Polyethylene compositions, films, and articles

Abstract

Examples of polyethylene compositions are provided, comprising: a first polyethylene portion having at least one peak in a melt flow profile obtained by an improved comonomer composition distribution (iCCD) analysis method within a temperature range of 40°C to 75°C, wherein the area of ​​the first polyethylene portion is the area of ​​the melt flow profile within the 40°C to 75°C range, and wherein the area of ​​the first polyethylene portion accounts for 45% to 65% of the total area of ​​the melt flow profile; and a second polyethylene portion including at least one peak in a melt flow profile within a temperature range of 85°C to 110°C, wherein the area of ​​the second polyethylene portion is the area of ​​the melt flow profile within the 85°C to 110°C range, and wherein the area of ​​the second polyethylene portion accounts for 15% to 35% of the total area of ​​the melt flow profile; wherein the polyethylene composition has a density of 0.905 g / cm³ to 0.918 g / cm³, a melt index (I²) of 0.7 g / 10 min to 3.5 g / 10 min, and wherein the composition has a melt index ratio (I¹⁰ / I²) satisfying the following equation: I¹⁰ / I² 2<7.0 - 1.2 log(I 2).

Description

Technical Field

[0001] This application relates to polymer compositions, films and articles including such polyethylene compositions. Prior Technology

[0002] The use of polyolefin compositions in encapsulation applications is well-known. Such polyolefin compositions can be produced using a variety of conventional methods. Various polymerization techniques employing different catalyst systems have been used to produce such polyolefin compositions suitable for encapsulation applications. However, despite research efforts in developing compositions suitable for encapsulation applications in some embodiments, there remains a need for improved polyethylene compositions suitable for encapsulation applications that achieve a good balance between properties and processability at the desired polymer composition density. Summary of the Invention

[0003] This application discloses polyethylene compositions, films, multilayer structures, and articles thereof suitable for encapsulation applications. In some embodiments, the polyethylene compositions disclosed herein are suitable as sealant layers for use as films in encapsulation applications.

[0004] Conventional films, such as those utilizing a sealant layer, typically require a trade-off between the hot tack onset temperature, the heat seal onset temperature, or both, and the total film density. The density of the composition can affect the processing characteristics of the film. For example, films containing conventional polyethylene compositions with relatively low density often exhibit lower hot tack onset temperatures, heat seal onset temperatures, or both, compared to films containing compositions with relatively high total density. Due to the extremely low melting point and viscous or sticky nature of the material, polyethylene compositions with relatively low density can also be particularly difficult to process in conventional blown film applications. Conversely, films with relatively high total density typically exhibit higher hot tack onset temperatures, heat seal onset temperatures, or both. In some encapsulation applications, lower hot tack and heat seal onset temperatures can be desirable polymer performance characteristics. Therefore, there is still a need for polyethylene compositions that provide improved hot tack window, hot tack strength, and / or heat seal onset temperature when used in the sealant layer of a film. In various embodiments, when used in a sealant layer, the polyethylene compositions disclosed in this invention can be used in films to provide improved hot tack window, hot tack strength, and / or heat-sealing initiation temperature.

[0005] As described in detail herein, polymer compositions can be evaluated by modified comonomer composition distribution (iCCD) analysis. Embodiments of the present invention can satisfy the aforementioned requirements regarding a wide hot tack window, hot tack strength, and / or heat-sealing onset temperature by providing polyethylene compositions in some embodiments comprising at least two polyethylene fractions, as analyzed by iCCD within a specific temperature range, each polyethylene fraction representing a desired percentage of the total area of ​​the melt-off curve. Such polyethylene compositions can have the desired hot tack window, hot tack strength, and / or heat-sealing onset temperature, or both, while having, for example, a density of at least 0.905 g / cm³. Without being bound by theory, it is believed that at least some of the polyethylene compositions described in this invention possess such characteristics at least in part due to specific multi-peak melt-off curves, wherein the first and second polyethylene fractions exhibit peaks at 40°C to 75°C and 85°C to 110°C, respectively, in the melt-off curves analyzed by iCCD.

[0006] According to one or more embodiments, a polyethylene composition suitable for encapsulation applications comprises: (a) a first polyethylene portion having a single peak in a dissolution curve of 40°C to 75°C in a temperature range of 40°C to 75°C using an iCCD analysis method, wherein the area of ​​the first polyethylene portion is the area below the single peak of the first polyethylene portion between 40°C and 75°C in the dissolution curve, and wherein the area of ​​the first polyethylene portion accounts for 45% to 65% of the total area of ​​the dissolution curve; and (b) a second polyethylene portion having a temperature range of 85°C to 110°C in a dissolution curve of 85°C to 110°C in a temperature range of 85°C to 110°C in the dissolution curve, wherein the area of ​​the second polyethylene portion is the area below the single peak of the second polyethylene portion between 85°C and 110°C in the dissolution curve, and wherein the area of ​​the second polyethylene portion is the area below at least one peak of the second polyethylene portion between 85°C and 110°C in the dissolution curve, and wherein the area of ​​the second polyethylene portion accounts for 15% to 35% of the total area of ​​the dissolution curve; wherein the polyethylene composition has a content of 0.905 g / cm³ to 0.918 g / cm³. The composition has a density of 3 and a melt index (I2) of 0.7 g / 10 min to 3.5 g / 10 min, and wherein the composition has a melt index ratio (I10 / I2) that satisfies the following equation: I10 / I2 < 7.0 - 1.2 log(I2).

[0007] According to one or more embodiments, the membrane may include the polyethylene composition described above or in any other embodiment described herein.

[0008] According to one or more embodiments, the article may include the polyethylene composition described above or in any other embodiment described herein. Simple Explanation of the Diagram

[0009] The following detailed description of specific embodiments of the invention can be best understood when read in conjunction with the accompanying drawings, wherein similar structures are indicated by similar element symbols, and in these accompanying drawings:

[0010] Figure 1 schematically depicts the iCCD dissociation curves according to one or more embodiments of the present invention; and

[0011] Figure 2 schematically depicts a reactor system suitable for producing polyethylene according to one or more embodiments of the present invention. Implementation

[0012] This document describes examples of polyethylene compositions. Such polyethylene compositions can be used, for example, in encapsulation applications. The polyethylene composition may comprise a first polyethylene portion and a second polyethylene portion. The polyethylene composition may be contained in films (including single-layer and multi-layer films) or other articles such as multilayer structures and encapsulations.

[0013] As described herein, "polyethylene" or "ethylene polymer" refers to a polymer comprising more than half (>50 mol%) 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); very low-density polyethylene (VLDPE); single-point catalytic linear low-density polyethylene, including linear and substantially linear low-density resins (m-LLDPE); vinyl plastomers (POP) and vinyl elastomers (POE); medium-density polyethylene (MDPE); and high-density polyethylene (HDPE). These polyethylene materials are generally known in the art; however, the following description may help to understand the differences between some of these different polyethylene resins.

[0014] As used herein, the term "composition" means the materials constituting the composition and the mixture of reaction products and decomposition products formed from the materials of the composition.

[0015] The term "LDPE" can also be referred to as "high-pressure ethylene polymer" or "highly branched polyethylene," and can be defined as polymers produced by partial or full homopolymerization or copolymerization with free radical initiators such as peroxides in an autoclave or tubular reactor at pressures above 14,500 psi (100 MPa) (see, for example, US 4,599,392, which is hereby incorporated by reference). LDPE resins typically have densities ranging from 0.916 to 0.935 g / cm³.

[0016] The term "LLDPE" includes resins produced using conventional Ziegler-Natta catalyst systems and chromium-based catalyst systems, as well as single-point catalysts (including, but not limited to, substituted mono- or dicyclopentadienyl catalysts (commonly known as metallocenes), confined geometry catalysts, phosphine imine catalysts, and polyvalent aryloxy ether catalysts (commonly known as diphenylphenoxy)), and also includes linear, substantially linear, or heterogeneous polyethylene copolymers or homopolymers. LLDPE contains fewer long-chain branchings than LDPE and comprises substantially linear ethylene polymers, further defined in U.S. Patents 5,272,236, 5,278,272, 5,582,923, and 5,733,155; homogeneous branched linear ethylene polymer compositions, such as those in U.S. Patent 3,645,992; heterogeneous branched ethylene polymers, such as those prepared according to the process disclosed in U.S. Patent 4,076,698; and / or blends thereof (such as those disclosed in U.S. 3,914,342 or U.S. 5,854,045). LLDPE can be prepared by gas-phase, solution-phase, or slurry polymerization or any combination thereof, using any type of reactor or reactor configuration known in the art.

[0017] The term "MDPE" refers to polyethylene with a density of 0.924 to 0.936 g / cm³. MDPE is typically produced using chromium or Ziegler-Natta catalysts or single-point catalysts (including, but not limited to, substituted mono- or dicyclopentadienyl catalysts (commonly known as metallocenes), confined geometry catalysts, phosphine imine catalysts, and polyvalent aryloxy ether catalysts (commonly known as diphenylphenoxy)).

[0018] The term "HDPE" refers to polyethylene with a density greater than about 0.935 g / cm³ and at most about 0.980 g / cm³, which is typically prepared using Ziegler-Natta catalysts, chromium catalysts, or single-point catalysts (including but not limited to substituted mono- or dicyclopentadienyl catalysts (commonly known as metallocenes), confined geometry catalysts, phosphine imine catalysts, and polyvalent aryloxy ether catalysts (commonly known as diphenylphenoxy)).

[0019] The term "ULDPE" refers to polyethylene with a density of 0.855 to 0.912 g / cm³, typically prepared using Ziegler-Natta catalysts, chromium catalysts, or single-point catalysts (including, but not limited to, substituted mono- or dicyclopentadienyl catalysts (commonly known as metallocenes), confined geometry catalysts, phosphine imine catalysts, and polyvalent aryloxy ether catalysts (commonly known as diphenylphenoxys)). ULDPE includes, but is not limited to, polyethylene (vinyl) plastomers and polyethylene (vinyl) elastomers. Polyethylene (vinyl) elastomers or plastomers typically have a density of 0.855 to 0.912 g / cm³.

[0020] The terms "blender," "polymer blend," and similar terms 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. Blenders are not laminates, but one or more layers of a laminate may contain blends. Such blends can be prepared as dry blends, in-situ formed (e.g., in a reactor), melt blends, or using other techniques known to those skilled in the art.

[0021] Unless otherwise stated, implied by 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 methods as of the filing date of this invention.

[0022] The terms "comprising," "including," "having," and their derivatives are not intended to exclude the presence of any additional components, steps, or procedures, whether or not they are specifically disclosed. For the avoidance of any doubt, unless stated to the contrary, all compositions claimed by the use of the term "comprising" may contain any additional additives, adjuvants, or compounds, whether polymerized or otherwise. The term "consisting of" excludes any components, steps, or procedures not specifically described or listed.

[0023] [Polyethylene Composition and Characterization] []

[0024] In one or more embodiments, the density of the polyethylene composition may be from 0.905 g / cm³ to 0.918 g / cm³. For example, the densities of the polyethylene compositions disclosed in this invention may be 0.905 g / cm³ to 0.916 g / cm³, 0.905 g / cm³ to 0.915 g / cm³, 0.905 g / cm³ to 0.914 g / cm³, 0.905 g / cm³ to 0.912 g / cm³, 0.907 g / cm³ to 0.918 g / cm³, 0.907 g / cm³ to 0.916 g / cm³, 0.907 g / cm³ to 0.914 g / cm³, 0.907 g / cm³ to 0.912 g / cm³, 0.909 g / cm³ to 0.918 g / cm³, 0.909 g / cm³ to 0.916 ...16 g / cm³, 0.916 g / cm³, 0.916 g / cm³, 0.916 g / cm³, 0.916 g / cm³, 0.916 g / cm³, 0.916 g / cm³ 3 to 0.914 g / cm³, 0.910 g / cm³ to 0.918 g / cm³, 0.910 g / cm³ to 0.916 g / cm³, 0.910 g / cm³ to 0.914 g / cm³, or any combination of these ranges.

[0025] In one or more embodiments, the melt index (I2) of the polyethylene composition may be from 0.70 g / 10 min to 3.5 g / 10 min. For example, in one or more embodiments, the melt index (I2) of the polyethylene composition may be 0.7 g / 10 min to 3.0 g / 10 min, 0.7 g / 10 min to 2.5 g / 10 min, 0.7 g / 10 min to 2.0 g / 10 min, 0.7 g / 10 min to 1.5 g / 10 min, 0.85 g / 10 min to 3.5 g / 10 min, 0.85 g / 10 min to 3.0 g / 10 min, 0.85 g / 10 min to 2.5 g / 10 min, 0.85 g / 10 min to 2.0 g / 10 min, 0.85 g / 10 min to 1.5 g / 10 min, or any combination of these ranges.

[0026] In one or more embodiments, the melt index ratio (I10 / I2) of the polyethylene composition may be less than 7.0. For example, in one or more embodiments, the melt index ratio (I10 / I2) of the polyethylene composition may be 6.0 to 6.9, 6.0 to 6.7, 6.0 to 6.4, or any combination of these ranges.

[0027] In one or more embodiments, the polyethylene composition may have a melt index ratio (I10 / I2) that satisfies the following equation: I10 / I2 < 7.0 - 1.2 log (I2).

[0028] In one or more embodiments, the molecular weight comonomer distribution index (MWCDI) of the polyethylene composition may be less than 1.0. For example, in one or more embodiments, the MWCDI of the polyethylene composition may be 0.0 to 2.0, 0.0 to 1.5, 0.0 to 1.0, 0.0 to 0.5, 0.1 to 1.0, 0.1 to 1.5, or any combination of these ranges.

[0029] According to one or more embodiments, the weight-average molecular weight (Mw) of the polyethylene composition may be in the range of 100,000 to 130,000 g / mole. For example, in one or more embodiments, the weight-average molecular weight (Mw) of the polyethylene composition may be 105,000 to 130,000 g / mole, 105,000 to 125,000 g / mole, 105,000 to 120,000 g / mole, 105,000 to 115,000 g / mole, 110,000 to 130,000 g / mole, 110,000 to 125,000 g / mole, 110,000 to 120,000 g / mole, 115,000 to 130,000 g / mole, or any combination of these ranges.

[0030] According to one or more embodiments, the molecular weight distribution of the polyethylene composition may be in the range of 2.0 to 4.0, expressed as the ratio of weight average molecular weight to number average molecular weight (Mw / Mn). For example, the molecular weight distribution of the polyethylene composition may be 2.0 to 3.5, 2.5 to 4.0, 2.5 to 3.5, 2.0 to 3.3, 2.0 to 3.2, 2.5 to 3.3, 2.5 to 3.2, or any combination of these ranges. As described in this invention, the molecular weight distribution can be calculated using gel permeation chromatography (GPC) techniques as described herein.

[0031] According to one or more embodiments, the z-average molecular weight (Mz) of the polyethylene composition may be less than 300,000 g / mole. For example, the z-average molecular weight (Mz) of the polyethylene composition may be 230,000 to 300,000 g / mole, 240,000 to 300,000 g / mole, 250,000 to 300,000 g / mole, 260,000 to 300,000 g / mole, 270,000 to 300,000 g / mole, 230,000 to 290,000 g / mole, 240,000 to 290,000 g / mole, 250,000 to 290,000 g / mole, 260,000 to 290,000 g / mole, 270,000 to 290,000 g / mole, or any combination of these ranges.

