Polyethylene composition, oriented polyethylene film and article containing same

Abstract

Disclosed are polyethylene compositions comprising three polyethylene components, oriented polyethylene films comprising such polyethylene compositions, laminates comprising such polyethylene compositions, and articles comprising such polyethylene compositions. The polyethylene compositions can have good processability and stretchability (e.g., high throughput speeds during film casting) into oriented polyethylene films, and oriented polyethylene films made from such polyethylene compositions can be compatible with polyethylene recycle streams and can have a desirable balance of stretchability, elongation, modulus, haze, and clarity.

Description

[Technical Field]

[0001] The present invention relates to polyethylene compositions, oriented polyethylene films comprising such polyethylene compositions, laminates comprising such polyethylene compositions, and articles comprising such polyethylene compositions. [Background technology]

[0002] Introduction As global interest in reducing packaging waste and making flexible packaging more sustainable grows, increasing efforts are being made to develop materials and technologies that enhance the sustainability of flexible packaging. Flexible packaging film structures are often formed from multiple types of polymer materials, including, for example, polyethylene, polypropylene, ethylene vinyl alcohol, polyethylene terephthalate, polyamide, etc. Such materials are typically combined to achieve a balance of properties that cannot be achieved with a single type of material. However, due to the differences between these materials, the final packaging is typically not easily recyclable. Therefore, there is also a movement toward single-component structures (e.g., all-polyethylene structures) to improve recyclability profiles. For example, all-polyethylene structures require enhanced certain performance metrics (e.g., mechanical properties) to improve recyclability while maintaining the performance levels expected of these structures when formed from different polymer materials. Therefore, new resins and processing technologies are needed to overcome the performance deficiencies of polyethylene compared to other types of materials.

[0003] One such relatively new material technology on the processing side is biaxially oriented polyethylene (BOPE) film. Such BOPE films are formed by cast extrusion, then oriented in the machine direction (MD), followed by orientation in the cross direction (TD) on a tenter frame. Alternatively, the processes may also be performed simultaneously. Due to the molecular structure, microstructure, and crystallization kinetics of polyethylene, it is often difficult to biaxially orient conventional polyethylene. Furthermore, balancing the optical and stiffness properties of BOPE films made from conventional polyethylene is difficult, and such BOPE films may have a lower modulus due to the lower density of the polyethylene resins that can be used for biaxial orientation, which can adversely affect the temperature resistance and processability of the film.

[0004] Thus, there remains a need for polyethylene compositions that have good processability and stretchability into oriented polyethylene films, while exhibiting higher densities associated with higher melting points and therefore higher heat resistance (e.g., higher throughput speeds during film casting and packaging processes), as well as oriented polyethylene films that may be compatible with polyethylene recycle streams and have a desirable balance of stretchability, elongation, modulus, haze, and clarity. Summary of the Invention

[0005] The present invention provides polyethylene compositions suitable for processing into oriented polyethylene films, and oriented polyethylene films having desirable properties, such as a desirable balance of stretchability, elongation, modulus, haze, and clarity. The polyethylene compositions, in some embodiments, can advantageously expand the operating window for stretching films to provide oriented polyethylene films and can be processed at high throughput rates during film casting. The polyethylene compositions, in some embodiments, can provide a one-pellet solution without the need for blends or skin layers, and can produce films with a desirable balance of optical properties and stiffness compared to existing films.

[0006] In one aspect, the present invention provides a method for producing a pharmaceutical composition comprising: (a) 15 to 25 weight percent of a first polyethylene component having a molecular weight (Mw) greater than 200,000 g / mole and a density between 0.925 and 0.945 g / cc; (b) 20 to 35 weight percent of a second polyethylene component having a molecular weight (Mw) of less than 80,000 g / mole and a density of 0.915 to 0.950 g / cc; (c) 40 to 65 weight percent of a third polyethylene component having a molecular weight (Mw) of less than 100,000 g / mole and a density of 0.940 to 0.965 g / cc, The polyethylene composition has a density of 0.935 to 0.958 g / cc, a melt index (I2) of 0.5 to 5 g / 10 min, and a melt index (I2) of 0.5 to 5 g / 10 min, and is represented by the following formula: weight fraction of the first polyethylene component * SCB logMw4~5 * Meet Mz (conventional GPC) > 230,000.

[0007] In another aspect, the present invention relates to a uniaxially oriented film. The uniaxially oriented film may comprise the polyethylene composition disclosed herein.

[0008] In another aspect, the present invention relates to a biaxially oriented film. The biaxially oriented film may comprise the polyethylene composition disclosed herein.

[0009] In another aspect, the invention relates to a laminate, in some embodiments, the laminate includes a first film comprising a polyethylene sealant film, polypropylene, or polyamide, and a biaxially oriented film according to an embodiment disclosed herein, wherein the first film is laminated to the biaxially oriented film.

[0010] In another aspect, the invention relates to an article. In some embodiments, the article comprises any of the laminates, films, and / or polyethylene compositions disclosed herein.

[0011] These and other embodiments are described in more detail in the detailed description. [Brief explanation of the drawings]

[0012] The following detailed description of certain embodiments of the present disclosure can be best understood when read in conjunction with the following drawings, in which like structure is indicated with like reference numerals and in which: [Figure 1] 1 is a schematic representation of reactor stream feed data flows for inventive compositions and comparative compositions disclosed herein. DETAILED DESCRIPTION OF THE INVENTION

[0013] Unless otherwise stated to the contrary, implied from the context, or customary in the art, all parts and percentages are by weight, all temperatures are in degrees Celsius, and all test methods are current as of the filing date of this disclosure.

[0014] As used herein, the term "composition" refers to the mixture of materials that make up the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0015] The term "polymer" means a polymeric compound prepared by polymerizing monomers, whether of the same or different types. Thus, the generic term polymer encompasses the term homopolymer, as defined below, and the term interpolymer, as defined below. Minor impurities (e.g., catalyst residues) may be incorporated into and / or present within the polymer. The polymer may be a single polymer, a polymer blend, or a polymer mixture, including a mixture of polymers formed in situ during polymerization.

[0016] As used herein, the term "homopolymer" refers to a polymer prepared from only one type of monomer, with the understanding that trace amounts of impurities may be incorporated into the polymer structure.

[0017] As used herein, the term "interpolymer" refers to a polymer prepared by the polymerization of at least two different types of monomers. Thus, the generic term interpolymer includes copolymers (used to refer to polymers prepared from two different types of monomers) and polymers prepared from three or more different types of monomers.

[0018] As used herein, the terms "olefin-based polymer" or "polyolefin" refer to a polymer that comprises, in polymerized form, a majority amount (based on the weight of the polymer) of an olefin monomer, e.g., ethylene or propylene, and may optionally include one or more comonomers.

[0019] As used herein, the term "ethylene / α-olefin interpolymer" refers to an interpolymer that, in polymerized form, contains a majority amount (greater than 50 mole %) of units derived from ethylene monomer, with the balance being derived from one or more α-olefins. Typical α-olefins used to form ethylene / α-olefin interpolymers are C3 to C6 10 It is an alkene.

[0020] As used herein, the term "ethylene / α-olefin copolymer" refers to a copolymer that contains, in polymerized form, a majority amount (greater than 50 mole %) of ethylene monomer and an α-olefin as the only two monomers.

[0021] As used herein, the term "α-olefin" refers to an alkene having a double bond in the primary or alpha (α) position.

[0022] "Polyethylene" or "ethylene-based polymer" refers to a polymer containing a majority (greater than 50 mol%) of units derived from ethylene monomers. This includes polyethylene homopolymers and copolymers (meaning units derived from two or more comonomers). Common forms of polyethylene known in the art include low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ultra-low-density polyethylene (ULDPE), single-site catalyzed linear low-density polyethylene (m-LLDPE), including both linear and substantially linear low-density resins, ethylene-based plastomers (POP) and ethylene-based elastomers (POE), medium-density polyethylene (MDPE), and high-density polyethylene (HDPE). These polyethylene materials are generally well known in the art. However, the following discussion may be helpful in understanding the differences between some of these different polyethylene resins.

[0023] The term "LDPE," which may also be referred to as "high pressure ethylene polymer" or "highly branched polyethylene," is defined to mean that the polymer is partially or fully homopolymerized or copolymerized in an autoclave or tubular reactor at pressures above 14,500 psi (100 MPa) using a free radical initiator, such as peroxide (see, for example, U.S. Pat. No. 4,599,392, incorporated herein by reference). LDPE resins typically have a viscosity of 0.916 to 0.935 g / cm. 3 The density is in the range of

[0024] The term "LLDPE" includes both resins made using single-site catalysts, including, but not limited to, traditional Ziegler-Natta catalyst systems and chromium-based catalysts, as well as mono- or bis-cyclopentadienyl catalysts (typically referred to as metallocenes), constrained geometry catalysts, pyridylamine catalysts, phosphinimine catalysts, and polyhydric aryloxy ether catalysts (typically referred to as bisphenylphenoxy), and includes linear, substantially linear, or heterogeneous polyethylene copolymers or homopolymers. LLDPE contains less long chain branching than LDPE and includes substantially linear ethylene polymers, as further defined in U.S. Patent Nos. 5,272,236, 5,278,272, 5,582,923, and 5,733,155; homogeneously branched linear ethylene polymer compositions such as those in U.S. Patent No. 3,645,992; heterogeneously branched ethylene polymers such as those prepared according to the process disclosed in U.S. Patent No. 4,076,698; and / or blends thereof (such as those disclosed in U.S. Patent No. 3,914,342 or 5,854,045). LLDPE may be made via gas phase, solution phase, or slurry polymerization, or any combination thereof, using any type of reactor or reactor configuration known in the art.

[0025] The term "MDPE" refers to 0.926-0.935 g / cm 3"MDPE" refers to polyethylene having a density of greater than 2.5, typically produced using chromium or Ziegler-Natta catalysts, or using single-site catalysts including, but not limited to, substituted mono- or bis-cyclopentadienyl catalysts (typically referred to as metallocenes), constrained geometry catalysts, pyridylamine catalysts, phosphinimine catalysts, and polyaryloxy ether catalysts (typically referred to as bisphenylphenoxy), and typically has a molecular weight distribution ("MWD") greater than 2.5.

[0026] The term "HDPE" refers to a polymer having a density of about 0.935 g / cm, typically prepared using a single-site catalyst, including, but not limited to, Ziegler-Natta, chromium, or substituted mono- or bis-cyclopentadienyl catalysts (typically referred to as metallocenes), constrained geometry catalysts, pyridylamine catalysts, phosphinimine catalysts, and polyaryloxy ether catalysts (typically referred to as bisphenylphenoxy). 3 Super ~ maximum approx. 0.980g / cm 3 It refers to polyethylene having a density of

[0027] The term "ULDPE" refers to polymers with a yield of 0.855 to 0.912 g / cm, typically prepared using single-site catalysts, including, but not limited to, Ziegler-Natta catalysts, chromium catalysts, or substituted mono- or bis-cyclopentadienyl catalysts (typically referred to as metallocenes), constrained geometry catalysts, pyridylamine catalysts, phosphinimine catalysts, and polyaryloxy ether catalysts (typically referred to as bisphenylphenoxy). 3 ULDPE refers to polyethylene with a density of 0.855 to 0.912 g / cm. Examples of ULDPE include, but are not limited to, polyethylene (ethylene-based) plastomers and polyethylene (ethylene-based) elastomers. Polyethylene (ethylene-based) elastomer plastomers generally have a density of 0.855 to 0.912 g / cm. 3 It has a density of

[0028] The terms "blend" and "polymer blend" refer to a composition of two or more polymers. Such blends may or may not be miscible. Such blends may or may not be phase separated. Such blends may or may not contain one or more domain configurations as determined from transmission electron spectroscopy, light scattering, X-ray scattering, and any other method known in the art. A blend is not a laminate, although one or more layers of a laminate may contain the blend. Such blends may be prepared as dry blends or may be formed in situ (e.g., in a reactor), as melt blends, or using other techniques known to those skilled in the art.

[0029] The term "multimodal" refers to a composition that can be characterized as having at least three polymer minor components with varying densities and weight-average molecular weights, and can optionally also have different melt index values. In one embodiment, multimodality can be defined by having at least three distinct peaks in a gel permeation chromatography (GPC) chromatogram showing a molecular weight distribution. In another embodiment, multimodality can be defined by having at least three distinct peaks in a crystallization elution fractionation (CEF) chromatogram showing a short-chain branching distribution. In another embodiment, multimodality can be defined by having at least three distinct peaks in an improved comonomer composition distribution (iCCD) elution profile. Multimodality includes compositions having three peaks in GPC, CEF, or iCCD, as well as compositions having more or fewer than three peaks, so long as the composition can be characterized as having at least (three) polymer minor components with varying densities and weight-average molecular weights according to the following test methods.

[0030] The term "trimodal polymer" refers to a multimodal ethylene-based polymer having three major components: a first polyethylene component, a second polyethylene component, and a third polyethylene component.

[0031] A "polyethylene component," e.g., a "first polyethylene component," a "second polyethylene component," or a "third polyethylene component," refers to a subcomponent of a polyethylene component (i.e., a multimodal or trimodal polymer) disclosed herein, each subcomponent comprising ethylene monomer and optionally a C3 to C6 12 It is a polyethylene containing an alpha-olefin comonomer.

