Thermoplastic compositions comprising bimodal polyethylene and articles made therefrom

Abstract

In various embodiments, bimodal polyethylene may comprise a high molecular weight component and a low molecular weight component. Bimodal polyethylene may have a molecular weight of 0.933 g / cm³. 3 Up to 0.960 g / cm 3 Density, melt index (I2) from 0.3 dg / min to 1.2 dg / min, melt flow ratio (MFR) greater than 80.0 21 Molecular weight distribution greater than 10 (M) w / M n The bimodal polyethylene is provided with a reverse comonomer distribution and a shear thinning index ranging from 5.0 to 20.0. A method for preparing the bimodal polyethylene and articles made from it are also provided.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 061,369, filed August 5, 2020, the entire disclosure of which is hereby incorporated by reference. Technical Field

[0003] The embodiments of this disclosure generally relate to thermoplastic compositions, and more particularly to thermoplastic compositions comprising bimodal polyethylene and articles made therefrom. Background Technology

[0004] When manufacturing insulation and sheathing layers for wires and cables, both the properties (e.g., mechanical properties, resistance to environmental stress cracking, etc.) and processability of the thermoplastic compositions used in the manufacturing process are critical to ensure both manufacturing success and long-term durability during use. While some thermoplastic compositions can possess excellent mechanical properties, such as elongation at break, these superior mechanical properties are often achieved at the expense of processability, resistance to environmental stress cracking, or a combination thereof. Conversely, other thermoplastic compositions may achieve excellent processability at the expense of mechanical properties, resistance to environmental stress cracking, or a combination thereof. Therefore, there remains a continuous need for thermoplastic compositions that balance mechanical properties and processability while maintaining resistance to environmental stress cracking. Summary of the Invention

[0005] The embodiments of this disclosure meet these needs by providing bimodal polyethylene comprising both high-molecular-weight and low-molecular-weight components. The bimodal polyethylene may have a molecular weight of 0.933 g / cm³. 3 Up to 0.960 g / cm 3 Density, melt index (I2) from 0.3 dg / min to 1.2 dg / min, melt flow ratio (MFR) greater than or equal to 80.0 21 Molecular weight distribution greater than or equal to 10 (M) w / M n ), reverse comonomer distribution and shear thinning index of 5.0 to 20.0.

[0006] These and additional features provided by the embodiments of this disclosure will be more fully understood from the following detailed description. Detailed Implementation

[0007] As noted in this article, when manufacturing insulation and sheathing layers for wires and cables, both the properties (e.g., mechanical properties, resistance to environmental stress cracking, etc.) and processability of the thermoplastic compositions used to manufacture the insulation and sheathing layers are critical to ensure both manufacturing success and long-term durability during use. Typically, high-density polyethylene is used to produce thermoplastic compositions to obtain insulation and sheathing layers with improved mechanical properties, and thus improved abrasion resistance for durability and a reduced coefficient of friction for ease of installation. However, high-density polyethylene generally results in poor resistance to environmental stress cracking in the insulation and sheathing layers, leading to brittle fracture. While reducing the density of polyethylene, its melt index, and increasing the load melt index can improve the resistance to environmental stress cracking in the insulation and sheathing layers, this can also reduce the mechanical properties of the insulation and sheathing layers and the processability of the polyethylene.

[0008] The embodiments of this disclosure relate to bimodal polyethylene with a high shear thinning index, exhibiting excellent processability while also achieving significant mechanical properties and resistance to environmental stress cracking. In particular, the embodiments of this disclosure relate to bimodal polyethylene comprising a high molecular weight component and a low molecular weight component. This bimodal polyethylene may have a molecular weight of 0.933 g / cm³. 3 Up to 0.960 g / cm 3 Density, melt index (I2) of 0.3 dg / min to 1.2 dg / min, and melt flow ratio (MFR) greater than or equal to 80.0. 21 Molecular weight distribution greater than or equal to 10 (M) w / M n ), reverse copolymer distribution, and shear thinning index of 5.0 to 20.0.

[0009] The term "polymer" refers to a polymeric compound prepared by polymerizing the same or different types of monomers. Therefore, the general term polymer includes homopolymers, which are polymers prepared by polymerizing only one type of monomer, and copolymers, which are polymers prepared by polymerizing two or more different monomers.

[0010] "Interpolymer" refers to a polymer prepared by polymerizing at least two different types of monomers. Therefore, the general term interpolymer includes copolymers and other polymers prepared by polymerizing two or more different monomers, such as terpolymers.

[0011] The term "unimodal polymer" refers to a polymer characterized by having only one fraction with a common density, weight-average molecular weight, and optional melt index value. A unimodal polymer is also characterized by having only one distinct peak in a gel permeation chromatography (GPC) chromatogram depicting the molecular weight distribution of the composition.

[0012] The term "multimodal polymer" refers to a polymer characterized by having at least two fractions with different densities, weight-average molecular weights, and optionally melt index values. A multimodal polymer is also characterized by having at least two distinct peaks in a gel permeation chromatography (GPC) chromatogram depicting the molecular weight distribution of the composition. Therefore, the general term multimodal polymer includes bimodal polymers having two main fractions: a first fraction, which may be a low molecular weight fraction and / or component; and a second fraction, which may be a high molecular weight fraction and / or component.

[0013] The terms "polyolefin," "polyolefin polymer," and "polyolefin resin" refer to substances produced by making simple olefins (also known as olefins, which have the general formula C) into polyolefins. n H 2n Polyolefins are polymers prepared by polymerization of monomers. Therefore, the general term polyolefins includes polymers prepared by polymerizing ethylene monomers with or without one or more comonomers (such as polyethylene) and polymers prepared by polymerizing propylene monomers with or without one or more comonomers (such as polypropylene).

[0014] The terms "polyethylene" and "vinyl polymer" refer to polyolefins containing more than 50 molar percentages (%) of ethylene monomer-derived units, including polyethylene homopolymers and copolymers. Common forms of polyethylene known in the art include low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ultra-low-density polyethylene (ULDPE), very low-density polyethylene (VLDPE), medium-density polyethylene (MDPE), and high-density polyethylene (HDPE).

[0015] The term "melt flow ratio" refers to the ratio of the polymer's melt index. Therefore, the general term melt flow ratio includes the polymer's high-load melt index (I0). 21 The ratio of the polymer's melt flow ratio to its melt index (I2), also known as the "MFR". 21 ".

[0016] The term "molecular weight distribution" refers to the ratio of the molecular weights of a polymer. Therefore, the general term molecular weight distribution includes: the weight-average molecular weight (M...) of the polymer. w ) and the number-average molecular weight of the polymer (Mn The ratio of molecular weight distribution (M) to molecular weight distribution (M) is also known as the ratio of molecular weight distribution (M). w / M n )”; and the z-average molecular weight of the polymer (M z ) and the weight-average molecular weight of the polymer (M w The ratio of molecular weight distribution (M) to molecular weight distribution (M) is also known as the ratio of molecular weight distribution (M). z / M w )".

[0017] The term "shear thinning index" refers to the ratio of the complex viscosity of a polymer. Therefore, the general term shear thinning index includes the ratio of the complex viscosity of a polymer at a frequency of 0.1 radians per second (rad / s) to the complex viscosity of the polymer at a frequency of 100 rad / s.

[0018] The term "composition" refers to a mixture of materials comprising the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0019] The terms “comprising,” “including,” “having,” and their derivatives are not intended to exclude the presence of any additional components, steps, or procedures, whether or not they are specifically disclosed. For the avoidance of any doubt, unless stated to the contrary, all compositions claimed using the term “comprising” may include any additional additives, adjuvants, or compounds, whether polymerized or otherwise. In contrast, the term “consisting of” excludes from the scope of any subsequent description any other components, steps, or procedures except those not essential for operability. The term “consisting of” excludes any components, steps, or procedures not specifically described or listed.

[0020] In the implementation scheme, bimodal polyethylene can have a content greater than or equal to 0.933 g / cm³. 3 Such as greater than or equal to 0.936 g / cm³ 3 ≥0.939 g / cm 3 ≥0.942 g / cm 3 ≥0.945 g / cm³ 3 ≥0.948 g / cm 3 ≥0.951 g / cm³ 3 ≥0.954 g / cm 3 or greater than or equal to 0.957 g / cm³ 3 The density. Bimodal polyethylene can also have a density of less than or equal to 0.960 g / cm³. 3 Such as less than or equal to 0.957 g / cm³ 3Less than or equal to 0.954 g / cm³ 3 Less than or equal to 0.951 g / cm³ 3 Less than or equal to 0.948 g / cm³ 3 Less than or equal to 0.945 g / cm 3 Less than or equal to 0.942 g / cm³ 3 Less than or equal to 0.939 g / cm³ 3 or less than or equal to 0.936 g / cm³ 3 The density. For example, bimodal polyethylene can have a density of 0.933 g / cm³. 3 Up to 0.960 g / cm 3 0.933g / cm 3 Up to 0.957 g / cm 3 0.933g / cm 3 Up to 0.954 g / cm 3 0.933g / cm 3 Up to 0.951 g / cm 3 0.933g / cm 3 Up to 0.948 g / cm 3 0.933g / cm 3 Up to 0.945 g / cm 3 0.933g / cm 3 Up to 0.942 g / cm 3 0.933g / cm 3 Up to 0.9390 g / cm 3 0.933g / cm 3 Up to 0.936 g / cm 3 0.936 g / cm 3 Up to 0.960 g / cm 3 0.936 g / cm 3 Up to 0.957 g / cm 3 0.936 g / cm 3 Up to 0.954 g / cm 3 0.936 g / cm 3 Up to 0.951 g / cm 3 0.936 g / cm 3 Up to 0.948 g / cm 3 0.936 g / cm 3 Up to 0.945 g / cm 3 0.936 g / cm 3 Up to 0.942 g / cm 3 0.936 g / cm 3 Up to 0.939 g / cm 30.939 g / cm 3 Up to 0.960 g / cm 3 0.939 g / cm 3 Up to 0.957 g / cm 3 0.939 g / cm 3 Up to 0.954 g / cm 3 0.939 g / cm 3 Up to 0.951 g / cm 3 0.939 g / cm 3 Up to 0.948 g / cm 3 0.939 g / cm 3 Up to 0.945 g / cm 3 0.939 g / cm 3 Up to 0.942 g / cm 3 0.942 g / cm 3 Up to 0.960 g / cm 3 0.942 g / cm 3 Up to 0.957 g / cm 3 0.942 g / cm 3 Up to 0.954 g / cm 3 0.942 g / cm 3 Up to 0.951 g / cm 3 0.942 g / cm 3 Up to 0.948 g / cm 3 0.942 g / cm 3 Up to 0.945 g / cm 3 0.945g / cm 3 Up to 0.960 g / cm 3 0.945g / cm 3 Up to 0.957 g / cm 3 0.945g / cm 3 Up to 0.954 g / cm 3 0.945g / cm 3 Up to 0.951 g / cm 3 0.945g / cm 3 Up to 0.948 g / cm 3 0.948g / cm 3 Up to 0.960 g / cm 3 0.948g / cm 3 Up to 0.957 g / cm 3 0.948g / cm 3 Up to 0.954 g / cm 3 0.948 g / cm 3 Up to 0.951 g / cm3 0.951 g / cm 3 Up to 0.960 g / cm 3 0.951 g / cm 3 Up to 0.957 g / cm 3 0.951 g / cm 3 Up to 0.954 g / cm 3 0.954 g / cm 3 Up to 0.960 g / cm 3 0.954 g / cm 3 Up to 0.957 g / cm 3 Or 0.957 g / cm 3 Up to 0.960 g / cm 3 The density. As mentioned above, when the density of bimodal polyethylene is greater than, for example, 0.960 g / cm³. 3 When the density of bimodal polyethylene is less than, for example, 0.933 g / cm³, products made from it may exhibit poor resistance to environmental stress cracking, which can lead to brittle fracture of the insulation and sheath layers. In contrast, when the density of bimodal polyethylene is less than, for example, 0.933 g / cm³, it is much more stable. 3 At this time, the mechanical properties of the product and the processability of bimodal polyethylene may decrease.

[0021] In the embodiments, bimodal polyethylene can have a melt index (I2) greater than or equal to 0.3 dg / min, such as greater than or equal to 0.4 dg / min, greater than or equal to 0.5 dg / min, greater than or equal to 0.6 dg / min, greater than or equal to 0.7 dg / min, greater than or equal to 0.8 dg / min, greater than or equal to 0.9 dg / min, greater than or equal to 1.0 dg / min, or greater than or equal to 1.1 dg / min. Bimodal polyethylene can also have a melt index (I2) less than or equal to 1.2 dg / min, such as less than or equal to 1.1 dg / min, less than or equal to 1.0 dg / min, less than or equal to 0.9 dg / min, less than or equal to 0.8 dg / min, less than or equal to 0.7 dg / min, less than or equal to 0.6 dg / min, less than or equal to 0.5 dg / min, or less than or equal to 0.4 dg / min.For example, bimodal polyethylene can have a flux of 0.3 dg / min to 1.2 dg / min, 0.3 dg / min to 1.1 dg / min, 0.3 dg / min to 1.0 dg / min, 0.3 dg / min to 0.9 dg / min, 0.3 dg / min to 0.8 dg / min, 0.3 dg / min to 0.7 dg / min, 0.3 dg / min to 0.6 dg / min, 0.3 dg / min to 0.5 dg / min, 0.3 dg / min to 0.4 dg / min, 0.4 dg / min to 1.2 dg / min, or 0.4 dg / min to 1.1 dg / min. n, 0.4 dg / min to 1.0 dg / min, 0.4 dg / min to 0.9 dg / min, 0.4 dg / min to 0.8 dg / min, 0.4 dg / min to 0.7 dg / min, 0.4 dg / min to 0.6 dg / min, 0.4 dg / min to 0.5 dg / min, 0.5 dg / min to 1.2 dg / min, 0.5 dg / min to 1.1 dg / min, 0.5 dg / min to 1.0 dg / min, 0.5 dg / min to 0.9 dg / min, 0.5 dg / min to 0.8 dg / min, 0.5 dg / min to 0.7dg / min, 0.5dg / min to 0.6dg / min, 0.6dg / min to 1.2dg / min, 0.6dg / min to 1.1dg / min, 0.6dg / min to 1.0dg / min, 0.6dg / min to 0.9dg / min, 0.6d g / min to 0.8dg / min, 0.6dg / min to 0.7dg / min, 0.7dg / min to 1.2dg / min, 0.7dg / min to 1.1dg / min, 0.7dg / min to 1.0dg / min, 0.7dg / min to 0.9dg / min, Melt index (I2) of 0.7 dg / min to 0.8 dg / min, 0.8 dg / min to 1.2 dg / min, 0.8 dg / min to 1.1 dg / min, 0.8 dg / min to 1.0 dg / min, 0.8 dg / min to 0.9 dg / min, 0.9 dg / min to 1.2 dg / min, 0.9 dg / min to 1.1 dg / min, 0.9 dg / min to 1.0 dg / min, 1.0 dg / min to 1.2 dg / min, 1.0 dg / min to 1.1 dg / min, or 1.1 dg / min to 1.2 dg / min.