[0032] According to one or more additional embodiments, the zero-shear viscosity ratio of the polyethylene composition may be less than 2.0. For example, the zero-shear viscosity ratio of the polyethylene composition may be less than 1.9, less than 1.8, less than 1.7, less than 1.6, less than 1.5, less than 1.4, less than 1.3, less than 1.2, or even less than 1.1. In one or more embodiments, the zero-shear viscosity ratio of the polyethylene composition may be at least 1.0. In embodiments, the zero-shear viscosity ratio of the polyethylene composition may be 1.0 to 2.0, 1.0 to 1.8, 1.0 to 1.6, 1.0 to 1.4, 1.0 to 1.2, 1.2 to 2.0, 1.2 to 1.8, 1.2 to 1.6, 1.2 to 1.4, 1.4 to 2.0, 1.4 to 1.8, 1.4 to 1.6, 1.6 to 2.0, 1.6 to 1.8, or 1.8 to 2.0, or any combination of these ranges.

[0033] tan δ (tan δ) is a measure of how closely a material approximates a fully elastic solid (where d = 0°, tan δ = 0) or a fully Newtonian liquid (where d = 90°, tan δ ≈ infinity). Therefore, a lower tan δ value reflects greater elasticity. tan δ is a function of the long chain branching (LCB) and molecular weight distribution (MWD) at the same total molecular weight. A higher tan δ value indicates a lower LCB. In the examples, the tan δ of the polyethylene composition at 0.1 radians / second and 190°C... δ is 6 to 100, 6 to 90, 6 to 80, 6 to 70, 6 to 60, 6 to 50, 6 to 40, 6 to 30, 6 to 20, 20 to 100, 20 to 90, 20 to 80, 20 to 70, 20 to 60, 20 to 50, 20 to 40, 20 to 30, 30 to 100, 30 to 90, 30 to 80, 30 to 70, 30 to 60, 30 to 50, 30 to 40. 40 to 100, 40 to 90, 40 to 80, 40 to 70, 40 to 60, 40 to 50, 50 to 100, 50 to 90, 50 to 80, 50 to 70, 50 to 60, 60 to 100, 60 to 90, 60 to 80, 60 to 70, 70 to 100, 70 to 90, 70 to 80, 80 to 100, 80 to 90 or 90 to 100 or any combination of these ranges.

[0034] As described herein, a "part" of polyethylene refers to a portion of the total polyethylene composition. The embodiments disclosed herein may include at least a "first polyethylene part" and a "second polyethylene part." Embodiments may also include a "third polyethylene part." The various parts included in the polyethylene composition may be defined by their temperature range in a dissolution profile obtained by an iCCD (Integrated Comonomer Composition Distribution) analysis method. For example, a polyethylene part may be defined by a range from lower to higher temperatures. It should be understood that two or more polyethylene fractions may overlap. In one or more embodiments, a polyethylene part may typically be correlated with a peak or trough in the iCCD data. In one or more embodiments, a particular polyethylene part may represent a specified percentage of the total area of ​​the polyethylene composition, as defined by iCCD analysis of a dissolution profile. Unless otherwise specified, any dissolution profile mentioned herein is a dissolution profile observed by iCCD. Examples of such parts will be better understood in light of the embodiments provided herein.

[0035] Generally, the first portion may contain at least one peak within the temperature range of the first portion. The second portion may contain at least one peak within the temperature range of the second portion. The polyethylene composition described herein may be referred to as "multimodal," meaning that it contains at least two peaks in its melt-off curve. In the embodiments, the polyethylene composition described herein may contain two peaks ("bimodal"), three peaks ("trimodal"), or more than three peaks in its melt-off curve. The first polyethylene area portion, the second polyethylene portion, and the third polyethylene portion may each constitute a portion of the total mass of the polyethylene composition.

[0036] Referring to the iCCD distribution, Figure 1 schematically depicts the sample iCCD distribution.

[0100] Generally, Figure 1 depicts several features of the iCCD curve of the polyethylene composition described in this invention, such as the first polyethylene portion, the second portion, the third polyethylene portion, etc., which are discussed in detail herein. Therefore, Figure 1 can be used as a reference regarding the disclosure related to the iCCD curve provided herein.

[0037] Specifically, the first polyethylene portion is described

[0102] Second polyethylene part

[0104] Third polyethylene part

[0106] First polyethylene part

[0102] Has peaks

[0112] And the second polyethylene portion

[0104] Has peaks

[0114] It should be understood that the curves in Figure 1 are not derived from experiments or observations, but are provided for the purpose of describing specific characteristics of the iCCD dissolution curve.

[0038] In one or more embodiments, one or more of the first polyethylene portion and the second polyethylene portion may have a single peak. As used herein, "single peak" means an iCCD in which a particular portion contains only a single peak. That is, in some embodiments, the iCCD of one or more of the first polyethylene portion and the second polyethylene portion contains only an upwardly sloping region and a subsequently downwardly sloping region to form a single peak.

[0039] It should be understood that peaks in one or more of the first and second polyethylene portions may not be formed by local minimums in the corresponding polyethylene portion at the defined temperature boundary. That is, the peaks must be peaks across the entire spectral range, not peaks formed by the threshold temperature of the polyethylene portion. For example, if a polyethylene portion contains a single peak followed by a single valley (sloping upwards, then downwards, then upwards), then only a single peak will exist in such a polyethylene portion.

[0040] In one or more embodiments, the first polyethylene portion

[0102] This can be the area between 40°C and 75°C in the melting curve. In an additional embodiment, the first polyethylene portion

[0102] can be the area in the dissolution curve within any combination of the temperature ranges of 40°C to 60°C, 40°C to 50°C, 40°C to 70°C, 40°C to 65°C, 50°C to 75°C, 50°C to 70°C, 50°C to 65°C, 60°C to 75°C, 60°C to 70°C, or dissolution curves via iCCD.

[0041] According to one or more embodiments, the area of ​​the first polyethylene portion may account for 45% to 65% of the total area of ​​the melt-off curve. For example, the area of ​​the first polyethylene portion may account for 45% to 60%, 45% to 55%, 45% to 50%, 50% to 65%, 50% to 60%, 50% to 55%, 55% to 65%, or any combination thereof of the total area of ​​the melt-off curve.

[0042] In one or more embodiments, the first polyethylene portion

[0102] It can have at least one peak in the temperature range of 40°C to 75°C in the dissolution curve of iCCD.

[0112] . In one or more embodiments, the first polyethylene portion

[0102] At least one peak may be present in the dissolution curve of the iCCD within the temperature ranges of 40°C to 60°C, 40°C to 50°C, 40°C to 70°C, 40°C to 65°C, 50°C to 75°C, 50°C to 70°C, 50°C to 65°C, 60°C to 75°C, 60°C to 70°C, or any combination thereof.

[0112] .

[0043] In one or more embodiments, the weight-average molecular weight (Mw) of the first polyethylene fraction may be less than or equal to 150,000 g / mol, such as 100,000 g / mol to 150,000 g / mol, 110,000 g / mol to 150,000 g / mol, 120,000 g / mol to 150,000 g / mol, 100,000 g / mol to 140,000 g / mol, 110,000 g / mol to 140,000 g / mol, 120,000 g / mol to 140,000 g / mol, or any combination of these ranges. The molecular weight of the polyethylene fraction may be calculated based on iCCD results, as described below.

[0044] A temperature range of 40°C to 75°C for the first polyethylene portion is desirable because it corresponds to the low-density component of the polyethylene composition. In embodiments, the low-density component may provide a low hot-tack initiation temperature, a heat-sealing initiation temperature, or both. Therefore, increasing the first polyethylene portion to include a low-density component is beneficial.

[0102] This makes it possible to form an airtight seal in an encapsulation comprising a sealant layer of such resin at a lower sealing temperature.

[0045] In one or more embodiments, the second polyethylene portion

[0104] This can be the area between 85°C and 110°C in the melting curve. In an additional embodiment, the second polyethylene portion

[0104] can be the area of ​​the dissolution curve at 85°C to 105°C, 85°C to 100°C, 85°C to 90°C, 90°C to 110°C, 90°C to 105°C, 90°C to 100°C, 95°C to 110°C, 95°C to 105°C, 100°C to 110°C, or any combination of dissolution curves via iCCD.

[0046] According to one or more embodiments, the area of ​​the second polyethylene portion may account for 15% to 35% of the total area of ​​the melt-off curve. For example, the area of ​​the second polyethylene portion may account for 20% to 35%, 25% to 35%, 15% to 30%, 20% to 30%, 20% to 25%, 15% to 25%, 15% to 20%, 20% to 30%, 20% to 25%, 25% to 30%, or any combination thereof, of the total area of ​​the melt-off curve.

[0047] In one or more embodiments, the second polyethylene portion

[0104] It can have at least one peak in the temperature range of 85°C to 110°C in the dissolution curve of iCCD.

[0114] . In one or more embodiments, the second polyethylene portion

[0104] At least one peak may be present in the dissolution curve of the iCCD within the temperature range of 85°C to 105°C, 85°C to 100°C, 85°C to 90°C, 90°C to 110°C, 90°C to 105°C, 90°C to 100°C, 95°C to 110°C, 95°C to 105°C, 100°C to 110°C, or any combination thereof.

[0114] .

[0048] In one or more embodiments, the weight-average molecular weight (Mw) of the second polyethylene fraction may be less than or equal to 190,000 g / mol, such as 95,000 g / mol to 190,000 g / mol, 100,000 g / mol to 190,000 g / mol, 105,000 g / mol to 190,000 g / mol, 110,000 g / mol to 190,000 g / mol, 95,000 g / mol to 180,000 g / mol, 100,000 g / mol to 180,000 g / mol, 105,000 g / mol to 180,000 g / mol, 110,000 g / mol to 180,000 g / mol, 95,000 g / mol to 150,000 g / mol, 100,000 g / mol to 150,000 g / mol, 100,000 g / mol to 180,000 g / mol. The molecular weight of the polyethylene fraction can be calculated based on iCCD results, as described below. The ranges are from 105,000 g / mol to 150,000 g / mol, 110,000 g / mol to 150,000 g / mol, or any combination thereof.

[0049] A temperature range of 85°C to 110°C for the second polyethylene portion is desirable because it corresponds to the high-density component. In the embodiments, increasing the high-density component increases the total density of the polyethylene composition. Therefore, increasing the second polyethylene portion...

[0104] This allows for the addition of a high-density component and provides a polyethylene composition with a higher total density. Additionally, the addition of a second polyethylene portion...

[0104] This can improve the barrier properties of the polyethylene composition. Unbound from theory, it is believed that larger crystals form in the high-density portions, providing a rough surface. The rough surface reduces the contact area, thereby improving the barrier properties of the polyethylene composition.

[0050] In one or more embodiments, the polyethylene composition may have a local minimum in the 75°C to 85°C temperature range of the iCCD dissolution profile. This local minimum may fall within the first polyethylene portion.

[0102] Peak

[0112] with the second polyethylene portion

[0104] Peak

[0114] between.

[0051] In one or more embodiments, the third polyethylene portion

[0106] can be the area of ​​75°C to 85°C in the dissolution curve of iCCD.

[0052] According to one or more embodiments, the area of ​​the third polyethylene portion may account for less than 25% of the total area of ​​the melt-off curve (e.g., less than 23%, less than 22%, or less than 20% of the total area of ​​the melt-off curve). For example, the area of ​​the third polyethylene portion may account for 5% to 25%, 8% to 25%, 10% to 25%, 12% to 25%, 15% to 25%, 5% to 23%, 8% to 23%, 10% to 23%, 12% to 23%, 15% to 23%, or any combination thereof of the total area of ​​the melt-off curve.

[0053] In one or more embodiments, the weight-average molecular weight (Mw) of the third polyethylene fraction may be less than or equal to 140,000 g / mol, such as 80,000 g / mol to 140,000 g / mol, 85,000 g / mol to 140,000 g / mol, 90,000 g / mol to 140,000 g / mol, 95,000 g / mol to 140,000 g / mol, 100,000 g / mol to 140,000 g / mol, 85,000 g / mol to 130,000 g / mol, 90,000 g / mol to 130,000 g / mol, 95,000 g / mol to 130,000 g / mol, 100,000 g / mol to 130,000 g / mol, 85,000 g / mol to 125,000 g / mol. The molecular weight of the polyethylene fraction can be calculated based on iCCD results, as described below. The ranges are 90,000 g / mol to 125,000 g / mol, 95,000 g / mol to 125,000 g / mol, 100,000 g / mol to 125,000 g / mol, or any combination thereof.

[0054] In various embodiments, the ratio of the weight average molecular weight (Mw) of the polyethylene composition in the plurality of polyethylene portions can be important. In one or more embodiments, the ratio of Mw in the first polyethylene portion (40°C to 75°C) to Mw in the third polyethylene portion (75°C to 85°C) (i.e., the Mw of the first polyethylene portion divided by the Mw of the third polyethylene portion) is 0.90 to 1.6. For example, the ratio of Mw in the first polyethylene portion (40°C to 75°C) to Mw in the third polyethylene portion (75°C to 85°C) (i.e., the Mw of the first polyethylene portion divided by the Mw of the third polyethylene portion) can be 1.0 to 1.6, 1.1 to 1.6, 1.2 to 1.6, 0.90 to 1.5, 1.0 to 1.5, 1.1 to 1.5, 1.2 to 1.5, 0.90 to 1.4, 1.0 to 1.4, 1.1 to 1.4, or any combination of these ranges.

[0055] In one or more embodiments, the ratio of Mw in the third polyethylene portion (75°C to 85°C) to Mw in the second polyethylene portion (85°C to 110°C) (i.e., Mw in the third polyethylene portion divided by Mw in the second polyethylene portion) is 0.50 to 1.5. For example, the ratio of Mw in the third polyethylene portion (75°C to 85°C) to Mw in the second polyethylene portion (85°C to 110°C) (i.e., Mw in the third polyethylene portion divided by Mw in the second polyethylene portion) may be 0.50 to 1.4, 0.50 to 1.3, 0.50 to 1.2, 0.50 to 1.1, 0.50 to 1.0, 0.50 to 0.90, 0.60 to 1.4, 0.60 to 1.3, 0.60 to 1.2, 0.60 to 1.1, 0.60 to 1.0, 0.60 to 0.90, 0.70 to 1.4, 0.70 to 1.3, 0.70 to 1.2, 0.70 to 1.1, 0.70 to 1.0, 0.70 to 0.90, or any combination of these ranges.

[0056] In one or more embodiments, the polyethylene composition is formed by polymerization of ethylene with a comonomer such as a C3-C12 olefin. The comonomer is intended to include C6-C9 olefins, such as 1-octene and 1-hexene. In one or more embodiments, the comonomer is 1-octene.

