Thermoplastic compositions containing bimodal polyethylene and articles manufactured therefrom

Abstract

In various embodiments, the bimodal polyethylene may include a high molecular weight component and a low molecular weight component. The bimodal polyethylene has a viscosity of 0.933 grams per centimeter (g / cm 3 )~0.960g / cm 3 Density of 0.3 decigrams per minute (dg / min) to 1.2 dg / min, Melt Index (I2) of 0.3 decigrams per minute (dg / min) to 1.2 dg / min, and Melt Flow Ratio (MFR) of over 80.0 21 ) and a molecular weight distribution (M w / M n ), an inverse comonomer distribution, and a shear thinning index of 5.0 to 20.0. Methods for producing the bimodal polyethylene, and articles made from the bimodal polyethylene are also provided.

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application claims priority to U.S. Provisional Patent Application No. 63 / 061,369, filed on 5 August 2020, the entire disclosure of which is incorporated herein by reference.

[0002] (Field of invention) Embodiments of this disclosure generally relate to thermoplastic compositions, in particular to thermoplastic compositions comprising bimodal polyethylene and articles manufactured therefrom. [Background technology]

[0003] When manufacturing insulators and jacket layers for wires and cables, both the performance (e.g., mechanical properties, resistance to environmental stress cracking, etc.) and processability of the thermoplastic composition used in the manufacture of the insulators and jacket layers are crucial to ensuring both success in manufacturing and long-term durability in use. Some thermoplastic compositions may possess excellent mechanical properties, such as elongation at break, but these excellent mechanical properties are typically achieved at the expense of processability, resistance to environmental stress cracking, or a combination thereof. In contrast, 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 need for thermoplastic compositions that balance mechanical properties and processability while maintaining resistance to environmental stress cracking. [Overview of the project]

[0004] Embodiments of this disclosure address these needs by providing bimodal polyethylene containing high molecular weight and low molecular weight components. Bimodal polyethylene has a molecular weight of 0.933 grams / cm³ (g / cm³). 3 ) ~0.960g / cm³ 3 The density, the melt index (I2) of 0.3 decigrams / min (dg / min) to 1.2 dg / min, and the melt flow ratio (MFR) of 80.0 or higher. 21) and molecular weight distribution of 10 or more (M w / M n It may have a reverse comonomer distribution and a shear viscosity index of 5.0 to 20.0.

[0005] These and further features provided by embodiments of this disclosure will be better understood by considering the following detailed description. [Modes for carrying out the invention]

[0006] As mentioned above, when manufacturing insulators and jacket layers for wires and cables, both the performance (e.g., mechanical properties, resistance to environmental stress cracking, etc.) and processability of the thermoplastic composition used in the manufacture of the insulators and jacket layers are important to ensure both successful manufacturing and long-term durability in use. Typically, high-density polyethylene is used to produce thermoplastic compositions in order to achieve insulators and jacket layers with improved mechanical properties, resulting in improved abrasion resistance for durability and a reduced coefficient of friction for ease of installation. However, high-density polyethylene generally results in insulators and jacket layers with low resistance to environmental stress cracking, which leads to brittle fracture of the insulators and jacket layers. Reducing the density, melt index, and high-load melt index of polyethylene can improve the resistance to environmental stress cracking of insulators and jacket layers, but this can also reduce the mechanical properties of the insulators and jacket layers as well as the processability of the polyethylene.

[0007] Embodiments of this disclosure relate to bimodal polyethylene that exhibits excellent processability and a high shear viscosity index, while also achieving remarkable mechanical properties and resistance to environmental stress cracking. In particular, embodiments of this disclosure relate to bimodal polyethylene containing high molecular weight and low molecular weight components. The bimodal polyethylene has a molecular weight of 0.933 g / cm³. 3 ~0.960g / cm 3 The density, the melt index (I2) of 0.3 dg / min to 1.2 dg / min, and the melt flow ratio (MFR) of 80.0 or higher. 21 ) and molecular weight distribution of 10 or more (Mw / M n ) and an inverse comonomer distribution, and a shear thinning index of 5.0 to 20.0.

[0008] The term "polymer" refers to a polymer compound prepared by polymerizing monomers, whether of the same kind or different kinds. Thus, the general term "polymer" includes homopolymers, which are polymers prepared by polymerizing only one kind of monomer, and copolymers, which are polymers prepared by polymerizing two or more different monomers.

[0009] The term "interpolymer" refers to a polymer prepared by polymerizing at least two different monomers. Thus, the general term "interpolymer" includes copolymers and other polymers prepared by polymerizing more than two different monomers, such as terpolymers.

[0010] The term "monomodal polymer" may refer to a polymer characterized by having only one fraction with a common density, weight average molecular weight, and optionally, melt index value. A monomodal polymer may also be characterized by having only one distinct peak in a gel permeation chromatography (GPC) chromatogram showing the molecular weight distribution of the composition.

[0011] The term "multimodal polymer" may refer to a polymer characterized by having at least two fractions with various densities, weight average molecular weights, and optionally, melt index values. A multimodal polymer may be characterized by having at least two distinct peaks in a gel permeation chromatography (GPC) chromatogram showing the molecular weight distribution of the composition. Thus, the general term "multimodal polymer" includes bimodal polymers having two main fractions: a first fraction that may be a low molecular weight fraction and / or component, and a second fraction that may be a high molecular weight fraction and / or component.

[0012] The terms "polyolefin," "polyolefin polymer," and "polyolefin resin" refer to simple olefins (also called alkenes, with general formula C11). n H 2n This refers to polymers prepared by polymerizing monomers (containing) such monomers. Therefore, the general term polyolefin 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.

[0013] The terms "polyethylene" and "ethylene polymer" refer to polyolefins containing units derived from more than 50 mole percent (%) of ethylene monomer, 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).

[0014] The term "melt flow ratio" refers to the ratio of the melt indices of polymers. Therefore, the general term "melt flow ratio" refers to the ratio of the high-load metal index (I²) of the polymer to the melt index (I²) of the polymer. 21 ) includes the ratio of "MFR 21 It is sometimes referred to as "[...]."

[0015] The term "molecular weight distribution" refers to the ratio of molecular weights of polymers. The general term "molecular weight distribution" refers to the weight-average molecular weight (M) of the polymer. wThe number average molecular weight (M) of the polymer in question. n ) Ratio to ("Molecular weight distribution (M w / M n ) (sometimes referred to as "), and the z-average molecular weight (M) of the polymer. z The weight-average molecular weight (M) of the polymer in question. w ) Ratio to ("Molecular weight distribution (M z / M w This includes (sometimes referred to as ")").

[0016] The term "shear viscosity index" refers to the ratio of the complex viscosities of a polymer. Therefore, the general term shear viscosity index includes the ratio of the complex viscosity of a polymer at a frequency of 0.1 rad / s to the complex viscosity of a polymer at a frequency of 100 radians / second (rad / s).

[0017] The term "composition" refers to a mixture of materials containing the composition, as well as reaction and decomposition products formed from the materials of the composition.

[0018] The terms “comprising,” “including,” and “having,” and their derivatives, are not intended to exclude the existence of any additional components, steps, or procedures, whether or not they are specifically disclosed. To avoid any doubt, all compositions claimed through the use of the term “comprising” may include any additional additives, adjuvants, or compounds, whether polymeric or otherwise, unless otherwise stated. In contrast, the term “essentially consisting of” excludes any other components, steps, or procedures from any subsequently enumerated scope, except those not essential to operability. The term “consisting of” excludes any components, steps, or procedures not specifically described or enumerated.

[0019] In this embodiment, the bimodal polyethylene is 0.933 g / cm³ 3 For example, 0.936 g / cm³ 3 More than 0.939g / cm3 More than 0.942g / cm 3 More than 0.945g / cm 3 More than 0.948g / cm 3 More than 0.951g / cm 3 More than 0.954g / cm 3 Above, or 0.957 g / cm³ 3 It may have a density greater than the above. Bimodal polyethylene also has a density of 0.960 g / cm³. 3 For example, 0.957 g / cm³ 3 Below, 0.954g / cm 3 Below, 0.951g / cm 3 Below, 0.948g / cm 3 Below, 0.945g / cm 3 Below, 0.942g / cm 3 Below, 0.939g / cm 3 The following, or 0.936 g / cm³ 3 It may have the following densities. For example, bimodal polyethylene has a density of 0.933 g / cm³. 3 ~0.960g / cm 3 , 0.933 g / cm³ 3 ~0.957 g / cm³ 3 , 0.933 g / cm³ 3 ~0.954 g / cm³ 3 , 0.933 g / cm³ 3 ~0.951 g / cm³ 3 , 0.933 g / cm³ 3 ~0.948 g / cm³ 3 , 0.933 g / cm³ 3 ~0.945g / cm 3 , 0.933 g / cm³ 3 ~0.942 g / cm³ 3 , 0.933 g / cm³ 3 ~0.9390g / cm 3 , 0.933 g / cm³ 3 ~0.936 g / cm³ 3 , 0.936 g / cm³ 3 ~0.960g / cm 3 , 0.936 g / cm³ 3 ~0.957 g / cm³ 3 , 0.936 g / cm³ 3 ~0.954 g / cm³ 3、0.936g / cm 3 ~0.951g / cm 3 、0.936g / cm 3 ~0.948g / cm 3 、0.936g / cm 3 ~0.945g / cm 3 、0.936g / cm 3 ~0.942g / cm 3 、0.936g / cm 3 ~0.939g / cm 3 、0.939g / cm 3 ~0.960g / cm 3 、0.939g / cm 3 ~0.957g / cm 3 、0.939g / cm 3 ~0.954g / cm 3 、0.939g / cm 3 ~0.951g / cm 3 、0.939g / cm 3 ~0.948g / cm 3 、0.939g / cm 3 ~0.945g / cm 3 、0.939g / cm 3 ~0.942g / cm 3 、0.942g / cm 3 ~0.960g / cm 3 、0.942g / cm 3 ~0.957g / cm 3 、0.942g / cm 3 ~0.954g / cm 3 、0.942g / cm 3 ~0.951g / cm 3 、0.942g / cm 3 ~0.948g / cm 3 、0.942g / cm 3 ~0.945g / cm 3 、0.945g / cm 3 ~0.960g / cm 3 、0.945g / cm 3 ~0.957g / cm 3 、0.945g / cm 3 ~0.954g / cm 3 、0.945g / cm 3 ~0.951g / cm3 , 0.945 g / cm³ 3 ~0.948 g / cm³ 3 , 0.948 g / cm³ 3 ~0.960g / cm 3 , 0.948 g / cm³ 3 ~0.957 g / cm³ 3 , 0.948 g / cm³ 3 ~0.954 g / cm³ 3 , 0.948 g / cm³ 3 ~0.951 g / cm³ 3 , 0.951 g / cm³ 3 ~0.960g / cm 3 , 0.951 g / cm³ 3 ~0.957 g / cm³ 3 , 0.951 g / cm³ 3 ~0.954 g / cm³ 3 , 0.954 g / cm³ 3 ~0.960g / cm 3 , 0.954 g / cm³ 3 ~0.957 g / cm³ 3 , or 0.957 g / cm³ 3 ~0.960g / cm 3 It may have a density of, for example, 0.960 g / cm³. As mentioned above, the density of bimodal polyethylene may be, for example, 0.960 g / cm³. 3 If the density exceeds a certain level, articles made from bimodal polyethylene may have poor resistance to environmental stress cracking, which can lead to brittle fracture of the insulator and jacket layers. In contrast, if the density of bimodal polyethylene is, for example, 0.933 g / cm³, 3 If the value is less than the specified value, the mechanical properties of the article and the processability of bimodal polyethylene may be reduced.

[0020] In the embodiment, bimodal polyethylene may have a melt index (I2) of 0.3 dg / min or more, for example, 0.4 dg / min or more, 0.5 dg / min or more, 0.6 dg / min or more, 0.7 dg / min or more, 0.8 dg / min or more, 0.9 dg / min or more, 1.0 dg / min or more, or 1.1 dg / min or more. Bimodal polyethylene may also have a melt index (I2) of 1.2 dg / min or less, for example, 1.1 dg / min or less, 1.0 dg / min or less, 0.9 dg / min or less, 0.8 dg / min or less, 0.7 dg / min or less, 0.6 dg / min or less, 0.5 dg / min or less, or 0.4 dg / min or less.For example, bimodal polyethylene has concentrations of 0.3dg / min to 1.2dg / min, 0.3dg / min to 1.1dg / min, 0.3dg / min to 1.0dg / min, 0.3dg / min to 0.9dg / min, 0.3dg / min to 0.8dg / min, 0.3dg / min to 0.7dg / min, 0.3dg / min to 0.6dg / min, 0.3dg / min to 0.5dg / min, 0.3dg / min to 0.4dg / min, 0.4dg / min to 1.2dg / min, and 0.4dg / min to 1.1dg / min. min, 0.4dg / min~1.0dg / min, 0.4dg / min~0.9dg / min, 0.4dg / min~0.8dg / min, 0.4dg / min~0.7dg / min, 0.4dg / min~0.6dg / min, 0.4dg / min~0.5d g / min, 0.5dg / min~1.2dg / min, 0.5dg / min~1.1dg / min, 0.5dg / min~1.0dg / min, 0.5dg / min~0.9dg / min, 0.5dg / min~0.8dg / min, 0.5dg / min~0.7 dg / 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, 0.6dg / 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, 0.7dg / min to It may have a melt index (I2) of 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 1.0 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.