[0022] In the implementation scheme, bimodal polyethylene can have a high load melt index (I) greater than or equal to 25.0 dg / min, such as greater than or equal to 35.0 dg / min, greater than or equal to 45.0 dg / min, greater than or equal to 55.0 dg / min, greater than or equal to 65.0 dg / min, greater than or equal to 75.0 dg / min, greater than or equal to 85.0 dg / min, greater than or equal to 95.0 dg / min, greater than or equal to 105.0 dg / min, or greater than or equal to 115.0 dg / min. 21 Bimodal polyethylene can also have a high load melt index (I0) of less than or equal to 125.0 dg / min, such as less than or equal to 115.0 dg / min, less than or equal to 105.0 dg / min, less than or equal to 95.0 dg / min, less than or equal to 85.0 dg / min, less than or equal to 75.0 dg / min, less than or equal to 65.0 dg / min, less than or equal to 55.0 dg / min, less than or equal to 45.0 dg / min, or less than or equal to 35.0 dg / min. 21). For example, 25.0dg / min to 125.0dg / min, 25.0dg / min to 115.0dg / min, 25.0dg / min to 105.0dg / min, 25.0dg / min to 95.0dg / min, 25.0dg / min to 85.0dg / mi n, 25.0dg / min to 75.0dg / min, 25.0dg / min to 65.0dg / min, 25.0dg / min to 55.0dg / min, 25.0dg / min to 45.0dg / min, 25.0dg / min to 35.0dg / min, 35.0dg / min to 1 25.0 dg / min, 35.0 dg / min to 115.0 dg / min, 35.0 dg / min to 105.0 dg / min, 35.0 dg / min to 95.0 dg / min, 35.0 dg / min to 85.0 dg / min, 35.0 dg / min to 75.0 dg / min, 35.0 dg / min to 65.0 dg / min, 35.0 dg / min to 55.0 dg / min, 35.0 dg / min to 45.0 dg / min, 45.0 dg / min to 125.0 dg / min, 45.0 dg / min to 115.0 dg / min, 45.0 dg / min to 10 5.0 dg / min, 45.0 dg / min to 95.0 dg / min, 45.0 dg / min to 85.0 dg / min, 45.0 dg / min to 75.0 dg / min, 45.0 dg / min to 65.0 dg / min, 45.0 dg / min to 55.0 dg / min, 55.0 dg / min to 125.0 dg / min, 55.0 dg / min to 115.0 dg / min, 55.0 dg / min to 105.0 dg / min, 55.0 dg / min to 95.0 dg / min, 55.0 dg / min to 85.0 dg / min, 55.0 dg / min to 75. 0 dg / min, 55.0 dg / min to 65.0 dg / min, 65.0 dg / min to 125.0 dg / min, 65.0 dg / min to 115.0 dg / min, 65.0 dg / min to 105.0 dg / min, 65.0 dg / min to 95.0 dg / min, 65.0 dg / min to 85.0 dg / min, 65.0 dg / min to 75.0 dg / min, 75.0 dg / min to 125.0 dg / min, 75.0 dg / min to 115.0 dg / min, 75.0 dg / min to 105.0 dg / min, 75.0 dg / min to 95.High-load melt flow index (I) of 0 dg / min, 75.0 dg / min to 85.0 dg / min, 85.0 dg / min to 125.0 dg / min, 85.0 dg / min to 115.0 dg / min, 85.0 dg / min to 105.0 dg / min, 85.0 dg / min to 95.0 dg / min, 95.0 dg / min to 125.0 dg / min, 95.0 dg / min to 115.0 dg / min, 95.0 dg / min to 105.0 dg / min, 105.0 dg / min to 125.0 dg / min, 105.0 dg / min to 115.0 dg / min or 115.0 dg / min to 125.0 dg / min. 21 ).

[0023] In the implementation scheme, bimodal polyethylene may have a melt flow ratio (MFR) greater than or equal to 80.0, such as greater than or equal to 90.0, greater than or equal to 100.0, greater than or equal to 110.0, greater than or equal to 120.0, greater than or equal to 130.0, or greater than or equal to 140.0. 21 Bimodal polyethylene can also have melt flow ratios (MFRs) less than or equal to 150.0, such as less than or equal to 140.0, less than or equal to 130.0, less than or equal to 120.0, less than or equal to 110.0, less than or equal to 100.0, or less than or equal to 90.0. 21 For example, bimodal polyethylene can have a content of 80.0 to 150.0, 80.0 to 140.0, 80.0 to 130.0, 80.0 to 120.0, 80.0 to 110.0, 80.0 to 100.0, 80.0 to 90.0, 90.0 to 150.0, 90.0 to 140.0, 90.0 to 130.0, 90.0 to 120.0, 90.0 to 110.0, 90.0 to 100.0, 100.0 to 150.0, 100.0 Melt flow ratios (MFRs) of 140.0, 100.0 to 130.0, 100.0 to 120.0, 100.0 to 110.0, 110.0 to 150.0, 110.0 to 140.0, 110.0 to 130.0, 110.0 to 120.0, 120.0 to 150.0, 120.0 to 140.0, 120.0 to 130.0, 130.0 to 150.0, 130.0 to 140.0, or 140.0 to 150.0 21 When the melt flow ratio (MFR) of bimodal polyethylene is... 21When the melt flow ratio (MFR) of bimodal polyethylene is less than, for example, 80.0, thermoplastic compositions containing bimodal polyethylene may not have sufficient processability to manufacture articles, such as insulation and sheathing layers for wires and cables. Furthermore, when the melt flow ratio (MFR) of bimodal polyethylene is less than, for example, 80.0, thermoplastic compositions containing bimodal polyethylene may not have sufficient processability to manufacture articles, such as insulation and sheathing layers for wires and cables. 21 When the value is less than, for example, 80.0, the insulation and sheathing layers containing bimodal polyethylene may not have the wire smoothness value required for some applications.

[0024] In the embodiments, bimodal polyethylene may have a number-average molecular weight (Mn) greater than or equal to 5,000 g / mol, such as greater than or equal to 10,000 g / mol, greater than or equal to 15,000 g / mol, greater than or equal to 20,000 g / mol, or greater than or equal to 25,000 g / mol. n Bimodal polyethylene can also have a number-average molecular weight (Mn) of less than or equal to 30,000 g / mol, such as less than or equal to 25,000 g / mol, less than or equal to 20,000 g / mol, less than or equal to 15,000 g / mol, or less than or equal to 10,000 g / mol. n For example, bimodal polyethylene can have concentrations of 5,000 g / mol to 30,000 g / mol, 5,000 g / mol to 25,000 g / mol, 5,000 g / mol to 20,000 g / mol, 5,000 g / mol to 15,000 g / mol, 5,000 g / mol to 10,000 g / mol, 10,000 g / mol to 30,000 g / mol, 10,000 g / mol to 25,000 g / mol, 10,000 g / mol to Number-average molecular weights (Mi) of 20,000 g / mol, 10,000 g / mol to 15,000 g / mol, 15,000 g / mol to 30,000 g / mol, 15,000 g / mol to 25,000 g / mol, 15,000 g / mol to 20,000 g / mol, 20,000 g / mol to 30,000 g / mol, 20,000 g / mol to 25,000 g / mol, or 25,000 g / mol to 30,000 g / mol. n ).

[0025] In the embodiments, bimodal polyethylene may have a weight-average molecular weight (M0.05) greater than or equal to 100,000 g / mol, such as greater than or equal to 115,000 g / mol, greater than or equal to 130,000 g / mol, greater than or equal to 145,000 g / mol, or greater than or equal to 160,000 g / mol. wBimodal polyethylene can also have a weight-average molecular weight (Mg) of less than or equal to 175,000 g / mol, such as less than or equal to 160,000 g / mol, less than or equal to 145,000 g / mol, less than or equal to 130,000 g / mol, or less than or equal to 115,000 g / mol. w For example, bimodal polyethylene can have concentrations of 100,000 g / mol to 175,000 g / mol, 100,000 g / mol to 160,000 g / mol, 100,000 g / mol to 145,000 g / mol, 100,000 g / mol to 130,000 g / mol, 100,000 g / mol to 115,000 g / mol, 115,000 g / mol to 175,000 g / mol, 115,000 g / mol to 160,000 g / mol, and 115,000 g / mol. Weight-average molecular weight (M) from 115,000 g / mol to 130,000 g / mol, 130,000 g / mol to 175,000 g / mol, 130,000 g / mol to 160,000 g / mol, 130,000 g / mol to 145,000 g / mol, 145,000 g / mol to 175,000 g / mol, 145,000 g / mol to 160,000 g / mol, or 160,000 g / mol to 175,000 g / mol. w ).

[0026] In the implementation scheme, bimodal polyethylene may have a z-average molecular weight (Mg) greater than or equal to 500,000 g / mol, such as greater than or equal to 700,000 g / mol, greater than or equal to 900,000 g / mol, greater than or equal to 1,100,000 g / mol, greater than or equal to 1,300,000 g / mol, greater than or equal to 1,500,000 g / mol, greater than or equal to 1,700,000 g / mol, greater than or equal to 1,900,000 g / mol, greater than or equal to 2,100,000 g / mol, greater than or equal to 2,300,000 g / mol, or greater than or equal to 2,500,000 g / mol. zBimodal polyethylene can also have a z-average molecular weight (Mg) of less than or equal to 2,700,000 g / mol, such as less than or equal to 2,500,000 g / mol, less than or equal to 2,300,000 g / mol, less than or equal to 2,100,000 g / mol, less than or equal to 1,900,000 g / mol, less than or equal to 1,700,000 g / mol, less than or equal to 1,500,000 g / mol, less than or equal to 1,300,000 g / mol, less than or equal to 1,100,000 g / mol, less than or equal to 900,000 g / mol, or less than or equal to 700,000 g / mol. z For example, bimodal polyethylene can have concentrations from 500,000 g / mol to 1,500,000 g / mol, 500,000 g / mol to 1,300,000 g / mol, 500,000 g / mol to 1,100,000 g / mol, 500,000 g / mol to 900,000 g / mol, 500,000 g / mol to 700,000 g / mol, 700,000 g / mol to 1,500,000 g / mol, 700,000 g / mol to 1,300,000 g / mol, 700,000 g / mol to 1,100,000 g / mol, 500,000 g / mol to 900,000 g / mol, 500,000 g / mol to 700,000 g / mol, 700,000 g / mol to 1,1 ... z-average molecular weight (M2) of 100,000 g / mol, 700,000 g / mol to 900,000 g / mol, 900,000 g / mol to 1,500,000 g / mol, 900,000 g / mol to 1,300,000 g / mol, 900,000 g / mol to 1,100,000 g / mol, 1,100,000 g / mol to 1,500,000 g / mol, 1,100,000 g / mol to 1,300,000 g / mol, or 1,300,000 g / mol to 1,500,000 g / mol z ).

[0027] In the implementation plan, the weight-average molecular weight (M) of bimodal polyethylene is... w ) and the number-average molecular weight (M) of bimodal polyethylene n The ratio can be greater than or equal to 10, such as greater than or equal to 12, greater than or equal to 14, greater than or equal to 16, or greater than or equal to 18. The weight-average molecular weight (M) of bimodal polyethylene... w ) and the number-average molecular weight (M) of bimodal polyethylene n The ratio can also be less than or equal to 20, such as less than or equal to 18, less than or equal to 16, less than or equal to 14, or less than or equal to 12. For example, the weight-average molecular weight (M) of bimodal polyethylene w ) and the number-average molecular weight (M) of bimodal polyethylene nThe ratio of ) can be 10 to 20, 10 to 18, 10 to 16, 10 to 14, 10 to 12, 12 to 20, 12 to 18, 12 to 16, 12 to 14, 14 to 20, 14 to 18, 14 to 16, 16 to 20, 16 to 18, or 18 to 20. When the weight-average molecular weight (M) of bimodal polyethylene w ) and the number-average molecular weight (M) of bimodal polyethylene n When the ratio of bimodal polyethylene to its molecular weight is less than, for example, 10, the thermoplastic composition containing bimodal polyethylene may not have sufficient processability to manufacture articles, such as insulation and sheathing layers for wires and cables. Furthermore, when the weight-average molecular weight (M) of bimodal polyethylene is less than, for example, 10, the thermoplastic composition containing bimodal polyethylene may not have sufficient processability to manufacture articles, such as insulation and sheathing layers for wires and cables. w ) and the number-average molecular weight (M) of bimodal polyethylene n When the ratio is less than, for example, 10, the insulation and sheathing layers containing bimodal polyethylene may not have the wire smoothness values ​​required for some applications.

[0028] In the implementation plan, the z-average molecular weight (M) of bimodal polyethylene is... z ) and the weight-average molecular weight (M) of bimodal polyethylene w The ratio can be greater than or equal to 4, such as greater than or equal to 6, greater than or equal to 8, greater than or equal to 10, greater than or equal to 12, or greater than or equal to 14. The z-average molecular weight (M) of bimodal polyethylene... z ) and the weight-average molecular weight (M) of bimodal polyethylene w The ratio can also be less than or equal to 16, such as less than or equal to 14, less than or equal to 12, less than or equal to 10, less than or equal to 8, or less than or equal to 6. For example, the z-average molecular weight (M) of bimodal polyethylene z ) and the weight-average molecular weight (M) of bimodal polyethylene w The ratio can be 4 to 16, 4 to 14, 4 to 12, 4 to 10, 4 to 8, 4 to 6, 6 to 16, 6 to 14, 6 to 12, 6 to 10, 6 to 8, 8 to 16, 8 to 14, 8 to 12, 8 to 10, 10 to 16, 10 to 14, 10 to 12, 12 to 16, 12 to 14, or 14 to 16.

[0029] In the embodiments, the low molecular weight component of bimodal polyethylene may have a short-chain branched distribution (SCBD1) greater than or equal to 0.1, such as greater than or equal to 1.0, greater than or equal to 2.0, greater than or equal to 3.0, greater than or equal to 4.0, greater than or equal to 5.0, greater than or equal to 6.0, greater than or equal to 7.0, greater than or equal to 8.0, or greater than or equal to 9.0. The low molecular weight component of bimodal polyethylene may also have a short-chain branched distribution (SCBD1) less than or equal to 10.0, such as less than or equal to 9.0, less than or equal to 8.0, less than or equal to 7.0, less than or equal to 6.0, less than or equal to 5.0, less than or equal to 4.0, less than or equal to 3.0, less than or equal to 2.0, or less than or equal to 1.0. For example, the low molecular weight component of bimodal polyethylene can have a molecular weight of 0.1 to 10.0, 0.1 to 9.0, 0.1 to 8.0, 0.1 to 7.0, 0.1 to 6.0, 0.1 to 5.0, 0.1 to 4.0, 0.1 to 3.0, 0.1 to 2.0, 0.1 to 1.0, 1.0 to 10.0, 1.0 to 9.0, 1.0 to 8.0, 1.0 to 7.0, 1.0 to 6.0, 1.0 to 5.0, 1.0 to 4.0, 1.0 to 3.0, 1.0 to 2.0, 2.0 to 10.0, 2.0 to 9.0, 2.0 to 8.0, 2.0 to 7.0, 2.0 to 6.0, 2.0 to 5.0, 2.0 to 4.0, 2.0 to 3.0, or 3.0. Short-chain branched distributions (SCBD1) up to 10.0, 3.0 to 9.0, 3.0 to 8.0, 3.0 to 7.0, 3.0 to 6.0, 3.0 to 5.0, 3.0 to 4.0, 4.0 to 10.0, 4.0 to 9.0, 4.0 to 8.0, 4.0 to 7.0, 4.0 to 6.0, 4.0 to 5.0, 5.0 to 10.0, 5.0 to 9.0, 5.0 to 8.0, 5.0 to 7.0, 5.0 to 7.0, 5.0 to 6.0, 6.0 to 10.0, 6.0 to 9.0, 6.0 to 7.0, 7.0 to 10.0, 7.0 to 9.0, 7.0 to 8.0, 8.0 to 10.0, 8.0 to 9.0, or 9.0 to 10.0.

