Blow molded articles

Abstract

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

Description

84904-WO-PCT / DOW 84904 WO BLOW MOLDED ARTICLES 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 in their entirety herein. FIELD

[0002] This application relates to blow molded articles. More specifically, this application relates to blow molded articles comprising polyethylenes. Even more specifically, this application relates to blow molded articles comprising ethylene / alpha-olefin interpolymers. INTRODUCTION

[0003] Ampules and bottles used in medical applications need high heat resistance, environmental cracking resistance, and softness along with low haze. Low haze allows consumers to judge the quality of the contained product. Heat resistance ensures the bottles do not fail during heat sterilization and shorten the time for sterilization at a higher temperature. High environmental cracking resistance ensures the bottles do not fail during storage. Softness allows easy squeezing and product removal.

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

[0005] Higher densities can be achieved by blending high density polyethylene into LDPE. Conventionally, however, this sacrifices clarity. Alternatively higher density can be achieved by using linear polyethylenes, such as medium density polyethylene, produced using the solution polymerization, gas phase polymerization, or slurry polymerization process. However, the linear structure of these polyethylenes cause a lack of melt strength that eliminates the blow molding fabrication process.

[0006] A blow molded bottle with high environmental cracking resistance, softness and clarity is thus desirable. SUMMARY

[0007] A blow molded article comprising an ethylene / alpha-olefin interpolymer is disclosed. The ethylene / alpha-olefin interpolymer has a density of from 0.920g / cc to 0.950 g / cc, a melt index (I2)84904-WO-PCT / DOW 84904 WO of from 0.5 g / 10 minutes to 10.0 g / 10 minutes, a comonomer distribution breadth index (CDBI) greater than 55%. The ethylene alpha-olefin also has a CDFLS × LCBf × 100 of greater than 0.5 wherein the CDFLS and the LCBf are measured as described below. A blown molded article formed through blow molding an 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 10.0g / 10 minutes, a comonomer distribution breadth index (CDBI) greater than or equal to 55%, and a CDFLS × LCBf × 100 value greater than 0.5, wherein the CDFLS is calculated by measuring an area fraction of a molecular weight distribution obtained from absolute molecular weight distribution and the LCBf is measured as described below, into a bottle is also disclosed. DETAILED DESCRIPTION

[0008] The terms “comprising,” “including,” “having,” and their derivatives, are not intended to exclude the presence of any additional component, step or procedure, whether or not the same is specifically disclosed. In order to avoid any doubt, all compositions claimed through use of the term “comprising” may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary. In contrast, the term, “consisting essentially of” excludes from the scope of any succeeding recitation any other component, step or procedure, excepting those that are not essential to operability. The term “consisting of” excludes any component, step or procedure not specifically delineated or listed.

[0009] The term “polymer” refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type. The generic term polymer thus embraces the term “homopolymer,” usually employed to refer to polymers prepared from only one type of monomer as well as “copolymer” which refers to polymers prepared from two or more different monomers. The term “interpolymer,” as used herein, refers to a polymer prepared by the polymerization of at least two different types of monomers. The generic term interpolymer thus includes copolymers, and polymers prepared from more than two different types of monomers, such as terpolymers.

[0010] As used herein, a “polyolefin” refers to an olefin-based polymer. As used herein, an “olefin,” which may also be referred to as an “alkene,” refers to a linear, branched, or cyclic compound including carbon and hydrogen and having at least one double bond. As used herein, when a polymer or copolymer, e.g., the polyolefin elastomer, is referred to as comprising an olefin, the olefin present in the polymer or copolymer is the polymerized form of the olefin. For example, if the polyolefin elastomer is said to have an ethylene content of 75 wt% to 85 wt%, it is understood that the polymer unit in the polyolefin elastomer is derived from ethylene in the polymerization84904-WO-PCT / DOW 84904 WO reaction and the derived units are present at 75 wt% to 85 wt%, based on the total weight of the polyolefin elastomer.

[0011] As used herein, the term “polyethylene” refers to polymers comprising greater than 50% by weight of units which are derived from ethylene monomer, 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-site catalyzed 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 Article

[0013] The blow molded article can have a haze less than or equal to 55.0%. The blow molded article can have a haze of from 35 to 55%. All internal values and subranges are disclosed. For example, the blow molded article can have a haze of from 35 to 45 or 45 to 55%.

[0014] The blow molded article can have an oxygen transmission rate (OTR) of less than or equal to 1.00 cc / bottle / day. The blow molded article can have an oxygen transmission rate (OTR) of from 0.50 to 1.00 cc / bottle / day. All internal values and subranges are disclosed. For example, the blow molded article can have an oxygen transmission rate (OTR) of from 0.50 to 0.75 cc / bottle / day.

[0015] The blow molded article can have a top load of greater than or equal to 70 lb. The blow molded article can have a top load of from 70 to 90 lb. All internal values and subranges are disclosed. For example, the blow molded article can have a top load of from 70 to 80 lb. or from 80 to 90 lb.

[0016] The blow molded article can have an environmental stress cracking resistance (ESCR) of greater than or equal to 70 hours. The blow molded article can have an environmental stress cracking resistance (ESCR) of from 70 to 200 hours. All internal values and subranges are disclosed. For example, the blow molded article can have an environmental stress cracking resistance of from 70 to 100, 100 to 150, or 150 to 200 hours.

[0017] Ethylene / Alpha-Olefin Interpolymer

[0018] The blow molded article can comprise an ethylene / alpha-olefin interpolymer. The ethylene / alpha-olefin interpolymer can have a density of from 0.920 to 0.950 g / cc. All internal values and subranges are disclosed. For example, the ethylene / alpha-olefin interpolymer can have a density of from 0.925 to 0.945, 0.935 to 0.940, 0.935 to 0.945, or 0.930 to 0.940.84904-WO-PCT / DOW 84904 WO

[0019] The ethylene / alpha-olefin interpolymer can have a melt index (I2) of from 0.50 g / 10minutes. to 10.0 g / 10minutes. All internal values and subranges are disclosed. For example, the ethylene / alpha-olefin interpolymer can have a melt index (I2) of from 0.7 to 4.0, 1.0 to 3.0, or 3.0 to 10.0 g / 10minutes.

[0020] The ethylene / alpha-olefin interpolymer can have a melt index ratio (I10 / I2) of greater than or equal to 11. The ethylene / alpha-olefin interpolymer can have a melt index ratio (I10 / I2) of from 11 to 15. All individual values and subranges are disclosed. For example, the ethylene / alpha-olefin interpolymer can have a melt index ratio (I10 / I2) of from 11 to 13 or from 13 to 15.

[0021] The ethylene / alpha-olefin interpolymer can have a melt strength (MS) wherein the MS (in cN) and I2 (in g / 10minutes) interrelate according to the equation MS>8-4 / 3×I2. The ethylene / alpha-olefin can have a melt strength (MS) wherein the MS (in cN) and I2 (in ^ g / 10minutes) interrelate according to the equation ^^ > 10 −× ^2. The ethylene / alpha-olefin can have a melt strength (MS) wherein the MS (in cN) and I2 (in g / 10minutes) interrelate ^ according to the equation ^^ > 14.5 −× ^2.

[0022] The ethylene / alpha-olefin interpolymer can have a melt strength of at least 6.0 cN (centi Newton). The ethylene / alpha-olefin interpolymer can have a melt strength of from 6.0 to 12.0 cN. All internal values and subranges are included. For example, the ethylene / alpha-olefin interpolymer can have a melt strength of from 6.0 to 7.0, or from 11.0 to 12.0 cN.

[0023] The ethylene / alpha-olefin interpolymer can have a V0.1 / V100 value, as determined by Dynamic Mechanical Spectroscopy (DMS), of greater than or equal to 5.5. The ethylene / alpha- olefin interpolymer can have a V0.1 / V100 value, as determined by Dynamic Mechanical Spectroscopy, of from 5.5 to 20.0. All internal values and subranges are disclosed. For example, the ethylene / alpha-olefin interpolymer can have a V0.1 / V100 value of from 5.5 to 9.0, 7.0 to 9.0, 9.0 to 20.0, or 15.0 to 20.0.

[0024] The ethylene / alpha-olefin interpolymer can have a comonomer distribution (CDBI) greater than or equal to 55%. The ethylene / alpha-olefin interpolymer can have a CDBI of from 55 to 99%. All internal values and subranges are included. For example, the ethylene / alpha- olefin interpolymer can have a CDBI of from 55 to 72, or 72 to 99%.

[0025] The ethylene / alpha-olefin interpolymer can have a Vicat softening temperature of greater than or equal to 110°C. The ethylene / alpha-olefin interpolymer can have a Vicat softening temperature of from 110 to 120°C. All internal values and sub-ranges are included. For example,84904-WO-PCT / DOW 84904 WO the ethylene / alpha-olefin interpolymer can have a Vicat softening temperature of from 110 to 117°C, or from 117 to 120°C.

