Blow-molded articles

Abstract

A blow-molded article containing an ethylene / alpha-olefin interpolymer is disclosed. The ethylene / alpha-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%. Ethylene alpha-olefin also has a CDF greater than 0.5 LS ×LCBf×100 is also available, CDF LS The LCBf is measured as follows: density of 0.920 g / cc to 0.950 g / cc, melt index (I2) of 0.5 g / 10 min to 10.0 g / 10 min, comonomer distribution width index (CDBI) of ≥ 55%, and CDF greater than 0.5. LS ×LCBf × 100 value (in the formula, CDF LS Also disclosed are blow-molded articles formed by blow-molding an ethylene / alpha-olefin interpolymer into a bottle, the LCBf having LCBf (LCBf is calculated by measuring the area fraction of the molecular weight distribution obtained from the absolute molecular weight distribution, and LCBf is measured as described below).

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims the interests of U.S. Provisional Patent Application No. 63 / 510,777, filed on 28 June 2023, the contents of which are incorporated herein by reference in their entirety.

[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 / alpha-olefin interpolymer. [Background technology]

[0003] Ampoules and bottles used for medical purposes require high heat resistance, environmental crack resistance, and flexibility, along with low haze. Low haze allows consumers to judge the quality of the contained product. Heat resistance ensures that the bottle does not break during heat sterilization and shortens sterilization time at higher temperatures. High environmental crack resistance ensures that the bottle does not break during storage. Flexibility allows for easy squeezing and product removal.

[0004] Traditionally, medical ampoules and bottles are manufactured using high-pressure polymerized LDPE. This makes it difficult to achieve densities exceeding 0.925 g / cc. This, among other issues, limits the use of high temperatures for sterilization.

[0005] Higher densities can be achieved by blending high-density polyethylene with LDPE. However, conventionally, this comes at the expense of transparency. Alternatively, higher densities can be achieved by using linear polyethylene, such as medium-density polyethylene, produced using solution polymerization, gas-phase polymerization, or slurry polymerization processes. However, the linear structure of these polyethylenes results in a lack of melt strength, which eliminates the blow molding manufacturing process.

[0006] Therefore, blow-molded bottles with high environmental crack resistance, flexibility, and transparency are desirable. [Overview of the Initiative]

[0007] Blow-molded articles containing ethylene / alpha-olefin interpolymers are disclosed. The ethylene / alpha-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 breadth index (CDBI) greater than 55%. Ethylene alpha-olefin also has a CDF greater than 0.5 LS ×LCBf×100 is also available, CDF LS The LCBf is measured as follows: density of 0.920 g / cc to 0.950 g / cc, melt index (I2) of 0.5 g / 10 min to 10.0 g / 10 min, comonomer distribution width index (CDBI) of ≥ 55%, and CDF greater than 0.5. LS ×LCBf × 100 value (in the formula, CDF LS Also disclosed are blow-molded articles formed by blow-molding an ethylene / alpha-olefin interpolymer into a bottle, the LCBf having LCBf (LCBf is calculated by measuring the area fraction of the molecular weight distribution obtained from the absolute molecular weight distribution, and LCBf is measured as described below). [Modes for carrying out the invention]

[0008] The terms “comprising,” “including,” and “having,” and their derivatives, are not intended to exclude the presence of any additional components, processes, or procedures, whether or not they are specifically disclosed. To avoid any doubt, all compositions claimed through the use of the term “comprising” may, unless otherwise specified, include any additional additives, adjuvants, or compounds, whether polymeric or otherwise. In contrast, the term “consisting essentially of” excludes any other components, processes, or procedures from the scope of any subsequent description, except those not essential to operability. The term “consisting of” excludes any components, processes, or procedures not specifically described or enumerated.

[0009] The term "polymer" refers to a polymerizable compound prepared by polymerizing monomers, whether of the same or different types. Therefore, the general term "polymer" encompasses the term "homopolymer," commonly used to refer to a polymer prepared from only one type of monomer, and "copolymer," referring to a polymer 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 three or more different types of monomers, such as terpolymers.

[0010] As used herein, “polyolefin” refers to an olefinic polymer. As used herein, “olefin,” which may also be referred to as “alkene,” refers to a linear, branched, or cyclic compound containing 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 a polymeric form of the olefin. For example, when a polyolefin elastomer is said to have an ethylene content of 75% to 85% by weight, it is understood that the polymer units in the polyolefin elastomer are obtained from ethylene in the polymerization reaction, and the resulting units are present in an amount of 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 containing more than 50% by weight of units obtained from ethylene monomers and optionally one or more comonomers. This may include polyethylene homopolymers or copolymers (meaning units obtained 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-site catalyst linear low-density polyethylene (m-LLDPE), which includes both linear low-density resins and substantially linear low-density resins; medium-density polyethylene (MDPE); and high-density polyethylene (HDPE).

[0012] Blow-molded articles Blow-molded articles may have a haze of 55.0% or less. Blow-molded articles may have a haze of 35-55%. All values ​​and sub-ranges within the range are disclosed. For example, blow-molded articles may have a haze of 35-45% or 45-55%.

[0013] Blow-molded articles may have an oxygen transmission rate (OTR) of 1.00 cc / bottle / day or less. Blow-molded articles may have an oxygen transmission rate (OTR) of 0.50 to 1.00 cc / bottle / day. All values ​​and partial ranges within the range are disclosed. For example, blow-molded articles may have an oxygen transmission rate (OTR) of 0.50 to 0.75 cc / bottle / day.

[0014] Blow-molded articles can have a top load of 70 pounds or more. Blow-molded articles can have a top load of 70 to 90 pounds. All values ​​and partial ranges within the range are disclosed. For example, blow-molded articles can have a top load of 70 to 80 pounds or 80 to 90 pounds.

[0015] Blow-molded articles can have an environmental stress cracking resistance (ESCR) of 70 hours or more. Blow-molded articles can have an environmental stress cracking resistance (ESCR) of 70 to 200 hours. All values ​​and sub-ranges within the range are disclosed. For example, blow-molded articles can have an environmental stress cracking resistance of 70 to 100, 100 to 150, or 150 to 200 hours.

[0016] Ethylene / alpha-olefin interpolymer Blow-molded articles may contain ethylene / alpha-olefin interpolymers. These ethylene / alpha-olefin interpolymers can have densities ranging from 0.920 to 0.950 g / cc. All values ​​and sub-ranges within this range are disclosed. For example, ethylene / alpha-olefin interpolymers can have densities ranging from 0.925 to 0.945, 0.935 to 0.940, 0.935 to 0.945, or 0.930 to 0.940.

[0017] Ethylene / alpha-olefin interpolymers can have a melt index (I2) of 0.50 g / 10 min to 10.0 g / 10 min. All values ​​and subranges within this range are disclosed. For example, ethylene / alpha-olefin interpolymers can have a melt index (I2) of 0.7 to 4.0, 1.0 to 3.0, or 3.0 to 10.0 g / 10 min.

[0018] Ethylene / alpha-olefin interpolymers can have a melt index ratio (I10 / I2) of 11 or more. Ethylene / alpha-olefin interpolymers can have a melt index ratio (I10 / I2) of 11 to 15. All individual values ​​and subranges are disclosed. For example, ethylene / alpha-olefin interpolymers can have a melt index ratio (I10 / I2) of 11 to 13 or 13 to 15.

[0019] Ethylene / alpha-olefin interpolymers can have melt strength (MS), and MS (in cN units) and I2 (in g / 10 min units) correlate according to the formula MS > 8 - 4 / 3 × I2. Ethylene / alpha-olefins can have melt strength (MS), and MS (in cN units) and I2 (in g / 10 min units) correlate according to the formula

[0020]

number

[0021]

number

[0022] Ethylene / alpha-olefin interpolymers can have a melt strength of at least 6.0 cN (centineutons). Ethylene / alpha-olefin interpolymers can have a melt strength of 6.0 to 12.0 cN. This includes all values ​​within the range and partial ranges. For example, ethylene / alpha-olefin interpolymers can have a melt strength of 6.0 to 7.0, or 11.0 to 12.0 cN.

[0023] Ethylene / alpha-olefin interpolymers can have V0.1 / V100 values ​​greater than or equal to 5.5, as determined by dynamic mechanical spectroscopy (DMS). Ethylene / alpha-olefin interpolymers can have V0.1 / V100 values ​​between 5.5 and 20.0, as determined by dynamic mechanical spectroscopy. All values ​​and subranges within the range are disclosed. For example, ethylene / alpha-olefin interpolymers can have V0.1 / V100 values ​​between 5.5 and 9.0, 7.0 and 9.0, 9.0 and 20.0, or 15.0 and 20.0.

[0024] Ethylene / alpha-olefin interpolymers can have a comonomer distribution (CDBI) of 55% or more. Ethylene / alpha-olefin interpolymers can have a CDBI of 55–99%. This includes all values ​​within the range and sub-ranges. For example, ethylene / alpha-olefin interpolymers can have a CDBI of 55–72% or 72–99%.

[0025] Ethylene / alpha-olefin interpolymers can have a Vicat softening temperature of 110°C or higher. Ethylene / alpha-olefin interpolymers can have a Vicat softening temperature of 110–120°C. This includes all values ​​within the range and partial ranges. For example, ethylene / alpha-olefin interpolymers can have a Vicat softening temperature of 110–117°C or 117–120°C.

