Polyethylene composition

Abstract

A polyethylene composition having a balance of stiffness and performance properties is provided. The polyethylene composition may comprise, by improved comonomer composition distribution (iCCD) analysis, a first polyethylene fraction region defined by a region in the elution profile in the temperature range of 70°C to 97°C, a first peak in the elution profile in the temperature range of 70°C to 97°C, a second polyethylene fraction region defined by a region in the elution profile in the temperature range of 97°C to 110°C, and a second peak in the temperature range of 97°C to 110°C. The polyethylene composition may have a densitometric average molecular weight (Mg / cm) of 0.935 g / cm. 3 ~0.955g / cm 3 and a melt index (I2) of 1.0 g / 10 min to 10.0 g / 10 min. The ratio of the first polyethylene fraction domain to the second polyethylene fraction domain may be less than 2.0.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application is filed on June 30, 2020, which is incorporated herein by reference in its entirety. The benefit of U.S. Provisional Patent Application No. 63 / 046,396 is claimed.

[0002] FIELD OF THE INVENTION FIELD OF THE INVENTION The embodiments described herein relate generally to polymers, and more specifically to polyethylene. The present invention relates to a composition. [Background technology]

[0003] The use of polyolefin compositions in the formation of molded articles is generally known. Any conventional method can be employed to produce such polyolefin compositions. A variety of polymerization techniques using different catalyst systems have been developed to produce such polyolefins suitable for forming articles. It has been used to produce a soluble composition. Summary of the Invention

[0004] However, despite research efforts in developing compositions suitable for forming articles, There remains a need for compositions that have a balance of stiffness and performance properties that meet customer and industry demands. Furthermore, researchers have investigated the effect of, for example, downgauging (i.e., thinner wall thickness) or by reducing or eliminating relatively expensive materials. We are constantly looking for solutions that allow us to reduce material costs, for example downgauging. Although this can be achieved by using polymer resins with higher densities, Higher temperatures usually result in lower environmental stress crack resistance (ESCR). There is a need for compositions that have a balance of stiffness and performance properties that meet industry demands.

[0005] Embodiments of the present disclosure exhibit desirable stiffness without compromising performance characteristics, such as ESCR. Accordingly, embodiments of the present disclosure are directed to a polymeric article, When utilized in the production of It is possible to provide a polyethylene composition that can enable a reduction in the cost of materials used.

[0006] According to one or more embodiments, a polyethylene composition is provided. The temperature range of 70℃ to 97℃ was measured using an improved comonomer composition distribution (iCCD) analysis method. a first polyethylene fraction region defined by a region in the elution profile surrounding The first peak in the temperature range of 70°C to 97°C in the elution profile and the second peak in the temperature range of 97°C to 110°C A second polyethylene fraction defined by a region in the elution profile in the temperature range of The polyethylene composition may include a first peak in the temperature range of 97°C to 110°C and a second peak in the temperature range of 97°C to 110°C. The material is 0.935g / cm 3 ~0.955g / cm 3 Density and 1.0g / 10min~10 The first polyethylene fraction region may have a melt index (I2) of 0.0 g / 10 min. to the second polyethylene fraction region may be less than 2.0.

[0007] According to one or more embodiments, a polyethylene composition is provided. in the elution profile by improved comonomer composition distribution (iCCD) analysis. A first polyethylene fraction in the temperature range of 70°C to 97°C, comprising a first peak, The molecular weight of the fraction 1 (Mw(iCCD、70℃~97℃) ) a first polyethylene film having and the second polyethylene fraction in the temperature range of 97°C to 110°C in the elution profile. and a second polyethylene fraction comprising a second peak. The total molecular weight (Mw (iCCD) ), 0.935g / cm 3 ~0.955g / cm 3 and a melt index (I2) of 1.0 g / 10 min to 10.0 g / 10 min. The total molecular weight Mw (iCCD) The molecular weight of the first fraction (Mw (iCCD、70℃~9 7℃) ) may be less than 0.9.

[0008] According to one or more embodiments, an article is provided. The article may be a rotationally molded or injection molded article. An article may comprise the polyethylene composition.

[0009] These and other embodiments are described in the following detailed description in conjunction with the accompanying drawings. This is explained in more detail in [Brief explanation of the drawings]

[0010] The following detailed description of certain embodiments of the present disclosure, taken in conjunction with the following drawings, illustrates: This specification can be best understood by reading it in its entirety, where like structure is indicated with like reference numerals. do. [Figure 1] 1 is a graph showing the elution profile of polyethylene composition 1, according to one or more embodiments described herein. DETAILED DESCRIPTION OF THE INVENTION

[0011] Certain embodiments of the present application will now be described. These embodiments are provided for purposes of clarity and clarity. It is provided so as to be thorough and complete, and to fully convey the scope of the claimed subject matter to those skilled in the art.

[0012] The term "polymer" refers to a polymer formed by polymerizing monomers, whether of the same or different types. Therefore, the generic term polymer refers to a polymer compound prepared by The term "homopolymer" usually refers to a polymer prepared from only one type of monomer as well as the term "copolymer," which refers to a polymer prepared from two or more different monomers. As used herein, the term "interpolymer" includes at least It refers to a polymer prepared by polymerization of at least two different types of monomers. The general term interpolymer refers to polymers that are made up of more than two different types of polymers, such as terpolymers. The present invention includes copolymers or polymers prepared from mers.

[0013] "Polyethylene" or "ethylene-based polymer" means a polymer containing more than 50 mole percent ethylene monomer. "(ethylene)-based homopolymers" refers to polymers containing units derived from ethylene. or copolymers (meaning that the units are derived from two or more comonomers). Common forms of ethylene-based polymers known in the art include low density polyethylene (Low Density Polyethylene, LDPE), Linear Low Density Polyethylene Ultra Low Density Polyethylene (LLDPE) ylene, ULDPE), Very Low Density Polyethylene (VLD PE), including both linear low density resins and substantially linear low density resins, single-site Catalytic linear low density polyethylene (m-LLDPE), medium density polyethylene (Medium High Density Polyethylene (MDPE) and High Density Polyethylene Polyethylene (PE), but not limited to polyethylene (HDPE).

[0014] The term "LDPE" refers to "high pressure ethylene polymer" or "highly branched polyethylene." These polymers are sometimes called "polymers" and are produced using free radical initiators such as peroxides. and autoclave or tubular reactors at pressures exceeding 14,500 psi (100 MPa). is defined as meaning that the polymer is partially or completely homopolymerized or copolymerized in a vessel (e.g. See, for example, U.S. Pat. No. 4,599,392, which is incorporated herein by reference in its entirety. LDPE resins typically have a viscosity of 0.916 g / cm 3 ~0.940g / c m 3 The density is in the range of

[0015] The term "LLDPE" includes resins made using a Ziegler-Natta catalyst system. In addition, bismetallocene catalysts (sometimes called "m-LLDPE"), phosphine and single-site catalysts, including but not limited to constrained geometry catalysts. Resins produced by the method, and bis(biphenylphenoxy) catalysts (polyaryloxy ethers and post-metallocene molecular catalysts, including but not limited to, LLDPE includes resins made from linear, substantially linear, or heterogeneous ethylene glycol. LLDPE includes ethylene-based copolymers or homopolymers. LLDPE has fewer long chains than LDPE. and U.S. Patent Nos. 5,211,529, 5,222,532, each of which is incorporated herein by reference in its entirety. Nos. 72,236, 5,278,272, 5,582,923, and 5, 733,155, the entirety of which is a substantially linear ethylene polymer, as further defined in Such as in U.S. Pat. No. 3,645,992, which is incorporated herein by reference. A homogeneously branched linear ethylene polymer composition, the entire contents of which are incorporated herein by reference. It is prepared according to the process disclosed in U.S. Pat. No. 4,076,698, which is incorporated herein by reference. Heterogeneously branched ethylene polymers such as Nos. 3,914,342 and 5,854,000, which are incorporated herein by reference. The LLDPE resin may be any of the resins known in the art, including those disclosed in US Pat. Gas phase, solution phase, or slurry polymerization using a reactor or reactor configuration of the type It may be made by any combination thereof.

[0016] The term "MDPE" means 0.930 g / cm 3 ~0.950g / cm 3 The density of MDPE is typically a chromium or Ziegler-Natta polyethylene. using a catalyst, or a substituted mono- or bis-cyclopentadienyl catalyst (typically metallocenes), constrained geometry catalysts, phosphinimine catalysts, and polyvalent aryloxy catalysts. bisphenylphenoxy ether catalysts (typically called bisphenylphenoxy) MDPE is made using a single-site catalyst, not limited to: Note that more than one may be used.

[0017] The term "HDPE" generally refers to Ziegler-Natta catalyzed, chromium catalyzed, or substituted monolithic polyethylene. No- or bis-cyclopentadienyl catalysts (typically called metallocenes), Constrained geometry catalysts, phosphinimine catalysts, and polyaryloxyether catalysts (typically biaryloxyethers) single-site catalysts, including but not limited to those referred to as phenylphenoxy Prepared using 0.935 g / cm 3 Super~maximum 0.980g / cm 3 has a density of This refers to polyethylene.

[0018] The term "ULDPE" generally refers to Ziegler-Natta catalyzed, chromium catalyzed, or substituted mono- or bis-cyclopentadienyl catalysts (typically referred to as metallocenes); Constrained geometry catalysts, phosphinimine catalysts, and polyaryloxy ether catalysts (typically Single-site catalysts include, but are not limited to, bisphenylphenoxy (also known as bisphenylphenoxy). Prepared using a solvent, 0.855 g / cm 3 ~0.912g / cm 3 A particle with a density of ULDPE refers to polyethylene (ethylene-based) plastomer and Examples of suitable elastomers include, but are not limited to, polyethylene (ethylene-based) elastomers. Ethylene (ethylene-based) elastomer plastomers generally have a viscosity of 0.855 g / cm 3 ~0 .912g / cm 3 It has a density of

[0019] The terms "blend," "polymer blend," and the like refer to a composition of two or more polymers. Such blends may or may not be miscible. The blend may or may not be phase separated. Such a blend may be transparent or non-transparent. as determined from optical methods, light scattering, X-ray scattering, and any other method known in the art. The blend may or may not contain one or more domain configurations. Although not required, one or more layers of the laminate may contain the blend. It may be prepared as a dry blend and then mixed in situ (e.g., in a reactor) with a molten blend. or using other techniques known to those skilled in the art.

[0020] The terms "comprising," "including," and "having" and derivatives thereof, whether or not they are specifically disclosed. It is not intended to exclude the presence of additional ingredients, steps or procedures. To avoid confusion, the term "comprising" is used to refer to all that is claimed. The compositions, whether polymeric or otherwise, are intended to be non-limiting unless otherwise stated. In contrast, "from this" may include any additional additive, adjuvant, or compound. The term "consisting essentially of" refers to something that is not essential to operability. "With the exception of the preceding paragraphs, any other component, step, or procedure is excluded from the scope of any subsequent description." The term "consisting of" includes any and all information not specifically described or listed. Exclude any ingredient, step, or procedure that is

[0021] Various embodiments of the polyethylene composition are described below. Embodiments of the polyethylene composition exhibit improved stiffness when utilized in rotational molding applications. Furthermore, the polyethylene compositions described herein may provide a balance of excellent ESCR properties. This embodiment maintains the same rigidity and ESCR properties even when the thickness is reduced (downgauging). Such a balance can be provided.

[0022] As used herein, the polyethylene composition disclosed herein refers to a polyethylene copolymer comprising ethylene and C3~C 12 It may be formed from the polymerization of a comonomer such as an alkene. Examples include C6-C9 alkenes such as 1-octene and 1-hexene. In one embodiment, the comonomer is 1-octene. is 1-hexene.

[0023] In one or more embodiments, the polyethylene composition has a viscosity of 1000 MPa, as measured in accordance with ASTM D792. When 3 ~0.955g / cm 3 In an embodiment, , the polyethylene composition of the present disclosure has a modulus of elasticity of 0.93 when measured according to ASTM D792. 5g / cm 3 ~0.950g / cm 3 , 0.935g / cm 3 ~0.945g / cm 3 , 0.935g / cm 3 ~0.940g / cm 3 , 0.940g / cm 3 ~0.955g / cm 3 , 0.940g / cm 3 ~0.950g / cm 3 , 0.940g / cm 3 ~0.9 45g / cm 3 , 0.945g / cm 3 ~0.955g / cm 3 , 0.945g / cm 3 ~0.950g / cm 3 , 0.950g / cm3 ~0.955g / cm 3 , or these The density can be any combination of the ranges.