[0057] In one or more embodiments, the polyethylene composition disclosed in this invention may further include additional components, such as one or more additives. Such additives include, but are not limited to, antistatic agents; color enhancers; dyes; lubricants; fillers, such as TiO₂ or CaCO₃; opacifiers; nucleating agents; processing aids; pigments; primary antioxidants; secondary antioxidants; UV stabilizers; anti-blocking agents; slip agents; tackifiers; flame retardants; antimicrobial agents; deodorizing agents; antifungal agents; and combinations thereof. Based on the weight of the polyethylene composition containing such additives, the polyethylene composition may contain about 0.1 to about 10 percent of the combined weight of such additives.

[0058] [polymerization] []

[0059] The polyethylene compositions described herein can be produced using any known polymerization method. Such known polymerization methods include, but are not limited to, gas-phase polymerization, slurry polymerization, and solution polymerization, using one or more known reactors, such as loop reactors, isothermal reactors, stirred tank reactors, tubular flow reactors, plug flow reactors, parallel or series batch reactors, and / or any combination thereof. The polyethylene compositions can be produced, for example, using one or more loop reactors, isothermal reactors, and combinations thereof, via solution-phase polymerization.

[0060] Generally, solution-phase polymerization can be carried out in one or more well-mixed reactors, such as one or more isothermal loop reactors or one or more adiabatic reactors, at temperatures ranging from 115°C to 250°C (e.g., 115°C to 210°C) and at pressures ranging from 300 psi to 3,000 psi (e.g., 400 psi to 800 psi). In some embodiments, in a dual-reactor configuration, the temperature in the first reactor is in the range of 115°C to 190°C (e.g., 150°C to 180°C), and the temperature in the second reactor is in the range of 150°C to 250°C (e.g., 180°C to 220°C). In other embodiments, in a single reactor, the temperature is in the range of 115°C to 250°C (e.g., 115°C to 225°C).

[0061] Residence time in solution-phase polymerization can range from 2 to 30 minutes (e.g., 5 to 25 minutes). Ethylene, solvent, hydrogen, one or more catalyst systems, one or more cocatalysts (if applicable), and one or more comonomers (if applicable) are continuously fed into one or more reactors. Exemplary solvents include, but are not limited to, isoalkanes. For example, such solvents may be available under the name ISOPAR E from ExxonMobil Chemical (Houston, Texas). The resulting mixture of the polyethylene composition and solvent is then removed from the reactor, and the polyethylene composition is separated. The solvent is typically recovered via a solvent recovery unit, i.e., a heat exchanger and vapor-liquid separator, and then recycled back to the polymerization system.

[0062] In some embodiments, the polyethylene composition may be produced via solution polymerization in a dual-reactor system, such as a dual loop reactor system, wherein ethylene is polymerized in the presence of one or more catalyst systems and one or more comonomers. Additionally, one or more cocatalysts may be present. In another embodiment, the polyethylene composition may be produced via solution polymerization in a dual-reactor system, such as a single loop reactor followed by an adiabatic continuous stirred tank reactor (CSTR), wherein ethylene is polymerized in the presence of one or more catalyst systems and one or more comonomers. In yet another embodiment, the polyethylene composition may be produced via solution polymerization in a single-reactor system, such as a single loop reactor system, wherein ethylene is polymerized in the presence of two catalyst systems and one or more comonomers.

[0063] [Catalyst System] []

[0064] Specific embodiments of a catalyst system that may be used to produce the polyethylene compositions described herein are now described. It should be understood that the catalyst system of the present invention may be implemented in different forms and should not be considered as limited to the specific embodiments set forth herein. Rather, embodiments are provided so that the invention will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art. Without being bound by theory, it is believed that the catalyst system produces a mixture of low-density components in the temperature range of 40°C to 75°C in the dissolution profile obtained by iCCD analysis, which may therefore allow the polyethylene composition to achieve the desired thermoviscosity initiation temperature, heat-sealing initiation temperature, or both; and produces a high-density component in the temperature range of 85°C to 110°C in the dissolution profile obtained by iCCD analysis, which may therefore allow the polyethylene composition to achieve the desired barrier properties.

[0065] The term "independently chosen" is used herein to refer to R groups, such as R1, R2, R3, R4, and R5, which may be the same or different (e.g., R1, R2, R3, R4, and R5 may all be substituted alkyl groups, or R1 and R2 may be substituted alkyl groups and R3 may be aryl, etc.). The singular use includes the plural use and vice versa (e.g., hexane solvent, including hexane). The designation of an R group generally has a structure that is considered in this art to correspond to an R group having the stated name. These definitions are intended to supplement and illustrate, but do not exclude definitions known to those skilled in the art.

[0066] The term "primary catalyst" refers to a compound that exhibits catalytic activity when combined with an activator. The term "activator" refers to a compound that reacts chemically with the primary catalyst in a manner that converts the primary catalyst into a catalytically active catalyst. As used herein, the terms "co-catalyst" and "activator" are interchangeable.

[0067] When used to describe certain carbon-containing chemical groups, brackets of the form "(C xC y)" indicate that the unsubstituted form of the chemical group has x to y carbon atoms, inclusive. For example, (C 1-C 40)alkyl is an alkyl group in its unsubstituted form having 1 to 40 carbon atoms. In some embodiments and general structures, certain chemical groups may be substituted by one or more substituents such as RS. A chemical group with RS-substituted form defined using brackets "(C xC y)" may contain more than y carbon atoms, depending on the identity of any group RS. For example, "(C 1-C 40)alkyl group substituted by exactly one group RS, wherein RS is phenyl (-C 6H 5)" may contain 7 to 46 carbon atoms. Therefore, in general, when a chemical group defined using brackets "(C xC y)" is substituted by one or more substituents RS containing carbon atoms, the minimum and maximum total number of carbon atoms in the chemical group are determined by adding the sum of the number of carbon atoms from all substituents RS containing carbon atoms to both x and y.

[0068] The term "substitution" means that at least one hydrogen atom ((-H) bonded to a carbon atom or heteroatom corresponding to an unsubstituted compound or functional group is replaced by a substituent (e.g., Rs). The term "total substitution" means that every hydrogen atom (H) bonded to a carbon atom or heteroatom corresponding to an unsubstituted compound or functional group is replaced by a substituent (e.g., Rs). The term "multiple substitution" means that at least two, but fewer than all, hydrogen atoms bonded to carbon atoms or heteroatoms corresponding to unsubstituted compounds or functional groups are replaced by substituents.

[0069] The term "-H" refers to a hydrogen atom or a hydrogen group that is covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless explicitly stated otherwise.

[0070] The term "(C1-C40) hydrocarbon group" means a hydrocarbon group having 1 to 40 carbon atoms, and the term "(C1-C40) hydrocarbon group" means a hydrocarbon bimolecular group having 1 to 40 carbon atoms, wherein each hydrocarbon group and each hydrocarbon bimolecular group is aromatic or non-aromatic, saturated or unsaturated, straight or branched, cyclic (including monocyclic and polycyclic, fused and unfused polycyclic, including bicyclic; 3 or more carbon atoms) or acyclic, and is unsubstituted or substituted by one or more RS.

[0071] In this invention, the (C1-C40) hydrocarbon group may be an unsubstituted or substituted (C1-C40) alkyl, (C3-C40) cycloalkyl, (C3-C20) cycloalkyl-(C1-C20) alkylene, (C6-C40) aryl, or (C6-C20) aryl-(C1-C20) alkylene. In some embodiments, each of the aforementioned (C1-C40) hydrocarbon groups has a maximum of 20 carbon atoms (i.e., (C1-C20) hydrocarbon group) and in other embodiments, a maximum of 12 carbon atoms.

[0072] The terms "(C1-C40)alkyl" and "(C1-C18)alkyl" respectively mean a saturated straight-chain or branched hydrocarbon group having 1 to 40 carbon atoms or 1 to 18 carbon atoms, which is unsubstituted or substituted with one or more RS. Examples of unsubstituted (C1-C40)alkyl are unsubstituted (C1-C20)alkyl; unsubstituted (C1-C10)alkyl; unsubstituted (C1-C5)alkyl; methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2-butyl; 2-methylpropyl; 1,1-dimethylethyl; 1-pentyl; 1-hexyl; 1-heptyl; 1-nonyl; and 1-decyl. Examples of substituted (C1-C40) alkyl groups are substituted (C1-C20) alkyl groups, substituted (C1-C10) alkyl groups, trifluoromethyl, and [C45]alkyl groups. The term "[C45]alkyl" (in square brackets) means that the group including the substituent has a maximum of 45 carbon atoms, and is, for example, a (C27-C40) alkyl group corresponding to an RS-substituted (C1-C5) alkyl group. Each (C1-C5) alkyl group may be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl.

[0073] The term "(C 6-C 40) aryl" means an unsubstituted or (one or more RS) substituted monocyclic, bicyclic or tricyclic aromatic group having 6 to 40 carbon atoms, wherein at least 6 to 14 carbon atoms are aromatic ring carbon atoms, and the monocyclic, bicyclic or tricyclic group comprises 1, 2 or 3 rings respectively; wherein 1 ring is an aromatic ring, and 2 or 3 rings are independently fused or non-fused rings, and at least one of the 2 or 3 rings is an aromatic ring. Examples of unsubstituted (C 6-C 40) aryl groups include unsubstituted (C 6-C 20) aryl groups, unsubstituted (C 6-C 18) aryl groups; 2-(C 1-C 5) alkyl-phenyl groups; 2,4-bis(C 1-C 5) alkyl-phenyl groups; phenyl groups; geniyl groups; tetrahydrogeniyl groups; dicyclopentadienylphenyl groups; hexahydrodicyclopentadienylphenyl groups; indene groups; dihydroindene groups; naphthyl groups; tetrahydronaphthyl groups; and phenanthrene groups. Examples of substituted (C 6-C 40) aryl groups include substituted (C 1-C 20) aryl groups; substituted (C 6-C 18) aryl groups; 2,4-bis[(C 20)alkyl]-phenyl groups; polyfluorophenyl groups; pentafluorophenyl groups; and geni-9-one-l-yl groups.

[0074] The term "(C3-C40)cycloalkyl" means a saturated cycloalkyl group having 3 to 40 carbon atoms, which is unsubstituted or substituted with one or more RS. Other cycloalkyl groups (e.g., (CxCy)cycloalkyl) are defined similarly as having x to y carbon atoms and being unsubstituted or substituted with one or more RS. Examples of unsubstituted (C3-C40)cycloalkyl groups are unsubstituted (C3-C20)cycloalkyl, unsubstituted (C3-C10)cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Examples of substituted (C3-C40)cycloalkyl groups are substituted (C3-C20)cycloalkyl, substituted (C3-C10)cycloalkyl, cyclopentanone-2-yl, and 1-fluorocyclohexyl.

[0075] Examples of (C1-C40) alkyl groups include unsubstituted or substituted (C6-C40) aryl, (C3-C40) cycloalkyl, and (C1-C40) alkyl groups (e.g., (C1-C20) alkyl groups). In some embodiments, the bimolecular group is located on the same carbon atom (e.g., -CH2-) or on adjacent carbon atoms (i.e., 1,2-bimolecular groups), or separated by one, two, or more intermediate carbon atoms (e.g., 1,3-bimolecular, 1,4-bimolecular, etc.). Some bimolecular groups include α,ω-bimolecular groups. α,ω-bimolecular groups are bimolecular groups with the largest intercarbon backbone spacing between the group carbons. Some examples of (C 2-C 20) enylalkyl α,ω-diyl groups include ethyl-1,2-diyl (i.e., -CH 2CH 2-), propan-1,3-diyl (i.e., -CH 2CH 2CH 2-), and 2-methylpropan-1,3-diyl (i.e., -CH 2CH(CH 3)CH 2-). Some examples of (C 6-C 50) enylaryl α,ω-diyl groups include phenyl-1,4-diyl, naphth-2,6-diyl, or naphth-3,7-diyl.

[0076] The term "(C1-C40) alkylene" refers to a saturated straight-chain or branched bimolecular group (i.e., the group is not on a ring atom) having 1 to 40 carbon atoms, which is unsubstituted or substituted with one or more RS atoms. Examples of unsubstituted (C1-C50) alkylene are unsubstituted (C1-C20) alkylene, including unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C*HCH3 and -(CH2)4C*(H)(CH3), where "C*" indicates the carbon atom from which a hydrogen atom has been removed to form a secondary or tertiary alkyl group. Examples of substituted (C1-C50) alkyl groups are substituted (C1-C20) alkyl groups, -CF2-, -C(O)- and -(CH2)14C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted n-1,20-eicosyl). Since two RSs can combine to form (C1-C18) alkyl groups as previously mentioned, examples of substituted (C1-C50) alkyl groups 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.

[0077] The term "(C3-C40) cycloalkyl" means a cyclic bimolecular group having 3 to 40 carbon atoms (i.e., the group is on the ring atom) that is unsubstituted or substituted with one or more RS.

[0078] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of heteroatoms include O, S, S(O), S(O)₂, Si(RC)₂, P(RP), N(RN), -N=C(RC)₂, -Ge(RC)₂-, or -Si(RC)-, wherein each RC, each RN, and each RP is an unsubstituted (C₁-C₁₈) hydrocarbon group or -H. The term "heterohydrocarbon" refers to a molecule or molecular structure in which one or more carbon atoms are replaced by heteroatoms. The term "(C₁-C₄₀)heterohydrocarbon group" means a heterohydrocarbon group having 1 to 40 carbon atoms, and the term "(C₁-C₄₀)heterohydrocarbon group" means a heterohydrocarbon bimolecular group having 1 to 40 carbon atoms, and each heterohydrocarbon has one or more heteroatoms. The heteroalkyl group is attached to a carbon atom or a heteroatom, and the bimolecular group of the heteroalkyl group may be attached to: (1) one or two carbon atoms, (2) one or two heteroatoms, or (3) a carbon atom and a heteroatom. Each (C1-C50) heteroalkyl group and (C1-C50) extended heteroalkyl group may be unsubstituted or substituted by (one or more RS), aromatic or non-aromatic, saturated or unsaturated, straight or branched, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

[0079] (C1-C40) heteroalkyl groups can be unsubstituted or substituted (C1-C40) heteroalkyl, (C1-C40) alkyl-O-, (C1-C40) alkyl-S-, (C1-C40) alkyl-S(O)-, (C1-C40) alkyl-S(O)2-, (C1-C40) alkyl-Si(RC)2-, (C1C40) alkyl-N(RN)-, (C1C40) alkyl-P(RP)-, (C2-C40) heterocycloalkyl, (C2-C19) heterocycloalkyl-(C1-C20) alkylene, (C3-C20) cycloalkyl-(C1-C19) alkylene, (C2-C19) heterocycloalkyl-(C1-C20) alkylene, (C3-C20) cycloalkyl-(C1-C19) alkylene, (C2-C19) heterocycloalkyl-(C1-C20) alkylene, etc. (1-C 20) alkylene, (C 1-C 40) heteroaryl, (C 1-C 19) heteroaryl-(C 1-C 20) alkylene, (C 6-C 20) aryl-(C 1-C 19) alkylene or (C 1-C 19) heteroaryl-(C 1-C 20) alkylene.