[0026] Ethylene / alpha-olefin interpolymers can have a heat distortion temperature of 50°C or higher. Ethylene / alpha-olefin interpolymers can have a heat distortion temperature of 50 to 60°C. All values ​​and partial ranges within the range are disclosed. For example, ethylene / alpha-olefin interpolymers can have a heat distortion temperature of 55 to 59°C.

[0027] Ethylene / alpha-olefin interpolymers may have a hexane extract value of less than 1% by weight, based on the weight of the ethylene / alpha-olefin interpolymer. Ethylene / alpha-olefin interpolymers may have a hexane extract value of 0.1 to 1% by weight, based on the weight of the ethylene / alpha-olefin interpolymer. This includes all values ​​within the range and partial ranges. For example, ethylene / alpha-olefin interpolymers may have a hexane extract value of 0.2 to 0.6, or 0.2 to 0.5% by weight, based on the weight of the ethylene / alpha-olefin interpolymer.

[0028] Ethylene / alpha-olefin interpolymers can have a transparency of 65% or more. Ethylene / alpha-olefin interpolymers can have a transparency of 65-85%. This includes all values ​​within the range and sub-ranges. For example, ethylene / alpha-olefin interpolymers can have a transparency of 65-75% or 75-85%.

[0029] The ethylene / alpha-olefin interpolymer can have a melting temperature of 115 to 126 °C as measured by DSC. All values and sub-ranges within the range are included. For example, the ethylene / alpha-olefin interpolymer can have a melting temperature of 120 to 126 °C as measured by DSC.

[0030] The ethylene / alpha-olefin interpolymer can have a Mw (abs) / Mn (abs) and Mw (abs) and Mn (abs) are measured using triple detector gel permeation chromatography as described below. All values and sub-ranges within the range are included. For example, the ethylene / alpha-olefin interpolymer can have a Mw (abs) / Mn (abs) of 4.0 to 5.0, or 5.0 to 7.0.

[0031] The ethylene / alpha-olefin interpolymer can have a product of CDF LS and LCBf and 100 (CDF LS ×LCBf×100), where CDF LS and LCBf are measured as described below. All values and sub-ranges within the range are disclosed. For example, the ethylene / alpha-olefin interpolymer can have a product of CDF LS and LCBf and 100 of 0.75 to 3.0, or 3.0 to 10.0, where CDF LS and LCBf are measured as described below.

[0032] The ethylene / alpha-olefin interpolymer can have a Mn (abs) of 15,000 g / mol or more as measured using triple detector gel permeation chromatography as described below. The ethylene / alpha-olefin interpolymer can have a Mn of 15,000 to 20,000 g / mol as measured using triple detector gel permeation chromatography as described below.(abs) It may have all values ​​and subranges within the range. For example, ethylene / alpha-olefin interpolymers may have Mn in the range of 15,000 to 18,000 or 18,000 to 20,000 g / mol, as measured using triple detector gel permeation chromatography as described below. (abs) It can have.

[0033] Ethylene / alpha-olefin interpolymers are measured using triple detector gel permeation chromatography as described below, with a Mw of 65,000 g / mol or higher. (abs) It can have the following properties. The ethylene / alpha-olefin interpolymer is measured using triple detector gel permeation chromatography as described below, with a Mw of 65,000 to 125,000 g / mol. (abs) It may have all values ​​and subranges within the range. For example, ethylene / alpha-olefin interpolymers can have Mw of 65,000 to 75,000, or 75,000 to 125,000 g / mol, as measured using triple detector gel permeation chromatography as described below. (abs) It can have.

[0034] Ethylene / alpha-olefin interpolymers are measured using triple detector gel permeation chromatography as described below, with a Mz content of 500,000 g / mol or higher. (abs) It can have the following properties. The ethylene / alpha-olefin interpolymer is measured using triple detector gel permeation chromatography as described below, with a Mz content of 500,000 to 1,000,000 g / mol. (abs) It may have all values ​​and subranges within the range. For example, ethylene / alpha-olefin interpolymers are measured using triple detector gel permeation chromatography as described below, with Mz values ​​ranging from 500,000 to 750,000, or 750,000 to 1,000,000 g / mol. (abs) It can have.

[0035] Ethylene / alpha-olefin interpolymers have a light scattering cumulative detector fraction ratio (CDF) of 20.00% or higher. LS ) may have. Ethylene / alpha-olefin interpolymer may have 20.00-40.00% CDF LS It may have all values ​​and subranges within the range. For example, ethylene / alpha-olefin interpolymer may have 20.00-30.00% or 30.00-40.00% CDF LS It can have.

[0036] Ethylene / alpha-olefin interpolymers can have a long-chain branching frequency (LCBf) of 0.02 or higher. Ethylene / alpha-olefin interpolymers can have a long-chain branching frequency (LCBf) of 0.02 to 0.3. All values ​​within the range and subranges are disclosed. For example, ethylene / alpha-olefin interpolymers can have a long-chain branching frequency (LCBf) of 0.02 to 0.1 or 0.1 to 0.3.

[0037] Ethylene / alpha-olefin interpolymers can have an MWSCBDI of -1 or greater. Ethylene / alpha-olefin interpolymers can have an MWSCBDI of -1 to 1. All values ​​within the range and subranges are disclosed. For example, ethylene / alpha-olefin interpolymers can have an MWSCBDI of -1 to 0, or 0 to 1.

[0038] Polymerization of ethylene / alpha-olefin interpolymers The ethylene / alpha-olefin interpolymers described herein can be produced using any conventional polymerization process. Such conventional polymerization processes include, but are not limited to, slurry polymerization processes and solution polymerization processes using one or more conventional reactors, such as loop reactors, plug-flow reactors, isothermal reactors, stirred-tank reactors, and batch reactors, in parallel, in series, and / or any combination thereof. The ethylene / alpha-olefin interpolymers may also be produced, for example, by solution-phase polymerization processes using one or more loop reactors, plug-flow reactors, isothermal reactors, and combinations thereof.

[0039] Generally, solution-phase polymerization processes can be carried out in one or more well-mixed reactors, such as one or more isothermal loop reactors, one or more adiabatic reactors, or one or more plugged-flow reactors, or in two or more types of reactors, at temperatures in the range of 115–250°C (e.g., 115–210°C) and pressures in the range of 300–1,000 psi (e.g., 400–800 psi). In a double reactor, the temperature of the first reactor is in the range of 115–190°C (e.g., 160–180°C), and the temperature of the second reactor is in the range of 150–250°C (e.g., 180–220°C). In a single reactor, the reactor temperature is in the range of 115–250°C (e.g., 115–225°C).

[0040] The residence time in the solution-phase polymerization process can range from 2 to 30 minutes (e.g., 5 to 25 minutes). Ethylene, solvent, hydrogen, one or more catalyst systems, optionally one or more cocatalysts, and one or more comonomers are continuously supplied to one or more reactors. Examples of solvents include, but are not limited to, isoparaffins. For example, such solvents are commercially available from ExxonMobil Chemical Co., (Houston, Texas) under the name ISOPAR® E. The resulting mixture of the polyethylene composition and solvent is then removed from the reactor, and the polyethylene composition is isolated. The solvent is typically recovered via a solvent recovery unit, such as a heat exchanger and a gas-liquid separation drum, and then recycled back into the polymerization system.

[0041] Ethylene / alpha-olefin interpolymers can be produced by solution polymerization in a double reactor system, such as a double-loop reactor system, in the presence of one or more catalyst systems. One or more co-catalysts may be present. Ethylene-alpha-olefin copolymers can be produced by solution polymerization in a single reactor system, such as a single-loop reactor system, in the presence of two catalyst systems.

[0042] The term "independently selected" is used herein to mean R 1 , R 2 , R 3 , R 4 , and R 5 The R groups, such as R, may be the same or different (for example, R 1 , R 2 , R 3 , R 4 , and R 5 Even if all of them are substituted alkyl groups, 1 and R 2 is a substituted alkyl, and R 3It is used to indicate that the group may be an aryl group, etc. The use of the singular form includes the use of the plural form, and vice versa (for example, a hexane solvent contains multiple hexanes). A named R group generally has a structure that is recognized in the art as corresponding to the R group bearing that name. These definitions are intended to supplement and illustrate, and not to exclude, definitions known to those skilled in the art.

[0043] The term "procatalyst" refers to a compound that exhibits catalytic activity when combined with an activator. The term "activator" refers to a compound that chemically reacts with a procatalyst to convert it into a catalytically active catalyst. As used herein, the terms "cocatalyst" and "activator" are interchangeable.

[0044] When used to describe a specific carbon-carbon-containing chemical group, "(C x ~C y The parenthetical expression in the form of ")" means that the unsubstituted form of the chemical group has x carbon atoms to y carbon atoms, including x and y. 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 are R S It may be replaced by one or more substituents such as (C x ~C y The chemical group R defined using ) S The substitution version is any base R S Depending on its uniqueness, it may contain more than y carbon atoms. For example, "R S Strictly speaking, one group R is phenyl (-C6H5). S Replaced by (C1~C 40 )alkyl can contain 7 to 46 carbon atoms. Therefore, generally, the parenthetical "(C x ~C y A chemical group defined using ) is a substituent containing one or more carbon atoms R SWhen substituted by, the minimum and maximum total number of carbon atoms in that chemical group is, for both x and y, all carbon-carbon-containing substituents R S It is determined by adding up the total number of carbon atoms from each origin.

