Polyethylene composition, oriented polyethylene film, and article including same

Abstract

Polyethylene compositions comprising three polyethylene components, oriented polyethylene films comprising such polyethylene compositions, laminates comprising such polyethylene compositions, and articles comprising such polyethylene compositions are disclosed. The polyethylene composition can have good processability and stretchability of oriented polyethylene films (e.g., high pass rate during film casting), and the oriented polyethylene films produced from such polyethylene compositions can be compatible with polyethylene recycle streams and can have a desired balance of stretchability, elongation, modulus, haze, and transparency.

Description

Technical Field

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

[0002] Along with the global interest in reducing packaging waste and making flexible packaging more sustainable, people are working harder and harder to develop materials and technologies that can enhance the sustainability of flexible packaging.Flexible packaging film structures are usually formed by various types of polymer materials, and the polymer materials include for example polyethylene, polypropylene, ethylene vinyl alcohol, polyethylene terephthalate, polyamide, etc.These materials are usually combined to realize the property balance of the scope that exceeds the reach of single material type.However, due to the difference of these materials, final packaging is usually not easy to recycle.Therefore, also move towards single component structure (for example, full polyethylene structure), to improve the recyclability overview.For example, in the case of full polyethylene structure, it will be necessary to strengthen some performance indexes (for example, mechanical properties), to maintain the expected performance level of these structures when formed by different polymer materials, improve recyclability simultaneously.Therefore, it will be necessary to make up the performance defects of polyethylene with respect to other material types with new resins and processing technology.

[0003] A relatively new material technology in processing is biaxially oriented polyethylene (BOPE) film. Such BOPE films can be formed by cast extrusion, then oriented in the longitudinal direction (MD) in a tenter frame, and then oriented in the cross / transverse direction (TD). Alternatively, this process can also be performed simultaneously. Due to the molecular structure, microstructure and crystallization dynamics of polyethylene, it is generally difficult to biaxially orient conventional polyethylene. In addition, it is difficult to balance the optical properties and stiffness properties of the BOPE film made of conventional polyethylene, and since the density of the polyethylene resin that can be used for biaxial orientation is relatively low, such BOPE films may have a lower modulus, which may have a negative impact on the temperature resistance and processability of the film.

[0004] Thus, there remains a need for polyethylene compositions having good processability and stretchability into oriented polyethylene films while exhibiting higher density associated with higher melting points and thus higher heat resistance (e.g., high throughput during film casting and packaging processes), and for oriented polyethylene films that are compatible with polyethylene recycling streams and have a desired balance of stretchability, elongation, modulus, haze and clarity. Summary of the invention

[0005] The invention provides a polyethylene composition suitable for being processed into an oriented polyethylene film and an oriented polyethylene film with a desired balance of desired properties such as stretchability, elongation, modulus, haze and transparency. In some embodiments, the polyethylene composition can advantageously expand the operating window to stretch the film to obtain the oriented polyethylene film and can be processed with a high throughput rate during film casting. In some embodiments, the polyethylene composition can provide a single particle solution without the need for a blend or a skin layer, and can produce a film with a desired balance of optics and rigidity compared to existing films.

[0006] In one aspect, the present invention relates to a polyethylene composition comprising:

[0007] (a) 15 weight percent to 25 weight percent of a first polyethylene component having a molecular weight (Mw) greater than 200,000 g / mol and a density from 0.925 g / cc to 0.945 g / cc;

[0008] (b) 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; and

[0009] (c) 40 weight percent 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 g / cc to 0.965 g / cc; and

[0010] The polyethylene composition has a density of 0.935 g / cc to 0.958 g / cc, a melt index (I 2 ), and satisfies the following equation: first polyethylene component weight fraction × SCB logMw4-5 ×Mz (conventional GPC)>230,000.

[0011] In another aspect, the present invention is directed to a uniaxially oriented film.The uniaxially oriented film may include the polyethylene composition disclosed herein.

[0012] In another aspect, the present invention is directed to a biaxially oriented film.The biaxially oriented film may include the polyethylene composition disclosed herein.

[0013] In another aspect, the invention relates to a laminate. In some embodiments, the laminate comprises: a first film comprising a polyethylene sealant film, polypropylene, or polyamide; and a biaxially oriented film according to embodiments disclosed herein, wherein the first film is laminated to the biaxially oriented film.

[0014] In another aspect, the invention relates to an article. In some embodiments, the article includes any of the laminates, films, and / or polyethylene compositions disclosed herein.

[0015] These and other embodiments are described in more detail in the detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] The following detailed description of certain embodiments of the present disclosure may be best understood when taken in conjunction with the following drawings, in which like reference numerals are used to indicate like structures and in which:

[0017] Figure 1 is a graphical depiction of reactor stream feed data flow for the inventive and comparative compositions disclosed herein. DETAILED DESCRIPTION

[0018] Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percentages are by weight, all temperatures are in °C, and all test methods are current as of the filing date of this disclosure.

[0019] The term "composition" as used herein refers to a mixture of materials comprising the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0020] The term "polymer" refers to a polymeric compound prepared by polymerizing monomers of the same or different type. Thus, the generic term polymer encompasses the term homopolymer, as defined below, and the term interpolymer, as defined below. Trace amounts of impurities (e.g., catalyst residues) may be incorporated into and / or within the polymer. The polymer may be a single polymer, a polymer blend, or a polymer mixture, including a mixture of polymers formed in situ during polymerization.

[0021] 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 also be incorporated into the polymer structure.

[0022] As used herein, the term "interpolymer" refers to polymers prepared by polymerizing at least two different types of monomers. The generic term interpolymer thus includes copolymers (used to refer to polymers prepared from two different types of monomers) and polymers prepared from more than two different types of monomers.

[0023] As used herein, the term "olefinic polymer" or "polyolefin" refers to a polymer that includes, in polymerized form, a major amount of an olefin monomer, such as ethylene or propylene (by weight of the polymer), and optionally may include one or more comonomers.

[0024] As used herein, the term "ethylene / α-olefin interpolymer" refers to an interpolymer that comprises, in polymerized form, a majority amount (>50 mol%) of units derived from ethylene monomer and the remainder of units derived from one or more α-olefins. Typical α-olefins used to form ethylene / α-olefin interpolymers are C 3 -C 10 Olefins.

[0025] As used herein, the term "ethylene / α-olefin copolymer" refers to a copolymer comprising, in polymerized form, a majority amount (>50 mol%) of ethylene monomer and an α-olefin as the only two monomer types.

[0026] As used herein, the term "α-olefin" refers to an olefin having a double bond at the primary or α (alpha) position.

[0027] "Polyethylene" or "ethylene-based polymer" shall mean a polymer comprising a majority amount (>50 mol%) of units derived from ethylene monomers. This includes polyethylene homopolymers or 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, including linear and substantially linear low density resins (m-LLDPE); ethylene-based plastomers (POPs) and ethylene-based elastomers (POEs); medium density polyethylene (MDPE); and high density polyethylene (HDPE). These polyethylene materials are generally known in the art; however, the following description may be helpful in understanding the differences between some of these different polyethylene resins.

[0028] The term "LDPE" may also be referred to as "high pressure ethylene polymer" or "highly branched polyethylene" and is defined to mean a polymer that is partially or completely homopolymerized or copolymerized in an autoclave or tubular reactor at pressures above 14,500 psi (100 MPa) using a free radical initiator such as a peroxide (see, e.g., U.S. Pat. No. 4,599,392, which is hereby incorporated by reference). LDPE resins typically have a molecular weight of 0.916 g / cm 3 Up to 0.935g / cm 3 density within the range of .

[0029] The term "LLDPE" includes those produced using conventional Ziegler-Natta catalyst systems. catalyst system) and a chromium-based catalyst system and a single-site catalyst (including but not limited to substituted mono- or dicyclopentadienyl catalysts (commonly referred to as metallocenes), constrained geometry catalysts, pyridylamine catalysts, phosphinimine catalysts, and polyvalent aryloxyether catalysts (commonly referred to as bisphenylphenoxy) and comprises linear, substantially linear or heterogeneous polyethylene copolymers or homopolymers. LLDPE includes less long chain branching than LDPE and comprises substantially linear ethylene polymers, which are further defined in U.S. Pat. No. 5,272,236, U.S. Pat. No. 5,278,272, U.S. Pat. No. 5,582,923 and U.S. Pat. No. 5,733,155; homogeneously branched linear ethylene polymer compositions, such as those in U.S. Pat. No. 3,645,992; heterogeneously branched ethylene polymers, such as those prepared according to the process disclosed in U.S. Pat. No. 4,076,698; and / or blends thereof (such as U.S. Pat. No. 3,914,342 or U.S. Pat. No. 5,733,155). 5,854,045). LLDPE can be made by gas phase, solution phase or slurry polymerization, or any combination thereof, using any type of reactor or reactor configuration known in the art.

[0030] The term "MDPE" refers to a polyethylene with a density of 0.926 g / cm 3 Up to 0.935g / cm 3 "MDPE" is typically produced using chromium or Ziegler-Natta catalysts or using single-site catalysts, including but not limited to substituted mono- or bis-cyclopentadienyl catalysts (commonly referred to as metallocenes), constrained geometry catalysts, pyridylamine catalysts, phosphinimine catalysts, and polyvalent aryloxyether catalysts (commonly referred to as bisphenylphenoxy), and typically has a molecular weight distribution ("MWD") greater than 2.5.

[0031] The term "HDPE" refers to a polyethylene having a density greater than about 0.935 g / cm 3 and at most about 0.980 g / cm 3 The polyethylene is generally prepared using a Ziegler-Natta catalyst, a chromium catalyst or a single-site catalyst (including but not limited to substituted mono- or bis-cyclopentadienyl catalysts (commonly referred to as metallocenes), constrained geometry catalysts, pyridylamine catalysts, phosphinimine catalysts and polyvalent catalysts aryloxyether catalysts (commonly referred to as bisphenylphenoxy).

[0032] The term "ULDPE" refers to a polyethylene with a density of 0.855 g / cm 3 Up to 0.912g / cm 3Polyethylene (ULDPE) is generally prepared using Ziegler-Natta catalysts, chromium catalysts or single-site catalysts (including but not limited to substituted mono- or di-cyclopentadienyl catalysts (commonly known as metallocenes), constrained geometry catalysts, pyridine amine catalysts, phosphinimine catalysts and multivalent catalysts (commonly known as bisphenylphenoxy). ULDPE includes but is not limited to polyethylene (based on ethylene) plastomers and polyethylene (based on ethylene) elastomers. Polyethylene (based on ethylene) elastomer plastomers generally have a molecular weight of 0.855 to 0.912 g / cm 3 density.

[0033] The terms "blend" and "polymer blend" mean 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 by transmission electron spectroscopy, light scattering, x-ray scattering, and any other method known in the art. A blend is not a laminate, but one or more layers of a laminate may contain a blend. Such blends may be prepared as dry blends, in situ formation (e.g., in a reactor), melt blends, or using other techniques known to those skilled in the art.

[0034] The term "multimodal" means a composition that can be characterized by having at least three (3) polymer subcomponents with varying densities and weight average molecular weights, and optionally, the composition can also have different melt index values. In one embodiment, multimodal can be defined by having at least three different peaks in a gel permeation chromatography (GPC) chromatogram showing molecular weight distribution. In another embodiment, multimodal can be defined by having at least three different peaks in a crystallization elution fractionation (CEF) chromatogram showing short chain branching distribution. In another embodiment, multimodal can be defined by having at least three different peaks in an improved comonomer composition distribution (iCCD) elution curve. Multimodal includes compositions having three peaks in GPC, CEF or iCCD, as well as compositions having more or less than three peaks, as long as the composition can be characterized as having at least (3) polymer subcomponents with different densities and weight average molecular weights according to the following test methods.

[0035] The term "trimodal polymer" means a multimodal ethylene polymer having three main components: a first polyethylene component, a second polyethylene component and a third polyethylene component.

[0036] A “polyethylene component”, e.g., a “first polyethylene component”, “second polyethylene component” or “third polyethylene component” refers to a subcomponent (i.e., a multimodal or trimodal polymer) of the polyethylene composition disclosed herein, wherein each subcomponent is a polyethylene monomer comprising ethylene and optionally C3 -C 12 Polyethylene with alpha-olefin comonomers.

[0037] The terms "comprising," "including," "having," and derivatives thereof are not intended to exclude the presence of any additional components, steps, or procedures, whether or not specifically disclosed. For the avoidance of any doubt, all compositions claimed through use of the term "comprising" may include any additional additives, adjuvants, or compounds, whether polymeric or otherwise, unless stated to the contrary. In contrast, the term "consisting essentially of excludes from the scope of any subsequently recited component, step, or procedure, except those that are not essential to operability. The term "consisting of excludes any component, step, or procedure not specifically recited or listed.

[0038] The present invention generally relates to polyethylene compositions that can be suitable for oriented films. When incorporated into oriented films, the polyethylene compositions can provide desired performance characteristics, such as desired clarity, reduced haze, and improved modulus. Without wishing to be bound by theory, it is believed that the unique design of the polyethylene composition - comprising, for example, a three-component composition and a first polyethylene component weight fraction, a Z-average molecular weight (Mz), and an average short chain branching level (SCB) in the fraction between log (Mw) 4.0 and 5.0 logMw4-5 )—provides improved processability, stretchability, and performance characteristics. The polyethylene compositions of the present invention can be incorporated into uniaxially oriented films, biaxially oriented films, laminates, and articles having enhanced performance characteristics such as desired clarity, reduced haze, and improved modulus. In some embodiments, because the present compositions are polyethylene-based, the films, laminates, and articles can be formed entirely or substantially entirely of polyethylene, thereby making the films, laminates, and articles more easily recyclable.

