. Hasseger, Dynamics ofPolymeric Liquids, Volume 1, Fluid Mechanics , 2nd edition, John Wiley & Sons (1987). In 0.1 sec -1 tan δ below, at 100 sec -1 tan δ below, at 0.1 sec -1 The viscosity at 100 sec -1 The viscosity at HLMI and the viscosity at HLMI stress (the viscosity of the polymer at its HLMI stress) characteristics were determined using the Carreau-Yasuda (CY) empirical model.

[0078] Tensile properties, such as yield strength, elongation at break, and tensile modulus, were determined according to ASTM D638 at 23°C. Tangent modulus and flexural modulus (1% secant and 2% secant) were determined according to ASTM D790 at 23°C. Notched constant toughness stress (NCLS) was determined according to ASTM F2136 at 4.125 MPa (600 psi). The measured failure time (in hours) is the result of the NCLS test. Strain hardening modulus (SHM) was determined according to ISO 18488. Heat deflection temperature (HDT) was determined according to ASTM D648 (at 66 psi).

[0079] Metal content (such as the amount of catalyst residue in ethylene polymers or products) can be determined by ICP analysis on a PerkinElmerOptima 8300 instrument. Polymer samples can be ashed overnight in a Thermolyne furnace with sulfuric acid, followed by acid digestion in a HotBlock with HCl and HNO3 (3:1 v:v).

[0080] Examples 1-4, C5-C6 and 7-10 Comparative Example 5 (C5) is a commercially available unimodal resin from Chevron Phillips Chemical Company LP. Comparative Example 6 (C6) is a commercially available bimodal resin from The Dow Chemical Company. Examples 1-4 of the present invention were prepared in a large-scale dual-loop slurry reactor system at a nominal reactor pressure of 650 psi, and the polymerization conditions in the first reactor (RxA) and the second reactor (RxB) are summarized in Table A. The residence times in RxA and RxB independently ranged from 30 to 90 minutes, and in most cases from 45 to 75 minutes. Typically, the residence times in each reactor were approximately the same (e.g., within + / - 10%). The solid Ziegler-Natta catalyst had an average d50 particle size of 4-8 micrometers and a particle size span of approximately 1.5 ((d90-d10) / d50). The catalyst nominally contains 5.5-9.5 wt.% titanium (e.g., in the form of TiCl4 and / or TiCl3) and 10-15 wt.% magnesium (e.g., in the form of MgCl2 support). Optionally, the catalyst may contain an internal donor.

[0081] Tables 1-8 summarize the polymer properties of Examples 1-4 and, where appropriate, Comparative Examples C5-C6. As shown in Table 3, the ESCR performance of the polymers of Examples 1 and 3 is at least an order of magnitude higher than that of the polymer of Comparative Example C5. Examples 2 and 4 (if tested) are expected to have similar ESCR performance (over 3,000 hours) to Examples 1 and 3.

[0082] The polymers of Examples 1-4 have a melt index of 0.3-0.4 g / 10 min, a high-load melt index of 25-40 g / 10 min, and a melt index of 0.950-0.955 g / cm³. 3 Its density, HMW HL275 value of 4.9-6 g / 10 min, and 0.93-0.935 g / cm³ 3 The HMW density is shown in Table 1-3. Figure 1 The molecular weight distribution (logarithm of polymer amount to molecular weight) of the polymers in Examples 1-4 is described, and Table 4 summarizes the molecular weight characterization. Tables 5-6 summarize the deconvolutiond molecular weight data and corresponding molecular weight parameters of the LMW and HMW components of the polymers in Examples 1-4.

[0083] Tables 7-8 summarize the rheological properties of the polymers from Examples 1-4 and Comparative Examples C5-C6. Compared to C5, the polymers from Examples 1-4 exhibit significantly lower zero-shear viscosity and relaxation time, as well as significantly higher CY-a parameters and a relaxation time within 0.1 sec. -1The value of tan d under [condition]. Compared to C6, the polymers of Examples 1-4 have lower relaxation times, CY-a parameters, and [value] at 0.1 sec. -1 The lower tan d, the higher at 100 sec -1 The lower tan d, and much lower at 100 sec -1 The viscosity at that point.

[0084] Tensile, bending, NCLS, SHM, and HDT properties are summarized in Tables 9-10, and Figure 2 This indicates a density between 0.91 and 0.97 g / cm³. 3 The relationship between HDT and polymer density for various ethylene polymers within the range is shown in Tables 9-10. Examples 7-10 represent the test values ​​for the ethylene polymers of the present invention, which cover and represent Examples 1-4, but the specific ethylene polymers of Examples 1-4 were not tested for the physical properties listed in Tables 9-10. Of particular note is that Examples 7-10 exhibit significantly higher yield strength, tensile modulus, and NCLS than Comparative Examples C5-C6.