[0045] The term "substitution" refers to the substitution of a carbon atom or heteroatom or at least one hydrogen atom (-H) bonded to a functional group of the corresponding unsubstituted compound (e.g., R S The term "oversubstituted" means that all hydrogen atoms (H) bonded to the carbon or heteroatom or functional group of the corresponding unsubstituted compound are replaced by substituents (e.g., R S This means that the atoms are replaced by the substituents. The term "polysubstituted" means that at least two, but fewer than all, hydrogen atoms bonded to the carbon atoms, heteroatoms, or functional groups of the corresponding unsubstituted compound are replaced by substituents.

[0046] The term "-H" refers to hydrogen or a hydrogen radical covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and mean the same thing unless otherwise specified.

[0047] (C1~C 50 The term "hydrocarbyl" refers to a hydrocarbon radical consisting of 1 to 50 carbon atoms. 50 The term "hydrocarbylene" means a hydrocarbon diradical having 1 to 50 carbon atoms, and each hydrocarbon radical and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, linear or branched, cyclic (including monocyclic and polycyclic, condensed and non-condensed polycyclic, e.g., bicyclic; with 3 or more carbon atoms) or acyclic, and is unsubstituted or has one or more R S It has been replaced by.

[0048] In this disclosure, (C1~C 50 Hydrocarbyl is either unsubstituted or substituted (C1-C 50 ) alkyl, (C3~C 50 )Cycloalkyl, (C3~C 20)Cycloalkyl-(C1~C 20 ) Alkilen, (C6~C 40 )aryl, or (C6~C 20 )aryl-(C1~C 20 ) It could be an alkylene.

[0049] (C1~C 50 )alkyl" and "(C1~C 18 The term "alkyl" refers to each of the following: unsubstituted or one or more R S This refers to saturated linear or branched hydrocarbon radicals consisting of 1 to 50 carbon atoms or 1 to 18 carbon atoms, which are substituted by (C1-C). 50 Examples of alkyl groups include 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. Substituted (C1~C 50 Examples of alkyl groups include substitutions (C1~C 20 ) alkyl, substituted (C1~C 10 ) alkyl, trifluoromethyl, and [C 45 It is alkyl. [C 45 The term ]alkyl (in square brackets) means that there are up to 45 carbon atoms in the radical, including substituents, for example, one R is (C1-C5)alkyl. S Replaced by (C 27 ~C 40 Each (C1-C5) alkyl group may be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl.

[0050] (C6~C 50 The term "aryl" refers to a group of 6 to 50 carbon atoms, either unsubstituted or substituted (one or more R) atoms. Smeans a monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radical, with at least 6 to 14 of the 6 to 50 carbon atoms being aromatic ring carbon atoms. The monocyclic aromatic hydrocarbon radical contains one aromatic ring. The bicyclic aromatic hydrocarbon radical has two rings. The tricyclic aromatic hydrocarbon radical has three rings, while in the case where a bicyclic or tricyclic aromatic hydrocarbon radical exists, at least one of the rings of the radical is aromatic. The one or more other rings of the aromatic radical can be independently fused or unfused, and aromatic or non-aromatic. Unsubstituted (C6-C 50 ) aryl examples are unsubstituted (C6-C 20 ) aryl, unsubstituted (C6-C 18 ) aryl, 2-(C1-C5) alkylphenyl, 2,4-bis(C1-C5) alkylphenyl, phenyl, fluorenyl, tetrahydrofluorenyl, indacenyl, hexahydroindacenyl, indenyl, dihydroindenyl, naphthyl, tetrahydronaphthyl, and phenanthrene. Substituted (C6-C 50 ) aryl examples are substituted (C1-C 20 ) aryl, substituted (C6-C 18 ) aryl, 2,4-bis[(C 20 ) alkyl]-phenyl, polyfluorophenyl, pentafluorophenyl, and fluoren-9-one-1-yl.

[0051] The term “(C3-C 50 ) cycloalkyl” means a saturated cyclic hydrocarbon radical of 3 to 50 carbon atoms that is unsubstituted or substituted by one or more R S . Other cycloalkyl groups (e.g., (C x -C y ) cycloalkyl) are defined in a similar manner as having x to y carbon atoms and being either unsubstituted or substituted by one or more R S . Examples of unsubstituted (C3-C 50 ) cycloalkyl are unsubstituted (C3-C 20 ) cycloalkyl, unsubstituted (C3-C 10These are cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Substitutions (C3~C 50 Examples of cycloalkyl groups include substitutions (C3~C 20 )Cycloalkyl, substituted (C3~C 10 These are cycloalkyl, cyclopentanon-2-yl, and 1-fluorocyclohexyl.

[0052] (C1~C 50 Examples of hydrocarbylenes include unsubstituted or substituted (C6~C 50 ) Alliren, (C3~C 50 )Cycloalkylene, and (C1~C 50 )Alkylene (for example, (C1~C 20 Examples include alkylenes. Diradicals can be on the same carbon atom (e.g., -CH2-), on adjacent carbon atoms (i.e., 1,2-diradical), or separated by one, two, or three or more interposing carbon atoms (e.g., 1,3-diradical, 1,4-diradical, etc.). Some diradicals include 1,2-, 1,3-, 1,4-, or α,ω-diradicals, while others include 1,2-diradicals. The α,ω-diradical is a diradical with the largest possible carbon skeleton spacing between radical carbons. (C2~C 20 Some examples of alkylene α,ω-diradicals include ethane-1,2-diyl (i.e., -CH2CH2-), propane-1,3-diyl (i.e., -CH2CH2CH2-), and 2-methylpropane-1,3-diyl (i.e., -CH2CH(CH3)CH2-). (C6~C 50 Some examples of arylene α,ω-diradicals include phenyl-1,4-diyl, naphthalene-2,6-diyl, or naphthalene-3,7-diyl.

[0053] (C1~C 50 The term "alkylene" refers to an unsubstituted or one or more R SThis refers to saturated linear or branched diradicals of 1 to 50 carbon atoms that are substituted by (i.e., the radical does not reside on the ring atom). Unsubstituted (C1~C 50 Examples of alkylenes include unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, and -CH2C. * HCH3 and -(CH2)4C * (H)(CH3)(in the formula, “C * This includes unsubstituted (C1-C) atoms, which are carbon atoms from which a hydrogen atom has been removed to form a secondary or tertiary alkyl radical. 20 ) is an alkylene. Substitution (C1~C 50 ) An example of alkylene is substitution (C1~C 20 ) Alkylene, -CF2-, -C(O)-, and -(CH2) 14 It is C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted n-1,20-eicosylene). As mentioned above, there are two R S They come together, (C1~C 18 ) Because alkylenes can be formed, substitution (C1~C 50 Examples of alkylenes 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.

[0054] (C3~C 50 The term "cycloalkylene" refers to an unsubstituted or one or more R S This refers to a cyclic diradical consisting of 3 to 50 carbon atoms, substituted by (i.e., the radical resides on the ring atom).

[0055] 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(R N ), -N=C(R C)2, -Ge(R C )2-, or -Si(R C )-(in the formula, each R C , each R N , and each R P is non-substitutable (C1~C 18 Examples include hydrocarbyl or -H.

[0056] The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more carbon atoms are replaced by heteroatoms.

[0057] (C1~C 50 The term "heterohydrocarbyl" refers to a heterohydrocarbon radical consisting of 1 to 50 carbon atoms. 50 The term "heterohydrocarbylene" refers to a heterohydrocarbon diradical with 1 to 50 carbon atoms, where each heterohydrocarbon has one or more heteroatoms. (C1~C 50 ) Heterohydrocarbyl or (C1~C 50 A heterohydrocarbylene heterohydrocarbon has one or more heteroatoms. The radical of a heterohydrocarbylene may reside on a carbon atom or on a heteroatom. Two radicals of a heterohydrocarbylene may reside on a single carbon atom or on a single heteroatom. In addition, one of the two radicals of a diradical may reside on a carbon atom and the other radical on a different carbon atom, or one of the two radicals may reside on a carbon atom and the other on a heteroatom, or one of the two radicals may reside on a heteroatom and the other radical on a different heteroatom. Each (C1~C 50 )heterohydrocarbyl and (C1~C 50 ) Heterohydrocarbylenes are either unsubstituted or substituted (one or more R S It may be aromatic or non-aromatic, saturated or unsaturated, linear or branched, cyclic (including monocyclic and polycyclic, condensed and non-condensed polycyclic) or acyclic.

[0058] (C1~C 50 ) Heterohydrocarbyls are either unsubstituted or substituted (C1~C 50) Heteroalkyl, (C1~C 50 ) Hydrocarbyl-O-, (C1~C 50 ) Hydrocarbyl-S-, (C1~C 50 ) Hydrocarbyl-S(O)-, (C1~C 50 )hydrocarbyl-S(O)2-, (C1~C 50 ) Hydrocarbyl-Si(R C )2-, (C l ~C 50 ) Hydrocarbyl-N(R N )-, (C1~C 50 ) Hydrocarbyl-P(R P )-, (C2~C 50 ) Heterocycloalkyl, (C2~C 19 ) Heterocycloalkyl-(C1~C 20 ) Alkilen, (C3~C 20 )Cycloalkyl-(C1~C 19 ) Heteroalkylene, (C2~C 19 ) Heterocycloalkyl-(C1~C 20 ) Heteroalkylene, (C1~C 50 ) Heteroaryl, (C1~C 19 ) Heteroaryl-(C1~C 20 ) Alkilen, (C6~C 20 )aryl-(C1~C 19 ) Heteroalkylene, or (C1~C 19 ) Heteroaryl-(C1~C 20 ) It may be a heteroalkylene.

