Blow molded article

Abstract

A blown article comprising an ethylene / alpha-olefin interpolymer is disclosed. The ethylene / alpha-olefin interpolymer has a density of from 0.920 g / cc to 0.950 g / cc, a melt index (I2) of from 0.5 g / 10 minutes to 10.0 g / 10 minutes, a comonomer distribution width index (CDBI) of greater than 55%. The ethylene alpha-olefin also has a CDFLS * LCBf * 100 of greater than 0.5, wherein the CDFLS and LCBf are measured as described below. Also disclosed is a blow molded article formed by blow molding an ethylene / alpha-olefin interpolymer into a bottle, the ethylene / alpha-olefin interpolymer having a density of from 0.920 g / cc to 0.950 g / cc, a melt index (I2) of from 0.5 g / 10 minutes to 10.0 g / 10 minutes, a comonomer distribution width index (CDBI) of greater than or equal to 55%, and a CDFLS * LCBf * 100 value of greater than 0.5, wherein the CDFLS is calculated by measuring the area fraction of the molecular weight distribution obtained from the absolute molecular weight distribution, and the LCBf is measured as described below.

Description

Cross-reference to related applications

[0001] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 510,777, filed June 28, 2023, the contents of which are incorporated herein by reference in their entirety. Technical Field

[0002] This application relates to blow-molded articles. More specifically, this application relates to blow-molded articles comprising polyethylene. Even more specifically, this application relates to blow-molded articles comprising ethylene / α-olefin interpolymers. Background Technology

[0003] Ampoules and bottles used in medical applications require high heat resistance, resistance to environmental cracking, flexibility, and low fogging. Low fogging allows consumers to assess the quality of the product contained within. Heat resistance ensures the bottle does not fail during heat sterilization and reduces sterilization time at higher temperatures. High resistance to environmental cracking ensures the bottle does not fail during storage. Flexibility allows for easy squeezing and product removal.

[0004] Conventionally, medical ampoules and bottles are produced using high-pressure polymerized LDPE. This makes it difficult to achieve a density greater than 0.925 g / cc. This limits the use of high-temperature sterilization, among other issues.

[0005] Higher densities can be achieved by blending high-density polyethylene (HDPE) into LDPE. However, this typically comes at the cost of transparency. Alternatively, higher densities can be achieved using linear polyethylene (such as medium-density polyethylene), which is produced using solution polymerization, gas-phase polymerization, or slurry polymerization methods. However, the linear structure of these polyethylenes results in a lack of melt strength, which eliminates the possibility of blow molding.

[0006] Therefore, blow-molded bottles with high resistance to environmental cracking, softness, and transparency are desired. Summary of the Invention

[0007] A blow-molded article comprising an ethylene / α-olefin interpolymer is disclosed. The ethylene / α-olefin interpolymer has a density of 0.920 g / cc to 0.950 g / cc, a melt index (I2) of 0.5 g / 10 min to 10.0 g / 10 min, and a comonomer distribution width index (CDBI) greater than 55%. The ethylene α-olefin also has a CDF greater than 0.5. LS × LCBf × 100, where the CDF LSThe LCBf values ​​are measured as described below. A blow-molded article formed by blow molding an ethylene / α-olefin interpolymer into a bottle is also disclosed, the ethylene / α-olefin interpolymer having a density of 0.920 g / cc to 0.950 g / cc, a melt index (I2) of 0.5 g / 10 min to 10.0 g / 10 min, a comonomer distribution width index (CDBI) greater than or equal to 55%, and a CDF greater than 0.5. LS × LCBf × 100 value, where the CDF LS It is calculated by measuring the area fraction of the molecular weight distribution obtained from the absolute molecular weight distribution, and this LCBf is measured as described below. Detailed Implementation

[0008] The terms “comprising,” “including,” “having,” and their derivatives are not intended to exclude the presence of any additional components, steps, or procedures, whether or not such components, steps, or procedures are specifically disclosed. For the avoidance of any doubt, unless stated to the contrary, all compositions claimed using the term “comprising” may include any additional additives, adjuvants, or compounds, whether polymerized or otherwise. In contrast, the term “consistently comprising” excludes any other components, steps, or procedures from any subsequently listed scope, except those that are not essential for operability. The term “consisting of” excludes any components, steps, or procedures not specifically described or listed.

[0009] The term "polymer" refers to a polymeric compound prepared by polymerizing monomers, whether of the same or different types. Therefore, the general term "polymer" encompasses the term "homopolymer," which is typically used to refer to polymers prepared from only one type of monomer, and the term "copolymer," which refers to polymers prepared from two or more different monomers. As used herein, the term "interpolymer" refers to a polymer prepared by polymerizing at least two different types of monomers. Therefore, the general term "interpolymer" includes copolymers and polymers prepared from more than two different types of monomers (such as terpolymers).

[0010] As used herein, “polyolefin” refers to an olefin-based polymer. As used herein, “olefin,” also referred to as “alkene,” refers to a straight-chain, branched, or cyclic compound comprising carbon and hydrogen and having at least one double bond. As used herein, when a polymer or copolymer, such as a polyolefin elastomer, is referred to as containing an olefin, the olefin present in the polymer or copolymer is in a polymeric form of the olefin. For example, when a polyolefin elastomer is described as having an ethylene content of 75% to 85% by weight, it should be understood that the polymer units in the polyolefin elastomer are derived from ethylene in the polymerization reaction, and the derived units are present at 75% to 85% by weight based on the total weight of the polyolefin elastomer.

[0011] As used herein, the term "polyethylene" refers to a polymer comprising more than 50% by weight of units derived from ethylene monomers, and optionally one or more comonomers. This may include polyethylene homopolymers or copolymers (meaning units derived from two or more comonomers). Common forms of polyethylene known in the art include low-density polyethylene (LDPE); linear low-density polyethylene (LLDPE); ultra-low-density polyethylene (ULDPE); very low-density polyethylene (VLDPE); single-point catalytic linear low-density polyethylene, including both linear and substantially linear low-density resins (m-LLDPE); medium-density polyethylene (MDPE); and high-density polyethylene (HDPE).

[0012] blow molded products

[0013] Blow-molded articles may have a haze of less than or equal to 55.0%. Blow-molded articles may have a haze of 35% to 55%. All internal values ​​and sub-ranges are disclosed. For example, blow-molded articles may have a haze of 35% to 45% or 45% to 55%.

[0014] Blow-molded products may have an oxygen permeability (OTR) of less than or equal to 1.00 cc / bottle / day. Blow-molded products may have an OTR of 0.50 cc / bottle / day to 1.00 cc / bottle / day. All internal values ​​and sub-ranges are disclosed. For example, blow-molded products may have an OTR of 0.50 cc / bottle / day to 0.75 cc / bottle / day.

[0015] Blow-molded products may have a maximum load of 70 lb or greater. Blow-molded products may have a maximum load of 70 lb to 90 lb. All internal values ​​and sub-ranges are disclosed. For example, blow-molded products may have a maximum load of 70 lb to 80 lb or 80 lb to 90 lb.

[0016] Blow-molded articles may have an environmental stress cracking resistance (ESCR) of 70 hours or greater. Blow-molded articles may have an environmental stress cracking resistance (ESCR) ranging from 70 hours to 200 hours. All internal values ​​and sub-ranges are disclosed. For example, blow-molded articles may have an environmental stress cracking resistance of 70 hours to 100 hours, 100 hours to 150 hours, or 150 hours to 200 hours.

[0017] Ethylene / α-olefin interpolymer

[0018] Blow-molded articles may contain ethylene / α-olefin interpolymers. The ethylene / α-olefin interpolymers may have densities from 0.920 g / cc to 0.950 g / cc. All internal values ​​and sub-ranges are disclosed. For example, the ethylene / α-olefin interpolymers may have densities from 0.925 to 0.945, 0.935 to 0.940, 0.935 to 0.945, or 0.930 to 0.940.

[0019] Ethylene / α-olefin interpolymers may have a melt index (I2) ranging from 0.50 g / 10 min to 10.0 g / 10 min. All internal values ​​and sub-ranges are disclosed. For example, ethylene / α-olefin interpolymers may have a melt index (I2) ranging from 0.7 g / 10 min to 4.0 g / 10 min, 1.0 g / 10 min to 3.0 g / 10 min, or 3.0 g / 10 min to 10.0 g / 10 min.

[0020] Ethylene / α-olefin interpolymers may have a melt index ratio (I10 / I2) greater than or equal to 11. Ethylene / α-olefin interpolymers may have a melt index ratio (I10 / I2) from 11 to 15. All individual values ​​and sub-ranges are disclosed. For example, ethylene / α-olefin interpolymers may have a melt index ratio (I10 / I2) from 11 to 13 or from 13 to 15.

[0021] Ethylene / α-olefin interpolymers can have melt strength (MS), where MS (as cN) and I2 (as g / 10 min) are interrelated according to the equation MS > 8 - 4 / 3 × I2. Ethylene / α-olefins can have melt strength (MS), where MS (as cN) and I2 (as g / 10 min) are interrelated according to the equation... Interrelated. Ethylene / α-olefins can have melt strength (MS), where MS (as cN) and I2 (as g / 10 min) are related according to the equation Interrelated.

[0022] Ethylene / α-olefin interpolymers may have a melt strength of at least 6.0 cN (centine Newtons). Ethylene / α-olefin interpolymers may have a melt strength from 6.0 cN to 12.0 cN, including all internal values ​​and sub-ranges. For example, ethylene / α-olefin interpolymers may have a melt strength from 6.0 cN to 7.0 cN or from 11.0 cN to 12.0 cN.

[0023] Ethylene / α-olefin interpolymers may have a V0.1 / V100 value greater than or equal to 5.5, as determined by dynamic mechanical spectroscopy (DMS). Ethylene / α-olefin interpolymers may have a V0.1 / V100 value from 5.5 to 20.0, as determined by dynamic mechanical spectroscopy. All internal values ​​and sub-ranges are disclosed. For example, ethylene / α-olefin interpolymers may have V0.1 / V100 values ​​from 5.5 to 9.0, 7.0 to 9.0, 9.0 to 20.0, or 15.0 to 20.0.