[0080] The term "(C3-C40) heteroaryl" refers to a monocyclic, bicyclic, or tricyclic heteroaryl group having 4 to 40 total carbon atoms and 1 to 10 heteroatoms, either unsubstituted or substituted with one or more RS atoms, wherein the monocyclic, bicyclic, or tricyclic group comprises one, two, or three rings, wherein two or three rings are independently fused or non-fused rings, and at least one of the two or three rings is a heteroaryl ring. Other heteroaryl groups (generally, for example, (CxCy) heteroaryl groups, such as (C4-C12) heteroaryl groups) are defined similarly as having x to y carbon atoms (such as 4 to 12 carbon atoms) and being unsubstituted or substituted with one or more RS atoms. Monocyclic heteroaryl groups are 5- or 6-membered rings. 5-membered rings have 5 minus h carbon atoms, where h is the number of heteroatoms and can be 1, 2, or 3; and each heteroatom can be O, S, N, or P. Examples of 5-membered heterocyclic aromatic groups are pyrrolo-1-yl; pyrrolo-2-yl; furan-3-yl; thiophen-2-yl; pyrazol-1-yl; iso Azol-2-yl; Isothiazol-5-yl; Imidazol-2-yl; Azol-4-yl; Thiazol-2-yl; 1,2,4-triazol-1-yl; 1,3,4- Diazol-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 heteroaryl groups are pyridin-2-yl; pyrimidin-2-yl; and pyridinium-2-yl. -2-yl. The bicyclic heteroaryl group can be a fused 5,6-ring system or a 6,6-ring system. Examples of fused 5,6-ring bicyclic heteroaryl groups are indole-1-yl; and benzimidazol-1-yl. Examples of fused 6,6-ring bicyclic heteroaryl groups are quinoline-2-yl; and isoquinoline-1-yl. The tricyclic heteroaryl group can be a fused 5,6,5-ring system; a 5,6,6-ring system; a 6,5,6-ring system; or a 6,6,6-ring system. An example of a fused 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indole-1-yl. An example of a fused 5,6,6-ring system is 1H-benzo[f]indole-1-yl. An example of a fused 6,5,6-ring system is 9H-carbazole-9-yl. An example of a fused 6,5,6-cyclic system is 9H-carbazole-9-yl. An example of a fused 6,6,6-cyclic system is acridine-9-yl.

[0081] The aforementioned heteroalkyl groups may be saturated straight-chain or branched-chain groups containing (C1-C50) carbon atoms or a few carbon atoms and one or more heteroatoms. Similarly, the extended heteroalkyl groups may be saturated straight-chain or branched-chain bimolecular groups containing 1 to 50 carbon atoms and one or more heteroatoms. The heteroatoms as defined above may include Si(RC)3, Ge(RC)3, Si(RC)2, Ge(RC)2, P(RP)2, P(RP), N(RN)2, N(RN), N, O, ORC, S, SRC, S(O), and S(O)2, wherein each of the heteroalkyl and extended heteroalkyl groups is unsubstituted or substituted with one or more RS.

[0082] Examples of unsubstituted (C 2-C 40) heterocyclic alkyl groups include unsubstituted (C 2-C 20) heterocyclic alkyl groups, unsubstituted (C 2-C 10) heterocyclic alkyl groups, aziridin-1-yl, oxetane-2-yl, tetrahydrofuran-3-yl, pyrrolidin-1-yl, tetrahydrothiophene-S,S-dioxo-2-yl, morpholin-4-yl, and 1,4-dioxane-1-yl. Alkyl-2-yl, hexahydroazino-4-yl, 3-oxacyclooctyl, 5-thiocyclononyl and 2-azacyclodecyl.

[0083] The term "halogen atom" or "halogen" refers to a fluorine (F), chlorine (Cl), bromine (Br), or iodine (I) group. The term "halogen ion" refers to a halogen atom in anionic form: fluorine (F-), chlorine (Cl-), bromine (Br-), or iodine (I-).

[0084] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon parabonding bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, and carbon-silicon double bonds. In the case of a saturated chemical group substituted with one or more substituents RS, one or more double bonds and / or parabonding bonds may or may not be present in the substituent RS. The term "unsaturated" means containing one or more carbon-carbon double bonds, carbon-carbon parabonding bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, and carbon-silicon double bonds, but not containing any such double bonds that may be present in the substituent RS (if desired) or in the (hetero)aromatic ring (if desired).

[0085] According to some embodiments, a catalyst system for producing a polyethylene composition comprises a metal-ligand complex according to formula (I):

[0086] In formula (I), M is a metal selected from titanium, zirconium, or hafnium, which is in a +2, +3, or +4 positive oxidation state; n is 0, 1, or 2; when n is 1, X is a monodentate or bidentate ligand; when n is 2, each X is a monodentate ligand and may be the same or different; the metal-ligand complex is generally charge-neutral; each Z is independently selected from -O-, -S-, -N(RN)-, or -P(RP)-; L is a (C1-C40) alkylene group or a (C1-C40) heteroalkylene group, wherein the (C1-C40) alkylene group has a portion of a main chain of 1 to 10 carbon atoms connecting the two Z groups (L bonds) in formula (I), or the (C1-C40) heteroalkylene group has a portion of a main chain of 1 to 10 atoms connecting the two Z groups in formula (I), wherein (C1-C40) ... The 1-C 40) heteroalkyl group has 1 to 10 atoms as the connecting group, and each of the 1 to 10 atoms in the main chain is independently a carbon atom or a heteroatom, wherein each heteroatom is independently O, S, S(O), S(O)2, Si(RC)2, Ge(RC)2, P(RC) or N(RC), wherein each RC is independently a (C 1-C 30) hydrocarbon group or a (C 1-C 30) heteroalkyl group; R1 and R8 are independently selected from the following groups: -H, (C 1-C 40) hydrocarbon group, (C 1-C 40) heteroalkyl group, -Si(RC)3, -Ge(RC)3, -P(RP)2, -N(RN)2, -ORC, -SRC, -NO2, -CN, -CF3, RCS(O)-, RCS(O)2-, (RC)2C=N-, R CC(O)O-, R COC(O)-, R CC(O)N(RN)-, (RN) 2NC(O)-, halogens and groups having formula (II), (III) or (IV):

[0087] In formulas (II), (III) and (IV), R 31-35, R 41-48 or R 51-59 are independently selected from (C 1-C 40) hydrocarbon groups, (C 1-C 40) heterohydrocarbon groups, -Si(RC) 3, -Ge(RC) 3, -P(RP) 2, -N(RN) 2, -N=CHR C, -OR C, -SR C, -NO 2, -CN, -CF 3, R CS(O)-, R CS(O) 2-, (RC) 2C=N-, R CC(O)O-, R COC(O)-, R CC(O)N(RN)-, (RN) 2NC(O)-, halogen or -H, provided that at least one of R 1 or R 8 is a group having formula (II), (III) or (IV).

[0088] In formula (I), R2-4, R5-7 and R9-16 are each independently selected from (C1-C40) hydrocarbon groups, (C1-C40) heterohydrocarbon groups, -Si(RC)3, -Ge(RC)3, -P(RP)2, -N(RN)2, -N=CHRC, -ORC, -SRC, -NO2, -CN, -CF3, RCS(O)-, RCS(O)2-, (RC)2C=N-, RCC(O)O-, RCOC(O)-, RCC(O)N(RN)-, (RC)2NC(O)-, halogens and -H.

[0089] In one exemplary embodiment of using a dual loop reactor, the main catalyst used in the first loop is [[2,2'''-[[bis[1-methylethyl)germanene]bis(methyleneoxy-κO)]bis[3'',5,5''-tris(1,1-dimethylethyl)-5'-octyl[1,1':3',1''-triphenyl]-2'-ol-κO]](2-)]dimethyl-zirconium, having the chemical formula C86H128F2GeO4Zr and the following structure (V):

[0090] In some embodiments, a polyethylene composition is formed using a first catalyst according to formula (I) in a first reactor and a Ziegler-Natta catalyst in a second reactor.

[0091] The Ziegler-Natta catalyst used in the second reactor for the preparation of polyethylene compositions is a typical supported Ziegler catalyst, particularly useful at high polymerization temperatures in solution processes. Examples of such compositions are those 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 4,612,300; 4,314,912; and 4,547,475, the teachings of which are incorporated herein by reference.

[0092] Particularly suitable organomagnesium compounds include, for example, hydrocarbon-soluble dialkyl magnesiums, such as dialkyl magnesiums and diaryl magnesiums. Exemplary suitable dialkyl magnesiums particularly include n-butyl-dibutyl magnesium, diisopropyl magnesium, di-n-hexyl magnesium, isopropyl-n-butyl magnesium, ethyl-n-hexyl magnesium, ethyl-n-butyl magnesium, di-n-octyl magnesium, and others, wherein the alkyl group has 1 to 20 carbon atoms. Exemplary suitable diaryl magnesiums include diphenyl magnesium, diphenylmethyl magnesium, and xylyl magnesium. Suitable organomagnesium compounds include alkyl and aryl magnesium alkoxides and aryl oxides; and aryl and alkyl magnesium halides, while halogen-free organomagnesium compounds are more desirable.

[0093] Halogen sources include active nonmetallic halides, metallic halides, and hydrogen chloride. Suitable nonmetallic halides are represented by the formula R'X, where R' is hydrogen or an active monovalent organic group, and X is a halogen. Particularly suitable nonmetallic halides include, for example, hydrogen halides and active organohalides, such as tertiary alkyl halides, allyl halides, benzyl halides, and other active hydrocarbon halides. An active organohalide means a hydrocarbon halide containing an unstable halogen, said halogen being at least as active as the halogen of secondary butyl chloride, preferably as active as tertiary butyl chloride (i.e., readily lost to another compound). In addition to organic monohalides, it should be understood that, as defined above, active organic dihalides, trihalides, and other polyhalides are also preferable. Examples of preferred active nonmetallic halides include hydrogen chloride, hydrogen bromide, tributyl chloride, tripentyl bromide, allyl chloride, benzyl chloride, crotonyl chloride, methylvinyl carbinyl chloride, α-phenylethyl bromide, diphenylmethyl chloride, and their analogues. Hydrogen chloride, tributyl chloride, allyl chloride, and benzyl chloride are preferred.

[0094] Suitable metal halides include halides represented by the formula MRy-a Xa, where: M is a group IIB, IIIA, or IVA metal of the Mendeleev periodic table; R is a monovalent organic group; X is a halogen; y has a value corresponding to the valence of M; and "a" has a value from 1 to y. Preferred metal halides are aluminum halides of the formula AlR 3-aX a, where each R is independently a hydrocarbon group, such as an alkyl group; X is a halogen; and a has a value from 1 to 3. Alkyl aluminum halides are most preferred, such as triethylaluminum trichloroethylene, diethylaluminum chloride, ethylaluminum dichloride, and diethylaluminum bromide, with ethylaluminum dichloride being particularly preferred. Alternatively, metal halides such as aluminum trichloride, or combinations of aluminum trichloride and alkyl aluminum halides, or trialkylaluminum compounds, are suitable.

[0095] Any of the known Ziegler-Natta transition metal compounds can be effectively used as the transition metal component in the preparation of supported catalysts. Typically, the transition metal component is a compound of group IVB, VB, or VIB metals. The transition metal component is generally represented by the following formulas: TrX' 4-q(OR1)q, TrX' 4-q, and (R2)q.

[0096] Tr is a group IVB, VB or VIB metal, preferably a group IVB or VB metal, preferably titanium, vanadium or zirconium; q is 0 or equal to or less than 4; X' is a halogen, and R1 is an alkyl, aryl or cycloalkyl group having 1 to 20 carbon atoms; and R2 is an alkyl, aryl, aralkyl, substituted aralkyl or similar group.

[0097] Aryl, aralkyl, and substituted aralkyl groups contain 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. When the transition metal compound contains a hydrocarbon group R2 (which is alkyl, cycloalkyl, aryl, or aralkyl), the hydrocarbon group preferably does not contain a hydrogen atom at the β position relative to the metal carbon bond. Exemplary but non-limiting examples of aralkyl groups are methyl, neopentyl, 2,2-dimethylbutyl, 2,2-dimethylhexyl, aryl groups such as benzyl, and cycloalkyl groups such as 1-norbornyl. If desired, mixtures of these transition metal compounds may be used.

[0098] Illustrative examples of transition metal compounds include TiCl₄, TiBr₄, Ti(OC₂H₅)₃Cl, Ti(OC₂H₅)Cl₃, Ti(OC₄H₹)₃Cl, Ti(OC₃H₇)₂Cl₂, Ti(OC₆H₁₃)₂Cl₂, Ti(OC₈H₁₇)₂Br₂, Ti(OC₁₂H₂₅)Cl₃, Ti(O-iC₃H₇)₄, and Ti(O-nC₄H₹)₄. Illustrative examples of vanadium compounds include VCl₄, VOCl₃, VO(OC₂H₅)₃, and VO(OC₄H₹)₃. Illustrative examples of zirconium compounds include ZrCl₄, ZrCl₃(OC₂H₅), ZrCl₂(OC₂H₅)₂, ZrCl(OC₂H₅)₃, Zr(OC₂H₅)₄, ZrCl₃(OC₄H₹), ZrCl₂(OC₄H₹)₂, and ZrCl(OC₄H₹)₃.

[0099] Inorganic oxide supports can be used in the preparation of catalysts, and the support can be any particulate oxide or a mixture of oxides that has been dehydrated thermally or chemically, so that it is substantially free of adsorbed water. See U.S. Patents 4,612,300; 4,314,912; and 4,547,475, the teachings of which are incorporated herein by reference.

[0100] [Co-catalyst components] []

[0101] Catalytic activity can be achieved by any technique known in this art for activating metal-based catalysts for olefin polymerization reactions, including metal-ligand complexes of formula (I). For example, catalytic activity can be achieved by contacting the complex with an activated co-catalyst, or by combining the complex with an activated co-catalyst. Suitable activated co-catalysts used herein include alkylaluminum; polymeric or oligomeric aluminum oxanes (also known as aluminum oxanes); neutral Lewis acids; and non-polymeric, non-coordinated, ion-forming compounds (including those used under oxidizing conditions). Suitable activation technique is bulk electrolysis. Combinations of one or more of the aforementioned activated co-catalysts and techniques are also considered. The term "alkylaluminum" means monoalkylaluminum dihydrogenide or monoalkylaluminum dihalide, dialkylaluminum hydride or dialkylaluminum halide or trialkylaluminum. Examples of polymeric or oligomeric aluminum oxanes include methylaluminoxane, triisobutylaluminum-modified methylaluminoxane, and isobutylaluminoxane.

[0102] Lewis acid activators (co-catalysts) comprise group 13 metal compounds containing one to three (C1-C20) hydrocarbon substituents as described herein. In one embodiment, the group 13 metal compound is a trisomatic ((C1-C20) hydrocarbon)-substituted aluminum or a trisomatic ((C1-C20) hydrocarbon)-boron compound. In other embodiments, the group 13 metal compound is a trisomatic (hydrocarbon)-substituted aluminum, a trisomatic ((C1-C20) hydrocarbon)-boron compound, a trisomatic ((C1-C10) alkyl)aluminum, a trisomatic ((C6-C18) aryl)boron compound, or its halogenated (including perhalogenated) derivatives. In still other embodiments, the group 13 metal compound is a trisomatic (fluoro-substituted phenyl)borane or a trisomatic (pentafluorophenyl)borane. In some embodiments, the activating cocatalyst is a triphenylmethyltetrafluoroborate (C1-C20)alkyl borate (e.g., triphenylmethyltetrafluoroborate) or triphenyl(C1-C20)alkyl borate triphenyl(C1-C20)alkyl ammonium (e.g., bis(octadecyl)methylammonium)tetra(pentafluorophenyl)borate). As used herein, the term "ammonium" means a nitrogen cation that is (C1-C20)alkyl)4N+, (C1-C20)alkyl)3N(H)+, (C1-C20)alkyl)2N(H)2+, (C1-C20)alkylN(H)3+, or N(H)4+, wherein the (C1-C20)alkyl groups may be the same or different when two or more are present.