[0039] In one aspect, the polyethylene composition comprises:

[0040] (a) 15 weight percent to 25 weight percent of a first polyethylene component having a molecular weight (Mw) greater than 200,000 g / mol and a density from 0.925 g / cc to 0.945 g / cc;

[0041] (b) 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; and

[0042] (c) 40 weight percent 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 g / cc to 0.965 g / cc; and

[0043] The polyethylene composition has a density of 0.935 g / cc to 0.958 g / cc, a melt index (I 2 ), and satisfies the following equation:

[0044] Weight fraction of first polyethylene component × SCB logMw4-5 ×Mz (conventional GPC)>230,000.

[0045] In the preceding equation, "first polyethylene component weight fraction" 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 would have a "first polyethylene component weight fraction" value of 0.25. "SCB logMw4-5 " is the average short chain branching level in the fraction between log (Mw) 4.0 and 5.0 of the polyethylene composition as measured according to the following test method. "Mz (Conventional GPC)" is the Z-average molecular weight of the polyethylene composition as measured according to the following Conventional GPC test method. For example, the polyethylene composition disclosed herein can have 21 weight percent of the first polyethylene component, an SCB of 4.28 logMw4-5 and an Mz (conventional GPC) of 367,362 g / mol, which is equal to 330,185 (ie, 0.21×4.28×367,362=330,185) and is greater than 230,000. In some embodiments, the first polyethylene component weight fraction×SCB logMw4-5 ×Mz (conventional GPC) > 250,000, or alternatively > 275,000, or alternatively > 300,000, or alternatively > 325,000.

[0046] In some embodiments, the polyethylene composition has an average short chain branching level (SCB) in the fraction between log (Mw) 4.0 and 5.0 greater than 3.50 SCB / 1000C and less than 10.00 SCB / 1000C. logMw4-5 ).

[0047] In some embodiments, the first polyethylene component has a peak temperature greater than 99.5°C in an elution curve via an improved comonomer composition distribution (iCCD). 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 10 / I 2 In some embodiments, the polyethylene composition has an Mz (conventional GPC) of 250,000 g / mol to 450,000 g / mol.

[0048] A polyethylene composition may comprise a combination of two or more embodiments as described herein.

[0049] Polyethylene composition

[0050] The polyethylene composition according to the embodiments disclosed herein includes ethylene monomer and at least one C 3 -C 12 The polymerization reaction product of alpha-olefin comonomers. The one or more alpha-olefin comonomers of the polyethylene composition can be selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene, or in the alternative, from the group consisting of 1-butene, 1-hexene and 1-octene, or in the alternative, from the group consisting of 1-hexene and 1-octene.

[0051] The polyethylene composition has a density of 0.935 g / cc to 0.958 g / cc, a melt index (I) of 0.5 g / 10 min to 5.0 g / 10 min, and a 2 ), and satisfies the following equation: first polyethylene component weight fraction × SCB logMw4-5 × Mz (conventional GPC)> 230,000. The polyethylene composition can have a density of 0.935 g / cc to 0.958 g / cc, or 0.936 g / cc to 0.954 g / cc, or 0.935 g / cc to 0.950 g / cc, or 0.935 g / cc to 0.945 g / cc, or 0.936 g / cc to 0.945 g / cc. The polyethylene composition can have a melt index (I) of 0.5 g / 10 min to 5.0 g / 10 min, or 0.5 g / 10 min to 3.0 g / 10 min, or 0.5 g / 10 min to 2.0 g / 10 min, or 1.0 g / min to 2.0 g / min. 2In one or more embodiments, the polyethylene composition has an average short chain branching (SCB) level (SCB) in the fraction between log (Mw) 4.0 and 5.0 of greater than 3.50 SCB / 1000C, such as 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. logMw4-5 In one or more embodiments, the average SCB level (SCB) in the largest fraction between log(Mw) 4.0 and 5.0 logMw4-5 ) is 8.00 SCB / 1000C or 7.0 SCB / 1000C. SCB is measured according to the test method described below logMw4-5 .

[0052] The polyethylene composition can 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 can have an Mw / Mn of 7.0 to 15.0, or 8.0 to 15, or 7.0 to 14.0, or 7.0 to 13.0. 10 / I 2 .

[0053] The polyethylene composition disclosed herein has three components: a first polyethylene component, a second polyethylene component, and a third polyethylene component.

[0054] The polyethylene composition includes the first polyethylene component of 15 weight percents to 25 weight percents based on the gross weight of the polyethylene composition, and the first polyethylene component has a molecular weight (Mw) (also referred to as weight average molecular weight) greater than 200,000g / mol and a density of 0.925g / cc to 0.945g / cc. All individual values ​​and subranges of 15 weight percents to 25 weight percents are disclosed herein and are included. For example, the polyethylene composition may include the first polyethylene component of 15 weight percents, 16 weight percents, 17 weight percents, 18 weight percents, 19 weight percents, 20 weight percents, 21 weight percents, 22 weight percents, 23 weight percents or 24 weight percents to 25 weight percents, 24 weight percents, 23 weight percents, 22 weight percents, 21 weight percents, 20 weight percents, 19 weight percents, 18 weight percents, 17 weight percents or 16 weight percents based on the gross weight of the polyethylene composition. The first polyethylene component can have greater than 200,000g / mol, or greater than 210,000g / mol, or greater than 250,000g / mol, or greater than 280,000g / mol, or greater than 300,000g / mol, or greater than 310,000g / mol, or 210,000g / mol to 400,000g / mol molecular weight (Mw), wherein molecular weight (Mw) can be measured according to the following test method. The first polyethylene component can have a density of 0.925g / cc to 0.945g / cc, or 0.930g / cc to 0.945g / cc, or 0.930g / cc to 0.940g / cc. According to the density of the equation calculation polyethylene composition component (for example, the first polyethylene component, the second polyethylene component and the 3rd polyethylene component) provided in the following test method part.

[0055] In some embodiments, the first polyethylene component has a peak temperature greater than 99.5° C. in an elution curve via improved comonomer composition distribution (iCCD). In some embodiments, the first polyethylene component is a homopolymer. In some embodiments, the first polyethylene component may include C 3 -C 12 Alpha-olefin comonomers. Exemplary alpha-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene. The one or more alpha-olefin comonomers of the first polyethylene component may be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene, or in the alternative, from the group consisting of 1-butene, 1-hexene, and 1-octene, or in the alternative, from the group consisting of 1-hexene and 1-octene.

[0056] The polyethylene composition includes 20 weight percents to 35 weight percents of the second polyethylene component, and the second polyethylene component has a molecular weight (Mw) less than 80,000g / mol and a density of 0.915g / cc to 0.950g / cc. All individual values ​​and subranges of 20 weight percents to 35 weight percents are disclosed herein and are included. For example, the polyethylene composition can include 20 weight percents, 21 weight percents, 22 weight percents, 23 weight percents, 24 weight percents, 25 weight percents, 26 weight percents, 27 weight percents, 28 weight percents, 29 weight percents, 30 weight percents, 31 weight percents, 32 weight percents, 33 weight percents or 34 weight percents to 35 weight percents, 34 weight percents, 33 weight percents, 32 weight percents, 31 weight percents, 30 weight percents, 29 weight percents, 28 weight percents, 27 weight percents, 26 weight percents, 25 weight percents, 24 weight percents, 23 weight percents, 22 weight percents or 21 weight percents of the second polyethylene component. The second polyethylene component can 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 15,000 g / mol to 75,000 g / mol, wherein the molecular weight (Mw) can be measured according to the following test method. The second polyethylene component can have a density of 0.915 g / cc to 0.950 g / cc, or 0.915 g / cc to 0.940 g / cc, or 0.915 g / cc to 0.935 g / cc, or 0.915 g / cc to 0.930 g / cc, or 0.915 g / cc to 0.925 g / cc.

[0057] The second polyethylene component may have different levels of C 3 -C 12 α-olefin comonomer incorporation. In one embodiment, the second polyethylene component may have a higher C 3 -C 12 α-olefin comonomer incorporation. For example, the second polyethylene component can have 2 weight percent to 20 weight percent C 3 -C 12 α-olefin comonomer, or 3 to 19 weight percent of C 3 -C 12 α-olefin comonomer, or 5 to 17 weight percent of C 3 -C 12α-Olefin Comonomers. 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 in the alternative, from the group consisting of 1-butene, 1-hexene and 1-octene, or in the alternative, from the group consisting of 1-hexene and 1-octene.

[0058] The polyethylene composition includes the 3rd polyethylene component of 40 weight percent to 65 weight percent, and the 3rd polyethylene component has a molecular weight (Mw) less than 100,000g / mol and a density of 0.940g / cc to 0.965g / cc. All individual values ​​and subranges of 40 weight percent to 65 weight percent are disclosed herein and are included. For example, the polyethylene composition can include the 3rd polyethylene component of 40 weight percent, 41 weight percent, 43 weight percent, 45 weight percent, 47 weight percent, 49 weight percent, 51 weight percent, 53 weight percent, 55 weight percent, 57 weight percent, 59 weight percent, 61 weight percent or 63 weight percent to 65 weight percent, 63 weight percent, 61 weight percent, 59 weight percent, 57 weight percent, 55 weight percent, 53 weight percent, 51 weight percent, 49 weight percent, 47 weight percent, 45 weight percent, 43 weight percent or 41 weight percent.

[0059] The third polyethylene component can 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 15,000 g / mol to 90,000 g / mol, wherein the molecular weight (Mw) can be measured according to the following test method. The third polyethylene component can have a density of 0.940 g / cc to 0.965 g / cc, or 0.942 g / cc to 0.965 g / cc, or 0.942 g / cc to 0.963 g / cc.

[0060] The third polyethylene component may have a different level of C 3 -C 12 α-olefin comonomer incorporation. In one embodiment, the third polyethylene component may have a lower C 3 -C 12 α-olefin comonomer incorporation. For example, the third polyethylene component may have less than 10 weight percent C 3 -C 12 α-olefin comonomer, or 0.5 weight percent to less than 10 weight percent of C 3 -C 12α-olefin comonomer, or 2 weight percent to less than 10 weight percent of C 3 -C 12 α-Olefin Comonomers. 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 in the alternative, from the group consisting of 1-butene, 1-hexene and 1-octene, or in the alternative, from the group consisting of 1-hexene and 1-octene.

[0061] Polymerization and catalysts

[0062] Various polymerization process embodiments are considered suitable for producing polyethylene compositions. In one or more embodiments, the polyethylene composition is produced by a solution polymerization process in a dual reactor system. These dual solution polymerization reactors can be conventional reactors, for example, loop reactors, isothermal reactors, adiabatic reactors, and continuous stirred tank reactors in parallel and series, and any combination thereof. In one embodiment, the polyethylene composition can be produced in two loop reactors configured in series, the first solution polymerization reactor temperature is in the range of 115°C to 200°C, for example, 135°C to 165°C, and the second solution polymerization reactor temperature is in the range of 150°C to 215°C, for example, 185°C to 212°C. In the solution polymerization process, ethylene monomer, one or more C 3 -C 12 An alpha-olefin comonomer, a solvent, one or more catalyst systems, and optionally hydrogen are continuously fed to dual solution polymerization reactors (ie, a first solution polymerization reactor and a second solution polymerization reactor).

[0063] Various catalysts are considered suitable. These catalysts may include, but are not limited to, Ziegler-Natta catalysts, chromium catalysts, metallocene catalysts, post-metallocene catalysts, constrained geometry complex (CGC) catalysts, phosphinimine catalysts, pyridineamine catalysts, or bis(biphenyl phenoxy) catalysts. Details and examples of CGC catalysts are provided in U.S. Patents Nos. 5,272,236, 5,278,272, 6,812,289, and WO Publication 93 / 08221, all of which are incorporated herein by reference. Details and examples of bis(biphenyl phenoxy) catalysts are provided in U.S. Patents Nos. 6,869,904; 7,030,256; 8,101,696; 8,058,373; 9,029,487, all of which are incorporated herein by reference. Details and examples of pyridinamine catalysts are provided in WO publication 18 / 170138, the entire contents of which are incorporated herein by reference. The catalyst used in the solution polymerization reactor can be varied 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 are used in the solution polymerization reactor to vary the density, melt index, comonomer incorporation, etc. of the first polyethylene component, the second polyethylene component, and the third polyethylene component. Without being bound by theory, varying these parameters of the first polyethylene component, the second polyethylene component, and the third polyethylene component can provide a multimodal polyethylene composition with a desired combination of toughness and processability.

[0064] In one or more embodiments, the first solution polymerization reactor, the second solution polymerization reactor, or both may contain two catalysts. In a specific embodiment, the first solution polymerization reactor may contain two catalysts, and the second solution polymerization reactor located downstream of the first solution polymerization reactor contains a catalyst. The two catalysts of the first solution polymerization reactor are homogeneous catalysts, while the catalyst of the second solution polymerization reactor may contain a homogeneous catalyst, a heterogeneous catalyst, or both. Homogeneous catalysts (commonly referred to as single-site catalysts) are organic metal compounds that usually have discontinuous molecular structures, and in the case of preparing interpolymers, are used to prepare polymers with narrow molecular weight distribution and narrow composition distribution. Homogeneous catalysts can be dissolved in a solution process, or loaded to be used in a particle formation process (such as a slurry or gas phase). Heterogeneous catalysts are not discrete compounds, but are produced by a reaction mixture of a metal compound and a precursor to form a complex, and the reaction mixture has multiple active sites on a certain form of particle. Polymers produced via homogeneous catalysts generally show a wider molecular weight distribution than homogeneous catalysts, and in the case of interpolymers, show a wider composition distribution. In an exemplary embodiment, the catalyst in the first reactor may be a different homogeneous catalyst with different reaction rates in the first reactor environment.