[0024] Ethylene / α-olefin interpolymers may have a comonomer distribution (CDBI) greater than or equal to 55%. Ethylene / α-olefin interpolymers may have a CDBI from 55% to 99%, including all internal values ​​and sub-ranges. For example, ethylene / α-olefin interpolymers may have a CDBI from 55% to 72% or from 72% to 99%.

[0025] Ethylene / α-olefin interpolymers may have a Vicat softening temperature greater than or equal to 110°C. Ethylene / α-olefin interpolymers may have Vicat softening temperatures ranging from 110°C to 120°C. All internal values ​​and sub-ranges are included. For example, ethylene / α-olefin interpolymers may have Vicat softening temperatures ranging from 110°C to 117°C or from 117°C to 120°C.

[0026] Ethylene / α-olefin interpolymers may have a heat distortion temperature greater than or equal to 50°C. Ethylene / α-olefin interpolymers may have a heat distortion temperature ranging from 50°C to 60°C. All internal values ​​and sub-ranges are disclosed. For example, ethylene / α-olefin interpolymers may have a heat distortion temperature ranging from 55°C to 59°C.

[0027] Ethylene / α-olefin interpolymers may have a hexane extractability value of less than 1 wt% based on the weight of the ethylene / α-olefin interpolymer. Ethylene / α-olefin interpolymers may have a hexane extractability value of 0.1 wt% to 1 wt% based on the weight of the ethylene / α-olefin interpolymer. This includes all internal values ​​and sub-ranges. For example, ethylene / α-olefin interpolymers may have a hexane extractability value of 0.2 wt% to 0.6 wt% or 0.2 wt% to 0.5 wt% based on the weight of the ethylene / α-olefin interpolymer.

[0028] Ethylene / α-olefin interpolymers can have a transparency of 65% or higher. Ethylene / α-olefin interpolymers can have a transparency of 65% to 85%. This includes all internal values ​​and sub-ranges. For example, ethylene / α-olefin interpolymers can have a transparency of 65% to 75% or 75% to 85%.

[0029] Ethylene / α-olefin interpolymers may have melting temperatures ranging from 115°C to 126°C as measured by DSC. This includes all internal values ​​and sub-ranges. For example, ethylene / α-olefin interpolymers may have melting temperatures ranging from 120°C to 126°C as measured by DSC.

[0030] Ethylene / α-olefin interpolymers can have a Mw of 4.0 to 7.0. (abs) / Mn (abs) Mw (abs) and Mn (abs) It was measured using triple detector gel permeation chromatography as described below. All internal values ​​and sub-ranges are included. For example, ethylene / α-olefin interpolymers may have a Mw of 4.0 to 5.0 or 5.0 to 7.0. (abs) / Mn (abs) .

[0031] Ethylene / α-olefin interpolymers can have a CDF of 0.50 to 10. LS The product of LCBf and 100 (CDF) LS ×LCBf×100), where CDF LS The CDF and LCBf are measured as described below. All internal values ​​and sub-ranges are disclosed. For example, ethylene / α-olefin interpolymers may have CDFs from 0.75 to 3.0 or from 3.0 to 10.0. LS The product of LCBf and 100, where CDF LS LCBf is measured as described below.

[0032] Ethylene / α-olefin interpolymers may have a Mn content greater than or equal to 15,000 g / mol, as measured by triple detector gel permeation chromatography as described below. (abs) Ethylene / α-olefin interpolymers may have Mn content ranging from 15,000 g / mol to 20,000 g / mol, as measured using a triple detector gel permeation chromatography method as described below. (abs) All internal values ​​and sub-ranges are disclosed. For example, ethylene / α-olefin interpolymers may have Mn values ​​of 15,000 g / mol to 18,000 g / mol or 18,000 g / mol to 20,000 g / mol, as measured using triple detector gel permeation chromatography as described below. (abs) .

[0033] Ethylene / α-olefin interpolymers may have a Mw of greater than or equal to 65,000 g / mol, as measured by triple detector gel permeation chromatography as described below. (abs) Ethylene / α-olefin interpolymers can have a Mw of 65,000 g / mol to 125,000 g / mol, as measured using triple detector gel permeation chromatography as described below. (abs) All internal values ​​and sub-ranges are disclosed. For example, ethylene / α-olefin interpolymers may have Mw values ​​of 65,000 g / mol to 75,000 g / mol or 75,000 g / mol to 125,000 g / mol, as measured using triple detector gel permeation chromatography as described below. (abs) .

[0034] Ethylene / α-olefin interpolymers may have an Mz greater than or equal to 500,000 g / mol, as measured by triple detector gel permeation chromatography as described below. (abs) Ethylene / α-olefin interpolymers may have an Mz of 500,000 g / mol to 1,000,000 g / mol, as measured using triple detector gel permeation chromatography as described below. (abs) All internal values ​​and sub-ranges are disclosed. For example, ethylene / α-olefin interpolymers can have Mz values ​​from 500,000 g / mol to 750,000 g / mol or from 750,000 g / mol to 1,000,000 g / mol, as measured using triple detector gel permeation chromatography as described below. (abs) .

[0035] Ethylene / α-olefin interpolymers may have a light scattering cumulative detector fraction ratio (CDF) greater than or equal to 20.00%. LS Ethylene / α-olefin interpolymers can have a CDF of 20.00% to 40.00%. LS All internal values ​​and sub-ranges are disclosed. For example, ethylene / α-olefin interpolymers can have a CDF of 20.00% to 30.00% or 30.00% to 40.00%. LS .

[0036] Ethylene / α-olefin interpolymers may have a long-chain branching frequency (LCBf) greater than or equal to 0.02. Ethylene / α-olefin interpolymers may have a long-chain branching frequency (LCBf) from 0.02 to 0.3. All internal values ​​and sub-ranges are disclosed. For example, ethylene / α-olefin interpolymers may have a long-chain branching frequency (LCBf) from 0.02 to 0.1 or from 0.1 to 0.3.

[0037] Ethylene / α-olefin interpolymers may have a MWSCBDI greater than or equal to -1. Ethylene / α-olefin interpolymers may have a MWSCBDI ranging from -1 to 1. All internal values ​​and sub-ranges are disclosed. For example, ethylene / α-olefin interpolymers may have a MWSCBDI ranging from -1 to 0 or from 0 to 1.

[0038] Polymerization of ethylene / α-olefin interpolymers

[0039] The ethylene-α-olefin interpolymers described herein can be produced using any conventional polymerization method. Such conventional polymerization methods include, but are not limited to, slurry polymerization methods and solution polymerization methods using one or more conventional reactors, such as parallel or series loop reactors, plug flow reactors, isothermal reactors, stirred tank reactors, batch reactors, and / or any combination thereof. Ethylene / α-olefin interpolymers can be produced, for example, via solution-phase polymerization using one or more loop reactors, plug flow reactors, isothermal reactors, and combinations thereof.

[0040] Typically, solution-phase polymerization can be carried out at temperatures ranging from 115°C to 250°C (e.g., 115°C to 210°C) and pressures ranging from 300 psi to 1,000 psi (e.g., 400 psi to 800 psi) in one or more well-mixed reactors, such as one or more isothermal loop reactors, one or more adiabatic reactors, one or more plug flow reactors, or in more than one type of reactor. In a two-reactor system, the temperature in the first reactor is in the range of 115°C to 190°C (e.g., 160°C to 180°C), and the temperature in the second reactor is in the range of 150°C to 250°C (e.g., 180°C to 220°C). In a single-reactor system, the temperature in the reactor is in the range of 115°C to 250°C (e.g., 115°C to 225°C).

[0041] Residence times in solution-phase polymerization methods can range from 2 minutes to 30 minutes (e.g., 5 minutes to 25 minutes). Ethylene, solvent, hydrogen, one or more catalyst systems, optionally one or more cocatalysts, and one or more comonomers are continuously fed into one or more reactors. Exemplary solvents include, but are not limited to, isoparaffins. For example, such solvents may be named ISOPAR. ™ E was purchased commercially from ExxonMobil Chemical Co., Houston, Texas. The resulting mixture of the polyethylene composition and solvent was then removed from the reactor and the polyethylene composition was separated. The solvent was typically recovered via a solvent recovery unit (i.e., a heat exchanger and vapor-liquid separator drum) and subsequently recycled back into the polymerization system.

[0042] Ethylene / α-olefin interpolymers can be produced via solution polymerization in a two-reactor system, such as a two-loop reactor system, wherein ethylene is polymerized in the presence of one or more catalyst systems. One or more co-catalysts may be present. Ethylene-α-olefin copolymers can be produced via solution polymerization in a single-reactor system, such as a single-loop reactor system, wherein ethylene is polymerized in the presence of two catalyst systems.

[0043] The term "independently chosen" is used in this document to indicate R groups (such as R...). 1 R 2 R 3 R 4 and R 5 ) can be the same or different (e.g., R) 1 R 2 R 3 R 4 and R 5 Both can be substituted alkyl groups, or R 1 and R 2 It can be a substituted alkyl group, and R 3 (This can be aryl, etc.). Using the singular form includes using the plural form, and vice versa (e.g., hexane solvent contains hexane). The named R group will generally have a structure recognized in the art as corresponding to the R group having that name. These definitions are intended to supplement and illustrate, rather than exclude, definitions known to those skilled in the art.

[0044] The term "procatalyst" refers to a compound that exhibits catalytic activity when combined with an activator. The term "activator" refers to a compound that reacts chemically with the procatalyst in a manner that converts the procatalyst into a catalytically active catalyst. As used herein, the terms "co-catalyst" and "activator" are interchangeable.