[0103] Combinations of neutral Lewis acid activators (co-catalysts) include mixtures of trialkyl((C1-C4)alkyl)aluminum and trialkyl((C6-C18)aryl)boron halides, particularly trialkyl(pentafluorophenyl)boranes. Other examples are combinations of such neutral Lewis acid mixtures with polymeric or oligomeric aluminum oxanes, and combinations of single neutral Lewis acids (especially trialkyl(pentafluorophenyl)boranes) with polymeric or oligomeric aluminum oxanes.

[0104] A catalyst system comprising a metal-ligand complex of formula (I) can be activated to form an active catalyst composition by combining it with one or more co-catalysts, such as cation-forming co-catalysts, strong Lewis acids, or combinations thereof. Suitable activating co-catalysts include polymeric or oligomeric aluminum oxanes, particularly methylaluminoxanes, and inert, compatible, non-coordinated, ion-forming compounds. Exemplary suitable co-catalysts include, but are not limited to, modified methylaluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetra(pentafluorophenyl)boronic acid (1-)amine, and combinations thereof.

[0105] In some embodiments, one or more of the aforementioned activating cocatalysts are used in combination with each other. Particularly preferred combinations are mixtures of tris((C1-C4)alkyl)aluminum, tris((C1-C4)alkyl)methylborane, or ammonium borate with oligomeric or polymeric aluminum oxane compounds. The ratio of the total mole number of one or more metal-ligand complexes of formula (I) to the total mole number of one or more activating cocatalysts is from 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. In some embodiments, when only aluminum oxanes are used as activating cocatalysts, the mole number of aluminum used is preferably at least 10 times the mole number of the metal-ligand complex of formula (I). For example, in some other embodiments, when only tris(pentafluorophenyl)borane is used as the activating cocatalyst, the mole ratio of the tris(pentafluorophenyl)borane used to the total mole ratio of the metal-ligand complex of one or more formulas (I) is 0.5:1 to 10:1, 1:1 to 6:1, or 1:1 to 5:1. The remaining activating cocatalyst is generally used in moles approximately equal to the total mole amount of the metal-ligand complex of one or more formulas (I).

[0106] [membrane] []

[0107] In some embodiments, the embodiments disclosed herein relate to films formed from any of the polyethylene compositions disclosed herein. In some embodiments, the film may be a blown film or a cast film. In some embodiments, the film may be an extrusion-coated film. In some embodiments, the film may be a single-layer film. In some embodiments, the film may be a multilayer film. In some embodiments, the film may be a multilayer film. In some embodiments of multilayer films comprising the polyethylene compositions disclosed herein, the multilayer film may comprise the polyethylene compositions of the present invention in the outer and / or inner layers. In some embodiments, the polyethylene compositions disclosed herein may be used to provide a sealant layer in a multilayer film. For example, the polyethylene compositions disclosed herein may be in the outer layer of a multilayer film formed by co-extrusion via a blown film or a cast film method. The sealant layer may provide a heat-sealable surface. As used herein, a heat-sealable surface is a surface that allows the surface of the film to be heat-sealed to another surface of the same film or to the surface of another film or substrate.

[0108] In one or more embodiments, the polyethylene composition disclosed in this invention may be blended with other polymers, such as other polyethylenes or even other non-polyethylene-based polymers. For example, the polyethylene composition disclosed in this invention may be blended with known polyethylene compositions, such as, but not limited to, LDPE, LLDPE, HDPE, MDPE and / or polyethylene-based plastomers or elastomers known to those skilled in the art.

[0109] The amount of polyethylene composition used in the membrane in the embodiments of the present invention can be determined by many factors, including, for example, whether the membrane is a single-layer membrane or a multilayer membrane, other layers in the membrane (if it is a multilayer membrane), the end-use application of the membrane, and other factors.

[0110] The membrane of this invention can have various thicknesses. The membrane thickness can be determined by many factors, including, for example, whether the membrane is a single-layer or multilayer membrane, the other layers in the membrane (if it is a multilayer membrane), the desired properties of the membrane, the end-use application of the membrane, the equipment used to manufacture the membrane, and other factors. In some embodiments, the membrane of this invention has a thickness of up to 10 mils. For example, the membrane thickness can be from a lower limit of 0.25 mils, 0.5 mils, 0.7 mils, 1.0 mils, 1.75 mils, or 2.0 mils to an upper limit of 4.0 mils, 6.0 mils, 8.0 mils, or 10 mils. In the embodiments, the thickness of the membrane may be 0.25 mil to 2.0 mil, 0.25 mil to 1.75 mil, 0.25 mil to 1.0 mil, 0.25 mil to 0.7 mil, 0.25 mil to 0.5 mil, 0.5 mil to 2.0 mil, 0.5 mil to 1.75 mil, 0.5 mil to 1.0 mil, 0.5 mil to 0.7 mil, 0.7 mil to 2.0 mil, 0.7 mil to 1.75 mil, 0.7 mil to 1.0 mil, 1.0 mil to 2.0 mil, 1.0 mil to 1.75 mil, 1.75 mil to 2.0 mil, or any combination thereof.

[0111] In embodiments where the membrane includes a multilayer membrane, the number of layers in the membrane can be determined by many factors, including, for example, the desired properties of the membrane, the desired thickness of the membrane, the inclusions in the other layers of the membrane, the end-use application of the membrane, the equipment that can be used to manufacture the membrane, and other factors. In various embodiments, the multilayer blown membrane may include up to 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11 layers.

[0112] In some embodiments, the polyethylene composition may be used in more than one layer of the membrane. In various embodiments, other layers within the multilayer membrane of the present invention may include polymers selected from: the polyethylene composition disclosed herein, LLDPE, VLDPE (very low density polyethylene), MDPE, LDPE, HDPE, HMWHDPE (high molecular weight HDPE), propylene-based polymers, polyolefin plastomers (POP), polyolefin elastomers (POE), olefin block copolymers (OBC), ethylene vinyl acetate, ethylene acrylate, ethylene methacrylate, ethylene methyl acrylate, ethylene ethyl acrylate, ethylene butyl acrylate, isobutylene, maleic anhydride-grafted polyolefins, ionomers of any of the foregoing, or combinations thereof. In some embodiments, the multilayer membrane of the present invention may include one or more connecting layers known to those skilled in the art.

[0113] In additional embodiments of the polyolefin film described herein, other layers (sometimes in addition to the barrier layer) may be adhered to, for example, a polyethylene film via an adhesive layer. The adhesive layer can be used to adhere layers of different materials. For example, a barrier layer comprising ethylene vinyl alcohol (EVOH) may be adhered to a polyethylene material via an adhesive layer (i.e., an adhesive layer comprising maleic anhydride-grafted polyethylene). For example, the polyolefin film may further include other layers typically included in a multilayer structure, depending on the application, including, for example, other barrier layers, structural or strength layers, sealant layers, other adhesive layers, other polyethylene layers, polypropylene layers, etc. In additional embodiments, a printing layer may be included, which may be an ink layer applied to the film to display product details and other packaging information in various colors.

[0114] It should be understood that any of the foregoing layers may further include one or more additives as known to those skilled in the art, such as antioxidants, UV stabilizers, heat stabilizers, slip agents, anti-caking agents, pigments or colorants, processing aids, crosslinking catalysts, flame retardants, fillers, and foaming agents. In some embodiments, the polyethylene composition includes up to 5% by weight of such additional additives. This document includes and discloses all individual values ​​and sub-ranges from 0 to 5% by weight; for example, the total amount of additives in the polymer blend may be from a lower limit of 0, 0.5, 1, 1.5, 2, or 2.5% by weight to an upper limit of 1.5, 2, 2.5, 3, 3.5, 4, 4.5, or 5% by weight. In the embodiments, the total amount of additives in the polymer blend can be 0% to 5% by weight, 0% to 4.5% by weight, 0% to 4% by weight, 0% to 3.5% by weight, 0% to 3% by weight, 0% to 2.5% by weight, 0% to 2% by weight, 0% to 1.5% by weight, 0% to 1% by weight, 0% to 0.5% by weight, 0.5% to 5% by weight, 0.5% to 4.5% by weight, 0.5% to 4% by weight, 0% to 4% by weight, 0% to 5% by weight, 0% to 4.5% by weight, 0% to 4% by weight, 0% to 5% by weight, 0% to 4% by weight, 0% to 5% by weight, 0% to 4% by weight, 0% to 5% by weight, 0% to 5% by weight, 0% to 4.5% by weight, 0% to 4% by weight, 0% to 5% by weight, 0% to 5% by weight, 0% to 5% by weight, 0% to 5% by weight, 0% to 4.5% by weight, 0% to ... 0.5% to 3.5% by weight, 0.5% to 3% by weight, 0.5% to 2.5% by weight, 0.5% to 2% by weight, 0.5% to 1.5% by weight, 0.5% to 1% by weight, 1% to 5% by weight, 1% to 4.5% by weight, 1% to 4% by weight, 1% to 3.5% by weight, 1% to 3% by weight, 1% to 2.5% by weight, 1% to 2% by weight, 1% to 1.5% by weight, 1.5% by weight % to 5 wt%, 1.5 wt% to 4.5 wt%, 1.5 wt% to 4 wt%, 1.5 wt% to 3.5 wt%, 1.5 wt% to 3 wt%, 1.5 wt% to 2.5 wt%, 1.5 wt% to 2 wt%, 2 wt% to 5 wt%, 2 wt% to 4.5 wt%, 2 wt% to 4 wt%, 2 wt% to 3.5 wt%, 2 wt% to 3 wt%, 2 wt% to 2.5 wt%, 2.5 wt% to 5 wt%, 2.5 wt% to 4.5% by weight, 2.5% to 4% by weight, 2.5% to 3.5% by weight, 2.5% to 3% by weight, 3% to 5% by weight, 3% to 4.5% by weight, 3% to 4% by weight, 3% to 3.5% by weight, 3.5% to 5% by weight, 3.5% to 4.5% by weight, 3.5% to 4% by weight, 4% to 5% by weight, 4% to 4.5% by weight or 4.5% to 5% by weight or any combination of these ranges.

[0115] As a polyethylene composition, according to some embodiments, the polyethylene compositions disclosed in this invention can be incorporated into multilayer films and articles, which are primarily (if not substantially or entirely) composed of polyolefins or more preferably polyethylene, in order to provide films and articles that are easier to recycle. The polyethylene compositions of this invention are particularly advantageous for demonstrating films in which the film is primarily formed of polyethylene. For example, in addition to other advantages that can be provided by using such polymers, single-layer or multilayer films in which the film primarily comprises polyethylene can have an improved recyclability profile. In some embodiments, the film comprises 90% by weight or more polyethylene by total weight. In other embodiments, the film comprises 91% by weight or more, 92% by weight or more, 93% by weight or more, 94% by weight or more, 95% by weight or more, 96% by weight or more, 97% by weight or more, 98% by weight or more, or 99% by weight or more polyethylene by total weight.

[0116] In some embodiments, a film comprising a layer formed from the polyethylene composition disclosed in this invention may be laminated to another film substrate. The substrate may comprise films including polyester, nylon, polypropylene, polyethylene, and combinations thereof. For a preferred recyclable substrate, a biaxially oriented polyethylene (BOPE) substrate, a processing direction oriented polyethylene (MDO) substrate, or a co-extruded polyethylene film may be included in a layered structure.

[0117] In some embodiments, the film of the present invention may be corona treated and / or printed (e.g., reverse or surface printing) using techniques known to those skilled in the art.

[0118] In some embodiments, the membrane of the present invention may be uniaxial (e.g., in the processing direction) or biaxially oriented using techniques known to those skilled in the art.

[0119] In embodiments, when measured according to the methods described below, films comprising the polyethylene compositions of the present invention may have a barrier force of less than 40 mN / inch or less than 35 mN / inch. Similar methods can be used to observe the barrier force of single-layer and other multilayer films. In embodiments of single-layer and other multilayer films, a barrier force comparable to or smaller than that of comparative films not utilizing the polyethylene compositions described herein may be present.

[0120] [thing] []

[0121] Embodiments of the present invention also relate to articles formed from or containing the polyethylene compositions of the present invention (i.e., via a film containing the polyethylene composition of the present invention), such as encapsulations. Such encapsulations can be formed from any of the polyethylene compositions of the present invention described herein (i.e., via a film containing the polyethylene-based composition of the present invention). Such encapsulations formed from any of the polyethylene compositions of the present invention can be sealed by various sealing methods known in the art (such as heat sealing).

[0122] Examples of such articles may include flexible packaging, pouches, stand-up pouches, and pre-made packaging or pouches. In some embodiments, the multilayer films or laminates of the present invention may be used for food packaging. Examples of foods that may be included in such packaging include meats, cheeses, cereals, nuts, snacks, juices, sauces, and other foods. Based on the teachings herein and based on the specific purpose for which the packaging is used (e.g., the type of food, the quantity of food, etc.), such packaging may be formed using techniques known to those skilled in the art.

[0123] Low heat-sealing initiation temperatures, such as those provided by the polyethylene compositions of this invention, may be particularly desirable for automated packaging systems in which the encapsulated articles are loaded into the package during manufacturing. Lower heat-sealing initiation temperatures can improve packaging productivity by minimizing the time and energy required to heat and cool the sealant. In the case of recyclable polyethylene packaging, the sealing temperature of the inner sealant layer being significantly lower than that of the outer polyethylene layer allows heat sealing to be performed over a wider temperature range, commonly referred to as the heat-sealing window. Some examples of such automated packaging equipment are called vertical form-fill-seal (VFFS) machines or horizontal form-fill-seal (HFFS) machines.

[0124] [Testing Method]

[0125] Unless otherwise indicated herein, the following analytical methods are used in describing the embodiments of the present invention:

[0126] Melt Flow Index

[0127] The melt flow indexes I2 (or I2) and I10 (or I10) of the polymer samples were measured according to ASTM D-1238 (Method B) at 190°C and under loads of 2.16 kg and 10 kg, respectively. The values ​​are reported in grams per 10 minutes.

[0128] [density]

[0129] Samples for density measurement were prepared according to ASTM D4703. Measurements were performed within one hour of sample compression according to ASTM D792 Method B.