[0030] In the implementation scheme, the high molecular weight component of bimodal polyethylene may have a short-chain branched distribution (SCBD2) with a molecular weight greater than or equal to 3.0, such as greater than or equal to 4.0, greater than or equal to 5.0, greater than or equal to 6.0, greater than or equal to 7.0, greater than or equal to 8.0, greater than or equal to 9.0, greater than or equal to 10.0, greater than or equal to 11.0, greater than or equal to 12.0, greater than or equal to 13.0, greater than or equal to 14.0, greater than or equal to 15.0, greater than or equal to 16.0, greater than or equal to 17.0, greater than or equal to 18.0, or greater than or equal to 19.0. The high molecular weight component of bimodal polyethylene can also have a short-chain branched distribution (SCBD2) with a molecular weight of less than or equal to 20.0, such as less than or equal to 19.0, less than or equal to 18.0, less than or equal to 17.0, less than or equal to 16.0, less than or equal to 15.0, less than or equal to 14.0, less than or equal to 13.0, less than or equal to 12.0, less than or equal to 11.0, less than or equal to 10.0, less than or equal to 9.0, less than or equal to 8.0, less than or equal to 7.0, less than or equal to 6.0, less than or equal to 5.0, or less than or equal to 4.0. For example, the high molecular weight components of bimodal polyethylene can have values ​​of 3.0 to 20.0, 3.0 to 19.0, 3.0 to 18.0, 3.0 to 17.0, 3.0 to 16.0, 3.0 to 15.0, 3.0 to 14.0, 3.0 to 13.0, 3.0 to 12.0, 3.0 to 11.0, 3.0 to 10.0, 3.0 to 9.0, 3.0 to 8.0, 3.0 to 7.0, 3.0 to 6.0. 5.0 to 5.0, 3.0 to 4.0, 4.0 to 20.0, 4.0 to 19.0, 4.0 to 18.0, 4.0 to 17.0, 4.0 to 16.0, 4.0 to 15.0, 4.0 to 14.0, 4.0 to 13.0, 4.0 to 12.0, 4.0 to 11.0, 4.0 to 10.0, 4.0 to 9.0, 4.0 to 8.0, 4.0 to 7.0, 4.0 to 6.0, 4.0 to 5.0, 5.0 to 20.0, 5.0 to 19.0, 5.0 to 18.0, 5.0 to 17.0, 5.0 to 16.0, 5.0 to 15.0, 5.0 to 14.0, 5.0 to 13.0, 5.0 to 12.0, 5.0 to 11.0, 5.0 to 10.0, 5.0 to 9.0, 5.0 to 8.0, 5.0 to 7.0, 5.0 to 6.0, 6.0 to 20.0, 6.0 to 19 0, 6.0 to 18.0, 6.0 to 17.0, 6.0 to 16.0, 6.0 to 15.0, 6.0 to 14.0, 6.0 to 13.0, 6.0 to 12.0, 6.0 to 11.0, 6.0 to 10.0, 6.0 to 9.0, 6.0 to 8.0, 6.0 to 7.0, 7.0 to 20.0, 7.0 to 19.0, 7.0 to 18.0, 7.0 to 17.0, 7.0 to 16.0.0, 7.0 to 15.0, 7.0 to 14.0, 7.0 to 13.0, 7.0 to 12.0, 7.0 to 11.0, 7.0 to 10.0, 7.0 to 9.0, 7.0 to 8.0, 8.0 to 20.0, 8.0 to 19.0, 8.0 to 18.0, 8.0 to 17.0, 8.0 to 16.0, 8.0 to 15.0, 8.0 to 14.0, 8.0 to 13.0, 8.0 to 12.0, 8.0 to 11.0, 8.0 to 10.0, 8.0 to 9.0, 9.0 to 20.0, 9.0 to 19.0, 9.0 to 18.0, 9.0 to 17.0, 9.0 to 16.0, 9.0 to 15.0, 9.0 to 14.0, 9.0 to 13.0, 9.0 to 12.0, 9.0 to 11.0, 9.0 to 10.0, 10.0 to 20.0, 10.0 to 19.0, 10.0 to 18.0, 10.0 to 17.0, 10.0 to 16.0, 10.0 to 15.0, 10.0 to 14.0, 10.0 to 13.0, 10.0 to 12.0, 10.0 to 11.0, 11.0 to 20.0, 11.0 to 19.0, 11.0 to 18.0, 11.0 to 17.0, 11. 0 to 16.0, 11.0 to 15.0, 11.0 to 14.0, 11.0 to 13.0, 11.0 to 12.0, 12.0 to 20.0, 12.0 to 19.0, 12.0 to 18.0, 12.0 to 17.0, 12.0 to 16.0, 12.0 to 15.0, 12.0 to 14.0, 12.0 to 13.0, 13.0 to 20.0, 13.0 to 19.0, 13.0 to 18.0, 13.0 to 17.0, 13.0 to 16.0, 13.0 to 15.0, 13.0 to 14.0, 14.0 to 20.0, 14. Short-chain branched distributions (SCBD2) with values ​​from 0 to 19.0, 14.0 to 18.0, 14.0 to 17.0, 14.0 to 16.0, 14.0 to 15.0, 15.0 to 20.0, 15.0 to 19.0, 15.0 to 18.0, 15.0 to 17.0, 17.0 to 20.0, 17.0 to 18.0, 18.0 to 20.0, 18.0 to 19.0, or 19.0 to 20.0.

[0031] In the embodiments, bimodal polyethylene may have a reverse comonomer distribution. More simply, in the embodiments, the ratio of the short-chain branching distribution (SCBD2) of the high molecular weight component of the bimodal polyethylene to the short-chain branching distribution (SCBD1) of the low molecular weight component of the bimodal polyethylene may be greater than 1.0. Without being constrained by any particular theory, it is believed that bimodal polyethylene with a reverse comonomer distribution can have improved environmental stress cracking resistance (ESCR) and balanced mechanical properties compared to bimodal polyethylene with a normal or flat comonomer distribution.

[0032] In the embodiments, the complex viscosity of bimodal polyethylene at 190°C and a frequency of 0.1 rad / s can be greater than or equal to 5,000 Pa·s, such as greater than or equal to 10,000 Pa·s, greater than or equal to 15,000 Pa·s, greater than or equal to 20,000 Pa·s, greater than or equal to 25,000 Pa·s, or greater than or equal to 30,000 Pa·s. The complex viscosity of bimodal polyethylene at 190°C and a frequency of 0.1 rad / s can also be less than or equal to 35,000 Pa·s, such as less than or equal to 30,000 Pa·s, less than or equal to 25,000 Pa·s, less than or equal to 20,000 Pa·s, less than or equal to 15,000 Pa·s, or less than or equal to 10,000 Pa·s. For example, the complex viscosity of bimodal polyethylene at 190°C and a frequency of 0.1 rad / s can be 5,000 Pa·s to 35,000 Pa·s, 5,000 Pa·s to 30,000 Pa·s, 5,000 Pa·s to 25,000 Pa·s, 5,000 Pa·s to 20,000 Pa·s, 5,000 Pa·s to 15,000 Pa·s, 5,000 Pa·s to 10,000 Pa·s, 10,000 Pa·s to 35,000 Pa·s, 10,000 Pa·s to 30,000 Pa·s, 10,000 Pa·s to 25,000 Pa·s, and 10,000 Pa·s to 20,000 Pa·s. •s, 10,000 Pa·s to 15,000 Pa·s, 15,000 Pa·s to 35,000 Pa·s, 15,000 Pa·s to 30,000 Pa·s, 15,000 Pa·s to 25,000 Pa·s, 15,000 Pa·s to 20,000 Pa·s, 20,000 Pa·s to 35,000 Pa·s, 20,000 Pa·s to 30,000 Pa·s, 20,000 Pa·s to 25,000 Pa·s, 25,000 Pa·s to 35,000 Pa·s, 25,000 Pa·s to 30,000 Pa·s or 30,000 Pa·s to 35,000 Pa·s.

[0033] In the embodiments, the complex viscosity of bimodal polyethylene at 190°C and a frequency of 1.0 rad / s can be greater than or equal to 5,000 Pa·s, such as greater than or equal to 7,500 Pa·s, greater than or equal to 10,000 Pa·s, greater than or equal to 12,500 Pa·s, greater than or equal to 15,000 Pa·s, or greater than or equal to 17,500 Pa·s. The complex viscosity of bimodal polyethylene at 190°C and a frequency of 1.0 rad / s can also be less than or equal to 20,000 Pa·s, such as less than or equal to 17,500 Pa·s, less than or equal to 15,000 Pa·s, less than or equal to 12,500 Pa·s, less than or equal to 10,000 Pa·s, or less than or equal to 7,500 Pa·s. For example, the complex viscosity of bimodal polyethylene at 190°C and a frequency of 1.0 rad / s can be 5,000 Pa·s to 20,000 Pa·s, 5,000 Pa·s to 17,500 Pa·s, 5,000 Pa·s to 15,000 Pa·s, 5,000 Pa·s to 12,500 Pa·s, 5,000 Pa·s to 10,000 Pa·s, 5,000 Pa·s to 7,500 Pa·s, 7,500 Pa·s to 20,000 Pa·s, 7,500 Pa·s to 17,500 Pa·s, 7,500 Pa·s to 15,000 Pa·s, and 7,500 Pa·s to 12,500 Pa·s. s, 7,500 Pa·s to 10,000 Pa·s, 10,000 Pa·s to 20,000 Pa·s, 10,000 Pa·s to 17,500 Pa·s, 10,000 Pa·s to 15,000 Pa·s, 12,500 Pa·s to 15,000 Pa·s, 12,500 Pa·s to 20,000 Pa·s, 12,500 Pa·s to 17,500 Pa·s, 12,500 Pa·s to 15,000 Pa·s, 15,000 Pa·s to 20,000 Pa·s, 5,000 Pa·s to 17,500 Pa·s or 17,500 Pa·s to 20,000 Pa·s.

[0034] In the implementation scheme, the complex viscosity of bimodal polyethylene at 190°C and a frequency of 10 rad / s can be greater than or equal to 1,000 Pa·s, greater than or equal to 2,000 Pa·s, such as greater than or equal to 3,000 Pa·s, greater than or equal to 4,000 Pa·s, greater than or equal to 5,000 Pa·s, greater than or equal to 6,000 Pa·s, greater than or equal to 7,000 Pa·s, greater than or equal to 8,000 Pa·s, or greater than or equal to 9,000 Pa·s. The complex viscosity of bimodal polyethylene at 190°C and a frequency of 10 rad / s can also be less than or equal to 10,000 Pa·s, such as less than or equal to 9,000 Pa·s, less than or equal to 8,000 Pa·s, less than or equal to 7,000 Pa·s, less than or equal to 6,000 Pa·s, less than or equal to 5,000 Pa·s, less than or equal to 4,000 Pa·s, less than or equal to 3,000 Pa·s, or less than or equal to 2,000 Pa·s.For example, the complex viscosity of bimodal polyethylene at 190°C and a frequency of 10 rad / s can be 1,000 Pa·s to 10,000 Pa·s, 1,000 Pa·s to 9,000 Pa·s, 1,000 Pa·s to 8,000 Pa·s, 1,000 Pa·s to 7,000 Pa·s, 1,000 Pa·s to 6,000 Pa·s, 1,000 Pa·s to 5,000 Pa·s, 1,000 Pa·s to 4,000 Pa·s, 1,000 Pa·s to 3,000 Pa·s, 1,000 Pa·s to 2,000 Pa·s, 2,000 Pa·s to 10,000 Pa·s. 2,000 Pa·s to 9,000 Pa·s, 2,000 Pa·s to 8,000 Pa·s, 2,000 Pa·s to 7,000 Pa·s, 2,000 Pa·s to 6,000 Pa·s, 2,000 Pa·s to 5,000 Pa·s, 2,000 Pa·s to 4,000 Pa·s, 2,000 Pa·s to 3,000 Pa·s, 3,000 Pa·s to 10,000 Pa·s, 3,000 Pa·s to 9,000 Pa·s, 3,000 Pa·s to 8,000 Pa·s, 3,000 Pa·s to 7,000 Pa·s, 3,000 Pa·s to 6,000 Pa·s Pa·s, 3,000 Pa·s to 5,000 Pa·s, 3,000 Pa·s to 4,000 Pa·s, 4,000 Pa·s to 10,000 Pa·s, 4,000 Pa·s to 9,000 Pa·s, 4,000 Pa·s to 8,000 Pa·s, 4,000 Pa·s to 7,000 Pa·s, 4,000 Pa·s to 6,000 Pa·s, 4,000 Pa·s to 5,000 Pa·s, 5,000 Pa·s to 10,000 Pa·s, 5,000 Pa·s to 9,000 Pa·s, 5,000 Pa·s to 8,000 Pa·s, 5 ...9,000 Pa·s, 5,000 Pa·s to 8,000 Pa·s, 5,000 Pa·s to 9,000 Pa·s, 5,000 Pa·s to 8,000 Pa·s, 5,000 Pa·s to 9,000 Pa·s, 5,000 Pa·s to 9,000 Pa·s, 5,000 Pa·s to 8,000 Pa·s, 5,000 Pa·s to 9,000 Pa·s, 5,0 s to 7,000 Pa·s, 5,000 Pa·s to 6,000 Pa·s, 6,000 Pa·s to 10,000 Pa·s, 6,000 Pa·s to 9,000 Pa·s, 6,000 Pa·s to 8,000 Pa·s, 6,000 Pa·s to 7,000 Pa·s, 7,000 Pa·s to 10,000 Pa·s, 7,000 Pa·s to 9,000 Pa·s, 7,000 Pa·s to 8,000 Pa·s, 8,000 Pa·s to 10,000 Pa·s, 8,000 Pa·s to 9,000 Pa·s or 9,000 Pa·s to 10,000 Pa·s.

[0035] In the embodiments, the complex viscosity of bimodal polyethylene at 190°C and a frequency of 100 rad / s can be greater than or equal to 500 Pa·s, such as greater than or equal to 800 Pa·s, greater than or equal to 1,100 Pa·s, greater than or equal to 1,400 Pa·s, or greater than or equal to 1,700 Pa·s. The complex viscosity of bimodal polyethylene at 190°C and a frequency of 100 rad / s can also be less than or equal to 2,000 Pa·s, such as less than or equal to 1,700 Pa·s, less than or equal to 1,400 Pa·s, less than or equal to 1,100 Pa·s, or less than or equal to 800 Pa·s. For example, the complex viscosity of bimodal polyethylene at 190°C and a frequency of 100 rad / s can be 500 Pa·s to 2,000 Pa·s, 500 Pa·s to 1,700 Pa·s, 500 Pa·s to 1,400 Pa·s, 500 Pa·s to 1,100 Pa·s, 500 Pa·s to 800 Pa·s, 800 Pa·s to 2,000 Pa·s, and 800 Pa·s to 1,700 Pa·s. 800 Pa·s to 1,400 Pa·s, 800 Pa·s to 1,100 Pa·s, 1,100 Pa·s to 2,000 Pa·s, 1,100 Pa·s to 1,700 Pa·s, 1,100 Pa·s to 1,400 Pa·s, 1,400 Pa·s to 2,000 Pa·s, 1,400 Pa·s to 1,700 Pa·s, or 1,700 Pa·s to 2,000 Pa·s.