[0021] In the embodiment, bimodal polyethylene has a high load melt index (I) of 25.0 dg / min or more, for example, 35.0 dg / min or more, 45.0 dg / min or more, 55.0 dg / min or more, 65.0 dg / min or more, 75.0 dg / min or more, 85.0 dg / min or more, 95.0 dg / min or more, 105.0 dg / min or more, or 115.0 dg / min or more. 21Bimodal polyethylene may also have a high load melt index (I) of 125.0 dg / min or less, for example, 115.0 dg / min or less, 105.0 dg / min or less, 95.0 dg / min or less, 85.0 dg / min or less, 75.0 dg / min or less, 65.0 dg / min or less, 55.0 dg / min or less, 45.0 dg / min or less, or 35.0 dg / min or less. 21) may have. For example, bimodal polyethylene may have 25.0 dg / min to 125.0 dg / min, 25.0 dg / min to 115.0 dg / min, 25.0 dg / min to 105.0 dg / min, 25.0 dg / min to 95.0 dg / min, 25.0 dg / min to 85.0 dg / min, 25.0 dg / min to 75.0 dg / min, 25.0 dg / min to 65.0 dg / min, 25.0 dg / min to 55.0 dg / min, 25.0 dg / min to 45.0 dg / min, 25.0 dg / min to 35.0 dg / min, 35.0 dg / min to 125.0 dg / min, 35.0 dg / min to 115.0 dg / min, and 35.0 dg / min to 10 5.0 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 / 125.0 dg / min, 45.0 dg / min to 115.0 dg / min, 45.0 dg / min to 105.0 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 0.0dg / min to 55.0dg / min, 55.0dg / min to 125.0dg / min, 55.0dg / min to 115.0dg / min, 55.0dg / min to 105.0dg / min, 55.0dg / min to 95.0dg / min, 55.0dg / min to 85.0dg / min, 55.0dg / min to 75.0dg g / 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 95.0 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.High-load melt index (I.) of 0 dg / min, 105.0 dg / min to 115.0 dg / min, or 115.0 dg / min to 125.0 dg / min. 21 ) may have.

[0022] In the embodiment, the bimodal polyethylene has a melt flow ratio (MFR) of 80.0 or higher, for example, 90.0 or higher, 100.0 or higher, 110.0 or higher, 120.0 or higher, 130.0 or higher, or 140.0 or higher. 21 Bimodal polyethylene may also have a melt flow ratio (MFR) of 150.0 or less, for example, 140.0 or less, 130.0 or less, 120.0 or less, 110.0 or less, 100.0 or less, or 90.0 or less. 21 ) may have. For example, bimodal polyethylene may have 80.0~150.0, 80.0~140.0, 80.0~130.0, 80.0~120.0, 80.0~110.0, 80.0~100.0, 80.0~90.0, 90.0~150.0, 90.0~140.0, 90.0~130.0, 90.0~120.0, 90.0~110.0, 90.0~100.0, 100.0~150.0, 100.0~ Melt flow ratio (MFR) of 140.0, 100.0~130.0, 100.0~120.0, 100.0~110.0, 110.0~150.0, 110.0~140.0, 110.0~130.0, 110.0~120.0, 120.0~150.0, 120.0~140.0, 120.0~130.0, 130.0~150.0, 130.0~140.0, or 140.0~150.0 21 ) may have. Melt flow ratio (MFR) of bimodal polyethylene. 21 If the melt flow ratio (MFR) of bimodal polyethylene is, for example, less than 80.0, the thermoplastic composition containing bimodal polyethylene may not have suitable processability for manufacturing articles such as insulators and jacket layers for wires and cables. Furthermore, if the melt flow ratio (MFR) of bimodal polyethylene is less than 80.0, the thermoplastic composition containing bimodal polyethylene may not have suitable processability for manufacturing articles such as insulators and jacket layers for wires and cables. 21 If the value is, for example, less than 80.0, the insulator and jacket layer containing bimodal polyethylene may not have the wire smoothness value required for some applications.

[0023] In the embodiment, the bimodal polyethylene has a number average molecular weight (M) of 5,000 g / mol or more, for example, 10,000 g / mol or more, 15,000 g / mol or more, 20,000 g / mol or more, or 25,000 g / mol or more. n Bimodal polyethylene may also have a number average molecular weight (M) of 30,000 g / mol or less, for example, 25,000 g / mol or less, 20,000 g / mol or less, 15,000 g / mol or less, or 10,000 g / mol or less. n ) may have. For example, bimodal polyethylene may have 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 weight (M) 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 ) may have.

[0024] In this embodiment, the bimodal polyethylene has a weight-average molecular weight (M) of 100,000 g / mol or more, for example, 115,000 g / mol or more, 130,000 g / mol or more, 145,000 g / mol or more, or 160,000 g / mol or more. w Bimodal polyethylene may also have a weight-average molecular weight (M) of 175,000 g / mol or less, for example, 160,000 g / mol or less, 145,000 g / mol or less, 130,000 g / mol or less, or 115,000 g / mol or less. w) may have. For example, bimodal polyethylene may have 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) of 145,000 g / mol, 115,000 g / mol, 130,000 g / mol, 130,000 g / mol, 175,000 g / mol, 130,000 g / mol, 160,000 g / mol, 130,000 g / mol, 145,000 g / mol, 145,000 g / mol, 175,000 g / mol, 145,000 g / mol, 160,000 g / mol, or 175,000 g / mol. w ) may have.

[0025] In this embodiment, the bimodal polyethylene has a z-average molecular weight (M) of 500,000 g / mol or more, for example, 700,000 g / mol or more, 900,000 g / mol or more, 1,100,000 g / mol or more, 1,300,000 g / mol or more, 1,500,000 g / mol or more, 1,700,000 g / mol or more, 1,900,000 g / mol or more, 2,100,000 g / mol or more, 2,300,000 g / mol or more, or 2,500,000 g / mol or more. z Bimodal polyethylene may also have a z-average molecular weight (M) of 2,700,000 g / mol or less, for example, 2,500,000 g / mol or less, 2,300,000 g / mol or less, 2,100,000 g / mol or less, 1,900,000 g / mol or less, 1,700,000 g / mol or less, 1,500,000 g / mol or less, 1,300,000 g / mol or less, 1,100,000 g / mol or less, 900,000 g / mol or less, or 700,000 g / mol or less. z) may have. For example, bimodal polyethylene may have 500,000 g / mol~1,500,000 g / mol, 500,000 g / mol~1,300,000 g / mol, 500,000 g / mol~1,100,000 g / mol, 500,000 g / mol~900,000 g / mol, 500,000 g / mol~700,000 g / mol, 700,000 g / mol~1,500,000 g / mol, 700,000 g / mol~1,300,000 g / mol, 700,000 g / mol~1, The z-average molecular weight (M) 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 ) may have.

[0026] In the embodiment, the number average molecular weight (M) of bimodal polyethylene. n The weight-average molecular weight (M) of bimodal polyethylene relative to ) w The ratio of ) may be 10 or more, for example, 12 or more, 14 or more, 16 or more, or 18 or more. Number average molecular weight (M) of bimodal polyethylene n The weight-average molecular weight (M) of bimodal polyethylene relative to ) w The ratio of (M) may be 20 or less, for example, 18 or less, 16 or less, 14 or less, or 12 or less. For example, the number average molecular weight (M) of bimodal polyethylene. n The weight-average molecular weight (M) of bimodal polyethylene relative to ) w The ratio of (M) can be 10-20, 10-18, 10-16, 10-14, 10-12, 12-20, 12-18, 12-16, 12-14, 14-20, 14-18, 14-16, 16-20, 16-18, or 18-20. The number average molecular weight (M) of bimodal polyethylene. n The weight-average molecular weight (M) of bimodal polyethylene relative to ) wIf the ratio of (M) is, for example, less than 10, the thermoplastic composition containing bimodal polyethylene may not have suitable processability for manufacturing articles such as insulators and jacket layers for wires and cables. Furthermore, if the number average molecular weight (M) of bimodal polyethylene is less than 10, the thermoplastic composition containing bimodal polyethylene may not have suitable processability for manufacturing articles such as insulators and jacket layers for wires and cables. n The weight-average molecular weight (M) of bimodal polyethylene relative to ) w If the ratio of ) is, for example, less than 10, the insulator and jacket layer containing bimodal polyethylene may not have the wire smoothness value required for some applications.

[0027] In this embodiment, the weight-average molecular weight (M) of bimodal polyethylene is w ) relative to the z-average molecular weight (M) of bimodal polyethylene z The ratio of ) can be 4 or more, for example, 6 or more, 8 or more, 10 or more, 12 or more, or 14 or more. The weight-average molecular weight (M) of bimodal polyethylene. w ) relative to the z-average molecular weight (M) of bimodal polyethylene z The ratio of ) may also be 16 or less, for example, 14 or less, 12 or less, 10 or less, 8 or less, or 6 or less. For example, the weight-average molecular weight (M) of bimodal polyethylene. w ) relative to the z-average molecular weight (M) of bimodal polyethylene z The ratios of ) can be 4-16, 4-14, 4-12, 4-10, 4-8, 4-6, 6-16, 6-14, 6-12, 6-10, 6-8, 8-16, 8-14, 8-12, 8-10, 10-16, 10-14, 10-12, 12-16, 12-14, or 14-16.

[0028] In the embodiment, the low molecular weight component of bimodal polyethylene may have a short chain branching distribution (SCBD1) of 0.1 or more, for example, 1.0 or more, 2.0 or more, 3.0 or more, 4.0 or more, 5.0 or more, 6.0 or more, 7.0 or more, 8.0 or more, or 9.0 or more. The low molecular weight component of bimodal polyethylene may also have a short chain branching distribution (SCBD1) of 10.0 or less, for example, 9.0 or less, 8.0 or less, 7.0 or less, 6.0 or less, 5.0 or less, 4.0 or less, 3.0 or less, 2.0 or less, or 1.0 or less. For example, the low molecular weight components of bimodal polyethylene are 0.1-10.0, 0.1-9.0, 0.1-8.0, 0.1-7.0, 0.1-6.0, 0.1-5.0, 0.1-4.0, 0.1-3.0, 0.1-2.0, 0.1-1.0, 1.0-10.0, 1.0-9.0, 1.0-8.0, 1.0-7.0, 1.0-6.0, 1.0-5.0, 1.0-4.0, 1.0-3.0, 1.0-2.0, 2.0-10.0, 2.0-9.0, 2.0-8.0, 2.0-7.0, 2.0-6.0, 2.0-5.0, 2.0-4.0, 2.0-3.0, and 3.0-1. It may have a short-chain branched distribution (SCBD1) of 0.0, 3.0~9.0, 3.0~8.0, 3.0~7.0, 3.0~6.0, 3.0~5.0, 3.0~4.0, 4.0~10.0, 4.0~9.0, 4.0~8.0, 4.0~7.0, 4.0~6.0, 4.0~5.0, 5.0~10.0, 5.0~9.0, 5.0~8.0, 5.0~7.0, 5.0~6.0, 6.0~10.0, 6.0~9.0, 6.0~8.0, 6.0~7.0, 7.0~10.0, 7.0~9.0, 7.0~8.0, 8.0~10.0, 8.0~9.0, or 9.0~10.0.

[0029] In the embodiment, the high molecular weight component of bimodal polyethylene may have a short-chain branched distribution (SCBD2) of 3.0 or more, for example, 4.0 or more, 5.0 or more, 6.0 or more, 7.0 or more, 8.0 or more, 9.0 or more, 10.0 or more, 11.0 or more, 12.0 or more, 13.0 or more, 14.0 or more, 15.0 or more, 16.0 or more, 17.0 or more, 18.0 or more, or 19.0 or more. The high molecular weight component of bimodal polyethylene may also have a short-chain branched distribution (SCBD2) of 20.0 or less, for example, 19.0 or less, 18.0 or less, 17.0 or less, 16.0 or less, 15.0 or less, 14.0 or less, 13.0 or less, 12.0 or less, 11.0 or less, 10.0 or less, 9.0 or less, 8.0 or less, 7.0 or less, 6.0 or less, 5.0 or less, or 4.0 or less. For example, the high molecular weight components of bimodal polyethylene are 3.0-20.0, 3.0-19.0, 3.0-18.0, 3.0-17.0, 3.0-16.0, 3.0-15.0, 3.0-14.0, 3.0-13.0, 3.0-12.0, 3.0-11.0, 3.0-10.0, 3.0-9.0, 3.0-8.0, 3.0-7.0, 3.0-6.0, 5.0-5.0, 3.0-4.0, 4.0~20.0, 4.0~19.0, 4.0~18.0, 4.0~17.0, 4.0~16.0, 4.0~15.0, 4.0~14.0, 4.0~13.0, 4.0~12.0, 4.0~11.0, 4.0~10.0, 4.0~9.0, 4.0~8.0, 4.0~7.0, 4.0~6.0, 4.0~5.0, 5.0~20.0, 5.0~19.0, 5.0~18.0, 5.0~ 17.0, 5.0~16.0, 5.0~15.0, 5.0~14.0, 5.0~13.0, 5.0~12.0, 5.0~11.0, 5.0~10.0, 5.0~9.0, 5.0~8.0, 5.0~7.0, 5.0~6.0, 6.0~20.0, 6.0~19.0, 6.0~18.0, 6.0~17.0, 6.0~16.0, 6.0~15.0, 6.0~14.0, 6.0~13. 0, 6.0~12.0, 6.0~11.0, 6.0~10.0, 6.0~9.0, 6.0~8.0, 6.0~7.0, 7.0~20.0, 7.0~19.0, 7.0~18.0, 7.0~17.0, 7.0~16.0, 7.0~15.0, 7.0~14.0, 7.0~13.0, 7.0~12.0, 7.0~11.0, 7.0~10.0, 7.0~9.0, 7.0~8.0, 8.0-20.0, 8.0-19.0, 8.0-18.0, 8.0-17.0, 8.0-16.0, 8.0-15.0, 8.0-14.0, 8.0-13.0, 8.0-12.0, 8.0-11.0, 8.0-10.0, 8.0-9.0, 9.0-20.0, 9.0-19.0, 9.0-18.0, 9.0-17.0, 9.0-16.0, 9.0-15.0, 9.0-14.0, 9.0-13.0, 9.0-12.0, 9.0-11. 0, 9.0~10.0, 10.0~20.0, 10.0~19.0, 10.0~18.0, 10.0~17.0, 10.0~16.0, 10.0~15.0, 10.0~14.0, 10.0~13.0, 10.0~12.0, 10.0~11.0, 11.0~20.0, 11.0~19.0, 11.0~18.0, 11.0~17.0, 11.0~16.0, 11.0~15.0, 11.0~14.0, 11.0~13.0, 11. 0-12.0, 12.0-20.0, 12.0-19.0, 12.0-18.0, 12.0-17.0, 12.0-16.0, 12.0-15.0, 12.0-14.0, 12.0-13.0, 13.0-20.0, 13.0-19.0, 13.0-18.0, 13.0-17.0, 13.0-16.0, 13.0-15.0, 13.0-14.0, 14.0-20.0, 14.0-19.0, 14.0-18.0, 14.0-17 It may have a short-chain branched distribution (SCBD2) of 0, 14.0-16.0, 14.0-15.0, 15.0-20.0, 15.0-19.0, 15.0-18.0, 15.0-17.0, 15.0-16.0, 16.0-20.0, 16.0-19.0, 16.0-18.0, 16.0-17.0, 17.0-20.0, 17.0-19.0, 17.0-18.0, 18.0-20.0, 18.0-19.0, or 19.0-20.0.