[0026] The ethylene / alpha-olefin interpolymer can have a heat deflection temperature of greater than or equal to 50°C. The ethylene / alpha-olefin interpolymer can have a heat deflection temperature of from 50 to 60°C. All internal values and sub-ranges are disclosed. For example, the ethylene / alpha-olefin interpolymer can have a heat deflection temperature of from 55 to 59°C.

[0027] The ethylene / alpha-olefin interpolymer can have a hexane extractable value of less than 1 wt.% based on the weight of the ethylene / alpha-olefin interpolymer. The ethylene / alpha-olefin interpolymer can have a hexane extractable value of from 0.1 to 1 wt.% based on the weight of the ethylene / alpha-olefin interpolymer. All internal values and sub-ranges are included. For example, the ethylene / alpha-olefin interpolymer can have a hexane extractable value of from 0.2 to 0.6, or 0.2 to 0.5 wt.% based on the weight of the ethylene / alpha-olefin interpolymer.

[0028] The ethylene / alpha-olefin interpolymer can have a clarity greater than or equal to 65%. The ethylene / alpha-olefin interpolymer can have a clarity of from 65 to 85%. All internal values and sub-ranges are included. For example, the ethylene / alpha-olefin interpolymer can have a clarity of from 65 to 75 or 75 to 85%.

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

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

[0031] The ethylene / alpha-olefin interpolymer can have a product of the CDFLS, the LCBf, and 100 (CDFLS×LCBf×100) of from 0.50 to 10 wherein the CDFLS and LCBf are measured as described below. All internal values and subranges are disclosed. For example, the ethylene / alpha-olefin interpolymer can have a product of the CDFLS, the LCBf, and 100 of from 0.75 to 3.0, or 3.0 to 10.0 wherein the CDFLS and LCBf are measured as described below.

[0032] The ethylene / alpha-olefin interpolymer can have a Mn(abs)measured using triple detector gel permeation chromatography as described below of greater than or equal to 15,000 g / mol. The ethylene / alpha-olefin interpolymer can have a Mn(abs) measured using triple detector gel84904-WO-PCT / DOW 84904 WO permeation chromatography as described below of from 15,000 to 20,000 g / mol. All internal values and subranges are disclosed. For example, the ethylene / alpha-olefin interpolymer can have a Mn(abs) measured using triple detector gel permeation chromatography as described below of 15,000 to 18,000 or 18,000 to 20,000 g / mol.

[0033] The ethylene / alpha-olefin interpolymer can have a Mw(abs)measured using triple detector gel permeation chromatography as described below of greater than or equal to 65,000 g / mol. The ethylene / alpha-olefin interpolymer can have a Mw(abs) measured using triple detector gel permeation chromatography as described below of from 65,000 to 125,000 g / mol. All internal values and subranges are disclosed. For example, the ethylene / alpha-olefin interpolymer can have a Mw(abs) measured using triple detector gel permeation chromatography as described below of from 65,000 to 75,000 or of from 75,000 to 125,000 g / mol.

[0034] The ethylene / alpha-olefin interpolymer can have a Mz(abs) measured using triple detector gel permeation chromatography as described below of greater than or equal to 500,000 g / mol. The ethylene / alpha-olefin interpolymer can have a Mz(abs)measured using triple detector gel permeation chromatography as described below of from 500,000 to 1,000,000 g / mol. All internal values and subranges are disclosed. For example, the ethylene / alpha-olefin interpolymer can have a Mz(abs) measured using triple detector gel permeation chromatography as described below of from 500,000 to 750,000 or of from 750,000 to 1,000,000 g / mol.

[0035] The ethylene / alpha-olefin interpolymer can have a light scattering cumulative detector fraction ratio (CDFLS) greater than or equal to 20.00%. The ethylene / alpha-olefin interpolymer can have a CDFLSof from 20.00 to 40.00%. All internal values and subranges are disclosed. For example, the ethylene / alpha-olefin interpolymer can have a CDFLS of from 20.00 to 30.00% or from 30.00 to 40.00%.

[0036] The ethylene / alpha-olefin interpolymer can have a long chain branching frequency (LCBf) of greater than or equal to 0.02. The ethylene / alpha-olefin interpolymer can have a long chain branching frequency (LCBf) of from 0.02 to 0.3. All internal values and subranges are disclosed. For example, the ethylene / alpha-olefin interpolymer can have a long chain branching frequency (LCBf) of from 0.02 to 0.1 or from 0.1 to 0.3.

[0037] The ethylene / alpha-olefin interpolymer can have a MWSCBDI greater than or equal to - 1. The ethylene / alpha-olefin interpolymer can have a MWSCBDI of from -1 to 1. All internal values and subranges are disclosed. For example, the ethylene / alpha-olefin interpolymer can have a MWSCBDI of from -1 to 0 or from 0 to 1.

[0038] Polymerization of the ethylene / alpha-olefin interpolymer84904-WO-PCT / DOW 84904 WO

[0039] Any conventional polymerization process may be employed to produce the ethylene / alpha- olefin interpolymer described herein. Such conventional polymerization processes include, but are not limited to, slurry polymerization processes, solution polymerization process, using one or more conventional reactors, e.g., loop reactors, plug flow reactors isothermal reactors, stirred tank reactors, batch reactors in parallel, series, and / or any combinations thereof. The ethylene / alpha- olefin interpolymer may, for example, be produced via solution phase polymerization process using one or more, but not limited to, loop reactors, plug flow reactors, isothermal reactors, and combinations thereof.

[0040] In general, the solution phase polymerization process may occur 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 reactors of more than one type at a temperature in the range of from 115 to 250ºC (e.g., from 115 to 210ºC), and at pressures in the range of from 300 to 1,000 psi (e.g., from 400 to 800 psi). In a dual reactor, the temperature in the first reactor is in the range of from 115 to 190ºC (e.g., from 160 to 180ºC), and the second reactor temperature is in the range of 150 to 250ºC (e.g., from 180 to 220ºC). In a single reactor, the temperature in the reactor is in the range of from 115 to 250ºC (e.g., from 115 to 225ºC).

[0041] The residence time in the solution phase polymerization process may be in the range of from 2 to 30 minutes (e.g., from 5 to 25 minutes). Ethylene, solvent, hydrogen, one or more catalyst systems, optionally one or more cocatalysts, and one or more comonomers are fed continuously to one or more reactors. Exemplary solvents include, but are not limited to, isoparaffins. For example, such solvents are commercially available under the name ISOPARTME from ExxonMobil Chemical Co., Houston, Texas. The resultant mixture of the polyethylene composition and solvent is then removed from the reactor and the polyethylene composition is isolated. Solvent is typically recovered via a solvent recovery unit, e.g., heat exchangers and vapor liquid separator drum, and is then recycled back into the polymerization system.

[0042] The ethylene / alpha-olefin interpolymer may be produced via solution polymerization in a dual reactor system, for example a dual loop reactor system, wherein ethylene is polymerized in the presence of one or more catalyst systems. One or more cocatalysts may be present. The ethylene-alpha-olefin copolymer may be produced via solution polymerization in a single reactor system, for example a single loop reactor system, wherein ethylene is polymerized in the presence of two catalyst systems.

[0043] The term “independently selected” is used herein to indicate that the R groups, such as, R1, R2, R3, R4, and R5can be identical or different (e.g., R1, R2, R3, R4, and R5may all be84904-WO-PCT / DOW 84904 WO substituted alkyls or R1and R2may be a substituted alkyl and R3may be an aryl, etc.). Use of the singular includes use of the plural and vice versa (e.g., a hexane solvent, includes hexanes). A named R group will generally have the structure that is recognized in the art as corresponding to R groups having that name. These definitions are intended to supplement and illustrate, not preclude, the definitions known to those of skill in the art.

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

[0045] When used to describe certain carbon atom-containing chemical groups, a parenthetical expression having the form “(Cx-Cy)” means that the unsubstituted form of the chemical group has from x carbon atoms to y carbon atoms, inclusive of x and y. For example, a (C1-C40)alkyl is an alkyl group having from 1 to 40 carbon atoms in its unsubstituted form. In some general structures, certain chemical groups may be substituted by one or more substituents such as RS. An RSsubstituted version of a chemical group defined using the “(Cx-Cy)” parenthetical may contain more than y carbon atoms depending on the identity of any groups RS. For example, a “(C1-C40) alkyl substituted with exactly one group RS, where RSis phenyl (−C6H5)” may contain from 7 to 46 carbon atoms. Thus, in general when a chemical group defined using the “(Cx-Cy)” parenthetical is substituted by one or more carbon atom-containing substituents RS, the minimum and maximum total number of carbon atoms of the chemical group is determined by adding to both x and y the combined sum of the number of carbon atoms from all the carbon atom-containing substituents RS.