[0036] In the implementation scheme, the ratio of the complex viscosity of bimodal polyethylene at 190°C and a frequency of 0.1 rad / s to the complex viscosity of bimodal polyethylene at 190°C and a frequency of 100 rad / s (i.e., the shear thinning index (SHI)) can be greater than or equal to 5.0, such as greater than or equal to 7.5, greater than or equal to 10.0, greater than or equal to 12.5, greater than or equal to 15.0, or greater than or equal to 17.5. The ratio of the complex viscosity of bimodal polyethylene at 190°C and a frequency of 0.1 rad / s to the complex viscosity of bimodal polyethylene at 190°C and a frequency of 100 rad / s can also be less than or equal to 20.0, such as less than or equal to 17.5, less than or equal to 15.0, less than or equal to 12.5, less than or equal to 10.0, or less than or equal to 7.5. For example, the ratio of the complex viscosity of bimodal polyethylene at 190°C and a frequency of 0.1 rad / s to the complex viscosity of bimodal polyethylene at 190°C and a frequency of 100 rad / s can be 5.0 to 20.0, 5.0 to 17.5, 5.0 to 15.0, 5.0 to 12.5, 5.0 to 10.0, 5.0 to 7.5, 7.5 to 20.0, 7.5 to 17.5, 7.5 to 15.0, 7.5 to 12.5, 7.5 to 10.0, 10.0 to 20.0, 10.0 to 17.5, 10.0 to 15.0, 10.0 to 12.5, 12.5 to 20.0, 12.5 to 17.5, 12.5 to 15.0, 15.0 to 20.0, 15.0 to 17.5, or 17.5 to 20.0. When the shear thinning index (SHI) of bimodal polyethylene is less than, for example, 5.0, thermoplastic compositions containing bimodal polyethylene may not have sufficient processability to manufacture articles, such as insulation and sheathing layers for wires and cables.

[0037] In the implementation scheme, bimodal polyethylene may be ethylene monomer and at least one C3-C 12 The polymerization product of α-olefin comonomers. For example, embodiments of bimodal polyethylene compositions may be polymerization products of ethylene monomers and 1-butene, 1-hexene, or both. Alternatively, embodiments of bimodal polyethylene compositions may be polymerization products of ethylene monomers and 1-butene, 1-octene, or both. Embodiments of bimodal polyethylene may also be polymerization products of ethylene monomers and 1-hexene, 1-octene, or both. In some embodiments, C3-C 12 The α-olefin comonomer does not have to be propylene. That is, at least one C3-C... 12 α-olefin comonomers may be substantially propylene-free. The term "substantially propylene-free" means that the material or mixture contains less than 1.0% by weight of the compound. For example, at least one C3-C group may be substantially propylene-free. 12The α-olefin comonomer may contain less than 1.0 wt.% propylene, such as less than 0.8 wt.% propylene, less than 0.6 wt.% propylene, less than 0.4 wt.% propylene or less than 0.2 wt.% propylene.

[0038] In embodiments, bimodal polyethylene can be produced in a single reactor using a catalyst system. As used herein, a “catalyst system” may comprise a main catalyst, a trim catalyst, and optionally at least one activator. The catalyst system may also include other components, such as a support, and is not limited to a main catalyst, a trim catalyst, and optionally at least one activator. Embodiments of the catalyst system may include a main catalyst and a metallocene trim catalyst. Embodiments of the catalyst system may also include one or more additives commonly used in the field of olefin polymerization. For example, embodiments of the catalyst system may include one or more continuous additives, flow aids, and antistatic agents. In embodiments, the reactor may be a gas-phase reactor, but a slurry-phase reactor may also be used.

[0039] An embodiment of the catalyst system may include at least one catalyst for producing a high molecular weight fraction of bimodal polyethylene by polymerization (sometimes referred to herein as the “HMW catalyst”), and at least one catalyst compound for producing a low molecular weight fraction of bimodal polyethylene by polymerization (sometimes referred to herein as the “LMW catalyst”).

[0040] HMW and LMW catalysts can exhibit different hydrogen responses. That is, when the molar ratio of hydrogen to ethylene (H2 / C2 molar ratio) is changed, the average molecular weight of polyethylene produced from each catalyst can change differently. The term "high hydrogen response" refers to a catalyst that exhibits a relatively large change in the average molecular weight of polyethylene when the H2 / C2 molar ratio is changed by a set amount. The term "low hydrogen response" refers to a catalyst that exhibits a relatively low change in the average molecular weight of polyethylene when the H2 / C2 molar ratio is changed by the same set amount.

[0041] HMW and LMW catalysts can have different comonomer responses. That is, the comonomer content, such as weight percentage, of polyethylene prepared from each of the catalyst compounds can differ. The term "good binder" refers to a catalyst that exhibits a relatively high degree of comonomer binding, while a "poor binder" binds relatively fewer comonomers. For a catalyst system using a relatively good binder HMW catalyst and a relatively poor binder LMW catalyst, a "reverse comonomer distribution" with a higher comonomer content is produced in the HMW component. Conversely, a good binder LMW catalyst used with a poor binder HMW catalyst produces a "normal comonomer distribution."

[0042] An embodiment of the catalyst system may be referred to as a "bimodal catalyst system." Such catalyst systems produce bimodal polyethylene compositions with separate, identifiable high and low molecular weight distributions. The term "bimodal catalyst system" can include any formulation, mixture, or system comprising at least two different catalyst compounds, each having the same or different metal groups but typically different ligand or catalyst structures, including "dual catalysts." Alternatively, each different catalyst compound in the bimodal catalyst system is present on a single support particle; in this case, the dual catalyst is considered a supported catalyst. However, the term "bimodal catalyst system" also broadly includes systems or mixtures in which one catalyst is present on one set of support particles and the other on another set of support particles. In such embodiments, two supported catalysts are introduced simultaneously or sequentially into a single reactor, and polymerization takes place in the presence of both supported catalyst sets. Alternatively, a bimodal catalyst system may comprise a mixture of unsupported catalysts in slurry form.

[0043] Implementations of the catalyst system may include a main catalyst and a trimming catalyst. In such implementations, the main catalyst comprises at least one catalyst compound (“main catalyst compound”) and a support, and may also include an activator and / or any other additives such as those described above. The main catalyst may be delivered as a slurry in a hydrocarbon diluent such as mineral oil. The trimming catalyst comprises a trimming catalyst compound. This trimming catalyst compound may also be present in the main catalyst system. The trimming catalyst may also include a solvent such as hydrocarbons, and other additives.

[0044] Embodiments of the fine-tuning catalyst compound may include molecular catalyst compounds, such as, for example, metallocene catalyst compounds. In some embodiments, the fine-tuning catalyst can be used to produce low molecular weight polymer fractions. In such embodiments, the main catalyst can be used to produce high molecular weight polymer fractions.

[0045] Embodiments of the main catalyst compound may comprise one or more catalyst compounds containing a Group 15 metal. Compounds containing a Group 15 metal typically comprise a Group 3 to Group 14 metal atom, or a Group 3 to Group 7, or a Group 4 to Group 6, or a Group 4 metal atom, bonded to at least one leaving group and at least two Group 15 atoms, at least one of which is also bonded to a Group 15 or Group 16 atom via another group. At least one of the Group 15 atoms may be bonded to a Group 15 or Group 16 atom via another group, which may be C1 to C2. 20Hydrocarbon group, heteroatom-containing group, silicon, germanium, tin, lead or phosphorus, wherein the group 15 or group 16 atoms may be unbonded or bonded to hydrogen, a group containing group 14 atoms, halogen or heteroatom-containing group, and each of the two group 15 atoms is also bonded to a cyclic group, and may optionally be bonded to hydrogen, halogen, heteroatom or hydrocarbon group or heteroatom-containing group.

[0046] Compounds containing Group 15 metals can be represented by the following formula:

[0047]

[0048] or

[0049]

[0050] Wherein M is a transition metal from Group 3 to Group 12, or a main group metal from Group 13 or Group 14, or a metal from Group 4, Group 5, or Group 6, or a Group 4 metal, or zirconium, titanium, or hafnium, and each X is independently a leaving group. X can be an anionic leaving group. X can be hydrogen, a hydrocarbon group, a heteroatom, or a halogen. X can be alkyl, y can be 0 or 1 (when y is 0, the group L' is not present), n is the oxidation state of M, which can be +3, +4, or +5, or can be +4, m is the formal charge of the YZL or YZL' ligand, which can be 0, -1, -2, or -3, or can be -2, L is a Group 15 or Group 16 element, preferably nitrogen, L' is a Group 15 or Group 16 element or a group containing Group 14, preferably carbon, silicon, or germanium, Y is a Group 15 element, preferably nitrogen or phosphorus, more preferably nitrogen, Z is a Group 15 element, preferably nitrogen or phosphorus, more preferably nitrogen, R 1 and R 2 Independently, they are C1 to C 20 Hydrocarbon group, heteroatom-containing group having up to 20 carbon atoms, silicon, germanium, tin, lead, halogen or phosphorus, preferably C2 to C3. 20 Alkyl groups, aryl groups, or aralkyl groups, more preferably straight-chain, branched, or cyclic C2 to C3 groups. 20 Alkyl groups, preferably C2 to C6 hydrocarbon groups. R 1 and R 2 They can also be interconnected, R 3 The group is absent or consists of hydrocarbon groups, hydrogen, halogens, or heteroatom-containing groups, preferably straight-chain, cyclic, or branched alkyl groups having 1 to 20 carbon atoms, more preferably R. 3 It does not exist; it is a hydrogen or alkyl group, with hydrogen being the most preferred. R 4 and R 5Independently comprising an alkyl group, an aryl group, a substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic aralkyl group, a substituted cyclic aralkyl group, or a polycyclic system, preferably having up to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and even more preferably C1 to C2. 20 Hydrocarbon groups, C1 to C 20 aryl group or C1 to C 20 Aryl groups, or groups containing heteroatoms, such as PR3, where R is an alkyl group, R 1 and R 2 They can be interconnected, and / or R 4 and R 5 They can be interconnected, R 6 and R 7 It is not present independently, or is hydrogen, alkyl group, halogen, heteroatom or hydrocarbon group, preferably a straight-chain, cyclic or branched alkyl group having 1 to 20 carbon atoms, more preferably not present, and *R is not present, or is hydrogen, a group containing a group 14 atom, halogen or a group containing a heteroatom.

[0051] The so-called "form charge of YZL or YZL' ligands" refers to the charge of the entire ligand in the absence of metal and leaving group X.

[0052] The so-called "R" 1 and R 2 "Also interconnected" refers to R 1 and R 2 They can bond directly to each other or through other groups. "R" 4 and R 5 "Also interconnected" refers to R 4 and R 5 They can bond directly to each other or through other groups.

[0053] The alkyl group can be a straight-chain or branched alkyl group, or an alkenyl, alkynyl, cycloalkyl, or aryl, acyl, aromatic acyl, alkoxy, aryloxy, alkylthio, dialkylamino, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, alkyl- or dialkyl-carbamoyl, acyloxy, acylamino, aromatic acylamino, straight-chain, branched, or cyclic alkylene groups, or combinations thereof. Araneyl groups are defined as substituted aryl groups.

[0054] R 4 and R 5 It can be independently represented by the group indicated by the following formula 3:

[0055]

[0056] Where R 8 To R 12 Each independently consists of hydrogen, C1 to C40 Alkyl groups, halogens, heteroatoms, heteroatom-containing groups comprising up to 40 carbon atoms, preferably C1 to C2. 20 Straight-chain or branched alkyl groups, preferably methyl, ethyl, propyl, or butyl, and any two R groups can form a cyclic group and / or a heterocyclic group. The cyclic group can be aromatic. R 9 R 10 and R 12 It can be independently methyl, ethyl, propyl, or butyl (including all isomers). In a preferred embodiment, any three of the R groups in Formula 3 can be methyl groups, and any two of the other R groups in Formula 3 can be hydrogen. In a preferred embodiment of the invention, R 9 R 10 and R 12 It is methyl, and R 8 and R 11 It is hydrogen.

[0057] R 4 and R 5 All of them can be groups represented by the following formula 4:

[0058]

[0059]

[0060] Where M is a Group 4 metal, preferably zirconium, titanium, or hafnium, and even more preferably zirconium; each of L, Y, and Z is nitrogen; R 1 and R 2 Each of them is -CH2-CH2-; R 3 It is hydrogen; and R 6 and R 7 It does not exist.

[0061] Compounds containing Group 15 elements and metals can be compound 1 (also known as "bis(arylamide)dibenzylzirconium", as shown below):

[0062]

[0063] In the representation of compound 1, "Bn" represents the benzyl group.

[0064] Catalyst compounds containing Group 15 metals can be prepared by methods known in the art. In some cases, the methods disclosed in European Patent Application Publication EP 0 893 454 A1, U.S. Patent 5,889,128, and the references cited in U.S. Patent 5,889,128 are suitable.

[0065] In some embodiments, the direct synthesis of these compounds involves reacting a neutral ligand (e.g., YZL or YZL' of Formula 1 or 2) with Mn X n (M is a metal from Group 3 to Group 14, n is the oxidation state of M, and each X is an anionic group, such as a halide ion) The mixture is reacted in a noncoordinate or weakly coordinated solvent (such as ether, toluene, xylene, benzene, dichloromethane and / or hexane or other solvents with a boiling point above 60 °C) at 20 °C to 150 °C (such as 20 °C to 100 °C) for 24 hours or longer, followed by treatment of the mixture with an excess (such as four equivalents or more) of an alkylating agent, such as an ether containing methyl magnesium bromide. The magnesium salt is removed by filtration, and the metal complex is separated by standard techniques.

[0066] Compounds containing Group 15 metals can be prepared by a method comprising the following steps: reacting a neutral ligand (e.g., YZL or YZL' of Formula 1 or 2) with a compound of Formula M n X n The compound (where M is a metal from Group 3 to Group 14, n is the oxidation state of M, and each X is an anion leaving group) is reacted in a noncoordinate or weakly coordinated solvent at a temperature of 20°C or higher (preferably 20 to 100°C), followed by treatment of the mixture with an excess of alkylating agent, and then recovery of the metal complex. The solvent may have a boiling point above 60°C, such as toluene, xylene, benzene, and / or hexane. The solvent may include ethers and / or dichloromethane.

[0067] Typically, metallocene compounds can comprise semi-sandwich and full-sandwich compounds having one or more ligands bonded to at least one metal atom. A typical metallocene compound is usually described as containing one or more ligands and one or more leaving groups bonded to at least one metal atom.

[0068] Ligands are typically represented by one or more open-ring, acyclic, or fused-ring or ring systems, or combinations thereof. These ligands, preferably rings or ring systems, may consist of atoms selected from Groups 13 to 16 of the periodic table. Atoms may be freely selected from the group consisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorus, germanium, boron, and aluminum, or combinations thereof. Rings or ring systems may consist of carbon atoms, such as, but not limited to, those cyclopentadienyl ligands or cyclopentadienyl-type ligand structures, or other similar functional ligand structures such as pentadiene, cyclooctatetraenidyl, or imide ligands. Metal atoms may be selected from Groups 3 to 15 of the periodic table and from lanthanides or actinides. The metal may be from Groups 4 to 12, or transition metals from Groups 4, 5, and 6, or transition metals from Group 4.