[0130] [Method for Measuring Creep Zero-Shear Viscosity] [, , ]

[0131] Zero shear viscosity was obtained via creep testing, performed at 190°C on an AR-G2 stress-controlled rheometer (TA Instruments; New Castle, Del) using parallel plates with a diameter of 25 mm. The rheometer oven was set to the test temperature for at least 30 minutes, after which the components were zeroed. At the test temperature, compression-molded sample trays were inserted between the plates and allowed to equilibrate for 5 minutes. The upper plate was then lowered to 50 μm above the desired test gap (1.5 mm). Any excess material was trimmed, and the upper plate was lowered to the desired gap. Measurements were taken at a flow rate of 5 L / min under nitrogen purging. The preset creep time was set to 2 hours. [, , ]

[0132] A constant low shear stress of 20 Pa was applied to all samples to ensure that the steady-state shear rate was sufficiently low and within the Newtonian region. In this study, the obtained steady-state shear rates for the samples ranged from 10⁻³ to 10⁻⁴ s⁻¹. Steady-state conditions were determined by linear regression of all data obtained within the last 10% time window of the log(J(t)) vs. log(t) graph, where J(t) is the creep compliance and t is the creep time. If the slope of the linear regression was greater than 0.97, steady-state conditions were considered met, and the creep test was stopped. In all cases in this study, the slope met the criterion within 2 hours. The steady-state shear rate was determined by the slope of the linear regression of all data points within the last 10% time window of the η vs. t graph, where η is the strain. Zero-shear viscosity was determined by the ratio of the applied stress to the steady-state shear rate. [, , ]

[0133] To determine whether the sample degraded during the creep test, the same sample was subjected to small-amplitude oscillatory shear tests ranging from 0.1 to 100 rad / s before and after the creep test. The complex viscosity values ​​of the two tests were compared. If the difference in viscosity values ​​at 0.1 rad / s was greater than 5%, the sample was considered to have degraded during the creep test, and the results were discarded. [, , ]

[0134] Gel permeation chromatography (GPC) [GPC] [)] [, , ]

[0135] The chromatography system consisted of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatography system equipped with an internal IR5 infrared detector. The autosampler oven compartment was set at 160°C, and the column compartment at 150°C. The columns used were four Agilent "Mixed A" 30 cm 20 μm linear mixed-bed columns and a 20 μm pre-column column. The chromatography solvent was 1,2,4-trichlorobenzene containing 200 ppm butylated hydroxytoluene (BHT). The solvent source was purged with nitrogen. The injection volume was 200 μL, and the flow rate was 1.0 mL / min. [, , ]

[0136] The calibration of the GPC column assembly was performed using 21 polystyrene standards with narrow molecular weight distributions ranging from 580 to 8,400,000, arranged in a mixture of six "mixtures," with individual molecular weights differing by at least tenfold. The standards were purchased from Agilent Technologies. For molecular weights equal to or greater than 1,000,000, 0.025 g was used in 50 mL of solvent, and for molecular weights less than 1,000,000, 0.05 g was used in 50 mL of solvent. The polystyrene standards were dissolved at 80°C with gentle stirring for 30 minutes. The peak molecular weights of the polystyrene standards were converted to polyethylene molecular weights using Equation 1 (e.g., Williams and Ward, J. Polym.Sci., Polym.Let., 6, 621 (1968)): [, , ] (Equation 1) Where M is the molecular weight, A is 0.4315 and B is 1.0.

[0137] A fifth-order multi-vertex model was used to fit individual polyethylene equivalent calibration points. Small adjustments were made to A (from approximately 0.375 to 0.445) to correct for column resolution and band spread effects, resulting in linear homopolymer polyethylene standards at 120,000 Mw.

[0138] Total disc counts were performed on the GPC column assembly using decane (prepared as 0.04 g in 50 mL TCB, dissolved by gentle stirring for 20 minutes). Disc counts for 200 μL injection volumes were performed according to the following equations (Equation 2) and symmetry was assessed (Equation 3): (Equation 2) Where RV is the retention volume in milliliters, peak width is in milliliters, maximum peak value is the maximum height of the peak, and ½ height is ½ height of the maximum peak value. (Equation 3) Where RV is the retention volume in milliliters, and peak width is in milliliters, the maximum peak value is the highest point of the peak, one-tenth height is 1 / 10 of the maximum peak value, and the latter peak refers to the tail of the peak at a retention volume later than the maximum peak value, while the former peak refers to the front of the peak at a retention volume earlier than the maximum peak value. The disk count of the chromatography system should be greater than 18,000, and the symmetry should be between 0.98 and 1.22.

[0139] Samples were prepared semi-automatically using PolymerChar "Instrument Control" software, with a target sample weight of 2 mg / ml. The solvent (containing 200 ppm BHT) was added to a pre-nitrogen-filled, partition-capped vial via a PolymerChar high-temperature autosampler. The sample was dissolved at 160°C for 2 hours with "low-speed" oscillation.

[0140] The calculations of Mn (GPC), Mw (GPC), and Mz (GPC) are based on GPC results. The polyethylene equivalent molecular weight is obtained by subtracting the IR tomographic plot from the baseline at each equidistant data collection point (i) using PolymerChar GPC-IR tomography instrument internal IR5 detector (measurement channel) according to Equations 4 to 6, and using PolymerChar GPCOne™ software. (Equation 4) (Equation 5) (Equation 6)

[0141] To monitor deviations over time, a flow rate marker (decane) is introduced into each sample via a micropump controlled by a PolymerChar GPC-IR system. This flow rate marker (FM) is used to linearly correct the pump flow rate (nominal flow rate) of each sample by comparing the RV of the individual decane peak within the sample (RV (FM sample)) with the RV of the decane peak within the narrow standard calibration (RV (FM calibration)). It is then assumed that any change in the decane marker peak over time is linearly related to the flow rate (effective flow rate) throughout the operation. To promote the highest accuracy in the RV measurement of the flow marker peak, a least-squares fitting convention is used to fit the peak of the flow marker concentration chromatography to a quadratic equation. The first derivative of the quadratic equation is then used to solve for the true peak position. After calibration based on the flow marker peak, the effective flow rate (for narrow standard calibration) is calculated according to Equation 7. Flow marker peak processing is performed via PolymerChar GPCOne™ software. An acceptable flow rate correction should ensure that the effective flow rate is within + / - 0.5% of the nominal flow rate. Flow rate (effective) = Flow rate (nominal) * (RV (FM calibration) / RV (FM sample)) (Equation 7)

[0142] [Molecular weight comonomer distribution index ()] [MWCDI] [)]

[0143] The GPC-IR high-temperature chromatography system from PolymerChar (Valencia, Spain) is equipped with a Precision Detectors (Amherst, MA) 2-angle laser light scattering detector (model 2040) and an IR5 infrared detector (GPC-IR), as well as four capillary viscometers, all from PolymerChar. The 15-degree angle of the light scattering detector is used for calculation purposes. Data collection is performed using PolymerChar instrument control software and data acquisition interface. The system is also equipped with an online solvent degassing unit and suction system from Agilent Technologies (Santa Clara, CA).

[0144] The injection temperature was controlled at 150°C. Four 20-micron "Mixed-A" light scattering columns from Polymer Laboratories (Shropshire, UK) were used. The solvent was 1,2,4-trichlorobenzene. Samples were prepared at a concentration of 0.1 g polymer in 50 mL of solvent. Both the chromatography solvent and the sample preparation solvent contained 200 ppm of butylated hydroxytoluene (BHT). Both solvent sources were purged with nitrogen. The ethylene polymer sample was gently stirred at 160°C for three hours. The injection volume was 200 μL, and the flow rate was 1 mL / min.

[0145] The calibration of the GPC column assembly was performed using 21 polystyrene standards with a narrow molecular weight distribution, ranging from 580 to 8,400,000 g / mole. These standards were prepared in six "mixture" solutions, with individual molecular weights differing by at least tenfold. The standards were purchased from Polymer Laboratories (Shropshire UK). For molecular weights equal to or greater than 1,000,000 g / mole, the polystyrene standards were prepared at a concentration of 0.025 g in 50 mL of solvent, and for molecular weights less than 1,000,000 g / mole, at a concentration of 0.050 g in 50 mL of solvent. The polystyrene standards were dissolved at 80°C with gentle stirring for 30 minutes. The narrow standard mixtures were operated first, following a decreasing order of the highest molecular weight component to minimize degradation. The peak molecular weight of polystyrene standards was converted to the molecular weight of polyethylene using Equation 1 (e.g., Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)): Where M is the molecular weight, A is approximately 0.40, and B equals 1.0. The value of A is adjusted between 0.375 and 0.445 (depending on the efficiency of a specific column assembly) so that the weight-average molecular weight of NBS 1475A (NIST) linear polyethylene corresponds to 52,000 g / mole, as calculated by the following equation: (Equation 8) (Equation 9) In Equations 8 and 9, RV represents the column retention volume collected at a rate of 1 point per second (linear interval). IR is the baseline-reduced IR detector signal from the measurement channel of the GPC instrument, in volts, and MPE is the polyethylene equivalent in MW determined by Equation 1 above. Data calculations were performed using GPC One software (version 2.013H) from PolymerChar.

[0146] The IR5 detector ratio was calibrated using at least ten ethylene polymer standards (polyethylene homopolymer and ethylene / octene copolymer; narrow molecular weight distribution and uniform comonomer distribution). These standards had known short-chain branching (SCB) frequencies (measured by 13C NMR as described above), ranging from 0 SCB / 1000 total C for homopolymers to approximately 50 SCB / 1000 total C, where total C = carbon in the main chain + carbon in the branches. The weight-average molecular weight of each standard ranged from 36,000 g / mole to 126,000 g / mole, as determined by the GPC-LALS processing method described above. The molecular weight distribution (Mw / Mn) of each standard ranged from 2.0 to 2.5, as determined by the GPC-LALS processing method described above. The polymer characteristics of the SCB standards are shown in Table A. Table A: "SCB" Standard Products Comonomer weight % IR5 area ratio SCB / 1000 Total C Mw Mw / Mn 23.1 0.2411 28.9 37,300 2.22 14.0 0.2152 17.5 36,000 2.19 0.0 0.1809 0.0 38,400 2.20 35.9 0.2708 44.9 42,200 2.18 5.4 0.1959 6.8 37,400 2.16 8.6 0.2043 10.8 36,800 2.20 39.2 0.2770 49.0 125,600 2.22 1.1 0.1810 1.4 107,000 2.09 14.3 0.2161 17.9 103,600 2.20 9.4 0.2031 11.8 103,200 2.26

[0147] For each of the "SCB" standards, calculate the "IR5 area ratio (or "IR5 methyl channel area / IR5 measurement channel area") of the "area response of the IR5 methyl channel sensor minus the baseline" and the "area response of the IR5 measurement channel sensor minus the baseline" (including standard filters and filter wheels supplied by PolymerChar: part number IR5_FWM01 as part of the GPC-IR instrument). Construct a linear fit of the SCB frequency to the "IR5 area ratio" according to the following Equation 10: SCB / 1000 total C = A0 + [A1 x (IR5 methyl channel area / IR5 measurement channel area)] (Equation 10), Where A0 is the intercept of "SCB / 1000 total C" when "IR5 area ratio" is zero, and A1 is the slope of "SCB / 1000 total C" relative to "IR5 area ratio" and represents the increase of "SCB / 1000 total C" as "IR5 area ratio" changes.

[0148] A series of linear baseline-subtracting chromatographic heights were established for the chromatograms generated by the IR5 methyl channel sensor, varying with the column dissociation volume to produce baseline-corrected chromatograms (methyl channels). A series of linear baseline-subtracting chromatographic heights were also established for the chromatograms generated by the IR5 measurement channel, varying with the column dissociation volume to produce baseline-corrected chromatograms (measurement channels).

[0149] The "IR5 height ratio" of the "baseline-corrected chromatography (methyl channel)" and the "baseline-corrected chromatography (measurement channel)" is calculated at each column dissociation volume index (each isometric index, representing 1 data point per second at a dissociation rate of 1 ml / min) spanning the sample integration limit. The "IR5 height ratio" is multiplied by a coefficient A1, and a coefficient A0 is added to this result to produce the predicted SCB frequency of the sample. The result is then converted to comonomer mole percentage in Equation 11 as follows: Comonomer mole percentage = {SCBf / [SCBf + ((1000 - SCBf * comonomer length) / 2)]} * 100 (Equation 11) Where "SCBf" is "SCB per 1000 total C", and for octene, "comonomer length" is 8, for hexene it is 6, and so on.

[0150] The dissolution volume indices were converted to molecular weight values ​​(Mwi) using the method of Williams and Ward (described above; Equation 1). The percentage of comonomer moles (y-axis) was plotted as a function of Log(Mwi), and the slope was calculated between long Mwi values ​​of 15,000 g / moles and long Mwi values ​​of 150,000 g / moles (this calculation ignores end-group corrections at the chain ends). An EXCEL linear regression was used to calculate the slope between 15,000 and 150,000 g / moles of Mwi (inclusive of both 15,000 and 150,000 g / moles). This slope was defined as the molecular weight comonomer distribution index (MWCDI = molecular weight comonomer distribution index).

[0151] [Improved Method for Comonomer Content Distribution Analysis] [iCCD] [)] []

[0152] An improved method for analyzing comonomer content (iCCD) was developed in 2015 (Cong and Parrott et al., WO2017040127A1). iCCD testing was performed using a Crystallization Separation Fractionation (CEF) instrument (PolymerChar, Spain), equipped with an IR-5 detector (PolymerChar, Spain) and a two-angle light scattering detector model 2040 (Precision Detectors, currently Agilent Technologies). A protective column was installed only before the IR-5 detector in the detector oven, filled with 20-27 micrometer glass (MoSCi, USA) in 5 cm or 10 cm (length) × 1 / 4'' (ID) stainless steel. o-Dichlorobenzene (ODCB, 99% anhydrous or industrial grade) was used. Silicone 40 (particle size 0.2-0.5 mm, catalog number 10181-3) was obtained from EMD Chemicals (which could be used to dry the ODCB solvent beforehand). The CEF instrument is equipped with an autosampler with N2 purging capability. Before use, the ODCB is purged with dry nitrogen (N2) for one hour. Sample preparation is performed using the autosampler at 4 mg / ml (unless otherwise specified) at 160°C with shaking for 1 hour. The injection volume is 300 μl. iCCD temperature profile: crystallization from 105°C to 30°C at 3°C / min, thermal equilibration at 30°C for 2 minutes (including dissolution time of the soluble fraction, set to 2 minutes), and dissolution from 30°C to 140°C at 3°C / min. The flow rate during crystallization is 0.0 ml / min. The flow rate during dissolution is 0.50 ml / min. Data is collected at one data point / second.

[0153] An iCCD column was filled with gold-coated nickel particles (Bright 7GNM8-NiS, Nippon Chemical Industrial Co.) in a 15 cm (length) × 1 / 4'' (ID) stainless steel tube. The column filling and conditioning system utilized the slurry method according to the references (Cong, R.; Parrott, A.; Hollis, C.; Cheatham, M. WO2017040127A1). The final pressure for TCB slurry filling was 150 bar.