[0024] In one or more embodiments, the polyethylene composition has an AST at 190°C and 2.16 kg When measured according to M D-1238, 1.0g / 10min (g / 10min) to 10.0g In an embodiment, the polyethylene composition may have a melt index (I2) of 1 / 10 minutes. is 1.0 when measured according to ASTM D-1238 at 190°C and 2.16 kg g / 10 minutes~8.0g / 10 minutes, 1.0g / 10 minutes~6.0g / 10 minutes, 1.0g / 10 min~4.0g / 10min, 1.0g / 10min~2.0g / 10min, 2.0g / 10min~10 .0g / 10min, 2.0g / 10min~8.0g / 10min, 2.0g / 10min~6.0g / 10 minutes, 2.0g / 10 minutes~4.0g / 10 minutes, 4.0g / 10 minutes~10.0g / 10 minutes , 4.0g / 10min~8.0g / 10min, 4.0g / 10min~6.0g / 10min, 6.0 g / 10 minutes~10.0g / 10 minutes, 6.0g / 10 minutes~8.0g / 10 minutes, 8.0g / 1 Melt index from 0 min to 10.0 g / 10 min, or any combination of these ranges (I2).

[0025] In one or more embodiments, the polyethylene composition may comprise a polyethylene glycol copolymer having a viscosity of 5.5 to 9.5, a viscosity of 5.5 to 9.0, 5.5~8.5, 5.5~8.0, 5.5~7.5, 5.5~7.0, 5.5~6.5, 5.5~6.0, 6.0~9.5, 6.0~9.0, 6.0~8.5, 6.0~8.0, 6.0~7.5, 6.0~7.0, 6.0~6.5, 6.5~9.5, 6.5~9.0, 6.5~8.5, 6.5~8.0, 6.5~7.5, 6.5~7.0, 7.0~9.5, 7.5~9.0, 7.0~8.5, 7.0~8.0, 7.0~7.5, 7.5~9.5, 7.5~9.0, 7.5~8.5, 7.5~8.0, 8.0~9.5, 8.0~9.0, 8.0 to 8.5, 8.5 to 9.5, 8.5 to 9.0, 9.0 to 9.5, or any of these ranges The melt index ratio (I 10 / I2).

[0026] According to one or more embodiments, the polyethylene composition has a zero shear viscosity ratio of less than 2.0. In an embodiment, the polyethylene composition may have a molecular weight of 1.0 to 2.0, 1.0 to 1.8, 1 .0~1.6, 1.0~1.4, 1.0~1.2, 1.2~2.0, 1.2~1.8, 1 .2~1.6, 1.2~1.4, 1.4~2.0, 1.4~1.8, 1.4~1.6, 1 .6~2.0, 1.6~1.8, 1.8~3.0, 1.8~2.8, 1.8~2.6, 1 The viscosity may have a zero shear viscosity ratio of from 0.8 to 2.0, or any combination of these ranges.

[0027] In embodiments, the polyethylene composition has a viscosity of 1000 MPa as measured by conventional GPC techniques as described herein. When the test was performed, the z-average molecular weight (M z (GPC) According to one or more embodiments, the polyethylene composition may have the following properties: 150,000 g / mol to 35,000 g / mol as measured by conventional GPC techniques as described in the specification 0,000g / mol, 150,000g / mol~300,000g / mol, 150 ,000g / mol~250,000g / mol, 150,000g / mol~200, 000g / mol, 200,000g / mol~400,000g / mol, 200,0 00g / mol~350,000g / mol, 200,000g / mol~300,00 0g / mol, 200,000g / mol~250,000g / mol, 250,000 g / mol~400,000g / mol, 250,000g / mol~350,000g / mol, 250,000g / mol~300,000g / mol, 300,000g / mol~400,000g / mol, 300,000g / mol~350,000g / m ol, 350,000g / mol to 400,000g / mol, or any value within these ranges Combination of Mz (GPC) may have:

[0028] In an embodiment, the polyethylene composition has a viscosity of 10,000 saturates as measured by conventional GPC. Number average molecular weight (Mn) in the range of 0.00 to 50,000 g / mol (GPC) ) can be used. For example, the number average molecular weight may be from a lower limit of 10,000, 20,000, or 25,000 g / mol. to an upper limit of 35,000, 40,000, 45,000, or 50,000 g / mol could be.

[0029] In an embodiment, the polyethylene composition has a viscosity of 60.0 mmHg as measured by conventional GPC. Weight average molecular weight (Mw) in the range of 00 to 200,000 g / mol (GPC) ) For example, the number average molecular weight, as measured by conventional GPC techniques described herein, is 60,000g / mol~180,000g / mol, 60,000g / mol~160 ,000g / mol, 60,000g / mol~140,000g / mol, 60,00 0g / mol~120,000g / mol, 60,000g / mol~100,000g / mol, 60,000g / mol~80,000g / mol, 60,000g / mol ~70,000g / mol, 70,000g / mol~180,000g / mol, 70 ,000g / mol~160,000g / mol, 70,000g / mol~140,0 00g / mol, 70,000g / mol~120,000g / mol, 70,000g / mol~100,000g / mol, 70,000g / mol~80,000g / mol l, 80,000g / mol~200,000g / mol, 80,000g / mol~1 80,000g / mol, 80,000g / mol~160,000g / mol, 80, 000g / mol~140,000g / mol, 80,000g / mol~120,00 0g / mol, 80,000g / mol~100,000g / mol, 100,000g / mol~200,000g / mol, 100,000g / mol~180,000g / mol, 100,000g / mol~160,000g / mol, 100,000g / m ol~140,000g / mol, 100,000g / mol~120,000g / mol l, 120,000g / mol~200,000g / mol, 120,000g / mol ~180,000g / mol, 120,000g / mol~160,000g / mol, 120,000g / mol~140,000g / mol, 140,000g / mol~2 00,000g / mol, 140,000g / mol~180,000g / mol, 14 0,000g / mol~160,000g / mol, 160,000g / mol~200 ,000g / mol, 160,000g / mol~180,000g / mol, 180, 000g / mol to 200,000g / mol, or any combination of these ranges could be.

[0030] According to an embodiment, the polyethylene composition has, as measured by conventional GPC techniques: The ratio of weight average molecular weight to number average molecular weight (Mw) is in the range of 2.0 to 4.5. (GPC) / Mn (GPC) In an embodiment, the polyethylene may have a molecular weight distribution expressed as The composition is 2.0-4.0, 2.0-3.5, 2.0-3.0, 2.0-2.5, 2.5 ~4.5, 2.5~4.0, 2.5~3.5, 2.5~3.0, 3.0~4.5, 3.0 ~4.0, 3.0~3.5, 3.5~4.5, 3.5~4.0, 4.0~4.5, or The molecular weight distribution may be any combination of these ranges. The molecular weight distribution may be calculated according to conventional GPC techniques as described herein.

[0031] In embodiments, the polyethylene composition has a viscosity of 1000 MPa as measured by conventional GPC techniques as described herein. When the ratio of z-average molecular weight to weight-average molecular weight (Mz) is 1.8 to 3.5, (GPC ) / Mw (GPC) According to one or more embodiments, the polyethylene composition may have , 1.8 to 3.5, 1.8 to 3.5, as measured by the light scattering GPC technique described herein 3.0, 1.8~2.5, 1.8~2.0, 2.0~3.5, 2.0~3.0, 2.0~ Weight average z-average molecular weight of 2.5, 2.5-3.5, 2.5-3.0, or 3.0-3.5 Ratio to average molecular weight (Mz (GPC) / Mw (GPC) ).

[0032] As used herein, a polyethylene "fraction" refers to a component of a multimodal polyethylene composition. The embodiments disclosed herein include at least a "first polyethylene The various polyethylene fractions contained in the polyethylene composition include the "second polyethylene fraction" and the "second polyethylene fraction." The fractions were analyzed by improved comonomer composition distribution (iCCD) analysis to determine their elution profiles. Unless otherwise specified, the compounds referred to herein may be quantified by their temperature range. All elution profiles shown are elution profiles observed by iCCD. Examples of such fractions are better understood in view of the examples provided herein. Generally, the first fraction may contain a peak within the temperature range of the first fraction, and the second fraction may contain a peak within the temperature range of the first fraction. The fraction may include a peak within the temperature range of the second fraction. The polyethylene composition may be referred to as "multimodal" because means that they contain at least two peaks in their elution profile.

[0033] In relation to the iCCD distributions being described, FIG. 1 illustrates a sample iCCD distribution 100. FIG. 1 generally illustrates the first fraction, second fraction, and semi-pilot fractions discussed in detail herein. Some of the iCCD profiles of the polyethylene compositions described herein, such as peak widths, Thus, FIG. 1 shows the characteristics associated with the iCCD profile provided herein. The disclosure of the first fraction 102 and the second fraction 103 may be used as a reference. The first fraction 102 has a peak 104, and the second fraction 106 has a peak 106. Each fraction has a half-peak width of 110 and 112. The iCCD elution profile of an exemplary embodiment of the polyethylene composition described herein It is understood that the information provided is for informational purposes only to describe the specific characteristics of the file. should be.

[0034] In one or more embodiments, the polyethylene composition is Improved Comonomer Composition Distribution (iCCD) Analysis Method for Regions in the Elution Profile The first polyethylene surface may have a first polyethylene fraction region defined by a first polyethylene surface. The integral fraction is sometimes referred to herein as the "first mass fraction" of the polyethylene composition. The mass of the polymer fraction in the product may correspond to the total relative mass of the polymer fraction in the product.

[0035] In an embodiment, the first polyethylene fraction is It may have at least one peak within the temperature range of 70° C. to 97° C. In the iCCD elution profile, the first polyethylene fraction region is at 70 °C. This may encompass the region in the elution profile under the peak in the temperature range of 0 to 97°C. In an embodiment, the first polyethylene fraction has an elution profile measured by iCCD of 70 As used herein, "single peak" may have a single peak within the temperature range of 97°C to 97°C. "Group Peak" refers to an iCCD where a particular fraction contains only one peak. In some embodiments, the iCCD in the first polyethylene fraction is followed by an upward sloping region. In one or more embodiments, the peak includes only a region of slight downward sloping slope. The single peak of the first polyethylene fraction is at temperatures between 70°C and 95°C and between 70°C and 93°C. It can be present in the temperature range of 70°C to 97°C.

[0036] The peaks in the first polyethylene fraction represent the respective polyethylene peaks at defined temperature boundaries. It should be understood that this may not be formed due to minima in the ethylene fraction. That is, the peak is not formed by the threshold temperature of the polyethylene fraction. , must be a peak in terms of the entire range. For example, a single If a peak is present in the polyethylene fraction (an upward slope followed by a downward slope followed by an upward slope), (inclination of the orientation), such a polyethylene fraction would have only a single peak. .

[0037] According to one or more embodiments, the first polyethylene fraction region is the overall polyethylene fraction of the elution profile. Less than 60% of the area (e.g., less than 55% or less than 50% of the total area of ​​the elution profile) For example, the first polyethylene fraction area may comprise 1% of the total area of ​​the elution profile. ~60%, e.g., 1%-55%, 1%-50%, 1%-4% of the total area of ​​the elution profile 5%, 1% to 40%, 1% to 35%, 1% to 30%, 1% to 25%, 1% to 20%, 1% ~15%, 1%~10%, 1%~5%, 5%~60%, 5%~55%, 5%~50%, 5 %~45%, 5%~40%, 5%~35%, 5%~30%, 5%~25%, 5%~20% , 5%~15%, 5%~10%, 10%~60%, 10%~55%, 10%~50%, 1 0%~45%, 10%~40%, 10%~35%, 10%~30%, 10%~25%, 1 0%~20%, 10%~15%, 15%~60%, 15%~55%, 15%~50%, 1 5%~45%, 15%~40%, 15%~35%, 15%~30%, 15%~25%, 1 5%~20%, 20%~60%, 20%~55%, 20%~50%, 20%~45%, 2 0%~40%, 20%~35%, 20%~30%, 20%~25%, 25%~60%, 2 5%~55%, 25%~50%, 25%~45%, 25%~40%, 25%~40%, 2 5%~35%, 25%~30%, 30%~60%, 30%~55%, 30%~50%, 3 0%~45%, 30%~40%, 40%~60%, 40%~55%, 40%~50%, 5 It may be comprised between 0% and 60%, or any combination of these ranges.

[0038] In one or more embodiments, the first polymer fraction at a temperature range of 70° C. to 97° C. is The molecular weight of the first fraction ( Mw (iCCD、70℃~97℃) In an embodiment, the molecular weight of the first fraction may correspond to (Mw (iCCD、70℃~97℃) ) is 80,000g / mol~180,000g / mol, 80,000g / mol~160,000g / mol, 80,000g / mol l~140,000g / mol, 80,000g / mol~120,000g / mol, 80,000g / mol~100,000g / mol, 100,000g / mol~18 0,000g / mol, 100,000g / mol~160,000g / mol, 100 ,000g / mol~140,000g / mol, 100,000g / mol~120, 000g / mol, 120,000g / mol~180,000g / mol, 120,0 00g / mol~160,000g / mol, 120,000g / mol~140,00 0g / mol, 140,000g / mol~180,000g / mol, 140,000 g / mol~160,000g / mol, 160,000g / mol~180,000g / mol, or any combination of these ranges.