[0085] Table A – Aggregation Conditions

[0086] Table 1 – Polymer Pellet Properties

[0087] Table 2 – Characteristics of HMW Component Reactor A

[0088] Table 3 – Characteristics of LMW Component Reactor A

[0089] Table 4 – Molecular weight characterization (molecular weight in kg / mol)

[0090] Table 5 – Molecular Weight Characterization (kg / mol) – LMW Components

[0091] Table 6 – Molecular Weight Characterization (kg / mol) – HMW Components

[0092] Table 7 – Rheological properties at 190℃

[0093] Table 8 – Rheological properties at 190℃

[0094] Table 9 – Physical Properties

[0095] Table 10 – Physical Properties

[0096] Example 11 For initial processability comparisons, samples of the ethylene polymers of the present invention, representing Examples 1-4, and a sample of Comparative Example C5 were extruded on a Krauss Maffei laboratory-scale extrusion line (45 mm, 36:1 L / D grooved feed) to produce 2” DR11 tubing (pressure rating 160 psi, size ratio (DR) 11, which is the ratio of the tubing's average outer diameter to its minimum wall thickness), as summarized in Table 11 below. In summary, the bimodal polymers of the present invention exhibit excellent processing and performance characteristics with only minor deviations compared to the standard unimodal conduit resin of Comparative Example C5.

[0097] Table 11 – Extrusion Summary of Example 11

[0098] Examples 12-15 The bimodal ethylene polymer of the present invention was also evaluated on several large-scale production lines, including 165 mm, 100 mm, 75 mm, and 65 mm extruders with smooth orifice and grooved feed designs. IPS 40 conduits were produced in diameters of 1.25”, 1.685”, and 4.0”. These experiments were initiated using unimodal comparative example C5 to produce acceptable conduits before conversion to the bimodal ethylene polymer of the present invention (representing Examples 1-4), while monitoring processing conditions and making any necessary adjustments to maintain acceptable conduit production. Furthermore, an in-plant regrind content varying from 30-50 wt.% was used in a 4.0” diameter conduit experiment.

[0099] For Example 12, the resin was compounded online with carbon black masterbatch and fed into a 100 mm, 30:1 L / D smooth-orifice extruder. 30:1 L / D presents a greater challenge for mixing compared to higher L / D ratios. Yields on smooth-orifice feeds are highly rheologically dependent (e.g., MI, HLMI, viscosity) compared to grooved feeds. Extruder parameters (e.g., 24 ft / min traction) and pipe dimensions (2” black pipe) were used to provide a baseline before the transition from the unimodal comparative Example C5 polymer. Once the bimodal polymer of the present invention was fully transitioned, data showed that the extruder pressure increased by only about 7%–10%. Wall thickness remained constant with constant traction speed and pipe production rate. Once the pipe dimensions, outer and inner surface areas, and traction speed were confirmed to be acceptable, pipe samples were collected and subjected to a cold shock test, in which all samples passed.

[0100] For Example 13, the resin and carbon black masterbatch were in-line compounded and fed together with 30-50 wt.% of internal single-peak recycled material into a 165 mm grooved feed extruder to produce 4.0” IPS 40 tubing (black). Compared to single-peak C5, the extrusion line using the bimodal ethylene polymer of the present invention produced tubing with stable operating conditions and dimensions within the specification range, requiring only minimal adjustments. The melt temperature was 436℉, and the traction speed was 62 ft / min. Surprisingly, the die pressure was lower when using the polymer of the present invention compared to the single-peak C5 polymer, and the polymer of the present invention ultimately continued to run for approximately 20 hours, indicating that productivity or line speed could potentially increase by 15% due to the lower die pressure.

[0101] For Example 14, resin and carbon black masterbatch were in-line compounded and fed into a 65 mm grooved feed extruder to produce 1.25” IPS 40 tubing (black). The process response of melt temperature, melt pressure, screw torque, and traction speed was monitored while keeping the screw speed constant. As shown in Table 12 below, screw torque and melt pressure increased slightly, while melt temperature and traction speed remained unaffected. Tube dimensions were measured and easily adjusted to maintain standard tolerances. The wall thickness remained constant with the traction speed or tube production rate unchanged.