[0030] In embodiments, bimodal polyethylene may have an inverse comonomer distribution. More precisely, in embodiments, the ratio of the short-chain branching distribution of the high-molecular-weight components (SCBD2) to the short-chain branching distribution of the low-molecular-weight components (SCBD1) of bimodal polyethylene may be greater than 1.0. While not bound by any particular theory, bimodal polyethylene with an inverse comonomer distribution is thought to have improved environmental stress cracking resistance (ESCR) and balanced mechanical properties compared to bimodal polyethylene with a normal or flat comonomer distribution.

[0031] In the embodiment, the complex viscosity of bimodal polyethylene at 190°C and a frequency of 0.1 rad / s may be 5,000 Pa·s or more, for example, 10,000 Pa·s or more, 15,000 Pa·s or more, 20,000 Pa·s or more, 25,000 Pa·s or more, or 30,000 Pa·s or more. The complex viscosity of bimodal polyethylene at 190°C and a frequency of 0.1 rad / s may also be 35,000 Pa·s or less, for example, 30,000 Pa·s or less, 25,000 Pa·s or less, 20,000 Pa·s or less, 15,000 Pa·s or less, or 10,000 Pa·s or less. For example, the complex viscosity of bimodal polyethylene at 190°C and a frequency of 0.1 rad / s is 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. a·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.

[0032] In the embodiment, the complex viscosity of bimodal polyethylene at 190°C and a frequency of 1.0 rad / s may be 5,000 Pa·s or more, for example, 7,500 Pa·s or more, 10,000 Pa·s or more, 12,500 Pa·s or more, 15,000 Pa·s or more, or 17,500 Pa·s or more. The complex viscosity of bimodal polyethylene at 190°C and a frequency of 1.0 rad / s may also be 20,000 Pa·s or less, for example, 17,500 Pa·s or less, 15,000 Pa·s or less, 12,500 Pa·s or less, 10,000 Pa·s or less, or 7,500 Pa·s or less. For example, the complex viscosity of bimodal polyethylene at 190°C and a frequency of 1.0 rad / s is 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. It may be 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.

[0033] In the embodiment, the complex viscosity of bimodal polyethylene at 190°C and a frequency of 10 rad / s may be 1,000 Pa·s or more, 2,000 Pa·s or more, for example, 3,000 Pa·s or more, 4,000 Pa·s or more, 5,000 Pa·s or more, 6,000 Pa·s or more, 7,000 Pa·s or more, 8,000 Pa·s or more, or 9,000 Pa·s or more. The complex viscosity of bimodal polyethylene at 190°C and a frequency of 10 rad / s may also be 10,000 Pa·s or less, for example, 9,000 Pa·s or less, 8,000 Pa·s or less, 7,000 Pa·s or less, 6,000 Pa·s or less, 5,000 Pa·s or less, 4,000 Pa·s or less, 3,000 Pa·s or less, or 2,000 Pa·s or less.For example, the complex viscosity of bimodal polyethylene at 190°C and a frequency of 10 rad / s is 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. a·s, 2,000Pa·s~9,000Pa·s, 2,000Pa·s~8,000Pa·s, 2,000Pa·s~7,000Pa·s, 2,000Pa·s~6,000Pa·s, 2,000Pa·s~5,000Pa·s, 2,000Pa·s~4,000P a·s, 2,000Pa·s~3,000Pa·s, 3,000Pa·s~10,000Pa·s, 3,000Pa·s~9,000Pa·s, 3,000Pa·s~8,000Pa·s, 3,000Pa·s~7, 000Pa·s, 3,000Pa·s~6,000 Pa·s, 3,000Pa·s~5,000Pa·s, 3,000Pa·s~4,000Pa·s, 4,000Pa·s~10,000Pa·s, 4,000Pa·s~9,000Pa·s, 4,000Pa·s~8,000Pa·s, 4,000Pa·s~7,0 00Pa s, 4, 000Pa s~6, 000Pa s, 4, 000Pa s~5, 000Pa s, 5, 000Pa s~10, 000Pa s, 5, 000Pa s~9, 000Pa s, 5, 000Pa s~8, 000Pa s, 5, 000Pa s~7, Possible ranges include 000 Pa·s, 5,000 Pa·s ~ 6,000 Pa·s, 6,000 Pa·s ~ 10,000 Pa·s, 6,000 Pa·s ~ 9,000 Pa·s, 6,000 Pa·s ~ 8,000 Pa·s, 6,000 Pa·s ~ 7,000 Pa·s, 7,000 Pa·s ~ 10,000 Pa·s, 7,000 Pa·s ~ 9,000 Pa·s, 7,000 Pa·s ~ 8,000 Pa·s, 8,000 Pa·s ~ 10,000 Pa·s, 8,000 Pa·s ~ 9,000 Pa·s, or 9,000 Pa·s ~ 10,000 Pa·s.

[0034] In the embodiment, the complex viscosity of bimodal polyethylene at 190°C and a frequency of 100 rad / s may be 500 Pa·s or more, for example, 800 Pa·s or more, 1,100 Pa·s or more, 1,400 Pa·s or more, or 1,700 Pa·s or more. The complex viscosity of bimodal polyethylene at 190°C and a frequency of 100 rad / s may be 2,000 Pa·s or less, for example, 1,700 Pa·s or less, 1,400 Pa·s or less, 1,100 Pa·s or less, or 800 Pa·s or less. For example, the complex viscosity of bimodal polyethylene at 190°C and a frequency of 100 rad / s is 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. It may be 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.

[0035] In the embodiment, 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)) may be 5.0 or greater, for example, 7.5 or greater, 10.0 or greater, 12.5 or greater, 15.0 or greater, or 17.5 or greater. 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 may also be 20.0 or less, for example, 17.5 or less, 15.0 or less, 12.5 or less, 10.0 or less, or 7.5 or less. 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 is 5.0-20.0, 5.0-17.5, 5.0-15.0, 5.0-12.5, 5.0-10.0, 5.0-7.5, and 7.5-20. The values ​​may be 0, 7.5-17.5, 7.5-15.0, 7.5-12.5, 7.5-10.0, 10.0-20.0, 10.0-17.5, 10.0-15.0, 10.0-12.5, 12.5-20.0, 12.5-17.5, 12.5-15.0, 15.0-20.0, 15.0-17.5, or 17.5-20.0. If the shear viscosity index (SHI) of bimodal polyethylene is, for example, less than 5.0, the thermoplastic composition containing bimodal polyethylene may not have suitable processability for manufacturing articles such as insulators and jacket layers for wires and cables.

[0036] In the embodiment, the bimodal polyethylene is composed of an ethylene monomer and at least one C3-C3 group. 12It may be a polymerization reaction product with α-olefin comonomers. For example, an embodiment of the bimodal polyethylene composition may be a polymerization reaction product of ethylene monomer with 1-butene, 1-hexene, or both. Alternatively, an embodiment of the bimodal polyethylene composition may be a polymerization reaction product of ethylene monomer with 1-butene, 1-octene, or both. An embodiment of bimodal polyethylene may also be a polymerization reaction product of ethylene monomer with 1-hexene, 1-octene, or both. In some embodiments, C3~C 12 The α-olefin comonomer does not have to be propylene. That is, it can be at least one C3-C3 compound. 12 α-olefin comonomers may be substantially free of propylene. The term "substantially free" of a compound means that the material or mixture contains less than 1.0% by weight of the compound. For example, at least one C3-C compound may be substantially free of propylene. 12 The α-olefin comonomer may contain less than 1.0% by weight of propylene, for example, less than 0.8% by weight of propylene, less than 0.6% by weight of propylene, less than 0.4% by weight of propylene, or less than 0.2% by weight of propylene.

[0037] In embodiments, bimodal polyethylene can be produced using a catalyst system in a single reactor. As used herein, “catalyst system” may comprise a main catalyst, a trim catalyst, and optionally at least one activator. The catalyst system may also comprise other components, such as a support, and is not limited to the main catalyst, the trim catalyst, and optionally at least one activator. Embodiments of the catalyst system may comprise a main catalyst and a metallocentrimal catalyst. Embodiments of the catalyst system may also comprise one or more additives commonly used in the art of olefin polymerization. For example, embodiments of the catalyst system may comprise one or more continuity additives, flow aids, and antistatic aids. In embodiments, the reactor may be a gas-phase reactor, but a slurry-phase reactor may also be used.

[0038] Embodiments of the catalyst system may include at least one catalyst (sometimes referred to herein as the "HMW catalyst") for producing a high molecular weight fraction of bimodal polyethylene by polymerization, and at least one catalyst compound (sometimes referred to herein as the "LMW catalyst") for producing a low molecular weight fraction of bimodal polyethylene by polymerization.

[0039] HMW catalysts and LMW catalysts can have different hydrogen responses. That is, when the molar ratio of hydrogen gas to ethylene (H2 / C2 molar ratio) is changed, the change in the average molecular weight of polyethylene produced by each catalyst can differ. The term "high hydrogen response" refers to a catalyst that shows a relatively large change in the average molecular weight of polyethylene when the H2 / C2 molar ratio changes by a set amount. The term "low hydrogen response" refers to a catalyst that shows a relatively small change in the average molecular weight of polyethylene when the H2 / C2 molar ratio changes by the same set amount.

[0040] HMW catalysts and LMW catalysts can have different comonomer responses. That is, the comonomer content, such as the weight percentage of polyethylene produced by each catalyst compound, can differ. The term "good incorporateor" refers to a catalyst that exhibits a relatively high degree of comonomer integration, while a "poor incorporateor" chains relatively few comonomers. For catalyst systems using an HMW catalyst, which is a relatively good incorporateor, and an LMW catalyst, which is a relatively poor incorporateor, a "reverse comonomer distribution" occurs with a higher comonomer content in the HMW component. Conversely, an LMW catalyst, which is a good incorporateor, used with an HMW catalyst, which is a poor incorporateor, produces a "normal comonomer distribution."

[0041] Embodiments of a catalyst system may be referred to as a “bimodal catalyst system.” Such a catalyst system produces a bimodal polyethylene composition having distinctly identifiable high molecular weight and low molecular weight distributions. The term “bimodal catalyst system” may include any formulation, mixture, or system comprising at least two different catalyst compounds, each having the same or different metal groups but generally having different ligands or catalyst structures, including a “binary catalyst.” Alternatively, each different catalyst compound of a bimodal catalyst system may reside on a single support particle, in which case the binary catalyst is considered a supported catalyst. However, the term “bimodal catalyst system” also broadly includes systems or mixtures in which one of the catalysts resides on one aggregate of support particles and the other catalyst resides on another aggregate of support particles. In such embodiments, the two supported catalysts are introduced into a single reactor either simultaneously or sequentially, and polymerization is carried out in the presence of the aggregate of the two supported catalysts. Alternatively, a bimodal catalyst system may include a mixture of unsupported catalysts in slurry form.

[0042] Embodiments of the catalyst system may include a main catalyst and a trim catalyst. In such embodiments, 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 as described above. The main catalyst may be supplied as a slurry in a hydrocarbon diluent such as mineral oil. The trim catalyst comprises a trim catalyst compound, which may also be present in the main catalyst system. The trim catalyst may also include a solvent such as a hydrocarbon and other additives.

[0043] Embodiments of the trim catalyst compound may include, for example, molecular catalyst compounds such as metallocene catalyst compounds. In some embodiments, the trim catalyst may be used to produce a low molecular weight polymer fraction. In such embodiments, the main catalyst may be used to produce a high molecular weight polymer fraction.

[0044] Embodiments of the main catalyst compound may include one or more Group 15 metal-containing catalyst compounds. The Group 15 metal-containing compounds generally include at least one leaving group and at least two Group 15 atoms bonded to Group 3-14 metal atoms, or Group 3-7 metal atoms, or Group 4-6 metal atoms, or Group 4 metal atoms, at least one of which is also bonded to a Group 15 or Group 16 atom through another group. At least one of the Group 15 atoms is C1-C 20 The group 15 or group 16 atoms may be bonded through another group which may be a hydrocarbon group, a heteroatom-containing group, silicon, germanium, tin, lead, or phosphorus, and the group 15 or group 16 atoms may be unbonded or bonded to hydrogen, a group 14 atom-containing group, a halogen, or a heteroatom-containing group, and each of the two group 15 atoms may be bonded to a cyclic group which may optionally be bonded to hydrogen, a halogen, a heteroatom, or a hydrocarbyl group or a heteroatom-containing group.