[0045] When used to describe certain carbon-containing chemical groups, it has the form "(C x -C y The insertion of ")" indicates that the unsubstituted form of the chemical group has x to y carbon atoms, inclusive. For example, (C1-C 40 Alkyl groups are alkyl groups having 1 to 40 carbon atoms in their unsubstituted form. In some general structures, certain chemical groups may be replaced by one or more substituents such as R. S Replace. Use the parenthetical phrase "(C x -C y The chemical group defined by )” is R S The substituted form can contain more than y carbon atoms, depending on any group R. S The identity. For example, "by only one group R" SReplacement (C1-C) 40 )alkyl (wherein R) S The phenyl group (-C6H5) can contain 7 to 46 carbon atoms. Therefore, it is common practice to use the parenthetical phrase "(C6H5)" when referring to phenyl groups. x -C y The chemical group defined as ")" is substituent for one or more carbon atoms by one or more substituents R. S During substitution, both x and y are added with substituents R from all carbon-containing groups. S The minimum and maximum total number of carbon atoms in a chemical group are determined by the sum of the combinations of carbon atoms.

[0046] The term "substitution" means that at least one hydrogen atom (-H) bonded to a carbon atom or heteroatom of the corresponding unsubstituted compound or functional group is substituted by a substituent (e.g., R). S Substitution. The term "total substitution" means that each hydrogen atom (H) bonded to the carbon atom or heteroatom of the corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R). S Substitution. The term "multi-substitution" means that at least two, but fewer than all, of the hydrogen atoms bonded to the carbon or heteroatom of the corresponding unsubstituted compound or functional group are replaced by substituents.

[0047] The term "-H" refers to a hydrogen atom or a hydrogen radical that is covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless explicitly stated otherwise.

[0048] The term "(C1-C)" 50 "(C1-C) hydrocarbon radical" refers to a hydrocarbon free radical having 1 to 50 carbon atoms, and the term "(C1-C) hydrocarbon radical" is also used in this context. 50 "Hydrocarbonyl" refers to a hydrocarbon diradical having 1 to 50 carbon atoms, wherein each hydrocarbon radical and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, straight-chain or branched, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic, including bicyclic; 3 or more carbon atoms) or acyclic, and is unsubstituted or via one or more R... S replace.

[0049] In this disclosure, (C1-C 40 The hydrocarbon group can be unsubstituted or substituted (C1-C2). 40 )alkyl, (C3-C 40 )cycloalkyl, (C3-C 20 )cycloalkyl-(C1-C 20 )alkylene, (C6-C 40 ) aryl or (C6-C 20 )aryl-(C1-C 20 )alkylene.

[0050] The term "(C1-C)" 50 alkyl and (C1-C) 18 "alkyl" refers to a saturated straight-chain or branched hydrocarbon radical having 1 to 50 carbon atoms or 1 to 18 carbon atoms, wherein the hydrocarbon radical is unsubstituted or has been modified by one or more R groups. S Replacement. Unreplaced (C1-C) 50 Examples of alkyl groups are unsubstituted (C1-C1) alkyl groups. 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. Substituted (C1-C5)alkyl 50 Examples of alkyl groups are substituted (C1-C2) 20 )alkyl, substituted (C1-C 10 )alkyl, trifluoromethyl and [C 45 Alkyl group. The term "[C]" 45 Alkyl (in square brackets) means that the free radical (including substituents) contains a maximum of 45 carbon atoms, and is, for example, each radical is converted by an R group. S Replacement (C) 27 -C 40 The RS is a (C1-C5) alkyl group. Each (C1-C5) alkyl group may be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl.

[0051] The term "(C6-C)" 50 "Aryl" refers to an unsubstituted or substituted compound with 6 to 50 carbon atoms (one or more R groups). S A substituted monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radical, wherein at least 6 to 14 carbon atoms are aromatic ring carbon atoms. A monocyclic aromatic hydrocarbon radical comprises one aromatic ring. A bicyclic aromatic hydrocarbon radical has two rings. And a tricyclic aromatic hydrocarbon radical has three rings. When a bicyclic or tricyclic aromatic hydrocarbon radical is present, at least one ring of the radical is aromatic. The other one or more rings of the aromatic radical may be independently fused or unfused and aromatic or non-aromatic. Unsubstituted (C6-C) 50 An example of an aryl group is the unsubstituted (C6-C) 20 ) aryl; unsubstituted (C6-C 18) aryl; 2-(C1-C5)alkyl-phenyl; 2,4-bis(C1-C5)alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; dicyclopentadienylphenyl; hexahydrodicyclopentadienylphenyl; indene; dihydroindene; naphthyl; tetrahydronaphthyl; and phenanthrene. Substituted (C6-C 50 Examples of aryl groups are substituted (C1-C) 20 ) aryl; substituted (C6-C 18 )aryl; 2,4-bis[(C 20 [alkyl]-phenyl; polyfluorophenyl; pentafluorophenyl; and fluorene-9-one-1-yl.

[0052] The term "(C3-C)" 50 "Cycloalkyl" means an unsubstituted or alkyl group having 3 to 50 carbon atoms, or with one or more R atoms. S Substituted saturated cyclic hydrocarbon radicals. Other cycloalkyl groups (e.g., (C x -C y Cycloalkyl groups are defined in a similar manner as having x to y carbon atoms and being unsubstituted or derived from one or more R groups. S Replaced. Unreplaced (C3-C) 50 Examples of cycloalkyl groups are unsubstituted (C3-C4) 20 )cycloalkyl, unsubstituted (C3-C 10 Cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Substituted (C3-C) 50 Examples of cycloalkyl groups are substituted (C3-C4) 20 )cycloalkyl, substituted (C3-C 10 )cycloalkyl, cyclopentanone-2-yl and 1-fluorocyclohexyl.

[0053] (C1-C 50 Examples of alkylene groups include unsubstituted or substituted (C6-C) groups. 50 ()Asyl, (C3-C 50 )cycloalkylene and (C1-C 50 )alkylene (e.g., (C1-C 20 Alkylene). Biradicals can be on the same carbon atom (e.g., -CH2-), on adjacent carbon atoms (i.e., 1,2-biradicals), or separated by one, two, or more than two intermediate carbon atoms (e.g., 1,3-biradicals, 1,4-biradicals, etc.). Some biradicals include 1,2-biradicals, 1,3-biradicals, 1,4-biradicals, or α,ω-biradicals and other 1,2-biradicals. α,ω-biradicals are biradicals with the largest intercarbon backbone spacing between the group carbons. (C2-C) 20Some examples of alkylene α,ω-diradicals include ethyl-1,2-diyl (i.e., -CH2CH2-), propan-1,3-diyl (i.e., -CH2CH2CH2-), and 2-methylpropan-1,3-diyl (i.e., -CH2CH(CH3)CH2-). (C6-C) 50 Some examples of arylene α,ω-diradicals include phenyl-1,4-diyl, naphth-2,6-diyl, or naphth-3,7-diyl.

[0054] The term "(C1-C)" 50 "alkylene" means an unsubstituted or alkylene group having 1 to 50 carbon atoms, or derived from one or more R groups. S Substituted saturated straight-chain or branched diradicals (i.e., the radical is not on a ring atom). Unsubstituted (C1-C) 50 Examples of alkylene groups are unsubstituted (C1-C1) 20 Alkylenes, including unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C*HCH3 and -(CH2)4C*(H)(CH3), where "C*" indicates the carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl radical. Substituted (C1-C 50 Examples of alkylene groups are substituted (C1-C2) 20 Alkylene, -CF2-, -C(O)-, and -(CH2) 14 C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted n-1,20-eicosene). As previously mentioned, the two R... S They can combine to form (C1-C) 18 )alkylene, substituted (C1-C 50 Examples of alkylene groups also include 1,2-bis(methylene)cyclopentane, 1,2-bis(methylene)cyclohexane, 2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane and 2,3-bis(methylene)bicyclo[2.2.2]octane.

[0055] The term "(C3-C)" 50 "Cycloalkylene" means an unsubstituted or alkylene oxide having 3 to 50 carbon atoms, or with one or more R atoms. S Substituted cyclic diradicals (i.e., radicals on ring atoms).

[0056] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of heteroatoms include O, S, S(O), S(O)₂, and Si(R). C 2. P(R) P ), N(RN -N=C(R) C )2、-Ge(R C )2- or -Si(R C )-, where each R C Each R N and each R P It is unreplaced (C1-C) 18 ) Hydrocarbon group or -H.

[0057] The term "heterohydrocarbon" refers to a molecule or molecular framework in which one or more carbon atoms are replaced by heteroatoms.

[0058] The term "(C1-C)" 50 "(C1-C50)" refers to a heterohydrocarbon radical having 1 to 50 carbon atoms, and the term "(C1-C50)" is used in conjunction with the meaning of "(C1-C50)" in this context. 50 "Hypohydrocarbon radical" refers to a heterohydrocarbon diradical having 1 to 50 carbon atoms, and each heterohydrocarbon has one or more heteroatoms. (C1-C) 50 ) heterohydrocarbon group or (C1-C 50 The heteroalkyl group has one or more heteroatoms. The radical of the heteroalkyl group can be on a carbon atom or a heteroatom. The two radicals of the heteroalkyl group can be on a single carbon atom or a single heteroatom. Additionally, in a diradical group, one radical can be on a carbon atom and the other radical can be on a different carbon atom; one radical can be on a carbon atom and the other radical on a heteroatom; or one radical can be on a heteroatom and the other radical on a different heteroatom. Each (C1-C2) 50 ) heterohydrocarbon groups and (C1-C 50 The heteroalkyl group can be unsubstituted or substituted with (one or more R groups). S The substituted aromatic or non-aromatic, saturated or unsaturated, straight or branched, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

[0059] (C1-C 50 Heteroalkyl groups can be unsubstituted or substituted (C1-C2). 50 (heteroalkyl, (C1-C) 50 )hydrocarbon group -O-, (C1-C 50 )hydrocarbon group -S-, (C1-C 50 )hydrocarbon group -S(O)-, (C1-C 50 )hydrocarbon group -S(O)2-, (C1-C 50 )hydrocarbon-Si(R C )2-、(C1-C 50 )hydrocarbon-N(R N )-、(C1-C50 )hydrocarbon-P(R P )-、(C2-C 50 Heterocyclic alkyl groups, (C2-C 19 Heterocyclic alkyl-(C1-C) 20 )alkylene, (C3-C 20 )cycloalkyl-(C1-C 19 (Hypoalkylene, (C2-C) 19 Heterocyclic alkyl-(C1-C) 20 (Hypoalkylene, (C1-C) 50 () heteroaryl, (C1-C 19 ) heteroaryl-(C1-C 20 )alkylene, (C6-C 20 )aryl-(C1-C 19 )heteroalkyl or (C1-C 19 ) heteroaryl-(C1-C 20 Heteroalkyl groups.