[0065] Bis(biphenyl phenoxy) catalyst is an example of a homogeneous catalyst. Other examples of homogeneous catalysts include constrained geometry catalysts or pyridine amine catalysts. Examples of heterogeneous catalysts may include heterogeneous Ziegler-Natta catalysts that are particularly useful at high polymerization temperatures for solution processes. Examples of such Ziegler-Natta catalysts are catalysts derived from organomagnesium compounds, alkyl halides or aluminum halides or hydrogen chloride and transition metal compounds. Examples of such catalysts are described in U.S. Patents No. 4,314,912 (Lowery, Jr et al.), No. 4,547,475 (Glass et al.) and No. 4,612,300 (Coleman, III), the teachings of which are incorporated herein by reference.

[0066] Particularly suitable organomagnesium compounds include, for example, hydrocarbon-soluble dihydrocarbylmagnesiums, such as dialkylmagnesiums and diarylmagnesiums. Exemplary suitable dialkylmagnesiums particularly include: n-butyl-sec-butylmagnesium, diisopropylmagnesium, di-n-hexylmagnesium, isopropyl-n-butylmagnesium, ethyl-n-hexylmagnesium, ethyl-n-butylmagnesium, di-n-octylmagnesium, and other dialkylmagnesiums in which the alkyl group has 1 to 20 carbon atoms. Exemplary suitable diarylmagnesiums include diphenylmagnesium, dibenzylmagnesium, and ditolylmagnesium. Suitable organomagnesium compounds include alkylmagnesium and arylmagnesium alkoxides and phenoxides and arylmagnesium and alkylmagnesium halides, more preferably halogen-free organomagnesium compounds.

[0067] The bis(biphenylphenoxy) catalyst is a multi-component catalyst system comprising a bis(biphenylphenoxy) procatalyst, a cocatalyst and further optional ingredients. The bis(biphenylphenoxy) procatalyst may comprise a metal-ligand complex according to formula (I):

[0068]

[0069] In formula (I), M is a metal selected from titanium, zirconium or hafnium, the metal having a formal oxidation state of +2, +3 or +4; n is 0, 1 or 2; when n is 1, X is a monodentate ligand or a bidentate ligand; when n is 2, each X is a monodentate ligand and is the same or different; the metal-ligand complex as a whole is electrically neutral; O is O (oxygen atom); each Z is independently selected from -O-, -S-, -N(R N )-or-P(R P )-; L is (C 1 -C 40 )alkylene or (C 1 -C 40 )heteroalkylene, wherein (C 1 -C 40 ) the alkylene group has a moiety (to which L is bonded) comprising a 1-carbon atom to a 10-carbon atom connecting main chain connecting the two Z groups in formula (I), or (C 1-C 40 ) heteroalkylene has a moiety comprising a 1-atom to 10-atom connecting backbone linking two Z groups in formula (I), wherein (C 1 -C 40 ) wherein each of the 1-atom to 10-atom connected main chain of the heteroalkylene group is independently a carbon atom or a heteroatom, wherein each heteroatom is independently O, S, S(O), S(O) 2 、Si(R C ) 2 , Ge(R C ) 2 , P(R C ) or N(R C ), where each R C Independently (C 1 -C 30 ) alkyl or (C 1 -C 30 ) heteroalkyl; R 1 and R 8 Independently selected from the group consisting of: (C 1 -C 40 ) alkyl, (C 1 -C 40 ) heteroalkyl, -Si(R C ) 3 , -Ge(R C ) 3 、-P(R P ) 2 、-N(R N ) 2 、-OR C 、-SR C 、-NO 2 、-CN、-CF 3 , R C S(O)-、R C S(O) 2 -、(R C ) 2 C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R N )-、(R N ) 2 NC(O)-, halogen and a group of formula (II), formula (III) or formula (IV):

[0070]

[0071] In formula (II), formula (III) and formula (IV), R 31-35, R 41-48 or R 51-59 Each of which is independently selected from (C 1 -C 40 ) alkyl, (C 1 -C 40 ) heteroalkyl, -Si(R C ) 3 , -Ge(R C ) 3 、-P(R P ) 2 、-N(R N ) 2 、-OR C 、-SR C 、-NO 2 、-CN、-CF 3 , R C S(O)-、R C S(O) 2 -、(R C ) 2 C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R N )-、(R N ) 2 NC(O)-, halogen or -H, provided that R 1 or R 8 At least one of the groups is a group having formula (II), formula (III) or formula (IV).

[0072] In formula (I), R 2-4 , R 5-7 and R 9-16 Each of which is independently selected from (C 1 -C 40 ) alkyl, (C 1 -C 40 ) heteroalkyl, -Si(R C ) 3 , -Ge(R C ) 3 、-P(R P ) 2 、-N(R N ) 2 -OR C 、-SR C 、-NO 2 、-CN、-CF 3 , R C S(O)-、R C S(O) 2 -、(RC ) 2 C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R N )-、(R C ) 2 NC(O)-, halogen, and -H.

[0073] Specific embodiments of the catalyst system will now be described. It should be understood that the catalyst system of the present disclosure can be embodied in different forms and should not be construed as being limited to the specific embodiments set forth in the present disclosure. On the contrary, embodiments are provided so that the present disclosure will be thorough and complete, and the embodiments will fully convey the scope of the subject matter to those skilled in the art.

[0074] The term "independently selected" is used herein to refer to R groups (such as R 1 , R 2 , R 3 , R 4 and R 5 ) can be the same or different (e.g., R 1 , R 2 , R 3 , R 4 and R 5 can be substituted alkyl, or R 1 and R 2 may be a substituted alkyl group and R 3 The use of the singular encompasses the use of the plural, and vice versa (e.g., a hexane solvent encompasses a plurality of hexanes). A named R group will generally have an art-recognized structure corresponding to the R group having that name. These definitions are intended to supplement and illustrate, but not to exclude, definitions known to those skilled in the art.

[0075] 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 the procatalyst in a manner that converts the procatalyst into a catalytically active catalyst. As used herein, the terms "procatalyst" and "activator" are interchangeable terms.

[0076] When used to describe certain chemical groups containing carbon atoms, the form "(C x -C y )" means that the unsubstituted form of the chemical group has x to y carbon atoms, including x and y. For example, (C 1 -C 40)alkyl is an alkyl group having 1 to 40 carbon atoms in unsubstituted form. In some embodiments and general structures, certain chemical groups may be substituted with one or more substituents such as RS. The parenthetical phrase "(C x -C y )" defined by R S Substituted versions may contain more than y carbon atoms, depending on the number of any group R S For example, "being only one group R S Replaced (C 1 -C 40 ) alkyl (where R S It is phenyl (-C 6 H 5 )”) can contain from 7 to 46 carbon atoms. Thus, in general, when the parenthetical phrase “(C x -C y )" is replaced by one or more substituents R containing carbon atoms. S When substituted, both x and y are added to the substituents R from all carbon atoms containing S The combined sum of the number of carbon atoms is used to determine the minimum and maximum total number of carbon atoms in a chemical group.

[0077] In some embodiments, each of the chemical groups (eg, X, R, etc.) of the metal-ligand complex of formula (I) may be unsubstituted, such that no R S In other embodiments, at least one of the chemical groups of the metal-ligand complex of formula (I) may independently contain one or more than one R S In some embodiments, 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 does not exceed 10. For example, if each R 1-5 By two R S Then X and Z cannot be replaced by R S In another embodiment, R in the chemical group of the metal-ligand complex of formula (I) S The total number of Rs may not exceed 5 S When two or more R S When bonded to the same chemical group of the metal-ligand complex of formula (I), each R S Independently bonded to the same or different carbon atoms or heteroatoms, and may include persubstitution of chemical groups.

[0078] The term "substituted" means that at least one hydrogen atom (-H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R S The term "fully substituted" means that each hydrogen atom (H) bonded to a carbon atom or heteroatom of the corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R S The term "polysubstituted" means that at least two but less than all hydrogen atoms bonded to carbon atoms or heteroatoms of the corresponding unsubstituted compound or functional group are replaced by substituents.

[0079] The term "-H" means a hydrogen or a hydrogen group covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless expressly specified otherwise.

[0080] The term “(C 1 -C 40 )hydrocarbyl" means a hydrocarbon group having 1 to 40 carbon atoms, and the term "(C 1 -C 40 )alkylene group" means a hydrocarbon diradical having 1 to 40 carbon atoms, wherein each hydrocarbon group and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, straight chain or branched, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic, including bicyclic; 3 or more carbon atoms) or acyclic, and is unsubstituted or replaced by one or more R S replace.

[0081] In the present disclosure, (C 1 -C 40 ) The hydrocarbon group may be unsubstituted or substituted (C 1 -C 40 ) alkyl, (C 3 -C 40 )cycloalkyl, (C 3 -C 20 )cycloalkyl-(C 1 -C 20 ) alkylene, (C 6 -C 40 ) aryl or (C 6 -C 20 )Aryl-(C 1 -C 20 In some embodiments, the aforementioned (C 1 -C 40 ) Each of the hydrocarbyl groups has a maximum of 20 carbon atoms (i.e., (C 1 -C 20 )alkyl), and in other embodiments, has up to 12 carbon atoms.

[0082] The term “(C1 -C 40 )alkyl" and "(C 1 -C 18 ) alkyl means a saturated straight or branched hydrocarbon group having 1 to 40 carbon atoms or 1 to 18 carbon atoms, respectively, which is unsubstituted or substituted with one or more R S Substituted. Unsubstituted (C 1 -C 40 Examples of alkyl groups are unsubstituted (C 1 -C 20 ) alkyl; unsubstituted (C 1 -C 10 ) alkyl; unsubstituted (C 1 -C 5 )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. Substituted (C 1 -C 40 Examples of alkyl groups are substituted (C 1 -C 20 ) alkyl, substituted (C 1 -C 10 ) alkyl, trifluoromethyl and [C 45 ] alkyl. The term "[C 45 ] alkyl" (with square brackets) means that there are up to 45 carbon atoms in the group (including substituents) and that, for example, each of the R S Replaced (C 27 -C 40 ) alkyl, the R S Yes (C 1 -C 5 ) alkyl. Each (C 1 -C 5 ) The alkyl group may be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl or 1,1-dimethylethyl.

[0083] The term “(C 6 -C 40 ) aryl" means an unsubstituted or substituted aryl having 6 to 40 carbon atoms (one or more R S ) substituted monocyclic, bicyclic or tricyclic aromatic hydrocarbon group, at least 6 to 14 carbon atoms of the aromatic hydrocarbon group are aromatic ring carbon atoms, and the monocyclic, bicyclic or tricyclic group includes 1, 2 or 3 rings respectively; wherein 1 ring is an aromatic ring, and 2 or 3 rings are independently condensed rings or non-condensed rings, and at least one of the 2 or 3 rings is an aromatic ring. Unsubstituted (C 6 -C 40) aryl groups are exemplified by unsubstituted (C 6 -C 20 ) aryl; unsubstituted (C 6 -C 18 )aryl; 2-(C 1 -C 5 )alkyl-phenyl; 2,4-bis(C 1 -C 5 ) alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; dicyclopentadienylphenyl; hexahydrodicyclopentadienylphenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene. Substituted (C 6 -C 40 ) aryl groups are exemplified by substituted (C 1 -C 20 ) aryl; substituted (C 6 -C 18 )aryl; 2,4-bis[(C 20 )alkyl]-phenyl; polyfluorophenyl; pentafluorophenyl; and fluoren-9-on-1-yl.

[0084] The term “(C 3 -C 40 )Cycloalkyl refers to a cycloalkyl having 3 to 40 carbon atoms which is unsubstituted or substituted with one or more R S Other cycloalkyl groups (e.g., (C x -C y )cycloalkyl) is defined in a similar manner as having x to y carbon atoms and being unsubstituted or substituted with one or more R S Substituted. Unsubstituted (C 3 -C 40 Examples of cycloalkyl groups are unsubstituted (C 3 -C 20 )cycloalkyl, unsubstituted (C 3 -C 10 )cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl. 3 -C 40 Examples of cycloalkyl groups are substituted (C 3 -C 20 )cycloalkyl, substituted (C 3 -C 10 )cycloalkyl, cyclopentanone-2-yl and 1-fluorocyclohexyl.

[0085] (C 1 -C 40 Examples of the alkylene group include unsubstituted or substituted (C 6 -C 40 ) arylene, (C 3-C 40 )cycloalkylene and (C 1 -C 40 ) alkylene (e.g., (C 1 -C 20 In some embodiments, the two radicals are on the same carbon atom (e.g., -CH 2 -) or located on adjacent carbon atoms (i.e., 1,2-diradicals), or separated by one, two, or more than two intervening carbon atoms (e.g., 1,3-diradicals, 1,4-diradicals, etc.). Some diradicals include α,ω-diradicals. α,ω-diradicals are diradicals with the largest carbon backbone spacing between radical carbons. (C 2 -C 20 Some examples of alkylene α,ω-diyl radicals include ethane-1,2-diyl (ie, -CH 2 CH 2 -), propane-1,3-diyl (i.e., -CH 2 CH 2 CH 2 -), 2-methylpropane-1,3-diyl (i.e., -CH 2 CH(CH 3 )CH 2 -). (C 6 -C 40 Some examples of arylene α,ω-diyl include phenyl-1,4-diyl, naphthalene-2,6-diyl, or naphthalene-3,7-diyl.