[0039] In one or more embodiments, the polyethylene composition has an improved comonomer composition distribution (i The second point was measured in the temperature range of 97℃ to 110℃ by the CCD analysis. As used herein, a second polyethylene fraction region may have a second polyethylene fraction region. is the region in the elution profile under the second polyethylene fraction between 97°C and 110°C. The area fraction of the second polyethylene may be defined as "second mass fraction" herein. The total relative mass of the polymer fractions in the polyethylene composition may correspond to the total relative mass of the polymer fractions in the polyethylene composition, referred to as the "mass of the polymer fractions."

[0040] In one or more embodiments, the second polyethylene fraction is analyzed by iCCD elution profile. The second polyethylene may have a single peak in the temperature range of 97°C to 110°C. The peaks in the polyethylene fractions correspond to the peaks in the respective polyethylene fractions at the defined temperature boundaries. It should be understood that the peak may not be formed by a local minimum. , the peak formed by the threshold temperature of the polyethylene fraction, but not the entire range For example, a single peak followed by a single valley is If present in the ethylene fraction (upward slope followed by downward slope followed by upward slope), In the polyethylene fraction, only a single peak is present. Due to the low molecular weight, high density components at 0°C, polyethylene must maintain the lower density fraction. Therefore, a higher overall density can be achieved, and the second A temperature range of the polyethylene fraction may be desirable.

[0041] According to one or more embodiments, the second polyethylene fraction region is the overall polyethylene fraction of the elution profile. 30% or more of the area (e.g., 40%, 50%, 60% or more of the total area of ​​the elution profile) % or more, or 70% or more). For example, the second polyethylene fraction region may comprise 30%~80%, 30%~70%, 30%~60%, 30%~5% of the total area of ​​the profile 0%, 30% to 40%, 40% to 80%, 40% to 70%, 40% to 60%, 40% to 5 0%, 50%~80%, 50%~70%, 50%~60%, 60%~80%, 60%~7 It may comprise 0%, or 70% to 80%.

[0042] According to some embodiments, the molecular weight of the overall polyethylene composition (Mw (iCCD) ) The molecular weight of the first fraction (Mw (iCCD、70℃~97℃) ) is less than 0.90 Less than (e.g., less than 0.88, less than 0.86, less than 0.84, less than 0.82, less than 0.80) For example, the molecular weight of the first fraction of the entire polyethylene composition may be The ratios are 0.80-0.90, 0.80-0.88, 0.80-0.86, and 0.80-0. 84, 0.80-0.82, 0.82-0.90, 0.82-0.88, 0.82-0. 86, 0.82~0.84, 0.84~0.90, 0.84~0.88, 0.84~0. It can be 0.86, 0.86 to 0.90, 0.86 to 0.88, or 0.88 to 0.90. Without being bound by theory, having a ratio of less than 0.9 is believed to be due to the low density component (70°C The first fraction (below 97°C) has a molecular weight higher than the average molecular weight of the entire polyethylene composition. Therefore, the lower density component with a higher molecular weight is can promote bond chain formation in the polymer matrix of the polyethylene composition; This can be beneficial for ESCR and toughness properties.

[0043] According to some embodiments, the ratio of the first mass fraction to the second mass fraction is 2.0 less than (e.g., less than 1.8, less than 1.6, less than 1.4, less than 1.2, or less than 1.0) For example, the ratio of the first mass fraction to the second mass fraction may be 0.6 to 2.0, 0.6~1.8, 0.6~1.6, 0.6~1.4, 0.6~1.2, 0.6~1.0, 0.6~0.8, 0.8~2.0, 0.8~1.8, 0.8~1.6, 0.8~1.4, 0.8~1.2, 0.8~1.0, 1.0~2.0, 1.0~1.8, 1.0~1.6, 1.0~1.4, 1.0~1.2, 1.2~2.0, 1.2~1.8, 1.2~1.6, 1.2~1.4, 1.4~2.0, 1.4~1.8, 1.4~1.6, 1.6~2.0, It may be 1.6 to 1.8, or 1.8 to 2.0. Without being bound by theory, A lower value for this ratio indicates a lower density, higher molecular weight component (70°C to 97°C). The first fraction) is less, but the polyethylene composition as a whole is less likely to contain ESCR and It may still exhibit improved properties such as toughness. The polyethylene composition has a second temperature range of 7°C to 110°C, which improves the flow of the product. As will be described later in this disclosure, Improved flow is beneficial to various article fabrication methods and allows for more complex article designs. It can be.

[0044] Embodiments of the polyethylene compositions described herein may have a tensile strength of 50% or less (e.g., 40% Comonomer Distribution Breadth Index 50 (CDBI50) of 30% or less, 30% or less, and 40% or less As used herein, CDBI50 can be further characterized as the total molar CO2 ratio. Polymer molecules with a comonomer content within 50 percent of the median monomer content This is defined as the weight percent of the comonomers in the polymer. In a further embodiment, the polyethylene composition is Ingredients: 10%~50%, 10%~40%, 10%~30%, 10%~20%, 20%~ 50%, 20% to 40%, 20% to 30%, 30% to 50%, 30% to 40%, or 40 Without being bound by theory, it is believed that the CDBI50 may be less than 50%. Having a CDBI50 represents a broader comonomer distribution, This reflects a wide density split that cannot be achieved with the propylene composition. A wide density split can promote high levels of chain formation from the low density, high molecular weight fraction, which This contributes to the overall ESCR and toughness properties. It may contribute to the necessary stiffness properties that may allow gauging.

[0045] Polymerization of polyethylene compositions Any conventional polymerization process can be used to produce polyethylene compositions in the presence of the catalyst system of the present disclosure. Such conventional polymerization processes may include one or more conventional reactors, such as loop reactors, isothermal reactors, adiabatic reactors, fluidized bed gas phase reactors, stirred reactors, Use of tank reactors, batch reactors, etc., in parallel, in series, or in any combination solution polymerization process, gas phase polymerization process, slurry phase polymerization process, and combinations thereof These include, but are not limited to, combinations of

[0046] The polyethylene composition can be produced, for example, in one or more loop reactors, adiabatic reactors, and their Generally, the polymers can be produced via a solution phase polymerization process using a combination of The combined process may comprise one or more reactors, such as one or more loop reactors and / or one or more adiabatic reactors. In the above well-mixed reactor, 115 to 250°C, for example, 135 to 200°C Temperature range and 300 psig to 1000 psig, for example, 450 psig to 750 It can be carried out at pressures in the psig range.

[0047] In one embodiment, the polyethylene composition is prepared by subjecting the first reactor temperature to 115 to 200°C, e.g. The first reactor temperature is in the range of 150 to 210°C, for example 185 It can be produced in two loop reactors in series configuration, with temperatures in the range of 100°C to 200°C. The polyethylene composition is produced when the reactor temperature is 115 to 200°C, for example, 130 to 190°C. The residence time in a solution phase polymerization process can be in the range of Typically, the reaction time is in the range of 2 to 40 minutes, for example, 5 to 20 minutes. a catalyst system of the present invention, optionally one or more cocatalysts, and optionally one or more comonomers, The solvent is continuously fed to the reactor. An exemplary solvent is isoparaffin. For example, such solvents include, but are not limited to, ExxonMobil Chemistry. This polyethylene composition is commercially available from Pharma under the name ISOPAR E. and solvent are removed from the reactor or reactors to produce a polyethylene composition. The solvent is typically separated in a solvent recovery unit, i.e., using a heat exchanger and a separator vessel. The solvent is then recycled back into the polymerization system.

[0048] In one embodiment, ethylene and optionally one or more α-olefins are mixed in one reactor. in the presence of one or more catalyst systems to form a first ethylene-based polymer, and optionally one or more α-olefins in a second reactor in the presence of one or more catalytic systems. a dual reactor system, wherein the first ethylene polymer is polymerized in the presence of a second ethylene polymer to form a second ethylene-based polymer; For example, polyethylene compositions can be produced via a solution polymerization process in a dual loop reactor system. In addition, one or more co-catalysts may be present. Polymerization of olefins and optionally one or more α-olefins in the presence of one or more catalyst systems. In a single reactor system, e.g., a single loop reactor system, a solution polymerization process In addition, one or more cocatalysts may be present to produce the polyethylene composition. .

[0049] catalyst system The polyethylene compositions described herein may be prepared in one or more embodiments using Specific embodiments of catalyst systems that can be used are described herein. The catalyst systems of the present disclosure can be used in different forms. The present disclosure may be embodied in various forms and should not be construed as being limited to the specific embodiments described herein. It should be understood that this disclosure is not intended to be exhaustive or complete. , which are provided to fully convey the scope of the subject matter to those skilled in the art.

[0050] The term "independently selected" refers to 1 , R 2 , R 3 , R 4 , and R 5 R groups such as may be the same or different (e.g., R 1 , R2 , R 3 , R 4 , and R 5 but , all substituted alkyl, or R 1 and R 2 is a substituted alkyl, and R 3 But, Ali The use of the singular includes the plural. Use of the numeral form is included, and vice versa (e.g., hexane solvent is plural hexanes). A named R group generally corresponds to an R group that has that name in the art. These definitions are intended to be indicative of the definitions known to those skilled in the art. , are intended to supplement and illustrate, not exclude.

[0051] The term "procatalyst" refers to a compound that has catalytic activity when combined with an activator. The term "activator" refers to a compound that converts a procatalyst into a catalytically active catalyst. As used herein, "cocatalyst" and "activator" refer to compounds that chemically react with the catalyst. The terms "activator" and "activator" are interchangeable terms.

[0052] When used to describe a chemical group containing a particular carbon atom, "(C x ~C y A bracketed expression having the form "x" means that the unsubstituted form of the chemical group is x number of substituted groups, inclusive of x and y. It means that there are y carbon atoms from carbon atom. For example, (C1 to C 40 )Archi The alkyl group is an alkyl group having 1 to 40 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups are R S one or more substituents such as It can be replaced by the parenthesized "(Cx -C y ) of chemical groups, defined using R S Substituted versions may be formed by adding any group R S may contain more than y carbon atoms depending on the identity of For example, "R S exactly one group R is phenyl (-C6H5) S replaced with (C1~C 40 The alkyl group may contain from 7 to 46 carbon atoms. , parenthesized "(C x ~C y )" that contains one or more carbon atoms. Substituent R contained S When substituted by, the minimum and maximum total number of carbon atoms in the chemical group are , both x and y are substituents R containing all carbon atoms S Add the total number of carbon atoms from It is determined by

[0053] The term "substituted" refers to a carbon or heteroatom or functional group of the corresponding unsubstituted compound. At least one hydrogen atom (-H) attached to the group is replaced by a substituent (e.g., R S ) by The term "hypersubstituted" means that the corresponding unsubstituted compound or functional group All hydrogen atoms (H) attached to carbon atoms or heteroatoms of S ) by The term "polysubstituted" means that the corresponding unsubstituted compound or or at least two, but more than all, of the carbon or heteroatoms of the functional group It means that a small number of hydrogen atoms are replaced by a substituent.

[0054] The term "-H" means a hydrogen or hydrogen radical that is covalently bonded to another atom "Hydrogen" and "-H" are interchangeable and mean the same thing unless otherwise specified. .

[0055] "(C1~C 40 The term "hydrocarbyl" refers to a hydrocarbon of 1 to 40 carbon atoms. It means a radical, "(C1~C 40 The term "hydrocarbylene" refers to a group of 1 to 40 means a hydrocarbon diradical of carbon atoms, each hydrocarbon radical and each hydrocarbon diradical may be aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (monocyclic and polycyclic, is acyclic (3 or more carbon atoms, including fused and non-fused polycyclic, including bicyclic), unsubstituted or one or more R S has been replaced by

[0056] In the present disclosure, (C1 to C 40 ) Hydrocarbyl is unsubstituted or substituted (C1-C 40 ) Alkyl, (C3-C 40 ) cycloalkyl, (C3-C 20 )Cycloalkyl- (C1~C 20 ) Alkylene, (C6-C 40 ) aryl, or (C6-C 20 ) Ally Ru-(C1~C 20 In some embodiments, the above (C1 to ) alkylene may be C 40 Each of the hydrocarbyl groups has up to 20 carbon atoms (i.e., (C C 20 ) hydrocarbyl), in embodiments having up to 12 carbon atoms.