[0060] The term "(C4-C)" 50 "Heteroaryl" refers to an unsubstituted or substituted aryl group having 4 to 50 total carbon atoms and 1 to 10 heteroatoms. S A heteroaromatic hydrocarbon free radical consisting of a monocyclic, bicyclic, or tricyclic ring. A monocyclic heteroaromatic hydrocarbon free radical comprises one heteroaromatic ring; a bicyclic heteroaromatic hydrocarbon free radical has two rings; and a tricyclic heteroaromatic hydrocarbon free radical has three rings. When a bicyclic or tricyclic heteroaromatic hydrocarbon free radical is present, at least one ring in the free radical is heteroaromatic. The other one or more rings of the heteroaromatic free radical may be independently fused or unfused and aromatic or nonaromatic. Other heteroaromatic groups (e.g., typically (C...) x -C y ) heteroaryl groups, such as (C4-C 12 (Heteroaryl) is defined in a similar manner as having x to y carbon atoms (e.g., 4 to 12 carbon atoms) and being unsubstituted or via one or more R... SSubstituted. Monocyclic heteroaromatic hydrocarbon radicals are 5-membered or 6-membered rings. A 5-membered ring has 5 minus h carbon atoms, where h is the number of heteroatoms and can be 1, 2, 3, or 4; and each heteroatom can be O, S, N, or P. Examples of 5-membered heteroaromatic hydrocarbon radicals include pyrrolo-1-yl; pyrrolo-2-yl; furan-3-yl; thiophene-2-yl; pyrazol-1-yl; isoxazol-2-yl; isothiazol-5-yl; imidazole-2-yl; oxazol-4-yl; thiazol-2-yl; 1,2,4-triazol-1-yl; 1,3,4-oxadiazol-2-yl; 1,3,4-thiadiazol-2-yl; tetrazol-1-yl; tetrazol-2-yl; and tetrazol-5-yl. A 6-membered ring has 6 minus h carbon atoms, where h is the number of heteroatoms and can be 1 or 2, and the heteroatom can be N or P. Examples of 6-membered ring heteroaromatic hydrocarbon free radicals include pyridin-2-yl; pyrimidin-2-yl; and pyrazin-2-yl. Bicyclic heteroaromatic hydrocarbon free radicals can be fused 5,6- or 6,6-cyclic systems. Examples of fused 5,6-cyclic bicyclic heteroaromatic hydrocarbon free radicals are indole-1-yl; and benzimidazol-1-yl. Examples of fused 6,6-cyclic bicyclic heteroaromatic hydrocarbon free radicals are quinoline-2-yl; and isoquinoline-1-yl. Tricyclic heteroaromatic hydrocarbon free radicals can be fused 5,6,5-cyclic systems; 5,6,6-cyclic systems; 6,5,6-cyclic systems; or 6,6,6-cyclic systems. An example of a fused 5,6,5-cyclic system is 1,7-dihydropyrrolo[3,2-f]indole-1-yl. An example of a fused 5,6,6-cyclic system is 1H-benzo[f]indole-1-yl. An example of a fused 6,6,6-cyclic system is acridine-9-yl.

[0061] The term "(C1-C)" 50 "(C1-C1)" refers to a saturated straight-chain or branched radical containing one to fifty carbon atoms or fewer, and one or more heteroatoms. 50 "Hypoalkylene" refers to a saturated straight-chain or branched diradical containing 1 to 50 carbon atoms and one or more heteroatoms. The heteroatoms of heteroalkylene or hypoalkylene groups may include Si(R) C 3. Ge(R) C 3. Si(R) C )2、Ge(R C 2. P(R) P 2. P(R) P ), N(R N )2、N(R N ), N, O, OR C , S, SR C S(O) and S(O)2, wherein each of the heteroalkyl and heteroalkylene groups is unsubstituted or via one or more R S replace.

[0062] Unreplaced (C2-C) 40 Examples of heterocyclic alkyl groups include unsubstituted (C2-C4) alkyl groups. 20 Heterocyclic alkyl groups, unsubstituted (C2-C) 10 Heterocyclic alkyl groups, aziridin-1-yl, oxetane-2-yl, tetrahydrofuran-3-yl, pyrrolidine-1-yl, tetrahydrothiophene-S,S-dioxo-2-yl, morpholino-4-yl, 1,4-dioxane-2-yl, hexahydroaza-4-yl, 3-oxacyclooctyl, 5-thiocyclononyl, and 2-azacyclodecyl.

[0063] The term "halogen atom" or "halogen" refers to a free radical of a fluorine (F), chlorine (Cl), bromine (Br), or iodine (I) atom. The term "halide" refers to the anionic form of a halogen atom: the fluoride ion (F...). - ), chloride ions (Cl) - ), bromide ions (Br) - ) or iodide ions (I - ).

[0064] The term "saturated" refers to the absence of carbon-carbon double bonds, carbon-carbon triple bonds, and (in groups containing heteroatoms) carbon-nitrogen double bonds, carbon-phosphorus double bonds, and carbon-silicon double bonds. In saturated chemical groups, the presence of one or more substituents R... S In the case of substitution, one or more double and / or triple bonds may or may not be present in the substituent R. S In Chinese, the term "unsaturated" means containing one or more carbon-carbon double bonds, carbon-carbon triple bonds, or (in groups containing heteroatoms) one or more carbon-nitrogen double bonds, carbon-phosphorus double bonds, or carbon-silicon double bonds, excluding those that may exist in the substituent R. S Double bonds in (if any) or (hetero)aromatic rings (if any).

[0065] The disclosed ethylene / α-olefin interpolymer compositions can be produced using a variety of different catalyst systems. The following examples are provided to fully convey the scope of this disclosure to those skilled in the art. The ethylene / α-olefin interpolymer compositions can be polymerized using a catalyst system comprising a metal-ligand complex of structure I to form a first ethylene-based polymer; and ethylene and comonomers can be polymerized in the presence of a catalyst system comprising a different metal-ligand complex of structure I or a metal-ligand complex of structure V to form a second ethylene-based polymer; wherein structure I and structure V are as follows:

[0066]

[0067] in:

[0068] In formula (I), M1 is titanium, zirconium, hafnium, or scandium. In formulas (I) and (V), each X is independently selected from C1-C 50 ) hydrocarbon group, (C1-C 50 heteroalkyl groups, -CH2Si(R) C ) 3-Q (OR C ) Q 、-Si(R C ) 3Q (OR C ) Q -OSi(R) C ) 3Q (OR C ) Q -CH2Ge(R) C ) 3-Q (OR C ) Q -Ge(R) C ) 3Q (OR C ) Q -P(R) C ) 2W (OR C ) W -P(O)(R C ) 2-W (OR C ) W -N(R) C )2、-NH(R C ), -N(Si(R) C )3)2、-NR C Si(R C )3、-NHSi(R C 3. -OR C -SR C , -NO2, -CN, -CF3, -OCF3, -S(O)R C -S(O)2R C -OS(O)2R C -N=C(R) C )2、-N=CH(R C -N=CH2, -N=P(R) C 3. -OC(O)R C -C(O)OR C -N(R) C )C(O)R C -N(R) C )C(O)H、-NHC(O)R C -C(O)N(R) C)2、-C(O)NHR C -C(O)NH2, halogens, B(R) Y 4. Al(R) Y )4 or Ga(R Y )4 or monodentate ligands of hydrogen, wherein each R C Independently for (C1-C 30 ) hydrocarbon group or (C1-C 30 ) heterohydrocarbon groups, and each Q is 0, 1, 2 or 3, each W is 0, 1 or 2; each R Y -H, (C1-C 30 A hydrocarbon group or halogen atom, wherein two X ligands can be linked to form a metal cyclic ring.

[0069] In equations (I) and (V), each Y is independently a Lewis base; optionally, X and Y may be connected to form a ring. The subscript m is 1 or 2; and the subscript n is 0, 1, and 2.

[0070] In equation (I), R 1 and R 16 Independently select from the following groups: -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 heterohydrocarbon group, -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-、-N=C(R C )2、R C C(O)O-、R C OC(O)-, R C C(O)N(R)-、(R C 2NC(O)-, halogens, free radicals having formula (II), free radicals having formula (III), and free radicals having formula (IV):

[0071] In equations (II), (III), and (IV), R 17-21 R 22-29 and R 30-38 Each is independently selected from -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 heterohydrocarbon group, -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 C )2NC(O)- or halogen.

[0072] In equation (I), R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 R 14 and R 15 Independently selected from -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 heterohydrocarbon group, -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)-、(R C )2NC(O)- and halogens.

[0073] In equation (I), L is (C1-C 40 ) hydrocarbon group or (C1-C 40 ) Heterohydrocarbon group.

[0074] In equation (I), each R in equation (I) C R P and R NIndependently for (C1-C 30 ) hydrocarbon group, (C1-C 30 () Heterohydrocarbon group or -H.

[0075] In formula (V), M2 is titanium, zirconium, or hafnium; R 39 R 40 R 41 R 42 and R 43 Independently for (C1-C 50 ) hydrocarbon group, (C 1- C 50 ) heterohydrocarbon group, wherein R 40 R 41 R 42 and R 43 Any of the elements in R can be optionally connected to form a ring structure; 44 R 45 and R 46 Independently for (C1-C 20 ) hydrocarbon group, (C1-C 20 (C6-C) heterohydrocarbon group, (C6-C) 30 )Aryl, (C5-C 30 ) heteroaryl, of which R 44 R 45 and R 46 The two can be arbitrarily connected to form a loop.