[0102] For Example 15, resin was fed into a 75 mm smooth-hole extruder to produce 1.25” IPS 40 conduit tubing. After converting from a single-peak C5 conduit resin to (100% original) the ethylene polymer of this invention, the focus again was on maintaining a constant screw speed and monitoring changes in melt temperature, motor load, and traction speed. With the screw speed kept constant, the melt temperature increased only slightly, and the motor load increased by just over 8%. The traction speed remained substantially the same without any adjustments. Maintaining a consistent production rate while extruding the ethylene polymer of this invention presented no challenge. Tube dimensions were measured, and process parameters were easily adjusted to maintain standard tolerances. Tube wall thickness values ​​remained constant with the traction speed or tube production rate unchanged. Table 13 provides a summary of Example 15.

[0103] In summary, these examples demonstrate that the bimodal polymer of the present invention can replace the single-peaked C5 resin of the comparative example, which has the same pipe dimensional tolerances, traction machine feet per minute output and overall processability, but with significantly improved ESCR performance, as shown in Table 3 above.

[0104] Table 12. Extrusion Summary of Example 14

[0105] Table 13. Extrusion Summary of Example 15

[0106] Examples 16-18 and C5-C6 In Table 14, Examples 16-18 are test values ​​covering and representing the ethylene polymers of the present invention described in Examples 1-4 and Examples 7-10 above. Thermal stability was determined according to ASTM D3350, heat distortion temperature (HDT) was determined according to ASTM D648 (at 66 psi) as described above, and oxidation induction time (OIT) was determined according to ASTM D3895. Of particular note in Table 14 are the thermal stability values ​​exceeding 250°C, HDT values ​​in the range of 72°C-87°C, and OIT values ​​of approximately 1 hour or more, each of which is significantly higher than that of Comparative Examples C5-C6.

[0107] Table 14 – Characteristics of Examples 16-18

[0108] This invention has been described herein with reference to numerous aspects and specific embodiments. Many variations will occur to those skilled in the art from the detailed description. All such apparent variations are within the full scope of the appended claims. Other aspects of the invention may include, but are not limited to, the following (aspects are described as “comprising”, but alternatively, may be “consistent with” or “comprises with”): Aspect 1. An ethylene polymer having (or characterized by) a melt index (MI) in the range of 0.15 to 0.5 g / 10 min, a high load melt index (HLMI) in the range of 15 to 50 g / 10 min, and a melt index of 0.94 to 0.96 g / cm³. 3 The density ranges from 3 to 8 g / 10 min, and the higher molecular weight components and lower molecular weight components, wherein the higher molecular weight components have (or are characterized by) an HMW HL275 in the range of 0.92 to 0.94 g / cm³. 3 HMW density within the range.

[0109] Aspect 2. The polymer as defined in Aspect 1, wherein the melt index (MI) is in any range disclosed herein, for example, 0.15 to 0.45, 0.15 to 0.4, 0.2 to 0.5, 0.2 to 0.4, 0.2 to 0.35, 0.25 to 0.5, 0.25 to 0.45, 0.25 to 0.4, 0.27 to 0.5, 0.27 to 0.45, 0.27 to 0.4 or 0.3 to 0.4 g / 10 min.

[0110] Aspect 3. The polymer as defined in aspect 1 or 2, wherein the high load melt index (HLMI) is in any range disclosed herein, for example, 15 to 45, 15 to 40, 20 to 50, 20 to 45, 20 to 40, 25 to 50, 25 to 45, 25 to 40, 27 to 45 or 27 to 40 g / 10 min.

[0111] Aspect 4. The polymer as defined in any of the preceding aspects, wherein the density is within any range disclosed herein, for example, 0.94 to 0.958, 0.94 to 0.954, 0.945 to 0.96, 0.945 to 0.958, 0.945 to 0.954, 0.947 to 0.958, 0.947 to 0.954, 0.949 to 0.958, 0.949 to 0.955, or 0.949 to 0.953 g / cm³. 3 .

[0112] Aspect 5. The polymer as defined in any of the preceding aspects, wherein the HMW HL275 is within any range disclosed herein, for example, 3 to 7, 3 to 6.5, 3.5 to 7.5, 3.5 to 7, 3.5 to 6.5, 4 to 7.5, 4 to 7, 4.2 to 8, 4.2 to 7.5, 4.2 to 7, 4.2 to 6.5, 4.5 to 8, 4.5 to 7.5, 4.5 to 7, 4.5 to 6.5 or 4.9 to 6.1 g / 10 min.