[0045] Group 15 metal-containing compounds can be represented by the following formula:

[0046] [ka] In the formula, M is a transition metal from Group 3 to Group 12, or a main group metal from Group 13 or Group 14, or a Group 4, Group 5 or Group 6 metal, or a Group 4 metal, or zirconium, titanium, or hafnium, and each X is independently a leaving group. X may be an anionic leaving group. X may be hydrogen, a hydrocarbyl group, a heteroatom, or a halogen. X may be an alkyl group, y may be 0 or 1 (if y is 0, L' is absent), n is the oxidation state of M, which may be +3, +4, or +5, or may be +4, m is the formal charge of the YZL or YZL' ligand, which may be 0, -1, -2, or -3, or may be -2, L is a group 15 or group 16 element, preferably nitrogen, L' is a group 15 or group 16 element or group 14 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 These are, independently, C1~C 20 Hydrocarbon groups, heteroatom-containing groups having up to 20 carbon atoms, silicon, germanium, tin, lead, halogen, or phosphorus, preferably C2-C 20 Alkyl, aryl, or aralkyl group, more preferably linear, branched, or cyclic C2-C 20 Alkyl groups, most preferably C2-C6 hydrocarbon groups. 1 and R 2 They may also be interconnected with each other, R 3 It is either absent, or contains hydrocarbon groups, hydrogen, halogens, heteroatom-containing groups, preferably linear, cyclic, or branched alkyl groups having 1 to 20 carbon atoms, more preferably R 3 is either absent, or is hydrogen or an alkyl group, most preferably hydrogen, R 4 and R 5These are independently alkyl groups, aryl groups, substituted aryl groups, cyclic alkyl groups, substituted cyclic alkyl groups, cyclic aralkyl groups, substituted cyclic aralkyl groups, or polycyclic groups, preferably having up to 20 carbon atoms, more preferably having 3 to 10 carbon atoms, and even more preferably C1 to C 20 hydrocarbon group, C1~C 20 Aryl group, or C1-C 20 It has an aralkyl group or a heteroatom-containing group, for example, PR3, where R is an alkyl group, 1 and R 2 They may be interconnected with each other, and / or R 4 and R 5 R may be interconnected with each other, 6 and R 7 These are, independently, absent, or hydrogen, alkyl groups, halogens, heteroatoms, or hydrocarbyl groups, preferably linear, cyclic, or branched alkyl groups having 1 to 20 carbon atoms, more preferably absent. * R is either absent, or is a hydrogen, group 14 atom-containing group, halogen, or heteroatom-containing group.

[0047] "Formal charge of YZL or YZL' ligand" refers to the total charge of the ligand in the absence of metal and leaving group X.

[0048] "R 1 and R 2 "They may be interconnected" means R 1 and R 2 This means that they may be directly bonded to each other, or they may be bonded to each other through other groups. 4 and R 5 "They may also be interconnected" means R 4 and R 5 This means that they may be directly bonded to each other, or they may be bonded to each other through other groups.

[0049] Alkyl radicals can be linear or branched alkyl radicals, or alkenyl radicals, alkynyl radicals, cycloalkyl radicals or aryl radicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbamoyl radicals, alkyl or dialkylcarbamoyl radicals, acyloxy radicals, acylamino radicals, aroylamino radicals, linear, branched or cyclic alkylene radicals, or combinations thereof. An aralkyl group is defined as a substituted aryl group.

[0050] R 4 and R 5 These can independently be a group represented by the following equation 3,

[0051] [ka] In the formula, R 8 ~R 12 These are, independently, hydrogen, C1~C 40 Alkyl groups, halides, heteroatoms, heteroatom-containing groups containing up to 40 carbon atoms, preferably C1-C 20 The R groups are linear or branched alkyl groups, preferably methyl, ethyl, propyl, or butyl groups, and any two R groups may form a cyclic group and / or a heterocyclic group. The cyclic group may be aromatic. 9 , R 10 and R 12 R can independently be a methyl, ethyl, propyl, or butyl group (including all isomers). In a preferred embodiment, any three of the R groups in formula 3 may be methyl groups, and any two of the other R groups in formula 3 may be hydrogen. In a preferred embodiment of the present invention, R 9 , R 10 and R 12 It is methyl, and R 8 and R 11 It is hydrogen.

[0052] R 4 and R 5 These can all be groups represented by the following equation 4,

[0053] [ka] In the formula, M is a Group 4 metal, preferably zirconium, titanium, or hafnium, and more preferably zirconium. Each of L, Y, and Z is nitrogen, and R 1 and R 2 Each of them is -CH2-CH2-, and R 3 is hydrogen, R 6 and R 7 It does not exist.

[0054] Group 15 and metal-containing compounds may be compound 1 shown below (also known as "bis(arylamide)Zr dibenzyl").

[0055] [ka] In the notation for Compound 1, "Bn" represents the benzyl group.

[0056] Group 15 and metal-containing catalyst compounds can be prepared by methods known in the art. In some cases, the methods disclosed in European Patent Application Publication No. 0893454(A1), U.S. Patent No. 5,889,128, and the references cited in U.S. Patent No. 5,889,128 are preferred.

[0057] In some embodiments, the direct synthesis of these compounds involves adding a neutral ligand (e.g., YZL or YZL' of formula 1 or 2) to M n X nThe process involves reacting a metal (where M is a group 3-14 metal, n is the oxidation state of M, and each X is an anionic group such as a halide) with a non-coordinating or weakly coordinating solvent (such as ether, toluene, xylene, benzene, methylene chloride, and / or hexane, or other solvents with a boiling point above 60°C) at 20-150°C (e.g., 20-100°C) for 24 hours or more, and then treating the mixture with an excess (e.g., 4 equivalents or more) alkylating agent such as methylmagnesium bromide in ether. The magnesium salt is removed by filtration, and the metal complex is isolated by standard techniques.

[0058] Group 15 and metal-containing compounds use a neutral ligand (e.g., YZL or YZL' of formula 1 or 2) in formula M n X n The metal complex may be prepared by a method comprising reacting a compound represented by (where M is a metal of group 3 to 14, n is the oxidation state of M, and each X is an anionic leaving group) in a non-coordinating or weakly coordinating solvent at 20°C or higher (preferably 20 to 100°C), then treating the mixture with an excess alkylating agent, and then recovering the metal complex. The solvent may have a boiling point above 60°C, such as toluene, xylene, benzene, and / or hexane. The solvent may also include ether and / or methylene chloride.

[0059] Generally, metallocene compounds may include half-sandwich compounds and full-sandwich compounds having one or more ligands bonded to at least one metal atom. Typical metallocene compounds are generally described as containing one or more ligands bonded to at least one metal atom and one or more leaving groups.

[0060] Ligands are generally represented by one or more open rings, acyclic rings, fused rings 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. The atoms may be selected from the group consisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorus, germanium, boron, and aluminum, or combinations thereof. The rings or ring systems may consist of carbon atoms, such as cyclopentadienyl ligands or cyclopentadienyl-type ligand structures, or other similar functional ligand structures such as pentadiene, cyclooctatetraendiyl, or imide ligands, but are not limited to these. Metal atoms may be selected from groups 3 to 15 of the periodic table and the lanthanide or actinide series. The metals may be from groups 4 to 12, or transition metals from groups 4, 5, and 6, or the transition metals may be from group 4.

[0061] The catalyst composition may contain one or more metallocene catalyst compounds represented by the following formula 5, L A L B MQ n formula 5 In the formula, M is a metal atom from the periodic table of elements, and may be from the metals of Groups 3 through 12 of the periodic table, or from the lanthanide or actinide series. M may be a transition metal of Group 4, Group 5, or Group 6, or M may be a transition metal of Group 4, or M may be zirconium, hafnium, or titanium. Ligand L A and L BThis may be an open ring, acyclic, or fused ring or ring system, and may 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 ligand, cyclopentaphenantrenyl ligand, indenyl ligand, benzoindenyl ligand, fluorenyl ligand, octahydrofluorenyl ligand, cyclooctatetraendiyl ligand, cyclopentacyclododecene ligand, azulenyl ligand, azulene ligand, pentalene ligand, phosphoyl ligand, phosphineimine (International Publication No. 99 / 40125), pyrrolyl ligand, pyrozolyl ligand, carbazolyl ligand, borabenzene ligand, and their hydrogenated versions, such as tetrahydroindenyl ligand. A and L B L can be any other ligand structure that can π-bond to M. A and L B The atomic molecular weight of L may exceed 60 a.mu or 65 a.mu. A and L B It may contain one or more heteroatoms, such as nitrogen, silicon, boron, germanium, sulfur, and phosphorus, in combination with a carbon atom to form an open ring, acyclic, or preferably fused ring or cyclic system, such as a heterocyclopentadienyl auxiliary ligand. A and L B Ligands include, but are not limited to, amides, phosphides, alkoxides, aryloxides, imides, carbolides, borollides, porphyrins, phthalocyanines, choline, and other polyazo macrorings. Independently, each L A and L B L can be the same or different type of ligand bonded to M. In one of the options of Equation 5, L A and L B Only one of these may exist.

[0062] Independently, each L A and L BThe substituent R may be unsubstituted or substituted with a combination of substituents R. Non-limiting examples of substituent R include hydrogen, or one or more from the group selected from linear, branched alkyl radicals or alkenyl radicals, alkynyl radicals, cycloalkyl radicals or aryl radicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbamoyl radicals, alkyl or dialkylcarbamoyl radicals, acyloxy radicals, acylamino radicals, aroylamino radicals, linear, branched or cyclic alkylene radicals, or combinations thereof. In preferred embodiments, substituent R has up to 50 nonhydrogen atoms, preferably 1 to 30 carbon atoms, and may 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 groups, and all their isomers, such as tertiary butyl and isopropyl. Other hydrocarbyl radicals include hydrocarbyl-substituted organic metalloid radicals containing fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl, and trimethylsilyl, trimethylgermyl, methyldiethylsilyl, etc.; halocarbyl-substituted organic metalloid radicals containing tris(trifluoromethyl)-silyl, methyl-bis(difluoromethyl)silyl, bromomethyldimethylgermyl, etc.; disubstituted boron radicals containing, for example, dimethylboron; and disubstituted pnictogen radicals containing dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, methoxy, ethoxy, propoxy, phenoxy, methyl sulfide, and ethyl sulfide.Examples of non-hydrogen substituents R include, but are not limited to, atoms such as carbon, silicon, boron, aluminum, nitrogen, phosphorus, oxygen, tin, sulfur, and germanium, and include olefins such as vinyl-terminated ligands, e.g., but-3-enyl, propa-2-enyl, and hexa-5-enyl olefinic unsaturated substituents. Furthermore, at least two R groups, preferably two adjacent R groups, bond to form a ring structure having 3 to 30 atoms selected from carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminum, boron, or combinations thereof. In addition, substituent R can form a carbon σ bond to the metal M.

[0063] At least one other ligand, such as a leaving group Q, may be bonded to the metal M. Q may be a monoanionic unstable ligand having a sigma bond to M. Depending on the oxidation state of the metal, the value of n may be 0, 1, or 2, as equation 5 above represents a neutral metallocene catalyst compound.

[0064] Non-limiting examples of Q ligands include weak bases such as amines, phosphines, ethers, carboxylates, dienes, hydrocarbyl radicals having 1 to 20 carbon atoms, hydrides or halogens, or combinations thereof. Two or more Qs may form part of a fused ring or ring system. Other examples of Q ligands include substituents of R such as cyclobutyl, cyclohexyl, heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene, methylene, methoxy, ethoxy, propoxy, phenoxy, bis(N-methylanilide), dimethylamide, and dimethylphosphine radicals.

[0065] The catalyst composition is L of formula V. A and L B However, it may include one or more metallocene catalyst compounds that are crosslinked with each other by at least one crosslinking group A, as represented by formula 6. L A AL B MQ n formula 6 The compound of formula 6 is known as a crosslinked metallocene catalyst compound.A , L B M, Q, and n are as defined above. Non-limiting examples of bridging group A include, but are not limited to, bridging groups containing at least one group 13-16 atom, often referred to as a divalent moiety, such as at least one of carbon, oxygen, nitrogen, silicon, aluminum, boron, germanium, and tin atoms, or combinations thereof. Bridging group A may contain carbon, silicon, or germanium atoms, preferably A contains at least one silicon atom or at least one carbon atom. Bridging group A may also contain substituents R as defined above, including halogens and iron. Non-limiting examples of crosslinking group A may be represented by R'2C, R'2Si, R'2Si, R'2Si, R'2Ge, R'P, where R' is independently a radical group which is a hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organic metalloid, halocarbyl-substituted organic metalloid, disubstituted boron, disubstituted pnictogen, substituted chalcogen, or halogen, or two or more R' may be bonded together to form a ring or ring system. The crosslinking metallocene catalyst compound of formula 4 may have two or more crosslinking groups A (European Patent No. 0664301(B1)).

[0066] The metallocene catalyst compound is ligand L of formulas 5 and 6. A and L B The above R substituent may be replaced by the same or different number of substituents on each ligand. Ligands L of formulas V and VI A and L B They may be different from one another.

[0067] The main catalyst system includes a main catalyst compound represented by the above formula 2, such as a compound having the formula [(2,3,4,5,6-Me5C6)NCH2CH2]2NHZrBn2, where 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 can be represented by the above formula V, such as a zirconocene compound like (n-butylcyclopentadienyl)2-zirconium(IV) dichloride or (propylcyclopentadienyl)(1,3-dimethyl-4,5,6,7-tetrahydroindenyl)zirconium(IV)dimethyl.