[0032] The terms "comprising," "including," "having," and their derivatives are not intended to exclude the presence of any additional component, step, or procedure, whether specifically disclosed or not. For the avoidance of doubt, all compositions claimed through the use of the term "comprising" may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless otherwise stated to the contrary. In contrast, the term "consisting essentially of" excludes from the scope of any succeeding description any other component, step, or procedure, except those that are not essential to operability. The term "consisting of" excludes any component, step, or procedure not specifically delineated or listed.

[0033] The present invention relates generally to polyethylene compositions that may be suitable for oriented films. When incorporated into oriented films, the polyethylene compositions may provide desirable performance properties, such as desirable clarity, reduced haze, and improved modulus. Without being bound by theory, for example, it is believed that the ternary composition and the weight fraction of the first polyethylene component, the Z-average molecular weight (Mz), and the average level of short chain branching (SCB) in the portion between 4.0 and 5.0 log(Mw) may be related to the tensile strength of the polyethylene composition. logMw4~5 The unique design of the polyethylene composition, including a desirable balance of olefins, is believed to result in improved processability, stretchability, and performance properties. The polyethylene compositions of the present invention can be incorporated into uniaxially oriented films, biaxially oriented films, laminates, and articles with enhanced performance properties, such as desirable clarity, reduced haze, and improved modulus. Because the compositions of the present invention are polyethylene-based, in some embodiments, films, laminates, and articles can be formed entirely or substantially entirely from polyethylene, making the films, laminates, and articles more easily recyclable.

[0034] In one aspect, the polyethylene composition comprises: (a) 15 to 25 weight percent of a first polyethylene component having a molecular weight (Mw) greater than 200,000 g / mole and a density of 0.925 to 0.945 g / cc; (b) 20 to 35 weight percent of a second polyethylene component having a molecular weight (Mw) of less than 80,000 g / mole and a density of 0.915 to 0.950 g / cc; (c) 40 to 65 weight percent of a third polyethylene component having a molecular weight (Mw) of less than 100,000 g / mole and a density of 0.940 to 0.965 g / cc; The polyethylene composition has a density of 0.935 to 0.958 g / cc, a melt index (I2) of 0.5 to 5 g / 10 minutes, and a melt index (I2) satisfying the following formula: Weight fraction of first polyethylene component * SCB logMw4~5 * Meet Mz (conventional GPC) > 230,000.

[0035] In the above formula, "weight fraction of first polyethylene component" is the weight percent of the first polyethylene component converted to a fraction. For example, a composition having 25 weight percent of the first polyethylene component has a value of 0.25 for "weight fraction of first polyethylene component." logMw4~5 " is the average short chain branching level in the portion of the polyethylene composition between log(Mw) 4.0 and 5.0, measured according to the following test method. "Mz (conventional GPC)" is the Z-average molecular weight of the polyethylene composition, measured according to the following prior art GPC test method. For example, the polyethylene composition disclosed herein may comprise 21 wt. % of a first polyethylene component, an SCB of 4.28, logMw4~5 and Mz (conventional GPC) of 367,362 g / mol, which is 330,185 (i.e., 0.21 * 4.28 * 367,362=330,185), which may be greater than 230,000. In some embodiments, the weight fraction of the first polyethylene component * SCB logMw4~5 * Mz (conventional GPC) is >250,000, alternatively >275,000, alternatively >300,000, alternatively >325,000.

[0036] In some embodiments, the polyethylene composition has an average short chain branching level (SCB logMw4~5 )

[0037] In some embodiments, the first polyethylene component has an improved comonomer composition distribution (iCCD) elution profile with a peak temperature greater than 99.5°C. In some embodiments, the polyethylene composition has an Mz / Mw of 3.5 to 4.5. In some embodiments, the polyethylene composition has a molecular weight distribution (Mw / Mn) of 4.2 to 10.0. In some embodiments, the polyethylene composition has an I of 7.0 to 15.0. 10 / I2. In some embodiments, the polyethylene composition has a Mz (conventional GPC) of 250,000 to 450,000 g / mol.

[0038] The polyethylene composition may comprise a combination of two or more of the embodiments described herein.

[0039] Polyethylene composition The polyethylene composition according to the embodiments disclosed herein comprises a copolymer of ethylene monomer and at least one C3-C6 12 The polyethylene composition includes a polymerization reaction product with an α-olefin comonomer, wherein the one or more α-olefin comonomers of the polyethylene composition may be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene, or alternatively, from the group consisting of 1-butene, 1-hexene, and 1-octene, or alternatively, from the group consisting of 1-hexene and 1-octene.

[0040] The polyethylene composition has a density of 0.935 to 0.958 g / cc, a melt index (I2) of 0.5 to 5.0 g / 10 min, and a melt index (I2) of 0.5 to 5.0 g / 10 min expressed by the following formula: weight fraction of the first polyethylene component * SCB logMw4~5 * The polyethylene composition may have a density of 0.935 to 0.958 g / cc, or 0.936 to 0.954 g / cc, or 0.935 to 0.950 g / cc, or 0.935 to 0.945 g / cc, or 0.936 to 0.945 g / cc. The polyethylene composition may have a melt index (I2) of 0.5 to 5.0 g / 10 min, or 0.5 to 3.0 g / 10 min, or 0.5 to 2.0 g / 10 min, or 1.0 to 2.0 g / min. In one or more embodiments, the polyethylene composition has an average short chain branching (SCB) level (SCB) in the portion between 4.0 and 5.0 log(Mw) that is greater than 3.50 SCB / 1000C, e.g., greater than 4.00 SCB / 1000C, greater than 4.50 SCB / 1000C, greater than 5.00 SCB / 1000C, greater than 5.50 SCB / 1000C, or greater than 6.00 SCB / 1000C. logMw4~5In one or more embodiments, the maximum average SCB level (SCB) in the portion between 4.0 and 5.0 log(Mw) is logMw4~5 ) is 8.00SCB / 1000C or 7.0SCB / 1000C. SCB logMw4~5 is measured according to the test method described herein below.

[0041] The polyethylene composition may have a molecular weight distribution (Mw / Mn) of 4.2 to 10.0, or 4.2 to 8.0, or 4.2 to 6.0, or 4.3 to 6.0. The polyethylene composition may have an I of 7.0 to 15.0, or 8.0 to 15, or 7.0 to 14.0, or 7.0 to 13.0. 10 / I2.

[0042] The polyethylene compositions disclosed herein have three components: a first polyethylene component, a second polyethylene component, and a third polyethylene component.

[0043] The polyethylene composition comprises 15 to 25 weight percent of a first polyethylene component, based on the total weight of the polyethylene composition, having a molecular weight (Mw) (also known as weight average molecular weight) greater than 200,000 g / mol and a density of 0.925 to 0.945 g / cc. All individual values ​​and subranges between 15 and 25 weight percent are disclosed and included herein. For example, the polyethylene composition may comprise 15, 16, 17, 18, 19, 20, 21, 22, 23, or 24 to 25, 24, 23, 22, 21, 20, 19, 18, 17, or 16 weight percent of the first polyethylene component, based on the total weight of the polyethylene composition. The first polyethylene component may have a molecular weight (Mw) of greater than 200,000 g / mol, or greater than 210,000 g / mol, or greater than 250,000 g / mol, or greater than 280,000 g / mol, or greater than 300,000 g / mol, or greater than 310,000 g / mol, or from 210,000 g / mol to 400,000 g / mol, where the molecular weight (Mw) can be measured according to the following test method. The first polyethylene component may have a density of 0.925 to 0.945 g / cc, 0.930 to 0.945 g / cc, or 0.930 to 0.940 g / cc. The densities of the components of the polyethylene composition (e.g., the first polyethylene component, the second polyethylene component, and the third polyethylene component) are calculated from the equations set forth in the Test Methods section below.

[0044] In some embodiments, the first polyethylene component has an improved comonomer composition distribution (iCCD) elution profile with a peak temperature greater than 99.5°C. In some embodiments, the first polymer component is a homopolymer. In some embodiments, the first polyethylene component is a C3-C 12The first polyethylene component may include an α-olefin comonomer. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene. The one or more α-olefin comonomers of the first polyethylene component may be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene, or alternatively, from the group consisting of 1-butene, 1-hexene, and 1-octene, or alternatively, from the group consisting of 1-hexene and 1-octene.

[0045] The polyethylene composition comprises 20 to 35 weight percent of a second polyethylene component having a molecular weight (Mw) of less than 80,000 g / mol and a density of 0.915 to 0.950 g / cc. All individual values ​​and subranges between 20 and 35 weight percent are disclosed and included herein. For example, the polyethylene composition may comprise 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, or 34-35, 34, 33, 32, 31, 30, 29, 28, 27, 26, 25, 24, 23, 22, or 21 weight percent of the second polyethylene component, based on the total weight of the polyethylene composition. The second polyethylene component may have a molecular weight (Mw) of less than 80,000 g / mol, or less than 70,000 g / mol, or less than 60,000 g / mol, or less than 55,000 g / mol, or from 15,000 g / mol to 75,000 g / mol, where the molecular weight (Mw) can be measured according to the following test method. The second polyethylene component may have a density of 0.915 to 0.950 g / cc, or 0.915 to 0.940 g / cc, or 0.915 to 0.935 g / cc, or 0.915 to 0.930 g / cc, or 0.915 to 0.925 g / cc.

[0046] The second polyethylene component contains various levels of C3 to C 12 In one embodiment, the second polyethylene component may have a higher C3-C6 α-olefin comonomer incorporation than the first polyethylene component. 12For example, the second polyethylene component may have 2 to 20 weight percent C3 to C6 α-olefin comonomer incorporation. 12 α-olefin comonomer, or 3 to 19 weight percent C3 to C 12 α-olefin comonomer, or 5 to 17 weight percent C3 to C 12 The one or more α-olefin comonomers of the second polyethylene component may be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene, or alternatively, from the group consisting of 1-butene, 1-hexene, and 1-octene, or alternatively, from the group consisting of 1-hexene and 1-octene.

[0047] The polyethylene composition comprises 40 to 65 weight percent of a third polyethylene component having a molecular weight (Mw) of less than 100,000 g / mol and a density of 0.940 to 0.965 g / cc. All individual values ​​and subranges between 40 and 65 weight percent are disclosed and included herein. For example, the polyethylene composition may comprise 40, 41, 43, 45, 47, 49, 51, 53, 55, 57, 59, 61, or 63-65, 63, 61, 59, 57, 55, 53, 51, 49, 47, 45, 43, or 41 weight percent of the third polyethylene component, based on the total weight of the polyethylene composition. The third polyethylene component may have a molecular weight (Mw) of less than 100,000 g / mol, or less than 90,000 g / mol, or less than 80,000 g / mol, or from 15,000 g / mol to 90,000 g / mol, where the molecular weight (Mw) can be measured according to the following test method. The third polyethylene component may have a density of 0.940 to 0.965 g / cc, or 0.942 to 0.965 g / cc, or 0.942 to 0.963 g / cc.

[0048] The third polyethylene component is made up of various levels of C3 to C 12 In one embodiment, the third polyethylene component may have a lower C3-C6 α-olefin comonomer incorporation than the first polyethylene component. 12For example, the third polyethylene component may have less than 10 weight percent C3-C6 α-olefin comonomer incorporation. 12 α-olefin comonomer, or 0.5 to less than 10 weight percent C3-C 12 α-olefin comonomer, or 2 to less than 10 weight percent C3-C 12 The one or more α-olefin comonomers of the third polyethylene component may be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene, or alternatively, from the group consisting of 1-butene, 1-hexene, and 1-octene, or alternatively, from the group consisting of 1-hexene and 1-octene.

[0049] Polymerization and Catalysts Various polymerization process embodiments are contemplated as suitable for producing the polyethylene composition. In one or more embodiments, the polyethylene composition is produced through a solution polymerization process in a dual reactor system. These dual solution polymerization reactors can be conventional reactors, such as loop reactors, isothermal reactors, adiabatic reactors, and continuous stirred tank reactors in parallel, series, and any combination thereof. In one embodiment, the polyethylene composition can be produced in two loop reactors in a series configuration, with the temperature of the first solution polymerization reactor ranging from 115 to 200°C, e.g., from 135 to 165°C, and the temperature of the second solution polymerization reactor ranging from 150 to 215°C, e.g., from 185 to 212°C. The solution polymerization process involves the production of ethylene monomer, one or more C3-C6 olefins, and / or olefins containing ethylene, propylene, propylene glycol, propylene glycol, propylene glycol olefins ... 12 The α-olefin comonomer, solvent, one or more catalyst systems, and optionally hydrogen may be continuously fed to a dual solution polymerization reactor (ie, a first solution polymerization reactor and a second solution polymerization reactor).

[0050] Various catalysts are contemplated as suitable. These may include, but are not limited to, Ziegler-Natta catalysts, chromium catalysts, metallocene catalysts, post-metallocene catalysts, constrained geometry complex (CGC) catalysts, phosphinimine catalysts, pyridylamine catalysts, or bis(biphenylphenoxy) catalysts. Details and examples of CGC catalysts are described in U.S. Patent Nos. 5,272,236, 5,278,272, 6,812,289, and WO 93 / 08221, all of which are incorporated herein by reference in their entireties. Details and examples of bis(biphenylphenoxy) catalysts are described in U.S. Patent Nos. 6,869,904, 7,030,256, 8,101,696, 8,058,373, and 9,029,487, all of which are incorporated herein by reference in their entireties. Details and examples of pyridylamine catalysts are described in WO 18 / 170138, which is incorporated herein by reference in its entirety. The catalysts utilized in the solution polymerization reactor can be different to impart different properties to the first polyethylene component, the second polyethylene component, and the third polyethylene component. For example, it is contemplated that different catalysts can be used in the solution polymerization reactor to vary the density, melt index, comonomer incorporation, etc., of the first polyethylene composition, the second polyethylene composition, and the third polyethylene composition. Without being bound by theory, varying these parameters of the first polyethylene composition, the second polyethylene composition, and the third polyethylene composition may enable the multimodal polyethylene composition to have a desirable combination of toughness and processability.