[0046] The term “substitution” means that at least one hydrogen atom (-H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or function group is replaced by a substituent (e.g. RS). The term “persubstitution” means that every hydrogen atom (H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., RS). The term “polysubstitution” means that at least two, but fewer than all, hydrogen atoms bonded to carbon atoms or heteroatoms of a corresponding unsubstituted compound or functional group are replaced by a substituent.

[0047] The term “-H” means a hydrogen or hydrogen radical that is covalently bonded to another atom. “Hydrogen” and “-H” are interchangeable, and unless clearly specified mean the same thing.

[0048] The term “(C1-C50)hydrocarbyl” means a hydrocarbon radical of from 1 to 50 carbon atoms and the term “(C1-C50)hydrocarbylene” means a hydrocarbon diradical of from 1 to 5084904-WO-PCT / DOW 84904 WO carbon atoms, in which each hydrocarbon radical and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, straight chain or branched chain, cyclic (including mono- and poly-cyclic, fused and non-fused polycyclic, including bicyclic; 3 carbon atoms or more) or acyclic and is unsubstituted or substituted by one or more RS.

[0049] In this disclosure, a (C1-C50)hydrocarbyl can be an unsubstituted or substituted (C1- C50)alkyl, (C3-C50)cycloalkyl, (C3-C20)cycloalkyl-(C1-C20)alkylene, (C6-C40)aryl, or (C6-C20)aryl- (C1-C20)alkylene.

[0050] The terms “(C1-C50)alkyl” and “(C1-C18)alkyl” mean a saturated straight or branched hydrocarbon radical of from 1 to 50 carbon atoms or from 1 to 18 carbon atoms, respectively, that is unsubstituted or substituted by one or more RS. Examples of unsubstituted (C1-C50)alkyl are unsubstituted (C1-C20)alkyl; unsubstituted (C1-C10)alkyl; unsubstituted (C1-C5)alkyl; methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2-butyl; 2-methylpropyl; 1,1-dimethylethyl; 1-pentyl; 1-hexyl; 1-heptyl; 1-nonyl; and 1-decyl. Examples of substituted (C1-C50)alkyl are substituted (C1- C20)alkyl, substituted (C1-C10)alkyl, trifluoromethyl, and [C45]alkyl. The term “[C45]alkyl” (with square brackets) means there is a maximum of 45 carbon atoms in the radical, including substituents, and is, for example, a (C27-C40)alkyl substituted by one RS, which is a (C1-C5)alkyl, respectively. Each (C1-C5)alkyl may be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl.

[0051] The term “(C6-C50)aryl” means an unsubstituted or substituted (by one or more RS) mono- , bi- or tricyclic aromatic hydrocarbon radical of from 6 to 50 carbon atoms, of which at least from 6 to 14 of the carbon atoms are aromatic ring carbon atoms. A monocyclic aromatic hydrocarbon radical includes one aromatic ring. A bicyclic aromatic hydrocarbon radical has two rings. While a tricyclic aromatic hydrocarbon radical has three rings. When the bicyclic or tricyclyc aromatic hydrocarbon radical is present, at least one of the rings of the radical is aromatic. The other ring or rings of the aromatic radical may be independently fused or non-fused and aromatic or non- aromatic. Examples of unsubstituted (C6-C50)aryl are unsubstituted (C6-C20)aryl unsubstituted (C6-C18)aryl; 2-(C1-C5)alkyl-phenyl; 2,4-bis(C1-C5)alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; indacenyl; hexahydroindacenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene. Examples of substituted (C6-C50)aryl are substituted (C1- C20)aryl; substituted (C6-C18)aryl; 2,4-bis[(C20)alkyl]-phenyl; polyfluorophenyl; pentafluorophenyl; and fluoren-9-one-l-yl.

[0052] The term “(C3-C50)cycloalkyl” means a saturated cyclic hydrocarbon radical of from 3 to 50 carbon atoms that is unsubstituted or substituted by one or more RS. Other cycloalkyl groups84904-WO-PCT / DOW 84904 WO (e.g., (Cx-Cy)cycloalkyl) are defined in an analogous manner as having from x to y carbon atoms and being either unsubstituted or substituted with one or more RS. Examples of unsubstituted (C3- C50)cycloalkyl are unsubstituted (C3-C20)cycloalkyl, unsubstituted (C3-C10)cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Examples of substituted (C3-C50)cycloalkyl are substituted (C3-C20)cycloalkyl, substituted (C3-C10)cycloalkyl, cyclopentanon-2-yl, and 1-fluorocyclohexyl.

[0053] Examples of (C1-C50)hydrocarbylene include unsubstituted or substituted (C6-C50)arylene, (C3-C50)cycloalkylene, and (C1-C50)alkylene (e.g., (C1-C20)alkylene). The diradicals may be on the same carbon atom (e.g., –CH2–) or on adjacent carbon atoms (i.e., 1,2-diradicals), or are spaced apart by one, two, or more than two intervening carbon atoms (e.g., 1,3-diradicals, 1,4-diradicals, etc.). Some diradicals include 1,2-, 1,3-, 1,4-, or an α,ω-diradical, and others a 1,2-diradical. The α,ω-diradical is a diradical that has maximum carbon backbone spacing between the radical carbons. Some examples of (C2-C20)alkylene α,ω-diradicals include ethan-1,2-diyl (i.e. –CH2CH2^), propan-1,3-diyl (i.e., –CH2CH2CH2–), 2-methylpropan-1,3-diyl (i.e., –CH2CH(CH3)CH2–). Some examples of (C6-C50)arylene α,ω-diradicals include phenyl-1,4-diyl, napthalen-2,6-diyl, or napthalen-3,7-diyl.

[0054] The term “(C1-C50)alkylene” means a saturated straight chain or branched chain diradical (i.e., the radicals are not on ring atoms) of from 1 to 50 carbon atoms that is unsubstituted or substituted by one or more RS. Examples of unsubstituted (C1-C50)alkylene are unsubstituted (C1- C20)alkylene, including unsubstituted ^CH2CH2 ^, ^(CH2)3 ^, ^(CH2)4 ^, ^(CH2)5 ^, ^(CH2)6 ^, ^(CH2)7 ^, ^(CH2)8 ^, ^CH2C*HCH3, and ^(CH2)4C*(H)(CH3), in which “C*” denotes a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl radical. Examples of substituted (C1-C50)alkylene are substituted (C1-C20)alkylene, ^CF2 ^, ^C(O) ^, and ^(CH2)14C(CH3)2(CH2)5 ^ (i.e., a 6,6-dimethyl substituted normal-1,20-eicosylene). Since as mentioned previously two RSmay be taken together to form a (C1-C18)alkylene, examples of substituted (C1-C50)alkylene also include l,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-C50)cycloalkylene” means a cyclic diradical (i.e., the radicals are on ring atoms) of from 3 to 50 carbon atoms that is unsubstituted or substituted by one or more RS.84904-WO-PCT / DOW 84904 WO

[0056] The term “heteroatom,” refers to an atom other than hydrogen or carbon. Examples of heteroatoms include O, S, S(O), S(O)2, Si(RC)2, P(RP), N(RN), -N=C(RC)2, -Ge(RC)2-, or -Si(RC)-, where each RC, each RN, and each RPis unsubstituted (C1-C18)hydrocarbyl or -H.

[0057] The term “heterohydrocarbon” refers to a molecule or molecular framework in which one or more carbon atoms are replaced with a heteroatom.

[0058] The term “(C1-C50)heterohydrocarbyl” means a heterohydrocarbon radical of from 1 to 50 carbon atoms and the term “(C1-C50)heterohydrocarbylene” means a heterohydrocarbon diradical of from 1 to 50 carbon atoms, and each heterohydrocarbon has one or more heteroatoms. The heterohydrocarbon of the (C1−C50)heterohydrocarbyl or the (C1−C50)heterohydrocarbylene has one or more heteroatoms. The radical of the heterohydrocarbyl may be on a carbon atom or a heteroatom. The two radicals of the heterohydrocarbylene may be on a single carbon atom or on a single heteroatom. Additionally, one of the two radicals of the diradical may be on a carbon atom and the other radical may be on a different carbon atom; one of the two radicals may be on a carbon atom and the other on a heteroatom; or one of the two radicals may be on a heteroatom and the other radical on a different heteroatom. Each (C1-C50)heterohydrocarbyl and (C1- C50)heterohydrocarbylene may be unsubstituted or substituted (by one or more RS), aromatic or non-aromatic, saturated or unsaturated, straight chain or branched chain, cyclic (including mono- and poly-cyclic, fused and non-fused polycyclic), or acyclic.