[0068] The molar ratio of HMW catalyst compound to LMW catalyst compound in the catalyst formulation may 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.

[0069] The trim catalyst may include a catalyst compound that can be represented by the following formula 7, specifically, formula 7 represents (1,3-dimethyl4,5,6,7-tetrahydroindene)(methylcyclopentadienyl)zirconiumdimethyl.

[0070] [ka]

[0071] As used herein, the term “activator” may include any combination of reagents that increase the rate at which a transition metal compound oligomerizes or polymerizes an unsaturated monomer, such as an olefin. Activators may also affect the molecular weight, degree of branching, comonomer content, or other properties of the oligomer or polymer. Transition metal compounds may be activated for oligomerization and / or polymerization catalysis in any manner sufficient to enable coordination or cationic oligomerization and / or polymerization.

[0072] Alumoxane activators can be used as one or more activators in a catalyst composition. Alumoxanes are generally oligomeric compounds containing the --Al(R)--O-- subunit (wherein R is an alkyl group). Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane, and isobutylalumoxane. Alkylalumoxanes and modified alkylalumoxanes are particularly suitable as catalyst activators when the abstractable ligand is a halide. Mixtures of different alumoxanes and modified alumoxanes may also be used. For further explanation, see U.S. Patents 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 European Patents Nos. 0561,476, 0279,586, 0516,476, and 0 See publication 594-218 and international publication 94 / 10180.

[0073] When the activator is an almoxane (modified or unmodified), the maximum amount of activator may be selected such that the Al / M ratio is 5000-fold molar excess relative to the catalyst precursor (per metal catalyst site). Alternatively, the minimum amount of activator to catalyst precursor may be set to a 1:1 molar ratio.

[0074] Examples of aluminum alkyl or organoaluminum compounds that can be used as activators (or scavengers) include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum.

[0075] The catalyst system may include a support material or carrier. For example, at least one catalyst compound and / or one or more activators may be deposited on, contacted with, vaporized therewith, bound thereto, incorporated therein, or adsorbed or absorbed in or on them. Thus, the catalyst compounds and other transition metal catalyst compounds and / or catalyst systems may be combined with one or more support materials or carriers using one of the loading methods well known in the art, or as described below. For example, a metallocene catalyst compound or catalyst system is in a loaded form if, for example, it is deposited on, contacted with, incorporated therein, or adsorbed or absorbed in or on them.

[0076] As used herein, the terms “support” and “carrier” are interchangeable and refer to any support material, including porous support materials such as talc, inorganic oxides, and inorganic chlorides. Other carriers include polystyrene, resin support materials such as polystyrene, functionalized or crosslinked organic support materials such as divinylbenzene polyolefin or other polymer compounds, zeolites, clays, or any other organic or inorganic support materials, or mixtures thereof.

[0077] Illustrative support materials, such as inorganic oxides, include metal oxides of Group 2, 3, 4, 5, 13, or 14. Preferred supports include silica, fumed silica, alumina (see, for example, International Publication No. 99 / 60033), silica-alumina, and mixtures thereof, which may or may not be dehydrated. Other useful supports include magnesia, titania, zirconia, magnesium chloride (U.S. Patent No. 5,965,477), montmorillonite (European Patent No. 0511665), phyllosilicates, zeolites, talc, and clay (U.S. Patent No. 6,034,187). Combinations of these support materials, such as silica-chromium, silica-alumina, and silica-titania, may also be used. Additional support materials include the porous acrylic polymers described in European Patent No. 0767184, which are incorporated herein by reference. Other supporting materials include nanocomposites such as those disclosed in International Publication No. 99 / 47598, aerogels such as those disclosed in International Publication No. 99 / 48605, spherulites such as those disclosed in U.S. Patent No. 5,972,510, and polymer beads such as those disclosed in International Publication No. 99 / 50311.

[0078] In some embodiments, all catalyst compounds in a catalyst system may be independently unsupported or supported on a support material, in which 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). A bimodal catalyst system comprises a mixture of unsupported catalyst compounds in slurry and / or solution form. The support material may be silica (e.g., fumed silica), alumina, clay, or talc. Fumed silica may be hydrophilic (untreated) or hydrophobic (treated). In some embodiments, 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 embodiments, the treatment agent is dimethyldichlorosilane.

[0079] In some embodiments, the supporting material, such as an inorganic oxide, is 10m 2 / g~about 700m 2 Surface area in the range of / g, 0.1cm 3 / g~4.0cm 3 Pore ​​volume may be in the range of / g, and average particle size may be in the range of 5 micrometers to 500 micrometers. Preferably, the surface area of ​​the support material is 50 m 2 / g~500m 2 Range of / g, 0.5cm 3 / g~3.5cm 3 The pore volume may be 1 / g and the average particle size may be 10 micrometers to 200 micrometers. Most preferably, the surface area of ​​the support material is 100 m 2 / g~400m 2 Range of / g, 0.8cm 3 / g~3.0cm 3The pore volume may be 1 / g and the average particle size may be 5 to 100 micrometers. The average pore diameter of the support is typically in the range of 10 to 1,000 angstroms, or 50 to 500 angstroms, and in some embodiments, 75 to 350 angstroms. Various other methods for supporting polymerization catalyst compounds or catalyst systems exist in the art. For example, metallocene catalyst compounds may contain polymer-binding ligands, such as those described in U.S. Patents 5,473,202 and 5,770,755. Metallocene catalyst compounds may be spray-dried, for example, as described in U.S. Patent 5,648,310. Supports used with metallocene catalyst compounds may be functionalized, as described in European Patent No. 0802203, or selected to have at least one substituent or leaving group, as described in U.S. Patent 5,688,880.

[0080] The polyethylene formulations disclosed herein may be prepared by a gas-phase process. The formulations may be prepared in a single reactor. The polyethylene formulations disclosed herein may also be prepared in a single gas-phase reactor. In one embodiment of the present invention, the reactor is a gas-phase fluidized bed polymerization reactor.

[0081] Polyethylene can be produced using stepwise gas-phase reactors. Commercial polymerization systems are described, for example, on pages 366-378 of "Volume 2, Metallocene-Based Polyolefins" (John Scheirs & W. Kaminsky, eds. John Wiley & Sons, Ltd. 2000), U.S. Patents No. 5,665,818, No. 5,677,375, and No. 6,472,484, and European Patent No. 0517,868 and European Patent No. 0794,200.

[0082] The gas phase process may utilize a fluidized bed reactor. A fluidized bed reactor may include a reaction zone and a so-called deceleration zone. The reaction zone may include a bed of growing polymer particles, formed polymer particles, and a small amount of catalyst particles, which are fluidized by a continuous flow of gaseous monomers and diluents to remove the heat of polymerization through the reaction zone. Optionally, a portion of the recirculated gas can be cooled and compressed to form a liquid, which, when reintroduced into the reaction zone, increases the heat removal capacity of the circulating gas flow. A suitable gas flow rate can be easily determined by simple experiments. The supply of gaseous monomers to the circulating gas flow may be at a rate equal to a rate that can remove particulate polymer products and associated monomers from the reactor and adjust the composition of the gas passing through the reactor to maintain an essentially steady-state gaseous composition within the reaction zone. The gas leaving the reaction zone may be sent to a deceleration zone where transport particles are removed. Finer transport particles and dust can be removed in a cyclone and / or microfilter. The gas may pass through a heat exchanger, where the heat of polymerization is removed, then compressed in a compressor, and subsequently returned to the reaction area. Details of additional reactors and means for operating the reactors are described, for example, in U.S. Patents 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, European Patent No. 0802202, and Belgian Patent No. 839,380.

[0083] The reactor temperature in a fluidized bed process may range from 30°C, 40°C, 50°C to 90°C, 100°C, 110°C, 120°C, or 150°C. Generally, the reactor temperature can be operated at the highest feasible temperature, taking into account the sintering temperature of the ethylene-based polymer product in the reactor. Regardless of the process used to produce polyolefins (e.g., bimodal polyethylene), the polymerization or reaction temperature should be below the melting or "sintering" temperature of the ethylene-based polymer being formed. Therefore, the upper temperature limit may be the melting temperature of the polyolefin produced in the reactor.

[0084] For example, as described on pages 76-78 of the "Polypropylene Handbook" (Hanser Publishers, 1996), hydrogen gas can be used in olefin polymerization to control the final properties of polyolefins. The amount of hydrogen in polymerization can be expressed, for example, as the molar ratio of ethylene or a blend of ethylene and 1-hexene or propylene to the total polymerizable monomer. The amount of hydrogen used in the polymerization process may be the amount necessary to achieve the desired MFR or FI of the final polyolefin resin. The amount of hydrogen used in the polymerization process may be the amount necessary to achieve the desired bimodal molecular weight distribution between the high molecular weight and low molecular weight components of a bimodal polyolefin.

[0085] The catalyst system may also be used to further control the properties of the polyethylene formulation. For example, the amount of trim catalyst may be adjusted to modify the in-reactor ratio of the catalyst compounds in the catalyst system to achieve a desired flow index or flow index split. The trim catalyst may be supplied directly to the reactor separately from the main catalyst compound of the catalyst system. The trim catalyst may also be mixed with the main catalyst compound of the catalyst system before being supplied to the reactor. The trim catalyst may be continuously mixed with other compounds of the catalyst system, and the resulting mixture may be continuously supplied to the reactor. The trim catalyst may be continuously mixed with a supported catalyst, and the resulting mixture may be continuously supplied to the reactor. The trim catalyst may be a supported or unsupported catalyst. If the trim catalyst is an unsupported catalyst, it may be supported "in-line," for example, by contact with a supported catalyst, before being supplied to the reactor. A supported trim catalyst may contain an activator that can activate the trim catalyst "in-line" before being supplied to the reactor.

[0086] The trim catalyst may 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, upon activation with a suitable activator, the active catalyst species resulting from the trim catalyst may be the same as the active catalyst species resulting from one of at least two different catalyst compounds of the catalyst. Those skilled in the art will understand, for example, that metallocene dihalides and metallocene dialkyls can produce the same active catalyst species when treated with a suitable activator. For example, metallocenes such as (cyclopentadienyl)(1,3-dimethyl-4,5,6,7-tetrahydroindenyl)zirconium(X)2 (wherein X can be a halide, alkyl, or any other leaving group as described above) can be used in dichloride form to prepare supported catalysts. When used as a trim catalyst, it may be provided in dialkyl form, such as dimethyl form. This may be advantageous in terms of solubility, for example, if the dialkyl form can have high solubility in aliphatic hydrocarbons.

[0087] The catalyst system may include at least one or more catalyst compounds containing titanium, zirconium, or hafnium atoms. The catalyst system may include at least one or more of the following: (Pentamethylcyclopentadienyl)(n-Propylcyclopentadienyl)MX2, (Tetramethylcyclopentadienyl)(n-Propylcyclopentadienyl)MX2, (Tetramethylcyclopentadienyl)(n-butylcyclopentadienyl)MX2, (n-propylcyclopentadienyl)(1,3-dimethyl-4,5,6,7-tetrahydroindenyl)MX2, (methylcyclopentadienyl)(1,3-dimethyl-4,5,6,7-tetrahydroindenyl)MX2, (cyclopentadienyl)(1,3-dimethyl-4,5,6,7-tetrahydroindenyl)MX2, (methylcyclopentadienyl)(1-methyl-4,5,6,7-tetrahydroindenyl)MX2, Me2Si(indenyl)2MX2, Me2Si(4,5,6,7-tetrahydroindenyl)2MX2, (n-propylcyclopentadienyl)2MX2, (n-butylcyclopentadienyl)2MX2, (1-methyl,3-butylcyclopentadienyl)2MX2, [HN(CH2CH2N(2,4,6-Me3C6H2))2]MX2, [HN(CH2CH2N(2,3,4,5,6-Me5C6))2MX2, and mixtures thereof (wherein M is Zr or Hf, and X is selected from F, Cl, Br, I, Me, benzyl, CH2SiMe3, and C1-C5 alkyl or alkenyl).

[0088] The molar ratio of hydrogen to total monomer (H2:monomer) may 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, and the desirable range may include any combination of any upper molar ratio limit and any lower molar ratio limit described herein.

[0089] In a gas-phase process (either single-stage or two-stage or more-stage), the pressures of one or more reactors can vary between 690 kPa (100 psig) and 3,448 kPa (500 psig). For example, they could be in the range of 1,379 kPa (200 psig) to 2,759 kPa (400 psig) or 1,724 kPa (250 psig) to 2,414 kPa (350 psig).

[0090] In embodiments, bimodal polyethylene may be used as a base component for producing thermoplastic compositions. In embodiments, the thermoplastic composition may optionally include 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 may be produced by physically mixing bimodal polyethylene and any optional additives at a macro level, for example, by melt blending or compounding.

[0091] In embodiments, the thermoplastic composition may contain bimodal polyethylene in an amount of 50.1% by weight or more, for example, 60.0% by weight or more, 70.0% by weight or more, 80.0% by weight or more, 90.0% by weight or more, 95.0% by weight or more, or 99.0% by weight or more. The thermoplastic composition may also contain bimodal polyethylene in an amount of 99.9% by weight or less, for example, 99.0% by weight or less, 95.0% by weight or less, 90.0% by weight or less, 80.0% by weight or less, 70.0% by weight or less, or 60.0% by weight or less. For example, thermoplastic compositions include those with a concentration of 50.1% to 99.9% by weight, 50.1% to 99.0% by weight, 50.1% to 95.0% by weight, 50.1% to 90.0% by weight, 50.1% to 80.0% by weight, 50.1% to 70.0% by weight, 50.1% to 60.0% by weight, 60.0% to 99.9% by weight, 60.0% to 99.0% by weight, 60.0% to 95.0% by weight, 60.0% to 90.0% by weight, 60.0% to 80.0% by weight, 60.0% to 70.0% by weight, 70.0% to 99.9% by weight, and 70%. It may contain bimodal polyethylene in amounts of 0% to 99.0% by weight, 70.0% to 95.0% by weight, 70.0% to 90.0% by weight, 70.0% to 80.0% by weight, 80.0% to 99.9% by weight, 80.0% to 99.0% by weight, 80.0% to 95.0% by weight, 80.0% to 90.0% by weight, 90.0% to 99.9% by weight, 90.0% to 99.0% by weight, 90.0% to 95.0% by weight, 95.0% to 99.9% by weight, or 99.0% to 99.9% by weight.