[0057] "(C1~C 40 ) alkyl" and "(C1-C 18 The term "alkyl" refers to and 1 to 40 carbon atoms or 1 to 18 carbon atoms, respectively, which may be unsubstituted or may have one or more substituted groups. R above S means a saturated straight-chain or branched hydrocarbon radical substituted by Exchange(C1~C 40 Examples of alkyl are unsubstituted (C1-C 20 ) Alkyl, unsubstituted (C1 C 10 ) alkyl, unsubstituted (C1-C5) alkyl, methyl, ethyl, 1-propyl, 2 -propyl, 1-butyl, 2-butyl, 2-methylpropyl, 1,1-dimethylethyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-nonyl, and 1-decyl. (C1~C 40 Examples of substituted (C1-C 20 ) Alkyl, substituted (C1-C 10 ) alkyl, trifluoromethyl, and [C 45 ] alkyl. 45 ]Arki The term "carbonyl" (bracketed) refers to a radical with up to 45 carbon atoms in the radical, including the substituents. is meant to be present, e.g., each R is (C1-C5) alkyl S to (C 27 ~C 40 Each (C1-C5) alkyl is ethyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-diethyl It may be methyl ethyl.

[0058] "(C6~C 40 The term "aryl" refers to a group of aryls containing 6 to 40 carbon atoms, In both cases, 6 to 14 carbon atoms are aromatic ring carbon atoms, unsubstituted or (one or more R S By means a substituted monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radical, Bicyclic or tricyclic radicals contain one, two, or three rings, respectively, where a monocyclic ring is aromatic, and the two or three rings are independently fused or non-fused, and the two or three rings At least one of them is aromatic. 40 Examples of alkyl are unsubstituted ( C6~C 20 ) Unsubstituted alkyl (C6-C 18 ) alkyl, 2-(C1-C5) alkyl Phenyl, 2,4-bis(C1-C5) alkylphenyl, phenyl, fluorenyl, tetramethylphenyl tetrahydrofluorenyl, indacenyl, hexahydroindacenyl, indenyl, dihydrofluorenyl Examples include benzoindenyl, naphthyl, tetrahydronaphthyl, and phenanthrene. Replacement (C6~C 40 Examples of substituted (C1-C 20 ) Alkyl, substituted (C6-C 18 )aryl, 2,4-bis[(C 20 ) alkyl]-phenyl, polyfluorophenyl Examples include phenyl, pentafluorophenyl, and fluoren-9-on-1-yl.

[0059] "(C3~C 40 The term "cycloalkyl" means unsubstituted or substituted with one or more substituted aryl groups. R S means a saturated cyclic hydrocarbon radical of 3 to 40 carbon atoms substituted with Other cycloalkyl groups, such as (C x ~C y )cycloalkyl) has x to y carbon atoms and is unsubstituted or has one or more R S Is it replaced by Unsubstituted (C3-C 40 ) Examples of cycloalkyl are: Unsubstituted (C3~C 20) Cycloalkyl, unsubstituted (C3-C 10 ) cycloalkyl, cyclo cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclo octyl, cyclononyl, and cyclodecyl. 40 ) Cycloalkane Examples of substituted (C3-C 20 ) Cycloalkyl, substituted (C3-C 10 )Cycloalkyl , cyclopentanon-2-yl, and 1-fluorocyclohexyl.

[0060] (C1~C 40 Examples of hydrocarbylene include unsubstituted or substituted (C6-C 40 )a Liren, (C3~C 40 ) cycloalkylene, and (C1-C 40 ) alkylene (e.g. Ba(C1~C 20 ) alkylene). In some embodiments, the diradical is , whether on the same carbon atom (e.g., -CH2-) or on adjacent carbon atoms (e.g., -CH2-). i.e., 1,2-diradicals), or one, two, or more than two intervening carbon atoms. separated by an electron (e.g., 1,3-diradical, 1,4-diradical, respectively) Some diradicals include α,ω-diradicals. α,ω-diradicals are radicals It is a diradical with the largest carbon skeleton spacing between carbon atoms (C2-C 20 ) Alkire Some examples of α,ω-diradicals include ethane-1,2-diyl (i.e., - CH2CH2-), propane-1,3-diyl (i.e., -CH2CH2CH2-), 2-Methylpropane-1,3-diyl (i.e., -CH2CH(CH3)CH2-) (C6~C 50Some examples of arylene α,ω-diradicals include: Phenyl-1,4-diyl, naphthalene-2,6-diyl, or naphthalene-3,7-diyl Examples include Il.

[0061] "(C1~C 40 The term "alkylene" refers to a group that is unsubstituted or has one or more R S saturated straight or branched chain diradicals of 1 to 40 carbon atoms substituted with (i.e. , the radical is not on a ring atom). 50 ) Examples of alkylene are: Unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, - (CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C * HCH3, and - (CH2)4C * (H) Unsubstituted (C1-C) containing CH3 20 ) alkylene, wherein "C * " refers to a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl radical. Represents atoms. Substitution (C1 to C 50 Examples of alkylene are substituted (C1-C 20 ) alkylene , -CF2-, -C(O)-, and -(CH2) 14 C(CH3)2(CH2)5-( That is, 6,6-dimethyl-substituted normal-1,20-eicosylene). , two R S together (C1~C 18 ) alkylene can be formed , replacement (C1~C 50 Examples of alkylene include 1,2-bis(methylene)cycloalkylene. Pentane, 1,2-bis(methylene)cyclohexane, 2,3-bis(methylene)-7, 7-Dimethyl-bicyclo[2.2.1]heptane and 2,3-bis(methylene)bicyclo[2.2.1]heptane Also mentioned is octane.

[0062] "(C3~C 40 The term "cycloalkylene" refers to a group that is unsubstituted or has one or more R S Cyclic diradicals of 3 to 40 carbon atoms (i.e., lanthanides) substituted by The divalent atom is on a ring atom.

[0063] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of heteroatoms include: are O, S, S(O), S(O)2, Si(R C )2, P(R P ), N(R N ), -N= C(R C )2, -Ge(R C )2-, or -Si(R C )-, wherein each R C , Each R N , and each R P is unsubstituted (C1 to C 18 ) hydrocarbyl or -H. The term "hydrocarbon" refers to a molecule or molecule in which one or more carbon atoms are replaced by a heteroatom. Refers to the molecular skeleton. (C1-C 40 The term "heterohydrocarbyl" refers to a group of 1 to 40 heterohydrocarbyl groups. means a heterohydrocarbon radical of carbon atoms, and 40 ) Heterohydrocarb The term "heterohydrocarbon" means a heterohydrocarbon diradical of 1 to 40 carbon atoms, Heterohydrocarbons have one or more heteroatoms. Heterohydrocarbyl radicals are (1) one or more heterohydrocarbyl diradicals present on a hydrogen atom or heteroatom; (2) two carbon atoms, (2) one or two heteroatoms, or (3) one carbon atom and one There can be two heteroatoms on each (C1 to C 50 ) heterohydrocarbyl and (C C 50 ) heterohydrocarbylene is unsubstituted or substituted (one or more R S by), fragrance aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (monocyclic and polycyclic, fused polycyclic) The ring structure may be acyclic (including fused polycyclic rings and non-fused polycyclic rings) or acyclic.

[0064] (C1~C 40 ) Heterohydrocarbyl is unsubstituted or substituted (C1-C 40 ) Haitai alkyl, (C1-C 40 ) hydrocarbyl-O-, (C1-C 40 ) Hydrocarbyl -S-, (C1~C 40 ) hydrocarbyl-S(O)-, (C1-C 40 ) Hydro Karubi Ru-S(O)2-, (C1-C 40 ) Hydrocarbyl-Si(R C )2-, (C1~C4 0) Hydrocarbyl-N(R N )-, (C1~C 40 ) hydrocarbyl-P(R P )-, (C2~C 40 ) heterocycloalkyl, (C2-C 19 ) heterocycloalkyl-(C 1~C 20 ) alkylene, (C3-C 20 )Cycloalkyl-(C1-C 19 ) Heteroa alkylene, (C2-C 19 )Heterocycloalkyl-(C1-C 20 ) Heteroalkylene , (C1~C 40 ) heteroaryl, (C1-C 19 )Heteroaryl-(C1-C20 ) Alkylene, (C6-C 20 )Aryl-(C1-C 19 ) heteroalkylene, or ( C1~C 19 )Heteroaryl-(C1-C 20 ) heteroalkylene.

[0065] "(C4~C 40 The term "heteroaryl" refers to a group of aryls having a total of 4 to 40 carbon atoms and 1 ~10 unsubstituted or substituted heteroatoms (one or more R S monocyclic, bicyclic, or means a tricyclic heteroaromatic hydrocarbon radical, and a monocyclic, bicyclic, or tricyclic radical is , each containing 1, 2, or 3 rings, the 2 or 3 rings being independently fused or It is non-fused and at least one of the two or three rings is heteroaromatic. Heteroaryl groups (e.g., generally (C x ~C y ) heteroaryl, for example (C4-C1 2) Heteroaryl) also refers to a group having x to y carbon atoms (e.g., 4 to 12 carbon atoms). and unsubstituted or one or more R S is defined as being replaced by A cyclic heteroaromatic hydrocarbon radical is a five- or six-membered ring. A five-membered ring is a ring with five minus It has h carbon atoms, where h is the number of heteroatoms and may be 1, 2, or 3, and each The heteroatom may be O, S, N, or P. The five-membered heteroaromatic hydrocarbon radical Examples are pyrrol-1-yl, pyrrol-2-yl, furan-3-yl, thiophene-2-yl yl, pyrazol-1-yl, isoxazol-2-yl, isothiazol-5-yl , imidazol-2-yl, oxazol-4-yl, thiazol-2-yl, 1,2, 4-triazol-1-yl, 1,3,4-oxadiazol-2-yl, 1,3,4- Thiadiazol-2-yl, tetrazol-1-yl, tetrazol-2-yl, and tetrazol-1-yl A six-membered ring has 6 minus h carbon atoms, where h is , is the number of heteroatoms, which may be 1 or 2, and the heteroatoms may be N or P. Examples of six-membered heteroaromatic hydrocarbon radicals are pyridin-2-yl, pyrimidin-2-yl, Bicyclic heteroaromatic hydrocarbon radicals include fused rings, ... The fused 5,6-ring bicyclic heteroaromatic hydrocarbons may be 5,6- or 6,6-ring systems. Examples of radicals are indol-1-yl and benzimidazol-1-yl. Examples of 6,6-ring bicyclic heteroaromatic hydrocarbon radicals are quinolin-2-yl, and The tricyclic heteroaromatic hydrocarbon radical is a fused 5,6, It can be a 5-, 5,6,6-, 6,5,6-, or 6,6,6-ring system. An example of a - ring system is 1,7-dihydropyrrolo[3,2-f]indol-1-yl. An example of a fused 5,6,6-ring system is 1H-benzo[f]indol-1-yl. An example of a 5,6-ring system is 9H-carbazol-9-yl. is 9H-carbazol-9-yl. An example of a fused 6,6,6-ring system is acridine- It is 9-yl.

[0066] The heteroalkyl group may be any of (C1-C 50 ) carbon atoms or fewer carbon atoms and helium It may be a saturated straight or branched chain radical containing one or more of the following atoms: Similarly, heteroalkylene contains 1 to 50 carbon atoms and one or more heteroatoms. It may be a saturated straight or branched chain diradical containing heteroatoms as defined above. The child is Si(R C )3, Ge(R C )3, Si(R C )2, Ge(R C )2, P(R P ) 2. P(R P ), N(R N )2, N(R N ), N, O, OR C , S, S.R. C ,S(O), and S(O)2, wherein each of the heteroalkyl and heteroalkylene groups is a non- Substitution or one or more R S is replaced by

[0067] Unsubstituted (C2~C 40 Examples of heterocycloalkyl include unsubstituted (C-C 20 ) Hetero Cycloalkyl, unsubstituted (C2-C 10 ) Heterocycloalkyl, aziridin-l-yl , oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-1-yl, tet Hydrothiophene-S,S-dioxid-2-yl, morpholin-4-yl, 1,4- Dioxan-2-yl, hexahydroazepin-4-yl, 3-oxa-cyclooctyl , 5-thio-cyclononyl, and 2-aza-cyclodecyl.

[0068] The term "halogen atom" or "halogen" refers to a fluorine atom (F), a chlorine atom (Cl "Halide" means a radical of an iodine atom (I), a bromine atom (Br), or an iodine atom (I). The term refers to the halogen atoms: fluoride (F - ), chloride (Cl - ), bromide (Br - ) , or iodide (I -) means the anionic form of

[0069] The term "saturated" refers to carbon-carbon double bonds, carbon-carbon triple bonds, and (heteroatoms) (in a carbon-containing group) means the absence of carbon-nitrogen, carbon-phosphorus, and carbon-silicon double bonds. A saturated chemical group is one or more substituents R S If replaced by one or more The double and / or triple bonds may optionally be substituted with substituents R S It may or may not be present in The term "unsaturated" refers to a group of atoms that has one or more carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, and carbon-silicon double bonds , provided that the substituent R S If present or may be present in , is meant to exclude any double bonds that may be present in (hetero)aromatic rings.