[0113] Aspect 6. The polymer as defined in any of the preceding aspects, wherein the HMW density is within any range disclosed herein, for example, 0.92 to 0.935, 0.925 to 0.94, 0.925 to 0.938, 0.925 to 0.935, 0.928 to 0.94, 0.928 to 0.938, 0.928 to 0.935, 0.93 to 0.94, 0.93 to 0.938, or 0.93 to 0.935 g / cm³. 3 .

[0114] Aspect 7. The polymer as defined in any of the preceding aspects, wherein the ethylene polymer has an HLMI / MI ratio within any range disclosed herein, for example, 80 to 130, 85 to 125, 85 to 120, 85 to 115, 90 to 130, 90 to 125, 90 to 120, 90 to 115, 95 to 125, 95 to 120, or 95 to 115.

[0115] Aspect 8. A polymer as defined in any of the preceding aspects, wherein said ethylene polymer has Mn in any range disclosed herein, for example, 7,000 to 16,000, 8,000 to 15,000, 9,000 to 15,000, 9,000 to 14,000 or 10,000 to 14,000 g / mol.

[0116] Aspect 9. A polymer as defined in any of the preceding aspects, wherein said ethylene polymer has a Mw in any range disclosed herein, for example, 150,000 to 280,000, 150,000 to 250,000, 150,000 to 225,000, 160,000 to 260,000, 160,000 to 240,000, 160,000 to 220,000, 170,000 to 260,000, 170,000 to 220,000, 180,000 to 250,000, 180,000 to 225,000, or 180,000 to 205,000 g / mol.

[0117] Aspect 10. A polymer as defined in any of the preceding aspects, wherein said ethylene polymer has an Mz in any range disclosed herein, for example, 700,000 to 1,900,000, 800,000 to 1,800,000, 850,000 to 1,750,000, 900,000 to 1,700,000, 950,000 to 1,650,000 or 1,000,000 to 1,600,000 g / mol.

[0118] Aspect 11. A polymer as defined in any of the preceding aspects, wherein the ethylene polymer has a Mw / Mn ratio within any range disclosed herein, for example, 10 to 20, 11 to 20, 11 to 19, 12 to 20, 12 to 19, 12 to 18, 13 to 20, 13 to 19 or 13 to 18.

[0119] Aspect 12. The polymer as defined in any of the preceding aspects, wherein the ethylene polymer has an Mz / Mw ratio within any range disclosed herein, for example, 4 to 10, 4 to 9, 4 to 8, 4.5 to 10, 4.5 to 9, 4.5 to 8.5, 4.5 to 8, 5 to 10, 5 to 9, 5 to 8, 5.25 to 9, 5.25 to 8, 5.5 to 9, or 5.5 to 8.

[0120] Aspect 13. A polymer as defined in any of the preceding aspects, wherein the ethylene polymer has an IB parameter within any range disclosed herein, for example, 1.7 to 2.4, 1.7 to 2.3, 1.7 to 2.2, 1.8 to 2.3, 1.8 to 2.2, 1.8 to 2.1, 1.9 to 2.3, 1.9 to 2.2, 2 to 2.4, 2 to 2.3, 2 to 2.2, or 2 to 2.1.

[0121] Aspect 14. A polymer as defined in any of the preceding aspects, wherein said ethylene polymer has environmental stress cracking resistance (ESCR) within any range disclosed herein, for example, at least 1,000 hours, at least 1,500 hours, at least 2,000 hours, at least 2,500 hours, at least 2,800 hours, at least 3,000 hours, or at least 3,500 hours (Condition B, 10% Igepal).

[0122] Aspect 15. A polymer as defined in any of the preceding aspects, wherein said ethylene polymer has a zero shear viscosity (η0) within any range disclosed herein, for example, 40,000 to 140,000, 50,000 to 130,000, 50,000 to 110,000, 50,000 to 100,000, 60,000 to 120,000, 60,000 to 100,000, 60,000 to 90,000, or 70,000 to 85,000 Pa-sec.

[0123] Aspect 16. A polymer as defined in any of the preceding aspects, wherein said ethylene polymer has a strength within any range disclosed herein, for example, 1.8 to 3.2, 2 to 3, 2.1 to 2.8, 2.1 to 2.7, 2.2 to 2.7, 2.3 to 2.7, or 2.3 to 2.6 degrees in 0.1 sec. -1 The tan δ (tan d or tangent δ) below.