[0092] In the embodiments, the thermoplastic composition may contain a UV stabilizer in an amount of 0.0% by weight or more, for example, 1.0% by weight or more, 2.0% by weight or more, 3.0% by weight or more, or 4.0% by weight or more. The thermoplastic composition may contain a UV stabilizer in an amount of 5.0% by weight or less, for example, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, or 1.0% by weight or less. For example, a thermoplastic composition may contain an ultraviolet stabilizer in an amount of 0.0% to 5.0% by weight, 0.0% to 4.0% by weight, 0.0% to 3.0% by weight, 0.0% to 2.0% by weight, 0.0% to 1.0% by weight, 1.0% to 5.0% by weight, 1.0% to 4.0% by weight, 1.0% to 3.0% by weight, 1.0% to 2.0% by weight, 2.0% to 5.0% by weight, 2.0% to 4.0% by weight, 2.0% to 3.0% by weight, 3.0% to 5.0% by weight, 3.0% to 4.0% by weight, or 4.0% to 5.0% by weight.

[0093] In embodiments, the thermoplastic composition may contain a first antioxidant in an amount of 0.1% by weight or more, for example, 0.4% by weight or more, or 0.7% by weight or more. The thermoplastic composition may also contain a first antioxidant in an amount of 1.0% by weight or less, for example, 0.7% by weight or less, or 0.4% by weight or less. For example, the thermoplastic composition may contain a first antioxidant in an amount of 0.1% to 1.0% by weight, 0.1% to 0.7% by weight, 0.1% to 0.4% by weight, 0.4% to 1.0% by weight, 0.4% to 0.7% by weight, or 0.7% to 1.0% by weight. In embodiments, the thermoplastic composition may contain a second antioxidant in an amount of 0.0% by weight or more, for example, 0.2% to 0.4% by weight or more, 0.6% by weight or more, or 0.8% by weight or more. The thermoplastic composition may also contain a second antioxidant in an amount of 1.0% by weight or less, for example, 0.8% by weight or less, 0.6% by weight or less, 0.4% by weight or less, or 0.2% by weight or less. For example, a thermoplastic composition may contain a first antioxidant in an amount of 0.0% to 1.0% by weight, 0.0% to 0.8% by weight, 0.0% to 0.6% by weight, 0.0% to 0.4% by weight, 0.0% to 0.2% by weight, 0.2% to 1.0% by weight, 0.2% to 0.8% by weight, 0.2% to 0.6% by weight, 0.2% to 0.4% by weight, 0.4% to 1.0% by weight, 0.4% to 0.8% by weight, 0.4% to 0.6% by weight, 0.6% to 1.0% by weight, 0.6% to 0.8% by weight, or 0.8% to 1.0% by weight.

[0094] In the embodiments, the thermoplastic composition may contain a processing aid in an amount of 0.0% by weight or more, for example, 0.2% by weight or more, 0.4% by weight or more, 0.6% by weight or more, or 0.8% by weight or more. The thermoplastic composition may also contain a processing aid in an amount of 1.0% by weight or less, for example, 0.8% by weight or less, 0.6% by weight or less, 0.4% by weight or less, or 0.2% by weight or less. For example, a thermoplastic composition may contain processing aids in amounts of 0.0% to 1.0% by weight, 0.0% to 0.8% by weight, 0.0% to 0.6% by weight, 0.0% to 0.4% by weight, 0.0% to 0.2% by weight, 0.2% to 1.0% by weight, 0.2% to 0.8% by weight, 0.2% to 0.6% by weight, 0.2% to 0.4% by weight, 0.4% to 1.0% by weight, 0.4% to 0.8% by weight, 0.4% to 0.6% by weight, 0.6% to 1.0% by weight, 0.6% to 0.8% by weight, or 0.8% to 1.0% by weight.

[0095] In the embodiments, the thermoplastic composition may contain a flame retardant in an amount of 0.0% by weight or more, for example, 0.2% by weight or more, 0.4% by weight or more, 0.6% by weight or more, or 0.8% by weight or more. The thermoplastic composition may also contain a flame retardant in an amount of 1.0% by weight or less, for example, 0.8% by weight or less, 0.6% by weight or less, 0.4% by weight or less, or 0.2% by weight or less. For example, a thermoplastic composition may contain a flame retardant in amounts of 0.0% to 1.0% by weight, 0.0% to 0.8% by weight, 0.0% to 0.6% by weight, 0.0% to 0.4% by weight, 0.0% to 0.2% by weight, 0.2% to 1.0% by weight, 0.2% to 0.8% by weight, 0.2% to 0.6% by weight, 0.2% to 0.4% by weight, 0.4% to 1.0% by weight, 0.4% to 0.8% by weight, 0.4% to 0.6% by weight, 0.6% to 1.0% by weight, 0.6% to 0.8% by weight, or 0.8% to 1.0% by weight.

[0096] In the embodiments, the thermoplastic composition may contain a filler in an amount of 0.0% by weight or more, for example, 0.2% by weight or more, 0.4% by weight or more, 0.6% by weight or more, or 0.8% by weight or more. The thermoplastic composition may also contain a filler in an amount of 1.0% by weight or less, for example, 0.8% by weight or less, 0.6% by weight or less, 0.4% by weight or less, or 0.2% by weight or less. For example, a thermoplastic composition may contain fillers in amounts of 0.0% to 1.0% by weight, 0.0% to 0.8% by weight, 0.0% to 0.6% by weight, 0.0% to 0.4% by weight, 0.0% to 0.2% by weight, 0.2% to 1.0% by weight, 0.2% to 0.8% by weight, 0.2% to 0.6% by weight, 0.2% to 0.4% by weight, 0.4% to 1.0% by weight, 0.4% to 0.8% by weight, 0.4% to 0.6% by weight, 0.6% to 1.0% by weight, 0.6% to 0.8% by weight, or 0.8% to 1.0% by weight.

[0097] Bimodal polyethylene or thermoplastic compositions containing bimodal polyethylene can be used in a wide variety of products and end uses. Bimodal polyethylene or thermoplastic compositions containing 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, plastomers, high-pressure low-density polyethylene, high-density polyethylene, and polypropylene. Bimodal polyethylene, thermoplastic compositions containing bimodal polyethylene, and their blends can be used to produce blow-molded components or products in a variety of end uses. Bimodal polyethylene, thermoplastic compositions containing bimodal polyethylene, and their blends can be useful in molding operations such as extrusion and co-extrusion of films, sheets, and fibers, as well as in blow molding, injection molding, and rotational molding. Examples of films include shrink films, wraps, stretch films, sealing films, stretchable films, snack packaging, heavy-duty paper bags, shopping bags, baked and frozen food packaging, medical packaging, industrial liners, and blown or cast films formed by co-extrusion or lamination, which are useful as membranes in food-contact and non-food-contact applications. Fibers may include melt-spinning, solution-spinning, and melt-blown fiber operations for use in woven or non-woven fabrics to produce filters, diaper fabrics, medical clothing, and geotextiles. Examples of extruded articles include coatings for medical tubes, wires, and cables, pipes, geomembranes, and pond substrates. Examples of molded articles include single-layer and multi-layer structures in the form of bottles, tanks, large hollow articles, hard food containers, and toys.

[0098] In embodiments, a coated conductor can be manufactured using bimodal polyethylene, a thermoplastic composition containing bimodal polyethylene, and blends thereof. The coated conductor may include a conductive core and a coating layer 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 layer may include bimodal polyethylene, a thermoplastic composition containing 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 a metal wire, thereby causing electrical energy to flow through the metal wire; by sending pulses of light (e.g., infrared light) through an optical fiber, thereby causing light to be transmitted through the optical fiber; or by a combination thereof.

[0099] Environmental stress cracking resistance is a measure of an article's strength relating to its ability to resist failure due to stress crack growth. A high environmental stress cracking resistance value is important because the article should last throughout its designed service life. In embodiments, articles containing bimodal polyethylene, thermoplastic compositions containing bimodal polyethylene, or blends thereof may have an environmental stress cracking resistance (F0) of more than 24 hours, e.g., 48 hours or more, 96 hours or more, 192 hours or more, 384 hours or more, 768 hours or more, 1,536 hours or more, or more than 3,072 hours. Articles containing thermoplastic compositions may also have an environmental stress cracking resistance (F0) of less than 6,144 hours, e.g., 3,072 hours or less, 1,536 hours or less, 768 hours or less, 384 hours or less, 192 hours or less, 96 hours or less, or less than 48 hours. For example, articles containing this thermoplastic composition can withstand 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, and 96 hours. It may have environmental stress crack resistance (F0) of up to 384 hours, 96 hours to 192 hours, 192 hours to 6,144 hours, 192 hours to 3,072 hours, 192 hours to 1,536 hours, 192 hours to 768 hours, 192 hours to 384 hours, 384 hours to 6,144 hours, 384 hours to 3,072 hours, 384 hours to 1,536 hours, 384 hours to 768 hours, 768 hours to 6,144 hours, 768 hours to 3,072 hours, 768 hours to 1,536 hours, 1,536 hours to 6,144 hours, 1,536 hours to 3,072 hours, or 3,072 hours to 6,144 hours.

[0100] The degree of hardening (crosslinking) is determined by measuring high-temperature creep, and after elongation due to high-temperature creep, sample relaxation is measured using hot hardening. In the embodiment, articles containing thermoplastic compositions may have a hot hardening of 80 percent (%) or more, for example, 100% or more, 120% or more, 140% or more, 160% or more, or 180% or more. Articles containing thermoplastic compositions may also have a hot hardening of less than 200%, for example, 180% or less, 160% or less, 140% or less, 120% or less, or 100% or less. For example, an article containing a thermoplastic composition may have a hot curing rate of 80%~200%, 80%~180%, 80%~160%, 80%~140%, 80%~120%, 80%~100%, 100%~200%, 100%~180%, 100%~160%, 100%~140%, 100%~120%, 120%~200%, 120%~180%, 120%~160%, 120%~140%, 140%~200%, 140%~180%, 140%~160%, 160%~200%, 160%~180%, or 180%~200%.

[0101] Test method density Unless otherwise indicated, all densities disclosed herein are measured in grams per cubic centimeter (g / cm³) according to ASTM D792-08, Method B. 3 ) will be reported.

[0102] Samples for density measurement were prepared according to ASTM D4703-10. The samples were pressed at 10,000 psi (68 MPa) for 5 minutes at 190°C. The temperature was maintained at 190°C for the aforementioned 5 minutes, and then the pressure was increased to 30,000 psi (207 MPa) for 3 minutes. This was followed by holding at 21°C and 30,000 psi (207 MPa) for 1 minute. Measurements were performed within 1 hour of sample pressing.

[0103] Melt Index (I2) Unless otherwise specified, all melt index (I2) values ​​disclosed herein are measured according to ASTMD1238-10, Method B, at 190°C and a load of 2.16 kg, and are reported in decigrams per minute (dg / min).

[0104] High load melt index (I 21 ) Unless otherwise specified, all high-load melt index (I) disclosed herein 21 The values ​​were measured according to ASTM D1238-10, Method B, at 190°C and under a load of 21.6 kg, and reported in decigrams per minute (dg / min).

[0105] molecular weight Unless otherwise specified, weight-average molecular weight (M w ), number average molecular weight (M n ), and z-average molecular weight (M z All molecular weights disclosed herein, including those listed above, were measured using conventional gel permeation chromatography (GPC) and are reported in grams per mole (g / mol).

[0106] The chromatography system consisted of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5). The autosampler's oven compartment was set to 160 degrees Celsius (°C), and the column compartment was set to 150 degrees Celsius. The columns used were four Agilent "Mixed A" 30 cm, 20 micrometer linear mixed-bed columns. The chromatography solvent used was 1,2,4-trichlorobenzene containing 200 parts per million (ppm) of butylated hydroxytoluene (BHT). The solvent source was spurged with nitrogen. The injection volume used was 200 microliters, and the flow rate was 1.0 ml / min.

[0107] Calibration of the GPC column set was performed using 21 polystyrene standards with narrow molecular weight distributions, commercially available from Agilent Technologies, having molecular weights ranging from 580 g / mol to 8,400,000 g / mol. These standards were prepared in six "cocktail" mixtures with individual molecular weights separated by at least a tenfold. Polystyrene standards were prepared at a concentration of 0.025 grams per 50 ml of solvent for molecular weights greater than 1,000,000 g / mol, and 0.05 grams per 50 ml of solvent for molecular weights less than 1,000,000 g / mol. The polystyrene standards were dissolved at 80°C for 30 minutes with gentle stirring. The peak molecular weights of the polystyrene standards were converted to polyethylene molecular weights using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)). M polyethylene =A × (M polystyrene ) B equation 1 In the formula, M is the molecular weight, A has a value of 0.4315, and B is equal to 1.0.

[0108] A quintic polynomial was used to fit the respective polyethylene equivalent calibration points. A slight adjustment to A (approximately 0.375–0.445) was made to compensate for column resolution and band broadening effects so that the linear homopolymer polyethylene standard was obtained with a molecular weight of 120,000 g / mol.