[0076] Numerous activation cocatalysts and activation techniques have previously been taught regarding different metal-ligand complexes in the following U.S. patents: US 5,064,802, US 5,153,157, US 5,296,433, US 5,321,106, US 5,350,723, US 5,425,872, US 5,625,087, US 5,721,185, US 5,783,512, US 5,883,204, US 5,919,983, US 6,696,379, and US 7,163,907. Examples of suitable hydrocarbon oxides are disclosed in US 5,296,433. Examples of suitable Bronsted acid salts for addition polymerization catalysts are disclosed in US 5,064,802, US 5,919,983, and US 5,783,512. Examples of suitable salts of cationic oxidants and noncoordinate compatible anions as activating cocatalysts for addition polymerization catalysts are disclosed in US 5,321,106. Examples of suitable carbocation salts as activating cocatalysts for addition polymerization catalysts are disclosed in US 5,350,723. Examples of suitable silicion salts as activating cocatalysts for addition polymerization catalysts are disclosed in US 5,625,087. Examples of suitable complexes of alcohols, thiols, silanols, and oximes with tris(pentafluorophenyl)borane are disclosed in US 5,296,433. Some of these catalysts are also described in a portion of US6,515,155 B1, beginning at line 39 in column 50 and continuing through line 55 in column 56, only the portion described herein is incorporated herein by reference.

[0077] The catalyst system described above can be activated to form an active catalyst composition by combination with one or more cocatalysts, such as cation-forming cocatalysts, strong Lewis acids, or combinations thereof. Suitable cocatalysts include polymeric or oligomeric aluminum oxanes, particularly methylaluminoxanes, and inert, compatible, noncoordinate ion-forming compounds. Exemplary suitable cocatalysts include, but are not limited to, modified methylaluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetra(pentafluorophenyl)borate (1-)amine, triethylaluminum (TEA), and any combination thereof.

[0078] One or more of the aforementioned activation cocatalysts may be used in combination with each other. A combination of tris((C1-C4)alkyl)aluminum, tris((C1-C4)alkyl)borane or ammonium borate with oligomeric or polymeric aluminum oxane compounds may be used.

[0079] Product manufacturing

[0080] Blow-molded articles can be formed through extrusion blow molding, injection blow molding, injection stretch blow molding, and other methods. In all types, the substrate preform is softened. Once finished, the workpiece is clamped into a mold, and air is forced into the mold, causing the workpiece to expand until it conforms to the mold. In extrusion blow molding, a preform is formed by extruding molten plastic into a hollow tube, which is then placed in a metal mold. In injection molding, a substrate is injected onto a center pin, then allowed to expand and cool. In injection stretch molding, a substrate is injected onto a center pin, then stretched, typically above the glass transition temperature, and then blow-molded using a blow molding die. All of these methods are well known in the art.

[0081] Blow-molded products can also be formed using the blow-fill-seal process, an automated manufacturing process in which plastic containers such as bottles or ampoules are blow-molded, filled, and sealed in a continuous operation. It takes place in a sterile, enclosed area within the machine without human intervention and can therefore be used for the aseptic manufacture of sterile pharmaceutical or non-pharmaceutical liquid / semi-liquid unit dosage forms. The blow-fill-seal process functions similarly to conventional extrusion blow molding but is performed within a blow-fill-seal machine. First, molten plastic polymer is extruded into a tubular form and passed through an open two-part die to form the container. The die is then closed, which welds the bottom of the container. Simultaneously, the preform above the die is cut, or a filling needle is placed in the head of the preform without cutting it. Next, a filling mandrel with an air-blowing function is placed in the neck region of the sealed container. Sterile compressed air is then introduced through the filling mandrel to expand and form the container. For smaller ampoules, the container is formed by vacuum to avoid the compressed air system. After the container has been formed, the desired liquid is filled into the container through the filling mandrel unit. Next, the filling mandrel unit is lifted, and the head mold airtightly seals the container. Simultaneously, the head profile is formed using vacuum. In the final step, the mold is opened, and the completed container leaves the mold.

[0082] Ethylene / α-olefin interpolymers are formed into blow-molded articles using extrusion blow molding, injection blow molding, injection stretch blow molding, blow-fill-seal molding, or any other method known in the art, wherein the ethylene / α-olefin interpolymer has a density of 0.920 g / cc to 0.950 g / cc, a melt index (I2) of 0.5 g / 10 min to 10.0 g / 10 min, a comonomer distribution width index (CDBI) greater than or equal to 55%, and a CDF greater than 0.5. LS × LCBf × 100, where the CFL LS It is calculated by measuring the area fraction of the molecular weight distribution obtained from the absolute molecular weight distribution, and this LCBf is measured as described below.

[0083] Blow-molded articles may have a haze of less than or equal to 55.0%. Blow-molded articles formed by blow molding the above-described ethylene / α-olefin interpolymer into a thermoplastic melt tube may have a haze of 35% to 55%. All internal values ​​and sub-ranges are disclosed. For example, blow-molded articles formed by blow molding the above-described ethylene / α-olefin interpolymer into a thermoplastic melt tube may have a haze of 35% to 45% or 45% to 55%.

[0084] Blow-molded products may have an oxygen permeability (OTR) of less than or equal to 1.00 cc / bottle / day. Blow-molded products formed by blow molding the above-described ethylene / α-olefin interpolymer into thermoplastic melt tubes may have an OTR of 0.50 cc / bottle / day to 1.00 cc / bottle / day. All internal values ​​and sub-ranges are disclosed. For example, blow-molded products formed by blow molding the above-described ethylene / α-olefin interpolymer into thermoplastic melt tubes may have an OTR of 0.50 cc / bottle / day to 0.75 cc / bottle / day.

[0085] Blow-molded articles can have a maximum load of 70 lb or more. Blow-molded articles formed by blowing the above-described ethylene / α-olefin interpolymer into a thermoplastic melt tube can have a maximum load of 70 lb to 90 lb. All internal values ​​and sub-ranges are disclosed. For example, blow-molded articles can have a maximum load of 70 lb to 80 lb or 80 lb to 90 lb.

[0086] Blow-molded articles may have an environmental stress cracking resistance (ESCR) of 70 hours or more. Blow-molded articles formed by blow molding the above-described ethylene / α-olefin interpolymer into a thermoplastic melt tube may have an environmental stress cracking resistance (ESCR) of 70 hours to 200 hours. All internal values ​​and sub-ranges are disclosed. For example, blow-molded articles formed by blow molding the above-described ethylene / α-olefin interpolymer into a thermoplastic melt tube may have an environmental stress cracking resistance of 70 hours to 100 hours, 100 hours to 150 hours, or 150 hours to 200 hours.

[0087] Test methods

[0088] Maximum load

[0089] The maximum load on bottles was measured using a maximum load tester—Model 17-04 (available from Testing Machines, Inc., "TMI")—to determine the mechanical properties of blow-molded thermoplastic containers when loaded at a constant rate of compression flexure under column crushing conditions. Bottles were conditioned at room temperature for 48 hours and then placed upright on the bottom of the instrument at room temperature. Tests were conducted at a crosshead speed of 2 inches per minute, and flexure and load were measured until the yield point was reached. Five bottles were tested for each sample, and the average value was reported.

[0090] Oxygen permeability (OTR)

[0091] According to ASTM D3985, under ambient atmospheric conditions (23°C, 50% relative humidity, and 21% oxygen concentration), the MoconOX-TRAN... ® Oxygen permeability (OTR) of the test bottle on the OTR instrument on 2 / 21. The report is an average of two bottles.

[0092] Bottle fog

[0093] Measure haze according to ASTM D1003. Cut a sample from the bottle wall and conditioned at 23°C and 50% relative humidity for at least 40 hours. Prepare five individual 6-inch × 6-inch specimens and place them on plastic rings in a BYK Haze-Gard plus. Use metal rings to clamp the specimens firmly into the plastic rings, ensuring no noticeable wrinkles. Position the specimens as close as possible to the haze port and measure the haze. Measure and report the average total haze of the five specimens.

[0094] Bottle environmental stress cracking resistance (ESCR)

[0095] Prior to the Environmental Stress Cracking Resistance (ESCR) test, conditioned the bottle at room temperature for at least 24 hours. Set the temperature control chamber to 50°C. Fill the bottle with 10% IGEPAL, 1 / 4 to 1 / 3 full. ® / 90% deionized water solution. Apply and tighten the cap with the air hose to the bottle. Place the bottle in a temperature-controlled chamber and incubate for 1 hour. After 1 hour of incubation, retighten the cap and pressurize the bottle through the air hose on the cap. Maintain the pressure inside the bottle at 6 psi. Start the timer and record the time at which bottle failure is observed. Test five bottles for each sample.

[0096] density

[0097] Density is measured according to ASTM D792 and expressed in grams per cc.

[0098] Melt index (I2) and (I10)

[0099] Melt index (I2) and melt index (I10) were measured according to ASTM D-1238 at 190°C and 2.16 kg. Values ​​are reported in g / 10 min; these values ​​correspond to the number of grams eluted per 10 min.

[0100] Hexane extractables

[0101] The unmodified polymer and granulated polymer produced as described below were pressed in a Carver Press to a thickness of 3.0 to 4.0 mils. The granules were pressed at 3000 lbf for three minutes at 190°C, and then at 40000 lbf for three minutes at 190°C. Residue-free gloves were worn to prevent residual oil from the operator's hands from contaminating the membrane. The membrane was cut into 1-inch × 1-inch squares and weighed. Sufficient membrane sample was used so that 2.5 g of membrane sample was used for each extraction. The membrane was then extracted in a hot water bath at 49.5°C ± 0.5°C for 2 hours in a hexane container containing approximately 1000 ml of hexane. The hexane used was a mixture of isohexane (e.g., hexane (Optima), Fisher Chemical, a high-purity mobile phase for HPLC, and / or an extraction solvent for GC applications). Two hours later, the membrane was removed, rinsed in clean hexane, dried first with nitrogen, and then further dried for two hours in a vacuum oven (80°C ± 5°C) under full vacuum (ISOTEMP vacuum oven, model 281A, at approximately 30 inches of Hg). The membrane was then placed in a desiccator and allowed to cool to room temperature for at least one hour. The membrane was then weighed again, and the amount of mass loss due to extraction in hexane was calculated. [(Amount of mass loss / Initial weight of membrane) × 100] = Weight percentage of hexane-extractable material.