[0051] In one or more embodiments, the first solution polymerization reactor, the second solution polymerization reactor, or both may contain two catalysts. In certain embodiments, the first solution polymerization reactor may contain two catalysts, and the second solution polymerization reactor downstream of the first solution polymerization reactor contains one catalyst. The two catalysts in the first solution polymerization reactor are homogeneous catalysts, while the catalyst in the second solution polymerization reactor may contain a homogeneous catalyst, a heterogeneous catalyst, or both. Homogeneous, often referred to as single-site, catalysts are typically organometallic compounds with distinct molecular structures and are used to produce polymers with narrow molecular weight distributions and, when interpolymers are produced, narrow compositional distributions. Homogeneous catalysts can be dissolved in solution processes or supported for use in particle-forming processes such as slurry or gas phase. Heterogeneous catalysts are not discrete compounds, but rather result from a reaction mixture of a metal compound and a precursor that forms a complex with multiple active sites on some form of particle. Polymers produced via heterogeneous catalysis typically exhibit broader molecular weight distributions, and in the case of interpolymers, broader composition distributions than homogeneous catalysis. In an exemplary embodiment, the catalyst in the first reactor may be another homogeneous catalyst with a different reactivity ratio within the first reactor environment.

[0052] Bis(biphenylphenoxy) catalysts are an example of a homogeneous catalyst. Other examples of homogeneous catalysts include constrained geometry catalysts or pyridylamine catalysts. Examples of heterogeneous catalysts include heterogeneous Ziegler-Natta catalysts, which are particularly useful at the high polymerization temperatures of solution processes. Examples of such Ziegler-Natta catalysts are those derived from organomagnesium compounds, alkyl or aluminum halides or hydrogen chloride, and transition metal compounds. Examples of such catalysts are described in U.S. Pat. Nos. 4,314,912 (Lowery, Jr. et al.), 4,547,475 (Glass et al.), and 4,612,300 (Coleman, III), the teachings of which are incorporated herein by reference.

[0053] Particularly suitable organomagnesium compounds include hydrocarbon-soluble dihydrocarbyl magnesium compounds such as magnesium dialkyls and magnesium diaryls. Exemplary suitable magnesium dialkyls include, among others, n-butyl-secbutylmagnesium, diisopropylmagnesium, di-n-hexylmagnesium, isopropyl-n-butylmagnesium, ethyl-n-hexylmagnesium, ethyl-n-butylmagnesium, and di-n-octylmagnesium, wherein the alkyl has 1 to 20 carbon atoms. Exemplary suitable magnesium diaryls include diphenylmagnesium, dibenzylmagnesium, and ditolylmagnesium. Suitable organomagnesium compounds include alkyl and aryl magnesium alkoxides and aryloxides, and aryl and alkyl magnesium halides, with halogen-free organomagnesium compounds being more desirable.

[0054] The bis(biphenylphenoxy) catalyst is a multi-component catalyst system comprising a bis(biphenylphenoxy) procatalyst, a cocatalyst, and further optional components. The bis(biphenylphenoxy) procatalyst may comprise a metal-ligand complex according to formula (I):

[0055] [ka]

[0056] In formula (I), M is a metal selected from titanium, zirconium, or hafnium, the metal being in a +2, +3, or +4 formal oxidation state; n is 0, 1, or 2; when n is 1, X is a monodentate or bidentate ligand; when n is 2, each X is a monodentate ligand and is the same or different; the metal-ligand complex is overall charge neutral; O is O (oxygen atom); and each Z is independently -O-, -S-, -N(R N )-, or -P(R P )-, and L is selected from (C1 to C 40 ) hydrocarbylene or (C1-C 40) heterohydrocarbylene, (C1-C 40 ) Hydrocarbylene has a moiety containing a linker skeleton of 1 to 10 carbon atoms connecting the two Z groups in formula (I) (to which L is attached), or (C1 to C 40 ) Heterohydrocarbylene has a moiety containing a linker skeleton of 1 atom to 10 atoms connecting the two Z groups in formula (I), and (C1-C 40 Each of the 1 to 10 atoms of the 1 to 10 atom linker backbone of the heterohydrocarbylene is independently a carbon atom or a heteroatom, and each heteroatom is independently O, S, S(O), S(O), Si(R C )2, Ge(R C )2, P(R C ), or N(R C ) and independently, each R C is (C1~C 30 ) hydrocarbyl or (C1-C 30 ) heterohydrocarbyl, and R 1 and R 8 are independently (C1~C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R N )2NC(O)-, halogen, and a radical having formula (II), formula (III), or formula (IV).

[0057] [ka]

[0058] In formulas (II), (III), and (IV), R 31~35 , R 41~48 , or R 51~59 Each of R 1 or R 8 (C1 to C), provided that at least one of the radicals has the formula (II), the formula (III), or the formula (IV). 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R N )2NC(O)-, halogen, or -H.

[0059] In formula (I), R 2~4 , R 5~7 , and R 9~16 Each of (C1 to C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2-OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (RC )2NC(O)—, halogen, and —H.

[0060] Specific embodiments of the catalyst system will now be described. It should be understood that the catalyst system of the present disclosure may be embodied in different forms and should not be construed as limited to the specific embodiments set forth in this disclosure. Rather, the embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

[0061] The term "independently selected" refers to 1 , R 2 , R 3 , R 4 , and R 5 The R groups, such as R 1 , R 2 , R 3 , R 4 , and R 5 are all substituted alkyl, or R 1 and R 2 is a substituted alkyl, and R 3 The terms "a" and "an" are used herein to indicate that an R group is an aryl group, and the like. The use of the singular includes the use of the plural and vice versa (e.g., hexane solvent includes a plurality of hexanes). A named R group will generally have a structure recognized in the art as corresponding to the R group with that name. These definitions are intended to supplement and illustrate, not preclude, definitions known to those of skill in the art.

[0062] The term "procatalyst" refers to a compound that has catalytic activity when combined with an activator. The term "activator" refers to a compound that chemically reacts with a procatalyst to convert the procatalyst into a catalytically active catalyst. As used herein, the terms "cocatalyst" and "activator" are interchangeable terms.

[0063] When used to describe a chemical group containing a specific carbon atom, x ~Cy A bracketed expression having the form "(C1-C )" means that the unsubstituted form of the chemical group has from x carbon atoms to y carbon atoms, inclusive of x and y. For example, (C1-C 40 ) Alkyl is an alkyl group having 1 to 40 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups are S The parenthesized "(C x ~C y )" for the chemical group R S Substituted versions may be formed by adding any group R S may contain more than y carbon atoms depending on the identity of S exactly one group R is phenyl (-C6H5) S (C1~C 40 A "(C ) alkyl" can contain from 7 to 46 carbon atoms. Therefore, the parenthesized "(C ) alkyl" is generally used. x ~C y )" is a substituent R S When substituted by, the minimum and maximum total number of carbon atoms in the chemical group are the substituents R containing all carbon atoms in both x and y. S It is determined by adding the total number of carbon atoms from

[0064] In some embodiments, each of the chemical groups (e.g., X, R, etc.) of the metal-ligand complex of formula (I) can be unsubstituted, with R S In other embodiments, at least one of the chemical groups of the metal-ligand complex of formula (I) independently has one or more R S In some embodiments, the R in the chemical group of the metal-ligand complex of formula (I) S The total number of R in the chemical group does not exceed 20. S The total number of R does not exceed 10. For example, 1~5 There are two R S When X and Z are replaced by R SIn another embodiment, R in the chemical group of the metal-ligand complex of formula (I) S The total number of R may not exceed 5. S are attached to the same chemical group of the metal-ligand complex of formula (I), each R S are independently attached to the same or different carbon atoms or heteroatoms and may include per-substitution of chemical groups.

[0065] The term "substituted" means that at least one hydrogen atom (-H) bonded to a carbon or heteroatom or functional group of the corresponding unsubstituted compound is replaced by a substituent (e.g., R S The term "hypersubstituted" means that all hydrogen atoms (H) bonded to carbon atoms or heteroatoms of the corresponding unsubstituted compound or functional group are replaced by a substituent (e.g., R S The term "polysubstituted" means that at least two, but fewer than all, hydrogen atoms bonded to carbon atoms or heteroatoms of the corresponding unsubstituted compound or functional group are replaced by substituents.

[0066] The term "-H" means a hydrogen or hydrogen radical that is covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and mean the same thing unless otherwise specified.

[0067] "(C1~C 40 The term "(C1-C)hydrocarbyl" means a hydrocarbon radical of 1 to 40 carbon atoms. 40 The term "hydrocarbylene" means a hydrocarbon diradical of 1 to 40 carbon atoms, wherein each hydrocarbon radical and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic, including bicyclic, 3 or more carbon atoms) or acyclic, unsubstituted or substituted with one or more R S has been replaced by

[0068] In the present disclosure, (C1 to C40 ) Hydrocarbyl is unsubstituted or substituted (C1-C 40 ) Alkyl, (C3-C 40 ) cycloalkyl, (C3-C 20 )Cycloalkyl-(C1-C 20 ) Alkylene, (C6-C 40 ) aryl, or (C6-C 20 )Aryl-(C1-C 20 In some embodiments, the above (C1-C) alkylene may be 40 Each of the hydrocarbyl groups has up to 20 carbon atoms (i.e., (C1-C 20 ) hydrocarbyl), in other embodiments, having up to 12 carbon atoms.

[0069] "(C1~C 40 ) alkyl" and "(C1-C 18 The term "alkyl" refers to an alkyl group of 1 to 40 carbon atoms or 1 to 18 carbon atoms, unsubstituted or substituted with one or more R S means a saturated straight-chain or branched hydrocarbon radical substituted by an unsubstituted (C1-C 40 Examples of alkyl are unsubstituted (C1-C 20 ) Alkyl, unsubstituted (C1-C 10 ) alkyl, unsubstituted (C1-C5) alkyl, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methylpropyl, 1,1-dimethylethyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-nonyl, and 1-decyl. 40 Examples of substituted (C1-C 20 ) Alkyl, substituted (C1-C 10 ) alkyl, trifluoromethyl, and [C 45 ] alkyl. 45 The term "(C1-C5) alkyl" (with brackets) means that there are up to 45 carbon atoms in the radical, including the substituents, e.g., one R S replaced by (C 27 ~C 40Each (C1-C5)alkyl can be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl.

[0070] "(C6~C 40 The term "aryl" refers to an unsubstituted or (one or more R)aryl having 6 to 40 carbon atoms, of which at least 6 to 14 carbon atoms are aromatic ring carbon atoms. S means a monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radical substituted (by) a monocyclic, bicyclic, or tricyclic radical containing one, two, or three rings, respectively, wherein the monocyclic ring is aromatic and the two or three rings are independently fused or unfused, and at least one of the two or three rings is aromatic. 40 Examples of aryl are unsubstituted (C-C 20 ) Unsubstituted aryl (C6-C 18 )aryl, 2-(C1-C5)alkylphenyl, 2,4-bis(C1-C5)alkyl-phenyl, phenyl, fluorenyl, tetrahydrofluorenyl, indacenyl, hexahydroindacenyl, indenyl, dihydroindenyl, naphthyl, tetrahydronaphthyl, and phenanthrene. 40 Examples of aryl are substituted (C1-C 20 ) Aryl, substituted (C6-C 18 )aryl, 2,4-bis[(C 20 ) alkyl]-phenyl, polyfluorophenyl, pentafluorophenyl, and fluoren-9-on-1-yl.

[0071] "(C3~C 40 The term "cycloalkyl" refers to a group that is unsubstituted or has one or more R S means a saturated cyclic hydrocarbon radical of 3 to 40 carbon atoms, substituted with other cycloalkyl groups, such as (C x ~C y )cycloalkyl) has x to y carbon atoms and is unsubstituted or has one or more R SUnsubstituted (C3-C 40 Examples of cycloalkyl are unsubstituted (C-C 20 ) Cycloalkyl, unsubstituted (C3-C 10 ) cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. 40 Examples of cycloalkyl are substituted (C3-C 20 ) Cycloalkyl, substituted (C3-C 10 ) cycloalkyl, cyclopentanon-2-yl, and 1-fluorocyclohexyl.

[0072] (C1~C 40 Examples of hydrocarbylene include unsubstituted or substituted (C6-C 40 ) arylene, (C3-C 40 ) cycloalkylene, and (C1-C 40 ) alkylene (e.g. (C1-C 20 ) alkylene). In some embodiments, the diradicals can be on the same carbon atom (e.g., —CH2—) or on adjacent carbon atoms (i.e., 1,2-diradicals), or separated by one, two, or more carbon atoms (e.g., 1,3-diradicals, 1,4-diradicals, etc.). Some diradicals include α,ω-diradicals. α,ω-diradicals are diradicals with the greatest carbon backbone spacing between the radical carbons. (C2-C 20 Some examples of alkylene α,ω-diradicals include ethane-1,2-diyl (i.e., -CHCH-), propane-1,3-diyl (i.e., -CHCHCH-), and 2-methylpropane-1,3-diyl (i.e., -CHCH(CH)CH-). (C6-C 40 Some examples of arylene α,ω-diradicals include phenyl-1,4-diyl, naphthalene-2,6-diyl, or naphthalene-3,7-diyl.