[0154] The column temperature was calibrated using a mixture of reference material linear homopolymer polyethylene (with zero comonomer content, melt index (I2) of 1.0, degree of polymerization distribution Mw / Mn of approximately 2.6, 1.0 mg / ml by gel permeation chromatography) and eicosane (2 mg / ml) in an ODCB. The CEF temperature calibration consisted of four steps: (1) calculating the hysteresis, defined as the temperature shift between the measured peak dissociation temperature of eicosane and the dissociation temperature minus 30.00℃; (2) subtracting the temperature shift of the dissociation temperature from the original iCCD temperature data. It should be noted that this temperature shift is a function of experimental conditions such as dissociation temperature, dissociation flow rate, etc.; (3) Establish a linear calibration line to convert the dissociation temperature to the range of 30.00℃ to 140.00℃, so that the reference peak temperature of the linear homopolymer polyethylene is 101.0℃ and the peak temperature of eicosane is 30.0℃; (4) For the soluble portion measured isothermally at 30℃, according to the reference (Cerk and Cong et al., US 9,688,795), the dissociation temperature below 30.0℃ is linearly extrapolated by using a dissociation heating rate of 3℃ / min.

[0155] A correlation curve was constructed between the comonomer content and dissociation temperature of the iCCD using 12 reference materials (ethylene homopolymer and ethylene-octene random copolymer, prepared by a single-point metallocene catalyst, with an ethylene equivalent average molecular weight ranging from 35,000 to 128,000). All these reference materials were analyzed at 4 mg / mL in the same manner as previously specified. The reported dissociation peak temperature was linearly fitted to the following linear equation: y = -6.3515x + 101.00, where y represents the dissociation temperature of the iCCD and x represents octene molars, with an R² of 0.978.

[0156] Based on the Rayleigh-Gans-Debys approximation (Striegel and Yau, Modern Size Exclusion Liquid Chromatogram, pp. 242 and 263), the molecular weight of the polymer and the molecular weight of the polymer fraction were determined directly from the LS detector (90° angle) and the concentration detector (IR-5) by assuming a shape factor of 1 and all virial coefficients equal to zero. An integration window was set to integrate all chromatograms within the dissolution temperature range of 23.0 to 120 °C (temperature calibration specified above).

[0157] Calculating molecular weight (Mw) using iCCD involves the following four steps:

[0158] (1) Measurement of detector offset. Offset is defined as the geometric volume offset relative to the concentration detector LS. It is calculated as the difference in dissolution volume (mL) of the polymer peak between the concentration detector and the LS chromatogram. This difference is converted into temperature offset by using the dissolution heat rate and dissolution flow rate. Linear high-density polyethylene (with zero comonomer content, melt index (I²) of 1.0, and a degree of polymerization distribution Mw / Mn of approximately 2.6 by conventional gel permeation chromatography) was used. The same experimental conditions as the normal iCCD method described above were used, except for the following parameters: crystallization at 10 °C / min from 140 °C to 137 °C, thermal equilibration at 137 °C for 1 minute as the soluble fraction dissolution time, 7 minutes of soluble fraction (SF) time, and dissolution at 3 °C / min from 137 °C to 142 °C. The flow rate during crystallization was 0.0 ml / min. The flow rate during dissolution was 0.80 ml / min. The sample concentration was 1.0 mg / ml.

[0159] (2) Move each data point in the LS tomography to correct for inter-detector offsets before integration.

[0160] (3) Subtract the baseline LS and concentration chromatograms from the integral over the entire dissolution temperature range of step (1). The MW detector constant is calculated by using the area ratio of the integrated LS and concentration signals of known MW HDPE samples in the range of 100,000 to 140,000 Mw.

[0161] (4) The Mw of the polymer is calculated by using the ratio of the integrated light scattering detector (90-degree angle) to the concentration detector and the MW detector constant.

[0162] The half-peak width is defined as the temperature difference between the front and back of the maximum peak height. The front temperature at the half-peak height is searched forward from 35.0℃, while the back temperature is searched backward from 119.0℃ at the half-peak height.

[0163] [Zero shear viscosity ratio ()] [ZSVR] [)] [, , ]

[0164] ZSVR is defined as the ratio of the zero-shear viscosity (ZSV) of branched polyethylene to that of linear polyethylene at the same average molecular weight (Mw-gpc), according to the following equations 8 and 9: [, , ] (Equation 8) (Equation 9)

[0165] ZSV values ​​were obtained by creep testing at 190°C using the method described above. Mw-gpc values ​​were determined using the conventional GPC method (Equation 5 in the description of the conventional GPC method). The correlation between ZSV and Mw-gpc of linear polyethylene was established based on a series of linear polyethylene reference materials. A description of the ZSV-Mw relationship can be found in ANTEC proceeding: Karjala, Teresa P., Sammler, Robert L., Mangnus, Marc A., Hazlitt, Lonnie G., Johnson, Mark S., Hagen, Charles M. Jr., Huang, Joe WL, Reichek, Kenneth N., "Detection of low levels of long-chain branching in polyolefins", Annual Technical Conference - Society of Plastics Engineers (2008), Vol. 66, pp. 887-891. [Example] [, , ]

[0166] [Example] [1] [The polyethylene composition of the present invention] [1-3] [and comparative compositions] [C] [Preparation] [, , ]

[0167] [Polyethylene Composition of the Invention] [1] [and comparative compositions] [C] [Preparation] [, , ]

[0168] The polyethylene composition 1 of the present invention (abbreviated as "PE composition 1 of the present invention") is prepared by a method and using the catalyst and reactor described below, according to one or more embodiments. Comparative composition C (abbreviated as "Comparative composition C") is prepared by a method and using the catalyst and reactor described below. [, , ]

[0169] All raw materials (monomers and comonomers) and process solvents (narrow boiling range high-purity isoalkane solvent, Isopar-E) are purified using molecular sieves before being introduced into the reaction environment. Hydrogen is supplied at high purity under pressure and is not further purified. The reactor monomer feed stream is pressurized to above the reaction pressure via a mechanical compressor. The solvent and comonomer feed streams are pressurized to above the reaction pressure via pumps. Individual catalyst components are manually diluted in batches with purified solvents and pressurized to above the reaction pressure. All reaction feed flow rates are measured by mass flow meters and controlled by individual computer-controlled automatic valve systems.

[0170] The two reactor systems are used in series, as depicted in Figure 2. Each continuous solution polymerization reactor utilizes a flooded, non-adiabatic, isothermal, circulating loop reactor, mimicking a heat-removing continuous stirred tank reactor (CSTR). All fresh solvent, monomer, comonomer, hydrogen, and catalyst components can be independently controlled. The temperature of all fresh feed streams (solvent, monomer, comonomer, and hydrogen) entering each reactor is controlled by passing the feed stream through a heat exchanger to maintain a single solution phase. All fresh feed entering each polymerization reactor is injected into the reactor at two locations, with approximately equal reactor volumes between injection points. The fresh feed is controlled so that each injector contains half the total mass flow rate of the fresh feed. The catalyst components are injected into the polymerization reactor via injectors. The catalyst feed is computer-controlled to maintain monomer conversion at a specified target in each reactor. The co-catalyst components are fed based on a calculated specified molar ratio to the main catalyst components. Immediately after the feed injection points in each reactor, a static mixing element is used to mix the feed stream with the contents of the circulating polymerization reactor. The contents within each reactor are continuously circulated through heat exchangers, which are responsible for removing most of the heat from the reaction, and the temperature on the coolant side is responsible for maintaining the isothermal reaction environment at the specified temperature. Circulation around each reactor loop is provided by pumps.

[0171] The effluent from the first polymerization reactor (containing solvent, monomer, comonomer, hydrogen, catalyst components and polymer) leaves the first reactor loop and is added to the second reactor loop.

[0172] The effluent from the second reactor enters a zone where it is deactivated by adding and reacting with a suitable reactant (water). At the outlet of this same reactor, other additives for polymer stabilization are added (typical antioxidants suitable for stabilization during extrusion and membrane manufacturing, such as octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, tetra(methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate))methane, and tris(2,4-di-tert-butyl-phenyl)phosphite).

[0173] After catalyst deactivation and additive addition, the effluent from the second reactor enters the volatile matter removal system, where polymers are removed from the non-polymer stream. Granulated polymer melt is collected. The non-polymer stream passes through various sections of the equipment, separating most of the ethylene removed from the system. After passing through the purification system, most of the solvent and unreacted comonomers are recovered to the reactor. Small amounts of solvent and comonomers are removed during the self-processing.

[0174] The reactor material flow feed data corresponds to the values ​​in Table 1. This data is presented to account for the complexity of the solvent recovery system and to simplify the reaction system into a single-pass flow diagram. Table 2 shows the catalysts mentioned in Table 1.

[0175] [Polyethylene Composition of the Invention] [2-3] [Preparation]

[0176] The polyethylene compositions 2-3 of the present invention (abbreviated as "PE compositions of the present invention.#") are prepared by a method and using the catalyst and reactor described below, according to one or more embodiments.

[0177] All raw materials (monomers and comonomers) and process solvents (narrow boiling range high-purity isoalkane solvent, Isopar-E) are purified using molecular sieves before being introduced into the reaction environment. Hydrogen is supplied at high purity under pressure and is not further purified. The reactor monomer feed stream is pressurized to above the reaction pressure via a mechanical compressor. The solvent and comonomer feed streams are pressurized to above the reaction pressure via pumps. Individual catalyst components are manually diluted in batches with purified solvents and pressurized to above the reaction pressure. All reaction feed flow rates are measured by mass flow meters and controlled by individual computer-controlled automatic valve systems.

[0178] The two reactor systems are used in series, as depicted in Figure 2. The first reactor is a continuous solution polymerization reactor consisting of a flooded, non-adiabatic, isothermal, circulating loop reactor, mimicking a continuously stirred tank reactor (CSTR) with heat removal. All freshly prepared solvent, monomer, comonomer, hydrogen, and catalyst components can be independently controlled. The temperature of all freshly prepared feed streams (solvent, monomer, comonomer, and hydrogen) entering the first reactor is controlled by passing the feed stream through a heat exchanger to maintain a single solution phase. All freshly prepared feed to the first polymerization reactor is injected into the reactor at two locations, with approximately equal reactor volumes between each injection point. The freshly prepared feed is controlled so that each injector contains half the total mass flow rate of the freshly prepared feed. The catalyst components are injected separately from the freshly prepared feed into the polymerization reactor. The main catalyst component feed is computer-controlled to maintain the monomer conversion in the reactor at a specified value. The co-catalyst component is fed based on its molar ratio to the main catalyst component. Immediately following the feed injection points of each first reactor, a static mixing element is used to mix the feed stream with the contents of the circulating polymerization reactor. The contents of the first reactor are continuously circulated through heat exchangers, which are responsible for removing most of the heat of the reaction, and the temperature on the coolant side is responsible for maintaining the isothermal reaction environment at the specified temperature. Circulation around the first reactor loop is provided by a pump.

[0179] The second reactor is a continuous solution polymerization reactor consisting of a flooded, adiabatic continuously stirred tank reactor (CSTR). All fresh feed components (solvent, monomer, comonomer, hydrogen, and catalyst) can be independently controlled. The temperature of all fresh feed streams (solvent, monomer, comonomer, and hydrogen) to the second reactor is controlled by passing the feed stream through a heat exchanger to maintain a single solution phase. All fresh feed to the second polymerization reactor is injected into the reactor at one location. The catalyst component is injected separately from the fresh feed into the second polymerization reactor. The main catalyst component feed is computer-controlled to maintain the monomer conversion in the reactor at a specified value. The co-catalyst component is fed based on its molar ratio to the main catalyst component. Mixing in the second reactor is provided by a stirrer. The effluent from the first polymerization reactor (containing solvent, monomer, comonomer, hydrogen, catalyst component, and polymer) leaves the first reactor loop and is added to the second reactor separately from the fresh feed and catalyst feed components.

[0180] The effluent from the second reactor enters a zone where it is deactivated by adding and reacting with a suitable reactant (water). At the same reactor outlet location, other additives for polymer stabilization are added (typical antioxidants suitable for stabilization during extrusion and membrane manufacturing, such as octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, tetra(methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate))methane, and tris(2,4-di-tert-butyl-phenyl)phosphite).

[0181] After catalyst deactivation and additive addition, the effluent from the second reactor enters the volatile matter removal system, where polymers are removed from the non-polymer stream. Granulated polymer melt is collected. The non-polymer stream passes through various sections of the equipment, separating most of the ethylene removed from the system. After passing through the purification system, most of the solvent and unreacted comonomers are recovered to the reactor. Small amounts of solvent and comonomers are removed during the self-processing.

[0182] The reactor material flow feed data corresponds to the values ​​in Table 1. This data is presented to account for the complexity of the solvent recovery system and to simplify the reaction system into a single-pass flow diagram. Table 2 shows the catalysts mentioned in Table 1. [, , ] [] [surface] [1] [] [Polyethylene Composition of the Invention] [PE of this invention] [Composition 1] [PE of this invention] [Composition 2] [PE of this invention] [Composition 3] [Comparative Composition C] Reactor configuration type Dual Series Dual Series Dual Series Dual Series Comonomer type type 1-Octenene 1-Octenene 1-Octenene 1-Octenene The solvent / ethylene mass flow rate ratio of the first reactor feed g / g 4.22 5.61 5.15 4.63 The mass flow ratio of comonomer to ethylene in the first reactor feed g / g 0.41 0.40 0.60 0.42 The first reactor feed hydrogen / ethylene mass flow ratio g / g 1.26E-04 7.88E-05 1.00E-04 9.57E-05 Temperature of the first reactor ℃ 165 155 160 160 Pressure of the first reactor barg 50 43 43 50 Ethylene conversion rate in the first reactor % 91.0 94.6 87.7 93.4 First reactor catalyst type type Catalyst component A Catalyst component A Catalyst component A Catalyst component A First reactor catalyst metal type Zr Zr Zr Zr Type 1 auxiliary catalyst for the first reactor type Co-catalyst A Co-catalyst A Co-catalyst A Co-catalyst A Type 2 co-catalyst for the first reactor type Co-catalyst B Co-catalyst B Co-catalyst B Co-catalyst B The molar ratio (ratio of B to metal) of co-catalyst 1 to catalyst in the first reactor. ratio 1.2 1.0 1.1 1.1 The molar ratio (Al to metal ratio) of co-catalyst 2 to catalyst in the first reactor. ratio 31.1 17.9 17.9 21.3 First reactor residence time minute 13.2 17.5 18.4 9.8 Percentage of total ethylene feed sent to the first reactor weight% 58.2% 54.5% 54.1% 56.3% The second reactor feed solvent / ethylene mass flow ratio g / g 2.17 4.35 5.03 2.12 The second reactor feed comonomer / ethylene mass flow ratio g / g 0.099 0.101 0.275 0.071 The second reactor feed hydrogen / ethylene mass flow ratio g / g 1.04E-05 2.54E-04 2.40E-04 2.75E-04 Temperature of the second reactor ℃ 190 191 190 190 Pressure in the second reactor barg 50 43 43 51 Ethylene conversion rate in the second reactor % 84.3 83.4 84.1 83.2 Second reactor catalyst type type Catalyst component B Catalyst component B Catalyst component B Catalyst component C Second reactor catalyst metal type Ti Ti Ti Zr Second reactor co-catalyst type 1 type Co-catalyst A Type 2 auxiliary catalyst for the second reactor type Co-catalyst C Co-catalyst C Co-catalyst C Co-catalyst B The molar ratio (ratio of B to metal) of co-catalyst 1 to catalyst in the second reactor. mol / mol 1.2 The molar ratio (Al to metal ratio) of co-catalyst 2 to catalyst in the second reactor. mol / mol 1.5 1.3 1.3 13.0 Second reactor residence time minute 9.2 10.1 9.9 6.8 [] [, , ] [] [surface] [2] [] Catalyst component A Catalyst component B Ziegler-Natta type catalyst. The heterogeneous Ziegler-Natta type catalyst premix is ​​prepared, substantially according to U.S. Patent No. 4,612,300, by sequentially adding anhydrous magnesium chloride in ISOPAR E, a solution of EtAlCl₂ in heptane, and a solution of Ti(O-iPr)₄ in heptane to the volume of ISOPAR E, to obtain a composition containing a magnesium concentration of 0.20 M and a Mg / Al / Ti ratio of 40 / 12.5 / 3. Aliquots of this composition are further diluted with ISOPAR-E as needed to maintain the feed rate within the system capacity. The catalyst premix is ​​contacted with a dilute solution of Et₃Al at the Al / Ti molar ratio specified in Table 1 simultaneously with and before entering the polymerization reactor to obtain an active catalyst. Catalyst component C Co-catalyst A Co-catalyst B Modified methylaluminoxane Co-catalyst C Triethylaluminum