[0069] The catalyst composition may comprise one or more metallocene catalyst compounds represented by Formula 5:

[0070] LALBMQn

[0071] Formula 5

[0072] Where M is a metal atom in the periodic table, which can be a metal from Groups 3 to 12, a lanthanide, or an actinide. M can be a transition metal from Groups 4, 5, or 6, or M can be a Group 4 transition metal, or M can be zirconium, hafnium, or titanium. Ligand L A and L B It can be open-ring, acyclic, fused-ring, or cyclic, and can be any auxiliary ligand system, including unsubstituted or substituted cyclopentadienyl ligands or cyclopentadienyl-type ligands, heteroatom-substituted and / or heteroatom-containing cyclopentadienyl-type ligands. Non-limiting examples of ligands include cyclopentadienyl ligands, cyclopentanphenanthrene ligands, indene ligands, benzo[a]indene ligands, fluorenyl ligands, octahydrofluorenyl ligands, cyclooctatetraendiyl ligands, cyclopentacyclododecene ligands, azetenyl ligands, azulene ligands, cyclopentadienyl ligands, phosphoryl ligands, phosphineimides (WO 99 / 40125), pyrroleyl ligands, pyrazolyl ligands, carbazoleyl ligands, borobenzene ligands, etc., including their hydrogenated forms, such as tetrahydroindene ligands. A and L B It can be any other ligand structure capable of π-bonding to M. L A and L B The atomic molecular weight can exceed 60 Å·mu, or even 65 Å·mu. L A and L B It may contain one or more heteroatoms, such as nitrogen, silicon, boron, germanium, sulfur, and phosphorus, which combine with carbon atoms to form open-ring, acyclic, or preferably fused-ring or cyclic systems, such as heterocyclopentadienyl auxiliary ligands. Other L A and L B Ligands include, but are not limited to, amides, phosphides, alkoxides, aromatic oxides, imides, carbides, borides, porphyrins, phthalocyanines, turpentines, and other polyazo macrocycles. Independently, each L... A and L B It can be the same or a different type of ligand bonded to M. In an alternative to Equation 5, only L may be present. A and L B one.

[0073] Independently, each L A and L BThe substituent group R can be unsubstituted or substituted in combination. Non-limiting examples of substituent group R include one or more selected from the group consisting of: hydrogen, or straight-chain, branched alkyl, or alkenyl, alkynyl, cycloalkyl or aryl, acyl, aromatic acyl, alkoxy, aryloxy, alkylthio, dialkylamino, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, alkyl- or dialkyl-carbamoyl, acyloxy, amide, aromatic acylamino, straight-chain, branched or cyclic alkylene, or combinations thereof. In a preferred embodiment, the substituent R has up to 50 non-hydrogen atoms, preferably 1 to 30 carbon atoms, and may also be substituted with halogens or heteroatoms. Non-limiting examples of alkyl substituent R include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl, or phenyl, including all their isomers, such as tert-butyl, isopropyl, etc. Other hydrocarbon groups include fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl, and hydrocarbon-substituted organometallic groups, including trimethylsilyl, trimethylgermanyl, methyldiethylsilyl, etc.; and halocarbyl-substituted organometallic groups, including tris(trifluoromethyl)silyl, methyl-bis(difluoromethyl)silyl, bromomethyldimethylgermanyl, etc.; and disubstituted boron groups, including, for example, dimethylboron; and disubstituted phosphorus groups, including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine; and sulfur groups, including methoxy, ethoxy, propoxy, phenoxy, methyl sulfide, and ethyl sulfide. Non-hydrogen substituents R include carbon atoms, silicon, boron, aluminum, nitrogen, phosphorus, oxygen, tin, sulfur, germanium, etc., including alkenes, such as, but not limited to, olefinic unsaturated substituents, including vinyl-terminated ligands, such as but-3-enyl, prop-2-enyl, hex-5-enyl, etc. Furthermore, at least two R groups, preferably two adjacent R groups, are linked to form a ring structure having 3 to 30 atoms selected from carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminum, boron, or combinations thereof. Additionally, substituent R can form a carbon σ bond with the metal M.

[0074] Other ligands can be bonded to the metal M, such as at least one leaving group Q. Q can be a monoanionic unstable ligand with a σ bond to M. Depending on the oxidation state of the metal, the value of n can be 0, 1, or 2, such that Equation 5 above represents a neutral metallocene catalyst compound.

[0075] Non-limiting examples of Q ligands may include weak bases such as amines, phosphines, ethers, carboxylic esters, dienes, hydrocarbon groups having 1 to 20 carbon atoms, hydrides, or halogens, or combinations thereof. Two or more Qs may form part of a fused ring or a ring system. Other examples of Q ligands include those substituents of R as described above, including cyclobutyl, cyclohexyl, heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene, methylene, methoxy, ethoxy, propoxy, phenoxy, bis(N-methylaniline), dimethylamide, dimethylphosphide groups, etc.

[0076] The catalyst composition may comprise one or more metallocene catalyst compounds, wherein the L of formula V A and L B They are bridged to each other by at least one bridging group A, as shown in Equation 6:

[0077] LAALBMQn

[0078] Formula 6

[0079] The compound of formula 6 is called a bridged metallocene catalyst compound. L A L B M, Q, and n are as defined above. Non-limiting examples of bridging group A include bridging groups containing at least one group 13 to 16 atom, commonly referred to as a divalent moiety, such as, but not limited to, at least one or a combination of carbon, oxygen, nitrogen, silicon, aluminum, boron, germanium, and tin atoms. Bridging group A may contain carbon, silicon, or germanium atoms, preferably A containing at least one silicon atom or at least one carbon atom. Bridging group A may also contain a substituent R as defined above, including halogens and iron. Non-limiting examples of bridging group A may be represented by R'2C, R'2Si, R'2SiR'2Si, R'2Ge, R'P, wherein R' is independently a group that is a hydride, a hydrocarbon group, a substituted hydrocarbon group, a substituted halocarboyl group, a substituted halocarboyl group, a hydrocarbon-substituted organometallic, a halocarboyl-substituted organometallic, a disubstituted boron, a disubstituted phosphorus element, a substituted sulfide element, or a halogen, or two or more R's may be linked to form a ring or ring system. The bridged metallocene catalyst compound of Formula 4 may have two or more bridging groups A (EP 0 664 301Bl).

[0080] Metallocene catalyst compounds can be ligands L of formulas 5 and 6. A and ligand L B Those ligands whose R substituents are replaced by the same or different numbers of substituents on each ligand. The ligands L of formulas V and VI... A and L B They can be different from each other.

[0081] The main catalyst system includes a main catalyst compound represented by Formula 2 above, such as a compound having the formula [(2,3,4,5,6-Me5C6)NCH2CH2]2NHZrBn2, wherein 2,3,4,5,6-Me5C6 represents a pentamethylphenyl group and Bn is a benzyl group. Optionally, the main catalyst system may include a second main catalyst compound that may be represented by Formula V above, such as a zirconium diazophenate compound, such as (n-butylcyclopentadienyl)2-zirconium dichloride (IV) or (propylcyclopentadienyl)(1,3-dimethyl-4,5,6,7-tetrahydroindenyl)dimethylzirconium (IV).

[0082] The molar ratio of HMW catalyst compound to LMW catalyst compound in the catalyst formulation can be in the range of 1:20 to 20:1, or 1:10 to 10:1, or 1:5 to 5:1, or 1:1 to 5:1, or 1:1 to 3:1.

[0083] The fine-tuning catalyst may include a catalyst compound that can be represented by Formula 7; specifically, Formula 7 shows (1,3-dimethyl-4,5,6,7-tetrahydroindene)(methylcyclopentadienyl)dimethylzirconium:

[0084]

[0085] As used herein, the term "activator" can include any combination of agents that increase the rate at which transition metal compounds oligomerize or polymerize unsaturated monomers such as olefins. Activators can also affect the molecular weight, degree of branching, comonomer content, or other properties of the oligomer or polymer. Transition metal compounds can be activated for oligomerization and / or polymerization catalysis in any manner sufficient to allow coordination or cationic oligomerization and / or polymerization.

[0086] Aluminoxane activators can be used as activators for one or more catalyst compositions. Aluminoxanes are typically oligomers comprising --Al(R)--O-- subunits, where R is an alkyl group. Examples of aluminoxanes include methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, and isobutylaluminoxane. Alkylaluminoxanes and modified alkylaluminoxanes are suitable as catalyst activators, especially when the extractable ligand is a halide. Mixtures of different aluminoxanes and modified aluminoxanes can also be used. For further description, see U.S. Patent Nos. 4,665,208, 4,952,540, 5,041,584, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031 and EP 0 561 476, EP 0 279 586, EP 0 516 476, EP 0 594 218 and WO 94 / 10180.

[0087] When the activator is an aluminoxane (modified or unmodified), the maximum amount of activator can be selected as a 5000-fold molar excess of Al / M relative to the catalyst precursor (per metal catalytic site). Alternatively or additionally, the minimum amount of activator to catalyst precursor can be set to a 1:1 molar ratio.

[0088] Alkyl aluminum or organoaluminum compounds that can be used as activators (or scavengers) include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, etc.

[0089] Catalyst systems may include support materials or carriers. For example, at least one or more catalyst compounds and / or one or more activators may be deposited on, contacted with, co-vaporized with, combined with, incorporated into, adsorbed into, or absorbed therein or onto one or more supports or carriers. Therefore, the aforementioned catalyst compounds, as well as other transition metal catalyst compounds and / or catalyst systems, can be combined with one or more support materials or carriers using one of the support methods known in the art or described below. For example, metallocene catalyst compounds or catalyst systems may be in supported form, such as when deposited on, contacted with, incorporated into, adsorbed into, or absorbed therein or onto one or more supports or carriers.

[0090] As used herein, the terms “carrier” and “support” are used interchangeably and refer to any carrier material, including porous carrier materials such as talc, inorganic oxides, and inorganic chlorides. Other support materials include resin carrier materials such as polystyrene, functionalized or cross-linked organic carriers such as polystyrene, divinylbenzene polyolefins or other polymers, zeolites, clays, or any other organic or inorganic carrier materials, or mixtures thereof.

[0091] Exemplary support materials include inorganic oxides, including metal oxides of Groups 2, 3, 4, 5, 13, or 14. Preferred supports include dehydrated or non-dehydrated silica, fumed silica, alumina (see, for example, WO 99 / 60033), silica-alumina, and mixtures thereof. Other useful supports include magnesium oxide, titanium dioxide, zirconium oxide, magnesium chloride (US Patent 5,965,477), montmorillonite (EP 0 511 665), shale silicates, zeolites, talc, clay (US Patent 6,034,187), etc. Furthermore, combinations of these support materials can be used, such as silica-chromium, silica-alumina, silica-titanium dioxide, etc. Additional support materials may include those porous acrylic polymers described in EP 0 767 184, which is incorporated herein by reference. Other carrier materials include nanocomposites as disclosed in WO 99 / 47598, aerogels as disclosed in WO 99 / 48605, spheres as disclosed in U.S. Patent No. 5,972,510, and polymer beads as disclosed in WO 99 / 50311.

[0092] In some embodiments, all catalyst compounds in the catalyst system may be independently unsupported or supported on a support material; in the latter case, the catalyst system is a supported catalyst system. When each catalyst compound is supported, the catalyst compounds may be present on the same support material (e.g., the same particles) or on different support materials (e.g., different particles). Bimodal catalyst systems comprise mixtures of unsupported catalyst compounds in slurry and / or solution form. The support material may be silica (e.g., fumed silica), alumina, clay, or talc. The fumed silica may be hydrophilic (untreated) or alternatively hydrophobic (treated). In some aspects, the support is hydrophobic fumed silica, which can be prepared by treating untreated fumed silica with a treatment agent such as dimethyldichlorosilane, polydimethylsiloxane fluid, or hexamethyldisilazane. In some aspects, the treatment agent is dimethyldichlorosilane.

[0093] In some implementations, the carrier material, such as inorganic oxides, may have a thickness of 10m. 2 / g to 700m 2 Surface area within the range of / g, 0.1cm 3 / g to 4.0cm 3 The pore volume is in the range of / g and the average particle size is in the range of 5 micrometers to 500 micrometers. More preferably, the surface area of ​​the support material can be 50m². 2 / g to 500m 2 Within the range of / g, the pore volume is 0.5cm³. 3 / g to 3.5cm 3 The particle size is within the range of / g, and the average particle size is in the range of 10 micrometers to 200 micrometers. Most preferably, the surface area of ​​the carrier material can be 100m². 2 / g to 400m 2 Within the range of / g, the pore volume is 0.8cm³. 3 / g to 3.0cm 3 The particle size is in the range of / g, and the average particle size is in the range of 5 micrometers to 100 micrometers. The average pore size of the support is typically in the range of 10 angstroms to 1,000 angstroms, or 50 angstroms to 500 angstroms, and in some embodiments 75 angstroms to 350 angstroms. Various other methods exist in the art for supporting polymerization catalyst compounds or catalyst systems. For example, metallocene catalyst compounds may contain polymer-bound ligands, as described in, for example, U.S. Patents 5,473,202 and 5,770,755. Metallocene catalyst compounds may be spray-dried as described, for example, U.S. Patent 5,648,310. The support used with the metallocene catalyst compound may be functionalized, as described in EP 0 802 203, or selected with at least one substituent or leaving group as described in U.S. Patent 5,688,880.

[0094] The polyethylene formulations disclosed herein can be prepared by a gas-phase method. The formulations can be prepared in a single reactor. The polyethylene formulations disclosed herein can also be prepared in a single gas-phase reactor. In one embodiment of the invention, the reactor is a gas-phase fluidized bed polymerization reactor.

[0095] Polyethylene can be produced using a staged gas-phase reactor. Commercial polymerization systems are described, for example, in "Volume 2, Metallocene-Based Polyolefins", pp. 366–378 (edited by John Scheirs & W. Kaminsky, John Wiley & Sons, Ltd. 2000); U.S. Patents 5,665,818, 5,677,375, and 6,472,484; and EP 0 517 868 and EP 0 794 200.

[0096] Gas-phase methods can utilize fluidized bed reactors. A fluidized bed reactor may include a reaction zone and a so-called deceleration zone. The reaction zone may include a bed of grown polymer particles, formed polymer particles, and a small amount of catalyst particles, which is fluidized by a continuous flow of gaseous monomers and a diluent to remove the heat of polymerization through the reaction zone. Optionally, some of the recirculated gas may be cooled and compressed to form a liquid, which increases the heat removal capacity of the recirculated gas stream when it re-enters the reaction zone. A suitable gas flow rate can be easily determined through simple experiments. The rate at which gaseous monomers are added to the recirculated gas stream can be equal to the rate at which particulate polymer products and associated monomers can be discharged from the reactor, and the composition of the gas passing through the reactor can be adjusted to maintain a substantially steady-state gaseous composition within the reaction zone. The gas leaving the reaction zone passes through a deceleration zone, where entrained particles are removed. Fineer entrained particles and dust can be removed in cyclone dust collectors and / or fine filters. The gas may then pass through a heat exchanger, where the heat of polymerization can be removed, compressed in a compressor, and then returned to the reaction zone. Additional reactor details and methods for operating the reactor are described, for example, in U.S. Patent Nos. 3,709,853, 4,003,712, 4,011,382, 4,302,566, 4,543,399, 4,882,400, 5,352,749 and 5,541,270; EP 0802202; and Belgian Patent No. 839,380.

[0097] Reactor temperatures in fluidized bed processes can range from 30°C, 40°C, or 50°C to 90°C, 100°C, 110°C, 120°C, or 150°C. Typically, the reactor temperature is operated at the highest feasible temperature, taking into account the sintering temperature of the ethylene-based polymer product within the reactor. Regardless of the method used to prepare the polyolefin (e.g., bimodal polyethylene), the polymerization or reaction temperature should be below the melting or “sintering” temperature of the ethylene-based polymer to be formed. Therefore, the upper temperature limit can be the melting temperature of the polyolefin produced in the reactor.