[0086] The term “(C 1 -C 40 ) Alkylene means an unsubstituted or substituted group having 1 to 40 carbon atoms. S Substituted saturated straight or branched chain divalent groups (i.e., the divalent groups are not on ring atoms). Unsubstituted (C 1 -C 40 An example of an alkylene group is an unsubstituted (C 1 -C 20 ) alkylene, including unsubstituted -CH 2 CH 2 -、-(CH 2 ) 3 -、-(CH 2 ) 4 -、-(CH 2 ) 5 -、-(CH 2 ) 6 -、-(CH 2 ) 7 -、-(CH 2 ) 8 -、-CH 2C*HCH 3 and -(CH 2 ) 4 C*(H)(CH 3 ), wherein "C*" represents a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl group. 1 -C 40 An example of an alkylene group is a substituted (C 1 -C 20 )alkylene, -CF 2 -, -C(O)- and -(CH 2 ) 14 C(CH 3 ) 2 (CH 2 ) 5 - (i.e., 6,6-dimethyl-substituted n-1,20-eicosene). As mentioned above, the two R S can be combined to form (C 1 -C 18 ) alkylene, substituted (C 1 -C 40 Examples of the alkylene group 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.

[0087] The term “(C 3 -C 40 ) Cycloalkylene means a cycloalkylene group having 3 to 40 carbon atoms which is unsubstituted or substituted with one or more R S Substituted cyclic diradicals (ie, the diradical is on a ring atom).

[0088] 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 )-, where each R C and each R P is unsubstituted (C 1 -C 18 )alkyl or -H, and each R Nis unsubstituted (C 1 -C 18 )hydrocarbon. The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more carbon atoms are replaced by heteroatoms. 1 -C 40 )heteroalkyl" means a heteroalkyl group having 1 to 40 carbon atoms, and the term "(C 1 -C 40 The term "heteroalkylene" means a heteroalkyl diradical having from 1 to 40 carbon atoms, each of which has one or more heteroatoms. The radical of the heteroalkyl group is located on a carbon atom or a heteroatom, and the diradical of the heteroalkyl group can be located on: (1) one or two carbon atoms, (2) one or two heteroatoms, or (3) both carbon atoms and heteroatoms. Each (C 1 -C 40 ) heteroalkyl and (C 1 -C 40 ) heteroalkylene can be unsubstituted or substituted with (one or more R S ) substituted, aromatic or non-aromatic, saturated or unsaturated, linear or branched, cyclic (including mono- and polycyclic, fused and non-fused polycyclic) or acyclic.

[0089] (C 1 -C 40 ) The heteroalkyl group may be unsubstituted or substituted. 1 -C 40 Non-limiting examples of heteroalkyl groups include: 1 -C 40 ) heteroalkyl, (C 1 -C 40 )alkyl-O-, (C 1 -C 40 )alkyl-S-, (C 1 -C 40 )alkyl-S(O)-, (C 1 -C 40 )alkyl-S(O) 2 -、(C 1 -C 40 )alkyl-Si(R C ) 2 -、(C 1 -C 40 )alkyl-N(R N )-、(C 1 -C 40 )alkyl-P(R P )-、(C 2 -C 40 ) heterocycloalkyl, (C 2 -C 19 )heterocycloalkyl-(C1 -C 20 ) alkylene, (C 3 -C 20 )cycloalkyl-(C 1 -C 19 ) heteroalkylene, (C 2 -C 19 )heterocycloalkyl-(C 1 -C 20 ) heteroalkylene, (C 1 -C 50 ) heteroaryl, (C 1 -C 19 )heteroaryl-(C 1 -C 20 ) alkylene, (C 6 -C 20 )Aryl-(C 1 -C 19 )heteroalkylene or (C 1 -C 19 )heteroaryl-(C 1 -C 20 ) heteroalkylene.

[0090] The term “(C 1 -C 40 ) heteroaryl" means an unsubstituted or substituted (one or more R S ) substituted monocyclic, bicyclic or tricyclic heteroaromatic hydrocarbon groups, and the monocyclic, bicyclic or tricyclic groups include 1, 2 or 3 rings respectively; wherein 2 or 3 rings are independently fused or non-fused, and at least one of the 2 or 3 rings is heteroaromatic. Other heteroaryl groups (for example, usually (C x -C y ) heteroaryl, such as (C 1 -C 12 ) heteroaryl) is defined in a similar manner as having x to y carbon atoms (e.g., 1 to 12 carbon atoms) and being unsubstituted or substituted with one or more than one R Ssubstituted. The monocyclic heteroaromatic hydrocarbon group is a 5-membered or 6-membered ring. The 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 groups are: pyrrol-1-yl; piperidin-2-yl; furan-3-yl; thien-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. The 6-membered ring has 6 minus h carbon atoms, where h is the number of heteroatoms and can be 1 or 2, and the heteroatoms can be N or P. Examples of 6-membered ring heteroaromatic hydrocarbon groups are pyridin-2-yl; pyrimidin-2-yl; and pyrazin-2-yl. Bicyclic heteroaromatic hydrocarbon groups can be fused 5,6- or 6,6-ring systems. Examples of fused 5,6-ring system bicyclic heteroaromatic hydrocarbon groups are indol-1-yl; and benzimidazol-1-yl. Examples of fused 6,6-ring system bicyclic heteroaromatic hydrocarbon groups are quinolin-2-yl; and isoquinolin-1-yl. Bicyclic heteroaromatic hydrocarbon groups can be fused 5,6,5-ring systems; 5,6,6-ring systems; 6,5,6-ring systems; or 6,6,6-ring systems. Examples of fused 5,6,5-ring systems are 1,7-dihydropyrrolo[3,2-f]indol-1-yl. Examples of fused 5,6,6-ring systems are 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 acridin-9-yl.

[0091] The aforementioned heteroalkyl group may be 1 -C 40 ) carbon atoms or less and one or more heteroatoms. Similarly, heteroalkylene can be a saturated straight or branched chain diradical containing 1 to 50 carbon atoms and one or more heteroatoms. The heteroatoms defined above may 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, SR C , S(O) and S(O)2 , wherein each of heteroalkyl and heteroalkylene is unsubstituted or substituted with one or more R S replace.

[0092] Unsubstituted (C 2 -C 40 ) Examples of heterocycloalkyl groups are unsubstituted (C 2 -C 20 ) heterocycloalkyl, unsubstituted (C 2 -C 10 ) heterocycloalkyl, aziridine-1-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-1-yl, tetrahydrothiophene-S,S-dioxide-2-yl, morpholin-4-yl, 1,4-dioxane-2-yl, hexahydroazepine -4-yl, 3-oxa-cyclooctyl, 5-thio-cyclononyl and 2-aza-cyclodecyl.

[0093] The term "halogen atom" or "halogen" refers to 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 the anionic form of a halogen atom: a fluoride ion (F - ), chloride ion (Cl - ), bromide ion (Br - ) or iodide ion (I - ).

[0094] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in groups containing heteroatoms) carbon-nitrogen double bonds, carbon-phosphorus double bonds, and carbon-silicon double bonds. S In the case of substitution, one or more double bonds and / or triple bonds may or may not be present in the substituent R. S The term "unsaturated" means containing 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, excluding any substituents that may be present in the R S Such double bonds may be present in (hetero)aromatic rings (if any).

[0095] In some embodiments, the catalyst system comprising the metal-ligand complex of formula (I) can be catalytically active by any technique known in the art for activating a metal catalyst for olefin polymerization. For example, the catalyst system comprising the metal-ligand complex of formula (I) can be catalytically active by contacting the complex with an activating cocatalyst or combining the complex with an activating cocatalyst. Activating cocatalysts suitable for use herein include alkylaluminums; polymeric or oligomeric aluminoxanes (also referred to 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 aforementioned activating cocatalysts and techniques are also contemplated. The term "alkylaluminum" means a monoalkylaluminum dihydride or a monoalkylaluminum dihalide, a dialkylaluminum hydride or a dialkylaluminum halide, or a trialkylaluminum. Examples of polymeric or oligomeric aluminoxanes include methylaluminoxane, methylaluminoxane modified with triisobutylaluminum, tri-n-octylaluminum modified with methylaluminoxane isobutylaluminoxane.

[0096] The Lewis acid activator (cocatalyst) comprises 1 to 3 (C 1 -C 20 In one embodiment, the Group 13 metal compound is a tri(hydrocarbyl)-substituted aluminum, a tri(hydrocarbyl)-boron compound, a tri(C 1 -C 10 )alkyl)aluminum, tri((C 6 -C 18 ) aryl) boron compounds and halogenated (including perhalogenated) derivatives thereof. In other embodiments, the Group 13 metal compound is tri(fluoro-substituted phenyl) borane, tri(pentafluorophenyl) borane. In some embodiments, the activating cocatalyst is tetra((C 1 -C 20 ) alkyl borate (e.g., trityl tetrafluoroborate) or tris((C 1 -C 20 )alkyl)ammoniumtetra((C 1 -C 20 )alkyl)borane (e.g., bis(octadecyl)methylammoniumtetra(pentafluorophenyl)borane). As used herein, the term "ammonium" refers to a nitrogen cation that is ((C 1 -C 20 )alkyl) 4 N + 、((C 1 -C 20 )alkyl) 3 N(H) + 、((C 1 -C 20 )alkyl) 2N(H) 2 + , (C 1 -C 20 )Hydrocarbon N(H) 3 + or N(H) 4 + , where there are two or more (C 1 -C 20 ) hydrocarbon groups, they may be the same or different.

[0097] The combination of neutral Lewis acid activators (cocatalysts) comprises a mixture comprising tri((C 1 -C 4 )alkyl)aluminum and tri((C 6 -C 18 In some embodiments, the present invention provides a combination of a neutral Lewis acid mixture with a polymeric or oligomeric aluminoxane and a combination of a single neutral Lewis acid, especially tris(pentafluorophenyl)borane, with a polymeric or oligomeric aluminoxane. The molar ratio of (metal-ligand complex): (tris(pentafluorophenyl)borane): (aluminoxane) [e.g., (Group 4 metal-ligand complex): (tris(pentafluorophenyl)borane): (aluminoxane)] is 1:1:1 to 1:10:30, and in other embodiments is 1:1:1.5 to 1:5:10.

[0098] The catalyst system including the metal-ligand complex of formula (I) can be activated to form an active catalyst composition by combining with one or more cocatalysts (e.g., a cation-forming cocatalyst, a strong Lewis acid, or a combination thereof). Suitable activating cocatalysts include polymeric or oligomeric aluminoxanes (especially methylaluminoxane) and inert, compatible, non-coordinating ion-forming compounds. Exemplary suitable cocatalysts include, but are not limited to, modified methylaluminoxane (MMAO), bis(hydrogenated tallow alkyl) methyl, tetrakis(pentafluorophenyl)borate (1 - ) amines and combinations thereof.

[0099] In some embodiments, one or more of the aforementioned activating co-catalysts are used in combination with each other. A particularly preferred combination is three (C 1 -C 4 )alkyl)aluminum, tri((C 1 -C 4) hydrocarbon) borane or ammonium borate and a mixture of oligomeric or polymeric aluminoxane compounds. The ratio of the total moles of one or more metal-ligand complexes of formula (I) to the total moles of one or more activating cocatalysts is 1:10,000 to 100:1. In some embodiments, the ratio is at least 1:5000, in some other embodiments, at least 1:1000; and 10:1 or less, and in some other embodiments, 1:1 or less. When aluminoxane is used alone as an activating cocatalyst, the moles of aluminoxane employed are preferably at least 40 times the moles of the metal-ligand complex of formula (I). When tris(pentafluorophenyl)borane is used alone as an activating cocatalyst, in some other embodiments, the moles of tris(pentafluorophenyl)borane employed to the total moles of one or more metal-ligand complexes of formula (I) is 0.5:1 to 10:1, 1:1 to 6:1 or 1:1 to 5:1. The remaining activating co-catalyst 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).

[0100] Various solvents are contemplated, for example, aromatic solvents and paraffinic solvents. Exemplary solvents include, but are not limited to, isoparaffins. For example, such isoparaffin solvents can be purchased from ExxonMobil Chemical under the name ISOPAR E.

[0101] The reaction rate is determined by the polymerization process of ethylene and C 3 -C 12 The selectivity of the α-olefin comonomer is determined by the difference between the polymerization rate (i.e., selectivity) of the α-olefin comonomer and the polymerization catalyst. 3 -C 12 In some embodiments, the steric interaction of the polymerization catalyst results in a more selective polymerization of ethylene than an α-olefin (i.e., the catalyst preferentially polymerizes ethylene in the presence of an α-olefin). Again, without being bound by theory, it is believed that such steric interaction causes the catalyst (e.g., a homogeneous catalyst prepared with or from a metal-ligand complex of formula (I)) to adopt a conformation that substantially makes it easier for ethylene to approach M, or to adopt a conformation that is more reactive, or both (compared to a catalyst that allows an α-olefin to approach M or react).

[0102] A terminal copolymerization model is used for random copolymers in which the properties of the last monomer inserted determine the rate of subsequent monomer insertion. In this model, the type of insertion reaction is

[0103]

[0104] Among them C * Represents catalyst, Mi represents monomer i, and k ij is the rate constant with the following rate equation.