[0073] "(C1~C 40The term "alkylene" may be unsubstituted or may contain one or more R S means a saturated straight or branched chain diradical (i.e., the radical is not on a ring atom) of 1 to 40 carbon atoms, substituted with 40 Examples of alkylene are unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C * HCH3 and -(CH2)4C * Unsubstituted (C1-C, including (H)(CH3) 20 ) alkylene, wherein "C * " denotes a carbon atom from which a hydrogen atom has been removed to form a secondary or tertiary alkyl radical. 40 Examples of alkylene are substituted (C1-C 20 ) alkylene, -CF2-, -C(O)-, and -(CH2) 14 C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted normal-1,20-eicosylene). As already mentioned, two R S Based on these, (C1~C 18 ) alkylenes can be formed, so that examples of substituted (C1-C40) alkylenes also include 1,2-bis(methylene)cyclopentane, 1,2-bis(methylene)cyclohexane, 2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane, and 2,3-bis(methylene)bicyclo[2.2.2]octane.

[0074] "(C3~C 40 The term "cycloalkylene" may be unsubstituted or may contain one or more R S means a cyclic diradical (i.e., the radicals are on ring atoms) of 3 to 40 carbon atoms substituted by

[0075] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of groups containing one or more heteroatoms include O, S, S(O), S(O) 2、 Si(R C)2, P(R P ), N(R N ), -N=C(R C )2, -Ge(R C )2-, or -Si(R C )-, and each R C and each R P is unsubstituted (C1 to C 18 ) hydrocarbyl or —H, and each R N is unsubstituted (C1 to C 18 The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more carbon atoms are replaced with a heteroatom. 40 The term "(C1-C)heterohydrocarbyl" means a heterohydrocarbon radical of 1 to 40 carbon atoms. 40 The term "heterohydrocarbylene" means a heterohydrocarbon diradical of 1 to 40 carbon atoms, each heterohydrocarbon having one or more heteroatoms. The heterohydrocarbyl radical can be present on a carbon atom or a heteroatom, and the heterohydrocarbyl diradical can be present on (1) one or two carbon atoms, (2) one or two heteroatoms, or (3) one carbon atom and one heteroatom. Each (C1 to C 40 ) heterohydrocarbyl and (C1-C 40 ) heterohydrocarbylene is unsubstituted or (one or more R S They may be substituted (by), aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

[0076] (C1~C 40 ) Heterohydrocarbyl may be unsubstituted or substituted. (C1-C 40 Non-limiting examples of heterohydrocarbyls include (C1-C 40 ) heteroalkyl, (C1-C 40 ) hydrocarbyl-O-, (C1-C 40 ) hydrocarbyl-S-, (C1-C 40 ) hydrocarbyl-S(O)-, (C1-C 40) hydrocarbyl-S(O)2-, (C1-C 40 ) Hydrocarbyl-Si(R C )2-, (C l ~C 40 )hydrocarbyl-N(R N )-, (C l ~C 40 ) hydrocarbyl-P(R P )-, (C2~C 40 ) heterocycloalkyl, (C2-C 19 )Heterocycloalkyl-(C1-C 20 ) alkylene, (C3-C 20 )Cycloalkyl-(C1-C 19 ) heteroalkylene, (C2-C 19 )Heterocycloalkyl-(C1-C 20 ) heteroalkylene, (C1-C 50 ) heteroaryl, (C1-C 19 )Heteroaryl-(C1-C 20 ) Alkylene, (C6-C 20 )Aryl-(C1-C 19 ) heteroalkylene, or (C1-C 19 )Heteroaryl-(C1-C 20 ) heteroalkylene.

[0077] "(C1~C 40 The term "heteroaryl" refers to an unsubstituted or substituted (one or more R) heteroaryl group of a total of 1 to 40 carbon atoms and 1 to 10 heteroatoms. S

[0033] The term "heteroaromatic hydrocarbon radical" refers to a monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon radical (according to the formula (C)), wherein the monocyclic, bicyclic, or tricyclic radical contains one, two, or three rings, respectively, which are independently fused or unfused, and at least one of the two or three rings is heteroaromatic. Other heteroaryl groups (e.g., generally (C) x ~C y ) heteroaryl, such as (C1-C 12 ) heteroaryl) similarly has x to y carbon atoms (e.g., 1 to 12 carbon atoms) and is unsubstituted or substituted with one or more R SThe monocyclic heteroaromatic hydrocarbon radical is defined as being substituted by a 5-membered or 6-membered ring. A 5-membered ring has 5 minus h carbon atoms, where h is the number of heteroatoms and can be 1, 2, 3, or 4, and each heteroatom can be O, S, N, or P. Examples of 5-membered heteroaromatic hydrocarbon radicals include pyrrol-1-yl, pyrrol-2-yl, furan-3-yl, thiophen-2-yl, pyrazol-1-yl, isoxazol-2-yl, isothiazol-5-yl, imidazol-2-yl, oxazol-4-yl, thiazol-2-yl, 1,2,4-triazol-1-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, tetrazol-1-yl, tetrazol-2-yl, and tetrazol-5-yl. A 6-membered ring has 6 minus h carbon atoms, where h is the number of heteroatoms, which may be 1 or 2, and the heteroatoms may be N or P. Examples of 6-membered heteroaromatic hydrocarbon radicals include pyridin-2-yl, pyrimidin-2-yl, and pyrazin-2-yl. Bicyclic heteroaromatic hydrocarbon radicals may be fused 5,6- or 6,6-ring systems. Examples of fused 5,6-ring bicyclic heteroaromatic hydrocarbon radicals are indol-1-yl and benzimidazol-1-yl. Examples of fused 6,6-ring bicyclic heteroaromatic hydrocarbon radicals are quinolin-2-yl and isoquinolin-1-yl. Tricyclic heteroaromatic hydrocarbon radicals may be fused 5,6,5-, 5,6,6-, 6,5,6-, or 6,6,6-ring systems. An example of a fused 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indol-1-yl. An example of a fused 5,6,6-ring system is 1H-benzo[f]indol-1-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,6,6-ring system is acridine-9-yl.

[0078] The heteroalkyl group may be any of (C1-C 40) carbon atoms and one or more heteroatoms. Similarly, heteroalkylene may be a saturated straight or branched chain diradical containing 1 to 50 carbon atoms and one or more heteroatoms. Heteroatoms as defined above include Si(R C )3, Ge(R C )3, Si(R C )2, Ge(R C )2, P(R P )2, P(R P ), N(R N )2, N(R N ), N, O, OR C , S, S.R. C , S(O), and S(O)2, each of the heteroalkyl and heteroalkylene groups being unsubstituted or containing one or more R S is replaced by

[0079] Unsubstituted (C2~C 40 Examples of heterocycloalkyl include unsubstituted (C-C 20 ) Heterocycloalkyl, unsubstituted (C2-C 10 ) heterocycloalkyl, aziridin-l-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-l-yl, tetrahydrothiophene-S,S-dioxid-2-yl, morpholin-4-yl, 1,4-dioxan-2-yl, hexahydroazepin-4-yl, 3-oxa-cyclooctyl, 5-thio-cyclononyl, and 2-aza-cyclodecyl.

[0080] The term "halogen atom" or "halogen" means a radical of a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), or an iodine atom (I). The term "halide" refers to a radical of a fluoride (F - ), chloride (Cl - ), bromide (Br - ), or iodide (I - ) refers to the anionic form of a halogen atom.

[0081] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen double bonds, carbon-phosphorus double bonds, and carbon-silicon double bonds. A saturated chemical group is one or more substituents R S When substituted by, one or more double and / or triple bonds may optionally be substituted by a substituent R S The term "unsaturated" refers to the presence of one or more carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, and carbon-silicon double bonds, provided that the substituents R, if present, are not present in the group. S It is meant to exclude any double bonds that may be present in, or, if present, in, a (hetero)aromatic ring.

[0082] In some embodiments, catalyst systems comprising the metal-ligand complex of Formula (I) can be made catalytically active by any technique known in the art for activating metal-based catalysts for olefin polymerization reactions. For example, those comprising the metal-ligand complex of Formula (I) can be made catalytically active by contacting the complex with or combining the complex with an activating cocatalyst. Activating cocatalysts suitable for use herein include alkylaluminums, polymeric or oligomeric alumoxanes (also known as aluminoxanes), neutral Lewis acids, and non-polymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions). A suitable activation technique is bulk electrolysis. Combinations of one or more of the foregoing activating cocatalysts and techniques are also contemplated. The term "alkylaluminum" refers to monoalkylaluminum dihydrides or dihalides, dialkylaluminum hydrides or halides, or trialkylaluminums. Examples of polymeric or oligomeric alumoxanes include methylalumoxane, triisobutylaluminum modified methylalumoxane, tri-n-octylaluminum modified and methylalumoxane isobutylalumoxane.

[0083] The Lewis acid activator (co-catalyst) may be, as described herein, a compound having one to three (C1-C 20 In one embodiment, the Group 13 metal compounds include tri(hydrocarbyl)-substituted aluminum, tri(hydrocarbyl)-boron compounds, tri((C1-C 10 ) alkyl) aluminum, tri((C6-C 18 )aryl)boron compounds and their halogenated (including perhalogenated) derivatives. In further embodiments, the Group 13 metal compound is tris(fluoro-substituted phenyl)borane, tris(pentafluorophenyl)borane. In some embodiments, the activating co-catalyst is tetrakis((C1-C 20 )hydrocarbyl)borate (e.g., trityl tetrafluoroborate) or tri((C 20 )hydrocarbyl)ammonium tetra((C1-C 20 )hydrocarbyl)borane (e.g., bis(octadecyl)methylammonium tetrakis(pentafluorophenyl)borane). As used herein, the term "ammonium" refers to a ((C1-C 20 ) Hydrocarbyl) 4N + , ((C1~C 20 )hydrocarbyl)3N(H) + , ((C1~C 20 )hydrocarbyl)2N(H)2 + , (C1~C 20 ) Hydrocarbyl N(H)3 + , or N(H)4 + In the formula, each of (C1 to C 20 When two or more hydrocarbyls are present, they may be the same or different.

[0084] As a combination of neutral Lewis acid activators (cocatalysts), tri((C1-C4) alkyl)aluminum and halide tri((C6-C 18)aryl)boron compounds, particularly tris(pentafluorophenyl)borane. Other embodiments include such neutral Lewis acid mixtures in combination with polymeric or oligomeric alumoxanes, and combinations of a single neutral Lewis acid, particularly tris(pentafluorophenyl)borane, with polymeric or oligomeric alumoxanes. The molar ratio of (metal-ligand complex):(tris(pentafluorophenylborane):(alumoxane) [e.g., Group 4 metal-ligand complex):(tris(pentafluorophenylborane):(alumoxane)] is from 1:1:1 to 1:10:30, and in other embodiments, from 1:1:1.5 to 1:5:10.

[0085] Catalyst systems comprising the metal-ligand complexes of formula (I) can be activated to form active catalyst compositions by combining one or more cocatalysts, such as cation-forming cocatalysts, strong Lewis acids, or combinations thereof. Suitable activating cocatalysts include polymeric or oligomeric aluminoxanes, particularly methylaluminoxane, and inert, compatible, non-coordinating ion-forming compounds. Exemplary suitable cocatalysts include modified methylaluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyltetrakis(pentafluorophenyl)borate (1 - ) amines, and combinations thereof.

[0086] In some embodiments, one or more of the aforementioned activating cocatalysts are used in combination with one another. Particularly preferred combinations are mixtures of tri((C1-C4)hydrocarbyl)aluminum, tri((C1-C4)hydrocarbyl)borane, or ammonium borate with an oligomeric or polymeric alumoxane compound. The ratio of the total number of moles of the one or more metal-ligand complexes of Formula (I) to the total number of moles of the one or more activating cocatalysts is 1:10,000 to 100:1. In some embodiments, this ratio is at least 1:5000; in some other embodiments, it is at least 1:1000 and not more than 10:1; and in some other embodiments, it is not more than 1:1. When alumoxane is used alone as the activating cocatalyst, it is preferred that the number of moles of alumoxane used be at least 40 times the number of moles of the metal-ligand complex of Formula (I). When tris(pentafluorophenyl)borane is used alone as the activating cocatalyst, in some other embodiments, the number of moles of tris(pentafluorophenyl)borane used relative to the total number of moles of the one or more metal-ligand complexes of Formula (I) is from 0.5:1 to 10:1, from 1:1 to 6:1, or from 1:1 to 5:1. The remaining activating cocatalyst is generally used in a molar amount approximately equal to the total molar amount of the one or more metal-ligand complexes of Formula (I).

[0087] A variety of solvents are contemplated, including aromatic and paraffinic solvents. Exemplary solvents include, but are not limited to, isoparaffins. For example, such isoparaffinic solvents are commercially available from ExxonMobil Chemical under the name ISOPAR E.