[0070] According to some embodiments, the catalyst system for producing the polyethylene composition comprises a catalyst having a structure represented by formula (I ) including metal-ligand complexes with:

[0071] [ka]

[0072] In formula (I), M is a metal selected from titanium, zirconium, or hafnium. where the metal is in the +2, +3, or +4 formal oxidation state and n is 0, 1, or 2. and when n is 1, X is a monodentate or bidentate ligand, and when n is 2, Each X is a monodentate ligand, and may be the same or different, such that the metal-ligand complex is Each Z is independently -O-, -S-, -N(R N)-, or -P(R P )-, and L is selected from (C1 to C 40 ) hydrocarbylene or (C1-C 40 )He Tetrahydrocarbylene (C1-C 40 ) Hydrocarbylene is the two a portion containing a linker skeleton of 1 to 10 carbon atoms that connects the Z groups (including L is bonded to 40 ) Heterohydrocarbylene is a heterocyclic group represented by the formula ( I) has a portion containing a linker skeleton of 1 to 10 atoms that connects the two Z groups And (C1~C 40 ) Heterohydrocarbylene linker skeleton of 1 atom to 10 atoms Each of the 1 to 10 atoms in the hexavalent nucleus is independently a carbon atom or a heteroatom, and each heteroatom The children are independently O, S, S(O), S(O)2, Si(R C )2, Ge(R C )2, P (R C ), or N(R C ) and independently, each R C is (C1~C 30 ) Hydro Karubi or (C1~C 30 ) heterohydrocarbyl, and R 1 and R 8 are independently -H , (C1~C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si( R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N- , R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R N )2NC( O)-, a halogen, and a radical having formula (II), formula (III), or formula (IV). Selected from the group consisting of:

[0073] [ka]

[0074] In formulas (II), (III), and (IV), R 31~35 , R 41~48 , or R 51 ~59 Each of (C1 to C 40 ) hydrocarbyl, (C1-C 40 ) Hetero Hydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N ) 2. -N=CHR C , -OR C , -SR C , -NO2, -CN, -CF3, R C S(O) -, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R N )2NC(O)-, halogen, or -H However, R 1 or R 8 at least one of the formula (II), formula (III), or Provided that it is a radical having formula (IV):

[0075] In formula (I), R 2~4 , R 5~7 , and R 9~16 Each of (C1 to C4 0) Hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -G e(R C )3, -P(R P )2, -N(R N )2, -N=CHR C , -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N -, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C )2NC (O)-, halogen, and -H.

[0076] In some embodiments, the polyethylene composition is prepared by reacting a first copolymer of propylene glycol and propylene glycol according to formula (I) in a first reactor. is formed using a catalyst in one reactor and a different catalyst according to formula (I) in a second reactor.

[0077] In one exemplary embodiment using a dual loop reactor, the first loop uses The procatalyst is zirconium, [[2,2'''-[[bis[1-methylethyl]germylene bis(methyleneoxy-κO)]bis[3'',5,5''-tris(1,1-dimethylethyl) (ethylethyl)-5'-octyl[1,1':3',1''-terphenyl]-2'-ol dimethyl-, which has the chemical formula C 86 H 128 F2GeO4 Zr and having the following structure (V):

[0078] [ka]

[0079] In such an embodiment, the procatalyst used in the second loop may be zirconium, [[ 2,2'''-[1,3-propanediylbis(oxy-κO)]bis[3-[2,7- Bis(1,1-dimethylethyl)-9H-carbazol-9-yl]]-5'-(dimethylethyl) (1,1,3,3-tetramethylbutyl)-3'-methyl-5-(1,1,3,3-tetramethylbutyl) ,1]-biphenyl]-2-olato-κO]](2-)]dimethyl, and has the chemical formula C 10 7H 154 N2O4Si2Zr and having the following structure (VI):

[0080] [ka]

[0081] cocatalyst component The catalyst system comprising the metal-ligand complex of formula (I) activates metal-based catalysts in olefin polymerization reactions. The catalyst may be catalytically activated by any technique known in the art for catalytically activating the catalyst. For example, The system comprising the metal-ligand complex of formula (I) can be prepared by contacting the complex with an activating cocatalyst or by activating the complex. The catalyst may be made catalytically active by combining it with an activating cocatalyst. Suitable activating cocatalysts for use include alkylaluminum, polymers or oligomers. - Alumoxanes (also known as aluminoxanes), neutral Lewis acids, and non-polymeric non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions) The preferred activation technique is bulk electrolysis. Combinations of one or more thereof are also contemplated. The term "aluminum alkyl" , monoalkylaluminum dihydride or monoalkylaluminum dihalide, Dialkylaluminum hydride or dialkylaluminum halide, or trialuminum Examples of polymeric or oligomeric alumoxanes include: Methylalumoxane, triisobutylaluminum-modified methylalumoxane, and isobutylaluminum-modified methylalumoxane Examples include ethyl alumoxane.

[0082] The Lewis acid activator (cocatalyst) may be, as described herein, a compound having 1 to 3 (C1-C2 0) Group 13 metal compounds containing hydrocarbyl substituents. In one embodiment, Group 3 metal compounds are tri((C1-C 20 )hydrocarbyl)substituted aluminum or tri ((C1~C 20 In an embodiment, the Group 13 The metal compounds include tri(hydrocarbyl)-substituted aluminum, tri((C1-C 20 )Hi Tri((C1-C2)-boron compounds 10 ) alkyl) aluminum, tri ((C6~C 18 )aryl)boron compounds and their halogenation (perhalogenation) In a further embodiment, the Group 13 metal compound is a tris(fluoro) derivative. Some examples include tris(pentafluorophenyl)borane and tris(pentafluorophenyl)borane. In the form of an activating cocatalyst, the tris((C1-C 20 ) hydrocarbyl borates (e.g. Trityl tetrafluoroborate) or tri((C1-C20 )hydrocarbyl)ammonium Niumtetra ((C1~C 20 )hydrocarbyl)borane (e.g., bis(octadecyl) )methylammonium tetrakis(pentafluorophenyl)borane). When used in the context of 20 )hydrocarbyl) 4N + , ((C1~C 20 )hydrocarbyl)3N(H) + , ((C1~C 20 ) Hydro Carbyl)2N(H)2 + , (C1~C 20 ) Hydrocarbyl N(H)3 + , or N(H )4 + In the formula, each of (C1 to C 20 ) Hydrocarbyl is two If more than one is present, they may be the same or different.

[0083] As a combination of neutral Lewis acid activators (cocatalysts), tri((C1-C4) alkyl) (C6-C) aluminum and trihalides 18 )aryl)boron compounds, especially thiazolinone Examples include mixtures containing bis(pentafluorophenyl)borane. The form is a combination of such a neutral Lewis acid mixture with a polymeric or oligomeric alumoxane. The combination of a single neutral Lewis acid, especially tris(pentafluorophenyl)borane and poly( (Metal-ligand complex): (tri- or oligomeric alumoxane) S(pentafluorophenylborane):(alumoxane) [e.g., Group 4 metal-ligand complex):(tris(pentafluorophenylborane):(alumoxane)] The ratio is 1:1:1 to 1:10:30, in an embodiment 1:1:1.5 to 1:5:10. .

[0084] The catalyst system comprising the metal-ligand complex of formula (I) may be activated by the addition of one or more cocatalysts, e.g. Active in combination with a cation-forming cocatalyst, a strong Lewis acid, or a combination thereof Suitable activating cocatalysts include polymeric or oligomeric alkylene oxides, which may form catalyst compositions. Aluminoxanes, especially methylaluminoxanes, as well as inert, compatible, non-coordinating, ion-forming Examples of suitable cocatalysts include modified methylaluminoxane (modified methylaluminoxane). fied methyl aluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetra Kis(pentafluorophenyl)borate(1 - ) amines, and combinations thereof. Examples include, but are not limited to:

[0085] In some embodiments, one or more of the aforementioned activating co-catalysts are used in combination with each other. A particularly preferred combination is tri((C1-C4)hydrocarbyl)alcohol. ammonium, tri((C1-C4)hydrocarbyl)borane, or ammonium borate and o and mixtures of one or more oligomeric or polymeric alumoxane compounds of formula (I). The ratio of the total moles of metal-ligand complex to the total moles of one or more of the activating cocatalysts is In some embodiments, the ratio is at least 1:10,000 to 100:1. In some embodiments, the ratio is at least 1:5000, and in some embodiments, at least 1:1000, and in some embodiments, at least 10:1 or less, and in some embodiments, 1:1 or less. When used as a catalyst, the number of moles of alumoxane used is determined by the ratio of the metal- It is preferable that the number of moles is at least 100 times the number of moles of the ligand complex. When (triphenyl)borane is used alone as an activating cocatalyst, in some embodiments The number of moles of tris(penta)- The number of moles of fluorophenylborane is 0.5:1 to 10:1, 1:1 to 6:1, or 1 The remaining activating cocatalysts are generally one or more metal-coordinating cocatalysts of formula (I): It is used in a molar amount approximately equal to the total molar amount of the child complex.

[0086] Goods Embodiments of the present disclosure also include rotomolded and rotatably molded articles formed from the polyethylene films of the present disclosure. The present invention relates to articles such as injection molded articles. Such articles may be made using the polyesters of the present disclosure described herein. It may be formed from any of the polyethylene compositions.

[0087] Rotational molding, commonly called "rotomolding" or "rotocasting", Molding is widely used to form hollow articles, such as storage tanks, furniture, toys, canoes, etc. Rotational molded articles, such as boats and kayaks, and slides, are used in a variety of applications and industries. In particular, rotational molding allows materials to be molded into complex shapes, completing corners and narrow compartments. Generally, rotational molding involves filling the inside of a mold with a polymer resin. The filled mold is heated to melt the polymer resin, and the mold is rotated to melt the The molten resin is applied to the inside of the mold, the mold is cooled, and the molded article is removed from the mold. The integral hollow article can be made by rotational molding. Examples of such materials include toys, furniture, containers such as tanks and water bottles, and sporting goods such as Includes, but is not limited to, canoes and kayaks.

[0088] In polymer molding applications, including rotational molding and injection molding applications, for example, downgauging from the use of thinner walls or from the reduction or elimination of relatively expensive materials. Solutions are constantly being sought to enable material cost reduction by eliminating Traditionally, downgauging is achieved by using polymer resins with higher densities. Although it is possible to increase the density, increasing the density usually reduces the environmental stress crack resistance (ESCR). This results in a rotational molding grade that exhibits a balance of stiffness and ESCR properties that meets customer and industry requirements. There is a need for polyethylene compositions that can be utilized in a variety of applications.

[0089] Embodiments of the present disclosure provide a method for manufacturing a polyethylene composition having an E A wide range of components is required to achieve the desired stiffness without compromising SCR or impact characteristics. Thus, in accordance with the practice of the present disclosure, a polyethylene composition comprising a mer distribution can be provided. The morphology provides a balance of stiffness and ESCR properties when utilized in rotational molding applications. This can provide a polyethylene composition that can enable reduction in material costs. Additionally, the polyethylene compositions described herein allow for relatively easy fabrication processes and for more complex applications. It can exhibit flow and processability properties that enable product design.

[0090] In embodiments, the polyethylene composition is blended with one or more polyolefins to form a blend. A braid may be produced which can be rotationally molded into an article. The blend comprises a polyethylene composition as described herein and a linear low density polyethylene (LLD) PE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene In embodiments, the present invention may include blends with one or more of the following: polyethylene (HDPE) and polyethylene (HDPE). A polyethylene composition comprising the polyethylene composition described herein or a polyethylene composition described herein Providing a blend containing the ethylene composition provides a , may provide a balance of stiffness and ESCR properties.

[0091] The polyethylene compositions or blends comprising the polyethylene compositions described herein are well known in the art. one or more additives known to those skilled in the art, such as plasticizers, stabilizers including viscosity stabilizers, hydrolysis stabilizers, agents, primary and secondary antioxidants, ultraviolet absorbers, antistatic agents, dyes, pigments, or other colorants , inorganic fillers, flame retardants, lubricants, reinforcing agents such as glass fibers and flakes, synthetic (e.g. Aramid) fiber or pulp, foaming or expanding agents, processing aids, slip additives, silicones Anti-blocking agents such as talc or kaolin, release agents, tackifying resins, hindered amine light stabilizers (H It should be understood that the present invention may further include, for example, a combination of two or more thereof. Inorganic fillers such as calcium carbonate may be incorporated into the polyethylene composition. In some embodiments, the polyethylene composition comprises, based on the total weight of the polyethylene composition, It may contain up to 5 weight percent of such additional additives. The total amount of additives in the polyethylene composition is 0.2% by weight to 1.0% by weight based on the total weight of the polyethylene composition. 5% by weight, 0.2% to 4% by weight, 0.2% to 3% by weight, 0.2% to 2% by weight , 0.2wt%~1wt%, 0.2wt%~5wt%, 0.5wt%~5wt%, 0.5 Weight% ~ 4% by weight, 0.5% by weight ~ 3% by weight, 0.5% by weight ~ 2% by weight, 0.5% by weight ~ 1wt%, 1wt%~5wt%, 1wt%~4wt%, 1wt%~3wt%, 1wt%~ 2wt%, 2wt%~5wt%, 2wt%~4wt%, 2wt%~3wt%, 3wt%~ The additive may be present in an amount of 5% by weight, 3% to 4% by weight, or 4% to 5% by weight. Examples include dry blending, extrusion of a mixture of various components, and conventional masterbatching. This can be done by any known process such as technology.