[0105] R pij =k ij […M i C * ][M j ](Equation B)

[0106] The comonomer mole fraction (i=2) in the reaction medium is defined by the following equation:

[0107]

[0108] A simplified equation for comonomer composition can be derived as disclosed in George Odian, Principles of Polymerization, 2nd Edition, John Wiley and Sons, 1970, as follows:

[0109]

[0110] For 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:

[0111]

[0112] Also for this model, the polymer composition is simply a function of the temperature-dependent reactivity ratio and the mole fraction of the comonomer in the reactor. This is also true when reverse comonomer or monomer insertion may occur, or in cases where more than two monomers are copolymerized.

[0113] Well-known theoretical techniques can be used to predict the reaction rates used in the aforementioned models, or empirically derived from actual polymerization data. Suitable theoretical techniques have been disclosed, for example, BG Kyle, Chemical and Process Thermodynamics, 3rd edition, Prentice-Hall, 1999; and Redlich-Kwong-Soave (RKS) equation of state, Chemical Engineering Science, 1972, pp. 1197-1203. Commercially available software programs can be used to help derive reactivity ratios from experimentally derived data. An example of such software is Aspen Plus from Aspen Technology, Inc., Ten Canal Park, Cambridge, Massachusetts 02141-2201, USA.

[0114] membrane

[0115] The polyethylene composition according to the embodiments disclosed herein can be incorporated into the film. In some embodiments, such films are biaxially oriented. In some embodiments, such films are biaxially oriented using a tenter. In some embodiments, such films are uniaxially oriented in the longitudinal direction. In some embodiments, the uniaxially oriented film includes the polyethylene composition disclosed herein. The oriented film uses a polyethylene composition in at least one layer, and the composition can advantageously expand the operating window to stretch the film. For example, by expanding the operating window to carry out biaxial orientation, the polyethylene composition can be oriented, thereby causing the film stiffness to improve. In some embodiments, the oriented film can be used for packaging applications, and can be used as a lidding film or a label film.

[0116] In one aspect, the biaxially oriented film comprises at least one layer comprising a polyethylene composition comprising:

[0117] (a) 15 weight percent to 25 weight percent of a first polyethylene component having a molecular weight (Mw) greater than 200,000 g / mol and a density from 0.925 g / cc to 0.945 g / cc;

[0118] (b) 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; and

[0119] (c) 40 weight percent to 65 weight percent of a third polyethylene component, the third polyethylene component having a molecular weight (Mw) of less than 100,000 g / mol and a density of 0.940 g / cc to 0.965 g / cc; and

[0120] The polyethylene composition has a density of 0.935 g / cc to 0.958 g / cc, a melt index (I) of 0.5 g / 10 min to 5.0 g / 10 min, and a 2 ), and satisfies the following equation:

[0121] Weight fraction of first polyethylene component × SCB logMw4-5 ×Mz (conventional GPC)>230,000.

[0122] In some embodiments, the biaxially oriented film is a multilayer film. The number of layers in the film can depend on many factors, including, for example, the desired film properties, the desired film thickness, the content of other layers of the film, the end-use application of the film, the equipment that can be used to make the film, etc. For example, depending on the application, the multilayer film may also include other layers that are typically included in multilayer films, including, for example, sealant layers, barrier layers, tie layers, structural layers, etc. In various embodiments, the multilayer film may include up to 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11 layers.

[0123] In various embodiments, the other layers within the multilayer films of the present invention may include a polymer selected from the group consisting of the polyethylene compositions described herein, LLDPE, MDPE, LDPE, HDPE, HMWHDPE (high molecular weight HDPE), propylene-based polymers, polyolefin plastomers (POPs), polyolefin elastomers (POEs), olefin block copolymers (OBCs), 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.

[0124] In some embodiments, the biaxially oriented film is oriented in the machine direction at a stretch ratio of 2: 1 to 9: 1 and in the transverse direction at a stretch ratio of 2: 1 to 11: 1. In some embodiments, the biaxially oriented film is oriented in the machine direction at a stretch ratio of 2: 1 to 6: 1 and in the transverse direction at a stretch ratio of 2: 1 to 9: 1. In some embodiments, the biaxially oriented film is oriented in the machine direction at a stretch ratio of 4: 1 to 6: 1 and in the transverse direction at a stretch ratio of 6: 1 to 9: 1.

[0125] In some embodiments, the biaxially oriented film has a thickness of 5 microns to 50 microns.

[0126] In some embodiments, the biaxially oriented film further comprises an outer layer that is a sealant layer.

[0127] The biaxially oriented films disclosed herein can have desirable properties. For example, in some embodiments, the biaxially oriented films have at least one of the following: a haze value of less than 15%; a 2% secant modulus in the longitudinal direction of at least 600 MPa; a 2% secant modulus in the transverse direction of at least 900 MPa; a transparency of at least 35%; a longitudinal tensile strain at break of at least 160%; and a transverse tensile strain at break of at least 20%.

[0128] In another aspect, the invention relates to articles, such as food packaging. In one aspect, an article comprises any of the inventive polyethylene compositions disclosed herein.

[0129] In another aspect, the 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, an article comprises any of the laminates disclosed herein.

[0130] In another aspect, the present invention relates to a uniaxially oriented film comprising at least one layer comprising a polyethylene composition comprising:

[0131] (a) 15 weight percent to 25 weight percent of a first polyethylene component having a molecular weight (Mw) greater than 200,000 g / mol and a density from 0.925 g / cc to 0.945 g / cc;

[0132] (b) 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; and

[0133] (c) 40 weight percent to 65 weight percent of a third polyethylene component, the third polyethylene component having a molecular weight (Mw) of less than 100,000 g / mol and a density of 0.940 g / cc to 0.965 g / cc; and

[0134] The polyethylene composition has a density of 0.935 g / cc to 0.958 g / cc, a melt index (I) of 0.5 g / 10 min to 5.0 g / 10 min, and a 2 ), and satisfies the following equation:

[0135] Weight fraction of first polyethylene component × SCB logMw4-5×Mz (conventional GPC)>230,000.

[0136] In some embodiments, the uniaxially oriented film is oriented in the longitudinal direction at a stretch ratio of 4:1 to 20:1. In some embodiments, the uniaxially oriented film is oriented in the longitudinal direction at a stretch ratio of 4:1 to 16:1. In some embodiments, the uniaxially oriented film is oriented in the longitudinal direction at a stretch ratio of 4:1 to 12:1. In some embodiments, the uniaxially oriented film is oriented in the longitudinal direction at a stretch ratio of 4:1 to 10:1. In some embodiments, the uniaxially oriented film is oriented in the longitudinal direction at a stretch ratio of 4:1 to 9:1.

[0137] It should be understood that in some embodiments, any layer within the film may further contain one or more additives known to those skilled in the art (as well as those described above for polyethylene-based compositions), such as antioxidants, UV stabilizers, heat stabilizers, slip agents, anti-blocking agents, pigments or colorants, processing aids, cross-linking catalysts, flame retardants, fillers, and blowing agents.

[0138] By being polyethylene-based, according to some embodiments of the present invention, the polyethylene composition of the present invention can be incorporated into multilayer films and articles, and the multilayer films and articles are mainly (if not substantially or entirely) composed of polyethylene, to provide films and articles that are easier to recycle. For example, the film mainly comprising polyethylene has improved recyclability characteristics, and other advantages that can be provided using such polymers. For example, in some embodiments, in addition to additives, the oriented film is completely composed of ethylene-based polymers. Based on the gross weight of the oriented film, the oriented film can be included in 90 % by weight of ethylene-based polymers in some embodiments, or 95 % by weight of ethylene-based polymers in some embodiments, or 99 % by weight of ethylene-based polymers in some embodiments, or 99.9 % by weight of ethylene-based polymers in some embodiments, or 100 % by weight of ethylene-based polymers in some embodiments.

[0139] Biaxially oriented films can have various thicknesses before orientation, depending on, for example, the number of layers, the intended use of the film, and other factors. In some embodiments, such polyethylene films have a thickness of 320 to 3200 microns (typically, 640-1920 microns) before orientation.

[0140] Prior to orientation, the film may be formed using techniques known to those skilled in the art based on the teachings herein. For example, the film may 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 those layers that can be coextruded, the layers may be coextruded as a blown film or a cast film using techniques known to those skilled in the art based on the teachings herein.

[0141] In various embodiments, the film may be uniaxially oriented or biaxially oriented using techniques known to those of ordinary skill in the art.

[0142] In some embodiments in which the film is biaxially 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, based on the teachings of this article, the film can be biaxially oriented using other techniques known to those skilled in the art such as a double bubble orientation process. Typically, a tenter frame sequential biaxial orientation method is used, and the tenter frame is combined as part of a multilayer coextrusion production line. After extrusion from a flat die, the film is cooled on a cooling roller and immersed in a water bath filled with room temperature water. The cast film is then transferred to a series of rollers with different rotation speeds to achieve stretching in the longitudinal direction. There are several pairs of rollers in the MD stretching section of the production line, and the several pairs of rollers are oil-heated. Pairs of rollers are sequentially used as preheating rollers, stretching rollers, and rollers for relaxation and annealing. The temperature of each pair of rollers is controlled separately. After stretching in the longitudinal direction, the film web is transferred to a tenter frame hot air oven with a heating zone to stretch in the transverse direction. The first several zones are used for preheating, the subsequent zones are used for stretching, and then the final zone is used for annealing.

[0143] In some embodiments, when the multilayer film is uniaxially oriented, the film is oriented only in the longitudinal direction. Based on the teachings herein, as known to those of ordinary skill in the art, various processing parameters are considered suitable for stretching in the longitudinal direction. For example, a uniaxially oriented multilayer film can be oriented in the longitudinal direction at a stretch ratio greater than 1:1 and less than 8:1, or a stretch ratio of 4:1 to 8:1.

[0144] In some embodiments, after orientation, the machine direction oriented film has a thickness of 5 microns to 50 microns. In some embodiments, the machine direction oriented film has a thickness of 15 microns to 40 microns.

[0145] In some embodiments, the oriented film can be corona treated, plasma treated, or printed using techniques known to those skilled in the art, depending on, for example, the end-use application. In some embodiments, the oriented multilayer film can be surface coated with aluminum, silicon oxide, aluminum oxide, or other metals known to those of ordinary skill in the art based on the teachings herein.

[0146] Laminate

[0147] Embodiments of the present invention also include laminates incorporating oriented films. In some embodiments, biaxially oriented films according to embodiments of the present invention can be laminated to another film. In some embodiments, uniaxially oriented (e.g., longitudinally oriented) multilayer polyethylene films according to embodiments of the present invention can be laminated to another film.

[0148] Laminates according to embodiments of the present invention can be formed using techniques known to those of ordinary skill in the art based on the teachings herein. For example, an oriented multilayer polyethylene film can be laminated to another film using an adhesive. It is believed that various adhesive compositions are suitable for adhesives for preparing laminates. These adhesives may include polyurethanes, epoxies, acrylics, etc. In one embodiment, the laminate may include an adhesive layer comprising a polyurethane adhesive. The polyurethane adhesive may be solvent-free, water-based, or solvent-based. In addition, the polyurethane adhesive may be a two-part formulation. The weight or thickness of the adhesive layer may depend on a variety of 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 is applied to up to 5.0 g / m 2 , or 1.0 to 4.0 g / m 2 , or 2.0 to 3.0 g / m 2 .

[0149] Laminates according to some embodiments of the present invention may also be formed by extrusion lamination.

[0150] Products

[0151] Embodiments of the invention also relate to articles, such as packaging, formed from the oriented multilayer polyethylene films of the invention (or from laminates incorporating such films) or incorporating such films. Such packaging may be formed from any film or laminate described herein.

[0152] The example of such articles can include flexible packaging, pouches, stand-up pouches and pre-made packaging or pouches. In some embodiments, the oriented multilayer polyethylene film or laminate of the present invention can be used for food packaging. The example of the food that can be included in such packaging includes meat, cheese, cereals, nuts, juice, sauces, etc. Based on the teachings of this paper and based on the specific use of packaging (for example, the type of food, the amount of food, etc.), such packaging can be formed using technology known to those skilled in the art.

[0153] Test Method

[0154] The test method includes the following aspects:

[0155] Melt index (I 2 ) and (I 10 )

[0156] Melt index (I) was measured at 190°C and 2.16 kg according to ASTM D1238. 2 ) value. Similarly, the melt index (I 10) value. The value is reported in g / 10min, which corresponds to the number of grams eluted per 10 minutes. These data for the overall polyethylene composition are collected and reported in Tables 2 and 3. The melt index (I) of the first polyethylene component, the second polyethylene component, and the third polyethylene component are calculated according to Equation 17 and the deconvolution method described below. 2 ) values ​​are shown in Table 4.

[0157] density

[0158] Density measurements were performed on the overall polyethylene composition according to ASTM D792 Method B. The data are reported in Tables 2 and 3. For the first polyethylene component and the second polyethylene component, density values ​​were obtained using Equation 15 and the deconvolution method described below. For the third polyethylene component, density values ​​were calculated using Equation 16. Density is expressed in grams per cubic centimeter (g / cc or g / cm 3 The individual component density data are reported in Table 4.

[0159] Conventional (Conv.) Gel Permeation Chromatography (GPC)

[0160] Chromatographic system is composed of PolymerChar GPC-IR (Valencia, Spain) high temperature GPC chromatograph equipped with internal IR5 infrared detector (IR5). The automatic sampler oven chamber is set to 160 degrees Celsius, and the column chamber is set to 150 degrees Celsius. The column used is 4 Agilent "Mixed A" 30cm 20 micron linear mixed bed columns. The chromatographic solvent used is 1,2,4 trichlorobenzene and contains 200ppm of butylated hydroxytoluene (BHT). The solvent source is nitrogen sparged. The injection volume used is 200 microliters, and the flow rate is 1.0 ml / min.