[0109] The total plate count of the GPC column set was performed using decane (prepared with 0.04 g in 50 ml of TCB and dissolved for 20 minutes with gentle agitation). Plate count (Equation 2) and symmetry (Equation 3) were measured with 200 μL injections according to the following equations:

[0110]

number

[0111]

number

[0112] The sample was prepared semi-automatically using PolymerChar "Instrument Control" software. The sample was weight-targeted at 2 milligrams per milliliter (mg / ml), and the solvent (containing 200 ppm BHT) was added to a pre-spurged nitrogen-filled vial with a septum cap via a PolymerChar high-temperature autosampler. The sample was dissolved at 160°C for 2 hours with "low-speed" shaking.

[0113] Weight average molecular weight (M w(GPC) ), number average molecular weight (M n(GPC) ), and z-average molecular weight (M z(GPC) The calculation of ) was performed based on GPC results using the PolymerChar GPCOne™ software, baseline subtractive IR chromatograms at each equally spaced data acquisition point (i), and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve at point (i) from Equation 1, using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph following Equations 4-6.

[0114]

number

[0115] 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 track the respective decane peaks (RV) in the sample. (FM Sample) ) to narrow standard calibration (RV (FM Calibrated) By matching the decane peak and RV within ) the pump flow rate of each sample (flow rate) (Nominal) ) was used to linearly calibrate the flow rate. Then, any change in the time of the Decane marker peak was used over the entire run. (Effective) This is presumed to be related to a linear shift in ). To facilitate the highest accuracy of RV measurement of the flow marker peak, a least-squares fitting routine is used to fit the peaks 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 calibrating the system based on the flow marker peaks, the effective flow rate (for a narrow standard calibration) is calculated according to Equation 7. The processing of the flow marker peaks was performed via PolymerChar's GPCOne™ software. An acceptable flow rate correction is that the effective flow rate is within ±1 percent (%) of the apparent flow rate.

[0116]

number

[0117] A systematic approach to determining the multiple detector offset was carried out in a manner consistent with Balke, Mourey, et al. (Mourey and Balke, Chromatography Polym. Chpt 12, (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym. Chpt 13, (1992)), using PolymerChar GPCOne® software and broad homopolymer polyethylene standards (M w / M n >3) Optimize the results of the triple detector log(MW and IV) from the narrow standard calibration curve to the results of the narrow standard column calibration.

[0118] Absolute molecular weight data (GPC-LALS) were obtained using PolymerChar GPCOne® software in a format consistent with those published by Zimm (Zimm, BH, J. Chem. Phys., 16, 1099 (1948)) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987)). The total injection concentration used in determining the molecular weight was obtained from the mass detector area and mass detector constant, derived from one of the following: a suitable linear polyethylene homopolymer or a polyethylene standard material with a known weight-average molecular weight. The molecular weight calculated (using GPCOne®) was obtained using the light scattering constant and the refractive index concentration coefficient of 0.104, dn / dc, derived from the homopolymer polyethylene standard. Generally, the mass detector response (IR5) and light scattering constant (determined using GPCOne®) should be determined from linear standards having a molecular weight greater than approximately 50,000 g / mol, preferably greater than approximately 120,000 g / mol. Other respective moments, M n(Abs) and M z(Abs) This is calculated as follows, according to equations 8-9.

[0119]

number

[0120] Calibration of the IR5 detector ratio was performed using several ethylene polymers with known short-chain branching (SCB) frequencies (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 branching). Each standard had a weight-average molecular weight (M) ranging from 36,000 g / mol to 126,000 g / mol, determined by the GPC-LALS treatment method described above. w Each standard had a molecular weight distribution (Mw / Mn) of 2.0 to 2.5, as determined by the GPC-LALS treatment method described above.

[0121] The calculated "IR5 region ratio" (or "IR5 region ratio") of the "baseline subtraction region response of the IR5 methyl channel sensor" relative to the "baseline subtraction region response of the IR5 measurement channel sensor" Methyl Channel Area / IR5 Measurement Channel Area The following was calculated for each of the "SCB" standards. The linear fit of SCB frequency versus "IR5 domain ratio" was constructed according to equation 10 as follows:

[0122]

number

[0123] The calculation of the short-chain branching distribution of low molecular weight components (SCBD1), the short-chain branching distribution of high molecular weight components (SCBD2), and the comonomer ratio was based on GPC results using an internal IR5 detector (measurement channel) and SCB / 1000 total C for bimodal polyethylene. To calculate these values, the baseline subtractive IR chromatogram at equally spaced data acquisition points (i) and the SCBD surrounding the maximum value of the bimodal resin were determined. This calculation was performed using the top two abundance maximum values ​​LogM Maxima1 and LogM Maxima2 This is determined for polymers with a LogM greater than 3.5. Maxima1 This is the second LogM Maxima2 It is defined as the maximum value at lower molecular weights relative to . Here, m and n define the range in which SCBD1 is calculated, and m = (LogM Maxima1 -0.15) and n=(LogM Maxima1 (+0.15) Here, o and p define the range in which SCBD2 is calculated, and o = (LogM Maxima2 -0.15) and p=(LogM Maxima2 (+0.15)

[0124]

number

[0125] The comonomer distribution (also called the comonomer ratio) is defined according to Equation 13. Any value greater than 1.0 is considered an inverse 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.

[0126]

number

[0127] complex viscosity Unless otherwise indicated, all complex viscosities (η) disclosed herein are not included. *The time interval (Pa·s) is calculated using dynamic mechanical spectroscopy (DMS) and reported in pascal seconds (Pa·s).

[0128] The sample was compressed in air at a pressure of 25,000 psi for 5 minutes at 350°F to form a circular plaque measuring 3 mm thick by 1 inch. The sample was then removed from the compressor and allowed to cool.

[0129] A constant temperature-frequency sweep was performed using TA Instruments' Advanced Rheometric Expansion System (ARES) equipped with 25 mm (diameter) parallel plates under nitrogen purging. The sample was placed on the plate and melted at 190°C for 5 minutes. The plate was then closed to a 2 mm gap, the sample was trimmed (excess sample extending beyond the circumference of the 25 mm diameter plate was removed), and the test was then initiated. This method incorporated an additional 5-minute delay to allow for temperature equilibrium. The test was performed at 190°C over a frequency range of 0.1 radians / second (rad / s) to 100 rad / s with a constant strain amplitude of 10%.

[0130] Environmental stress cracking resistance (ESCR) Unless otherwise specified, all environmental stress crack resistance (ESCR) values ​​disclosed herein are F0 fracture times reported in hours and were measured on compression-molded specimens with a thickness of 75 mm in a 10% Igepal solution at 50°C according to ASTM D1693, Method B.

[0131] Tensile strength Unless otherwise indicated, all tensile strength values ​​disclosed herein are measured in accordance with ASTM D638-14, Type IV, on compression-molded specimens having a thickness of 75 mm, and are reported in megapascals (MPa) and / or pounds per square inch (psi).

[0132] stretch Unless otherwise indicated, all elongation values ​​disclosed herein are measured in accordance with ASTM D638-14, Type IV, for compression-molded specimens having a thickness of 75 mm, and are reported as percentages (%).

[0133] Wire smoothness Unless otherwise specified, all wire smoothness values ​​disclosed herein are calculated as the average surface roughness of coated conductor wire samples (14 American Wire Gauge (AWG) wires with a coating thickness of 10–15 mm) and reported in microinches (μ-in). Surface roughness values ​​were measured using a Mitutoyo SJ 400 surface roughness tester. Generally, relatively smooth wires have a lower average surface roughness than relatively rough wires.

[0134] High-temperature creep Unless otherwise specified, all high-temperature creep values ​​disclosed herein are measured according to ICEA T-28-562 and reported in elongation. A dogbone sample was prepared according to ASTM D412, Type D, and a 20 N / cm² pressure was applied to the lower end of the sample. 2 It was stretched at 200°C for 15 minutes using a weight. [Examples]

[0135] Example 1 Various bimodal polyethylene samples were produced by gas-phase polymerization in a single reactor. A primary catalyst, commercially available from Univation Technologies as UNIPOL®, was supplied to the polyethylene reactor via a 0.25-inch (") injection tube. A trim catalyst was also supplied to the polyethylene reactor via the same 0.25-inch injection tube at a rate sufficient to provide the desired resin flow index. The reactor gas composition was controlled by metering the feed to the polyethylene reactor at a rate sufficient to maintain the desired ethylene partial pressure, molar ratio of comonomers to ethylene (C2), molar ratio of hydrogen gas (H2) to ethylene (C2), and amount of isopentane. An additive, commercially available from Univation Technologies as CA-300, was supplied separately to the polyethylene reactor at a rate sufficient to maintain an additive concentration of approximately 45 parts per million by weight (ppmw), based on the ethylene supply rate to the reactor. 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, purging the discharge tank with nitrogen, then transferring it to a fiber pack, which was purged again with a mixture of nitrogen and water vapor. The process conditions used to produce each bimodal polyethylene sample are reported in Table 1.

[0136] [Table 1] a It is sold commercially by Univation Technologies as PRODIGY(trademark) BMC-200. bA spray-dried mixture in mineral oil slurry of bis(2-pentamethylphenylamide)ethyl)amine zirconium dibenzyl, (1,3-dimethyl-4,5,6,7-tetrahydroindene)(methylcyclopentadienyl) zirconium dimethyl, methylalumoxane (MAO), and fumed silica, commercially available from Cabot Corporation as CAB-O-SIL® TS-610. c A spray-dried mixture in mineral oil slurry of bis(2-pentamethylphenylamide)ethyl)amine zirconium dibenzyl, (cyclopentadienyl)(1,5-dimethylindenyl) zirconium dimethyl, methyl almoxane (MAO), and fumed silica commercially available from Cabot Corporation as CAB-O-SIL® TS-610. d It is sold commercially by Univation Technologies as PRODIGY(trademark) TR-200. e A mixture of 0.04 wt% (1,3-dimethyl4,5,6,7-tetrahydroindene)(methylcyclopentadienyl)zirconium dimethylbis(n-butylcyclopentadienyl)zirconium dimethyl in isopentane. f A mixture of 0.04 wt% (cyclopentadienyl)(1,5-dimethylindenyl)zirconium dimethyl in isopentane.

[0137] Characteristics of polyethylene examples Density, melt index (I2), and high-load melt index (I2) of the bimodal polyethylene sample from Example 1 and various commercially available samples. 21 ), and melt flow ratio (MFR) 21 Various characteristics, including those mentioned above, are reported in Table 2.

[0138] [Table 2] aCommercially available from The Dow Chemical Company as ELITE™ 5940G b Commercially available from The Dow Chemical Company as DFNA-4580NT c Commercially available from The Dow Chemical Company as ELITE™ 5940ST d Commercially available from Borealis AG as BORSTAR® HE6062 e Commercially available from The Dow Chemical Company as DFNB-3580 NT f Base polymer properties of CE-4 according to the technical datasheet

[0139] Molecular weight of polyethylene examples Weight-average molecular weight (M w ), number-average molecular weight (M n ), and z-average molecular weight (M z ) of the bimodal polyethylene sample of Example 1 and various commercially available samples are reported in Table 3.

[0140] [Table 3]

[0141] Comonomer distribution of polyethylene examples The short-chain branch distribution of the high molecular weight component (SCBD2) and the short-chain branch distribution of the low molecular weight component (SCBD1), as well as the comonomer distribution of the bimodal polyethylene sample of Example 1 and various commercially available samples are reported in Table 4.

[0142] [Table 4] a Unimodal polyethylene

[0143] Complex viscosity of polyethylene examples Table 5 reports the complex viscosities of the bimodal polyethylene sample from Example 1 and various commercially available samples.

[0144] [Table 5]

[0145] Properties of thermoplastic compositions Thermoplastic compositions were prepared by mixing various polymers, including the bimodal polyethylene sample from Example 1, with various additives using a 3 / 4” twin-screw extruder (temperature profile of 180 / 190 / 190°C and 60-mesh screen pack) at 60 rotations per minute (rpm). The components of the thermoplastic compositions and their various properties are reported in Tables 6-8.

[0146] [Table 6] a It is marketed by Dow Chemical Company as AXELERON® GP A-0037 BK CPD (containing 3.12% by weight of base resin and 2.55% by weight of carbon black). b It is marketed by 3M as Dynamar(trademark)FX 5912. c It is commercially available from Synchemer as Synox-TBM 6. d A mixture of 0.15% Irgafos 168 and 0.10% Irganox 1010. e It is sold by Addivant as NAUGARD(registered trademark) Super Q. f It is marketed by Dow Chemical Company as AXELERON (trademark) FO 6548 BK CPD.

[0147] [Table 7]

[0148] [Table 8]

[0149] The 2.5” line was a Davis Standard wire coating line equipped with a 24:1 polyethylene screw with a Maddox mixing head. Using this apparatus, samples with a final diameter of approximately 2.9 mm and a wall thickness of approximately 0.635 mm were produced on 14 AWG solid copper conductors (diameter 1.63 mm). The extrusion line was operated at a line speed of 300 ft / min.

[0150] The mini-wire line was a bra-bender type wire coating line equipped with a 3 / 4” diameter, 25:1 L / D general-purpose polyethylene screw. Using this apparatus, samples with a final diameter of approximately 2.2 mm and a wall thickness of approximately 0.254 mm were produced on 14 AWG solid copper conductor (diameter 1.63 mm). The extrusion line was operated at a line speed of 50 ft / min.