[0059] (C4~C 50 The term "heteroaryl" refers to a compound consisting of a total of 4 to 50 carbon atoms and 1 to 10 heteroatoms, either unsubstituted or substituted (one or more R atoms). SThis refers to monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon radicals (by ). A monocyclic heteroaromatic hydrocarbon radical contains one heteroaromatic ring, a bicyclic heteroaromatic hydrocarbon radical has two rings, and a tricyclic heteroaromatic hydrocarbon radical has three rings. If a bicyclic or tricyclic heteroaromatic hydrocarbon radical exists, at least one of the rings in the radical is heteroaromatic. One or more other rings in the heteroaromatic radical may independently be condensed or uncondensed, and aromatic or nonaromatic. Other heteroaryl groups (e.g., (C4~C)) 12 ) Generally (C) such as heteroaryls x ~C y A heteroaryl compound has x to y carbon atoms (e.g., 4 to 12 carbon atoms) and is either unsubstituted or has one or more R atoms. SIt is defined in a similar manner, assuming that it is substituted by . Monocyclic heteroaromatic hydrocarbon radicals are five-membered or six-membered rings. A five-membered ring has 5-h carbon atoms, where h is the number of heteroatoms, which can be 1, 2, 3, or 4, and each heteroatom can be O, S, N, or P. Examples of five-membered heteroaromatic hydrocarbon radicals include pyrrole-1-yl, pyrrole-2-yl, furan-3-yl, thiophen-2-yl, pyrazole-1-yl, isoxazole-2-yl, isothiazol-5-yl, imidazole-2-yl, oxazole-4-yl, thiazol-2-yl, 1,2,4-triazole-1-yl, 1,3,4-oxadiazole-2-yl, 1,3,4-thiadiazole-2-yl, tetrazole-1-yl, tetrazole-2-yl, and tetrazole-5-yl. A six-membered ring has 6-h carbon atoms, where h is the number of heteroatoms, which can be 1 or 2, and the heteroatoms can be N or P. Examples of six-membered ring heteroaromatic hydrocarbon radicals include pyridine-2-yl, pyrimidine-2-yl, and pyrazine-2-yl. Bicyclic heteroaromatic hydrocarbon radicals can be condensed 5,6- or 6,6-ring systems. Examples of condensed 5,6-ring bicyclic heteroaromatic hydrocarbon radicals are indole-1-yl and benzimidazole-1-yl. Examples of condensed 6,6-ring bicyclic heteroaromatic hydrocarbon radicals are quinoline-2-yl and isoquinoline-1-yl. Tricyclic heteroaromatic hydrocarbon radicals can be condensed 5,6,5, 5,6,6, 6,5,6, or 6,6,6-ring systems. An example of a condensed 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indole-1-yl. An example of a condensed 5,6,6-ring system is 1H-benzo[f]indole-1-yl. An example of a condensed 6,6,6-ring system is acridine-9-yl.

[0060] (C1~C 50 The term "(C1~C) heteroalkyl" refers to a saturated linear or branched radical containing 1 to 50 carbon atoms, or fewer carbon atoms and one or more heteroatoms. 50The term "heteroalkylene" refers to a saturated linear or branched diradical containing 1 to 50 carbon atoms and one or more heteroatoms. Examples of heteroatoms in heteroalkyl or heteroalkylene 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 Examples include S(O) and S(O)2, where each of the heteroalkyl and heteroalkylene groups is either unsubstituted or has one or more R S It has been replaced by.

[0061] Unsubstituted (C2~C 40 Examples of heterocycloalkyl groups include unsubstituted (C2~C 20 ) Heterocycloalkyl, unsubstituted (C2~C 10 Examples include heterocycloalkyls, aziridin-1-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidine-1-yl, tetrahydrothiophen-S,S-dioxide-2-yl, morpholine-4-yl, 1,4-dioxan-2-yl, hexahydroazepine-4-yl, 3-oxacyclooctyl, 5-thiocyclononyl, and 2-azacyclodecyl.

[0062] The terms "halogen atom" or "halogen" refer to the radicals of fluorine (F), chlorine (Cl), bromine (Br), or iodine (I). The term "halide" refers to the anionic form of the halogen atom (fluoride (F)). - ), chloride (Cl - ), bromide (Br - ), or iodide (I - It means )).

[0063] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, and carbon-silicon double bonds. A saturated chemical group has one or more substituents R S If substituted by, one or more double and / or triple bonds may optionally be substituted with substituent R S It may or may not be present. The term "unsaturated" means containing one or more carbon-carbon double bonds, carbon-carbon triple bonds, or (in heteroatom-containing groups) one or more carbon-nitrogen, carbon-phosphorus, or carbon-silicon double bonds, with substituent R S It does not contain any double bonds that may be present in (if any) or in (hetero) aromatic rings (if any).

[0064] The disclosed ethylene / alpha-olefin interpolymer compositions can be produced by several different catalyst systems. The examples described below are included to fully convey the scope of this disclosure to those skilled in the art. The ethylene / alpha-olefin interpolymer compositions can be polymerized using a catalyst system containing a metal-ligand complex of structure I to form a first ethylene-based polymer, and can be polymerized by polymerizing ethylene and comonomers in the presence of a catalyst system containing a different metal-ligand complex of structure I or a metal-ligand complex of structure V to form a second ethylene-based polymer, the structures I and V being as follows:

[0065] [ka]

[0066] In formula (I), M1 is titanium, zirconium, hafnium, or scandium. In formulas (I) and (V), each X is (C1~C 50 ) Hydrocarbyl, (C1~C 50 ) Heterohydrocarbyl, -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, halogen, B(R Y )4, Al(R Y )4, or Ga(R Y )4, or a monodentate ligand independently selected from hydrogen, where each R C (C1~C 30) Hydrocarbyl, or (C1~C 30 ) is a heterohydrocarbyl, where each Q is 0, 1, 2, or 3, each W is 0, 1, or 2, and each R Y is -H, (C1~C 30 ) is a hydrocarbyl or halogen atom, and the two X ligands can be bonded to form a metallacycle ring.

[0067] In formulas (I) and (V), each Y is independently a Lewis base, and X and Y may optionally combine to form a ring. The subscript m is 1 or 2, and the subscript n is 0, 1, and 2.

[0068] In equation (I), R 1 and R 16 is -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⁻, -N=C(R) C )2, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C A radical is independently selected from the group consisting of 2NC(O)-, halogens, radicals having formula (II), radicals having formula (III), and radicals having formula (IV).

[0069] [ka]

[0070] In equations (II), (III), and (IV), R 17~21 , R 22~29 , and R 30~38 Each of these is -H, (C1~C40 ) 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 C )2NC(O)-, or selected independently from halogens.

[0071] 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 is -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)-, (R C )2NC(O)-, and halogens are selected independently.

[0072] In equation (I), L is (C1~C 40 ) Hydrocarbylene or (C2~C 40 It is a heterohydrocarbylene.

[0073] In equation (I), each R in equation (I) C , R P , and R N (C1~C 30 ) Hydrocarbyl, (C1~C 30 (Heterohydrocarbyl) or -H.

[0074] In formula (V), M2 is titanium, zirconium, or hafnium, and R 39 , R 40 , R 41 , R 42 , and R 43 (C1~C 50 ) Hydrocarbyl, (C1~C 50 ) is a heterohydrocarbyl, R 40 , R 41 , R 42 , and R 43 Either of them can be optionally joined to form a ring structure, R 44 , R 45 , and R 46 (C1~C 20 ) Hydrocarbyl, (C1~C 20 ) Heterohydrocarbyl, (C6~C 30 )Aaryl, (C5~C 30 ) is a heteroaryl, R 44 , R 45 , and R 46 Two of them are arbitrarily joined to form a ring.

[0075] Many activated cocatalysts and activation techniques for various metal-ligand complexes have already been taught in U.S. Patents: 5,064,802, 5,153,157, 5,296,433, 5,321,106, 5,350,723, 5,425,872, 5,625,087, 5,721,185, 5,783,512, 5,883,204, 5,919,983, 6,696,379, and 7,163,907. Examples of suitable hydrocarbyl oxides are disclosed in U.S. Patent 5,296,433. Examples of suitable Brønsted salts for addition polymerization catalysts are disclosed in U.S. Patents 5,064,802, 5,919,983, and 5,783,512. Examples of suitable salts of cationic oxidizing agents and non-coordinating compatible anions as activating cocatalysts for addition polymerization catalysts are disclosed in U.S. Patent 5,321,106. Examples of suitable carbenium salts as activating cocatalysts for addition polymerization catalysts are disclosed in U.S. Patent 5,350,723. Examples of suitable silylium salts as activating cocatalysts for addition polymerization catalysts are disclosed in U.S. Patent 5,625,087. Examples of suitable complexes of alcohols, mercaptans, silanols, and oximes with tris(pentafluorophenyl)borane are disclosed in U.S. Patent 5,296,433. Some of these catalysts are also described in part of U.S. Patent No. 6,515,155(B1) (column 50, line 39 to column 56, line 55), only a portion of which is incorporated herein by reference.