[0183] [Example] [2] [Comparative Compositions] [AC] []

[0184] Table 3 identifies commercially available polyethylene compositions ("comparative PE compositions") AB as comparative polyethylene compositions. Comparative PE composition C is as described in Example 1 above. [, , ] [] [surface] [3] [Compare] [PE] [Composition] [Business Name (Manufacturing Company)] A ELITE™ AT 6410 (The Dow Chemical Company) B ELITE TMAT 6501 (The Dow Chemical Company)

[0185] [Example] [3] [Example] [1] [The polyethylene composition of the present invention] [1-3] [and examples] [2] [Comparison of polyethylene compositions] [AC] [Analysis] [, , ]

[0186] Table 4 reports the density and melt flow index (I 2) of polyethylene compositions 1-3 and comparative polyethylene composition AC of the present invention. Additionally, for some compositions, the molecular weight was measured using gel permeation chromatography (GPC), and the molecular weight comonomer distribution index (MWCDI) value was determined using the techniques described in the above-described test methods section. These values ​​are shown in Table 4. [surface] [4] [sample] [ID] [density] [(] [g / cm, 3 , ] [)] [I, 2, ] [(grams)] [ / 10] [minute)] [I, 10 , / I , 2, ] [M, w , ] [(] [g / mol] [)] [M, z , ] [(] [g / mol] [)] [M, w , / M , n , ] [MWCDI, , ] [ZSVR] Comparison of PE composition A 0.912 0.85 7.8 100967 217949 2.63 -0.42 Comparison of PE composition B 0.914 0.85 7.9 101163 220649 2.75 0.37 Comparison of PE composition C 0.906 0.78 7.1 107996 242813 2.53 0.42 1.80 This invention PE composition 1 0.913 0.84 6.2 115593 276749 2.66 0.42 1.42 This invention PE composition 2 0.912 0.94 6.8 113716 282857 2.90 1.40 This invention PE composition 3 0.908 0.89 6.5 116286 285791 3.02 1.83

[0187] The polyethylene compositions 1-3 of the present invention in Example 1 and the comparative polyethylene composition AC in Example 2 were analyzed by iCCD. Table 5 provides data generated from iCCD tests of all samples (polyethylene compositions 1-3 of the present invention in Example 1 and comparative polyethylene composition AC). Specifically, Table 5 contains the analysis of iCCD data for three polyethylene fractions: 40°C to 75°C, 75°C to 85°C, and 85°C to 110°C. [, , ] [] [surface] [5] [sample] [ID] [40℃-75℃] [75℃-85℃] [85℃-110℃] Comparison of PE composition A 31.3% 66.2% 1.97% Comparison of PE composition B 48.2% 33.8% 17.4% Comparison of PE composition C 55.8% 37.9% 5.1% PE composition 1 of the present invention 51.2% twenty one% 27% PE composition 2 of the present invention 55.7% 7.8% 34% PE composition 3 of the present invention 61.6% 11.9% 25%

[0188] Additionally, as described in the Test Methods section, the weight-average molecular weight (Mw) of each of the polyethylene compositions 1-3 and the comparative composition AC specified above was calculated using iCCD. The data is shown in Table 6. Table 6 also shows the ratio of Mw of the first polyethylene portion ([A], 40℃-75℃) to the Mw of the second polyethylene portion ([B], 75℃-85℃) ("[A] / [B]"), and the ratio of Mw of the second polyethylene portion ([B], 75℃-85℃) to the Mw of the third polyethylene portion ([C], 85℃-110℃) ("[B] / [C]"). [surface] [6] [sample] [ID] [40℃-75℃] [Middle] [M, w , ] [part,] [[A]] [75℃-85℃] [Middle] [M, w , ] [part,] [[B]] [85℃-110℃] [Middle] [M, w , ] [part,] [[C]] [[A] / [B]] [[B] / [C]] Comparison of PE composition A 71347 124278 114023 0.57 1.09 Comparison of PE composition B 102148 119478 129296 0.85 0.92 Comparison of PE composition C 120242 109497 130819 1.10 0.84 PE composition 1 of the present invention 114561 123885 142318 0.92 0.87 PE composition 2 of the present invention 125941 130656 105063 0.96 1.24 PE composition 3 of the present invention 137238 87119 109785 1.58 0.79

[0189] [Example] [4] Analysis of heat-sealing initiation temperature and hot-tack initiation temperature [, , ]

[0190] In Example 4, the heat-sealing initiation temperature, hot tack initiation temperature, and peak hot tack of the film comprising the polyethylene composition described herein are analyzed.

[0191] To analyze these properties, the multilayer film was co-extruded on an Alpine 7-layer blown film production line. This line is equipped with seven 30 L / D 50 mm single-screw extruders and 250 mm dies. A three-layer (skin, core, and sealant) film with a total thickness of 50 micrometers was produced. The skin / core / sealant layer thickness ratio was set at 1 / 3 / 1 (10 micrometers / 30 micrometers / 10 micrometers). The skin layer consisted of an 80 / 20 (by weight) DOWLEX™ 2045G / DOW™ LDPE 611A blend, both sourced from Dow Chemical. The core layer's base resin included the same blend as the skin layer, but additionally contained 500 ppm 10090 Slip PE MB (erucic acid amine, available from Ampacet) and 10063 Antiblock PE MB (available from Ampacet), added via dry blending. The polyethylene composition used in the sealant layer varied, as provided in Table 7. 750 ppm 10090 Slip PE MB and 2500 ppm 10063 Antiblock PE MB were introduced into the sealant layer via dry blending. The die gap was set at 78.7 mils, the blow-up ratio at 2.5, the melt temperature at 440℉-470℉, the output rate at 350 psi, and the frosting height at approximately 37 inches. Bubbles in the multilayer film were cut online and separated into two rolls. [, , ] [] [surface] [7] [sample] [Sealant layer] Comparison membrane A ELITE™ AT 6410 (The Dow Chemical Company) Comparison membrane B ELITE TMAT 6501 (The Dow Chemical Company) Comparison membrane C Comparison of PE composition C Membrane 1 of the present invention PE composition 1 of the present invention Membrane 2 of the present invention PE composition 2 of the present invention Membrane 3 of the present invention PE composition 3 of the present invention

[0192] Next, using a Nordmeccanica Super Combi 3000 laminator and an ADCOTE™ 577 / CR 87-124 solvent-based adhesive, each of the films 1-3 of the present invention and the comparative film AC was laminated onto a 12-micron-thick oriented polyethylene terephthalate (PET) film, wherein the ADCOTE™ 577 and CR 87-124 components were mixed in a weight ratio of 100:7. Before applying the solvent-based adhesive, a 1 kW corona discharge was applied to the skin side of each of the films 1-3 of the present invention and the comparative film AC. The adhesive was applied using a 11.5 bcm 150-channel quadrilateral, producing a coating weight of 1.75 lbs / rm via a gravure roller, followed by lamination at 160℉. The films were cured at 25°C and 40% relative humidity for at least 5-7 days for complete chemical curing to produce laminated films 1-3 and the comparative laminated film AC.

[0193] Using an Enepay commercial testing machine, the thermal tack of each of the laminates 1-3 and the comparative laminate AC was measured according to ASTM F-1921 (Method B). Prior to testing, the samples were conditioned at 23°C and 50% RH for at least 40 hours according to ASTM D-618 (Procedure A).

[0194]

[0195] Thin sheets measuring 8.5'' × 14'' were cut from the film, with the longest dimension in the processing direction. Strips 1'' wide and 14'' long were also cut from the film. These samples were tested at a series of temperatures, and the results were reported as the maximum load as a function of temperature. Typical temperature steps were 5°C or 10°C, with six repetitions at each temperature. Typical parameters used in the tests are as follows: Sample width: 25.4 mm (1.0 inch) Sealing pressure: 0.275 N / mm² Sealing time: 0.5 s Delay time: 0.18 s Peeling speed: 200 mm / s Sealing depth = 0.5 inches

[0196] Thermoviscosity curves were established by linear interpolation of the average maximum load measured at various temperatures. The lowest temperature at which the average maximum load of 4 N is achieved (defined as the thermoviscosity onset temperature) was determined from this curve and is reported in Table 8. The maximum average load (defined as peak thermoviscosity) determined from the thermoviscosity curve is also shown.

[0197] Using a commercial tensile testing machine, heat seal measurements were performed on each of laminates 1-3 and comparative laminate AC according to ASTM F-88 (Technical A).

[0198] Prior to cutting, the film is conditioned for at least 40 hours at 23°C (±2°C) and 50% (±10%) RH, according to ASTM D-618 (Program A). A sheet approximately 11 inches long and 8.5 inches wide is then cut from the film in the processing direction. The sheet is then heat-sealed in the processing direction on a Kopp heat sealer under typical conditions within a range of temperatures: Sealing pressure: 0.275 N / mm² Sealing time: 0.5 s (<1 mil) or 1.0 s (>1 mil) Sealing depth = 5mm

[0199] Before cutting into one-inch wide strips, conditioned the sealing sheet at 23°C (+2°C) and 50% RH (+10%) for at least 3 hours. Before testing, conditioned the sample after sealing at 23°C (±2°C) and 50% RH (±10%) for at least 24 hours.

[0200] For testing, the strip was loaded into the fixture of a tensile testing machine with an initial spacing of 2 inches, and stretched at a fixture separation rate of 10 inches / minute at 23°C (+2°C) and 50%RH (+10%). The strip was tested without support. Five repeated tests were performed at each sealing temperature.

[0201] The maximum load measured during the stripping process was determined at multiple sealing temperatures, and a heat-sealing curve was established by linear interpolation of the average maximum load measured at each temperature. From this curve, the temperature at which an average maximum load of 2 lb is achieved (defined as the heat-sealing initiation temperature) is determined and is provided in Table 8. [surface] [8] [sample] [Hot viscosity onset temperature ()] [℃] [)] Peak thermal viscosity () [N] [)] [Heat-sealing start temperature ()] [℃] [)] Laminated Comparison Film A 109 17.7 90 Laminated Comparison Film B 103 12.8 84 Laminated Comparison Film C 99 15.3 82 Laminated film 1 98 14.8 82 Laminated film 2 88 12.8 82 Laminated film 3 86 13.2 <80

[0202] It is known that the heat-sealing initiation temperature and the hot-tack initiation temperature are affected by the overall density of the polyethylene composition. Therefore, the appropriate comparisons in Table 8 are: (1) laminated films 1-2 to laminated comparison films 1-2; and (2) laminated film 3 to laminated comparison film C. As shown in Table 8, within each comparable group, the polyethylene compositions using some embodiments of the present invention exhibit the lowest hot-tack initiation temperature and the lowest heat-sealing initiation temperature compared to the comparison PE compositions.

[0203] Temperature of iCCD: iCCD temperature Mass: quality FIRST REACTOR: First Reactor FIRST REACTOR EFFLUENT: First reactor effluent Second Reactor Second Reactor Effluent: Effluent from the second reactor SOLVENT / ETHYLENE: Solvent / Ethylene HYDROGEN / ETHYLENE: Hydrogen / Ethylene COMONOMER / ETHYLENE: Comonomer / Ethylene

Claims

1. A polyethylene composition suitable for encapsulation applications, comprising: (a) a first polyethylene fraction having a single peak in a dissolution curve analyzed by an iCCD method within a temperature range of 40°C to 75°C, wherein the area of ​​the first polyethylene fraction is the area below the single peak of the first polyethylene fraction between 40°C and 75°C in the dissolution curve, and wherein the area of ​​the first polyethylene fraction accounts for 45% to 65% of the total area of ​​the dissolution curve; and (b) a second polyethylene fraction having at least one peak in a temperature range of 85°C to 110°C in the dissolution curve analyzed by an iCCD method, wherein the area of ​​the second polyethylene fraction is the area below the at least one peak of the second polyethylene fraction between 85°C and 110°C in the dissolution curve, and wherein the area of ​​the second polyethylene fraction accounts for 15% to 35% of the total area of ​​the dissolution curve; wherein the polyethylene composition has a content of 0.905 g / cm³ to 0.918 g / cm³. The composition has a density of g / cm3 and a melt index (I2) of 0.7 g / 10 min to 3.5 g / 10 min, and the composition has a melt index ratio (I10 / I2) that satisfies the following equation: I10 / I2 < 7.0 - 1.2 log(I2); wherein the melt indexes I2 and I10 are measured according to ASTM D-1238 (Method B) at 190°C and at loads of 2.16 kg and 10 kg, respectively.

2. The polyethylene composition of claim 1, wherein the ratio of the weight average molecular weight of the first polyethylene fraction in the temperature range of 40°C to 75°C in the dissolution curve by iCCD analysis to the weight average molecular weight of the third polyethylene fraction in the temperature range of 75°C to 85°C in the dissolution curve by iCCD analysis is 0.90 to 1.

6.

3. The polyethylene composition of claim 2, wherein the ratio of the weight average molecular weight of the third polyethylene fraction to the weight average molecular weight of the second polyethylene fraction in the temperature range of 85°C to 110°C in the dissolution profile obtained by iCCD analysis is 0.50 to 1.

50.

4. The polyethylene composition of any one of claims 1 to 3, wherein the polyethylene composition has a zero shear viscosity ratio of less than 2.

0.

5. A polyethylene composition according to any one of claims 1 to 3, wherein the polyethylene composition has a molecular weight distribution in the range of 2.0 to 3.5, the molecular weight distribution being expressed as the ratio of weight average molecular weight to number average molecular weight.

6. A polyethylene composition of any one of claims 1 to 3, wherein the polyethylene composition has a molecular weight comonomer distribution index (MWCDI) of less than 1.

0.

7. A membrane comprising a polyethylene composition as claimed in any one of claims 1 to 6.

8. A multilayer film comprising a sealant layer, wherein the sealant layer comprises a polyethylene composition as claimed in any one of claims 1 to 6.

9. An article comprising a polyethylene composition, wherein the polyethylene composition is any one of claims 1 to 6.

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