[0102] Melt strength (MS)

[0103] Melt strength tests were performed on a Rheotester 2000 capillary rheometer paired with a Gottfert Rheotens model 71.97. Tests were conducted using a 2 mm diameter and 30 mm long die at an entry angle of 180°. All tests were performed isothermally at 190°C.

[0104] The granular sample was loaded into a capillary tube and equilibrated at 190°C for 10 minutes. Then, a piston inside the tube applied a steady force to the molten sample for 38.16 seconds. -1The apparent wall shear rate is determined, and the melt is extruded through the die at an exit velocity of approximately 9.7 mm / s. The extrudate is then guided through a pair of serrated rheotens located 100 mm below the die exit and spaced 0.4 mm apart. The two rheotens travel at 2.4 mm / s. 2 The extruder was accelerated at a constant rate, and the response of the extrudate to the applied tensile force was measured. A graph of the force versus the Rheotens wheel speed was then created using the RtensEvaluations 2007 excel macro. The force at which fracture occurs in the melt is the melt strength, and the corresponding Rheotens wheel speed at fracture is considered the stretch limit.

[0105] Dynamic mechanical spectrometry (DMS)

[0106] First, the test sample was placed in a mold with a diameter of 1.5 inches and a thickness of 3.10 mm, and then compressed and molded at 190°C using a Carver hydraulic press at a pressure of 25,000 lbs for 6.5 minutes. The sample was equilibrated to room temperature before extraction.

[0107] Dynamic mechanical spectroscopy (DMS) frequency scans were performed using 25 mm parallel plates at 190 °C at frequencies ranging from 0.1 rad / s to 100 rad / s. The test gap separating these plates was 1.8 mm, and strains satisfying the linear viscoelastic condition were typically 10%. Each test was performed under a nitrogen atmosphere and isothermal conditions. To initiate the DMS test, the rheometer oven was first equilibrated at 190 °C for at least 30 minutes, and then the sample was loaded into the test geometry. The sample was then equilibrated in the oven with the door closed for 1 minute. The test gap was then set to 1.8 mm, and the sample was distributed for 5 minutes to release the generated normal forces. Afterward, the oven was quickly opened, and the sample was trimmed to eliminate any bulging. The DMS measurement was then initiated after the oven was closed again. During the test, the shear modulus (G'), viscous modulus (G''), and complex viscosity (v) were measured. The ratio of the complex viscosity at 0.1 rad / s to that at 100 rad / s (v0.1 / v100) can also be obtained.

[0108] Differential scanning calorimetry (DSC)

[0109] In preparation for differential scanning calorimetry (DSC) testing, the sample in granular form is first loaded into a 1-inch diameter, 0.13 mm thick mold and compressed into a thin film at 190°C and 25,000 lbs pressure for approximately 10 seconds. The resulting film is then cooled to room temperature. The film is then subjected to a punch press to remove a disc suitable for an aluminum DSC test chamber. The disc is then weighed individually (note: the sample weight is approximately 4 mg to 8 mg) and placed in the aluminum disc, which is then sealed before insertion into the DSC test chamber.

[0110] DSC testing was performed using a hot-cold-hot cycle according to ASTM standard D3418. First, the sample was equilibrated at 180°C and held isothermally for 5 minutes to remove heat and process history. Then, the sample was quenched to -40°C at a rate of 10°C / min and held isothermally again for 5 minutes during the cooling cycle. Finally, the sample was heated to 150°C at a rate of 10°C / min for a second heating cycle. For data analysis, the melting peak temperature and enthalpy of fusion were extracted from the second heating curve, while the enthalpy of crystallization was determined from the cooling curve. The enthalpy of fusion and the enthalpy of crystallization were obtained by integrating the DSC temperature spectrum from -20°C to the end of melting and crystallization, respectively. The heat of fusion of 100% crystalline polyethylene was taken as 292 J / g to calculate the wt% crystallinity. DSC testing was performed using a TA Instruments Q2000, and data analysis was performed via the TA Instruments Universal Analysis and TRIOS software packages.

[0111] Vicat softening temperature

[0112] The Vicat softening temperature was determined according to ASTM D12525. Specimens were cut from compression molded sheet using a suitable die to obtain samples 1.5 inches long, 0.5 inches wide, and approximately 0.125 inches thick. The samples were conditioned at approximately 23°C and 50% relative humidity for at least 40 hours prior to testing. The specimens were loaded into a CEAST HV6 container, and appropriate weights were added to apply a force of 10 N. The specimens were then placed in a bath containing silicone oil. After five minutes, the displacement initiator was zeroed, and the temperature was ramped up at 120°C / hour while monitoring the displacement. The Vicat temperature was defined as the temperature at which a needle penetrates 1 mm into the specimen.

[0113] Heat distortion temperature

[0114] Heat deflection temperature was measured following ASTM D648. A 5-inch long, 0.5-inch deep, and 0.125-inch wide sample was cut from compression molded sheet. The sample was conditioned at 23°C and 50% relative humidity for at least 40 hours. The sample was loaded into a CEAST HV6A insert along its edges using a 4-inch span, and appropriate weights were added to the center bar to generate a fiber stress of 0.455 MPa. The sample was then placed in a silicone oil bath, and the displacement sensor was zeroed after five minutes. The temperature was then ramped up at a specified rate of 120°C / hour while monitoring the displacement of the center bar. The heat deflection temperature was the temperature at which the bar displacement reached 0.25 mm.

[0115] transparency

[0116] Film transparency was measured according to ASTM D1746. After film production, the film was conditioned at 23°C and 50% relative humidity for at least 40 hours. The Zebedee Transparency Meter (Model CL-100) was heated for 30 minutes, and its internal calibration and standardization procedures were run. A 4.5-inch × 4.5-inch film sample was then cut from the conditioned film sheet and placed on the vacuum port of the sample holder, and the transparency was measured. Each sample was measured five times.

[0117] Triple detector gel permeation chromatography

[0118] The chromatographic system consisted of a PolymerChar GPC-IR high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5) connected to a Precision Detectors (now Agilent Technologies) 2-angle laser scattering (LS) detector model 2040 and four capillary viscometers (DV). For all absolute light scattering measurements, a 15-degree angle was used. The autosampler oven chamber was set to 160°C, and the column and detector chambers were set to 150°C. The column used was a four-column A Mixed A 30 cm 20 μm linear mixed-bed column. The chromatographic solvent used was 1,2,4-trichlorobenzene containing 200 ppm butylated hydroxytoluene (BHT). The solvent source was bubbled with nitrogen. The injection volume used was 200 μL, and the flow rate was 1.0 mL / min.

[0119] Total plate counts of the GPC column assembly were performed using decane, which was introduced into the blank sample via a micropump controlled by a PolymerChar GPC-IR system. For four Agilent Mixed A 30 cm 20 μm linear mixed-bed columns, the plate count of the chromatographic system should be greater than 18,000.

[0120] Samples were prepared semi-automatically using the PolymerChar instrument control software, with a target sample weight of 2 mg / ml. Solvent (containing 200 ppm BHT) was added to a pre-bubbled, diaphragm-capped vial via the PolymerChar high-temperature autosampler. The sample was dissolved at 160°C for two hours under low-speed shaking.

[0121] To monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by a PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate (nominal flow rate) for each sample by comparing the RV (RV(FM sample)) of the corresponding decane peak within the sample with the RV (RV(FM calibrated)) of the decane peak within the narrow standard calibration. It was then assumed that any variation in the decane marker peak time was linearly related to the flow rate (effective flow rate) throughout the run. After calibration based on the flow marker peak, the effective flow rate (relative to the narrow standard calibration) was calculated according to Equation 1. Processing of the flow marker peak was performed via PolymerChar GPCOne. ™ The software is complete. An acceptable flow rate correction should ensure that the effective flow rate is within + / - 0.5% of the nominal flow rate.

[0122] Flow rate (effective) = Flow rate (nominal) * (RV (FM calibrated) / RV (FM sample)) Equation 1)

[0123] To determine the offsets of the viscometer and light scattering detector relative to the IR5 detector, a systematic approach was used to determine the multi-detector offsets in a manner consistent with that published by Balke, Mourey et al. (Mourey and Balke, Chromatography Polym. Chapter 12, (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym. Chapter 13, (1992)), thereby using PolymerChar GPCOne. ™ The software optimizes the triple detector logarithmic (MW and IV) results from linear homopolymer polyethylene standards (3.5 > Mw / Mn > 2.2) with the narrow standard column calibration results from the narrow standard calibration curve.

[0124] Absolute molecular weight data were obtained using PolymerChar GPCOne. ™The software was obtained in a manner consistent with the following publications: Zimm, BH, J. Chem. Phys., 16, 1099 (1948) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987)). The total injection concentration used to determine the molecular weight was obtained from the mass detector area and the mass detector constant, derived from one of the suitable linear polyethylene homopolymers or polyethylene standards with known weight-average molecular weights. The calculated molecular weight (using GPCOne) ™ The light scattering constant and refractive index concentration coefficient dn / dc -0.104 were obtained using one or more polyethylene standards mentioned below. Typically, the mass detector response (IR5) and light scattering constant (using GPCOne) are also used. ™ The determination should be performed using linear standards with a molecular weight exceeding approximately 50,000 g / mol. Viscometer calibration (using GPCOne) ™ The determination can be performed using the method described by the manufacturer, or alternatively, by using published values ​​of a suitable linear standard (such as Standard Reference Material (SRM) 1475, available from the National Institute of Standards and Technology (NIST)). The viscometer constant is calculated using GPCOne. ™ The specific viscosity area (DV) of the standard to be used for calibration and the injection mass are related to its intrinsic viscosity. It is assumed that the chromatographic concentration is low enough to eliminate the effect of resolving the second virial coefficient (the effect of concentration on molecular weight).