[0076] The catalyst system described above can be activated to form an active catalyst composition by combining it with one or more cocatalysts, such as cation-forming cocatalysts, strong Lewis acids, or combinations thereof. Suitable cocatalysts for use include polymers or oligomeric aluminoxanes, particularly methyl aluminoxanes, and inert, compatible, non-coordinating, ion-forming compounds. Exemplary suitable cocatalysts include, but are not limited to, modified methyl aluminoxane (MMAO), bis(hydride-tulose alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-)amine, triethyl aluminum (TEA), and any combination thereof.

[0077] One or more of the aforementioned activated cocatalysts are used in combination with each other. A combination of tri((C1-C4)hydrocarbyl)aluminum, tri((C1-C4)hydrocarbyl)borane, or a mixture of ammonium borate and an oligomer or polymer-aluminoxane compound can be used.

[0078] Manufacturing of goods Blow-molded articles can be formed by extrusion blow molding, injection blow molding, and injection stretch blow molding. In all types, the substrate preform is softened. After this is complete, the workpiece is clamped into the mold, air is forced into the mold, and the workpiece is expanded until it conforms to the mold. In extrusion blow molding, the preform is formed by extruding molten plastic into a hollow tube and then placing it into a mold. In injection molding, the substrate is injected onto a core pin, then expanded and cooled. In injection stretch molding, the substrate is injected onto a core pin, then stretched at a temperature usually higher than the glass transition temperature, and then blown using blow molding. All of these processes are well understood in the art.

[0079] Blow-molded articles can also be formed by a blow-fill-seal process, which is an automated manufacturing process that blow-forms, fills, and seals plastic containers such as bottles or ampoules in a continuous operation. This is done without human intervention in a sterile, sealed area inside the machine and can therefore be used to aseptically produce sterile pharmaceutical or non-pharmaceutical liquid / semi-liquid unit dosage forms. The blow-fill-seal process functions similarly to conventional extrusion blow molding and is carried out in a blow-fill-seal machine. First, molten plastic polymer is extruded into a tubular shape, and a mold consisting of two open parts takes it, forming the container. Next, the mold is closed, welding the bottom of the container. At the same time, the parison above the mold is cut, or a filling needle is inserted into the parison head without cutting the parison. Next, a filling mandrel with blowing air functionality is placed in the neck area to seal the container. Then, sterile compressed air is introduced through the filling mandrel to inflate and form the container. For smaller ampoules, the compressed air system is avoided by vacuum forming the container instead. After forming the container, the desired liquid is filled into the container via a filling mandrel unit. Then, the filling mandrel unit is lifted, and the container is sealed by the head mold. At the same time, the head contour is formed by vacuum. In the final step, the mold is opened, and the finished container is removed from the mold.

[0080] Density of 0.920 g / cc to 0.950 g / cc, melt index (I2) of 0.5 g / 10 min to 10.0 g / 10 min, comonomer distribution width index (CDBI) of 55% or more, and CDF greater than 0.5. LS ×LCBf × 100 value (in the formula, CFL LS The ethylene / alpha-olefin interpolymer having LCBf (where LCBf is calculated by measuring the area fraction of the molecular weight distribution obtained from the absolute molecular weight distribution, and LCBf is measured as described below) is formed into a blow-molded article by extrusion blow molding, injection blow molding, injection stretch blow molding, blow filling and sealing, or any other method known in the art.

[0081] Blow-molded articles may have a haze of 55.0% or less. Blow-molded articles formed by blow-molding the above-mentioned ethylene / alpha-olefin interpolymer into a thermoplastic molten tube may have a haze of 35-55%. All values ​​and partial ranges within the range are disclosed. For example, blow-molded articles formed by blow-molding the above-mentioned ethylene / alpha-olefin interpolymer into a thermoplastic molten tube may have a haze of 35-45% or 45-55%.

[0082] Blow-molded articles can have an oxygen permeability (OTR) of 1.00 cc / bottle / day or less. Blow-molded articles formed by blow-molding the above-mentioned ethylene / alpha-olefin interpolymer into a thermoplastic molten tube can have an oxygen permeability (OTR) of 0.50 to 1.00 cc / bottle / day. All values ​​and partial ranges within the range are disclosed. For example, blow-molded articles formed by blow-molding the above-mentioned ethylene / alpha-olefin interpolymer into a thermoplastic molten tube can have an oxygen permeability (OTR) of 0.50 to 0.75 cc / bottle / day.

[0083] Blow-molded articles can have a top load of 70 pounds or more. Blow-molded articles formed by blow-molding the ethylene / alpha-olefin interpolymer described above into a thermoplastic molten tube can have a top load of 70 to 90 pounds. All values ​​and partial ranges within the range are disclosed. For example, blow-molded articles can have a top load of 70 to 80 pounds or 80 to 90 pounds.

[0084] Blow-molded articles can have an environmental stress crack resistance (ESCR) of 70 hours or more. Blow-molded articles formed by blow-molding the above-mentioned ethylene / alpha-olefin interpolymer into a thermoplastic molten tube can have an environmental stress crack resistance (ESCR) of 70 to 200 hours. All values ​​and partial ranges within the range are disclosed. For example, blow-molded articles formed by blow-molding the above-mentioned ethylene / alpha-olefin interpolymer into a thermoplastic molten tube can have an environmental stress crack resistance of 70 to 100, 100 to 150, or 150 to 200 hours.

[0085] Test method Top load The top load of the bottle is measured using a top load tester - Model 17-04 (commercially available from Testing Machines, Inc. "TMI") to determine the mechanical properties of the blown thermoplastic container under cylindrical collapse conditions with a constant compressive deformation rate. The bottles are conditioned at room temperature for 48 hours and placed empty in an upright position on the base of the instrument at room temperature. The experiment is conducted at a crosshead speed of 2 inches / min, and deformation and load are measured until the yield point is reached. Five bottles are tested per sample, and the average value is reported.

[0086] Oxygen transmission rate (OTR) The oxygen permeability (OTR) of the bottles will be tested according to ASTM D3985 using a Mocon OX-TRAN® 2 / 21 OTR instrument under environmental conditions (23°C, 50% relative humidity, and 21% oxygen concentration). The average value from two bottles will be reported.

[0087] Bottle Haze Measure the haze according to ASTM D1003. Cut a sample from the bottle wall and condition it at 23°C and 50% relative humidity for at least 40 hours. Prepare five separate 6-inch x 6-inch test specimens and place them on the plastic ring of the BYK Haze-Gard plus. Use a metal ring to clamp the test specimens inside the plastic ring, ensuring there are no obvious wrinkles in the specimens. 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 test specimens.

[0088] Bottle environmental stress crack resistance (ESCR) Before the Environmental Stress Crack Resistance (ESCR) test, condition the bottles at room temperature for at least 24 hours. Set the temperature control chamber to 50°C. Fill the bottles 1 / 4 to 1 / 3 full with 10% IGEPAL® / 90% deionized aqueous solution. Attach the cap with the air hose to the bottle and tighten it. Place the bottle in the temperature control chamber and condition for 1 hour. After 1 hour of conditioning, tighten the cap again and pressurize the bottle through the air hose in the cap. Maintain the pressure at 6 psi inside the bottle. Start the timer and record the time at which bottle failure is observed. Test five bottles for each sample.

[0089] density The density is measured according to ASTM D792 and expressed in grams / cc.

[0090] Melt index (I2) and (I10) Melt index (I2) and melt index (I10) are measured at 190°C and 2.16 kg according to ASTM D-1238. The values ​​are reported in g / 10 mins, which corresponds to the number of grams eluted per 10 minutes.

[0091] Hexane extract The unmodified polymerized pelletized polymer, prepared as described below, is pressed in a Carver Press to a thickness of 3.0–4.0 mil. The pellets are pressed at 190°C for 3 minutes at 3,000 pounds, then at 190°C for 3 minutes at 40,000 pounds. Residue-free gloves are worn to prevent contamination of the film with residual oil from the operator's hands. The film is cut into 1-inch x 1-inch squares and weighed. Sufficient film sample is used so that 2.5 g of film sample is used for each extraction. The film is then extracted for 2 hours in a hexane container containing approximately 1000 ml of hexane at 49.5 ± 0.5°C in a heated water bath. The hexane used is an isomerized hexane mixture (e.g., Hexanes (Optima), Fisher Chemical, a high-purity mobile phase for HPLC and / or an extraction solvent for GC applications (99.9% or higher by GC)). After 2 hours, the film is removed, rinsed in clean hexane, first dried with nitrogen, and then further dried for 2 hours in a fully vacuumed vacuum oven (80±5°C) (ISOTEMP Vacuum Oven, Model 281A, approximately 30 inch Hg). The film is then placed in a desiccator and cooled to room temperature for at least 1 hour. The film is then reweighed and the mass loss due to extraction in hexane is calculated: [(mass loss / initial weight of film) × 100] = weight percentage of hexane extractable material.

[0092] Melt strength (MS) The melt strength test is performed using a Rheotester 2000 capillary rheometer combined with a Gottfert Rheotens Model 71.97. A die with a diameter of 2 mm and a length of 30 mm is used for the test at an entry angle of 180°. All tests are performed isothermally at 190°C.