[0124] Aspect 17. A polymer as defined in any of the preceding aspects, wherein said ethylene polymer has a strength within any range disclosed herein, for example, 0.5 to 1, 0.5 to 0.9, 0.6 to 1, 0.6 to 0.9, 0.6 to 0.8, 0.65 to 0.9, 0.65 to 0.8, 0.7 to 0.9, or 0.7 to 0.8 degrees at 100 sec. -1 The tan δ (tan d or tangent δ) below.

[0125] Aspect 18. The polymer as defined in any of the preceding aspects, wherein the ethylene polymer has a CY-a parameter within any range disclosed herein, for example, 0.18 to 0.33, 0.2 to 0.32, 0.2 to 0.3, 0.22 to 0.3, 0.24 to 0.3, 0.24 to 0.28 or 0.25 to 0.28.

[0126] Aspect 19. The polymer as defined in any of the preceding aspects, wherein the ethylene polymer has a relaxation time (Tau(eta) or τ(η)) within any range disclosed herein, for example, 0.1 to 0.8, 0.2 to 0.7, 0.2 to 0.6, 0.3 to 0.7, 0.3 to 0.6 or 0.3 to 0.5 sec.

[0127] Aspect 20. A polymer as defined in any of the preceding aspects, wherein said ethylene polymer has a strength within any range disclosed herein, for example, 1,000 to 1,800, 1,100 to 1,700, 1,100 to 1,600, 1,100 to 1,500, 1,200 to 1,800, 1,200 to 1,700, 1,200 to 1,600, 1,200 to 1,500, 1,300 to 1,700, 1,300 to 1,600, or 1,300 to 1,500 Pa-sec. -1 The viscosity at the specified value (eta @ 100 or η @ 100).

[0128] Aspect 21. A polymer as defined in any of the preceding aspects, wherein said ethylene polymer has a range within any scope disclosed herein, for example, 14 to 24, 15 to 22, 16 to 21, 17 to 20, or 18 to 19, in 0.1 sec. -1 The viscosity at 100 sec (eta @ 0.1 or η @ 0.1) is compared with that at 100 sec. -1 The ratio of the viscosity (eta @ 100 or η @ 100) at the specified values.

[0129] Aspect 22. The polymer as defined in any of the preceding aspects, wherein the amount of said lower molecular weight component (determined by deconvolution based on the total polymer) is within any weight percentage range disclosed herein, for example, 40 to 60 wt.%, 40 to 55 wt.%, 42 to 55 wt.%, 45 to 55 wt.%, or 47 to 54 wt.%.

[0130] Aspect 23. The polymer as defined in any of the preceding aspects, wherein the higher molecular weight component has a Mw in any range disclosed herein, for example, 200,000 to 500,000, 250,000 to 450,000, 300,000 to 400,000 or 320,000 to 380,000 g / mol.

[0131] Aspect 24. The polymer as defined in any of the preceding aspects, wherein the higher molecular weight component has Mn in any range disclosed herein, for example, 25,000 to 55,000, 30,000 to 50,000, 33,000 to 47,000, 35,000 to 45,000 or 37,000 to 43,000 g / mol.

[0132] Aspect 25. The polymer as defined in any of the preceding aspects, wherein the higher molecular weight component has a Mw / Mn ratio in any range disclosed herein, for example, 6 to 11, 6 to 10, 6 to 9, 7 to 11, 7 to 10, 7 to 9, 8 to 11, 8 to 10 or 8 to 9.

[0133] Aspect 26. The polymer as defined in any of the preceding aspects, wherein the lower molecular weight component has a Mw in any range disclosed herein, for example, 25,000 to 50,000, 30,000 to 45,000, 30,000 to 40,000, 35,000 to 45,000 or 35,000 to 40,000 g / mol.

[0134] Aspect 27. The polymer as defined in any of the preceding aspects, wherein the lower molecular weight component has a Mw / Mn ratio in any range disclosed herein, for example, 4 to 8, 4.5 to 7.5, 4.5 to 7, 5 to 7.5, 5 to 7, 5.5 to 7, 5.5 to 7, 5.5 to 7, 5.5 to 6.5 or 5.8 to 6.2.

[0135] Aspect 28. The polymer as defined in any of the preceding aspects, wherein the amount of the higher molecular weight component (determined by comparing the ethylene consumption in the first reactor with the total ethylene consumption) is within any weight percentage range disclosed herein, for example, 40 to 60 wt.%, 42 to 58 wt.%, 42 to 55 wt.%, 42 to 52 wt.%, or 45 to 55 wt.%.