[0092] Embodiments of articles, such as rotomolded articles, can be made from the polyethylene compositions disclosed herein. Various methods for making rotomolded articles are well known to those skilled in the art. A variety of methodologies are contemplated.

[0093] Test Method Test methods include:

[0094] Melt Index The melt index I2 (or I2) and I of the polymer sample 10 (or I10), then Tests were conducted according to ASTM D-1238( The values ​​are reported in g / 10 min. The fraction of the polymer sample was , recovering product polymer from a reactor producing a particular fraction or portion of the polymer composition. For example, the first polyethylene fraction may be determined by the lower It can be recovered from reactors that produce higher density, higher molecular weight components. Before the measurement, the polymer solution is dried under vacuum.

[0095] density Samples for density measurements were prepared according to ASTM D4703. Measurements were performed at 100°C for 1 minute after sample pressing. The test was carried out in accordance with ASTM D792, Method B, within 2 hours.

[0096] Creep zero shear viscosity measurement method The zero shear viscosity was measured at 190°C using 25 mm diameter parallel plates under AR-G2 stress. Controlled rheometer (TA Instruments, New Castle, Del.) Before zeroing the fixture, the rheometer oven is The compression molded specimen disc is then heated to the test temperature for at least 30 minutes. The top plate is then inserted between the plates and allowed to equilibrate for 5 minutes. The desired test gap (1.5 μm) is lowered to 50 μm above the desired test gap. If there is any excess material, Trim and remove the upper plate to lower it to the desired gap. Measurements are taken at a flow rate of 5 L / min. The creep time is set to 2 hours.

[0097] To ensure that the steady-state shear rate is low enough in the Newtonian region, the test All materials are subjected to a constant low shear stress of 20 Pa. The resulting steady-state shear rate is The samples in the survey were 10 -3 ~10 -4 s -1 The steady state is in the range of All within the last 10% time window of a plot of log(J(t)) vs. log(t) is determined by taking a linear regression on the data, where J(t) is the creep coefficient where t is the creep time. The slope of the linear regression is greater than 0.97. If the creep test is stopped, it is considered that a steady state has been reached. In all cases, the gradient meets the criterion within 2 hours. The steady-state shear rate is the function of ε vs. t All lines of data points within the last 10% time window of the plot (ε is the strain) The zero shear viscosity is determined from the slope of the linear regression. The zero shear viscosity is a function of the steady-state shear rate of the applied stress. It is determined from the ratio of

[0098] To determine whether the specimen is degraded during the creep test, 0.1 to 100 ra Small amplitude oscillatory shear tests were performed on the same specimens at 1000 kJ / sec before and after the creep test. If the difference in viscosity values ​​at 0.1 rad / s is greater than 5%, the complex viscosity is The sample is considered to have deteriorated during the leap test and the results are discarded.

[0099] Gel Permeation Chromatography (GPC) The chromatography system is equipped with an internal IR5 infrared detector (IR5) High-temperature GPC chromatography at merChar GPC-IR (Valencia, Spain) Set the autosampler oven compartment to 160 degrees Celsius. The column compartment was set to 150°C. The columns used were four A Gilent "Mixed A" 30cm 20 micron linear mixed bed column and 20um The chromatographic solvent used was 1,2,4-trichlorobenzyl benzoate. benzene and 200 ppm butylated hydroxytoluene The solvent source was nitrogen sparged. The injection volume used was 20 The volume was 0 microliters and the flow rate was 1.0 milliliters / minute.

[0100] The calibration of the GPC column set was performed using two HPLC columns with molecular weights ranging from 580 to 8,400,000. A single narrow molecular weight distribution polystyrene standard was used, with at least one gap between each molecular weight. The standards were arranged in six "cocktail" mixtures, each spaced 10-fold apart. It was purchased from Lent Technologies. It has a molecular weight of over 1,000,000. For example, 0.025 grams in 50 milliliters of solvent yields less than 1,000,000 For molecular weight, use 0.05 g polystyrene standards in 50 ml solvent. Polystyrene standards were dissolved at 80°C for 30 minutes with gentle agitation. The peak molecular weights of the polystyrene standards were calculated using Equation 1 to calculate the polyethylene molecular weight. (Williams and Ward, J. Polym. Sci., Pol ym. Let., 6, 621 (1968)).

[0101]

number

[0102] A fifth-order polynomial was used to fit each polyethylene equivalent calibration point. With slight adjustment (approximately 0.375 to 0.445), linear homopolymer polyethylene The standard is 120,000MW (GPC) Column resolution and band broadening, as obtained The effect was corrected.

[0103] The total plate count of the GPC column set was calculated using decane (in 50 ml of TCB). The experiment was carried out using 0.04g of PEG-400 (prepared and dissolved for 20 minutes with gentle stirring). The rate count (Equation 2) and symmetry (Equation 3) are calculated for 200 microliters according to the following equations: Measured with an injection of 1000kJ / L:

[0104]

number

[0105]

number

[0106] The samples were analyzed using the PolymerChar "Instrument Control" software. The sample was prepared in a semi-automated manner using software, with a target weight of 2 mg / mL. Char via high-temperature autosampler with pre-nitrogen sparged septa cap (s A solvent (containing 200 ppm BHT) was added to a tetra-capped vial. The samples were dissolved under "slow" shaking at 160 degrees Celsius for 2 hours.

[0107] Mn (GPC) , Mw (GPC) , and Mz (GPC) The calculation of PolymerCh ar GPCOne™ software, the base at each equally spaced data collection point (i) Line-subtracted IR chromatogram and narrow standard for point (i) of Eq. Using the polyethylene equivalent molecular weight obtained from the calibration curve, calculate the Poly The internal IR5 detector (measurement channel) of the merChar GPC-IR chromatograph was used. Based on the GPC results.

[0108]

number

[0109] To monitor deviations over time, the PolymerChar GPC-IR system was used. A flow rate marker (decane) was introduced into each sample via a micropump controlled by the flow rate control. Using a flow rate marker (FM), the respective decane peaks (R V(FM sample)) and the decane peak within the narrow standard calibration (RV(FM calibrated)). By matching the RV, the pump flow rate (apparent flow rate) of each sample can be linearly adjusted. Any change in the time of the decane marker peak was then corrected for throughout the run. It is assumed that this is related to a linear shift in flow rate (effective flow rate). To facilitate the highest accuracy of the RV measurement of the flow marker concentration chromatogram peaks, A least squares fitting routine is used to fit the quadratic equation. Use the second derivative to solve for the true peak location. After calibration, the effective flow rate (for a narrow reference calibration) is calculated as Equation 7. Carpeak processing was performed via PolymerChar GPCOne™ software. The acceptable flow correction is when the effective flow rate is within + / - 0.5% of the apparent flow rate. It is what it should be.

[0110]

number

[0111] Improved Method for Comonomer Content Analysis (iCCD) An improved comonomer content analysis method (iCCD) was developed in 2015 (Con g and Parrott et al., International Publication No. 2017040127(A1). iCC The D test was performed using an IR-5 detector (PolymerChar, Spain) and two-angle light scattering detection. Model 2040 Precision Detectors (now Agilent) Crystallization Elution Fractionation (Crystallization Elution Fractionation) The test was carried out using a CEF (PolymerChar, Spain). Just before the IR-5 detector in the detector oven, place a 5 cm or 10 cm (long) x 1 / 4 inch (ID) stainless steel with 20-27 micron glass (MoSCi Corporation) A guard column packed with orthodichlorobenzene (orthodichlorobenzene, Inc., USA) was installed. o-dichlorobenzene, ODCB, 99% anhydrous grade or technical grade Silica gel 40 (particle size 0.2-0.0 mm) from EMD Chemicals was used. 0.5mm, Catalog No. 10181-3) was obtained (to dry off the ODCB solvent first). The dried silica was packed into three empty HT-GPC columns and the eluent The CEF instrument was equipped with an autosampler with N2 purging capability. Before use, the ODCB is sparged with dry nitrogen (N2) for 1 hour. Preparations were performed at 160°C for 1 hour with shaking using an autosampler (unless otherwise specified). The injection volume was 300 μL. The temperature profile of the iCCD was Crystallization from 105°C to 30°C at 3°C / min, followed by thermal equilibration at 30°C for 2 min (soluble fraction elution) (including setting the time to 2 min), elution from 30°C to 140°C at 3°C / min. The flow rate during crystallization is 0.0 mL / min. The flow rate during elution is 0.50 mL / min. Data is collected at 1 data point / second.

[0112] The iCCD column is made of gold in a 15 cm (length) x 1 / 4 inch (ID) stainless steel tube. Coated nickel particles (Bright 7GNM8-NiS, Nippon The column was packed and adjusted by the Chemical Industrial Co. , References (Cong, R.; Parrott, A.; Hollis, C.; Cheat The slurry method was carried out according to Ham, M. International Publication No. 2017040127(A1). The final pressure using the TCB slurry charge was 150 bar.

[0113] Linear homopolymer polyethylene (with zero comonomer content) is the reference material in ODCB. , melt index (I2) 1.0, polydispersity Mw(GPC) / Mn (GPC) Follow Approximately 2.6 and 1.0 mg / mL) and eicosane (2 mg / mL) were detected by conventional gel permeation chromatography. Column temperature calibration was performed by using a mixture of HCl and HCl (µg / mL). The calibration consisted of four steps: (1) measured peak elution of eicosane; Calculate the delay volume, defined as the temperature offset between the temperatures minus 30.00°C. (2) subtracting the temperature offset of the elution temperature from the iCCD raw temperature data. (Note that this temperature offset is a function of experimental conditions such as elution temperature and elution flow rate.) (3) A linear homopolymer polyethylene reference material has a peak temperature of 101.0°C. and eicosane has a peak temperature of 30.0°C. (4) creating a linear calibration line converting elution temperatures over a range of 30°C to 100°C; For the soluble fraction measured isothermally in °C, an elution temperature below 30.0 °C is used as the reference (C (Erk and Cong et al., U.S. Patent No. 9,688,795) Linearly extrapolating by using the exit heating rate.

[0114] Comonomer content versus iCCD elution temperature was measured using 12 reference materials (ethylene homopolymer and ethylene-octene random copolymers prepared with single-site metallocene catalysts ethylene equivalent weight average molecular weight in the range of 35,000 to 128,000) All of these reference materials were constructed using the previously designated 4 mg / mL The same analysis was performed. The reported elution peak temperatures were calculated using the linear equation y=-6.3515x. +101.00, where y represents the elution temperature of the iCCD and x represents the octet represents the mole percent, and R 2 was 0.978.

[0115] The molecular weight of the polymer and the molecular weight of the polymer fraction are the form factors of 1 and all the The Rayleigh-Gans-Debys approximation is achieved by assuming the al coefficients to be zero. (Striegel and Yau, "Modern Size Exclusion Li According to the "Quid Chromatogram", pages 242 and 263 The concentration was determined directly from the S detector (at a 90-degree angle) and the concentration detector (IR-5). Integrate all chromatograms over a 20°C range of elution temperatures (temperature calibration specified above) Set the integration window to

[0116] Molecular weight (Mw (iCCD) ) involves four steps: (1) A step of measuring the offset between detectors. The offset is the difference between the LS detector and the concentration detector. This is defined as the geometric volume offset between the concentration detector and the LS chromatograph. The elution rate is calculated as the difference between the elution volume (mL) of the polymer peak and the elution volume (mL) of the polymer peak. and elution flow rate are used to convert it into a temperature offset. Styrene (comonomer content zero, melt index (I2) 1.0, polydispersity M w / M n Conventional gel permeation chromatography uses approximately 2.6) parameters. The same experimental conditions as for the regular iCCD method described above are used, except for the temperature: 140 °C to 137 °C. Crystallize at 10 °C / min until 7 min. Thermal equilibration at 137 °C for 1 min. Elute the soluble fraction. The soluble fraction (SF) time during crystallization was eluted from 137°C to 142°C at 3°C / min. The flow rate during elution is 0.80 mL / min. The sample concentration is 1.0 mg / mL. (2) Shift each LS data point in the LS chromatogram to achieve inter-detector offset before integration. Correct the offset. (3) The baseline-subtracted LS and concentration chromatograms are obtained at the elution temperature of step (1). The MW detector constant is set to 100,000-140,000 MW. Using HDPE samples of known MW within a range of w and the area ratio between the LS and concentration integral signals It is calculated by: (4) The Mw of the polymer was determined using the ratio of the integrated light scattering detector (at a 90 degree angle) and the concentration detector. The MW detector constant was used to calculate the MW.