[0125] Absolute weight-average molecular weight (MW) (Abs) (using GPCOne) ™ The molecular weight and intrinsic viscosity responses are obtained by dividing the area of ​​the light scattering (LS) integral chromatogram (calculated from the light scattering constant) by the mass recovered from the mass constant and the area of ​​the mass detector (IR5). The molecular weight and intrinsic viscosity responses are at the chromatographic ends where the signal-to-noise ratio decreases (using GPCOne). ™ Linear extrapolation. Other corresponding moments Mn (Abs) and Mz (Abs) The calculation is based on Equation 2-4 as follows:

[0126]

[0127]

[0128]

[0129] Cumulative Detector Fraction (CDF) for Small-Angle Laser Light Scattering Detectors (“CDF”) LS The calculation of ” is performed using the following steps:

[0130] 1) Based on the decane flow labeling injection as described above, linear flow-corrected chromatogram.

[0131] 2) Perform the detector offset as described above.

[0132] 3) As mentioned above, the absolute molecular weight is calculated from light scattering.

[0133] 4) According to Equation 5, the cumulative detector fraction (CDF) of the small-angle laser light scattering (LALLS) chromatogram is calculated based on the peak height (H) of the high-to-low molecular weight (low-to-high retention volume) minus the baseline at each data slice (j). LS ).

[0134]

[0135] Long chain branching frequency

[0136] The long-chain branching frequency is calculated based on the difference between g', where g' is the ratio of the intrinsic viscosity of the polymer sample to the intrinsic viscosity of a linear polymer reference with the same molecular weight. In 3D GPC practice, a reference polyethylene homopolymer with approximately 120,000 g / mol Mw and approximately 3.0 polydispersity, free of detectable LCBs or SCBs, is injected at the start of each run queue to create a Mark-Houwink linear reference line. A first-order linear fit is applied to the logarithm of the intrinsic viscosity and the logarithm of the molecular weight data obtained in the logarithmic range of 4.5 g / mol to 5.8 g / mol to provide linear reference K and α values.

[0137] The polyethylene sample of interest was analyzed to obtain its intrinsic viscosity and molecular weight, and g at each chromatographic slice (i) was calculated according to Equation 6. i The value of ':

[0138]

[0139] The calculation used IV values ​​equivalent to the linear reference in the logarithmic molecular weight range of 4.5 g / mol to 5.8 g / mol and the same SCB content. 样品，i If there are differences in SCB content, the IV is vertically shifted by adjusting the K value from the Mark-Houwink plot. 线性参考，i Lines to illustrate the relationship with IV 样品，iCompared to SCB correction, the line is moved until a single contact point is formed with the linear reference line to create a tangent to the sample Mark-Houwink line at a logarithmic molecular weight of 4.5.

[0140] The Zimm-Stockmayer branching coefficient g is calculated from g', g' = g ε Using an ε factor of 0.5. The number of branches (B) along the polymer sample at each data slice (i). n This can be determined using Equation 7 (BH Zimm and WH Stockmayer, J. Chem. Phys. 17, 1301 (1949)):

[0141]

[0142] Finally, the average LCBf amount per 1000 carbons in the polymer of all slices (i) can be determined using Equation 8:

[0143]

[0144] Molecular weighted short chain branching distribution index (MWSCBDI)

[0145] Calibration for quantification of the IR5 detector was performed using at least ten ethylene-based polymer standards (octene as a comonomer), these at least ten ethylene-based polymer standards having a narrow SCB distribution and known comonomer content (e.g., by means of...). 13 The solutions (polyethylene homopolymer and ethylene / octene copolymer) were prepared from a single reactor via a single-point metallocene catalyst in a solution process (Qiu et al., Anal. Chem. 2009, 81, 8585-8589) using a C10 NMR method. The known monomer content ranged from 0 SCB / 1000 total C in the homopolymer to approximately 40 SCB / 1000 total C, where total C = carbon in the main chain + carbon in the branches. Each standard had a weight-average molecular weight of 36,000 g / mol to 126,000 g / mol as measured by GPC. Each standard had a molecular weight distribution (Mw / Mn) of 2.0 to 2.5. The polymer properties of the SCB standards are shown in Table A.

[0146] Table A: "SCB" Standard Products

[0147]

[0148] For each SCB standard, calculate the IR5 area ratio (or IR5) of the area response of the IR5 methyl channel sensor minus the baseline to the area response of the IR5 measurement channel sensor minus the baseline. 甲基通道面积 / IR5 测量通道面积 (For example, standard filters and filter wheels supplied by PolymerChar: include part number IR5_FWM01 as part of the GPC-IR instrument). The linear fit of the SCB frequency to the IR5 area ratio is constructed in the form of the following Equation 9:

[0149]

[0150] Where A0 is the SCB / 1000 total C intercept at an IR5 area ratio of zero, and A1 is the slope of SCB / 1000 total C relative to the IR5 area ratio, indicating how SCB / 1000 total C increases with the IR5 area ratio. For standard materials with narrow PDI and narrow SCBD, the IR5 area ratio is equal to the IR5 height ratio.

[0151] A series of linear subtractions of the baseline chromatographic height from the chromatograms generated by the IR5 methyl channel sensor, as a function of column elution volume, were used to generate baseline-corrected chromatograms (methyl channel). A series of linear subtractions of the baseline chromatographic height from the chromatograms generated by the IR5 measurement channel, as a function of column elution volume, were also used to generate baseline-corrected chromatograms (measurement channel).

[0152] At each chromatographic slice i, the SCB / 1000 total C (representing octene comonomer) and the absolute molecular weight (Mw) from light scattering were obtained. i As mentioned above, the data points are taken per second. Therefore, SCB / 1000 total C (y-axis) is used as Log(Mw) i The function calculation (x-axis) was performed. Linear regression was used in EXCEL to calculate Abs Mw at 15,000 g / mol. i With 150,000 g / mol Abs Mw i Between the selected SCB / 1000 total C and Abs Log(Mw) i The slope between the values ​​(end-base correction at the chain ends is omitted for this calculation). EXCEL linear regression was used to calculate Abs Mw from 15,000 g / mol to 150,000 g / mol. i The slope of the short-chain branching distribution between (and including the endpoints) on a logarithmic scale. This slope is defined as the molecular weight short-chain branching distribution coefficient (MWSCBDI).

[0153] iCCD and Composition Distribution Width Index (CDBI)

[0154] iCCD is an improved method for comonomer content distribution (CCD) analysis; and is based on the method described in WO2017040127A1. The test is performed using a Crystallization Elution Fractionation (CEF) instrument (available from Perimocha) equipped with an IR-5 detector and a dual-angle precision detector (model 2040 light scattering detector, available from Agilent Technologies). o-Dichlorobenzene (ODCB, 99% anhydrous or industrial grade) is used as the solvent. Silica gel 40 (with a particle size of 0.2 mm to about 0.5 mm; available from EMD Chemicals) is used to dry the ODCB solvent. The dried silica is packed into three empty HT-GPC columns (300 mm × 7.5 mm (ID)) to further purify the ODCB solvent as the eluent. The CEF instrument is equipped with an autosampler with nitrogen (N2) purging capability. ODCB is bubbled with dried N2 for 1 hour before use. Samples were prepared using an autosampler with a concentration of 4 mg / mL (unless otherwise specified) and agitated at 160 °C for 1 hour. The injection volume was 300 μL. The iCCD temperature profiles were as follows: crystallization from 105 °C to 30 °C at 3 °C / min; thermal equilibration at 30 °C for 2 minutes (including a 2-minute elution time for the soluble fraction); elution from 30 °C to 140 °C at 3 °C / min. The sample flow rate during crystallization was 0.0 mL / min. The sample flow rate during elution was 0.50 mL / min. Data were collected at one data point / second.

[0155] The iCCD column used was a 15cm (length) × ¼ inner diameter (ID) stainless steel tube filled with gold-coated nickel particles (Bright 7GNM8-NiS; available from Nippon Chemical Industrial Co.). The column was filled and conditioned using a slurry method as described in WO2017040127A1. The final pressure for the trichlorobenzene (TCB) slurry filling was 150 bar (10 MPa).

[0156] Column temperature calibration was performed using a mixture of the following substances: (i) 1.0 mg / mL unimodal linear homopolymer polyethylene (polyethylene with zero comonomer content, melt index (I2) of 1.0 g / 10 min and polydispersity (Mw / Mn) of approximately 2.6 as determined by the GPC test method described above) as “reference material”; and (ii) ODCB containing 0.5 mg / mL eicosane. iCCD temperature calibration consists of four steps: (1) calculating the delay volume, which is defined as the measured peak elution temperature of eicosane minus the temperature offset between 30.00 °C; (2) subtracting the temperature offset of the elution temperature from the raw iCCD temperature data (note that this temperature offset is a function of experimental conditions, such as elution temperature, elution flow rate, etc.); (3) generating a single-peak linear calibration line that converts the elution temperature between 30.00 °C and 140.00 °C, such that the single-peak linear homopolymer polyethylene reference material has a peak temperature of 101.0 °C and eicosane has a peak temperature of 30.0 °C; and (4) for the soluble fraction measured isothermally at 30 °C, linearly extrapolating the elution temperature below 30.0 °C by using an elution heating rate of 3 °C / min according to the method described in U.S. Patent No. 9,688,795. Use GPCOne software (available from Perimocha) to generate the SCBD distribution curve dWi / dT, where Wi is the mass at Ti and Ti is the calibrated elution temperature.

[0157] The elution fraction, expressed as a percentage by weight, is determined within a specific elution temperature range. It is defined as the area of ​​the iCCD spectrum minus the baseline within the specific temperature range divided by the total integrated area of ​​the iCCD elution chromatogram minus the baseline, multiplied by 100%.