[0059] The (C1-C50)heterohydrocarbyl may be unsubstituted or substituted (C1-C50)heteroalkyl, (C1-C50)hydrocarbyl-O-, (C1-C50)hydrocarbyl-S-, (C1-C50)hydrocarbyl-S(O) ^, (C1- C50)hydrocarbyl-S(O)2 ^, (C1-C50)hydrocarbyl-Si(RC)2 ^, (Cl-C50)hydrocarbyl-N(RN) ^, (Cl- C50)hydrocarbyl-P(RP) ^, (C2-C50)heterocycloalkyl, (C2-C19)heterocycloalkyl-(C1-C20)alkylene, (C3-C20)cycloalkyl-(C1-C19)heteroalkylene, (C2-C19)heterocycloalkyl-(C1-C20)heteroalkylene, (C1-C50)heteroaryl, (C1-C19)heteroaryl-(C1-C20)alkylene, (C6-C20)aryl-(C1-C19)heteroalkylene, or (C1-C19)heteroaryl-(C1-C20)heteroalkylene.

[0060] The term “(C4-C50)heteroaryl” means an unsubstituted or substituted (by one or more RS) mono-, bi- or tricyclic heteroaromatic hydrocarbon radical of from 4 to 50 total carbon atoms and from 1 to 10 heteroatoms. A monocyclic heteroaromatic hydrocarbon radical includes one heteroaromatic ring; a bicyclic heteroaromatic hydrocarbon radical has two rings; and a tricyclic heteroaromatic hydrocarbon radical has three rings. When the bicyclic or tricyclic heteroaromatic hydrocarbon radical is present, at least one of the rings in the radical is heteroaromatic. The other ring or rings of the heteroaromatic radical may be independently fused or non-fused and aromatic84904-WO-PCT / DOW 84904 WO or non-aromatic. Other heteroaryl groups (e.g., (Cx-Cy)heteroaryl generally, such as (C4- C12)heteroaryl) are defined in an analogous manner as having from x to y carbon atoms (such as 4 to 12 carbon atoms) and being unsubstituted or substituted by one or more than one RS. The monocyclic heteroaromatic hydrocarbon radical is a 5-membered ring or a 6 membered ring. The 5-membered ring has 5 minus h carbon atoms, wherein h is the number of heteroatoms and may be 1, 2, 3, or 4; and each heteroatom may be O, S, N, or P. Examples of 5-membered ring heteroaromatic hydrocarbon radicals include pyrrol-1-yl; pyrrol-2-yl; furan-3-yl; thiophen-2-yl; pyrazol-1-yl; isoxazol-2-yl; isothiazol-5-yl; imidazol-2-yl; oxazol-4-yl; thiazol-2-yl; 1,2,4-triazol- 1-yl; 1,3,4-oxadiazol-2-yl; 1,3,4-thiadiazol-2-yl; tetrazol-1-yl; tetrazol-2-yl; and tetrazol-5-yl. The 6-membered ring has 6 minus h carbon atoms, wherein h is the number of heteroatoms and may be 1 or 2 and the heteroatoms may be N or P. Examples of 6-membered ring heteroaromatic hydrocarbon radicals include pyridine-2-yl; pyrimidin-2-yl; and pyrazin-2-yl. The bicyclic heteroaromatic hydrocarbon radical can be a fused 5,6- or 6,6-ring system. Examples of the fused 5,6-ring system bicyclic heteroaromatic hydrocarbon radical are indol-1-yl; and benzimidazole- 1-yl. Examples of the fused 6,6-ring system bicyclic heteroaromatic hydrocarbon radical are quinolin-2-yl; and isoquinolin-1-yl. The tricyclic heteroaromatic hydrocarbon radical can be a fused 5,6,5-; 5,6,6-; 6,5,6-; or 6,6,6-ring system. An example of the fused 5,6,5-ring system is 1,7- dihydropyrrolo[3,2-f]indol-1-yl. An example of the fused 5,6,6-ring system is 1H-benzo[f] indol- 1-yl. An example of the fused 6,6,6-ring system is acrydin-9-yl.

[0061] The term “(C1−C50)heteroalkyl” means a saturated straight or branched chain radicals containing one to fifty carbon atoms, or fewer carbon atoms and one or more of the heteroatoms. The term “(C1−C50)heteroalkylene” means a saturated straight or branched chain diradicals containing from 1 to 50 carbon atoms and one or more than one heteroatoms. The heteroatoms of the heteroalkyls or the heteroalkylenes may include Si(RC)3, Ge(RC)3, Si(RC)2, Ge(RC)2, P(RP)2, P(RP), N(RN)2, N(RN), N, O, ORC, S, SRC, S(O), and S(O)2, wherein each of the heteroalkyl and heteroalkylene groups are unsubstituted or are substituted by one or more RS.

[0062] Examples of unsubstituted (C2-C40)heterocycloalkyl include unsubstituted (C2- C20)heterocycloalkyl, unsubstituted (C2-C10)heterocycloalkyl, aziridin-l-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-l-yl, tetrahydrothiophen-S,S-dioxide-2-yl, morpholin-4-yl, 1,4- dioxan-2-yl, hexahydroazepin-4-yl, 3-oxa-cyclooctyl, 5-thio-cyclononyl, and 2-aza-cyclodecyl.

[0063] The term “halogen atom” or “halogen” means the radical of a fluorine atom (F), chlorine atom (Cl), bromine atom (Br), or iodine atom (I). The term “halide” means the anionic form of the halogen atom: fluoride (F−), chloride (Cl−), bromide (Br−), or iodide (I−).84904-WO-PCT / DOW 84904 WO

[0064] The term “saturated” means lacking carbon–carbon double bonds, carbon–carbon triple bonds, and (in heteroatom-containing groups) carbon–nitrogen, carbon–phosphorous, and carbon–silicon double bonds. Where a saturated chemical group is substituted by one or more substituents RS, one or more double and / or triple bonds optionally may or may not be present in substituents RS. 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–phosphorous, or carbon–silicon double bonds, not including double bonds that may be present in substituents RS, if any, or in (hetero) aromatic rings, if any.

[0065] The disclosed ethylene / alpha-olefin interpolymer compositions can be produced by multiple different catalyst systems. The examples described below are included to fully convey the scope of the disclosure to those skilled in the art. The ethylene / alpha-olefin interpolymer composition can be polymerized using a catalyst system comprising a metal--ligand complex of Structure I to form a first ethylene-based polymer; and polymerizing ethylene and the comonomers 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; and wherein Structure I and Structure V are as follows:wherein:

[0066] In formula (I), M1 is titanium, zirconium, hafnium, or scandium. In formula (I) and formula (V), each X is a monodentate ligand independently chosen from (C1−C50)hydrocarbyl, (C1−C50)heterohydrocarbyl, -CH2Si(RC)3-Q(ORC)Q, −Si(RC)3Q(ORC)Q, -OSi(RC)3Q(ORC)Q, −CH2Ge(RC)3-Q(ORC)Q, −Ge(RC)3Q(ORC)Q, −P(RC)2W(ORC)W, −P(O)(RC)2-W(ORC)W, −N(RC)2,84904-WO-PCT / DOW 84904 WO −NH(RC), −N(Si(RC)3)2, −NRCSi(RC)3, −NHSi(RC)3, −ORC, −SRC, −NO2, −CN, −CF3, −OCF3, −S(O)RC, −S(O)2RC, −OS(O)2RC, −N=C(RC)2, −N=CH(RC), −N=CH2, −N=P(RC)3, −OC(O)RC, −C(O)ORC, −N(RC)C(O)RC, −N(RC)C(O)H, −NHC(O)RC, −C(O)N(RC)2, −C(O)NHRC, −C(O)NH2, a halogen, B(RY)4, Al(RY)4, or Ga(RY)4, or a hydrogen, wherein each RCis independently a (C1−C30)hydrocarbyl, or (C1−C30)heterohydrocarbyl, and each Q is 0, 1, 2 or 3, and each W is 0, 1, or 2; each RYis –H, (C1−C30)hydrocarbyl, or halogen atom, wherein two X ligands can be connected to form a metallacycle ring.

[0067] In formulas (I) and (V), each Y is independently Lewis Base; optionally, X and Y can be linked to form a ring. Subscript m is 1 or 2; and subscript n is 0, 1 and 2.

[0068] In formula (I), R1and R16are independently selected from the group consisting of –H, (C1–C40)hydrocarbyl, (C1–C40)heterohydrocarbyl, −Si(RC)3, −Ge(RC)3, −P(RP)2, −N(RN)2, −ORC, −SRC, −NO2, −CN, −CF3, RCS(O)−, RCS(O)2−, −N=C(RC)2, RCC(O)O−, RCOC(O)−, RCC(O)N(R)−, (RC)2NC(O)−, halogen, radicals having formula (II), radicals having formula (III), and radicals having formula (IV):RCC(O)O−, RCOC(O)−, RCC(O)N(R)−, (RC)2NC(O)−, and halogen.