[0088] The reactivity ratio is the ratio of C3 to C4 with ethylene and polymerization catalyst in the polymerization process. 12 The steric interactions of the polymerization catalyst are determined by the difference in polymerization rate (i.e., selectivity) between the α-olefin comonomer and the C3-C 12It is believed that this selectively results in the polymerization of ethylene over α-olefins, such as α-olefins (i.e., the catalyst preferentially polymerizes ethylene in the presence of α-olefins). Again, without being bound by theory, it is believed that such steric interactions cause the homogeneous catalyst prepared by or from the metal-ligand complex of formula (I) to adopt a conformation that allows ethylene to access M substantially more readily than the catalyst allows α-olefins, or to adopt a more readily reactive conformation, or both.

[0089] For random copolymers, where the properties of the last monomer inserted determine the rate of insertion of subsequent monomers, the terminal copolymerization model is used. In this model, the following types of insertion reactions occur:

[0090]

number

[0091]

number

[0092] The mole fraction of comonomer (i=2) in the reaction medium is defined by the following equation:

[0093]

number

[0094] As disclosed in George Odian, Principles of Polymerization, Second Edition, John Wiley and Sons, 1970, a simple equation for comonomer composition can be derived as follows:

[0095]

number

[0096] From this equation, the mole fraction of comonomer in the polymer depends only on the mole fraction of comonomer in the reaction medium and two temperature-dependent reactivity ratios defined in terms of the insertion rate constant as follows:

[0097]

number

[0098] In this model, the polymer composition is also a function of only the temperature-dependent reactivity ratio and the comonomer mole fraction in the reactor, even if reversed comonomer or monomer insertion can occur, or in the case of copolymerization of more than two monomers.

[0099] Reactivity ratios for use in the above-mentioned models can be predicted using well-known theoretical methods or empirically derived from actual polymerization data. Suitable theoretical methods are disclosed, for example, in BG Kyle, Chemical and Process Thermodynamics, Third Addition, Prentice-Hall, 1999, and Redlich-Kwong-Soave (RKS) Equation of State, Chemical Engineering Science, 1972, pp. 1197-1203. Commercially available software programs may be used to assist in the derivation of reactivity ratios from empirically derived data. One example of such software is Aspen Plus from Aspen Technology, Inc., Ten Canal Park, Cambridge, MA 02141-2201 USA.

[0100] film The polyethylene compositions according to embodiments disclosed herein can be incorporated into films. In some embodiments, such films are biaxially oriented. In some embodiments, such films are biaxially oriented using a tenter frame. In some embodiments, such films are uniaxially oriented in the machine direction. In some embodiments, the uniaxially oriented film comprises a polyethylene composition disclosed herein. The oriented film utilizes a polyethylene composition in at least one layer, which can advantageously expand the operating window for stretching the film. For example, expanding the operating window for biaxial orientation can orient the polyethylene composition, which can result in improved film stiffness. The oriented film, in some embodiments, can be used in packaging applications, such as as a lidding or label film.

[0101] In one embodiment, the biaxially oriented film comprises at least one layer comprising a polyethylene composition, the polyethylene composition comprising: (a) 15 to 25 weight percent of a first polyethylene component having a molecular weight (Mw) greater than 200,000 g / mole and a density of 0.925 to 0.945 g / cc; (b) 20 to 35 weight percent of a second polyethylene component having a molecular weight (Mw) of less than 80,000 g / mole and a density of 0.915 to 0.950 g / cc; (c) 40 to 65 weight percent of a third polyethylene component having a molecular weight (Mw) of less than 100,000 g / mole and a density of 0.940 to 0.965 g / cc; The polyethylene composition has a density of 0.935 to 0.958 g / cc, a melt index (I2) of 0.5 to 5.0 g / 10 minutes, and a melt index (I2) satisfying the following formula: Weight fraction of first polyethylene component * SCB logMw4~5 * Meet Mz (conventional GPC) > 230,000.

[0102] In some embodiments, the biaxially oriented film is a multilayer film. The number of layers in the film can vary depending on numerous factors, including, for example, the desired properties of the film, the desired thickness of the film, the content of other layers in the film, the end use of the film, the equipment available for manufacturing the film, etc. For example, the multilayer film can further include other layers typically included in multilayer films depending on the application, including, for example, sealant layers, barrier layers, tie layers, structural layers, etc. The multilayer film can be composed of up to 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11 layers in various embodiments.

[0103] Other layers within the multilayer films of the present invention, in various embodiments, may comprise a polymer selected from the polyethylene compositions described herein, LLDPE, MDPE, LDPE, HDPE, HMWHDPE (high molecular weight HDPE), propylene-based polymers, polyolefin plastomers (POP), polyolefin elastomers (POE), olefin block copolymers (OBC), ethylene vinyl acetate, ethylene acrylic acid, ethylene methacrylic acid, ethylene methyl acrylate, ethylene ethyl acrylate, ethylene butyl acrylate, isobutylene, maleic anhydride grafted polyolefins, ionomers of any of the foregoing, or combinations thereof.

[0104] In some embodiments, the biaxially oriented film is oriented in the machine direction with a stretch ratio of 2:1 to 9:1 and in the transverse direction with a stretch ratio of 2:1 to 11:1. In some embodiments, the biaxially oriented film is oriented in the machine direction with a stretch ratio of 2:1 to 6:1 and in the transverse direction with a stretch ratio of 2:1 to 9:1. In some embodiments, the biaxially oriented film is oriented in the machine direction with a stretch ratio of 4:1 to 6:1 and in the transverse direction with a stretch ratio of 6:1 to 9:1.

[0105] In some embodiments, the biaxially oriented film has a thickness of 5 to 50 μm.

[0106] In some embodiments, the biaxially oriented film further comprises an outer layer that is a sealant layer.

[0107] The biaxially oriented films disclosed herein can have desirable properties. For example, in some embodiments, the biaxially oriented films have at least one of a haze value of less than 15 percent, a 2 percent secant modulus in the machine direction of at least 600 MPa, a 2 percent secant modulus in the transverse direction of at least 900 MPa, a transparency of at least 35 percent, a tensile strain at break in the machine direction of at least 160%, and a tensile strain at break in the transverse direction of at least 20%.

[0108] In another aspect, the invention relates to an article, such as a food package, hi one aspect, the article comprises any of the inventive polyethylene compositions disclosed herein.

[0109] In another aspect, the present invention relates to laminates and articles formed from such laminates. In some embodiments, the laminate comprises a first film comprising a polyethylene sealant film, polypropylene, or polyamide, and a biaxially oriented film according to any of the embodiments disclosed herein, wherein the first film is laminated to the biaxially oriented film. In one aspect, the article comprises any of the laminates disclosed herein.

[0110] In another aspect, the present invention relates to a uniaxially oriented film, the uniaxially oriented film comprising: (a) 15 to 25 weight percent of a first polyethylene component having a molecular weight (Mw) greater than 200,000 g / mole and a density of 0.925 to 0.945 g / cc; (b) 20 to 35 weight percent of a second polyethylene component having a molecular weight (Mw) of less than 80,000 g / mole and a density of 0.915 to 0.950 g / cc; (c) 40 to 65 weight percent of a third polyethylene component having a molecular weight (Mw) of less than 100,000 g / mole and a density of 0.940 to 0.965 g / cc; The polyethylene composition has a density of 0.935 to 0.958 g / cc, a melt index (I2) of 0.5 to 5.0 g / 10 minutes, and a melt index (I2) satisfying the following formula: Weight fraction of first polyethylene component * SCB logMw4~5 * Meet Mz (conventional GPC) > 230,000.

[0111] In some embodiments, the uniaxially oriented film is machine-direction oriented at a stretch ratio of 4:1 to 20:1. In some embodiments, the uniaxially oriented film is machine-direction oriented at a stretch ratio of 4:1 to 16:1. In some embodiments, the uniaxially oriented film is machine-direction oriented at a stretch ratio of 4:1 to 12:1. In some embodiments, the uniaxially oriented film is machine-direction oriented at a stretch ratio of 4:1 to 10:1. In some embodiments, the uniaxially oriented film is machine-direction oriented at a stretch ratio of 4:1 to 9:1.

[0112] It should be understood that in some embodiments, any of the layers within the film may further comprise one or more additives known to those skilled in the art (in addition to those described above for the polyethylene-based composition), such as, for example, antioxidants, UV stabilizers, heat stabilizers, slip agents, antiblocking agents, pigments or colorants, processing aids, crosslinking catalysts, flame retardants, fillers, and blowing agents.

[0113] By being polyethylene-based, the polyethylene compositions of the present invention, according to some embodiments, can be incorporated into multilayer films and articles that are primarily, if not substantially or entirely, composed of polyethylene to provide more readily recyclable films and articles. For example, films comprising primarily polyethylene have improved recyclability profiles in addition to other benefits that the use of such polymers may provide. For example, in some embodiments, the oriented film is composed entirely of ethylene-based polymer, other than additives. The oriented film may, in some embodiments, comprise 90 wt.% ethylene-based polymer, in some embodiments 95 wt.% ethylene-based polymer, in some embodiments 99 wt.% ethylene-based polymer, in some embodiments 99.9 wt.% ethylene-based polymer, or in some embodiments 100 wt.% ethylene-based polymer, based on the total weight of the oriented film.

[0114] Biaxially oriented films can have a variety of thicknesses before orientation, depending, for example, on the number of layers, the intended use of the film, and other factors. Such polyethylene films, in some embodiments, have a thickness of 320 to 3200 microns (typically, 640 to 1920 microns) before orientation.

[0115] Prior to orientation, the film can be formed using techniques known to those skilled in the art based on the teachings herein. For example, the film can be prepared as a blown film (e.g., a water-quenched blown film) or a cast film. For example, in the case of a multilayer polyethylene film, for layers that can be coextruded, such layers can be coextruded as a blown film or a cast film using techniques known to those skilled in the art based on the teachings herein.

[0116] In various embodiments, the films can be uniaxially or biaxially oriented using techniques known to those skilled in the art.

[0117] In some embodiments in which the film is bilayer oriented, the film is biaxially oriented using a tenter frame sequential biaxial orientation process. Such techniques are generally known to those skilled in the art. In other embodiments, the film can also be biaxially oriented using other techniques known to those skilled in the art, such as a double bubble stretching process, based on the teachings herein. Generally, in a tenter frame sequential biaxial orientation process, a tenter frame is incorporated as part of a multilayer coextrusion line. After extrusion from a flat die, the film is cooled on a chill roll and immersed in a water bath filled with room temperature water. The cast film is then passed over a series of rollers with different rotation speeds to achieve stretching in the machine direction. The MD stretching segment of the production line has several pairs of rollers, all of which are oil heated. The pairs of rollers operate sequentially as preheating rollers, stretching rollers, and relaxation and annealing rollers. The temperature of each pair of rollers is controlled separately. After stretching in the machine direction, the film web passes through a tenter frame hot air oven with a heating zone to achieve stretching in the transverse direction. The first few zones are for preheating, followed by a zone for stretching, and then a final zone for annealing.

[0118] In some embodiments, when a multilayer film is uniaxially oriented, the film is oriented only in the longitudinal direction. Various processing parameters are contemplated as suitable for stretching in the machine direction, as would be known to one skilled in the art based on the teachings herein. For example, a uniaxially oriented multilayer film can be stretched in the machine direction at a stretch ratio greater than 1:1 and less than 8:1, or at a stretch ratio of 4:1 to 8:1.

[0119] In some embodiments, after stretching, the machine direction stretched film has a thickness of 5 to 50 microns, hi some embodiments, the machine direction stretched film has a thickness of 15 to 40 microns.

[0120] In some embodiments, depending on, for example, the end use application, the oriented film may be corona treated, plasma treated, or printed using techniques known to those skilled in the art. In some embodiments, the oriented multilayer film may be surface coated with aluminum, silicon oxide, aluminum oxide, or other metals known to those skilled in the art based on the teachings herein.

[0121] Laminate Embodiments of the present invention also include laminates incorporating oriented films. In some embodiments, a biaxially oriented film according to embodiments of the present invention can be laminated to another film. In some embodiments, a uniaxially oriented (e.g., machine-direction oriented) multilayer polyethylene film according to embodiments of the present invention can be laminated to another film.

[0122] Laminates according to embodiments of the present invention can be formed using techniques known to those skilled in the art based on the teachings herein. For example, an oriented multilayer polyethylene film can be laminated to another film using an adhesive. A variety of adhesive compositions are contemplated as suitable for the adhesive used in making the laminate. These may include polyurethanes, epoxies, acrylics, and the like. In one embodiment, the laminate can include an adhesive layer comprising a polyurethane adhesive. The polyurethane adhesive can be solventless, water-based, or solvent-based. Additionally, the polyurethane adhesive can be a two-part formulation. The weight or thickness of the adhesive layer can vary depending on many factors, including, for example, the desired thickness of the multilayer structure, the type of adhesive used, and other factors. In some embodiments, the adhesive layer can have a viscosity of up to 5.0 grams / m². 2 , or 1.0 to 4.0 g / m 2 , or 2.0 to 3.0 g / m 2 It is applied with.

[0123] Laminates according to some embodiments of the present invention can also be formed by extrusion lamination.

[0124] Goods Embodiments of the present invention also relate to articles, such as packaging, formed from or incorporating the oriented multilayer polyethylene films of the present invention (or from laminates incorporating such films). Such packaging can be formed from any of the films or laminates described herein.

[0125] Examples of such articles may include flexible packages, pouches, stand-alone pouches, and pre-formed packages or pouches. In some embodiments, the oriented multilayer polyethylene films or laminates of the present invention may be used in food packaging. Examples of foods that may be included in such packaging include meat, cheese, cereal, nuts, juice, sauce, etc. Such packaging may be formed using techniques known to those skilled in the art based on the teachings herein and on the particular application of the packaging (e.g., type of food, amount of food, etc.).