[0136] Aspect 29. The polymer as defined in any of the preceding aspects, wherein the higher molecular weight component has a (calculated) HLMI in any range disclosed herein, for example, 0.9 to 2.5, 1 to 2.4, 1.1 to 2.3, 1.3 to 2.2, 1.3 to 2, 1.4 to 2.2, 1.4 to 2, 1.5 to 2.2 or 1.5 to 2 g / 10 min.

[0137] Aspect 30. The polymer as defined in any of the preceding aspects, wherein said lower molecular weight component has a molecular weight within any range disclosed herein, for example, 0.96 to 0.975, 0.96 to 0.973, 0.962 to 0.975, 0.962 to 0.973, 0.965 to 0.975, or 0.965 to 0.973 g / cm³. 3 The (calculated) density.

[0138] Aspect 31. The polymer as defined in any of the preceding aspects, wherein the lower molecular weight component has a (calculated) HLMI in any range disclosed herein, for example, 800 to 3,000, 800 to 2,500, 1,000 to 3,000, 1,000 to 2,800, 1,000 to 2,500, 1,200 to 2,600 or 1,400 to 2,400 g / 10 min.

[0139] Aspect 32. The polymer as defined in any of the preceding aspects, wherein said ethylene polymer has a yield strength (ASTM D638 tensile) in any range disclosed herein, for example, 3,000 to 5,000, 3,300 to 4,700, 3,500 to 4,500, 3,500 to 4,200, 3,700 to 4,500 or 3,700 to 4,100 psi.

[0140] Aspect 33. The polymer as defined in any of the preceding aspects, wherein said ethylene polymer has an elongation at break (ASTM D638 tensile) within any range disclosed herein, for example, 700% to 1,000%, 700% to 950%, 750% to 950%, 800% to 1,000%, 800% to 950%, or 800% to 900%.

[0141] Aspect 34. A polymer as defined in any of the preceding aspects, wherein said ethylene polymer has a tensile modulus (ASTM D638 tensile) within any range disclosed herein, for example, 200,000 to 300,000, 200,000 to 280,000, 220,000 to 300,000, or 220,000 to 280,000 psi.

[0142] Aspect 35. A polymer as defined in any of the preceding aspects, wherein said ethylene polymer has a tangential modulus (ASTM D790 bending) within any range disclosed herein, for example, 150,000 to 250,000, 170,000 to 230,000, 180,000 to 220,000, or 190,000 to 210,000 psi.

[0143] Aspect 36. The polymer as defined in any of the preceding aspects, wherein the ethylene polymer has a flexural modulus (2% secant) (ASTM D790 flexural) within any range disclosed herein, for example, 100,000 to 180,000, 125,000 to 175,000, 140,000 to 160,000 or 145,000 to 155,000 psi.

[0144] Aspect 37. A polymer as defined in any of the preceding aspects, wherein said ethylene polymer has an NCLS (ASTM F2136) of any range disclosed herein, such as 80 to 1,000, 80 to 800, 100 to 1,000, 100 to 800, 150 to 1,000, 150 to 800, or 150 to 700 hours; additionally or alternatively, said ethylene polymer has an SHM (ISO) of any range disclosed herein, such as 20 to 40, 25 to 40, 25 to 38, 25 to 35, 28 to 40, 28 to 35, 30 to 40, 30 to 38, or 30 to 35 MPa. 18488); Additionally or alternatively, the ethylene polymer has an FNCT (ISO 16770, test temperature of 50°C and test force or pressure of 9 MPa, or test temperature of 80°C and test force or pressure of 6 MPa, or any other combination of test conditions disclosed herein) within any range disclosed herein, such as at least 100 hours, at least 200 hours, at least 500 hours, at least 1000 hours, at least 5,000 hours, at least 10,000 hours or at least 25,000 hours.

[0145] Aspect 38. A polymer as defined in any of the preceding aspects, wherein the ethylene polymer has an HDT (ASTM D648) within any range disclosed herein, for example, 60°C to 90°C, 60°C to 85°C, 65°C to 90°C, 65°C to 85°C, 70°C to 90°C, or 70°C to 85°C.

[0146] Aspect 39. The polymer as defined in any of the preceding aspects, wherein the ethylene polymer has thermal stability within any range disclosed herein, for example, 240°C to 270°C, 240°C to 260°C, 240°C to 255°C, 245°C to 265°C, 245°C to 255°C, or 250°C to 255°C (ASTM D3350).

[0147] Aspect 40. The polymer as defined in any of the preceding aspects, wherein the ethylene polymer has an oxidation induction time (OIT) (ASTM D3895) within any range disclosed herein, for example, 50 to 90 min, 50 to 75 min, 55 to 85 min, 55 to 75 min, or 55 to 70 min.