[0071] In formula (I), L is (C1–C40)hydrocarbylene or (C2–C40)heterohydrocarbylene.

[0072] In formula (I), each RC, RP, and RNin formula (I) is independently a (C1-C30)hydrocarbyl, (C1–C30)heterohydrocarbyl, or –H.

[0073] In formula (V), M2 is titanium, zirconium, or hafnium; R39, R40, R41, R42, and R43are independently (C1–C50)hydrocarbyl, (C1–C50)heterohydrocarbyl wherein any of the R40, R41, R42,84904-WO-PCT / DOW 84904 WO and R43optionally are connected to form a ring structure; R44, R45, and R46are independently (C1– C20)hydrocarbyl, (C1–C20)heterohydrocarbyl, (C6–C30)aryl, (C5–C30)heteroaryl wherein two of R44, R45, and R46are optionally connected to form a ring.

[0074] Many activating co-catalysts and activating techniques have been previously taught, with respect to 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 hydrocarbyloxides 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 a cationic oxidizing agent and a non- coordinating, compatible anion, as activating co-catalysts for addition polymerization catalysts, are disclosed in US 5,321,106. Examples of suitable carbenium salts as activating co-catalysts for addition polymerization catalysts are disclosed in US 5,350,723. Examples of suitable silylium salts, as activating co-catalysts for addition polymerization catalysts, are disclosed in US 5,625,087. Examples of suitable complexes of alcohols, mercaptans, 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 US 6,515,155 B1, beginning at column 50, at line 39, and going through column 56, at line 55, only the portion of which is incorporated by reference herein.

[0075] The above-described catalyst systems can be activated to form an active catalyst composition by combination with one or more cocatalysts, such as a cation forming cocatalyst, a strong Lewis acid, or a combination thereof. Suitable cocatalysts for use include polymeric or oligomeric aluminoxanes, especially methyl aluminoxane, as well as inert, compatible, noncoordinating, ion forming compounds. Exemplary suitable cocatalysts include, but are not limited to, modified methyl aluminoxane (MMAO), bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-) amine, triethyl aluminum (TEA), and any combinations thereof.

[0076] One or more of the foregoing activating co-catalysts are used in combination with each other. A combination of a mixture of a tri((C1-C4)hydrocarbyl)aluminum, tri((C1- C4)hydrocarbyl)borane, or an ammonium borate with an oligomeric or polymeric alumoxane compound, can be used.

[0077] Article Fabrication84904-WO-PCT / DOW 84904 WO

[0078] A blow molded article can be formed through extrusion blow molding, injection blow molding, or injection stretch blow molding. In all types a substrate preform is softened. Once this is completed the workpiece is clamped into a mold and air forced into the mold and the workpiece is inflated until it conforms to the mold. In extrusion blow molding the preform is formed by extruding melted plastic into a hollow tube that is then placed in the metal mold. In injection molding substrate is injected onto a core pin after which it is inflated and cooled. In injection stretch molding substrate is injected onto a core pin and then stretched usually above the glass transition temperature and then blown using blow molds. All of these processes are well understood in the art.

[0079] A blow molded article can also be formed through blow-fill-seal process, which is an automated manufacturing process by which plastic containers, such as bottles or ampoules are, in a continuous operation, blow-formed, filled, and sealed. It takes place in a sterile, enclosed area inside a machine, without human intervention, and thus can be used to aseptically manufacture sterile pharmaceutical or non-pharmaceutical liquid / semiliquid unit-dosage forms. The blow-fill- seal process functions similarly to conventional extrusion blow molding, and takes place within a blow-fill-seal machine. First, a melted plastic polymer is extruded in tubular form, and is taken over by an open two-part mold to form the container. Then, the mold closes which welds the bottom of the container. Simultaneously, the parison above the mold is cut, or the filling needles are placed in the parison head without the parison being cut. Next, a filling mandrel with blowing air function is placed in the neck area that seals the container. Sterile compressed air is then 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 the container has been formed, the desired liquid is filled into the container through the filling mandrel unit. Then the filling mandrel unit is lifted off, and the head mold hermetically seals the container. Simultaneously, the head contour is formed by vacuum. In the last step, the mold opens and the finished container leaves the mold.

[0080] An 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 / 10minutes to 10.0 g / 10minutes, a comonomer distribution breadth index (CDBI) greater than or equal to 55%, and a CDFLS × LCBf × 100 value greater than 0.5, wherein the CFLLS is calculated by measuring an area fraction of a molecular weight distribution obtained from absolute molecular weight distribution and the LCBf is measured as described below, is formed into a blow molded article using extrusion blow molding, injection blow molding, injection stretch blow molding, blow-fill-seal, or any other method known in the art.84904-WO-PCT / DOW 84904 WO

[0081] The blow molded article can have a haze less than or equal to 55.0%. The blow molded article formed by blow molding the ethylene / alpha-olefin interpolymer described above into a thermoplastic molten tube can have a haze of from 35 to 55%. All internal values and subranges are disclosed. For example, the blow molded article formed by blow molding the ethylene / alpha- olefin interpolymer described above into a thermoplastic molten tube can have a haze of from 35 to 45 or 45 to 55%.

[0082] The blow molded article can have an oxygen transmission rate (OTR) of less than or equal to 1.00cc / bottle / day. The blow molded article formed by blow molding the ethylene / alpha-olefin interpolymer described above into a thermoplastic molten tube can have an oxygen transmission rate (OTR) of from 0.50 to 1.00 cc / bottle / day. All internal values and subranges are disclosed. For example, the blow molded article formed by blow molding the ethylene / alpha-olefin interpolymer described above into a thermoplastic molten tube can have an oxygen transmission rate (OTR) of from 0.50 to 0.75 cc / bottle / day.

[0083] The blow molded article can have a top load of greater than or equal to 70 lb. The blow molded article formed by blow molding the ethylene / alpha-olefin interpolymer described above into a thermoplastic molten tube can have a top load of from 70 to 90 lb. All internal values and subranges are disclosed. For example, the blow molded article can have a top load of from 70 to 80 lb., or from 80 to 90 lb.

[0084] The blow molded article can have an environmental stress cracking resistance (ESCR) of greater than or equal to 70 hours. The blow molded article formed by blow molding the ethylene / alpha-olefin interpolymer described above into a thermoplastic molten tube can have an environmental stress cracking resistance (ESCR) of from 70 to 200 hours. All internal values and subranges are disclosed. For example, the blow molded article formed by blow molding the ethylene / alpha-olefin interpolymer described above into a thermoplastic molten tube can have an environmental stress cracking resistance of from 70 to 100, 100 to 150, or 150 to 200 hours. TESTING METHODS

[0085] Top Load

[0086] The bottle top load is measured using a Top Load Tester-Model 17-04 (commercially available from Testing Machines, Inc. “TMI”), to determine the mechanical properties of blown thermoplastic containers when loaded under columnar crush conditions at a constant rate of compressive deflection. Bottles are conditioned at room temperature for 48 hours and placed empty on the base of the instrument in the upright position at room temperature. The experiment84904-WO-PCT / DOW 84904 WO is conducted at a cross head speed of 2 inch / min and the deflection and load measured until the yield point is reached. Five bottles are tested per sample and average values are reported.

[0087] Oxygen Transmission Rate (OTR)

[0088] The oxygen transmission rate (OTR) of the bottles is tested on a Mocon OX-TRAN® 2 / 21 OTR instrument according to ASTM D3985 at environmental atmosphere conditions (23° C, 50% relative humidity and 21% Oxygen concentration). The average value from two bottles is reported.

[0089] Bottle Haze

[0090] Haze is measured according to ASTM D1003. A piece of sample is cut from the wall of the bottle and is conditioned for at least 40 hours at 23°C and 50% relative humidity. Five separate 6 inch by 6 inch specimens are prepared and placed on a plastic ring in a BYK Haze- Gard plus. A metal ring is used to clamp the specimen to the inside of the plastic ring such that there are no obvious sample wrinkles. The sample is placed as close as possible to the haze port and haze measured. Average total haze of five specimens is measured and reported.

[0091] Bottle Environmental Stress Cracking Resistance (ESCR)

[0092] Bottles are conditioned at room temperature for at least 24 hours before the environmental stress cracking resistance (ESCR) test. A temperature controlled chamber is set to 50° C. Bottles are filled ¼ to 1 / 3 full of a 10% IGEPAL® / 90% Deionized water solution. Caps with air hose are applied on the bottles and tightened. The bottles are placed in the temperature controlled chamber and conditioned for 1 hour. After the 1 hour conditioning, the cap is retightened and the bottle is pressurized through the air hose on the cap. The pressure is kept inside the bottle at 6 psi. The timer is started and the time when failure of the bottles is observed is recorded. Five bottles of each sample are tested.

[0093] Density

[0094] Density is measured in accordance with ASTM D792 and expressed in grams / cc.