[0093] The pelletized sample is loaded into a capillary barrel and equilibrated at 190°C for 10 minutes. Then, a constant force is applied to the molten sample by a piston inside the barrel for 38.16 seconds. -1The apparent wall shear rate is achieved, and the molten material is extruded through the die at an exit velocity of approximately 9.7 mm / s. The extruded material is then guided through a pair of serrated rheotens wheels located 100 mm below the die exit and spaced 0.4 mm apart. Both wheel pairs move at 2.4 mm / s 2 The extruder is accelerated at a constant speed, and its response to the applied tensile force is measured. Then, a plot of force against rheotens wheel speed is created using the RtensEvaluations 2007 Excel macro. The force at which cracking occurs in the molten material is considered the melt strength, and the corresponding rheotens wheel speed at which cracking occurs is considered the tensile limit.

[0094] Dynamic mechanical spectroscopy (DMS) First, the test sample is placed in a mold with a diameter of 1.5 inches and a thickness of 3.10 mm, and compressed using a Carver Hydraulic Press at 190°C for 6.5 minutes under a pressure of 25,000 pounds. Before extrusion, the sample is allowed to equilibrate to room temperature.

[0095] Dynamic mechanical spectroscopy (DMS) frequency sweeps are performed using 25 mm parallel plates at 190°C with frequencies ranging from 0.1 to 100 rad / s. The test gap separating the plates is 1.8 mm, and a strain satisfying linear viscoelastic conditions, typically 10%, is used. Each test is performed under nitrogen atmosphere and isothermal conditions. To begin the DMS test, the rheometer oven is first equilibrated at 190°C for at least 30 minutes, after which the sample is loaded into the test configuration. The sample is then equilibrated in the closed oven for 1 minute. Next, the test gap is set to 1.8 mm, and the sample is left for 5 minutes to allow the resulting normal force to subside. The oven is then quickly opened, and the sample is trimmed to remove any bulging. The oven is then closed again, and the DMS measurement is started. During the test, the shear modulus (G'), viscosity coefficient (G"), and complex viscosity (v) are measured. The ratio of the complex viscosity at 0.1 rad / s to the complex viscosity at 100 rad / s (v0.1 / v100) can also be obtained.

[0096] Differential Scanning Calorimetry (DSC) In preparation for a differential scanning calorimetry (DSC) test, the pellet-formed sample is first loaded into a mold with a diameter of 1 inch and a thickness of 0.13 mm, and compressed into a film at 190°C for approximately 10 seconds under a pressure of 25,000 pounds. The resulting film is then cooled to room temperature. The film is then subjected to a punch press to produce discs that fit into an aluminum DSC test pan. The discs are then individually weighed (note: sample weight is approximately 4-8 mg), placed in an aluminum pan, sealed, and inserted into the DSC test chamber.

[0097] In accordance with ASTM standard D3418, the DSC test is performed using a heating-cooling-heating cycle. First, the sample is equilibrated at 180°C and maintained isothermally for 5 minutes to remove thermal and process history. Next, the sample is quenched to -40°C at a rate of 10°C / min and maintained isothermally again for 5 minutes during the cooling cycle. Finally, for the second heating cycle, the sample is heated to 150°C at a rate of 10°C / min. For data analysis, the melting peak temperature and enthalpy of melting are extracted from the second heating curve, and the enthalpy of crystallization is determined from the cooling curve. The enthalpy of melting and enthalpy of crystallization are obtained by integrating the DSC thermogram from -20°C to the end of melting and crystallization, respectively. The degree of crystallinity by weight % is calculated assuming the heat of fusion of 100% crystalline polyethylene is 292 J / g. The DSC (Data Stabilization Sclerosis) test was conducted using TA Instruments Q2000, and data analysis was performed via TA Instruments' Universal Analysis and TRIOS software packages.

[0098] Vicat softening temperature The Vicat softening temperature is determined according to ASTM D12525. A specimen is cut from a compression-molded sheet using an appropriate die to obtain a sample measuring 1.5 inches in length, 0.5 inches in width, and approximately 0.125 inches in thickness. The specimen is conditioned at approximately 23°C and 50% relative humidity for at least 40 hours prior to testing. The specimen is loaded into a CEAST HV6 and a force of 10 N is applied to the specimen by adding an appropriate weight. The specimen is then placed in a bath containing silicone oil. After 5 minutes, the displacement inducer is set to zero, and the temperature is increased at 120°C / hour while monitoring the displacement. The Vicat temperature is defined as the temperature at which a needle penetrates 1 mm into the specimen.

[0099] Heat distortion temperature The thermal distortion temperature is measured according to ASTM D648. A sample measuring 5 inches in length, 0.5 inches in depth, and 0.125 inches in width is cut from a compression-molded sheet. The sample is conditioned at 23°C and 50% relative humidity for at least 40 hours. The specimen is loaded edge-side down into a CEAST HV6A using a 4-inch span, and an appropriate weight is applied to the central rod to impart a fiber stress of 0.455 MPa. The specimen is then placed in a silicone oil bath, and after 5 minutes, the displacement transducer is set to zero. The temperature is then increased at a specific rate of 120°C / hour while monitoring the displacement of the central rod. The thermal distortion temperature is the temperature at which the rod displacement reaches 0.25 mm.

[0100] transparency Film permeability is measured according to ASTM D1746. The film is conditioned at 23°C and 50% relative humidity for at least 40 hours after film formation. The Zebedee clearance meter model CL-100 is warmed for 30 minutes to perform internal calibration and scaling procedures. A 4.5 × 4.5 inch film sample is then cut from the conditioned film sheet, placed on the vacuum port of the sample holder, and its clearness is measured. Five copies are measured per sample.

[0101] Triple-detector gel permeation chromatography The chromatography system consists of a PolymerChar GPC-IR high-temperature GPC chromatograph with an internal IR5 infrared detector (IR5), and a 4-capillary viscometer (DV) coupled to a Precision Detectors (now Agilent Technologies) 2-angle laser light scattering (LS) detector Model 2040. A 15-degree angle is used for all absolute light scattering measurements. The autosampler's oven compartment is set to 160°C, and the column and detector compartments are set to 150°C. The columns used are four Agilent Mixed A 30cm 20-micron linear mixed-bed columns. The chromatography solvent used is 1,2,4-trichlorobenzene containing 200 ppm butylated hydroxytoluene (BHT). The solvent source is spurged with nitrogen. The injection volume used is 200 microliters, and the flow rate is 1.0 ml / min.

[0102] The total plate count of the GPC column set is performed using decane introduced into the blank sample via a micropump controlled by the PolymerChar GPC-IR system. The plate count of the chromatography system should be greater than 18,000 for four Agilent Mixed A 30 cm 20 micron linear mixed bed columns.

[0103] The sample is prepared semi-automatically using PolymerChar Instrument Control software, with a target weight of 2 mg / ml. The solvent (containing 200 ppm BHT) is added to a pre-nitrogen-spared vial with a septum cap via a PolymerChar high-temperature autosampler. The sample is dissolved at 160°C for 2 hours under low-speed shaking.

[0104] To monitor deviations over time, a flow marker (decane) is introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. This flow marker (FM) is used to linearly correct the pump flow rate (nominal flow rate) for each sample by matching the RV (RV(FM sample)) of each decane peak within the sample with the RV (RV(FM calibrated)) of the decane peak within the narrow standard calibration. It is assumed that any temporal change in the decane marker peak corresponds to a linear shift in the flow rate (effective flow rate) over the entire run. After calibrating the system based on the flow marker peaks, the effective flow rate (with respect to the narrow standard calibration) is calculated as shown in Equation 1. The processing of the flow marker peaks is performed via PolymerChar GPCOne® software. An acceptable flow rate correction should result in the effective flow rate being within ±0.5% of the nominal flow rate.

[0105] Effective flow rate = Nominal flow rate × (RV (FM calibrated) / RV (FM sample)) (Equation 1)

[0106] To determine the offsets of the viscometer and light scattering detectors from the IR5 detector, the multiple detector offsets were determined using a systematic method consistent with those published by Balke, Mourey et al. (Mourey and Balke, Chromatography Polym. Chpt 12, (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym. Chpt 13, (1992)). The results of the triple detector logs (MW and IV) from linear homopolymer polyethylene standards (3.5>Mw / Mn>2.2) with molecular weights in the range of 115,000–125,000 g / mol were optimized using PolymerChar GPCOne® software to obtain the results of narrow standard column calibration from a narrow standard calibration curve.

[0107] Absolute molecular weight data is obtained using PolymerChar GPCOne® software in a format consistent with that published by Zimm (Zimm, BH, J. Chem. Phys., 16, 1099 (1948)) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987)). The overall injection concentration used in determining the molecular weight is obtained from the mass detector area and mass detector constant, derived from one of the suitable linear polyethylene homopolymers or polyethylene standards of known weight-average molecular weight. The molecular weight calculated (using GPCOne®) is obtained using the light scattering constant derived from one or more of the polyethylene standards described below, and the refractive index concentration coefficient dn / dc of -0.104. In general, the mass detector response (IR5) and light scattering constant (determined using GPCOne®) should be determined from linear standards having a molecular weight greater than approximately 50,000 g / mol. Calibration of the viscometer (determined using GPCOne®) can be achieved using the method described by the manufacturer, or alternatively, by using the published values ​​of a suitable linear reference material such as Standard Reference Material (SRM) 1475 (available from the National Institute of Standards and Technology (NIST)). Viscometer constants (obtained using GPCOne®) are calculated, relating a specific viscosity area (DV) and injection mass for the calibration standard to its intrinsic viscosity. The chromatographic concentration is assumed to be low enough to eliminate the need to address the second viral coefficient effect (concentration effect on molecular weight).