[0117] The half-width is calculated as the temperature difference between the front and rear temperatures at half the maximum peak height. The forward temperature at half of the maximum peak is searched forward from 35.0°C. The rear temperature at halfway is searched from 119.0°C rearward.

[0118] Zero-shear viscosity ratio (ZSVR) ZSVR is calculated by the equivalent weight average molecular weight (Mw (GPC) ) The zero shear viscosity (ZSV) of branched polyethylene materials and the ZS of linear polyethylene materials It is defined as the ratio to V.

[0119]

number

[0120] ZSV values ​​were obtained from creep tests at 190°C using the method described above. (GPC) The value is determined by the conventional GPC method (Equation 5 in the description of the conventional GPC method). ZSV and Mw of crystalline polyethylene (GPC) The correlation between Established based on the reference material. (GPC) For an explanation of the relationship between TEC Bulletin: Karjala, Teresa P., Sammler, Robert L. .,Mangnus,Marc A.,Hazlitt,Lonnie G.,John son, Mark S., Hagen, Charles M. Jr., Huang, Jo e WL,Reichek,Kenneth N.,'Detection of low levels of long-chain branching in po lyolefins',Annual Technical Conference-S society of Plastics Engineers(2008),66th 887-891.

[0121] Dynamic Rheological Analysis To characterize the rheological behavior of substantially linear ethylene polymers, S Lai and GW Knight (ANTEC'93 Proceedings,Insi te(TM) Technology Polyolefins(ITP)-New R ules in the Structure / Rheology Relations hip of Ethylene&-01efin Copolymers,New O Ralleans, La., May 1993) Polymer "normalization as a result of long chain branching" Dow Rheology Institute, a novel rheological measurement that represents the "measured relaxation time" dex (DRI) was introduced. S. Lai et al. (ANTEC'94, Dow Rheol ogy Index (DRI) for Insite (TM) Technology P olyolefins(ITP):Unique structure-Process ing Relationships, pp.1814-1815) is based on the polymer backbone ITP (Dow's Insite Technology Polymer) incorporating long chain branching The rheology of ethylene-octene copolymers, known as lyolefins, Conventional cellulose is reported to be free of long chain branching (LCB) by the normalized equation: DRI was defined as the degree of deviation from the rheology of a linear homogeneous polyolefin:

[0122]

number

[0123]

number

[0124] Dynamic rheology measurements were performed in an inert atmosphere according to ASTM D4440. A dynamic rheometer (e.g., TA Ins) with parallel plates of 25 mm diameter was used in the rheometer mode. All experiments were performed on a rheometer (ARES rheometer, Instruments). The data were obtained by placing appropriately stabilized (with antioxidant additives) compression molded samples in parallel plates. Before inserting it onto the tray, it is allowed to thermally stabilize at 190°C for at least 30 minutes. , close the plates with a positive normal force registered on the meter to ensure good contact. After about 5 minutes at 190°C, the plates were gently compressed to trim away excess polymer around the perimeter of the plates. It takes another 10 minutes for the thermal stability and normal force to return to zero. Measurements were performed after equilibrating the sample at 190 °C for approximately 15 min and then under a full nitrogen blanket. It is executed below.

[0125] Two strain sweep (SS) experiments were first performed at 190 °C to cover all frequencies (e.g., 0 . The lower scale of the transducer over the range of 0.1 to 100 rad / s Determine the linear viscoelastic strain that produces a torque signal greater than 10%. This test is performed at a low applied frequency of 0.1 rad / s. The second SS experiment was performed at a higher applied frequency of 100 rad / s to determine the sensitivity of the This is to ensure that oscillatory rheology measurements do not induce structural changes to the polymer during testing. ensure that the selected applied strain is well within the linear viscoelastic region of the polymer. Furthermore, the strain rate is as low as 0.1 rad / s at the selected strain (determined by SS experiments). Time sweep (TS) experiments are performed at different applied frequencies to check the stability of the sample during testing. .

[0126] Storage modulus (or elastic modulus), loss modulus (or viscous modulus) (G''), complex modulus ( G * ), complex viscosity (η * ), and tan δ (ratio of loss modulus to storage modulus, G'VG') was obtained as a function of frequency (ω) at a given temperature (e.g., 190°C).

[0127] Instrumented Dart Impact The instrumented dart impact method was performed using an Instron CEAST 9350 impact tester. , measured on compression molded plaque specimens according to ASTM D3763. The device uses a 12.7 mm diameter tip with a shaped head. The facility is equipped with an environmental chamber for testing at 100 m. Typical specimen size is 100 m. The dimensions are m x 100 mm. The standard test speed is 200 m / min. The thickness of the plaque is 3. The test was carried out at a temperature of -40°C.

[0128] Comonomer Distribution Breadth Index (CDBI) CDBI50 (Composition Distribution Breadth Index) is a parameter used to characterize the resin composition distribution. This is a quantitative measure of the breath of the distribution. , within 50% (i.e., 50% on either side) of the median total molar comonomer content (Cmed) It is defined as the weight percent of copolymer molecules with comonomer content. The composition corresponds to the composition at which the cumulative integral is equal to 0.5. The difference between the cumulative integrals at Cmed is the CDBI50 of the copolymer. can be determined using separation techniques such as iCCD, ATREF, and CEF. CDBI50 values ​​range from 0 to 1, where larger values ​​indicate a narrower comonomer distribution. , small values ​​indicate a broad comonomer distribution. Along similar principles, CDBI25 Copolyesters with a comonomer content within 25% of the median comonomer content (Cmed) The composition is defined as the weight percent of the mer molecules. The difference between the cumulative integrals at d is the CDBI25 of the copolymer.

[0129] From data obtained from CEF, WO 93 / 03 CDBI50 is calculated using the method described in JP 2009-09333. Figure 1 shows a comparison of the comonomer distribution in the polymer with that expected from a Bernoulli distribution.

[0130] Environmental Stress Cracking Resistance (ESCR) The ESCR of the resin was measured according to ASTM D 1693-13. The sheets were compression molded into plaques according to TM Method D4703-10a (Procedure C). Within 24 hours after the test, a 38 mm x 13 mm test piece was cut using a die cutter. The thickness of the specimen depends on the ESCR method (A or B) being performed. Method A used a 3.15 mm thick specimen, while Method B used a 1.90 mm thick specimen. A test specimen with a thickness of m was used.

[0131] To perform the test, a controlled defect (notch) was placed on one surface of each specimen. 0 test specimens were bent and heated at 50°C with a surfactant (Igepal® CO-630) The concentration of surfactant was 10% in water. The number of specimens that failed was monitored. Failure was recorded and the result F50 was the point when 50% of the specimens failed. Equivalent to the time it took to make a loss (calculated by linear regression). [Example]

[0132] The following examples are intended to illustrate features of the present disclosure and are not intended to limit the scope of the disclosure. In the following experiments, embodiments of the polyethylene compositions described herein The performance of was analyzed.

[0133] Example 1: Preparation of polyethylene compositions 1 to 4 Polyethylene as described according to one or more embodiments of the Detailed Description Compositions 1-4 were prepared using the catalyst and reactor by the method described below.

[0134] All raw materials (monomers and comonomers) and process solvents are purified before being introduced into the reaction environment. (Shellsol SBP 100-140) was purified with molecular sieves. The reactor monomer feed stream was fed under pressure as a grade without further purification. The solvent and comonomer feeds were pressurized above the reaction pressure via a mechanical compressor. The mixture was pressurized via a pump to a pressure exceeding the reaction pressure. The batch was manually diluted and pressurized to the reaction pressure described above. All reaction feed streams were measured with mass flow meters. The valves were independently controlled by a computer-controlled automatic valve control system.

[0135] Two reactor systems were used in a series configuration. Each continuous solution polymerization reactor was liquid-filled. A non-adiabatic, isothermal, circulating, isothermal continuously stirred tank reactor All unused solvents, monomers, comonomers, hydrogen, and Independent control of catalyst component feeds was possible for each reactor (solvent, monomer, comonomer). All unused feed streams to the catalyst (hydrogen, and ethane) are removed by passing the feed streams through a heat exchanger. The temperature was controlled to maintain a single solution phase. The injector received half of the total unused feed mass flow rate. The catalyst components were pumped through the injection stinger. The catalyst feed was then injected into the polymerization reactors to maintain the monomer conversion of each reactor at a specific target. The cocatalyst components were added in a specific molar ratio calculated as follows: The primary catalyst component was fed.

[0136] The effluent from the first polymerization reactor (solvent, monomer, comonomer, hydrogen, catalyst components, and The polymer-containing mixture exited the first reactor and was added to the second reactor.

[0137] The second reactor effluent is deactivated by adding and reacting with a suitable reagent (water). At this same reactor exit point, other additives were added for polymer stabilization. Additive (octadecyl 3,5-di-tert-butyl-4-hydroxyhydroxybenzoate) was added. namate, tetrakis(methylene(3,5-di-tert-butyl-4-hydroxybenzoate) Drosinnamate))methane, and tris(2,4-di-Tert-butyl-phenyl) Typical antioxidants suitable for stabilization during extrusion and film fabrication, such as phosphites .

[0138] Following catalyst deactivation and additive addition, the reactor effluent is separated into a non-polymer stream and a non-polymer stream. The polymer melt was then pelletized and collected. The non-polymer stream was removed from the system.

[0139] Reactor flow feed data correspond to values ​​in Table 1. The data take into account the complexity of the solvent recycle system. and presents the reaction system as a once-through flow diagram for easier handling. Table 2 shows the catalysts referenced in Table 1.

[0140] [Table 1] * Solvent = Shellsol SBP 100-140

[0141] [Table 2]

[0142] Example 2: Preparation of polyethylene composition 5 Polyethylene as described according to one or more embodiments of the Detailed Description Composition 5 was prepared using the catalyst and reactor by the method described below.

[0143] The polyethylene composition 5 was prepared using a continuity additive (Univ. Technology CA-300 manufactured by es, LLC (Houston, Texas, USA), (methyl alcohol Luminoxan (MAO) activator, ethylene, hexene, mineral oil (Sonneborn H YDROBRITE 380 PO White), hydrogen gas, and ICA (at least 95% or at least 98% 2-methylbutane (isopentane, CH3(CH2 )2CH(CH3)2) and a microorganism containing at least pentane (CH3(CH2)3CH3)). The mixture was prepared using a 100% ethanol-based ... blend (a mixture consisting essentially of the above ingredients).

[0144] The catalyst used was bis(n-propylcyclopentadienyl)hafnium dimethyl (C AS No. 255885-01-9, BOCSCI Inc. (Shirley, New (available from BOC Sciences, a brand of BOC Sciences, New York, USA) To prepare the spray-dried catalyst system utilized to produce polyethylene composition 5, A Buchi B-290 mini spray dryer housed inside a nitrogen atmosphere glove box was used. The temperature was set to 65°C, and the outlet temperature was set to 60-70°C. bosil TS-610, 3.2 g), MAO in toluene (10 wt%, 21 g), and and bis(propylcyclopentadienyl)hafnium dimethyl (0.11 g) in toluene. The resulting mixture was introduced into an atomizer to generate droplets, and then The liquid was then evaporated by contact with a stream of hot nitrogen gas, thereby producing a powder. The powder was separated from the gas mixture in a cyclone separator, and the sd-Cat-1 powder (3.81 g) in a conical container. sd-Cat-1 was available as a dry powder or as a slurry in mineral oil. The resulting mixture can be fed to the gas phase polymerization reactor as a single unit.