[0098] Hydrogen can be used in olefin polymerization to control the final properties of polyolefins, as described on pages 76-78 of the "Polypropylene Handbook" (Hanser Publishers, 1996). The amount of hydrogen in polymerization can be expressed as a molar ratio relative to the total polymerizable monomers, such as ethylene or a blend of ethylene with 1-hexene or propylene. The amount of hydrogen used in the polymerization process can be the amount necessary to obtain the desired MFR or FI of the final polyolefin resin. The amount of hydrogen used in the polymerization process can also be the amount necessary to obtain the desired bimodal molecular weight distribution between the high molecular weight component and the low molecular weight component of the bimodal polyolefin.

[0099] The catalyst system can also be used to further control the properties of polyethylene formulations. For example, the amount of tuning catalyst can be adjusted to change the in-reactor ratio of the catalyst compounds in the catalyst system, thereby achieving the desired flow index or flow index split. The tuning catalyst can be fed directly into the reactor independently of the main catalyst compound of the catalyst system. Alternatively, the tuning catalyst can be mixed with the main catalyst compound of the catalyst system before being fed into the reactor. The tuning catalyst can also be continuously mixed with other compounds in the catalyst system, and the resulting mixture can be continuously fed into the reactor. The tuning catalyst can be continuously mixed with a supported catalyst, and the resulting mixture can be continuously fed into the reactor. The tuning catalyst can be a supported catalyst or an unsupported catalyst. When the tuning catalyst is an unsupported catalyst, it can be loaded "in-line," for example, by contacting a supported catalyst before being fed into the reactor. Supported tuning catalysts may contain an activator that can activate the tuning catalyst "in-line" before being fed into the reactor.

[0100] The fine-tuning catalyst can be provided in the same or different form as the main catalyst compound (or one of the main catalyst compounds) of the catalyst system. However, when activated with a suitable activator, the active catalyst material produced by the fine-tuning catalyst can be the same as that produced by one of at least two different catalyst compounds of the catalyst. Those skilled in the art will understand that, for example, metallocene dihalides and metallocene dialkyl compounds can produce the same active catalyst material when treated with a suitable activator. For example, metallocenes such as (cyclopentadienyl)(1,3-dimethyl-4,5,6,7-tetrahydroindenyl)zirconium(X)2 (where X can be a halide, alkyl group, or any other leaving group as described above) can be used in dichloride form to prepare supported catalysts. When used as a fine-tuning catalyst, it can be provided in dialkyl form such as dimethyl form. This may be advantageous in terms of solubility, where the dialkyl form may have enhanced solubility in, for example, aliphatic hydrocarbons.

[0101] The catalyst system may contain at least one, two, or more catalyst compounds comprising titanium, zirconium, or hafnium atoms. The catalyst system may contain at least one, two, or more of the following:

[0102] (pentamethylcyclopentadienyl)(n-propylcyclopentadienyl)MX2;

[0103] (tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)MX2;

[0104] (tetramethylcyclopentadienyl)(n-butylcyclopentadienyl)MX2;

[0105] (n-propylcyclopentadienyl)(1,3-dimethyl-4,5,6,7-tetrahydroindenyl)MX2;

[0106] (methylcyclopentadienyl)(1,3-dimethyl-4,5,6,7-tetrahydroindenyl)MX2;

[0107] (cyclopentadienyl)(1,3-dimethyl-4,5,6,7-tetrahydroindenyl)MX2;

[0108] (methylcyclopentadienyl)(1-methyl-4,5,6,7-tetrahydroindenyl)MX2;

[0109] Me2Si(indene)2MX2;

[0110] Me2Si(4,5,6,7-tetrahydroindenyl)2MX2;

[0111] (n-propylcyclopentadienyl)2MX2;

[0112] (n-Butylcyclopentadienyl)2MX2;

[0113] (1-Methyl, 3-butylcyclopentadienyl)2MX2;

[0114] [HN(CH2CH2N(2,4,6-Me3C6H2))2]MX2;

[0115] [HN(CH2CH2N(2,3,4,5,6-Me5C6))2]MX2;

[0116] And mixtures thereof, wherein M is Zr or Hf, and X is selected from F, Cl, Br, I, Me, benzyl, CH2SiMe3 and C1 to C5 alkyl or alkenyl.

[0117] The molar ratio of hydrogen to total monomers (H2: monomers) can be greater than 0.0001, greater than 0.0005, or greater than 0.001, and less than 10, less than 5, less than 3, or less than 0.10, wherein the desired range may include any combination of any upper limit and any lower limit of the molar ratio described herein.

[0118] In gas-phase processes (single-stage, two-stage, or multi-stage), the pressure of one or more reactors can vary between 690 kPa (100 psig) and 3,448 kPa (500 psig). For example, they can range from 1,379 kPa (200 psig) to 2,759 kPa (400 psig) or from 1,724 kPa (250 psig) to 2,414 kPa (350 psig).

[0119] In this embodiment, bimodal polyethylene can be used as a base component to produce the thermoplastic composition. In this embodiment, the thermoplastic composition may optionally contain one or more additives, such as antistatic agents, colorants, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, ultraviolet (UV) stabilizers, fillers, flame retardants, and combinations thereof. The thermoplastic composition can be produced by physically mixing bimodal polyethylene and any optional additives at a macroscopic level, such as by melt blending or compounding.

[0120] In embodiments, the thermoplastic composition may contain greater than or equal to 50.1% by weight, such as greater than or equal to 60.0% by weight, greater than or equal to 70.0% by weight, greater than or equal to 80.0% by weight, greater than or equal to 90.0% by weight, greater than or equal to 95.0% by weight, or greater than or equal to 99.0% by weight. The thermoplastic composition may also contain less than or equal to 99.9% by weight, such as less than or equal to 99.0% by weight, less than or equal to 95.0% by weight, less than or equal to 90.0% by weight, less than or equal to 80.0% by weight, less than or equal to 70.0% by weight, or less than or equal to 60.0% by weight. For example, the thermoplastic composition may contain 50.1 wt% to 99.9 wt%, 50.1 wt% to 99.0 wt%, 50.1 wt% to 95.0 wt%, 50.1 wt% to 90.0 wt%, 50.1 wt% to 80.0 wt%, 50.1 wt% to 70.0 wt%, 50.1 wt% to 60.0 wt%, 60.0 wt% to 99.9 wt%, 60.0 wt% to 99.0 wt%, 60.0 wt% to 95.0 wt%, 60.0 wt% to 90.0 wt%, 60.0 wt% to 80.0 wt%, 60.0 wt% to 70.0 wt%, and 70.0 wt% to 99.9 wt%. Bimodal polyethylene in amounts of 70.0 wt% to 99.0 wt%, 70.0 wt% to 95.0 wt%, 70.0 wt% to 90.0 wt%, 70.0 wt% to 80.0 wt%, 80.0 wt% to 99.9 wt%, 80.0 wt% to 99.0 wt%, 80.0 wt% to 95.0 wt%, 80.0 wt% to 90.0 wt%, 90.0 wt% to 99.9 wt%, 90.0 wt% to 99.0 wt%, 90.0 wt% to 95.0 wt%, 95.0 wt% to 99.9 wt%, 95.0 wt% to 99.0 wt%, or 99.0 wt% to 99.9 wt%.

[0121] In embodiments, the thermoplastic composition may contain an amount of UV stabilizer greater than or equal to 0.0 wt%, such as greater than or equal to 1.0 wt%, greater than or equal to 2.0 wt%, greater than or equal to 3.0 wt%, or greater than or equal to 4.0 wt%. The thermoplastic composition may also contain an amount of UV stabilizer less than or equal to 5.0 wt%, such as less than or equal to 4.0 wt%, less than or equal to 3.0 wt%, less than or equal to 2.0 wt%, or less than or equal to 1.0 wt%. For example, the thermoplastic composition may contain 0.0 wt% to 5.0 wt%, 0.0 wt% to 4.0 wt%, 0.0 wt% to 3.0 wt%, 0.0 wt% to 2.0 wt%, 0.0 wt% to 1.0 wt%, 1.0 wt% to 5.0 wt%, 1.0 wt% to 4.0 wt%, 1.0 wt% to 3.0 wt%, 1.0 wt% to 2.0 wt%, 2.0 wt% to 5.0 wt%, 2.0 wt% to 4.0 wt%, 2.0 wt% to 3.0 wt%, 3.0 wt% to 5.0 wt%, 3.0 wt% to 4.0 wt%, or 4.0 wt% to 5.0 wt% of UV stabilizer.

[0122] In embodiments, the thermoplastic composition may contain a first antioxidant in an amount greater than or equal to 0.1 wt%, such as greater than or equal to 0.4 wt%, or greater than or equal to 0.7 wt%. The thermoplastic composition may also contain a first antioxidant in an amount less than or equal to 1.0 wt%, such as less than or equal to 0.7 wt%, or less than or equal to 0.4 wt%. For example, the thermoplastic composition may contain a first antioxidant in an amount from 0.1 wt% to 1.0 wt%, 0.1 wt% to 0.7 wt%, 0.1 wt% to 0.4 wt%, 0.4 wt% to 1.0 wt%, 0.4 wt% to 0.7 wt%, or 0.7 wt% to 1.0 wt%. In embodiments, the thermoplastic composition may contain a second antioxidant in an amount greater than or equal to 0.0 wt%, such as greater than or equal to 0.2 wt%, greater than or equal to 0.4 wt%, greater than or equal to 0.6 wt%, or greater than or equal to 0.8 wt%. The thermoplastic composition may also contain a second antioxidant in an amount of less than or equal to 1.0% by weight, such as less than or equal to 0.8% by weight, less than or equal to 0.6% by weight, less than or equal to 0.4% by weight, or less than or equal to 0.2% by weight. For example, the thermoplastic composition may contain a first antioxidant in amounts of 0.0 wt% to 1.0 wt%, 0.0 wt% to 0.8 wt%, 0.0 wt% to 0.6 wt%, 0.0 wt% to 0.4 wt%, 0.0 wt% to 0.2 wt%, 0.2 wt% to 1.0 wt%, 0.2 wt% to 0.8 wt%, 0.2 wt% to 0.6 wt%, 0.2 wt% to 0.4 wt%, 0.4 wt% to 1.0 wt%, 0.4 wt% to 0.8 wt%, 0.4 wt% to 0.6 wt%, 0.6 wt% to 1.0 wt%, 0.6 wt% to 0.8 wt%, or 0.8 wt% to 1.0 wt%.

[0123] In embodiments, the thermoplastic composition may contain processing aids in amounts greater than or equal to 0.0 wt%, such as greater than or equal to 0.2 wt%, greater than or equal to 0.4 wt%, greater than or equal to 0.6 wt%, or greater than or equal to 0.8 wt%. The thermoplastic composition may also contain processing aids in amounts less than or equal to 1.0 wt%, such as less than or equal to 0.8 wt%, less than or equal to 0.6 wt%, less than or equal to 0.4 wt%, or less than or equal to 0.2 wt%. For example, the thermoplastic composition may contain processing aids in amounts of 0.0 wt% to 1.0 wt%, 0.0 wt% to 0.8 wt%, 0.0 wt% to 0.6 wt%, 0.0 wt% to 0.4 wt%, 0.0 wt% to 0.2 wt%, 0.2 wt% to 1.0 wt%, 0.2 wt% to 0.8 wt%, 0.2 wt% to 0.6 wt%, 0.2 wt% to 0.4 wt%, 0.4 wt% to 1.0 wt%, 0.4 wt% to 0.8 wt%, 0.4 wt% to 0.6 wt%, 0.6 wt% to 1.0 wt%, 0.6 wt% to 0.8 wt%, or 0.8 wt% to 1.0 wt%.

[0124] In embodiments, the thermoplastic composition may contain a flame retardant in an amount greater than or equal to 0.0 wt%, such as greater than or equal to 0.2 wt%, greater than or equal to 0.4 wt%, greater than or equal to 0.6 wt%, or greater than or equal to 0.8 wt%. The thermoplastic composition may also contain a flame retardant in an amount less than or equal to 1.0 wt%, such as less than or equal to 0.8 wt%, less than or equal to 0.6 wt%, less than or equal to 0.4 wt%, or less than or equal to 0.2 wt%. For example, the thermoplastic composition may contain 0.0 wt% to 1.0 wt%, 0.0 wt% to 0.8 wt%, 0.0 wt% to 0.6 wt%, 0.0 wt% to 0.4 wt%, 0.0 wt% to 0.2 wt%, 0.2 wt% to 1.0 wt%, 0.2 wt% to 0.8 wt%, 0.2 wt% to 0.6 wt%, 0.2 wt% to 0.4 wt%, 0.4 wt% to 1.0 wt%, 0.4 wt% to 0.8 wt%, 0.4 wt% to 0.6 wt%, 0.6 wt% to 1.0 wt%, 0.6 wt% to 0.8 wt%, or 0.8 wt% to 1.0 wt% of flame retardant.

[0125] In embodiments, the thermoplastic composition may contain filler in an amount greater than or equal to 0.0 wt%, such as greater than or equal to 0.2 wt%, greater than or equal to 0.4 wt%, greater than or equal to 0.6 wt%, or greater than or equal to 0.8 wt%. The thermoplastic composition may also contain filler in an amount less than or equal to 1.0 wt%, such as less than or equal to 0.8 wt%, less than or equal to 0.6 wt%, less than or equal to 0.4 wt%, or less than or equal to 0.2 wt%. For example, the thermoplastic composition may contain filler in amounts of 0.0 wt% to 1.0 wt%, 0.0 wt% to 0.8 wt%, 0.0 wt% to 0.6 wt%, 0.0 wt% to 0.4 wt%, 0.0 wt% to 0.2 wt%, 0.2 wt% to 1.0 wt%, 0.2 wt% to 0.8 wt%, 0.2 wt% to 0.6 wt%, 0.2 wt% to 0.4 wt%, 0.4 wt% to 1.0 wt%, 0.4 wt% to 0.8 wt%, 0.4 wt% to 0.6 wt%, 0.6 wt% to 1.0 wt%, 0.6 wt% to 0.8 wt%, or 0.8 wt% to 1.0 wt%.

[0126] Bimodal polyethylene or thermoplastic compositions containing bimodal polyethylene can be used in a wide variety of products and end-use applications. The bimodal polyethylene or thermoplastic compositions containing the bimodal polyethylene can also be blended and / or co-extruded with any other polymer. Non-limiting examples of other polymers include linear low-density polyethylene, elastomers, plasmids, high-density polyethylene, high-density polyethylene, polypropylene, etc. In a variety of other end-uses, the bimodal polyethylene, thermoplastic compositions containing the bimodal polyethylene, and blends thereof can be used to produce blow-molded parts or products. The bimodal polyethylene, thermoplastic compositions containing the bimodal polyethylene, and blends thereof can be used in forming operations such as film, sheet, and fiber extrusion and co-extrusion, as well as blow molding, injection molding, and rotational molding. Films can include blow-molded or cast films formed by co-extrusion or lamination, which can be used as shrink films, cling films, stretch films, sealing films, oriented films, snack packaging, heavy-duty bags, grocery store burlap bags, baked and frozen food packaging, medical packaging, industrial liners, and films in food contact and non-food contact applications. Fibers may include melt spinning, solution spinning, and meltblown fiber operations for use in woven or nonwoven forms to manufacture filter paper, diaper fabrics, medical clothing, and geotextiles. Extruded articles may include medical catheters, wire and cable coatings, pipes, geomembranes, and pond liners. Molded articles may include single-layer and multi-layer constructions in the form of bottles, cans, large hollow articles, rigid food containers, and toys.