[0161] The GPC column set was calibrated with 21 narrow molecular weight distribution polystyrene standards ranging from 580 to 8,400,000 molecular weights and arranged in 6 "cocktail" mixtures with at least ten times intervals between individual molecular weights. Standards were purchased from Agilent Technologies. For molecular weights equal to or greater than 1,000,000, 0.025 g of polystyrene standards were prepared in 50 ml of solvent, and for molecular weights less than 1,000,000, 0.05 g of polystyrene standards were prepared in 50 ml of solvent. The polystyrene standards were pre-dissolved at 80°C with gentle stirring for 30 minutes, then cooled and the room temperature solution was transferred to a 160°C autosampler dissolution oven to cool for 30 minutes. Polystyrene standard peak molecular weights were converted to polyethylene molecular weights using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)):

[0162] M 聚乙烯 =A×(M 聚苯乙烯 ) B (Equation 1)

[0163] Where M is the molecular weight, A has a value of 0.4129, and B equals 1.0.

[0164] A fifth order polynomial was used to fit the calibration points for the corresponding polyethylene equivalents. Total plate counts for the GPC column set were performed with decane, which was introduced into the blank sample via a micropump controlled by the PolymerChar GPC-IR system. The plate count for the chromatography system should be greater than 18,000 for 4 Agilent "Mixed A" 30 cm 20 micron linear mixed bed columns.

[0165] The samples were prepared semi-automatically using the PolymerChar "Instrument Control" software, where the target weight of the sample was set to 2 mg / ml, and the solvent (containing 200 ppm BHT) was added to a septum-capped vial previously sparged with nitrogen via the PolymerChar high temperature autosampler. The samples were dissolved at 160 degrees Celsius for 2 hours under "slow" shaking.

[0166] Based on the GPC results, the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR spectrometer was used, according to Equations 2-4, using the PolymerChar GPCOne TMThe software was used to calculate the Mn of the baseline-subtracted IR chromatogram at each equidistant data collection point (i) and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve at point (i) according to Equation 1. (GPC) 、Mw (GPC) and Mz (GPC) Calculation.

[0167]

[0168] To monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate for each sample (Flow Rate (Nominal)) by comparing the RV of the corresponding decane peak in the sample (RV (FM Sample)) with the RV of the decane peak in the narrow standard calibration (RV (FM Calibrated)). Any changes in the decane marker peak time were then assumed to be related to a linear change in flow rate (Flow Rate (Effective)) throughout the run. After calibrating the system based on the flow marker peak, the effective flow rate (relative to the narrow standard calibration) was calculated as Equation 5. TM The software completes the processing of the flow marker peak. An acceptable flow rate correction is such that the effective flow rate should be within + / - 0.5% of the nominal flow rate. Flow rate (effective) = flow rate (nominal) x (RV (FM calibrated) / RV (FM sample))

[0169] (Equation 5)

[0170] GPC measurements were performed on both the overall polyethylene composition and the polymer sampled from the first reactor containing the first polyethylene component and the second polyethylene component.

[0171] Improved comonomer content analysis method (iCCD)

[0172] An improved method for comonomer content analysis (iCCD) was developed in 2015 (Cong and Parrott et al., WO2017040127A1). The iCCD test was performed with a Crystallization Elution Fractionator (CEF) (PolymerChar, Spain) equipped with an IR-5 detector (PolymerChar, Spain) and a two-angle light scattering detector model 2040 (Precision Detectors, now Agilent Technologies). Just before the IR-5 detector in the detector oven, a 5 cm or 10 cm (length) X 1 / 4" (ID) stainless steel guard column filled with 20 μm-27 μm glass (MoSCi Corporation, USA) was installed. Ortho-dichlorobenzene (US ODCB, 99% anhydrous or technical grade) was used. From the EMD Chemicals obtained silica gel 40 (particle size 0.2-0.5 mm, catalog number 10181-3) (previously used for drying ODCB solvent). The dried silica was filled into three empty HT-GPC columns to further purify ODCB as eluent. The CEF instrument was equipped with an automatic sampler with N2 sweep function. ODCB was bubbled with dry nitrogen (N2) for one hour before use. Sample preparation was performed with an automatic sampler at a concentration of 4 mg / ml (unless otherwise specified) at 160°C, under shaking, for 1 hour. The injection volume was 300 μl. The temperature profile of the iCCD was: crystallization from 105°C to 30°C at 3°C / min, thermal equilibrium at 30°C for 2 minutes (including the elution time of the soluble fraction set to 2 minutes), 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 was 0.50 ml / min. Data were collected at a rate of one data point per second.

[0173] The iCCD column was filled with gold-plated nickel particles (Bright7GNM8-NiS, Nippon Chemical Industrial Co.) in a stainless steel tube of 15 cm (length) X 1 / 4" (ID). The column was filled and conditioned according to references (Cong, R.; Parrott, A.; Hollis, C.; Cheatham, M. WO2017040127A1). The final pressure of the TCB slurry filling was 150 bar.

[0174] The column temperature was calibrated by using a reference material, linear homopolymer polyethylene (with zero comonomer content, melt index (I2) of 1.0, polydispersity Mw / Mn of about 2.6 by conventional gel permeation chromatography, 1.0 mg / ml) and a mixture of ODCB containing eicosane (2 mg / ml). The iCCD temperature calibration consisted of four steps: (1) calculation of the delay volume, which was defined as the temperature offset between the measured peak elution temperature of eicosane minus 30.00°C; (2) subtraction of the temperature offset of the elution temperature from the iCCD raw temperature data. It should be noted that this temperature bias is a function of experimental conditions, such as elution temperature, elution flow rate, etc.; (3) Create a linear calibration line that converts elution temperature in the range of 30.00°C and 140.00°C, so that the linear homopolymer polyethylene reference has a peak temperature at 101.0°C and eicosane has a peak temperature at 30.0°C; (4) For the soluble fraction measured isothermally at 30°C, according to reference (Cerk and Cong et al., US9,688,795), the elution temperature below 30.0°C is linearly extrapolated by using an elution heating rate of 3°C / min.

[0175] The relationship between the comonomer content and the elution temperature of the iCCD was constructed by using 12 reference materials (ethylene homopolymers and ethylene-octene random copolymers made with single-site metallocene catalysts, with ethylene equivalent weight average molecular weights ranging from 35,000 to 128,000). All of these reference materials were analyzed in the same manner as the previously specified 4 mg / mL. The reported elution peak temperature follows the elution temperature of the iCCD at octene mole % to R2 of 0.978 in the figure.

[0176] The molecular weight of the polymer and the molecular weight of the polymer fractions were determined directly from the LS detector (90 degree angle) and the concentration detector (IR-5) by assuming a shape factor of 1 and all virial coefficients equal to zero according to the Rayleigh-Gans-Debys approximation (Striegel and Yau, Modern Size Exclusion Liquid Chromatogram, pp. 242 and 263). The integration window was set to integrate the entire chromatogram over the elution temperature range (temperature calibration specified above) from 23.0°C to 120°C.

[0177] Calculating molecular weight (Mw) from iCCD includes the following steps: measuring the inter-detector bias. The offset is defined as the geometric volume offset between the LS detector relative to 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. It is converted into a temperature offset by using the elution heat rate and the elution flow rate. Linear high-density polyethylene (with zero comonomer content, melt index (I2) of 1.0, and a polydispersity Mw / Mn of about 2.6 by conventional gel permeation chromatography) is used. The same experimental conditions as the above-mentioned normal iCCD method are used, except for the following parameters: crystallization from 140°C to 137°C at 10°C / min, thermal equilibrium at 137°C for 1 minute as the soluble fraction elution time, the soluble fraction (SF) time is 7 minutes, and elution from 137°C to 142°C at 3°C / min. The flow rate during crystallization is 0.0ml / min. The flow rate during elution is 0.80ml / min. The sample concentration is 1.0mg / ml. Prior to integration, each LS data point in the LS chromatogram was shifted to correct for inter-detector bias. The baseline-subtracted LS and concentration chromatograms were integrated over the entire elution temperature range of step (1). The MW detector constant was calculated by using known MW HDPE samples in the range of 100,000 Mw to 140,000 Mw and the area ratio of the LS and concentration integrated signals. The Mw of the polymer was calculated by using the ratio of the integrated light scattering detector (90 degree angle) to the concentration detector and using the MW detector constant.

[0178] exist Molecular weight calculation and calibration were performed in the software.

[0179] iCCD measurements were performed on both the overall polyethylene composition and the polymer sampled from the first reactor containing the first polyethylene component and the second polyethylene component.

[0180] Numerical Deconvolution of Bivariate Data

[0181] The density, molecular weight (Mw), and melt index (I) of the first polyethylene component, the second polyethylene component, and the third polyethylene component were obtained using numerical deconvolution of the bivariate data. 2 ). Use Microsoft Solver (2018) performs combined iCCD-SCBD (wt from iCCD iCCD (T) versus temperature (T)) and GPC-MWD (wt from conventional GPC GPC For iCCD-SCBD, the calculated weight fraction (wt %) was obtained using the method described in the iCCD section (in the range of about 23 to 120 °C).总和，iCCD The temperature (T) data were reduced to approximately 200 equally spaced data points to strike a balance between adequate iteration speed and temperature resolution. A single or a series of (up to 3 peaks per component) exponentially modified Gaussian distributions (Eq. 6) were summed to represent each component (wt C,iCCD (T)), and sum the components to give the total weight (wt) at any temperature (T) 总和，iCCD (T)), as shown in Equations 7A-7D.

[0182]

[0183] Wherein, C means component (C = 1, 2 or 3), P means peak (P = 1, 2 or 3), a 0,C,P is the chromatographic area of ​​the Pth peak of the Cth component in °C, a 1,C,P is the peak center of the Pth peak of the Cth component in °C, a 2,C,P is the peak width of the Pth peak of the Cth component in °C, a 3,C,P is the peak tailing of the Pth peak of the Cth component in °C, and T is the elution temperature in °C. In the case of iCCD-SCBD using a single exponentially modified Gaussian distribution to represent the components, y T,C,2 =y T,C,3 = 0. In the case of iCCD-SCBD using two exponentially modified Gaussian distributions to represent the components, only y T,C,3 =0.

[0184]

[0185] wt 总和,iCCD (T) = wt C1,iCCD (T)+wt C2,iCCD (T)+wt C3,iCCD (T) (Equation 7D)

[0186] The weight fraction of each component (wf C,iCCD ) can be expressed as

[0187] wf C1,iCCD =∫wt C1 (T)dT (Equation 8A)

[0188] wf C2,iCCD =∫wt C2 (T)dT (Equation 8B)

[0189] wf C3,iCCD =∫wt C3 (T)dT (Equation 8C)

[0190] ∫wt 总和,iCCD (T)dT = 1.00 (Equation 8D)

[0191] where wf C1,iCCD is the weight fraction of the first polyethylene component obtained from iCCD-SCBD deconvolution, wf C2,iCCD is the weight fraction of the second polyethylene component obtained from iCCD-SCBD deconvolution, wf C3,iCCD is the weight fraction of the third polyethylene component obtained from iCCD-SCBD deconvolution, and the sum of the fractions was normalized to 1.00.

[0192] For GPC-MWD, the MWD obtained from the conventional GPC description section was imported into the same spreadsheet at 0.011 g (MW / (g / mol)) increments between 2.00 and 7.00 (501 data points in total). The following equation shows the molecular weight of the sample at a weight average molecular weight of M. w，目标 And the polydispersity (M w / M n ) is 2.0.

[0193]

[0194] lg(M i+1 / (g / mol))-lg(M i / (g / mol))=0.01 (Equation 11) where wt F-S,i is lg(M i / (g / mol))(M i g / mol), i is an integer ranging from 0 to 500 to represent each data point on the GPC-MWD plot, and the corresponding lg(M i / (g / mol)) is 2+0.01×i.

[0195] Then, use the i / (g / mol)) is the sum of a series of normal distributions broadening the Flory-Schulz distribution. i The weight fraction of the normal distribution with a peak at 2.5447 W / (g / mol)) remains the same as the original Flory-Schulz distribution. The broadened Flory-Schulz distribution curve can be described by the following equation. where wt GPC (lg(M i / (g / mol))) is lg(M i / (g / mol)), j is an integer in the range of 0 to 500, and σ is the standard deviation of the normal distribution. Therefore, the molecular weight distribution curves of all three components can be expressed as the following equation. The number average molecular weight (M) can be calculated based on the broadened Flory-Schulz distribution n(GPC) ), weight average molecular weight (M w(GPC) ) and MWD(M w(GPC) / M n(GPC) ).

[0196] wt 总和,GPC (lg(M i / (g / mol)))=wt C1,GPC (lg(Mi / (g / mol)))+wt C2,GPC (lg(M i / (g / mol)))+wt C3,GPC (lg(M i / (g / mol))) (Equation 13D)

[0197] Where σ is the normal distribution width parameter, and the subscripts C1, C2, and C3 represent the first polyethylene component, the second polyethylene component, and the third polyethylene component, respectively. C1,GPC 、wf C2,GPC and wf C3,GPC are the weight fractions of the first polyethylene component, the second polyethylene component and the third polyethylene component from GPC-MWD, respectively.

[0198] Each of the paired components (first polyethylene component (C1), second polyethylene component (C2), and third polyethylene component (C3)) from iCCD-SCBD and GPC-MWD is considered to have equivalent mass for its respective technique as shown in Eq. 14A-E.