[0148] Aspect 41. A polymer as defined in any of the preceding aspects, wherein said ethylene polymer has I5 in any range disclosed herein, for example, 0.8 to 2.4, 1 to 2.2, 1 to 2, 1 to 1.8, 1.1 to 2.2, 1.1 to 2, 1.1 to 1.9, 1.2 to 2, 1.2 to 1.9, 1.2 to 1.8, 1.3 to 2.2, 1.3 to 2, 1.3 to 1.9 or 1.3 to 1.8 g / 10 min.

[0149] Aspect 42. The polymer as defined in any of the preceding aspects, wherein the ethylene polymer independently contains less than 0.1 ppm (by weight), less than 0.08 ppm, less than 0.05 ppm or less than 0.03 ppm of Hf, Zr or Cr.

[0150] Aspect 43. The polymer as defined in any of the preceding aspects, wherein the ethylene polymer has a bimodal molecular weight distribution.

[0151] Aspect 44. The polymer as defined in any of the preceding aspects, wherein the ethylene polymer comprises an ethylene / α-olefin copolymer.

[0152] Aspect 45. The polymer as defined in any of the preceding aspects, wherein the ethylene polymer comprises ethylene homopolymer, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer and / or ethylene / 1-octene copolymer.

[0153] Aspect 46. The polymer as defined in any of the preceding aspects, wherein the ethylene polymer comprises an ethylene / 1-hexene copolymer.

[0154] Aspect 47. A polymer composition comprising an ethylene polymer as defined in any of the preceding aspects and any suitable amount of post-consumption recycling (PCR) and / or post-industrial recycling (PIR) resin.

[0155] Aspect 48. An article comprising an ethylene polymer or polymer composition as defined in any of the preceding aspects.

[0156] Aspect 49. An article comprising an ethylene polymer or polymer composition as defined in any one of Aspects 1-47, wherein said article is an agricultural film, automotive part, bottle, chemical container, cylinder, inflatable bag, fiber or fabric, food packaging film or container, food service product, fuel tank, geomembrane, household container, liner, molded product, medical device or material, outdoor storage product, outdoor recreational equipment, pipe, sheet or tape, toy or traffic barrier.

[0157] Aspect 50. An article comprising an ethylene polymer or polymer composition as defined in any one of aspects 1-47, wherein the article is a wire, cable, or conduit.

Claims

1. An ethylene polymer, characterized by: Melt index (MI) in the range of 0.15 to 0.5 g / 10 min; High load melt index (HLMI) in the range of 15 to 50 g / 10 min; Between 0.94 and 0.96 g / cm 3 Density within the range; and A higher molecular weight component (HMW) and a lower molecular weight component (LMW), wherein the higher molecular weight component has (or is characterized by): HMW HL275 in the range of 3 to 8 g / 10 min; and Between 0.92 and 0.94 g / cm 3 HMW density within the range.

2. The polymer of claim 1, wherein: The melt flow index (MI) is in the range of 0.25 to 0.45 g / 10 min; The high-load melt index (HLMI) is in the range of 20 to 45 g / 10 min; The density is between 0.947 and 0.958 g / cm³. 3 Within the range; The HMW HL275 is in the range of 4.2 to 7 g / 10 min; and The density of the HMW is between 0.925 and 0.935 g / cm³. 3 Within the range.

3. The polymer of claim 1 or 2, wherein the ethylene polymer comprises: Environmental stress cracking resistance (ESCR) of at least 1,000 hours (ASTM D1693, Condition B, 10% Igepal); Within the range of 1,000 to 1,800 Pa-sec, in 100 sec -1 Viscosity at the specified values ​​(eta @ 100 or η @ 100); Notched constant toughness stress (NCLS) (ASTM F2136) in the range of 80 to 1,000 hours; or Any combination of them.

4. The polymer as claimed in any of the preceding claims, wherein the ethylene polymer has an environmental stress cracking resistance (ESCR) of at least 2,800 hours (ASTM D1693, Condition B, 10% Igepal).

5. The polymer as claimed in any of the preceding claims, wherein the ethylene polymer has a strength in the range of 1,200 to 1,600 Pa-sec at 100 sec. -1 The viscosity at the specified value (eta @ 100 or η @ 100).