[0151] As shown in Table 8, the thermoplastic composition containing the bimodal polyethylene of the present disclosure has an excellent balance between processability (e.g., reduced breaker plate pressure and improved wire smoothness) and performance (e.g., improved mechanical properties such as greater tensile strength at break and environmental stress crack resistance). As described herein, this balance between processability and performance is important to ensure both success in manufacturing and the long-term durability of insulation and jacket layers for wires and cables during use. For example, IE-2.1, when compared with CE-2.2, has excellent wire smoothness (i.e., processability) as well as environmental stress crack resistance, tensile strength at break, and elongation at break, despite having similar density and melt index (I2). Further, IE-2.2 and IE-2.3, when compared with CE-2.3, have improved breaker plate pressure and wire smoothness while maintaining similar environmental stress crack resistance and tensile strength at break despite having similar density and melt index (I2). Similarly, IE-2.4, when compared with CE-2.5, has improved breaker plate pressure and wire smoothness while maintaining similar environmental stress crack resistance and tensile strength at break despite having similar density and melt index (I2).

[0152] Example 2 Various bimodal polyethylenes were produced via gas-phase polymerization in a single reactor. The main catalyst, a spray-dried mixture in a mineral oil slurry of bis(2-pentamethylphenylamide)ethyl)amine zirconium dibenzyl, (1,3-dimethyl-4,5,6,7-tetrahydroindene)(methylcyclopentadienyl) zirconium dimethyl, methyl alumoxane (MAO), and fumed silica commercially available from Cabot Corporation as CAB-O-SIL® TS-610, was supplied to a polyethylene reactor commercially available from Univation Technologies as UNIPOL® via a 0.25” injection tube. A trim catalyst, a mixture of 0.04 wt% (1,3-dimethyl4,5,6,7-tetrahydroindene)(methylcyclopentadienyl) zirconium dimethylbis(n-butylcyclopentadienyl) zirconium dimethyl in isopentane, was also supplied to 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 to the polyethylene reactor at a rate sufficient to maintain the desired ethylene partial pressure, molar ratio of comonomer to ethylene (C2), molar ratio of hydrogen gas (H2) to ethylene (C2), and amount of isopentane. An additive commercially available from Univation Technologies as CA-300 was supplied separately to the polyethylene reactor at a rate sufficient to maintain an additive concentration of approximately 40 ppmw, based on the ethylene supply rate to the reactor. The polyethylene reactor temperature was maintained at 100°C, 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, purging the discharge tank with nitrogen, then transferring it to a fiber pack and purging again with a mixture of nitrogen and steam. The process conditions for each bimodal polyethylene and the various properties of the bimodal polyethylene are reported in Table 9.

[0153] [Table 9]

[0154] The dimensions and values ​​disclosed herein should not be understood as being strictly limited to the exact numerical values ​​listed. Instead, unless otherwise specified, each such dimension is intended to mean both the listed value and the functionally equivalent range surrounding that value. For example, "40 g / cm²". 3 The dimensions disclosed as "approximately 40g / cm²" are "approximately 40g / cm²". 3 This is intended to mean "...".

[0155] The symbols used in the equations contained herein refer to their standard meanings as understood in the field of mathematics. For example, "=" means equal, "×" means multiplication, "+" means addition, "-" means subtraction, ">" is the sign for "greater than", "<" is the sign for "less than", and " / " means division.

[0156] All documents referenced herein, including any cross-referenced or related patents or patent applications, and any patents or patent applications to which this application claims priority or interest, are incorporated herein by reference in their entirety unless expressly excluded or otherwise limited. No document reference constitutes prior art with respect to any embodiment disclosed or claimed herein, nor does it imply, suggest, or disclose any such embodiment, either alone or in combination with any other single or multiple references. Furthermore, if any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in any document incorporated by reference, the meaning or definition assigned to the term in this document shall prevail. Examples of the inventions of this application include the following: [1] A bimodal polyethylene containing a high molecular weight component and a low molecular weight component, wherein the bimodal polyethylene is When measured according to ASTM D792-13, Method B, the result was 0.933 g / cm³. 3 ~0.960g / cm 3 The density and According to ASTM D1238-10, when measured at 190°C and a load of 2.16 kg, the melt index (I) was 0.3 dg / min to 1.2 dg / min. 2 )and, A melt flow ratio (MFR) greater than 80.0 and less than or equal to 150.0. 21 ) and the melt flow ratio (MFR 21 ) is the melt index (I 2 ) for the high-load melt index (I 21 This is the ratio of the high-load melt index (I 21 The melt flow ratio (MFR) is measured according to ASTM D1238-10 at 190°C and a load of 21.6 kg. 21 )and, Molecular weight distribution exceeding 10.0 (M w / M n ) and the molecular weight distribution (M w / M n ) is the number average molecular weight (M) of the bimodal polyethylene. n ) and the weight-average molecular weight (M) of the bimodal polyethylene. w This is the ratio of the weight-average molecular weight (M w ) and the number average molecular weight (M n ) is measured using gel permeation chromatography (GPC), and the molecular weight distribution (M w / M n )and, Inverse comonomer distribution, wherein the short-chain branched distribution (SCBD) of the low molecular weight component. 1 ) and the short-chain branching distribution (SCBD) of the high molecular weight component. 2 The ratio of ) exceeds 1.0, and the short-chain branching distribution (SCBD) of the high molecular weight component. 2 ) and the short-chain branching distribution (SCBD) of the low molecular weight component. 1 ) is measured using gel permeation chromatography (GPC), and the inverse comonomer distribution is also measured. A shear viscosity index (SHI) of 5.0 to 20.0, wherein the shear viscosity index (SHI) is equal to the complex viscosity (η) of the bimodal polyethylene measured at 100 radians / second. * The complex viscosity (η) of the bimodal polyethylene measured at 0.1 radians / second relative to 100 * A bimodal polyethylene comprising a ratio of 0.1) and the complex viscosity of the bimodal polyethylene, wherein the shear viscosity index (SHI) is determined at 190°C using dynamic mechanical spectroscopy (DMS). [2] The bimodal polyethylene is 0.933 g / cm³ 3 ~0.945g / cm 3 The bimodal polyethylene described in [1] above, having the density of [1]. [3] The short-chain branching distribution (SCBD) of the high molecular weight component of the bimodal polyethylene. 2 The bimodal polyethylene described in [2] above, wherein the average branching number / 1000 carbon is 4.0 or greater. [4] The bimodal polyethylene is 0.945 g / cm³ 3 ~0.960g / cm 3 The bimodal polyethylene described in [1] above, having the density of [1]. [5] The short-chain branching distribution (SCBD) of the high molecular weight component of the bimodal polyethylene. 2 The bimodal polyethylene described in [4] above, wherein the average branching number / 1000 carbon is 3.0 or greater. [6] The bimodal polyethylene has a molecular weight distribution greater than 4.0 (M z / M w ) has the molecular weight distribution (M z / M w ) is the weight-average molecular weight (M) measured using GPC. w The z-average molecular weight (M) of the bimodal polyethylene relative to ) z A bimodal polyethylene as described in any one of the above [1] to [5], wherein the ratio is ) [7] A method for producing bimodal polyethylene as described in any one of the above [1] to [6], wherein the method comprises polymerizing ethylene with at least one 1-alkene comonomer by gas-phase polymerization in the presence of a main catalyst and a trim catalyst in a single reactor to produce the bimodal polyethylene. [8] A thermoplastic composition comprising 50.1% to 99.9% by weight of bimodal polyethylene as described in any one of [1] to [6] above, 0.1% to 1.0% by weight of a first antioxidant component, optionally 0.0% to 1.0% by weight of a second antioxidant, 0.0% to 5.0% by weight of an ultraviolet stabilizer, 0.0% to 1.0% by weight of a processing aid, 0.0% to 1.0% by weight of a flame retardant, and 0.0% to 1.0% by weight of a filler. [9] Articles manufactured using bimodal polyethylene as described in any one of the above items [1] to [6] or thermoplastic compositions as described in [8].

[10] The article is A conductive core, A coated conductor comprising a coating layer that at least partially covers the conductive core, The article according to [9], wherein the coating layer comprises a bimodal polyethylene as described in any one of [1] to [6] above, or a thermoplastic composition as described in [8] or [9] above.

[11] The article according to

[10] above, wherein the conductive core comprises a metal wire, an optical fiber, or both.

[12] Environmental stress crack resistance (ESCR) (F) for more than 48 hours when measured in a 10% Igepal solution at 50°C according to ASTM D1693-1, Method B. 0 The article described in any one of the above paragraphs [9] to

[11] , having )

[13] A method of transmitting electricity or light through a conductive core of a covered conductor as described in

[11] above, Applying a voltage across the metal wire, thereby causing electrical energy to flow through the metal wire, Sending light pulses through the optical fiber, thereby transmitting light through the optical fiber, or A method comprising applying a voltage across the metal wire and sending pulses of light through the optical fiber, thereby causing electrical energy to flow through the metal wire and light to be transmitted through the optical fiber.

Claims

1. A bimodal polyethylene containing high molecular weight components and low molecular weight components, the bimodal polyethylene Chilen, When measured according to ASTM D792-13, Method B, the result was 0.933 g / cm³. ３ ~ 0.960 g / cm ３ The density and Measurements were taken at 190°C and with a load of 2.16 kg according to ASTM D1238-10. In combination, the melt index (I) is 0.3 dg / min to 1.2 dg / min. ２ )and, A melt flow ratio (MFR) greater than 80.0 and less than or equal to 150.0 ２１ ) and The aforementioned melt flow ratio (MFR) ２１ ) is the melt index (I ２ ) the two High-load melt index of undulating polyethylene (I ２１ ) is the ratio of the high load melt Index (I ２１ ) However, according to ASTM D1238-10, 190°C and 21. The melt flow ratio (MFR) measured at a load of 6 kg ２１ ), and Molecular weight distribution exceeding 10.0 (M ｗ / M ｎ ) and the molecular weight distribution (M ｗ / M ｎ ) However, the number average molecular weight (M) of the bimodal polyethylene ｎ ) the bimodal polyethylene Weight average molecular weight (M ｗ This is the ratio of the weight-average molecular weight (M ｗ ) and the number average molecular weight (M ｎ ) is measured using gel permeation chromatography (GPC), and the molecular weight distribution ( M ｗ / M ｎ )and, Molecular weight distribution of 4-6 (M ｚ / M ｗ ) and the molecular weight distribution (M ｚ / M ｗ ) However, Weight average molecular weight (M ｗ ) measured using gel permeation chromatography (GPC). The z-average molecular weight (M) of the bimodal polyethylene is determined. ｚ The ratio of molecular weight distribution (M ｚ / M ｗ )and, 900,000 g / mo, measured using gel permeation chromatography (GPC). The z-average molecular weight (M) of l to 1,500,000 g / mol ｚ )and, Inverse comonomer distribution, wherein the short-chain branched distribution (SCBD) of the low molecular weight component １ ) The short-chain branching distribution of the aforementioned high molecular weight component (SCBD) ２ The ratio of ) exceeds 1.0, and the high molecular weight The aforementioned short-chain branching distribution (SCBD) ２ ) and the short-chain branching distribution (SCB) of the low molecular weight component D １ ) is measured using gel permeation chromatography (GPC), and the reverse comonomer content is measured. Cloth and, A shear viscosity index (SHI) of 5.0 to 20.0, wherein the shear viscosity index (SHI) ) is the complex viscosity (η) of the bimodal polyethylene measured at 100 radians / second. ＊ 100 The complex viscosity (η) of the bimodal polyethylene, measured at 0.1 radians / second, relative to ) ＊ 0 1) is the ratio, and the complex viscosity of the bimodal polyethylene is determined by dynamic mechanical spectroscopy (DMS). The shear viscosity index (SHI), determined at 190°C using ), and a bimodal polymer containing ethylene.

2. The aforementioned bimodal polyethylene is 0.933 g / cm³ ３ ~0.945g / cm ３ The density The bimodal polyethylene according to claim 1.

3. The short-chain branching distribution (SCBD) of the high molecular weight component of the bimodal polyethylene ２ ) but 4 The bimodal polyethylene according to claim 2, wherein the average branching number per 1000 carbon atoms is 0 or more.

4. The aforementioned bimodal polyethylene is 0.945 g / cm³ ３ ~0.960g / cm ３ The density The bimodal polyethylene according to claim 1.

5. The short-chain branching distribution (SCBD) of the high molecular weight component of the bimodal polyethylene ２ ) but 3 The bimodal polyethylene according to claim 4, wherein the average branching number per 1000 carbon atoms is 0 or more.

6. A method for producing bimodal polyethylene according to any one of claims 1 to 5. The above method involves, in the presence of a main catalyst and a trim catalyst in a single reactor, ethylene and at least It is polymerized by gas-phase polymerization with another 1-alkene comonomer, resulting in the bimodal polyethylene A method that includes producing n.

7. A thermoplastic composition comprising any one of claims 1 to 5, wherein 50.1% to 99.9% by weight is present. The bimodal polyethylene described in item 1 and 0.1% to 1.0% by weight of a first antioxidant In addition, optionally, 0.0% to 1.0% by weight of a second antioxidant and 0.0% by weight ~5.0% by weight of UV stabilizer, 0.0% to 1.0% by weight of processing aid, and 0.0% by weight A heat-resistant material containing a flame retardant in an amount of % to 1.0% by weight and a filler in an amount of 0.0% to 1.0% by weight. Plastic composition.

8. An article manufactured using bimodal polyethylene as described in any one of claims 1 to 5 or a thermoplastic composition as described in claim 7.

9. The aforementioned article, A conductive core, A coated conductor comprising a coating layer that at least partially covers the conductive core, The coating layer is made of bimodal polyethylene as described in any one of claims 1 to 5 or The article according to claim 8, comprising the thermoplastic composition according to claim 7.

10. The conductive core comprises a metal wire, an optical fiber, or both, as described in claim 9. The item.

11. The measurement was performed in a 10% igel solution at 50°C according to ASTM D1693-1, Method B. When set, the environmental stress crack resistance (ESCR) (F) exceeds 48 hours. ０ ) has a claim Articles specified in any one of paragraphs 8 to 10.

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