[0199] wf C1,iCCD +wf C2,iCCD +wf C3,iCCD =1.00 (Equation 14A)

[0200] wf C1,GPC +wf C2,GPC +wf C3,GPC =1.00 (Equation 14B)

[0201] wf C1,iCCD =wf C1,GPC (Equation 14C)

[0202] wf C2,iCCD =wf C2,GPC (Equation 14D)

[0203] wf C2,iCCD =wf C2,GPC (Equation 14E)

[0204] The relative weight yield of each component can be preliminarily estimated using process and catalyst data (including catalyst efficiency and reactor mass balance). Alternatively, the initial estimate of the weight fraction of each component can be compared by integrating the local area of ​​the iCCD-SCBD or GPC-MWD drawing of the polyethylene composition (especially the visible area with defined peaks or peak inflection points). For example, if the separation is good, the peak area of ​​each component in the iCCD-SCBD curve can be estimated by making the vertical line between the peaks drop. Patents WO201913394A1 and WO2019133373A1 both provide examples of iCCD-SCBD curves. The entire contents of these disclosures are incorporated herein. The association of the molecular weight order with the initial estimate of the molecular weight can be obtained by the peak position of the associated component region in the iCCD-SCBD and iCCD-MW drawings, and it should be expected to be consistent with the GPC-CC measured value. 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 mapping.

[0205] Initial estimates of the peak elution temperature, width and tailing for each component in the iCCD-SCBD can be obtained from calibrations of the peak elution temperature, width and tailing using a series of standard single-site samples for which we have measured comonomer content weight percent by NMR. These calibrations can also inform the individual component comonomer content from the measured peak elution temperature.

[0206] Microsoft The solver is programmed to minimize the combination of wt 总和，GPC (lgM i ) and the measured GPC-MWD; and wt 总和，iCCD The sum of squares of the residuals between (T) and the measured iCCD-SCBD (where the sampling widths and areas of the two observed distributions are normalized relative to each other). When the GPC-MWD and iCCD-SCBD fits converge simultaneously, they are weighted equally. Initial estimates of weight fractions and peak widths in iCCD-SCBD and molecular weight targets for each component are used to make Microsoft The solver starts as described in this article.

[0207] By using exponential correction Gaussian (EMG) peak fitting and in extreme cases by using addition to describe a single component of multiple (up to 3) EMG peak compensation in iCCD distort the co-crystallization effect of peak shape. The component produced by a single site catalyst can be modeled by a single EMG peak. The component produced by a Ziegler-Natta catalyst can be modeled by 1,2 or 3 EMG peaks or have a long tail facing low temperature, thereby being sufficient to meet the single EMG peak of the Ziegler-Natta component with extremely high density and extremely low molecular weight target on iCCD-SCBD drawing. In all cases, only a single widened Flory-Schulz distribution (Equation 13A-Equation 13C) is used, and weight fraction is assigned to the relevant sum of one or more components in the EMG component from iCCD-SCBD model (Equation 14A-Equation 14E).

[0208] For the first polyethylene component and the second polyethylene component produced via a single site catalyst, GPC deconvolution is determined by the normal distribution width parameter (σ) of Eq. 13A, Eq. 13B. C1 or C2 ) is limited to between 0.000 and 0.170 (corresponding to a polydispersity of approximately 2.00 to 2.33). In these cases, for the third polyethylene component, M in Eq. w，目标 is constrained to be the minimum because it is targeted to be the minimum according to this specific reaction scheme. It should be noted that it is not constrained to be the minimum in all possible cases according to the desired performance targets of the blend in the combined resin reactor. iCCD At the temperature at which the component peaks of the first polyethylene component and the second polyethylene component are observed on the (T) versus temperature curve), the iCCD-MW plot (M w(iCCD) M in the temperature curve w(iCCD) It is observed that the two weight average molecular weights (M) of the first polyethylene component and the second polyethylene component w，目标 ) ranking (preliminary estimate). Therefore, the order of the molecular weights of the three components is well known. The reactor mass balance yields the mass percentage (Wf) of Eq. 13C for the third polyethylene component, or alternatively, it can be calculated from deconvolution using Eq. 13D based on the strength of the known distribution model of iCCD and GPC, and the total weight fractions must add up to 1 (Eq. 14A-Eq. 14E).

[0209] In general, it has been found that using Approximately 20 solver iterations will usually converge well on a solution. If the order of the peaks of the iCCD-MW plot is inconsistent with the measured molecular weight and the observed comonomer wt.% measured by GPC-CC, the data must be reconciled by changing the iteration starting point (temperature or logMW) or slightly changing the width and tail factors in Excel so that the iterations will continue to converge to a consistent solution between the measurements, or the resolution of the measurement must be increased, or additional peaks can be added to the iCCD-SCBD to better approximate the elution peak shape of the individual components. If such components are prepared separately, the components can be modeled a priori by several EMG distributions.

[0210] Additionally, the predicted M for iCCD-MW can be generated by using the GPC-MWD weight average molecular weight of each of the components multiplied by the weight fraction of each of the components observed at each point along the iCCD-SCBD plot. w(iCCD) Response. Predicted M w(iCCD) Need to be compared with the M measured in iCCD-MW plot w(iCCD) The measured M values ​​of the individual components from the iCCD-MW and iCCD-SCBD plots can also be used by plotting the comonomer incorporation as a function of elution temperature based on a series of known copolymer standards. w(iCCD) The predicted GPC-CC plot needs to be consistent with the measured GPC-CC.

[0211] The peak temperature versus density dependence of the iCCD-SCBD data was obtained using a series of linear ethylene polymer standard resins polymerized by single-site catalysts with a melt index (I 2 ) is about 1 g / 10 min, or by GPC, the nominal weight average molecular weight is about 105,000 g / mol, and by GPC, the polydispersity (or MWD) is less than 2.3. At least 10 standard resins of known comonomer content, density, and molecular weight in the density range of 0.87 g / cc to 0.96 g / cc are used. The peak temperature and density data are fit to a 5th order polynomial curve to obtain a calibration curve.

[0212] By fitting the peak width and peak tail versus temperature for the above resins to a linear line, the correlation of the peak width and peak tail versus peak temperature is similarly obtained, which is very useful for initial estimation during the deconvolution process.

[0213] In the inventive resins presented herein, the first polyethylene component and the second polyethylene component are represented directly from the iCCD-SCBD deconvoluted plot as the first two peaks between elution temperatures of 35°C and 90°C. The "original density" (density 原始 ). By using Equation 15, the density 原始 Density (in g / cc) corrected to account for the contribution of molecular weight (in g / mol) 真实 (in g / cc):

[0214] density 真实 = Density 原始 -0.254g / cc×[lg(M w(GPC) / (g / mol))-5.02]

[0215] (Equation 15)

[0216] Among them, M w(GPC) is the weight average molecular weight of the single components deconvoluted from GPC-MWD.

[0217] The density of the first polyethylene component can be determined based on the known density of the resin, the density of the first polyethylene component 真实 , the density of the second polyethylene component 真实 And the weight fraction of each component, the density of the third polyethylene component is calculated according to the following Equation 16.

[0218]

[0219] The melt index (I) of each polyethylene component 2 ) can be estimated from its weight average molecular weight by the following equation:

[0220] lg(I 2 / (g / 10min))=-3.759×lg(M w(GPC) / (g / mol))+18.9 (Equation 17)

[0221] Among them, M w(GPC) is the weight average molecular weight (in g / mol) of the single component deconvoluted from the GPC-MWD curve, and I 2 is the melt index (in g / 10 min). Note that the amount of long chain branching can change the factor. In addition, to determine product composition, direct sampling of a single reactor with a single catalyst, sampling of the first reactor of a tandem dual reactor configuration, or sampling of both reactors of a parallel dual reactor configuration under the same reactor conditions can be used to help determine the density, melt index (I) of each individual component of the polyethylene composition. 2), GPC-MWD and iCCD-SCBD, especially when the reaction is effectively terminated after the sampling point. This allows for better confirmation in cases where the peak positions of the first polyethylene component and the second polyethylene component cannot be adequately determined from the 3-component mixture.

[0222] Direct inspection and quantification by analytical cross-fractionation in a GPC-TREF (e.g., a PolymerChar CFC unit equipped with online light scattering (Valencia, Spain)) and employing a similar calibration in a bivariate space representing SCBD and molecular weight and calibrating the relationship to density can also be used to measure the amount of each of the components or to more accurately distinguish between each of the components, particularly for initial estimates or in cases where high co-crystallization or low resolution / differentiation of materials may occur, particularly in the 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, Vol. 257, 2007, pp. 13-28. A. Ortín, B. Monrabal, J. Sancho-Tello) Adequate resolution must be obtained in both 1 g MW and temperature space and should be verified by direct composition ratio methods (e.g. IR-5 and light scattering molecular weight measurements). See 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, Vol. 330, 2013, pp. 63-80, A. Ortín, J. Montesinos, E. López, P. del Hierro, B. Monrabal, JR Torres-Lapasió, MC García- -Coque. Deconvolution of the components must use a similar set of equations and similar calibrations examined with a range of single-site resins and resin blends.

[0223] Branching measurement

[0224] SCB logMw4-5 (The average short chain branching level of log(Mw) is between 4.0 and 5.0) The composition was tested using GPC. The GPC system consisted of a 150°C high temperature chromatograph equipped with a Polymer Char IR-5 infrared detector, a dual angle light scattering detector (Agilent 1260) and a differential viscometer from Polymer Char. Four PL mixed A columns (7.5 mm x 300 mm) commercially available from Agilent 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) (such as commercially available from Sigma-Aldrich) were obtained. Eight hundred milligrams of BHT were added to four liters of TCB. TCB containing BHT is now referred to as "TCB". Sample preparation was performed with an autosampler at 2 mg / mL at 160°C for 3 hours. The injection volume was 200 ml. The temperature of the GPC was 150°C and the flow rate was 1 mL / min. The GPC was calibrated using a series of narrow molecular weight (Mw) polystyrene standards.

[0225] The GPC column set was calibrated with 21 narrow molecular weight distribution polystyrene standards ranging from 580 to 9,835,000 in a six-cocktail mixture arrangement with at least ten times of separation between individual molecular weights. A fifth-order polynomial was used to fit the corresponding polyethylene equivalent calibration points. The polystyrene standard peak molecular weights were converted to polyethylene molecular weights.

[0226] The composition and MWD were measured using an IR-5 infrared detector. The composition detector was calibrated using a series of copolymer standards with different comonomer levels. 13 NMR obtained the weight % comonomer levels of these samples. For each standard, the composition-related signals were collected and labeled as "measurement", "methylene" (CH 2 ) and "methyl" (CH 3 ). When performing molecular weight calibration, the "measurement" signal is used as the concentration signal, while the ratio of the "methyl" signal to the "methylene" signal is used for composition calculations. A graph of the comonomer weight % from NMR versus these ratios for a series of standards is plotted. Linear regression of the data results in a good fit of the data set. The comonomer weight % data can be converted to short chain branching in 1000 total carbon (SCB / 1000C).

[0227] Mw is the weight average molecular weight. logMw is the logarithm of the weight average molecular weight. logMw is the weight fraction of the moiety at a specific logMw. logMw is the short chain branching per 1000 carbons of the moiety at a specific logMw. The SCB in (SCB / 1000C) is calculated by the following equation: logMw4-5 :

[0228]

[0229] Haze

[0230] Haze was measured according to ASTM D1003 using a BYK Gardner haze meter.

[0231] transparency

[0232] Transparency was measured according to ASTM D1746.

[0233] Membrane stretching measurements

[0234] The tensile modulus (including machine direction (MD) modulus and transverse direction (TD) modulus) was measured according to the 2% secant modulus in ASTM D882. The tensile strain at break was measured according to ASTM D882.

[0235] Some embodiments of the present invention will now be described in detail in the following examples.

[0236] Example

[0237] Table of catalyst components for synthesizing polyethylene compositions

[0238] The synthetic procedures for the synthesis of the following metal-ligand complexes V and VI can be found in the following patent publications: WO2022015368A1 and WO2016014749A1, which are incorporated herein.

[0239]

[0240]

[0241] Polyethylene composition 1 of the present invention (Poly.1), polyethylene composition 2 of the present invention (Poly.2) and comparative polyethylene composition Production of C-Poly.3

[0242] Before being introduced into the reaction environment, all raw materials (monomers and comonomers) and process solvents (high-purity paraffin and cycloparaffin solvents with narrow boiling range) are purified with molecular sieves. High-purity hydrogen is supplied by a common pipeline and dried with molecular sieves. Reactor monomer feed stream is pressurized to greater than reaction pressure via a mechanical compressor. Solvent feed is pressurized to greater than reaction pressure via a pump. Comonomer feed is pressurized to greater than reaction pressure via a pump. Individual catalyst components are manually diluted in batches with purified solvent and pressurized to greater than reaction pressure. All reaction feed flows are measured with mass flow meters and independently controlled with metering pumps.

[0243] A dual series reactor configuration was used.

[0244] The first continuous solution polymerization reactor consists of a full liquid, nearly adiabatic and continuous stirred tank reactor (CSTR). It is possible to independently control all solvents, monomers, comonomers, hydrogen and catalyst component feeds. The temperature of the total feed stream (solvent, monomer, comonomer and hydrogen) entering the reactor is controlled by passing the feed stream through a heat exchanger. The total feed entering the polymerization reactor is injected into the reactor at one location. The catalyst component is injected into the polymerization reactor separately from other feeds. The computer controls the main catalyst component feed to maintain the reactor monomer conversion rate at a specified target. The second catalyst component feed is set to a specified molar ratio with the total catalyst (catalyst-B molar ratio = (catalyst-B) mol / (catalyst-A+catalyst-B) mol×100). Boron-containing cocatalyst components are fed based on a specified molar ratio with the total catalyst metal (primary + secondary) fed to the reactor. Feed Al-containing cocatalyst components to maintain a specified concentration of Al in the reactor. The agitator in the reactor is responsible for the continuous mixing of the reactants. The oil bath provides some fine tuning of reactor temperature control and does allow a certain amount of heat transfer from / into the reactor, allowing for deviation from adiabatic reactor behavior.