[0095] Melt Index (I2) and (I10)

[0096] Melt index (I2) and Melt index (I10) are measured in accordance with ASTM D-1238 at 190°C at 2.16 kg. The values are reported in g / 10minutes; which corresponds to grams eluted per 10 minutes.

[0097] Hexane Extractables

[0098] Unmodified polymerized and pelletized polymers, produced as described below, are pressed in a Carver Press at a thickness of 3.0-4.0 mils. The pellets are pressed at 190°C., for three minutes, at 3,000 lbf, and then at 190°C., for three minutes, at 40,000 lbf. Non-residue gloves are worn, so as to not contaminate films with residual oils from the hands of the operator. Films84904-WO-PCT / DOW 84904 WO are cut into “1 inch×1 inch” squares and weighed. Enough film samples are used, such that 2.5 g of film samples are used for each extraction. The films are then extracted for two hours, in a hexane vessel containing about 1000 ml of hexane at 49.5±0.5° C., in a heated water bath. The hexane used is an isomeric hexanes mixture (for example, Hexanes (Optima), Fisher Chemical, high purity mobile phase for HPLC and / or extraction solvent for GC applications (99.9% min by GC). After two hours, the films are removed, rinsed in clean hexane, initially dried with nitrogen, and then further dried in a vacuum oven (80±5° C.) at full vacuum (ISOTEMP Vacuum Oven, Model 281A at approximately 30 inches Hg) for two hours. The films are then placed in a desiccator and allowed to cool to room temperature for a minimum of one hour. The films are then reweighed, and the amount of mass loss due to extraction in hexane is calculated. The [(amount of mass loss / initial weight of film)×100]=the weight percent of hexane extractable substances.

[0099] Melt Strength (MS)

[0100] Melt strength testing is conducted on a Rheotester 2000 capillary rheometer paired with a rheotens model 71.97 manufactured by Gottfert. A 2mm diameter and 30mm long die is used for testing with an entry angle of 180°. All tests are performed isothermally at 190°C.

[0101] Sample in pellet form is loaded into the capillary barrel and allowed to equilibrate at 190°C for 10minutes. The piston inside the barrel then applies a steady force on the molten sample to achieve an apparent wall shear rate of 38.16s-1, and the melt is extruded through the die with an exit velocity of approximately 9.7 mm / s. The extrudate is then guided through the wheel pairs of the serrated rheotens located 100mm below the die exit and spaced 0.4mm apart. Both wheel pairs accelerate at a constant rate of 2.4mm / s2and measure the extrudate’s response to the applied extensional force. Plots of force with respect to rheotens wheel speed are then created using RtensEvaluations 2007 excel macros. The force at which fracture occurred in the melt is the melt strength and the corresponding rheotens wheel speed at fracture is considered the drawability limit.

[0102] Dynamic Mechanical Spectroscopy (DMS)

[0103] Test samples are initially placed into a 1.5 in. diameter, 3.10mm thick mold and compression molded at a pressure of 25,000 lbs for 6.5 min. at 190°C with a Carver Hydraulic Press. The sample is equilibrated to room temperature before extraction.

[0104] The dynamic mechanical spectroscopy (DMS) frequency sweep is conducted using 25mm parallel plates at frequencies ranging from 0.1 to 100 rad / s at 190oC. The test gap separating the plates is 1.8mm and a strain that satisfies linear viscoelastic conditions, typically 10%, is utilized. Each test is conducted under nitrogen atmosphere and isothermal conditions. To initiate the DMS84904-WO-PCT / DOW 84904 WO test, the rheometer oven is first allowed to equilibrate at 190oC for at least 30 min before loading the sample into the test geometry. The sample is then equilibrated in the oven, with the door closed, for 1 min. The test gap is then set to 1.8mm, and the sample is allotted 5 min. to relax the resulting normal force. Afterwards, the oven is quickly opened, and the sample is trimmed so that no bulge is present. The DMS measurement is then initiated after reclosing the oven. During the test, the shear elastic modulus (G’), viscous modulus (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.

[0105] Differential Scanning Calorimetry

[0106] In preparation for Differential Scanning Calorimetry (DSC) testing, pellet-form samples are first loaded into a 1 in. diameter mold of 0.13mm thickness and compression molded into a film under 25,000 lbs of pressure at 190oC for approximately 10 seconds. The resulting film is then cooled to room temperature. The film is then subjected to a punch press in order to extract a disk that will fit the aluminum DSC test pan. The disk is then weighed individually (note: sample weight is approximately 4-8mg), placed into the aluminum pan, and sealed before being inserted into the DSC test chamber.

[0107] In reference to ASTM standard D3418, the DSC test is conducted using a heat-cool-heat cycle. First the sample is equilibrated at 180oC and held isothermally for 5min. to remove thermal and process history. The sample is then quenched to -40oC at a rate of 10oC / min. and held isothermally once again for 5min. during the cool cycle. Lastly, the sample is heated at a rate of 10oC / min. to 150oC for the second heating cycle. For data analysis, the melting peak temperatures and enthalpy of fusion are extracted from the second heating curve, whereas the enthalpy of crystallization is determined from the cooling curve. The enthalpy of fusion and crystallization are obtained by integrating the DSC thermogram from -20oC to the end of melting and crystallization, respectively. The heat of fusion of 100% crystalline polyethylene is taken to be 292 J / g to calculate wt% crystallinity. The DSC tests are performed using the TA Instruments Q2000, and data analyses are conducted via TA Instruments Universal Analysis and TRIOS software packages.

[0108] VICAT Softening Temperature

[0109] Vicat softening temperature is determined by following ASTM D12525. Specimens are cut from a compression molded sheet with an appropriate die to give samples 1.5 inches in length, 0.5 inches in width, and approximately 0.125 inches in thickness. Samples are conditioned for at least 40 hours at around 23°C and 50% relative humidity prior to testing. The specimens are84904-WO-PCT / DOW 84904 WO loaded into a CEAST HV6 and appropriate weight added to give 10N of force on the specimen. Specimens are then lowered into a bath containing silicone oil. After five minutes, the displacement inducer is zeroed and the temperature ramped up by 120°C / hour and the displacement monitored. Vicat temperature is defined as the temperature at which the needle penetrates 1mm into the specimen.

[0110] Heat Deflection Temperature

[0111] Heat deflection temperature is measured by following ASTM D648. Samples with a 5- inch length, a 0.5-inch depth, and a 0.125-inch width are cut from a compression molded sheet. The samples are conditioned for at least 40 hours at 23°C and 50% relative humidity. Specimens are loaded edgewise into the CEAST HV6A using a span of 4 inches and appropriate weight added to the central rod to give fiber stress of 0.455 MPa. The specimens are then lowered into a silicone oil bath and after five minutes the displacement transducer is zeroed. The temperature is then ramped up at a specified rate of 120°C per hour while the displacement of the central rod is monitored. The heat deflection temperature is the temperature at which the rod displacement reaches 0.25mm.

[0112] Clarity

[0113] Film transparency is measured according to ASTM D1746. Film is conditioned for at least 40 hours after film production at 23°C and 50% relative humidity. A Zebedee clarity meter model CL-100 is warmed up for 30 minutes and an internal calibration and scaling procedure run. Samples of 4.5 x 4.5 inch film are then cut from the conditioned film sheet and placed over the sample holder vacuum port and the clarity is measured. Five replicates are measured per sample.

[0114] Triple Detector Gel Permeation Chromatography

[0115] The chromatographic system consists of a PolymerChar GPC-IR high temperature GPC chromatograph equipped with an internal IR5 infra-red detector (IR5) and 4-capillary viscometer (DV) coupled to a Precision Detectors (Now Agilent Technologies) 2-angle laser light scattering (LS) detector Model 2040. For all absolute light scattering measurements, the 15 degree angle is used for measurement. The autosampler oven compartment is set at 160ºC and the column and detector compartment are set at 150ºC. The columns used are 4 Agilent Mixed A 30cm 20-micron linear mixed-bed columns. The chromatographic solvent used is 1,2,4 trichlorobenzene with 200 ppm of butylated hydroxytoluene (BHT). The solvent source is nitrogen sparged. The injection volume used is 200 microliters and the flow rate is 1.0 milliliters / minute.

[0116] The total plate count of the GPC column set is performed with decane which is introduced into the blank sample via a micropump controlled with the PolymerChar GPC-IR system. The84904-WO-PCT / DOW 84904 WO plate count for the chromatographic system should be greater than 18,000 for the 4 Agilent Mixed A 30cm 20-micron linear mixed-bed columns.

[0117] Samples are prepared in a semi-automatic manner with the PolymerChar Instrument Control software, wherein the samples are weight-targeted at 2 mg / ml, and the solvent (containing 200ppm BHT) is added to a pre nitrogen-sparged septa-capped vial, via the PolymerChar high temperature autosampler. The samples are dissolved for 2 hours at 160ºC under low speed shaking.