[0108] Absolute weight average molecular weight (MW) (Abs)The ) is obtained (using GPCOne®) by dividing the light scattering (LS) integral chromatogram area (corrected for the light scattering constant) by the mass constant and the mass recovered from the mass detector (IR5) area. The molecular weight and intrinsic viscosity response are linearly extrapolated (using GPCOne®) at the edge of the chromatography where the signal to noise is low. The other respective moments are Mn (Abs) and Mz (Abs) This is calculated according to equations 2 to 4 as follows.

[0109]

number

[0110] Cumulative detector fractions (CDF) of low-angle laser light scattering detectors. LS The calculation of '' is achieved using the following steps. 1) Based on the decan flow marker injection described above, the chromatogram is linearly flow-corrected. 2) Perform detector offsetting as described above. 3) As described above, the absolute molecular weight is calculated from light scattering. 4) According to Equation 5, for each data slice (j), the cumulative detector fraction (CDF) of the low-angle laser light scattering (LALLS) chromatogram is calculated based on the baseline subtracted peak height (H) for high to low molecular weight (low to high retention volume). LS Calculate ).

[0111]

number

[0112] Long chain branching frequency The long-chain branching frequency is calculated based on the difference between g', which is the ratio of the intrinsic viscosity of the polymer sample to the intrinsic viscosity of a linear polymer reference material of the same molecular weight. In the 3D GPC implementation, a reference polyethylene homopolymer with no detectable LCBs or SCBs, an Mw of approximately 120,000 g / mol, and a polydispersity of approximately 3.0 is injected at the start of each run queue to establish the Mark-Houwink linear reference material line. The logarithmic viscosity obtained and the logarithmic molecular weight data within the molecular weight range of 4.5–5.8 g / mol are fitted with a first-order linear fit to obtain the K and α values ​​of the linear reference material.

[0113] The target polyethylene sample is analyzed to obtain its intrinsic viscosity and molecular weight, g i The value of ' is calculated for each chromatography slice (i) according to Equation 6, g i '=(IV 試料、i / IV 直鎖状参照物質、i ) (Formula 6) Here, the calculation is performed using IV at the same absolute molecular weight and SCB content as the linear reference substance within the log molecular weight range of 4.5 to 5.8 g / mol. 試料、i Use IV. If there is a difference in SCB content, 直鎖状参照物質、i The line is vertically shifted by adjusting the K value from the Mark-Houwink plot, and IV 試料、i The SCB correction compared to the above is explained. The shift is performed until the linear reference material line creates a single contact point that makes tangent to the sample Mark-Houwink line at a log molecular weight of 4.5.

[0114] The Zimm-Stockmayer branch coefficient g is defined using the epsilon coefficient of 0.5, where g', g'=g ε Calculate from the number of branches along the polymer sample in each data slice (i) (B n ) can be determined by using Equation 7 (BHZimm and WHStockmayer, J.Chem.Phys.17,1301(1949)).

[0115]

number

[0116] Finally, the average LCBf amount per 1000 carbon atoms in the polymer across all slices (i) is determined using Equation 8.

[0117]

number

[0118] Absolute molecular weight short-chain branching distribution index (MWSCBDI) Calibration of IR5 detector rationing is performed on homopolymers prepared from a single reactor using a single-site metallocene catalyst in a solution process, ranging from 0 SCB / 1000 total C atoms to approximately 40 SCB / 1000 total C atoms (where total C = carbon atoms in the main chain + carbon atoms in the branching), with a narrow SCB distribution and known comonomer content. 13 The study was conducted using at least 10 ethylene-based polymer standards (octene as a comonomer) (polyethylene homopolymer and ethylene / octene copolymer) measured by ¹³C NMR Method, Qiu et al., Anal. Chem. 2009, 81, 8585-8589. Each standard had a weight-average molecular weight ranging from 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.

[0119] [Table 1]

[0120] The ratio of the baseline subtracted area response of an IR5 methyl channel sensor to the baseline subtracted area response of an IR5 measuring channel sensor (or IR5) メチルチャネル面積 / IR5 測定チャネル面積Calculate the standard filters and filter wheels supplied by PolymerChar (Part Number IR5_FWM01, which were provided as part of the GPC-IR instrument) for each of the "SCB" reference materials. Construct a linear fit for the SCB frequency versus IR5 area ratio in the form of Equation 9 below: SCB / 1000 total C = A0 + [A1 × (IR5 メチルチャネル面積 / IR5 測定チャネル面積 )] (Equation 9) (In the formula, A0 is the intercept of SCB / 1000 total C at zero IR5 area ratio, and A1 is the slope of SCB / 1000 total C to IR5 area ratio, representing the increase in SCB / 1000 total C as a function of IR5 area ratio). The IR5 area ratio is equal to the IR5 height ratio for narrow PDI and narrow SCBD standard materials.

[0121] A baseline-corrected chromatogram (methyl channel) is created by establishing a series of linear baseline subtractive chromatography heights for the chromatogram produced by the IR5 methyl channel sensor as a function of column elution volume. A baseline-corrected chromatogram (measurement channel) is created by establishing a series of linear baseline subtractive chromatography heights for the chromatogram produced by the IR5 measurement channel as a function of column elution volume.

[0122] SCB / 1000 represents the total carbon of the octenomemonomer, and the absolute molecular weight (Mw) from light scattering. i ) is obtained for each chromatography slice i and taken as data points per second as described above. Therefore, the total C (y axis) of SCB / 1000 is Abs Log(Mw i It is calculated as a function of (x axis). Using Excel linear regression, select SCB / 1000 total C and 15,000 Abs Mw i Abs Mw i Abs Log(Mw iCalculate the slope between the values ​​(end group correction on the chain ends is omitted in this calculation). Use Excel linear regression to calculate Abs Mw for 15,000 to Abs 150,000 g / mol (including 15,000 and 150,000). i The slope on a logarithmic scale was calculated. This slope is defined as the absolute molecular weight short-chain branching distribution index (MWSCBDI).

[0123] iCCD and Composition Distribution Respiratory Index (CDBI) iCCD is an improved method for comonomer content distribution (CCD) analysis, based on the method described in International Publication No. 2017040127(A1). The test method is performed using a crystallization elution fractionation (CEF) instrument (available from Polymer Char) equipped with an IR-5 detector and a 2-angle precision detector light scattering detector model 2040 (available from Agilent Technology). Ortho-dichlorobenzene (ODCB, 99% anhydrous or industrial grade) is used as the solvent. The ODCB solvent can be dried using silica gel 40 (with particle size of 0.2 mm to 0.5 mm, available from EMD Chemicals). The dried silica is packed into three empty HT-GPC columns (with dimensions of 300 mm × 7.5 mm (ID)) to further purify the ODCB solvent as an eluent. The CEF instrument is equipped with an autosampler with nitrogen (N2) purging capability. Spurged the ODCB with dry N2 for 1 hour before use. Prepare the sample using an autosampler at 4 mg / mL (unless otherwise specified) with shaking at 160°C for 1 hour. The sample injection volume was 300 microliters (μL). The iCCD temperature profile was as follows: crystallization from 105°C to 30°C at 3°C / min; thermal equilibrium at 30°C for 2 minutes (including setting the soluble fraction elution time to 2 minutes); 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 was collected at 1 data point / second.

[0124] The iCCD columns used are 15 cm (length) x 1 / 4 inch (internal diameter, ID) stainless steel tubing packed with gold-plated nickel particles (Bright 7GNM8-NiS; available from Nippon Chemical Industrial Co., Ltd.). Column packing and conditioning are performed using the slurry method according to the method described in International Publication No. 2017040127(A1). The final pressure for trichlorobenzene (TCB) slurry packing is 150 bar (10 MPa).

[0125] Column temperature calibration is performed using (i) 1.0 mg / mL of monomodulus linear homopolymer polyethylene as a reference material (polyethylene with zero comonomer content, a melt index (I2) of 1.0 g / 10 min, and a polydispersity (Mw / Mn) of approximately 2.6 as determined by the GPC test method described above) and (ii) a mixture of 0.5 mg / mL of eicosane in ODCB. iCCD temperature calibration consisted of four steps: (1) calculating the delay volume, defined as the temperature offset between the measured peak elution temperature of eicosane and 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, e.g., elution temperature, elution flow rate); (3) creating a unimodal linear calibration curve that converts the elution temperature over the range of 30.00°C to 140.00°C such that the unimodal 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, elution temperatures below 30.0°C are linearly extrapolated by using an elution heating rate of 3°C / min according to the method described in U.S. Patent No. 9,688,795. Using the GPCOne software (available from PolymerChar), create the SCBD distribution curve dWi / dT (where Wi is the mass at Ti and Ti is the calibrated elution temperature).

[0126] The elution fraction (weight %) is determined within a specific elution temperature range. This is defined as dividing the area of ​​the baseline subtracted iCCD profile within that temperature range by the total integrated area of ​​the baseline subtracted iCCD elution chromatogram and multiplying by 100%.