[0126] Test Method Test methods include:

[0127] Melt index (I2) and (I 10 ) The melt index (I2) value is measured according to ASTM D1238 at 190°C and 2.16 kg. 10 ) values ​​are measured at 190°C and 10 kg according to ASTM D1238. These values ​​are reported in g / 10 min and correspond to grams eluted per 10 minutes. These data were collected for the entire polyethylene composition and are reported in Tables 2 and 3. The melt index (I2) values ​​for the first polyethylene component, the second polyethylene component, and the third polyethylene component were calculated according to Equation 17 and the deconvolution method described below and are reported in Table 4.

[0128] density Density measurements are made on the whole polyethylene composition according to ASTM D792, Method B. The data are reported in Tables 2 and 3. For the first and second polyethylene components, density values ​​can be obtained using Equation 15 and the deconvolution method below. For the third polyethylene component, density values ​​are calculated using Equation 16. Density is expressed in grams per cubic centimeter (g / cc or g / cm 3 ) units. Individual component density data are reported in Table 4.

[0129] Prior Art (Conventional) Gel Permeation Chromatography (GPC) The chromatography system consisted of a PolymerChar (Valencia, Spain) GPC-IR high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5). The autosampler oven compartment was set to 160 °C, and the column compartment was set to 150 °C. The columns used were four Agilent "Mixed A" 30 cm, 20 micron linear mixed-bed columns. The chromatography solvent used was 1,2,4-trichlorobenzene containing 200 ppm butylated hydroxytoluene (BHT). The solvent source was nitrogen sparged. The injection volume used was 200 microliters, and the flow rate was 1.0 milliliters / minute.

[0130] Calibration of the GPC column set was performed using 21 narrow molecular weight distribution polystyrene standards ranging from 580 to 8,400,000, arranged in six "cocktail" mixtures with at least 10-fold spacing between individual molecular weights. Standards were purchased from Agilent Technologies. Polystyrene standards were prepared at 0.025 grams in 50 milliliters of solvent for molecular weights above 1,000,000 and 0.05 grams in 50 milliliters of solvent for molecular weights below 1,000,000. The polystyrene standards were predissolved at 80°C with gentle agitation for 30 minutes, then cooled, and the room temperature solution was transferred to an autosampler dissolving oven at 160°C for 30 minutes to cool. 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 ポリエチレン =A×(M ポリスチレン ) B (Equation 1) where M is the molecular weight, A has a value of 0.4129, and B is equal to 1.0.

[0131] A fifth-order polynomial was used to fit each polyethylene-equivalent calibration point. A total plate count for the GPC column set was performed using decane as a blank sample introduced via a micropump controlled using a PolymerChar GPC-IR system. The plate count for the chromatography system should exceed 18,000 for four Agilent "Mixed A" 30 cm 20-micron linear mixed-bed columns.

[0132] Samples were prepared in a semi-automated fashion using PolymerChar's "Instrument Control" software, with a target sample weight of 2 mg / ml, and solvent (containing 200 ppm BHT) was added via a PolymerChar high-temperature autosampler to a pre-nitrogen-sparged, septum-capped vial. Samples were dissolved at 160°C for 2 hours under "slow" shaking.

[0133] Mn (GPC) , Mw (GPC) , and Mz (GPC) The calculation was based on GPC results using the internal IR5 detector (measurement channel) of a PolymerChar GPC-IR chromatograph according to Equations 2-4 using PolymerChar's GPCOne™ software, baseline-subtracted IR chromatograms at each equally spaced data collection point (i), and polyethylene equivalent molecular weights obtained from a narrow standard calibration curve for point (i) of Equation 1.

[0134]

number

[0135] To monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by a PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate (Flow Rate (Apparent)) for each sample by RV matching the respective decane peak in the sample (RV (FM Sample)) with that of the decane peak in the narrow standard calibration (RV (FM Calibrated)). Any change in the time of the decane marker peak is then assumed to be related to a linear shift in flow rate (Flow Rate (Effective)) throughout the run. After calibrating the system based on the flow rate marker peak, the effective flow rate (relative to the narrow standard calibration) is calculated as per Equation 5. Processing of the flow rate marker peak was performed via PolymerChar GPCOne™ software. An acceptable flow rate correction is such that the effective flow rate should be within ±0.5% of the apparent flow rate. Flow rate (effective) = Flow rate (apparent) * (RV(FM calibrated) / RV(FM sample)) (Equation 5)

[0136] GPC measurements are performed on both the total polyethylene composition and on the polymer sampled from the first reactor containing the first polyethylene component and the second polyethylene component.

[0137] Improved comonomer content analysis method (iCCD) An improved comonomer content analysis method (iCCD) was developed in 2015 (Cong and Parrott et al., WO 2017040127(A1)). iCCD experiments were performed using a Crystallization Elution Fractionation (CEF) instrument (PolymerChar, Spain) equipped with an IR-5 detector (PolymerChar, Spain) and a two-angle light scattering detector, Model 2040 (Precision Detectors, now Agilent Technologies). A 5 cm or 10 cm (length) x 1 / 4 inch (inner diameter) guard column packed with 20-27 micron glass (MoSCi Corporation, USA) on stainless steel was placed immediately before the IR-5 detector in the detector oven. Ortho-dichlorobenzene (ODCB, 99% anhydrous grade or technical grade) was used. Silica gel 40 (particle size 0.2–0.5 mm, catalog number 10181-3) was obtained from EMD Chemicals (which may be used to dry the ODCB solvent beforehand). The dried silica was packed into three empty HT-GPC columns to further purify the ODCB as the eluent. The CEF instrument was equipped with an autosampler with N2 purging capability. Before use, the ODCB was sparged with dry nitrogen (N2) and stirred for 1 h. Sample preparation was performed at 4 mg / mL (unless otherwise specified) using the autosampler at 160 °C for 1 h with shaking. The injection volume was 300 μL. The temperature profile for the iCCD was: crystallization from 105 °C to 30 °C at 3 °C / min, thermal equilibration at 30 °C for 2 min (including a 2-min soluble fraction elution time), and elution from 30 °C to 140 °C at 3 °C / min. The flow rate during crystallization was 0.0 mL / min. The flow rate during elution is 0.50 mL / min. Data is collected at 1 data point / second.

[0138] The iCCD column was packed with gold-coated nickel particles (Bright 7GNM8-NiS, Nippon Chemical Industrial Co.) in a 15 cm (length) × ¼ inch (inner diameter) stainless steel tube. Column packing and conditioning were performed using a slurry method according to reference (Cong, R.; Parrott, A.; Hollis, C.; Cheatham, M. International Publication No. 2017040127(A1)). The final pressure using TCB slurry packing was 150 bar.

[0139] Column temperature calibration was performed using a mixture of linear homopolymer polyethylene (ODCB reference material, zero comonomer content, melt index (I2) of 1.0, polydispersity Mw / Mn approximately 2.6 by conventional gel permeation chromatography, 1.0 mg / mL) and eicosane (2 mg / mL). iCCD temperature calibration consisted of four steps: (1) calculating the delay volume, defined as the temperature offset between the measured peak elution temperatures of eicosane minus 30.00 °C; and (2) subtracting the temperature offset of the elution temperature from the iCCD raw temperature data. Note that this temperature offset is a function of experimental conditions such as elution temperature, elution flow rate, etc.; (3) creating a linear calibration line converting elution temperatures over the range of 30.00°C to 140.00°C, such that a linear homopolymer polyethylene standard has a peak temperature at 101.0°C and eicosane has a peak temperature of 30.0°C; (4) linearly extrapolating elution temperatures below 30.0°C for soluble fractions measured isothermally at 30°C by using an elution heating rate of 3°C / min according to reference (Cerk and Cong et al., U.S. Pat. No. 9,688,795).

[0140] Comonomer content versus iCCD elution temperature was constructed using 12 reference materials (ethylene homopolymers and single-site metallocene-catalyzed ethylene-octene random copolymers with ethylene equivalent weight-average molecular weights ranging from 35,000 to 128,000). All of these reference materials were analyzed at 4 mg / mL using the same methodology as previously specified. The reported elution peak temperatures followed a plot of octene mole percent versus iCCD elution temperature with an R2 of 0.978.

[0141] The molecular weights of the polymer and polymer fractions were determined directly from the LS detector (at a 90-degree angle) and the concentration detector (IR-5) according to the Rayleigh-Gans-Debys approximation (Striegel and Yau, "Modern Size Exclusion Liquid Chromatogram," pp. 242 and 263) by assuming a form factor of 1 and all virial coefficients of zero. An integration window was set to integrate all chromatograms over the elution temperature range of 23.0–120 °C (temperature calibration specified above).

[0142] Calculating molecular weight (Mw) from iCCD involves measuring the inter-detector offset. The offset is defined as the geometric volume offset between the LS detector and the concentration detector. It is calculated as the difference in elution volume (mL) of the polymer peak between the concentration detector and the LS chromatogram. This is converted to a temperature offset using the elution heat rate and elution flow rate. Linear high-density polyethylene (zero comonomer content, melt index (I2) of 1.0, and polydispersity Mw / Mn of approximately 2.6 by conventional gel permeation chromatography) was used. The experimental conditions were the same as those for the standard iCCD method described above, except for the following parameters: crystallization from 140°C to 137°C at 10°C / min, thermal equilibration at 137°C for 1 minute as the soluble fraction elution time, soluble fraction (SF) time of 7 minutes, and elution from 137°C to 142°C at 3°C / min. The flow rate during crystallization was 0.0 mL / min. The flow rate during elution was 0.80 mL / min. The sample concentration is 1.0 mg / mL. Each LS data point in the LS chromatogram is shifted to correct for inter-detector offset before integration. The baseline-subtracted LS and concentration chromatograms are integrated over the entire elution temperature range of step (1). The MW detector constant is calculated by using HDPE samples of known MW in the range of 100,000 to 140,000 MW and the area ratio between the LS and concentration integrated signals. The MW of the polymer was calculated by using the ratio between the integrated light scattering detector (at a 90-degree angle) and the concentration detector and the MW detector constant.

[0143] Molecular weight calculations and calibrations were performed with GPCOne® software.

[0144] iCCD measurements are taken on both the total polyethylene composition and on the polymer sampled from the first reactor containing the first polyethylene component and the second polyethylene component.

[0145] Numerical deconvolution of bivariate data Numerical deconvolution of the bivariate data is used to obtain the density, molecular weight, and melt index (I2) of the first polyethylene component, the second polyethylene component, and the third polyethylene component. Microsoft Excel® Solver (2018) was used to calculate the iCCD-SCBD (wt iCCD (T) vs. temperature (T) plot) and GPC-MWD (wt GPC Numerical deconvolution of the combined data (lgMW) vs lgMW plot) was performed. For the iCCD-SCBD, the calculated weight fraction (wt sum,iCCD Data on temperature (T) (ranging from approximately 23 to 120 °C) obtained using the method described in the iCCD section versus temperature (T) were constrained to approximately 200 evenly spaced data points. A single or series of (up to three peaks per component) exponentially modified Gaussian distributions (Equation 6) were summed to obtain the weights for each component (wt C,iCCD (T)), and the total weight of these components (wt sum,iCCD (T)) was obtained at any temperature (T) as shown in Equations 7A-D.

[0146]

number

[0147]

number

[0148] The weight fraction of each component (wf C,iCCD )teeth,

[0149]

number

[0150] where wf C1,iCCD is the weight fraction of the first polyethylene component obtained from iCCD-SCBD deconvolution, and wf C2,iCCD is the weight fraction of the second polyethylene component obtained from iCCD-SCBD deconvolution, and wf C3,iCCD is the weight fraction of the third polyethylene component obtained from iCCD-SCBD deconvolution, with the sum of the fractions normalized to 1.00.

[0151] For GPC-MWD, the MWD obtained in the description section for conventional GPC was imported into the same spreadsheet from 2.00 to 7.00 in increments of 0.01 lg (MW / (g / mol)) (501 data points total). w,標的 , and a polydispersity (M w / M n The Flory-Schulz distribution with

[0152]

number

[0153] Then, for each lg(M i The Flory-Schulz distribution is expanded with a series of normal sums in lg(M i The weight fraction of the normal distribution (g / mol) is kept the same as the original Flory-Schulz distribution. The expanded Flory-Schulz distribution curve can be expressed as:

[0154]

number

[0155]

number

[0156] Each pair of components (first polyethylene component (C1), second polyethylene component (C2), and third polyethylene component (C3)) from iCCD-SCBD and GPC-MWD are considered to be equivalent masses for each technique, as shown in Equations 14A-E.

[0157]

number

[0158] Process and catalyst data, including catalyst efficiency and reactor mass balance, can be utilized to provide an initial estimate of the relative gravimetric production of each component. Alternatively, initial estimates of the weight fractions for each component can be compared by integrating subregions of the iCCD-SCBD or GPC-MWD plots of the polyethylene composition, particularly noting the visible regions with defined peaks or peak inflection points. For example, the peak areas of each component in the iCCD-SCBD curve can be estimated by lowering the vertical line between the peaks if they are sufficiently separated. Figure 2 in both WO 201913394(A1) and WO 2019133373(A1) provides examples of iCCD-SCBD curves. These publications are incorporated herein by reference in their entireties. Correlation of molecular weight order to initial estimates of molecular weight can be obtained from the peak locations of the relevant component regions in the iCCD-SCBD and iCCD-MW plots, which should be consistent with GPC-CC measurements. In some cases, initial assignments of peak areas and compositions can be obtained from multimodal GPC-MWD as a starting point and verified under iCCD-SCBD and iCCD-MW plots.