[0145] To produce polyethylene composition 5, the spray-dried catalyst system prepared above was sd-Cat-1 as a dry powder with two Pilot containing a bed of polyethylene granules Fluidized-bed gas-phase polymerization dual reactor including FB-GPP reactors (first reactor and second reactor) The system was supplied with 3 milliliters of continuity additive CA-300 as a 20% by weight solution in mineral oil. Dry sd-Cat-1 catalyst powder, ethanol, and ethanol were fed at a feed rate of 100 ml / hr (100 ml / hr). The method involves continuously feeding ethylene, hexene, and hydrogen (H2) into a fluidized bed of polyethylene granules. Polymerization was initiated in the first reactor by the addition of the cyclopentadiene copolymer. A ethylene polymer was produced and removed, which contained the active catalyst. The resulting material was transferred to the second reactor using the second reactor gas as the transport medium. Ethylene, hexene, and hydrogen (excluding fresh sd-CAT-1) were fed to the second reactor. Inert gas, nitrogen, and isopentane were used in both the first and second reactors. The remaining gas composition was made up of the polyethylene component extracted from the first reactor. The polyethylene component is then transferred to the second reactor. The ethylene content of the granular resin sample was measured directly. Before the measurement, the granular resin was heated to 2000 Stabilized with ppmw of butylated hydroxytoluene (BHT). First and second reactions The polymerization conditions for the first reactor and the properties of the granular resin from the second reactor are reported in Table 3. The polymer was then mixed with 4950 ppmw (ppmw) polymer available from Solvay. ) antioxidant and UV stabilizer additives. The mixture was fed to a continuous mixer (LCM-100 manufactured by Kobe Steel, Ltd.) and mixed with the The furnace is connected to a gear pump and closed to produce separate strands that are cut into pellets. The system was equipped with a melt filtration device and an underwater pelletization system for producing polyethylene. The overall properties of object 5 were measured directly on it.

[0146] [Table 3]

[0147] Example 3: Comparative Compositions A to C Table 4 identifies the commercially available polyethylene compositions of Comparative Polyethylene Compositions A-C.

[0148] [Table 4]

[0149] Example 4: Comparative Compositions D to F Comparative polyethylene compositions D to F were produced using the catalyst and reactor by the method described below. It was prepared using

[0150] All raw materials (monomers and comonomers) and process solvents are purified before being introduced into the reaction environment. (High purity isoparaffin solvent with narrow boiling range, Isopar-E) is purified by molecular sieve. Hydrogen was supplied under pressure as a high purity grade and no further purification was carried out. The reactor monomer feed stream was pressurized above the reaction pressure via a mechanical compressor. The catalyst and comonomer feeds were pressurized via pumps to a pressure above the reaction pressure. The reaction mixture was manually batch diluted with purified solvent and pressurized to the reaction pressure listed above. Feed flows were measured by mass flow meters and independently controlled by a computerized automatic valve control system.

[0151] Two reactor systems were used in a series configuration. Each continuous solution polymerization reactor had a heat removal A liquid-filled, non-adiabatic, isothermal circulation loop that mimics a continuous stirred tank reactor (CSTR) All unused solvent, monomer, comonomer, hydrogen, and catalyst components were removed from the reactor. Independent control of the feeds to each reactor (solvent, monomer, comonomer, and All unused feed streams to the reactor (hydrogen) are simply removed by passing the feed streams through a heat exchanger. The temperature was controlled to maintain one solution phase. All unused feeds to each polymerization reactor were taken at each injection. The unused feed was injected into the reactor at two locations with approximately equal reactor volumes between the locations. The catalyst components were controlled so that each injector received half of the total unused feed mass flow. The feed of the main catalyst components was injected into each reactor at specific targets. The cocatalyst component was computer-controlled to maintain a specific monomer conversion of 100%. The primary catalyst components were fed based on a molar ratio of 0.1 to 0.25. Immediately after each reactor feed injection point, the feed The stream was mixed with the contents of the circulation polymerization reactor using static mixing elements. A heat exchanger that removes most of the heat of reaction and a coolant side that maintains an isothermal reaction environment at a specific temperature. The temperature was continuously cycled. Circulation around each reactor loop was provided by a pump.

[0152] In a dual reactor series configuration, the effluent from the first polymerization reactor (solvent, monomer, comonomer) The reaction mixture (containing olefins, hydrogen, catalyst components, and polymer) exits the first reactor loop and is passed to the second reactor. was added to the vessel loop.

[0153] The second reactor effluent is then deactivated by adding and reacting with a suitable reagent (water). At this same reactor exit point, other additives were added to stabilize the polymer. The additive (octadecyl 3,5-di-tert-butyl-4-hydroxyhydroxide) Rosinnamate, tetrakis(methylene(3,5-di-tert-butyl-4-hydroxy) Tris(2,4-di-Tert-butyl-phenyl)methane, and tris(2,4-di-Tert-butyl-phenyl)methane Typical antioxidants suitable for stabilization during extrusion and film fabrication include methyl phosphites. agent).

[0154] Following catalyst deactivation and additive addition, the reactor effluent is separated into a non-polymer stream and a non-polymer stream. The polymer melt was then pelletized and collected. The non-polymer stream is separated by various equipment that separates the majority of the ethylene removed from the system. The solvent and most of the unreacted comonomer are passed through a purification system before passing through the reaction A small amount of solvent and comonomer was purged from the process.

[0155] Reactor stream feed data is shown in Table 5. The data takes into account the complexity of the solvent recycle system and The reaction system is presented as a once-through flow diagram for easier processing. Table 6 , indicates the catalyst referenced in Table 5.

[0156] [Table 5]

[0157] [Table 6]

[0158] Comparative polyethylene composition F was produced using a catalyst and a reactor by the method described below. It was prepared as follows.

[0159] All raw materials (monomers and comonomers) and process solvents are purified before being introduced into the reaction environment. (High purity isoparaffin solvent with narrow boiling range, Isopar-E) is purified by molecular sieve. Hydrogen is supplied under pressure as a high purity grade and is not further purified. The feed stream was pressurized via a mechanical compressor at a pressure above the reaction pressure. The catalyst feed was pressurized via a pump to a pressure above the reaction pressure. The reaction mixture was manually batch diluted with purified solvent and pressurized to the reaction pressure described above. The flow rates were measured by mass flow meters and independently controlled by a computerized automatic valve control system.

[0160] Two reactor systems were used in a parallel configuration. Each continuous solution polymerization reactor had a heat removal A liquid-filled, non-adiabatic, isothermal circulation loop that simulates a continuous stirred tank reactor (CSTR) All unused solvent, monomer, comonomer, hydrogen, and catalyst components were removed from the reactor. Independent control of the feeds to each reactor (solvent, monomer, comonomer, and All unused feed streams to the reactor (hydrogen) are simply removed by passing the feed streams through a heat exchanger. The temperature was controlled to maintain one solution phase. All unused feeds to each polymerization reactor were taken at each injection. The unused feed was injected into the reactor at two locations with approximately equal reactor volumes between the locations. The catalyst components were specially designed and controlled, with each injector receiving half of the total unused feed mass flow. The main catalyst components were injected into the polymerization reactor through a special injection stinger. The monomer conversion in each reactor was maintained at a target value of 0.01. The cocatalyst component was The primary catalyst components were fed to each reactor feed injection point based on the specific molar ratios calculated. Immediately after placement, the feed stream was mixed with the contents of the circulation polymerization reactor using a static mixing element. The reactor contents are passed through a heat exchanger that removes most of the heat of reaction and a gas exchanger that maintains an isothermal reaction environment at a specific temperature. The circulation around each reactor loop was controlled by a pump. So I provided it.

[0161] The effluent streams from the first and second polymerization reactors were combined before any further processing. The combined final reactor effluent is inactivated by the addition and reaction of a suitable reagent (water). At this same reactor exit point, a polymer was added to stabilize the polymer. Other additives were added (octadecyl 3,5-di-tert-butyl-4-hydroxybenzoyl) Hydrocinnamate, Tetrakis(methylene(3,5-di-Tert-butyl-4-hydroxybenzoate) Tris(2,4-di-Tert-butyl- Typical acids suitable for stabilization during extrusion and blown film fabrication include (phenyl) phosphite. anti-oxidation agent).

[0162] Following catalyst deactivation and additive addition, the reactor effluent is separated into a non-polymer stream and a non-polymer stream. The polymer melt was then pelletized and collected. The non-polymer stream passes through various parts of the equipment, which separates most of the ethylene. The majority of the solvent and unreacted comonomer was removed from the system. After passing through the reactor, a small amount of solvent and comonomer was recycled to the reactor. Do it.

[0163] Reactor stream feed data is shown in Table 7. The data takes into account the complexity of the solvent recycle system and The reaction system is displayed as a once-through flow diagram for easier processing. Table 6 shows the catalysts referenced in Table 7.

[0164] [Table 7]

[0165] Example 5: Comparison of polyethylene compositions 1 to 5 with comparative compositions A to F Comparative properties of polyethylene compositions 1 to 5 and comparative compositions A to F were determined using the test methods described herein. The results were measured and calculated according to the experimental method and are reported in Tables 8-10. 1 graphically illustrates the elution profile of polyethylene composition 1, according to one or more embodiments.

[0166] [Table 8] 1 Improved Comonomer Composition Distribution (ICCD) elution profile at 95°C Weight fraction of components eluting at temperatures above

[0167] [Table 9]

[0168] [Table 10]

[0169] Modifications and variations are permitted without departing from the scope of the present disclosure, as defined in the appended claims. It will be apparent that some aspects of the present disclosure may be implemented in a variety of ways. Although identified in the specification as preferred or particularly advantageous, the present disclosure does not necessarily It is contemplated that the present invention is not limited to these aspects.

Claims

1. 1. A polyethylene composition comprising: Improved comonomer composition distribution (iCCD) analysis in the temperature range of 70°C to 97°C A first polyethylene fraction region defined by a region in an elution profile according to the method and, a first peak in the temperature range of 70°C to 97°C in the elution profile; defined by the region in the dissolution profile between temperatures of 97°C and 110°C a second polyethylene fraction region; and and a second peak in the temperature range of 97°C to 110°C in the elution profile. fruit, 0.935 g / cm ３ ~0.955g / cm ３ Density: 1.0 g / 10 min to 10.0 g / 10 min melt index (I ２ ) and the first polyethylene fraction region a ratio of said second polyethylene fraction domain to said second polyethylene fraction domain of less than 2.

0.

2. The ratio of the weight average molecular weight to the number average molecular weight (Mw （ＧＰＣ ） / Mn （ＧＰＣ） ) the molecular weight distribution of the polyethylene of claim 1 Composition.

3. the second polyethylene fraction region is 30% to 80% of the total area of ​​the elution profile; 3. The polyethylene composition according to claim 1 or 2,

4. The polyethylene according to any one of claims 1 to 3, having a CDBI50 of 50% or less. Composition.

5. The polyethylene composition has an overall molecular weight (Mw （ｉＣＣＤ ） ) wherein the first polyethylene fraction has a first fraction determined by iCCD Molecular weight (Mw （ｉＣＣＤ、７０℃～９７℃） ) and the overall molecular weight (Mw （ｉＣＣＤ ） The molecular weight (Mw) of the first fraction （ｉＣＣＤ、７０℃～９７℃） ) is 0. The polyethylene composition according to any one of claims 1 to 4, wherein the molecular weight of the polyethylene composition is less than 9.

6. The polyethylene of any one of claims 1 to 5, having a zero shear viscosity ratio of less than 2.

0. Len composition.

7. ESCR F50 (10%, A) for more than 300 hours when measured according to D1693 The polyethylene composition according to any one of claims 1 to 6, comprising:

8. 1. A polyethylene composition comprising: 7 in elution profile by improved comonomer composition distribution (iCCD) analysis a first polyethylene fraction in the temperature range of 0°C to 97°C, comprising a first peak, The molecular weight of the first fraction (Mw （ｉＣＣＤ、７０℃～９７℃） ) a first polyethylene fraction comprising: A second polyethylene fraction in the temperature range of 97°C to 110°C in the elution profile a second polyethylene fraction comprising a second peak; The total molecular weight (Mw （ｉＣＣＤ） ), 0.935g / cm ３ ~0.955g / cm ３ Density: 1.0g / 10min to 10.0g / 10min Sex (I ２ ) The total molecular weight (Mw （ｉＣＣＤ） The molecular weight (Mw) of the first fraction （ｉＣＣＤ、７ ０℃～９７℃） ) is less than 0.

9.

9. The ratio of the weight average molecular weight to the number average molecular weight (Mw （ＧＰＣ ） / Mn （ＧＰＣ） 9. The polyethylene of claim 8, having a molecular weight distribution expressed as Composition.

10. the second polyethylene fraction region is 30% to 80% of the total area of ​​the elution profile; 10. The polyethylene composition according to claim 8 or 9,

11. The polyethylene according to any one of claims 8 to 10, having a CDBI50 of 50% or less. Len composition.

12. 12. The method of claim 8, wherein the ratio of the first mass fraction to the second mass fraction is less than 2.

0. The polyethylene composition according to any one of claims 1 to 14.

13. The polyester of any one of claims 8 to 12, having a zero shear viscosity ratio of less than 2.

0. Styrene composition.

14. ESCR F50 (10%, A) for more than 300 hours when measured according to D1693 The polyethylene composition according to any one of claims 8 to 13, comprising:

15. Production of rotomoulded articles comprising the polyethylene composition of any one of claims 1 to 14 method.

Images