6. The polymer as claimed in any of the preceding claims, wherein the ethylene polymer comprises: Notched constant toughness stress (NCLS) in the range of 150 to 800 hours (ASTM F2136); Full-notch creep test (FNCT) for at least 200 hours at a test temperature of 50°C and a test force or pressure of 9 MPa (ISO 16770); Full-notch creep test (FNCT) for at least 200 hours at a test temperature of 80°C and a test force or pressure of 6 MPa (ISO 16770); or Any combination of them.

7. The polymer as claimed in any of the preceding claims, wherein the ethylene polymer has a yield strength (ASTM D638 tensile strength) in the range of 3,000 to 5,000 psi.

8. The polymer as claimed in any of the preceding claims, wherein the ethylene polymer has a tensile modulus (ASTM D638 tensile) in the range of 200,000 to 300,000 psi.

9. The polymer as claimed in any of the preceding claims, wherein the ethylene polymer comprises: HLMI / MI ratio in the range of 80 to 130; I5 in the range of 1 to 2.2 g / 10 min; or Both.

10. The polymer as claimed in any of the preceding claims, wherein the ethylene polymer comprises: Mn in the range of 7,000 to 16,000 g / mol; Mw in the range of 150,000 to 280,000 g / mol; and Mz in the range of 700,000 to 1,900,000 g / mol.

11. The polymer as claimed in any of the preceding claims, wherein the ethylene polymer comprises: Within the range of 1.8 to 3.2 degrees, in 0.1 sec -1 The tan δ (tan d or tangent δ) below; Within the range of 0.5 to 1 degree, in 100 seconds -1 The tan δ (tan d or tangent δ) below; The CY-a parameter is in the range of 0.18 to 0.33; Relaxation time (Tau(eta) or τ(η)) in the range of 0.1 to 0.8 sec; or Any combination of them.

12. The polymer as claimed in any of the preceding claims, wherein the ethylene polymer comprises: Within the range of 2.2 to 2.7 degrees, at 0.1 sec -1 The tan δ (tan d or tangent δ) below; Within the range of 0.65 to 0.8 degrees, in 100 seconds -1 The tan δ (tan d or tangent δ) below; The CY-a parameter is in the range of 0.2 to 0.32; and Relaxation time (Tau(eta) or τ(η)) in the range of 0.3 to 0.7 sec.

13. The polymer as claimed in any of the preceding claims, wherein: The melt flow index (MI) is in the range of 0.2 to 0.5 g / 10 min; The high-load melt index (HLMI) is in the range of 25 to 40 g / 10 min; The density is between 0.947 and 0.954 g / cm³. 3 Within the range; The HMW HL275 is in the range of 4.2 to 6.5 g / 10 min; and The density of the HMW is between 0.925 and 0.938 g / cm³. 3 Within the range.

14. The polymer of claim 13, wherein the ethylene polymer comprises: Mn in the range of 7,000 to 16,000 g / mol; Mw in the range of 150,000 to 225,000 g / mol; and Mz in the range of 700,000 to 1,900,000 g / mol.

15. The polymer of claim 13 or 14, wherein the ethylene polymer has: The Mw / Mn ratio in the range of 12 to 20; and The Mz / Mw ratio is in the range of 5 to 9.

16. The polymer according to any one of claims 13-15, wherein: The higher molecular weight component is further characterized by an HMW Mw / Mn ratio in the range of 6 to 11; and The lower molecular weight component is characterized by an LMW (Mw / Mn) in the range of 4.5 to 7.5 and a concentration in the range of 0.962 to 0.975 g / cm³. 3 LMW density within the range.

17. The polymer as claimed in any of the preceding claims, wherein the ethylene polymer comprises: Strain hardening modulus (SHM) in the range of 20 to 40 MPa (ISO 18488); Heat distortion temperature (HDT) in the range of 70°C to 90°C (ASTM D648); Thermal stability in the range of 240°C to 260°C (ASTM D3350); Oxidation induction time (OIT) in the range of 50 to 75 minutes (ASTM D3895); or Any combination of them.

18. The polymer as claimed in any of the preceding claims, wherein the ethylene polymer comprises ethylene homopolymer, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer and / or ethylene / 1-octene copolymer.

19. The polymer as claimed in any of the preceding claims, wherein the ethylene polymer independently contains less than 0.1 ppm of hafnium, zirconium and chromium by weight.

20. A polymer composition comprising the polymer of any one of the preceding claims and a post-consumer recycling (PCR) resin and / or an industrial post-recycling (PIR) resin.

21. An article comprising the ethylene polymer or polymer composition as described in any of the preceding claims.

22. The article of claim 21, wherein the article is a wire, cable, or conduit.

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