[0245] The effluent from the first polymerization reactor exits the first reactor and is added to the second reactor separately from the other feeds entering the second reactor.

[0246] The second continuous solution polymerization reactor consists of a full liquid, nearly adiabatic and continuous stirred tank reactor (CSTR). It is possible to independently control all solvents, monomers, comonomers, hydrogen and catalyst component feeds. The total feed flow (solvent, monomer, comonomer and hydrogen) temperature entering the reactor is controlled by passing the feed stream through a heat exchanger. The total feed entering the polymerization reactor is injected into the reactor at one position. The catalyst component is separated from other feeds and injected into the polymerization reactor. The computer controls the main catalyst component feed to maintain the reactor monomer conversion under the specified target. The cocatalyst component is fed based on the specified molar ratio with the main catalyst component. The agitator in the reactor is responsible for the continuous mixing of the reactants. The oil bath provides some fine tuning of the reactor temperature control and does allow a certain amount of heat transfer from / into the reactor, thereby allowing deviation from the adiabatic reactor behavior.

[0247] In all reactor configurations, the second / final reactor effluent enters a zone where it is deactivated by the addition and reaction of a suitable reagent (usually water). At this same reactor outlet location, other additives may also 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 (usually the acid scavenger calcium stearate).

[0248] After catalyst deactivation and addition of any 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 separated polymer melt is pelletized and collected. Table 1A below provides reactor information for the following productions: Poly.1, Poly.2, and C-Poly.3

[0249] Table 1A - Reactor information for: Poly.1, Poly.2, C-Poly.3

[0250]

[0251]

[0252] The polyethylene composition 3 of the present invention (Poly.3), the polyethylene composition 4 of the present invention (Poly.4), the comparative polyethylene composition Production of Polyethylene Composition 1 (C-Poly.1) and Comparative Polyethylene Composition 2 (C-Poly.2)

[0253] All raw materials (monomers and comonomers) and process solvents (narrow boiling range high purity isoparaffin solvent, Isopar-E) were purified with molecular sieves before introduction into the reaction environment. Hydrogen was supplied under pressure in high purity grades without further purification. The reactor monomer feed stream was pressurized to greater than the reaction pressure via a mechanical compressor. The solvent and comonomer feeds were pressurized to greater than the reaction pressure via a pump. Individual catalyst components were manually diluted in batches with purified solvents and pressurized to greater than the reaction pressure. All reaction feed streams were measured with mass flow meters and independently controlled with computer automated valve control systems.

[0254] Two reactor systems are used in a series configuration. The first continuous solution polymerization reactor is composed of a non-adiabatic isothermal circulating loop reactor full of liquid that simulates a continuous stirred tank reactor (CSTR) with heat removal. All fresh solvents, monomers, comonomers, hydrogen and catalyst component feeds can be controlled independently. By passing the feed stream through a heat exchanger, the total fresh feed stream (solvent, monomer, comonomer and hydrogen) to the first reactor is temperature-controlled to maintain a single solution phase. The total fresh feed to each polymerization reactor is injected into the reactor at three locations, wherein there is a roughly equal reactor volume between each injection position. The fresh feed is controlled by each ejector that receives one-third of the total fresh feed mass flow. The catalyst component is injected into the polymerization reactor at two different locations, wherein the reactor volume between each injection position is similar and each injection receives half of the total flow. The computer controls the main catalyst component feed to maintain the reactor monomer conversion under a specified target. The second catalyst component feed is set to a specified molar ratio with the total catalyst (catalyst-B molar ratio = (catalyst-B) mol / (catalyst-A + catalyst-B) mol × 100). The boron-containing co-catalyst component is fed based on a specified molar ratio with the total catalyst metal (primary + secondary) fed to the reactor. The Al-containing co-catalyst component is fed to maintain a specified concentration of Al in the reactor. Immediately after each reactor feed or catalyst injection position, the material flow is mixed with the circulating polymerization reactor contents with a static mixing element. The contents of the reactor are continuously circulated through a heat exchanger, which is responsible for removing a large amount of reaction heat, and the temperature on the coolant side is responsible for maintaining the isothermal reaction environment at a specified temperature. Circulation around the reactor loop is provided by a pump. There is a sample system to collect material from the first loop reactor at regular intervals. After collection, the samples are dried in a vacuum oven and submitted for GPC and iCCD analysis. GPC and iCCD analysis provide a measure of the polymer split between the primary and secondary catalysts in the first reactor loop; the results can be used to adjust the secondary catalyst molar ratio to achieve the desired polymer split within the first reactor loop.

[0255] 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.

[0256] The second continuous solution polymerization reactor is composed of a non-adiabatic isothermal circulating loop reactor full of liquid that simulates a continuous stirred tank reactor (CSTR) with heat removal. All fresh solvents, monomers, comonomers, hydrogen and catalyst component feeds can be controlled independently. By passing the feed stream through a heat exchanger, the total fresh feed stream (solvent, monomer, comonomer and hydrogen) to the second reactor is temperature-controlled to maintain a single solution phase. The total fresh feed to each polymerization reactor is injected into the reactor at two locations, wherein there is a roughly equal reactor volume between each injection position. The fresh feed is controlled by receiving half of the total fresh feed mass flow rate with each injector. The catalyst component is injected into the polymerization reactor by an injection insertion tube. The computer controls the main catalyst component feed to maintain the reactor monomer conversion under a specified target. The cocatalyst component is fed based on a specified molar ratio with the main catalyst component. Immediately after each reactor feed and catalyst injection position, the material flow is mixed with the circulating polymerization reactor content with a static mixing element. The contents of each reactor are continuously circulated through a heat exchanger which is responsible for removing most of the heat of reaction and where the temperature on the coolant side is responsible for maintaining an isothermal reaction environment at a specified temperature. Circulation around each reactor loop is provided by a pump.

[0257] After leaving the second reactor loop, the second / final reactor effluent enters the post-reactor adiabatic tube, where the total volume is about 21.4% of the volume of the two loop reactors combined, where the reaction continues for a period of time before entering a mixing zone where the reaction is stopped by deactivating the catalyst with the addition and reaction of a suitable reagent (water). At this same reactor outlet location, other additives are added for polymer stabilization (typical antioxidants suitable for stabilization in extrusion and blown film manufacturing processes, such as 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 (usually the acid scavenger calcium stearate).

[0258] After catalyst deactivation and addition of additives, the reactor effluent enters a devolatilization system where polymer is removed from the non-polymer stream. The separated polymer melt is pelletized and collected. The non-polymer stream passes through various devices that separate most of the ethylene removed from the system. Most of the solvent and unreacted comonomer are recycled back to the reactor after passing through a purification system. Small amounts of solvent and comonomer are purged from the process.

[0259] Figure 1 The reactor stream feed data flows are graphically depicted in , which correspond to the values ​​in Table 1B for the production examples. The data are presented so that the complexity of the solvent recycle system is taken into account, and the reaction system can be simply treated as a once through flow diagram.

[0260] Table 1B - Reactor information for: Poly.3, Poly.4, C-Poly.1 and C-Poly.2

[0261]

[0262]

[0263] The density, melt index (I) and melt flow rate (W) of each of the inventive polyethylene composition and the comparative polyethylene composition were measured in accordance with the above test methods. 2 ), I 10 / I 2 , Mz, Mw / Mn, Mz / Mn and Log(Mw)4.0 to 5.0(SCB logMw4-5 ). Tables 2 and 3 below provide data on the composition.

[0264] Table 2 - Polyethylene composition data of the present invention

[0265]

[0266]

[0267] Table 3 - Comparative Polyethylene Composition Data

[0268]

[0269] The density, Mw, and weight percent (wt.%) of each of the components (comparisons) (i.e., polyethylene component 1 (comparison 1), polyethylene component 2 (comparison 2), and polyethylene component 3 (comparison 3)) were 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 values ​​of each of the compositions for the following equation: First polyethylene component weight fraction × SCB logMw4-5 × Mz (conventional GPC). Without being bound by theory, when the weight fraction of the first polyethylene component SCB logMw4-5 At Mz (conventional GPC) greater than 230,000, the properties and balance of properties result in improved and / or desirable processability, stretchability, and performance in films.

[0270] Table 4A

[0271]

[0272] *C-Poly.3 is a bimodal composition and has only two polyethylene components.

[0273] Table 4B - iCCD Peak Temperature of First Polyethylene Component

[0274]

[0275] Table 4C - First Polyethylene Component Weight Fraction x SCB logMw4-5 ×Mz(conventional GPC) value

[0276] <![CDATA[Weight fraction of the first polyethylene component × SCB logMw4-5 × Mz (conventional GPC)]]> Poly.1 397809 Poly.2 395668 Poly.3 368881 Poly.4 330185 C-Poly.1 224763 C-Poly.2 124831 C-Poly.3 0

[0277] A biaxially oriented film is formed using a polyethylene composition. Three films are formed from each of the polyethylene compositions of the present invention, so that a total of twelve (12) films of the present invention are made. Biaxial orientation is performed sequentially at a predetermined temperature in two different stretching chambers. The sheet sample is cut into 10 cm × 10 cm dimensions along the MD and TD directions, wherein the initial sheet thickness is 700 μm, and loaded onto a stretching frame, wherein five clamps are located at each of the four sides. A pneumatically driven clamp is used to clamp the sample edges, and then the stretching frame is transported to the first chamber. Longitudinal orientation (MDO) is performed in the first chamber. Afterwards, the longitudinally oriented sample is immediately sent to the second chamber for transverse orientation (TDO). In the MDO step, the sheet is firstly stretched at a desired temperature (T ) by hot air under forced convection. MDO =128°C) for 180 seconds and then stretched to 5 times in the longitudinal direction at a stretching rate of 500% / s. In the TDO step, the sample sheet was heated at a temperature of 128°C for 180 seconds and then stretched to 5 times in the longitudinal direction at a stretching rate of 500% / s. In the TDO step, the sample sheet was stretched to 8 times in the transverse direction at a stretching rate of 250% / s by allowing air to flow in the second chamber at a desired temperature (respectively, T TDO =124 ℃, 126 ℃ and 128 ℃, as indicated in the following table) cycle for 30 seconds to heat the sample. Therefore, the film is stretched in the horizontal direction at a ratio of 8: 1 and stretched in the longitudinal direction at a ratio of 5: 1, and the final film thickness is about 20 μm. The stretched film sample is then taken out from the stretching frame, aged for at least one week, and then the film properties are tested as described below in this section. Tables 5 and 6 below provide the properties of the film. The film of the present invention has the desired transparency, haze modulus and tensile properties. The film attempted to be formed by the comparative polyethylene composition is not stretchable, and the film breaks during stretching, so it cannot be formed.

[0278] Table 5

[0279]

[0280]

[0281] Table 6 - Modulus and tensile data

[0282]

Claims

1. A polyethylene composition, comprising: (a) 15 weight percent to 25 weight percent of a first polyethylene component, the first polyethylene component having a molecular weight (Mw) greater than 200,000 g / mol and a density of 0.925 g / cc to 0.945 g / cc; (b) 20 weight percent to 35 weight percent of a second polyethylene component, the second polyethylene component having a molecular weight (Mw) of less than 80,000 g / mol and a density of 0.915 g / cc to 0.950 g / cc; as well as (c) 40 weight percent to 65 weight percent of a third polyethylene component, the third polyethylene component having a molecular weight (Mw) of less than 100,000 g / mol and a density of 0.940 g / cc to 0.965 g / cc; and wherein the polyethylene composition has a density of 0.935 g / cc to 0.958 g / cc, A melt index I2 of 0.5 g / 10 min to 5.0 g / 10 min and satisfies the following equation: Weight fraction of first polyethylene component × SCB logMw4-5 ×Mz (conventional GPC)>230,000.

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

3. The polyethylene composition according to any preceding claim, wherein the first polyethylene component has a peak temperature greater than 99.5°C in an elution curve via improved comonomer composition distribution (iCCD).

4. The polyethylene composition of any preceding claim, wherein the polyethylene composition has an Mz / Mw of 2.5 to 4.

5.

5. The polyethylene composition of any preceding claim, wherein the polyethylene composition has a molecular weight distribution (Mw / Mn) of 4.2 to 10.

0.

6. The polyethylene composition of any preceding claim, wherein the polyethylene composition has an I of 7.0 to 15.

0. 10 / I2.

7. The polyethylene composition of any preceding claim, wherein the polyethylene composition has an Mz (conventional GPC) of 250,000 g / mol to 450,000 g / mol.

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

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

10. The biaxially oriented film of claim 9, wherein the biaxially oriented film is oriented in the machine direction at a stretch ratio of 2:1 to 9:1 and in the transverse direction at 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. 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%; a 2% secant modulus in the longitudinal direction of at least 600 MPa; a 2% secant modulus in the transverse direction of at least 900 MPa; a transparency of at least 35%; a longitudinal tensile strain at break of at least 160%; and a transverse tensile strain at break of at least 20%.

13. A laminate comprising: a first film comprising a polyethylene sealant film, polypropylene, or polyamide; as well as 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 according to any one of claims 9 to 12.

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