[0159] An initial estimate of the peak elution temperature, width, and tailing in the iCCD-SCBD for each component can be obtained from peak elution temperature, width, and tailing calibrations using a series of standard single-site samples with weight percent comonomer content measured by NMR. These calibrations can also provide information about the individual component comonomer content from the measured peak elution temperature.

[0160] Microsoft Excel® Solver is a sum,GPC (lgM i ) and the measured GPC-MWD, and the sum of squares of the residuals between wt sum,CEF The fit is programmed to minimize the sum of squares of the residuals between (T) and the measured iCCD-SCBD (the sampling widths and areas of the two observed distributions are normalized to each other). The GPC-MWD and iCCD-SCBD fits are weighted equally because they converge simultaneously. Initial guesses for weight fractions and peak widths in the iCCD-SCBD, as well as molecular weight targets for each component, are determined using Microsoft Excel® Solver as described herein.

[0161] The effect of cocrystallization, which distorts iCCD peak shapes, is corrected by the use of exponentially modified Gaussian (EMG) peak fits, or, in extreme cases, by the use of multiple (up to three) EMG peaks summed to represent a single component. Components produced by single-site catalysts can be modeled by a single EMG peak. Components produced by Ziegler-Natta catalysts can be modeled by one, two, or three EMG peaks, or by an EMG peak with a long low-temperature-facing tail sufficient for very dense, very small target Ziegler-Natta components on the iCCD-SCBD plot. In all cases, only a single expanded Flory-Schulz distribution (Equations 13A-C) is used, with weight fractions assigned as the associated sum of one or more EMG components from the iCCD-SCBD model (Equations 14A-E).

[0162] GPC deconvolution yielded normal distribution width parameters (σ) from Equations 13A and 13B of 0.000 to 0.170 (corresponding polydispersities of approximately 2.00 to 2.33) for the first and second polyethylene components made with a single-site catalyst. C1 or σ C2 ) is constrained by M in Equation 9. w,標的 is targeted to be minimized from this particular reaction scheme, and therefore is constrained to be the smallest for the third polyethylene component in these cases. Note that it is not constrained to be the smallest in all possible cases, but rather depends on the desired performance target of the in-reactor blend of the combined resins. The weight average molecular weights (M w,標的 ) ranking (preliminary estimate) is based on the iCCD-SCBD plot (wt iCCD The iCCD-MW plot (M) was measured at the temperature at which the peaks of the first polyethylene component and the second polyethylene component were observed on the iCCD-MW plot (M w(iCCD) M from the temperature curve w(iCCD) Therefore, the molecular weight order of the three components is known. The reactor mass balance can be calculated from deconvolution using Equation 13D to obtain the percent mass (Wf) of the third polyethylene component, Equation 13C, or, depending on the strength of the known distribution models for iCCD and GPC, the total weight fractions must sum to 1 (Equations 14A-E).

[0163] In general, we found that about 20 solver iterations usually reached good convergence on the solution using Excel®. If there was a discrepancy between the peak order versus measured molecular weight from the iCCD-MW plot and the observed comonomer weight percent measurement measured by GPC-CC, the data might need to be adjusted by changing the iteration start point (temperature or logMW) in Excel or slightly modifying the width and tail coefficients so that the iterations converge to a consistent solution between runs, or the resolution of the measurement might need to be increased, or additional peaks might be added to the iCCD-SCBD to better approximate the elution peak shapes of individual components. Such components, when individually prepared, can be pre-modeled via several EMG distributions.

[0164] In addition, the predicted M w(iCCD) The response can be generated by multiplying the weight average molecular weight by GPC-MWD of each component by the observed weight fraction of each component at each point along the iCCD-SCBD plot. w(iCCD) is the measured M in the iCCD-MW plot w(iCCD) By plotting comonomer incorporation as a function of elution temperature based on a series of known copolymer standards, the GPC-CC plot can be compared to the measured M of the individual components from the iCCD-MW and iCCD-SCBD plots. w(iCCD) and comonomer incorporation can also be used. The predicted GPC-CC plot should match the measured GPC-CC.

[0165] A peak temperature vs. density correlation for iCCD-SCBD data is obtained using a series of linear ethylene-based polymer standard resins polymerized from single-site catalysts with a melt index (I2) of approximately 1 g / 10 min, or a nominal weight average molecular weight by GPC of approximately 105,000 g / mol, and a polydispersity (or MWD) by GPC of less than 2.3. At least 10 standard resins with known comonomer content, density, and molecular weight within the density range of 0.87 to 0.96 g / cc are used. A calibration curve is obtained by fitting the peak temperature vs. density data to a fifth-order polynomial curve.

[0166] The correlation of peak width and peak tail versus peak temperature can also be obtained by fitting a straight line to the peak width and peak tail versus temperature for the resin, which is very useful as an initial estimate for the deconvolution process.

[0167] The first and second polyethylene components were shown as the first two peaks with elution temperatures between 35°C and 90°C in the resins of the present invention presented herein directly from the iCCD-SCBD deconvolution plot. 粗 ) was calculated from these observed peak positions using a calibration curve of peak temperature versus density. 粗 (g / cc) to account for the contribution of molecular weight (g / mol) to density using Equation 15 真 Corrected to (g / cc).

[0168] density 真 =density 粗 -0.254g / cc×[lg(M w(GPC) / (g / mol))-5.02] (Equation 15) In the formula, M w(GPC) is the weight average molecular weight of a single component deconvoluted from GPC-MWD.

[0169] The density of the third polyethylene component is calculated using the known density of the resin, the density of the first polyethylene component, and the density of the third polyethylene component according to Equation 16 below. 真 , the density of the second polyethylene component 真, and the weight fraction of each component.

[0170]

number

[0171] The melt index (I2) of each polyethylene component can be estimated from its weight average molecular weight using the following formula:

[0172] lg(I2 / (g / 10min))=-3.759×lg(M w(GPC) / (g / mol))+18.9 (Equation 17) In the formula, M w(GPC) where is the weight average molecular weight (g / mol) of a single component deconvoluted from the GPC-MWD curve, and I2 is the melt index (g / 10 min). Note that the coefficients may vary depending on the amount of long-chain branching. Also, to determine the product composition, direct sampling of a single reactor with a single catalyst at the same reactor conditions, sampling of the first reactor in a series dual-reactor configuration, or sampling of both reactors in a parallel dual-reactor configuration can be used to help determine the density, melt index (I2), GPC-MWD, and iCCD-SCBD of each individual component of the polyethylene composition, especially if the reaction is effectively stopped past the sampling point. This allows for better confirmation when the peak positions of the first and second polyethylene components cannot be properly determined from a ternary mixture.

[0173] Direct examination and quantification by analytical cross-fractionation on a GPC-TREF, such as a PolymerChar CFC unit (Valencia, Spain), equipped with online light scattering and calibrated for density relationships using similar calibrations in the bivariate space representing SCBD and molecular weight, can be used to measure the amount of each component or more accurately identify them, especially in cases where high cocrystallization or low resolution / discrimination of species may occur in both MWD and SCBD space. (Development of an Automated Cross-Fractionation Apparatus (TREF-GPC) for a Full Characterization of the Bivariate Distribution of Polyolefins. Polyolefin Characterization. Macromolecular Symposia, Volume 257, 2007, Pages 13-28. A. Ortin, B. Monrabal, J. Sancho-Tello). Adequate resolution must be achieved in both lgMW and temperature space, and validation should be performed through both direct composition calculations, e.g., IR-5 and light scattering molecular weight measurements. Characterization of Chemical Composition along the Molar Mass Distribution in Polyolefin Copolymers by GPC Using a Modern Filter-Based IR Detector. Polyolefin Characterization - ICPC 2012 Macromolecular Symposia Volume 330, 2013, Pages 63-80, A. Ortin, J. Montesinos, E. Lopez, P. del Hierro, B. Monrabal, J.R. Torres-Lapasio, M.C. Garcia-Alvarez-Coque. Component deconvolution requires the use of a similar set of equations and similar calibrations validated with a series of single-site resins and resin blends.

[0174] Branch Measurement SCB logMw4~5 (Average short-chain branching level in log(MW) between 4.0 and 5.0). The composition was tested using gel permeation chromatography (GPC). The GPC system consisted of a 150 °C high-temperature chromatograph equipped with a Polymer Char IR-5 infrared detector, a two-angle light scattering detector (Agilent 1260), and a Polymer Char differential viscometer. Four Agilent PL Mixed A columns (7.5 x 300 mm) were installed in series before the IR-5 detector in the detector oven. 1,2,4-trichlorobenzene (TCB, HPLC grade) and 2,5-di-tert-butyl-4-methylphenol (BHT) (e.g., commercially available from Sigma-Aldrich) were obtained. 800 milligrams of BHT were added to 4 liters of TCB. Here, the TCB containing BHT will be referred to simply as "TCB." Sample preparation was performed using an autosampler at 2 mg / mL with shaking at 160 °C for 3 hours. The injection volume was 200 mL. The GPC temperature is 150° C. and the flow rate is 1 mL / min. The GPC is calibrated using a series of narrow molecular weight (Mw) polystyrene standards.

[0175] Calibration of the GPC column set is performed using 21 narrow molecular weight distribution polystyrene standards ranging in molecular weight from 580 to 9,835,000, arranged in six "cocktail" mixtures with at least 10-year intervals between individual molecular weights. A fifth-order polynomial is used to fit each polyethylene-equivalent calibration point. The polystyrene standard peak molecular weights are converted to polyethylene molecular weights using Equation 1A.

[0176] Composition is measured along with MWD using an IR-5 infrared detector. The composition detector is calibrated using a series of copolymer standards with varying levels of comonomer. The weight percent comonomer levels of these samples are calculated using the C 13The composition-related signals are obtained by NMR. For each standard, composition-related signals are collected and labeled "measurement," "methylene" (CH2), and "methyl" (CH3). The "measurement" signal is used as the concentration signal when performing molecular weight calibration, and the ratio of the "methyl" and "methylene" signals is used for composition calculation. A plot of the weight percent comonomer from NMR versus these ratios is made for a series of standards. Linear regression of the data provides a good fit of the data set. The weight percent comonomer data can be converted to short-chain branches per 1000 total carbons (SCB / 1000C).

[0177] Mw is the weight average molecular weight. logMw is the logarithm of the weight average molecular weight. logMw is the weight fraction of the part at a particular logMw. logMw is the short chain branching per 1000 carbons of a moiety at a particular logMw. (SCB / 1000C) logMw4-5 is calculated by the following formula:

[0178]

number

[0179] Hayes Haze is measured according to ASTM D1003 using a BYK Gardner Haze-gard.

[0180] transparency Clarity is measured according to ASTM D1746.

[0181] Film Tensile Measurement Tensile modulus (including machine direction (MD) modulus and transverse direction (TD) modulus) is measured according to 2% secant modulus in ASTM D882. Tensile strain at break is measured according to ASTM D882.

[0182] Some embodiments of the present invention are described in detail in the following examples.

[0183] Example Table of catalyst components used in the synthesis of polyethylene compositions Synthetic procedures for synthesizing the following metal-ligand complexes V and VI can be found in WO 2022015368(A1) and WO 2016014749(A1), which are incorporated herein.

[0184] [ka]

[0185] [Table 1]

[0186] Preparation of Inventive Polyethylene Composition 1 (Poly1), Inventive Polyethylene Composition 2 (Poly2), and Comparative Polyethylene Composition 3 (CPoly3) All raw materials (monomers and comonomers) and process solvents (high-purity narrow-boiling range paraffinic and cycloparaffinic solvents) were purified with molecular sieves before being introduced into the reaction environment. High-purity hydrogen was supplied through a shared pipeline and dried with molecular sieves. The monomer feed stream to the reactor was pressurized to a pressure higher than the reaction pressure by a mechanical compressor. The solvent feed was pressurized to a pressure higher than the reaction pressure by a pump. The comonomer feed was pressurized to above the reaction pressure via a pump. The individual catalyst components were manually batch diluted with purified solvent and pressurized above the reaction pressure. All reaction feed streams were measured with mass flow meters and independently controlled with metering pumps.

[0187] A dual series reactor configuration was used.

[0188] The first continuous solution polymerization reactor consists of a liquid-filled, nearly adiabatic, continuous stirred tank reactor (CSTR). Independent control of all solvent, monomer, comonomer, hydrogen, and catalyst component feeds is possible. All reactor feed streams (solvent, monomer, comonomer, and hydrogen) are temperature controlled by passing the feed streams through heat exchangers. All feeds to the polymerization reactor are injected into the reactor at a single location. Catalyst components are injected into the polymerization reactor separately from the other feeds. The primary catalyst component feed is computer-controlled to maintain reactor monomer conversion at a specific target value. The secondary catalyst component feed is set at a specific molar ratio to the total catalyst (mole ratio of catalyst B = (catalyst B) moles / (catalyst A + catalyst B) moles). * 100). The boron-containing cocatalyst component is fed based on a specific molar ratio to the total catalyst metals (primary + secondary) fed to the reactor. The Al-containing cocatalyst component is fed to maintain a specific concentration of Al in the reactor. An agitator within the reactor is responsible for continuous mixing of the reactants. An oil bath allows for a certain amount of heat transfer to the reactor, providing some fine control of the reactor temperature and allowing deviation from adiabatic reactor behavior.