[0127] In some embodiments, the bimodal polyethylene, thermoplastic compositions comprising the bimodal polyethylene, and blends thereof can be used to manufacture a coated conductor. The coated conductor may include a conductive core and a coating covering at least a portion of the conductive core. The conductive core may include a metal wire, an optical fiber, or a combination thereof. The coating may include the bimodal polyethylene, a thermoplastic composition comprising the bimodal polyethylene, and blends thereof. Electricity, light, or a combination thereof can be transmitted through the conductive core of the coated conductor. This can be achieved by applying a voltage across the ends of a metal wire, which allows electrical energy to flow through the metal wire; by transmitting light pulses (e.g., infrared light) through an optical fiber, which allows light transmission through the optical fiber; or a combination thereof.

[0128] Environmental stress fracture resistance (F0) is a measure of an article's strength in resisting failure caused by stress crack growth. A high F0 value is important because the article should last for its designed service life. In embodiments, articles comprising bimodal polyethylene, thermoplastic compositions containing bimodal polyethylene, or blends thereof may have an F0 value greater than 24 hours, such as greater than or equal to 48 hours, greater than or equal to 96 hours, greater than or equal to 192 hours, greater than or equal to 384 hours, greater than or equal to 768 hours, greater than or equal to 1,536 hours, or greater than 3,072 hours. Articles comprising thermoplastic compositions may also have an F0 value less than 6,144 hours, such as less than or equal to 3,072 hours, less than or equal to 1,536 hours, less than or equal to 768 hours, less than or equal to 384 hours, less than or equal to 192 hours, less than or equal to 96 hours, or less than 48 hours. For example, articles containing thermoplastic compositions may have a lifespan of 24 hours to 6,144 hours, 24 hours to 3,072 hours, 24 hours to 1,536 hours, 24 hours to 768 hours, 24 hours to 384 hours, 24 hours to 192 hours, 24 hours to 96 hours, 24 hours to 48 hours, 48 ​​hours to 6,144 hours, 48 ​​hours to 3,072 hours, 48 ​​hours to 1,536 hours, 48 ​​hours to 768 hours, 48 ​​hours to 384 hours, 48 ​​hours to 192 hours, 48 ​​hours to 96 hours, 96 hours to 6,144 hours, 96 hours to 3,072 hours, 96 hours to 1,536 hours, 96 hours to 768 hours, 9... Environmental stress fracture resistance (F0) for 6 to 384 hours, 96 to 192 hours, 192 to 6,144 hours, 192 to 3,072 hours, 192 to 1,536 hours, 192 to 768 hours, 192 to 384 hours, 384 to 6,144 hours, 384 to 3,072 hours, 384 to 1,536 hours, 384 to 768 hours, 768 to 6,144 hours, 768 to 3,072 hours, 768 to 1,536 hours, 1,536 to 6,144 hours, 1,536 to 3,072 hours, or 3,072 to 6,144 hours.

[0129] Thermal creep is measured to determine the degree of curing (crosslinking), and thermal elongation is used to measure the relaxation of the sample after thermal creep elongation. In embodiments, articles containing thermoplastic compositions may have a thermal elongation of 80% or more, such as 100% or more, 120% or more, 140% or more, 160% or more, or 180% or more. Articles containing thermoplastic compositions may also have a thermal elongation of less than 200%, such as 180% or more, 160% or more, 140% or more, 120% or more, or 100% or more. For example, articles containing thermoplastic compositions may have thermal elongation of 80% to 200%, 80% to 180%, 80% to 160%, 80% to 140%, 80% to 120%, 80% to 100%, 100% to 200%, 100% to 180%, 100% to 160%, 100% to 140%, 100% to 120%, 120% to 200%, 120% to 180%, 120% to 160%, 120% to 140%, 140% to 200%, 140% to 180%, 140% to 160%, 160% to 200%, 160% to 180%, or 180% to 200%.

[0130] Test methods

[0131] density

[0132] Unless otherwise stated, all densities disclosed herein are measured according to ASTM D792-08 Method B and are expressed in grams per cubic centimeter (g / cm³). 3 )Report.

[0133] Samples for density measurement were prepared according to ASTM D4703-10. The samples were pressed at 10,000 psi (68 MPa) for five minutes at 190°C. The temperature was maintained at 190°C for the first five minutes, then the pressure was increased to 30,000 psi (207 MPa) for three minutes. This was followed by holding at 21°C and 30,000 psi (207 MPa) for one minute. Measurements were taken within one hour of sample pressing.

[0134] Melt index ( I2 )

[0135] Unless otherwise stated, all melt flow indexes (I2) disclosed herein were measured according to ASTM D1238-10 Method B at 190°C and 2.16 kg load and are reported in decigrams per minute (dg / min).

[0136] High load melt index ( I21 )

[0137] Unless otherwise stated, all high-load melt flow index (I) 21 All measurements were taken according to ASTM D1238-10 Method B at 190°C and a load of 21.6 kg, and reported in decigrams per minute (dg / min).

[0138] molecular weight

[0139] Unless otherwise stated, all molecular weights disclosed herein, including weight-average molecular weight (M... w Number-average molecular weight (M) n ) and z-average molecular weight (M z All measurements were performed using conventional gel permeation chromatography (GPC) and reported in grams per mole (g / mol).

[0140] The chromatographic system consisted of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector. The autosampler chamber was set to 160°C and the column chamber to 150°C. The columns used were four Agilent "Mixed A" 30 cm 20 μm linear mixed-bed columns. The chromatographic solvent used was 1,2,4-trichlorobenzene containing 200 parts per million (ppm) of butylated hydroxytoluene (BHT). The solvent source was nitrogen injection. The injection volume was 200 μL, and the flow rate was 1.0 mL / min.

[0141] GPC column calibration was performed using 21 narrow molecular weight polystyrene standards commercially available from Agilent Technologies, ranging in molecular weight from 580 g / mol to 8,400,000 g / mol, arranged in a six-cocktail mixture with individual molecular weights spaced at least tenfold apart. For molecular weights equal to or greater than 1,000,000 g / mol, the polystyrene standards were prepared at 0.025 g per 50 mL of solvent, and for molecular weights less than 1,000,000 g / mol, the standards were prepared at 0.05 g per 50 mL of solvent. The polystyrene standards were dissolved by gentle stirring at 80°C for 30 minutes. The peak molecular weight of polystyrene standards was converted to polyethylene molecular weight using Equation 1 (as described by Williams and Ward, *Journal of Polymer Science and Polymer Letters*, 6, 621 (1968)).

[0142] M 聚乙烯 =A×(M) 聚苯乙烯 ) B Equation 1, where M is the molecular weight, A has a value of 0.4315, and B equals 1.0.

[0143] A fifth-order polynomial was used to fit the calibration point for the corresponding polyethylene equivalent. A small adjustment to A (approximately 0.375 to 0.445) was made to correct for column resolution and band broadening effects, resulting in a linear homopolymer polyethylene standard with a molecular weight of 120,000 g / mol.

[0144] Total plate counts were performed on the GPC column assembly using decane (“0.04 g prepared in 50 mL TCB”, dissolved under slow stirring for 20 min). Plate counts and symmetry were measured at 200 μL injections according to the following equations (Equation 2) and (Equation 3):

[0145]

[0146] Where RV is the retention volume in milliliters, peak width is in milliliters, peak value is the maximum height of the peak, and 1 / 2 height is half the height of the peak value; and

[0147]

[0148] Where RV is the retention volume in milliliters, and peak width is in milliliters, peak maximum is the position of the peak value, one-tenth height is 1 / 10 of the peak maximum height, and a subsequent peak refers to the tail of a peak whose retention volume is later than the peak maximum, while a preceding peak refers to the front of a peak whose retention volume is earlier than the peak maximum. The plate count of the chromatographic system should be greater than 18,000, and the symmetry should be between 0.98 and 1.22.

[0149] Samples were prepared semi-automatically using PolymerChar Instrument Control software, with a target sample concentration of 2 mg / mL. Solvent (containing 200 ppm BHT) was added to a pre-bubbled, septum-capped vial via a PolymerChar high-temperature autosampler. The sample was then dissolved at 160°C for 2 hours with gentle shaking.

[0150] Based on the GPC results, using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph, according to Equations 4 to 6, the PolymerChar GPCOne was used. TMThe software calculates the weight-average molecular weight (Mb) of polyethylene based on the baseline-subtracted IR chromatograms at each equidistant data collection point (i) and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve at point (i) according to Equation 1. w(GPC) Number-average molecular weight (M) n(GPC) ) and z-average molecular weight (M z(GPC) ) calculation.

[0151]

[0152]

[0153]

[0154] To monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by a PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate (flow rate) for each sample using the following method. (标称) ): The RV (RV) of the corresponding decane peak in the sample. (FM样品) ) and the RV of the decane peak within the narrow standard calibration (RV) (经FM校准的) The comparison was then performed. It was then assumed that any variation in the peak time of the decane marker was correlated with the flow rate (flow rate) throughout the entire operation. (有效) The linear variation of the flow rate is related to the flow rate. To achieve the highest accuracy in measuring the RV of the flow marker peak, a least-squares fitting procedure is used to fit the peak of the flow marker concentration chromatogram to a quadratic equation. The first derivative of the quadratic equation is then used to solve for the true peak position. After calibration based on the flow marker peak, the effective flow rate (relative to narrow standard calibration) is calculated according to Equation 7. (Supported by PolymerChar GPCOne) TM The software processes the flow marker peaks. Acceptable flow rate correction ensures that the effective flow rate is within ±1% of the nominal flow rate.

[0155]

[0156] A systematic method for determining multi-detector offset was developed in conjunction with that of Balke, Mourey et al. (Mourey and Balke, Chromatography Polym., Chapter 12, (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym., Chapter 13 (1992)), using PolymerChar GPCOne. TM The software optimized the standard from the wide homopolymer polyethylene (M) w / Mn >3) triple detector logarithmic (MW and IV) results and narrow standard column calibration results from narrow standard calibration curves.

[0157] Absolute molecular weight data (GPC-LALS) were obtained using PolymerChar GPCOne. TM The software was obtained in a manner consistent with the following publications: Zimm (Zimm, BH, *Journal of Physical Chemistry*, 16, 1099 (1948)) and Kratochvil (Kratochvil, P., *Classical Light Scattering from Polymer Solutions*, Elsevier, Oxford, NY (1987)). The total injection concentration used for determining the molecular weight was obtained from the mass detector area and the mass detector constant, which was derived from one of suitable linear polyethylene homopolymers or polyethylene standards with known weight-average molecular weights. The calculated molecular weight (using GPCOne) TM The light scattering constant and refractive index concentration coefficient dn / dc of 0.104 from homopolymer polyethylene standards were used to obtain the values. Generally, the mass detector response (IR5) and light scattering constant (using GPCOne) are also used. TM The determination should be performed using a linear standard with a molecular weight exceeding about 50,000 g / mol, preferably exceeding about 120,000 g / mol. Other corresponding moments M are calculated as follows, according to Equations 8 to 9. n(Abs) and M z(Abs) :

[0158]

[0159]

[0160] The IR5 detector ratio was calibrated using a variety of ethylene-based polymers with known short-chain branching (SCB) frequencies (e.g., as determined by NMR), ranging from homopolymers (0 SCB / 1000 total C) to approximately 40 SCB / 1000 total C, where total C = carbon in the main chain + carbon in the branches. Each standard had a weight-average molecular weight (Mn) ranging from 36,000 g / mol to 126,000 g / mol. w The molecular weight distribution (Mw / Mn) of each standard is as determined by the GPC-LALS processing method described above. Each standard has a molecular weight distribution (Mw / Mn) of 2.0 to 2.5, as determined by the GPC-LALS processing method described above.

[0161] For each of the “SCB” standards, calculate the calculated “IR5 area ratio” (or “IR5 area ratio”) of the “area response of the IR5 methyl channel sensor minus the baseline” to the “area response of the IR5 measurement channel sensor minus the baseline”. 甲基通道面积 / IR5 测量通道面积 According to Equation 10, the following linear fit is constructed between the SCB frequency and the "IR5 area ratio":

[0162]

[0163] Where A0 is the zero intercept of "SCB / 1000 total C" under "IR5 area ratio", and A1 is the slope of "SCB / 1000 total C" with respect to "IR5 area ratio" and indicates that SCB / 1000 total C increases with "IR5 area ratio".

[0164] The short-chain branching distribution of the low molecular weight component (SCBD1), the short-chain branching distribution of the high molecular weight component (SCBD2), and the comonomer ratio were calculated based on GPC results using an internal IR5 detector (measurement channel) and the SCB / 1000 total C of bimodal polyethylene. To calculate these values, baseline-subtracted IR chromatograms were determined at equally spaced data collection points (i), and the SCBD was calculated for the two highest abundance values ​​of the bimodal resin. For polymers greater than LogM 3.5, the values ​​were calculated for the two highest abundance values ​​of LogM. 最大值1 and LogM 最大值2 Determine this calculation. LogM 最大值1 Defined relative to the second LogM 最大值2 The maximum value at lower molecular weights. Here, m and n define the molecular weight range for calculating SCBD1, where m = (LogM 最大值1 -0.15) and n = (LogM 最大值1 +0.15). Here, o and p define the molecular weight range for calculating SCBD2, where o = (LogM 最大值2 -0.15) and p = (LogM 最大值2 +0.15).

[0165]

[0166]

[0167] The comonomer distribution (also known as the comonomer ratio) is defined according to Equation 13. Any value greater than 1.0 is considered a reverse comonomer distribution, a value less than 1.0 is considered a normal comonomer distribution, and a value of 1.0 is considered a flat comonomer distribution.

[0168]

[0169] Complex viscosity

[0170] Unless otherwise stated, all complex viscosities (η*) disclosed herein are calculated using dynamic mechanical spectra (DMS) and reported in Pascal-seconds (Pa·s).

[0171] The sample was compressed and molded into a circular sheet measuring 3 mm thick by 1 inch in air at 350°F for five minutes under 25,000 psi pressure. The sample was then removed from the press and allowed to cool.

[0172] Isothermal frequency scanning was performed under nitrogen purging using a TA Instruments Advanced Rheological Extension System (ARES) equipped with a 25 mm (diameter) parallel plate. The sample was placed on the plate and allowed to melt at 190°C for five minutes. The plate was then brought close together with a 2 mm gap to trim the sample (removing any excess sample extending beyond the perimeter of the 25 mm diameter plate), and testing commenced. This method includes an additional five-minute delay to allow for temperature equilibration. Testing was conducted at 190°C over a frequency range of 0.1 rad / s to 100 rad / s at a constant strain amplitude of 10%.

[0173] Environmental Stress Resilience (ESCR)

[0174] Unless otherwise stated, all environmental stress cracking resistance (ESCR) values ​​disclosed herein are F0 failure times reported in hours and were measured for compression-molded specimens with a thickness of 75 mm at 50°C in 10% Igepal solution according to ASTM D1693 Method B.

[0175] Tensile strength

[0176] Unless otherwise stated, all tensile strength values ​​disclosed herein are measured according to ASTM D638-14 Type IV for compression-molded specimens with a thickness of 75 mm and are reported in megapascals (MPa) and / or pounds per square inch (psi).

[0177] elongation

[0178] Unless otherwise stated, all elongation values ​​disclosed herein are measured according to ASTM D638-14 Type IV for compression-molded specimens with a thickness of 75 mm and are reported as a percentage (%).

[0179] Wire smoothness

[0180] Unless otherwise stated, all wire smoothness values ​​disclosed herein are calculated as the average surface roughness of coated conductor wire samples (14 American Wire Gauge (AWG) wire with a coating thickness of 10 mm to 15 mm) and reported in microinches (μ-in). Surface roughness values ​​were measured using a Mitutoyo SJ 400 surface roughness tester. Generally, the average surface roughness of relatively smooth wires is less than that of relatively rough wires.