[0118] In order to monitor deviations over time, a flowrate marker (decane) is introduced into each sample via a micropump controlled with the PolymerChar GPC-IR system. This flowrate marker (FM) is used to linearly correct the pump flowrate (Flowrate(nominal)) for each sample by RV alignment of the respective decane peak within the sample (RV(FM Sample)) to that of the decane peak within the narrow standards calibration (RV(FM Calibrated)). Any changes in the time of the decane marker peak are then assumed to be related to a linear-shift in flowrate (Flowrate(effective)) for the entire run. After calibrating the system based on a flow marker peak, the effective flowrate (with respect to the narrow standards calibration) is calculated as in Equation 1. Processing of the flow marker peak is done via the PolymerChar GPCOne™ software. Acceptable flowrate correction is such that the effective flowrate should be within + / -0.5% of the nominal flowrate. Flowrate(effective) = Flowrate(nominal) * (RV(FM Calibrated) / RV(FM Sample)) (EQ.1)

[0119] For the determination of the viscometer and light scattering detector offsets from the IR5 detector, the multi-detector offsets are determined using the Systematic Approach in a manner consistent with that published by Balke, Mourey, et. al. (Mourey and Balke, Chromatography Polym. Chpt 12, (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym. Chpt 13, (1992)), optimizing triple detector log (MW and IV) results from a linear homopolymer polyethylene standard (3.5 > Mw / Mn > 2.2) with a molecular weight in the range of 115,000 to 125,000 g / mol to the narrow standard column calibration results from the narrow standards calibration curve using PolymerChar GPCOne™ software.

[0120] The absolute molecular weight data is obtained in a manner consistent with that published by Zimm (Zimm, B.H., J. Chem. Phys., 16, 1099 (1948)) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987)) using PolymerChar GPCOne™ software. The overall injected concentration, used in the determination of the molecular weight, is obtained from the mass detector area and the mass detector constant, derived from a suitable linear polyethylene homopolymer, or one of the polyethylene standards of known84904-WO-PCT / DOW 84904 WO weight-average molecular weight. The calculated molecular weights (using GPCOne™) are obtained using a light scattering constant, derived from one or more of the polyethylene standards mentioned below, and a refractive index concentration coefficient, dn / dc, of -0.104. Generally, the mass detector response (IR5) and the light scattering constant (determined using GPCOne™) should be determined from a linear standard with a molecular weight in excess of about 50,000 g / mole. The viscometer calibration (determined using GPCOne™) can be accomplished using the methods described by the manufacturer, or, alternatively, by using the published values of suitable linear standards, such as Standard Reference Materials (SRM) 1475 (available from National Institute of Standards and Technology (NIST)). A viscometer constant (obtained using GPCOne™) is calculated which relates specific viscosity area (DV) and injected mass for the calibration standard to its intrinsic viscosity. The chromatographic concentrations are assumed low enough to eliminate addressing 2nd viral coefficient effects (concentration effects on molecular weight).

[0121] The absolute weight average molecular weight (Mw(Abs)) is obtained (using GPCOne™) from the area of the light scattering (LS) integrated chromatogram (factored by the light scattering constant) divided by the mass recovered from the mass constant and the mass detector (IR5) area. The molecular weight and intrinsic viscosity responses are linearly extrapolated at chromatographic ends where signal to noise becomes low (using GPCOne™). Other respective moments, Mn(Abs) and Mz(Abs) are calculated according to equations 2-4 as follows:

[0122] The calculation of the cumulative detector fractions (CDF) for the low angle laser light scattering detector (“CDFLS”) are accomplished using the following steps: 1) Linearly flow correct the chromatogram based on decane flow marker injection as described above. 2) Perform detector offsets as described above. 3) Calculate absolute molecular weights from light scattering as described above. 4) Calculate the cumulative detector fraction (CDF) of the Low-Angle Laser Light Scattering (LALLS) chromatogram (CDFLS) based on its baseline-subtracted peak height (H) from high to84904-WO-PCT / DOW 84904 WO low molecular weight (low to high retention volume) at each data slice (j) according to Equation 5.

[0123] Long Chain Branching Frequency

[0124] The long chain branching frequency is calculated based on the differences between the g’, which is a ratio of the intrinsic viscosity of a polymer sample over a linear polymer reference with the same molecular weight. In 3D GPC practice, a reference polyethylene homopolymer, containing no detectable LCB or SCB, and with a Mw of approximately 120,000 g / mol and polydispersity around 3.0, is injected at the beginning of each run queue to establish the Mark- Houwink linear reference line. A first-order linear fit is applied to the obtained log of the intrinsic viscosity and log of the molecular weight data within the log of the molecular weight range of 4.5 to 5.8 g / mol to provide the linear reference K and α values.

[0125] A polyethylene sample of interest is analyzed to obtain intrinsic viscosity, molecular weight values, and the value of gi’ is calculated at each chromatographic slice (i) according to Equation 6: gi’ = (IVSample,i / IVlinear reference,i) (EQ. 6) where the calculation utilizes the IVSample,iat equivalent absolute molecular weight values and the same SCB content values to the linear reference within the log molecular weight range of 4.5 to 5.8 g / mol. If a difference in SCB content exists, the IVlinear reference,i line is vertically shifted by adjusting the K value from the Mark-Houwink Plot to account for the SCB correction compared to the IVSample,i. The shift is done until the linear reference line makes a single point of contact to make a tangent with the sample Mark-Houwink line at a log molecular weight of 4.5.

[0126] A Zimm-Stockmayer branching factor g is calculated from g’, g’= g^, using an epsilon factor of 0.5. The number of branches along the polymer sample (Bn) at each data slice (i) can be determined by using Equation 7, (B. H. Zimm and W. H. Stockmayer, J. Chem. Phys. 17, 1301 (1949)): (EQ. 7)

[0127] Finally, the average LCBf quantity per 1000 carbons in the polymer across all of the slices (i) is determined using Equation 8:84904-WO-PCT / DOW 84904 WO

[0128] Absolute Molecular Weight Short Chain Branching Distribution Index (MWSCBDI)

[0129] A calibration for the IR5 detector rationing was performed using at least ten ethylene- based polymer standards (Octene as comonomer) made by single-site metallocene catalysts from a single reactor in solution process (polyethylene homopolymer and ethylene / octene copolymers) of a narrow SCB distribution and known comonomer content (as measured by13C NMR Method, Qiu et al., Anal. Chem.2009, 81, 8585−8589), ranging from homopolymer (0 SCB / 1000 total C) to approximately 40 SCB / 1000 total C, where total C = carbons in backbone + carbons in branches. Each standard had a weight-average molecular weight from 36,000 g / mole to 126,000 g / mole measured by GPC. Each standard had a molecular weight distribution (Mw / Mn) from 2.0 to 2.5. Polymer properties for the SCB standards are shown in Table A. Table A: “SCB” Standards

[0130] The IR5 area ratio (or IR5Methyl Channel Area / IR5Measurement Channel Area) of the baseline- subtracted area response of the IR5 methyl channel sensor to the baseline-subtracted area response of IR5 measurement channel sensor (standard filters and filter wheel as supplied by PolymerChar: Part Number IR5_FWM01 included as part of the GPC-IR instrument) is calculated for each of the SCB standards. A linear fit of the SCB frequency versus the IR5 area ratio is constructed in the form of the following Equation 9:84904-WO-PCT / DOW 84904 WO SCB / 1000 total C = A0+ [A1x (IR5Methyl Channel Area / IR5Measurement Channel Area)] (EQ 9) where A0 is the SCB / 1000 total C intercept at an IR5 area ratio of zero, and A1 is the slope of the SCB / 1000 total C versus IR5 area ratio and represents the increase in the 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.

[0131] A series of linear baseline-subtracted chromatographic heights for the chromatogram generated by the IR5 methyl channel sensor is established as a function of column elution volume, to generate a baseline-corrected chromatogram (methyl channel). A series of linear baseline- subtracted chromatographic heights for the chromatogram generated by the IR5 measurement channel is established as a function of column elution volume, to generate a base-line-corrected chromatogram (measurement channel).

[0132] The SCB / 1000 total C, representing octene comonomer, and absolute molecular weight from light scattering (Mwi), are obtained at each chromatographic slice i, taken as a data point per second as described above. Hence the SCB / 1000 total C (y-axis) is calculated as a function of Abs Log(Mwi) (x-axis). An EXCEL linear regression is used to calculate the slope between selected SCB / 1000 total C and Abs Log(Mwi) values between an Abs Mwi of 15,000 and Abs Mwi of 150,000 g / mol (end group corrections on chain ends were omitted for this calculation). An EXCEL linear regression was used to calculate the slope between, and including, on the log scale of Abs Mwi from 15,000 to Abs 150,000 g / mol. This slope is defined as the absolute molecular weight short chain branching distribution index (MWSCBDI).