[0189] The effluent from the first polymerization reactor exits the first reactor and is added to the second reactor separately from the other feeds to the second reactor.

[0190] The second continuous solution polymerization reactor consists of a liquid-filled, nearly adiabatic continuous stirred tank reactor (CSTR). Independent control of all solvent, monomer, comonomer, hydrogen, and catalyst component feeds is possible. All reactor feed streams (solvent, monomer, comonomer, and hydrogen) are temperature-controlled by passing the feed streams through heat exchangers. All feeds to the polymerization reactor are injected into the reactor at a single location. Catalyst components are injected into the polymerization reactor separately from the other feeds. The primary catalyst component feed is computer-controlled to maintain reactor monomer conversion at a specific target value. Cocatalyst components are fed to the primary catalyst component based on a specified molar ratio. An agitator within the reactor provides continuous mixing of the reactants. An oil bath allows for some fine-tuning of reactor temperature control and allows for some heat transfer to the reactor, allowing deviation from adiabatic reactor behavior.

[0191] In all reactor configurations, the second / final reactor effluent enters a zone where it is deactivated by addition and reaction with a suitable reagent (typically water). At the outlet of this same reactor, other additives can be added for polymer stabilization (octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, tetrakis(methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate))methane, and tris(2,4-di-tert-butyl-phenyl)phosphite) and acid neutralization (a typical acid scavenger is calcium stearate).

[0192] After catalyst deactivation and the addition of optional additives, the reactor effluent enters a devolatilization system where the polymer is removed from the non-polymer stream. The non-polymer stream is removed from the system. The isolated polymer melt is pelletized and recovered. Table 1A below provides reactor information for the production of Poly1, Poly2, and C Poly3.

[0193] [Table 2]

[0194] Preparation of Inventive Polyethylene Composition 3 (Poly3), Inventive Polyethylene Composition 4 (Poly4), Comparative Polyethylene Composition 1 (CPoly1), and Comparative Polyethylene Composition 2 (CPoly2) All raw materials (monomers and comonomers) and process solvents (high-purity narrow-boiling range isoparaffinic solvent, Isopar-E) are purified with molecular sieves before being introduced into the reaction environment. Hydrogen is supplied under pressure as a high-purity grade and is not further purified. The monomer feed stream to the reactor is pressurized above the reaction pressure by a mechanical compressor. The solvent and comonomer feeds are pressurized above the reaction pressure by pumps. The individual catalyst components are manually batch diluted with purified solvent and pressurized above the reaction pressure. All reaction feed streams are metered using mass flow meters and independently controlled by computer-automated valve control systems.

[0195] Two reactor systems are used in a series configuration. The first continuous solution polymerization reactor consists of a liquid-filled, non-adiabatic, isothermal circulating loop reactor, simulating a continuous stirred tank reactor (CSTR) with heat removal. Independent control of all fresh solvent, monomer, comonomer, hydrogen, and catalyst component feeds is possible. All fresh feed streams to the first reactor (solvent, monomer, comonomer, and hydrogen) are temperature controlled to maintain a single solution phase by passing the feed streams through a heat exchanger. All fresh feed to each polymerization reactor is injected into the reactor at three locations, with approximately equal reactor volume between each injection location. The fresh feed is controlled so that each injector receives one-third of the total fresh feed mass flow rate. Catalyst components are injected into the polymerization reactor at two different locations with similar reactor volumes between each injection location, with each injection receiving half of the total flow rate. The main catalyst component feed is computer-controlled to maintain reactor monomer conversion at a specific target value. The secondary catalyst component feed is set to a specific molar ratio relative to the total catalyst (molar ratio of catalyst B = (moles of catalyst B) / (moles of catalyst A + catalyst B)). *100). The boron-containing cocatalyst component is fed based on a specific molar ratio relative to the total catalyst metals (primary + secondary) fed to the reactor. The Al-containing cocatalyst component is fed to maintain a specific Al concentration in the reactor. Immediately after each reactor feed or catalyst injection point, the stream is mixed with the contents of a circulating polymerization reactor with a static mixing element. The reactor contents are continuously circulated through a heat exchanger, which serves to remove the majority of the heat of reaction, with the coolant side temperature serving to maintain an isothermal reaction environment at a specified temperature. Circulation around the reactor loop is provided by a pump. A sample system is present to periodically collect material from the first loop reactor. After collection, the sample is dried in a vacuum oven and subjected to GPC and iCCD analysis. GPC and iCCD analysis provide a measure of the polymer partitioning between the primary and secondary catalysts in the first reactor loop, and the results can be used to adjust the secondary catalyst molar ratio to achieve the desired polymer partitioning in the first reactor loop.

[0196] The effluent from the first polymerization reactor (containing solvent, monomer, comonomer, hydrogen, catalyst components, and polymer) exits the first reactor and is added to the second reactor.

[0197] The second continuous solution polymerization reactor consists of a liquid-filled, non-adiabatic, isothermal circulating loop reactor that mimics a continuous stirred tank reactor (CSTR) with heat removal. Independent control of all fresh solvent, monomer, comonomer, hydrogen, and catalyst component feeds is possible. All fresh feed streams to the second reactor (solvent, monomer, comonomer, and hydrogen) are temperature controlled to maintain a single solution phase by passing the feed streams through heat exchangers. All fresh feed to each polymerization reactor is injected into the reactor at two points, with approximately equal reactor volume between each injection point. The fresh feed is controlled with each injector receiving half of the total fresh feed mass flow. Catalyst components are injected into the polymerization reactor through injection stingers. The main catalyst component feed is computer-controlled to maintain reactor monomer conversion at a specific target value. Cocatalyst components are fed to the primary catalyst component based on a specified molar ratio. Immediately after each reactor feed or catalyst injection point, the stream is mixed with the contents of a circulation polymerization reactor with static mixing elements. The contents of each reactor are continuously circulated through heat exchangers that serve to remove the majority of the heat of reaction, with the coolant side temperature serving to maintain an isothermal reaction environment at a specific temperature. Circulation around each reactor loop is provided by a pump.

[0198] Upon exiting the second reactor loop, the second / final reactor effluent enters a post-reactor adiabatic pipe with a total volume approximately 21.4% of the total volume of the combined two loop reactors, where the reaction continues for a period of time before entering a mixing zone where the reaction is stopped by adding and reacting with a suitable reagent (water) to deactivate the catalyst. At the exit point of this same reactor, other additives can be added for polymer stabilization (octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, tetrakis(methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate))methane, and tris(2,4-di-tert-butyl-phenyl)phosphite) and acid neutralization (a typical acid scavenger is calcium stearate).

[0199] Following catalyst deactivation and additive addition, the reactor effluent enters a devolatilization system where polymer is removed from the non-polymer stream. The isolated polymer melt is pelletized and recovered. The non-polymer stream passes through various equipment that separates most of the ethylene removed from the system. Most of the solvent and unreacted comonomer pass through a purification system before being recycled to the reactor. Small amounts of solvent and comonomer are purged from the process.

[0200] The reactor stream feed data flows corresponding to the values ​​in Table 1B used to generate the examples are illustrated diagrammatically in Figure 1. The data are displayed to allow for the complexity of the solvent recycle system and to allow for easier processing of the reaction system as a once-through flow diagram.

[0201] [Table 3]

[0202] The density, melt index (I2), and I of each of the polyethylene compositions of the present invention and the comparative polyethylene composition 10 / I2, Mz, Mw / Mn, Mz / Mn, and Log(Mw) of 4.0-5.0 (SCB logMw 4~5 ) is measured according to the Test Methods section above. Tables 2 and 3 below provide data on the compositions.

[0203] [Table 4]

[0204] [Table 5]

[0205] The density, Mw, and weight percent (wt.%) of each of the components (i.e., polyethylene component 1 (component 1), polyethylene component 2 (component 2), and polyethylene component 3 (component 3)) are measured according to the Test Methods section above. Table 4A provides the results. Table 4B below provides the iCCD peak temperature of the first polyethylene component of each of the compositions. Table 4C below provides the iCCD peak temperature of the first polyethylene component of each of the compositions according to the following formula: Weight Fraction of First Polyethylene Component * SCB logMw4~5 * The values ​​for each of the compositions are provided for Mz (conventional GPC). Without being bound by theory, the properties and balance of properties of the first polyethylene component are determined by the weight fraction, SCB, logMw4~5 Mz (conventional GPC) greater than 230,000 provides improved and / or desirable processability, stretchability, and performance in films.

[0206] [Table 6] * C Poly3 is a bimodal composition, having only two polyethylene components.

[0207] [Table 7]

[0208] [Table 8]

[0209] The polyethylene compositions are used to form biaxially oriented films. Three films are formed from each of the polyethylene compositions of the present invention. Thus, a total of 12 films of the present invention are produced. Biaxial orientation is carried out sequentially in two different stretching chambers at a predetermined temperature. Sheet samples are cut into 10x10cm sizes along the MD and TD directions (initial sheet thickness is 700um) and mounted on a stretching frame with five clips positioned on each of the four sides. The clips are pneumatically actuated to clamp the edges of the sample, and then the stretching frame is transferred into the first chamber. Machine direction orientation (MDO) is carried out in the first chamber. Immediately thereafter, the machine-oriented sample is sent to the second chamber for cross direction, i.e., transverse direction orientation (TDO). In the MDO process, the sample is first heated at a desired temperature (T MDO The sample sheet is heated by hot air with forced convection at a temperature (T = 128 °C) and then stretched 5 times in the machine direction at a stretch rate of 500% / s. In the TDO process, the sample is brought to the desired temperature (T) by circulating air in a second chamber before undergoing 8 times transverse orientation at a stretch rate of 250% / s. TDO The film is then heated to temperatures (124, 126, and 128°C) for 30 seconds. The film is thus stretched at a ratio of 8:1 in the transverse direction and 5:1 in the longitudinal direction, with a final film thickness of approximately 20 μm. The stretched film samples are then removed from the stretching frame and aged for at least one week before being tested for film properties as described below in this section. Tables 5 and 6 below provide the film properties. The inventive films have desirable clarity, haze, and tensile properties. Attempted films from the comparative polyethylene compositions were unstretchable, with the film breaking during stretching and therefore unformable.

[0210] [Table 9]

[0211] [Table 10]

Claims

1. 1. A polyethylene composition comprising: (a) 15 to 25 weight percent of a first polyethylene component having a molecular weight (Mw) greater than 200,000 g / mole and a density from 0.925 to 0.945 g / cc; (b) 20 to 35 weight percent of a second polyethylene component having a molecular weight (Mw) of less than 80,000 g / mole and a density of 0.915 to 0.950 g / cc; (c) 40 to 65 weight percent of a third polyethylene component having a molecular weight (Mw) of less than 100,000 g / mole and a density of 0.940 to 0.965 g / cc; The polyethylene composition has a density of 0.935 to 0.958 g / cc, a melt index (I ２ ) and having the formula: Weight Fraction of First Polyethylene Component ＊ SCB ｌｏｇＭｗ４～５ ＊ A polyethylene composition having Mz (conventional GPC) > 230,000.

2. The polyethylene composition has an average short chain branching level (SCB) in the portion between 4.0 and 5.0 log(Mw) that is greater than 3.50 SCB / 1000C and less than 10.00 SCB / 1000C. ｌｏｇＭｗ４～５ 2. The polyethylene composition of claim 1, wherein

3. The polyethylene composition according to any one of claims 1 to 2, wherein the first polyethylene component has an improved comonomer composition distribution (iCCD) elution profile with a peak temperature of more than 99.5°C.

4. The polyethylene composition according to any one of claims 1 to 3, wherein the polyethylene composition has an Mz / Mw of 2.5 to 4.

5.

5. The polyethylene composition according to any one of claims 1 to 4, wherein the polyethylene composition has a molecular weight distribution (Mw / Mn) of 4.2 to 10.

0.

6. The polyethylene composition has an I １０ / I ２ The polyethylene composition according to any one of claims 1 to 5, having

7. 7. The polyethylene composition according to any one of claims 1 to 6, wherein the polyethylene composition has a Mz (conventional GPC) of 250,000 to 450,000 g / mol.

8. A uniaxially oriented film comprising the polyethylene composition according to any one of claims 1 to 7.

9. A biaxially oriented film comprising the polyethylene composition according to any one of claims 1 to 7.

10. 10. The biaxially oriented film of claim 9, wherein the biaxially oriented film is oriented in the machine direction with a stretch ratio of 2:1 to 9:1 and in the transverse direction with a stretch ratio of 2:1 to 11:

1.

11. The biaxially oriented film according to claim 9 or 10, wherein the biaxially oriented film is a multilayer film.

12. 12. The biaxially oriented film of claim 9, 10, or 11, wherein the biaxially oriented film has at least one of a haze value of less than 15 percent, a 2 percent secant modulus in the machine direction of at least 600 MPa, a 2 percent secant modulus in the transverse direction of at least 900 MPa, a transparency of at least 35 percent, a tensile strain at break in the machine direction of at least 160%, and a tensile strain at break in the transverse direction of at least 20%.

13. A laminate, a first film comprising a polyethylene sealant film, polypropylene, or polyamide; A laminate comprising the biaxially oriented film according to any one of claims 9 to 12, wherein the first film is laminated to the biaxially oriented film.

14. An article comprising the biaxially oriented film of any one of claims 9 to 12.

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