[0158] The comonomer content was compared with the elution temperature of iCCD using a solution method with 12 reference materials (ethylene homopolymers and ethylene-octene random copolymers with ethylene equivalent weight-average molecular weights ranging from 35,000 to 128,000, prepared using a unit-point metallocene catalyst). All these reference materials were analyzed at 4 mg / mL in the same manner as previously specified. The correlation between the comonomer molar fraction and elution temperature (T, in degrees Celsius) follows the expression below:

[0159]

[0160] Composition Distribution Width Index (CDBI) is defined as the weight percentage of polymer molecules having a comonomer content within + / - 50% of the median total molar comonomer content (as reported in WO 93 / 03093). The CDBI of polyolefins can be conveniently calculated from techniques known in the art, such as, for example, temperature elution fractionation (“TREF”), such as SCBD data obtained from temperature elution fractionation as described below: Wild et al., Journal of Polymer Science, Poly.Phys.Ed., Vol. 20, 441 (1982); LD Cady, “The Role of Comonomer Type and Distribution in LLDPE Product Performance,” SPE Regional Technical Conference, Quaker Square Hilton, Akron, OH, 107-119 (October 1-2, 1985); and U.S. Patent Nos. 4,798,081 and 5,008,204.

[0161] In this paper, iCCD CDBI is calculated accordingly using the short-chain branching distribution measured by the iCCD method and the comonomer composition correlation as described above relative to the elution temperature.

[0162] Example

[0163] The materials used are listed in Table 1 below. The properties of these materials are listed in Tables 2 through 4. All commercial DOWN ™ Samples are available from Dow Chemical Company (DOW). ™ Chemical). Comparative Example A is 65% by weight of DOWN. ™ LDPE 91020Health and 35% by weight of UNIVAL ™ A blend of DMDA 6400 NT 7. Comparative Examples B and C are low-density polyethylene resins prepared by high-pressure free radical polymerization. Comparative Examples D, E, and F are polyethylene resins prepared by solution polymerization using a heterogeneous catalyst. Comparative Example G is 56% by weight of DOWN. ™ LDPE 91020 Health+ and 44% DOWN ™ Blend of DMDA-8007 NT 7.

[0164] Table 1: Materials and Properties

[0165]

[0166] *NM means not measured.

[0167] Table 2: Materials and Properties (continued) .

[0168]

[0169] Table 3: Materials and Properties (continued) .

[0170]

[0171] Table 4: Materials and Properties

[0172]

[0173] Production of Experimental Resin 1 and Experimental Resin 2

[0174] Table 5: Reactors and feed conditions used for synthesizing experimental resin 1 and experimental resin 2 .

[0175]

[0176] The raw materials (ethylene, 1-octene) and process solvent (a narrow-boiling-range, high-purity isoparaffin solvent, commercially available under the brand name Isopar E from ExxonMobil Corporation)) were purified using molecular sieves and then introduced into the reaction environment. Hydrogen was supplied at a high purity level in a pressurized cylinder without further purification. The reactor monomer feed (ethylene) stream was pressurized to a reaction pressure above 525 psig via a mechanical compressor. The solvent and comonomer (1-octene) feed streams were pressurized to a reaction pressure above 525 psig via a mechanical positive displacement pump. MMAO-3A, ​​commercially available from Nouryon, was used as an impurity remover. Each catalyst component (primary catalyst or co-catalyst) was manually diluted in batches with the purified solvent (Isopar E) to the specified component concentration and pressurized to a reaction pressure above 525 psig. The co-catalyst was [HNMe(C], commercially available from Boulder Scientific. 18 H 37 [B(C6F5)4], and used at a molar ratio of 1.2 relative to the co-catalyst. All reaction feed streams were measured by mass flow meters and independently controlled by a computer-automated valve control system.

[0177] Continuous solution polymerization is carried out in CSTR and / or plug flow reactors. The CSTR reactor independently controls all fresh solvent, monomer, comonomer, hydrogen, and catalyst component feeds. The plug flow reactor has independent control of the catalyst component feed. The combined temperature of solvent, monomer, comonomer, and hydrogen fed into the reactor is controlled at any temperature between 5°C and 50°C, typically 25°C. The fresh comonomer feed to the polymerization reactor is fed together with the solvent feed. The fresh solvent feed is typically controlled at half the total fresh feed mass flow rate received at each injector. The cocatalyst is fed based on a calculated specified molar ratio (1.2 molar equivalents) to the main catalyst. Immediately after each fresh injection point, the feed stream is mixed with the circulating polymerization reactor contents via a static mixing element. In dual-catalyst operation, the catalyst ratio is adjusted to obtain the desired polymer MI and density. The effluent from the polymerization reactor system (containing solvent, monomer, comonomer, hydrogen, catalyst component, and molten polymer) exits and passes through a control valve (responsible for maintaining the reactor system pressure at a specified target). As the feed stream leaves the reactor, it comes into contact with water to stop the reaction. Various additives, such as antioxidants, can also be added at this point. The feed stream then passes through another set of static mixing elements to uniformly disperse the catalyst, activator, and additives.

[0178] After the addition of additives, the effluent (containing solvent, monomers, comonomers, hydrogen, catalyst components, and molten polymer) passes through a heat exchanger to raise the flow temperature, thus preparing the polymer for separation from other lower-boiling-point reactive components. The flow then enters a secondary separation and de-volatiles system, where the polymer is removed from the solvent, hydrogen, and unreacted monomers and comonomers. The separated and de-volatiles polymer melt is pumped through a die specially designed for underwater granulation, cutting it into uniform solid granules, which are then dried and transferred to boxes for storage.

[0179] Bottle making

[0180] 14oz Boston round bottles with a target weight of 26g ± 0.5g were produced using a Bekum H-111 continuous extrusion blow molding machine equipped with a 50mm extruder and a MACO 6500* digital readout controller. Parison programming was used to run the blow molding equipment to ensure a consistent and uniform wall thickness distribution in the produced bottles. The extruder barrel temperature was maintained at 350℉. The extrusion rate was approximately 120g / min to 140g / min. For samples lacking sufficient melt strength, a lower extruder barrier temperature was used to improve melt strength and reduce sagging. The indenter weight was used to adjust the overall weight of the parison. This was used to compensate for the weight increase during bottle forming. Higher indenter weights correlated with wider die clearances, and vice versa. Detailed processing conditions are listed in Table 5. The target bottle weight for each produced bottle was 26g. The properties of the produced bottles are listed in Table 6.

[0181] Table 6: Bottle Manufacturing and Processing Conditions

[0182]

[0183] Table 7: Bottle Properties

[0184]

Claims

1. A blow-molded article comprising an ethylene / α-olefin interpolymer, said ethylene / α-olefin interpolymer having: Density ranging from 0.920 g / cc to 0.950 g / cc; Melt index (I2) from 0.5g / 10 minutes to 10.0g / 10 minutes; Comonomer distribution width index (CDBI) greater than or equal to 55%; CDF LS ; and LCBf; The CDF LS × LCBf × 100 is greater than 0.5, and The CDF LS The LCBf is calculated by measuring the area fraction of the molecular weight distribution obtained from the absolute molecular weight of greater than 500,000 g / mol from small-angle light scattering using GPC molecular weight distribution measurement, and the LCBf is measured as described in the specification.

2. The blow-molded article according to claim 1, wherein the ethylene / α-olefin interpolymer has a density of 0.925 g / cc to 0.945 g / cc.

3. The blow-molded article according to any of the preceding claims, wherein the ethylene / α-olefin interpolymer has a melt index (I2) of 0.7 g / 10 min to 4.0 g / 10 min.

4. The blow-molded article according to any of the preceding claims, wherein the ethylene / α-olefin interpolymer has a comonomer distribution width index (CDBI) of 55% to 99%.

5. The blow-molded article according to any of the preceding claims, wherein the ethylene / α-olefin interpolymer has a V0.1 / V100 value greater than or equal to 5.5 as determined by dynamic mechanical spectroscopy.

6. The blow-molded article according to any of the preceding claims, wherein the ethylene / α-olefin interpolymer has a V0.1 / V100 value of 5.5 to 20 as determined by dynamic mechanical spectroscopy.

7. The blow-molded article according to any of the preceding claims, wherein the ethylene / α-olefin interpolymer has a melt strength (MS), wherein the MS and I2 satisfy... Furthermore, the I2 is expressed in g / 10 min, and the MS is expressed in cN.

8. The blow-molded article according to any of the preceding claims, wherein the ethylene / α-olefin interpolymer has a Vicat softening temperature greater than or equal to 110°C.

9. The blow-molded article according to any of the preceding claims, wherein the ethylene / α-olefin interpolymer has a heat distortion temperature greater than or equal to 50°C.

10. The blow-molded article according to any of the preceding claims, wherein the ethylene / α-olefin interpolymer has a hexane extractability value of less than 1% by weight based on the weight of the ethylene / α-olefin interpolymer.

11. The blow-molded article according to any of the preceding claims, wherein the ethylene / α-olefin interpolymer has a transparency of 65% or more.

12. The blow-molded article according to any of the preceding claims, wherein the ethylene / α-olefin interpolymer has a melt peak temperature of 115°C to 126°C as measured by DSC.

13. The blow-molded article according to any of the preceding claims, wherein the ethylene / α-olefin interpolymer has a melt index ratio (I10 / I2) greater than or equal to 11 as measured according to ASTM 1238.

14. The blow-molded article according to any of the preceding claims, wherein the ethylene / α-olefin interpolymer has a Mw of 4.0 to 7.

0. (abs) / Mn (abs) The Mw (abs) and Mn (abs) It was measured using triple detector gel permeation chromatography.

15. The blow-molded article according to any of the preceding claims, wherein the ethylene / α-olefin interpolymer has a comonomer distribution width index of greater than or equal to 55%.

16. The blow-molded article according to any of the preceding claims, wherein the ethylene / α-olefin interpolymer has a CDF of 0.5 to 10. LS × LCBf × 100, wherein the CDF LS LCBf was measured as described in the instruction manual.

17. The blow-molded article according to any of the preceding claims, wherein the ethylene / α-olefin interpolymer has a MWSCBDI of -1.0 to 1.0.

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