[0181] thermal creep

[0182] Unless otherwise stated, all thermal creep values ​​disclosed herein are measured according to ICEA T-28-562 and reported as a percentage of elongation. Dog bone samples were prepared according to ASTM D412, type D, using a 20 N / cm² thermometer attached to the lower end of the sample. 2 The weights were stretched for 15 minutes at 200℃.

[0183] Example

[0184] Example 1

[0185] Multiple bimodal polyethylene samples were produced via gas-phase polymerization in a single reactor. The main catalyst was fed via a 0.25-inch (") injection tube into a reactor suitable for use as a UNIPOL catalyst. TM The polyethylene reactor was purchased from Univation Technologies. The fine-tuning catalyst was also fed into the polyethylene reactor via the same 0.25" injection tube at a rate sufficient to provide the desired resin flow index. The reactor gas composition was controlled by metering the feed into the polyethylene reactor at a rate sufficient to maintain the desired ethylene partial pressure, the molar ratio of comonomer to ethylene (C2), the molar ratio of hydrogen (H2) to ethylene (C2), and the amount of isopentane. Based on the ethylene feed rate to the reactor, an additive, commercially available as CA-300 from Univation Technologies, was separately fed into the polyethylene reactor at a rate sufficient to maintain an additive concentration of approximately 45 parts by weight per million parts by weight (ppmw). The polyethylene reactor temperature was maintained at the desired temperature, and the reactor residence time was approximately 2.0 to 2.5 hours. The reactor bed weight was maintained by discharging the granular resin into a discharge tank, which was purged with nitrogen and then again with a mixture of nitrogen and steam before being poured into the fiber bundles. The process conditions used to produce each bimodal polyethylene sample are reported in Table 1.

[0186] Table 1

[0187]

[0188] a As PRODIGY TM The BMC-200 was purchased from Univation Technologies.

[0189] b Contains bis(2-pentamethylphenylamide)ethyl)amine dibenzylzirconium, (1,3-dimethyl-4,5,6,7-tetrahydroindene)(methylcyclopentadienyl)dimethylzirconium, methylaluminoxane (MAO), and pyrolytic silica (which can be used as...). TS-610 is a spray-dried mixture of mineral oil slurry (obtained commercially from Cabot Corporation).

[0190] c Contains bis(2-pentamethylphenylamino)ethyl)amine dibenzylzirconium, (cyclopentadienyl)(1,5-dimethylindenyl)dimethylzirconium, methylaluminoxane (MAO), and pyrolytic silica (which can be used as...). TS-610 is a spray-dried mixture of mineral oil slurry (obtained commercially from Cabot Corporation).

[0191] d As PRODIGY TM The TR-200 was purchased from Univation Technologies.

[0192] e 0.04 wt% (1,3-dimethyl-4,5,6,7-tetrahydroindene)(methylcyclopentadienyl)dimethylzirconium bis(n-butylcyclopentadienyl)dimethylzirconium in isopentane

[0193] f 0.04 wt% (cyclopentadienyl)(1,5-dimethylindenyl)dimethylzirconium in isopentane

[0194] Characteristics of polyethylene examples

[0195] The bimodal polyethylene sample of Example 1 and various commercially available samples exhibit various properties, including density, melt index (I2), and high-load melt index (I). -21 ) and melt flow ratio (MFR) 21 The report is in Table 2.

[0196] Table 2

[0197]

[0198]

[0199] a Can be used as ELITE TM 5940G was purchased from Dow Chemical Company.

[0200] b Available commercially from Dow Chemical Company as DFNA-4580 NT.

[0201] c Can be used as ELITE TM 5940ST was purchased from Dow Chemical Company.

[0202] d As HE6062 was purchased from Borealis AG.

[0203] e Available commercially from Dow Chemical Company as DFNB-3580NT.

[0204] f Basic polymer properties of CE-4 per unit technical data sheet

[0205] The molecular weight of polyethylene in the examples

[0206] The molecular weights of the bimodal polyethylene sample from Example 1 and various commercially available samples, including weight-average molecular weight (M). w Number-average molecular weight (M) n ) and z-average molecular weight (M z The report is in Table 3.

[0207] Table 3

[0208]

[0209] Comonomer distribution in the polyethylene examples

[0210] The short-chain branching distribution (SCBD2) of the high molecular weight component and the short-chain branching distribution (SCBD1) of the low molecular weight component of the bimodal polyethylene sample of Example 1, as well as the comonomer distribution, are reported in Table 4.

[0211] Table 4

[0212]

[0213] a Single-peak polyethylene

[0214] Complex viscosity of polyethylene examples

[0215] The various complex viscosities of the bimodal polyethylene sample of Example 1 and various commercially available samples are reported in Table 5.

[0216] Table 5

[0217]

[0218]

[0219] Properties of thermoplastic compositions

[0220] Thermoplastic compositions were prepared by mixing various polymers (including the bimodal polyethylene sample of Example 1) with various additives using a 3 / 4" twin-screw extruder (180°C / 190°C / 190°C temperature distribution and 60-mesh screen pack) at 60 rpm. The components of the thermoplastic compositions and various properties of the thermoplastic compositions are reported in Tables 6 to 8.

[0221] Table 6

[0222]

[0223] a Can be used as AXELERON TM GP A-0037BK CPD was commercially available from Dow Chemical Company (comprising 3.12 wt% base resin and 2.55 wt% carbon black).

[0224] b As Dynamar TM FX 5912 was purchased from 3M.

[0225] c Purchased from Synox-TBM6 by Synhemer

[0226] d A mixture of 0.15% Irgafos 168 and 0.10% Irganox 1010

[0227] e Can be used as Super Q was purchased from Addivant.

[0228] f Can be used as AXELERON TM FO 6548 BK CPD was purchased from Dow Chemical Company.

[0229] Table 7

[0230]

[0231] Table 8

[0232]

[0233] The 2.5" production line is a Davis standard wire coating production line equipped with a 24:1 polyethylene type screw and Maddox mixing head. This equipment is used to produce samples with a final diameter of approximately 2.9 mm and a wall thickness of approximately 0.635 mm on 14 AWG solid copper conductor (1.63 mm in diameter). The extrusion line operates at a linear speed of 300 ft / min.

[0234] The micro wire production line is a Brabender-type wire coating production line equipped with a 3 / 4" diameter, 25:1 L / D general-purpose polyethylene screw. This equipment is used to produce samples with a final diameter of approximately 2.2 mm and a wall thickness of approximately 0.254 mm on 14 AWG solid copper conductor (1.63 mm in diameter). The extrusion line operates at a linear speed of 50 ft / min.

[0235] As shown in Table 8, the thermoplastic compositions containing bimodal polyethylene of this disclosure offer an excellent balance between processability (e.g., reduced perforated plate pressure and improved wire smoothness) and properties (e.g., improved mechanical properties, such as greater tensile strength at break and resistance to environmental stress cracking). As described herein, this balance between processability and properties is critical to ensure successful manufacturing and long-term durability of the insulation and sheathing layers used in wires and cables during service. For example, when compared to CE-2.2, despite having similar density and melt index (I2), IE-2.1 exhibits superior wire smoothness (i.e., processability) and resistance to environmental stress cracking, tensile strength at break, and elongation at break. Furthermore, when compared to CE-2.3, despite having similar density and melt index (I2), IE-2.2 and IE-2.3 offer improved perforated plate pressure and wire smoothness while maintaining similar resistance to environmental stress cracking and tensile strength at break. Similarly, when compared to CE-2.5, despite having similar density and melt index (I2), IE-2.4 offers improved perforated plate pressure and wire smoothness while maintaining similar resistance to environmental stress cracking and tensile strength at break.

[0236] Example 2

[0237] Various bimodal polyethylenes are produced via gas-phase polymerization in a single reactor. The main catalyst is fed into the polyethylene reactor (which can be used as a UNIPOL) via a 0.25" injection tube. TM (Purchased commercially from Univation Technologies), the main catalyst is dibenzyl zirconium containing bis(2-pentamethylphenylamide)ethyl)amine, (1,3-dimethyl-4,5,6,7-tetrahydroindene)(methylcyclopentadienyl)dimethylzirconium, methylaluminoxane (MAO), and pyrolytic silica (which can be used as...). TS-610 is a spray-dried mixture of mineral oil slurry (commercially available from Cabot Corporation). A fine-tuning catalyst, consisting of 0.04 wt% (1,3-dimethyl-4,5,6,7-tetrahydroindene)(methylcyclopentadienyl)dimethylzirconium, bis(n-butylcyclopentadienyl)dimethylzirconium, and isopentane, is also fed into the polyethylene reactor via the same 0.25" injection tube at a rate sufficient to provide the desired resin flow index. The reactor gas composition is controlled by metering the feed into the polyethylene reactor at a rate sufficient to maintain the desired ethylene partial pressure, the molar ratio of comonomer to ethylene (C2), the molar ratio of hydrogen (H2) to ethylene (C2), and the amount of isopentane. Based on the ethylene feed rate to the reactor, a rate sufficient to maintain an additive concentration of approximately 40 ppmw is also used as CA-300 from Univin Technologies. Additives, commercially available from [Technologies], are fed separately into the polyethylene reactor. The polyethylene reactor temperature is maintained at 100°C, and the reactor residence time is approximately 2.0 to 2.5 hours. The reactor bed weight is maintained by discharging granular resin into a discharge tank, which is purged with nitrogen and then again with a mixture of nitrogen and steam before being poured into the fiber bundles. The process conditions used for each type of bimodal polyethylene and the various properties of bimodal polyethylene are reported in Table 9.

[0238] Table 9

[0239]

[0240]

[0241] The dimensions and values ​​disclosed herein should not be construed as strictly limited to the precise numerical values ​​listed. In fact, unless otherwise specified, each such dimension is intended to represent both the stated value and the range of its functional equivalence. For example, the disclosed value is "40 g / cm³". 3The dimensions are intended to indicate "approximately 40g / cm³". 3 ".

[0242] The symbols used in the formulas included in this article refer to their standard meanings as understood in the field of mathematics. For example, "=" means equal to, "×" means multiplication, "+" means addition, "-" means subtraction, ">" is the "greater than" symbol, "<" is the "less than" symbol, and " / " means division.

[0243] Unless expressly excluded or otherwise limited, every document cited herein (if any), any cross-reference containing a claim to priority or right made by this application, or any related patent or patent application, is incorporated herein by reference in its entirety. No reference to any document acknowledges that it is prior art with respect to any embodiment disclosed or claimed herein, or that it teaches, illustrates, or discloses any such embodiment, alone or in combination with any other reference document or plural references. Furthermore, in the event of any conflict between the meaning or definition of any term in this document and the meaning or definition of the same term in any document incorporated herein by reference, the meaning or definition given to the term in this document shall prevail.

Claims

1. A bimodal polyethylene comprising a high molecular weight component and a low molecular weight component, wherein the bimodal polyethylene has: Density of 0.933 g / cm3to 0.960 g / cm3when measured according to ASTM D792-13 Method B 3 Density of 0.933 g / cm3to 0.960 g / cm3when measured according to ASTM D792-13 Method B 3 Density of 0.933 g / cm3to 0.960 Melt index I2, measured according to ASTM D1238-10 at 190°C and 2.16 kg load, ranges from 0.3 dg / min to 1.2 dg / min. Melt flow ratio (MFR) greater than 80.0 and less than or equal to 120.0 21 The melt flow ratio MFR 21 It is the high-load melt index I of the bimodal polyethylene 21 The ratio to the melt flow index I2, and the high-load melt flow index I 21 It was measured according to ASTM D1238-10 at 190°C and a load of 21.6 kg; Molecular weight distribution M greater than 10.0 w / M n The molecular weight distribution M w / M n The weight-average molecular weight M of the bimodal polyethylene is w The number-average molecular weight M of the bimodal polyethylene n The ratio, and the weight-average molecular weight M w and the number-average molecular weight M n It was measured using gel permeation chromatography (GPC). The reverse comonomer distribution, wherein the ratio of the short-chain branching distribution SCBD2 of the high molecular weight component to the short-chain branching distribution SCBD1 of the low molecular weight component is greater than 1.0, and the short-chain branching distributions SCBD2 of the high molecular weight component and SCBD1 of the low molecular weight component are measured using gel permeation chromatography (GPC), wherein the short-chain branching distribution SCBD2 of the high molecular weight component of the bimodal polyethylene is greater than 8.0 average branch number / 1000 carbons; and The shear thinning index SHI is between 5.0 and 20.0, wherein the shear thinning index SHI is the ratio of the complex viscosity η*0.1 of the bimodal polyethylene measured at 0.1 radians per second to the complex viscosity η*100 of the bimodal polyethylene measured at 100 radians per second, and the complex viscosity of the bimodal polyethylene is determined at 190°C using dynamic mechanical spectrometry (DMS).

2. The bimodal polyethylene according to claim 1, wherein the bimodal polyethylene has a content of 0.933 g / cm³. 3 Up to 0.945 g / cm 3 The density.

3. The bimodal polyethylene according to claim 1, wherein the bimodal polyethylene has a content of 0.945 g / cm³. 3 Up to 0.960 g / cm 3 The density.

4. The bimodal polyethylene according to claim 1, wherein the shear thinning index SHI is less than or equal to 15.

0.

5. The bimodal polyethylene according to any one of claims 1 to 4, wherein the bimodal polyethylene has a molecular weight distribution M greater than 4.

0. z / M w The molecular weight distribution M z / M w The z-average molecular weight M of the bimodal polyethylene, measured using GPC. z With weight-average molecular weight M w The ratio.

6. A method for preparing bimodal polyethylene according to any one of claims 1 to 5, the method comprising polymerizing ethylene and at least one 1-olefin comonomer in a single reactor by gas-phase polymerization in the presence of a main catalyst and a fine-tuning catalyst to prepare the bimodal polyethylene.

7. A thermoplastic composition comprising 50.1% to 99.9% by weight of bimodal polyethylene according to any one of claims 1 to 5; and 0.1% to 1.0% by weight of a first antioxidant component, and optionally 0.0% to 1.0% by weight of a second antioxidant; 0.0% to 5.0% by weight of UV stabilizer; 0.0% to 1.0% by weight of processing aids; 0.0% to 1.0% by weight of flame retardants; and 0.0% to 1.0% by weight of fillers.

8. An article of manufacture using bimodal polyethylene according to any one of claims 1 to 5 or a thermoplastic composition according to claim 7.

9. The article of claim 8, wherein the article is a coated conductor, the coated conductor comprising: Conductive core; as well as The coating at least partially covers the conductive core. The coating comprises bimodal polyethylene according to any one of claims 1 to 5 or the thermoplastic composition according to claim 7.

10. The article of claim 9, wherein the conductive core comprises a metal wire, an optical fiber, or both.

11. The article of manufacture according to any one of claims 8 to 10, wherein the article of manufacture comprises: When measured at 50°C in a 10% Igepal solution according to ASTM D1693-1 Method B, the environmental stress fracture resistance ESCR F0 is greater than 48 hours.

12. A method for transmitting electricity or light through an article of claim 10, the method comprising: A voltage is applied across the two ends of the metal wire, thereby allowing electrical energy to flow through the metal wire; Optical pulses are transmitted through the optical fiber, thereby enabling optical transmission through the optical fiber; or A voltage is applied across the two ends of the metal wire and an optical pulse is transmitted through the optical fiber, thereby causing electrical energy to flow through the metal wire and light to be transmitted through the optical fiber.

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