[0127] The comonomer content of iCCDs with respect to elution temperature is constructed in a solution process using 12 reference materials (ethylene homopolymers and ethylene-octene random copolymers prepared using single-site metallocene catalysts, with ethylene equivalent weight-average molecular weights ranging from 35,000 to 128,000). All of these reference materials are analyzed at 4 mg / mL using the same method previously specified. The correlation between comonomer mole fraction and elution temperature (T (Celsius)) follows the following formula. ln(1-comonor mole fraction) = -208.328 / (elution temperature (°C) + 273.12) + 0.55846 (Equation 10)

[0128] The Composition Distribution Index (CDBI) is defined as the weight percentage of polymer molecules having a comonomer content within + / - 50 percent of the median molar content of all comonomers (reported in International Publication No. 93 / 03093). Conveniently, the CDBI of polyolefins can be calculated from SCBD data obtained from known technologies in the art, such as temperature rising elution fractionation ("TREF"), as described in, for example, Wild, et al., Journal of Polymer Science, Poly. Phys. Ed., Vol. 20, 441 (1982); LDCady, "The Role of Comonomer Type and Distribution in LLDPE Product Performance," SPE Regional Technical Conference, Quaker Square Hilton, Akron, OH, 107-119 (Oct. 1-2, 1985); and U.S. Patent Nos. 4,798,081 and 5,008,204.

[0129] Therefore, in this specification, iCCD CDBI is calculated using the short-chain branching distribution measured by the iCCD method and the comonomer composition correlation with elution temperature as described above. [Examples]

[0130] The materials used are listed in Table 1 below. The properties of these materials are listed in Tables 2 to 4. All commercial DOW® samples are available from DOW® Chemical. Comparative Example A is a blend of 65 wt percent DOW® LDPE 91020 Health+ and 35 wt percent UNIVAL® DMDA 6400 NT 7. Comparative Examples B and C are low-density polyethylene resins produced by a high-pressure free-radical polymerization process. Comparative Examples D, E, and F are polyethylene resins produced using heterogeneous catalysts in a solution polymerization process. Comparative Example G is a blend of 56 wt percent DOW® LDPE 91020 Health+ and 44 wt percent DOW® DMDA-8007 NT 7.

[0131] [Table 2] * NM means not measured.

[0132] [Table 3]

[0133] [Table 4]

[0134] [Table 5]

[0135] Production of Experimental Resin 1 and Experimental Resin 2

[0136]

Table 6

[0137]

Chemical formula

[0138] The raw materials (ethylene, 1-octene) and the process solvent (a high purity isoparaffin solvent with a narrow boiling range under the trademark Isopar E, commercially available from ExxonMobil Corporation) are purified with molecular sieves before being introduced into the reaction environment. Hydrogen is supplied as a high purity grade into a pressurized cylinder and is not further purified. The reactor monomer feed (ethylene) stream is pressurized via a mechanical compressor to above the reaction pressure of 52psig. The solvent and comonomer (in 1-octene) feeds are pressurized via a mechanical positive displacement pump to above the reaction pressure of 525psig. MMAO-3A, commercially available from Nouryon, is used as an impurity scavenger. The individual catalyst components (pre-catalyst or co-catalyst) are manually diluted batchwise with a purification solvent (Isopar E) to the specified component concentration and pressured to above the reaction pressure of 525psig. The co-catalyst is [HNMe(C 18 H 37 )]2[B(C6F5)4], commercially available from Boulder Scientific, and is used at a ratio of 1.2 moles relative to the co-catalyst. All reaction feed streams are measured using mass flow meters and independently controlled by a valve control system automated by a computer.

[0139] Continuous solution polymerization is carried out in a CSTR and / or a plug flow reactor. The CSTR reactor independently controls all fresh solvent, monomer, comonomer, hydrogen, and catalyst component feeds. The plug flow reactor independently controls the catalyst component feed. The combined feed of solvent, monomer, comonomer, and hydrogen to the reactor is temperature-controlled to any temperature from 5°C to 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 by each injector that receives half of the fresh total feed mass flow rate. The cocatalyst is fed to the procatalyst based on a calculated specific molar ratio (1.2 molar equivalents). Immediately after each new injection location, the feed stream is mixed with the circulating polymerization reactor contents by a static mixing element. In the case of binary catalyst operation, the ratio of the catalysts is adjusted so that the desired polymer MI and density are obtained. The effluent from the polymerization reactor system (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) exits and passes through a control valve that serves to maintain the pressure of the reactor system at a specified target. When the stream exits the reactor, the stream is contacted with water to stop the reaction. Further, various additives such as antioxidants may be added at this point. Then, the stream passes through another set of static mixing elements to uniformly disperse the catalyst deactivator and additives.

[0140] After the addition of the additives, the effluent (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) passes through a heat exchanger that raises the stream temperature in preparation for the separation of the polymer from other more volatile reaction components. Then, the stream enters a two-stage separation and devolatilization system where the polymer is removed from the solvent, hydrogen, and unreacted monomer and comonomer. The separated and devolatilized polymer melt is pumped through a die specially designed for underwater pelletization, cut into uniform solid pellets, dried, and transferred to a box for storage.

[0141] Bottle production A 14-ounce Boston round-shaped bottle with a target bottle weight of 26 ± 0.5 grams is manufactured using a 50mm extruder and a MACO 6500. * The bottles are manufactured using a Bekum H-111 continuous extrusion blow molding machine equipped with a digital readout controller. The blow molding machine is operated using parison programming to ensure that a consistent and uniform sidewall thickness distribution is maintained in the manufactured bottles. The extruder barrel temperature is maintained at 350°F. The extrusion rate is approximately 120-140 g / min. For samples that do not have sufficient melt strength, a lower extruder barrier temperature is used to improve melt strength and reduce sagging. The weight of the parison is adjusted using the head weight. This can be used to compensate for additional weight in the bottle profiling. A higher head weight correlates with a wider die gap, and vice versa. Detailed processing conditions are shown in Table 5. The target bottle weight for each bottle manufactured was 26 grams. The characteristics of the manufactured bottles are shown in Table 6.

[0142] [Table 7]

[0143] [Table 8]

Claims

1. Densities of 0.920 g / cc to 0.950 g / cc, The melt index (I2) for 0.5g / 10 min to 10.0g / 10 min, A comonomer distribution index (CDBI) of 55% or more, CDF ＬＳ A blow-molded article comprising an ethylene / alpha-olefin interpolymer having LCBf, The CDF ＬＳ ×LCBf×100 is greater than 0.5, The CDF ＬＳ A blow-molded article in which the LCBf is calculated by measuring the area fraction of the molecular weight distribution obtained from the absolute molecular weight from low-angle light scattering of more than 500,000 g / mol using a GPC molecular weight distribution, and the LCBf is measured as described herein.

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

3. The blow-molded article according to claim 1 or 2, wherein the ethylene / alpha-olefin interpolymer has a melt index (I2) of 0.7 to 4.0 g / 10 min.

4. The blow-molded article according to any one of claims 1 to 3, wherein the ethylene / alpha-olefin interpolymer has a comonomer distribution width index (CDBI) of 55 to 99%.

5. The blow-molded article according to any one of claims 1 to 4, wherein the ethylene / alpha-olefin interpolymer has a V0.1 / V100 value of 5.5 or more, as determined by dynamic mechanical spectroscopy.

6. The blow-molded article according to any one of claims 1 to 5, wherein the ethylene / alpha-olefin interpolymer has a V0.1 / V100 value of 5.5 to 20, as determined by dynamic mechanical spectroscopy.

7. The ethylene / alpha-olefin interpolymer has melt strength (MS), and the MS and I2 are [Math 1] A blow-molded article according to any one of claims 1 to 6, wherein the condition is met, the I2 is expressed as g / 10 min, and the MS is expressed as cN.

8. The blow-molded article according to any one of claims 1 to 7, wherein the ethylene / alpha-olefin interpolymer has a Vicat softening temperature of 110°C or higher.

9. The blow-molded article according to any one of claims 1 to 8, wherein the ethylene / alpha-olefin interpolymer has a heat distortion temperature of 50°C or higher.

10. The blow-molded article according to any one of claims 1 to 9, wherein the ethylene / alpha-olefin interpolymer has a hexane extract value of less than 1% by weight based on the weight of the ethylene / alpha-olefin interpolymer.

11. The blow-molded article according to any one of claims 1 to 10, wherein the ethylene / alpha-olefin interpolymer has a transparency of 65% or more.

12. The blow-molded article according to any one of claims 1 to 11, wherein the ethylene / alpha-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 one of claims 1 to 12, wherein the ethylene / alpha-olefin interpolymer has a melt index ratio (I10 / I2) of 11 or more as measured according to ASTM 1238.

14. The ethylene / alpha-olefin interpolymer has a molecular weight of 4.0 to 7.0 Mw （ａｂｓ） / Mn （ａｂｓ） Having, the Mw （ａｂｓ） and the Mn （ａｂｓ） The blow-molded article according to any one of claims 1 to 13, wherein the measurement is performed by triple-detector gel permeation chromatography.

15. The blow-molded article according to any one of claims 1 to 14, wherein the ethylene / alpha-olefin interpolymer has a comonomer distribution width index of 55% or more.

16. The ethylene / alpha-olefin interpolymer has a CDF of 0.5 to 10 ＬＳ ×LCBf×100, and the CDF ＬＳ and the LCBf are measured as described herein, a blow molded article according to any one of claims 1 to 15.

17. The blow-molded article according to any one of claims 1 to 16, wherein the ethylene / alpha-olefin interpolymer has an MWSCBDI of -1.0 to 1.0.

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