[0133] iCCD and Composition Distribution Breath Index (CDBI)

[0134] iCCD, is an improved method for comonomer content distribution (CCD) analysis; and is based on the method described in WO2017040127A1. The test method is performed with crystallization elution fractionation (CEF) instrumentation (available from Polymer Char) equipped with an IR-5 detector and a two-angle precision detector light scattering detector Model 2040 (available from Agilent Technology). Ortho-dichlorobenzene (ODCB, 99 % anhydrous grade or technical grade) is used as solvent. Silica gel 40 (with a particle size of 0.2 mm to ~0.5 mm; available from EMD Chemicals) can be used to dry the ODCB solvent. Dried silica is packed into three emptied HT-GPC columns (with dimensions of 300 mm x 7.5 mm (ID)) to further purify the ODCB solvent as eluent. The CEF instrument is equipped with an autosampler with nitrogen (N2) purging capability. ODCB is sparged with dried N2for 1 hr before use. A sample is prepared using the autosampler at 4 mg / mL (unless otherwise specified) under shaking at 160° C. for 1 hour. The injection volume of the sample is 300 microliters (μL). The temperature profile of the84904-WO-PCT / DOW 84904 WO iCCD is as follows: crystallization at 3°C / minute from 105°C. to 30°C; thermal equilibrium at 30°C for 2 minutes (including Soluble Fraction Elution Time being set as 2 minutes); elution at 3°C / minute from 30°C to 140°C. The flow rate of the sample during crystallization is 0.0 mL / minute. The flow rate of the sample during elution is 0.50 mL / minute. The data was collected at one data point / second.

[0135] The iCCD column used is a 15 cm (length) x ¼ in internal diameter (ID) stainless tubing packed with gold coated nickel particles (Bright 7GNM8-NiS; available from Nippon Chemical Industrial Co.). The column packing and conditioning is carried out using a slurry method according to the method described in WO2017040127A1. The final pressure with trichlorobenzene (TCB) slurry packing is 150 bar (10MPa).

[0136] The column temperature calibration is performed by using a mixture of: (i) 1.0 mg / mL of a unimodal linear homopolymer polyethylene (a polyethylene having a zero comonomer content, a melt index (I2) of 1.0 g / 10minutes, and a polydispersity (Mw / Mn) of approximately 2.6 as determined by the GPC test method described above) as a reference material; and (ii) 0.5 mg / mL of Eicosane in ODCB. The 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 minus 30.00 °C, (2) subtracting the temperature offset of the elution temperature from iCCD raw temperature data (it is noted that this temperature offset is a function of experimental conditions, such as elution temperature, elution flow rate, etc.), (3) creating a unimodal linear calibration line transforming the elution temperature across a range of 30.00°C and 140.00°C so that the unimodal linear homopolymer polyethylene reference material had a peak temperature at 101.0°C and Eicosane had a peak temperature of 30.0°C, and (4) for the soluble fraction measured isothermally at 30 °C, the elution temperature below 30.0°C is extrapolated linearly by using the elution heating rate of 3°C / min according to the method described in U.S. Patent No. 9,688,795. GPCOne software (available from PolymerChar) is used to generate a SCBD distribution curve dWi / dT where Wi is the mass at Ti, and where Ti is the elution temperature after calibration.

[0137] The elution fraction, in wt.%, is determined at a specific elution temperature range. It is defined as the area of the baseline subtracted iCCD profile in a specific temperature range divided by the total integrated area of the baseline subtracted iCCD elution chromatogram multiplied by 100%.

[0138] The comonomer content versus elution temperature of iCCD is constructed by using 12 reference materials (ethylene homopolymer and ethylene-octene random copolymer made with single site metallocene catalyst, having ethylene equivalent weight average molecular weight84904-WO-PCT / DOW 84904 WO ranging from 35,000 to 128,000) with solution process. All these reference materials are analyzed the same way as specified previously at 4 mg / mL. The correlation between comonomer mol fraction versus elution temperature (T in Celsius) follows the following expression: ln(1-comonomer mol fraction) =-208.328 / (elution temperature in °C + 273.12) + 0.55846 (EQ 10)

[0139] The composition distribution breadth index (CDBI) is defined as the weight percent of the polymer molecules having a co-monomer content within + / -50 percent of the median total molar co-monomer content (as reported in WO 93 / 03093). The CDBI of polyolefins can be conveniently calculated from the SCBD data obtained from the techniques known in the art, such as, for example, temperature rising elution fractionation (“TREF”) as described, for example, by Wild, et al., Journal of Polymer Science, Poly. Phys. Ed., Vol. 20, 441 (1982); L. D. Cady, “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 in U.S. Patent Nos. 4,798,081 and 5,008,204.

[0140] Herein, iCCD CDBI is calculated accordingly by using short chain branching distribution measured by the iCCD method and with the comonomer composition correlation versus elution temperature as described above. EXAMPLES

[0141] Materials used are listed below in table 1. The listing of properties of these materials are continued in tables 2-4. All commercial DOWTMsamples are available from DOWTMChemical. Comparative A is a blend of 65 weight percent of DOW™ LDPE 91020 Health+ and 35 weight percent of UNIVAL™ DMDA 6400 NT 7. Comparatives B and C are low density polyethylene resins made in a high pressure free radical polymerization process. Comparatives D, E, and F are polyethylene resins made using heterogeneous catalyst in a solution polymerization process. Comparative G is a blend of 56 weight percent DOW™ LDPE 91020 Health+ and 44 weight percent of DOW™ DMDA-8007 NT 7. Table 1: Materials and Properties84904-WO-PCT / DOW 84904 WO* NM means not measured. Table 2: Materials and Properties cont.84904-WO-PCT / DOW 84904 WOTable 3: Materials and Properties cont.Table 4: Materials and Properties84904-WO-PCT / DOW 84904 WO

[0142] Production of Experimental Resin 1 and 2 Table 5: Reactor and Feed Conditions for the Synthesis of Experimental Resin 1 and 2.84904-WO-PCT / DOW 84904 WO

[0143] Raw materials (ethylene, 1-octene) and the process solvent (a narrow boiling range high- purity isoparaffinic solvent trademarked Isopar E commercially available from ExxonMobil Corporation) are purified with molecular sieves before introduction into the reaction environment. Hydrogen is supplied in pressurized cylinders as a high purity grade and is not further purified. The reactor monomer feed (ethylene) stream is pressurized via mechanical compressor to above reaction pressure at 525 psig. The solvent and comonomer (1-octene) feed are pressurized via a mechanical positive displacement pump to above reaction pressure at 525 psig. MMAO-3A, commercially available from Nouryon, is used as an impurity scavenger. The individual catalyst components (procatalyst or cocatalyst) are manually batch diluted to specified component concentrations with purified solvent (Isopar E) and pressured to above reaction pressure at 525 psig. The cocatalyst is [HNMe(C18H37)]2 [B(C6F5)4], commercially available from Boulder Scientific, and is used at a 1.2 molar ratio relative to the cocatalyst. All reaction feed flows are measured with mass flow meters and independently controlled with computer automated valve control systems.

[0144] The continuous solution polymerizations are carried out in a CSTR and / or a plug flow reactor. The CSTR reactors have independent control of all fresh solvent, monomer, comonomer, hydrogen, and catalyst component feeds. The plug flow reactor has independent control of catalyst component feeds. The combined solvent, monomer, comonomer and hydrogen feed to the reactors is temperature controlled to anywhere between 5°C to 50°C and typically 25°C. The fresh comonomer feed to the polymerization reactor is fed in with the solvent feed. The fresh solvent feed is controlled typically with each injector receiving half of the total fresh feed mass flow. The cocatalyst is fed based on a calculated specified molar ratio (1.2 molar equivalents) to the procatalysts. Immediately following each fresh injection location, the feed streams are mixed with the circulating polymerization reactor contents by static mixing elements. In the case of dual catalyst runs, the ratio of catalysts is adjusted to give the desired polymer MI and density. The84904-WO-PCT / DOW 84904 WO effluent from the polymerization reactor system (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) exits and passes through a control valve (responsible for maintaining the pressure of the reactor system at a specified target). As the stream exits the reactor, it is contacted with water to stop the reaction. In addition, various additives, such as antioxidants, could be added at this point. The stream then goes through another set of static mixing elements to evenly disperse the catalyst kill and additives.

[0145] Following additive addition, the effluent (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) passes through a heat exchanger to raise the stream temperature in preparation for separation of the polymer from the other lower boiling reaction components. The stream then enters a two-stage separation and devolatization system where the polymer was removed from the solvent, hydrogen, and unreacted monomer and comonomer. The separated and devolatized polymer melt is pumped through a die specially designed for underwater pelletization, cut into uniform solid pellets, dried, and transferred into a box for storage.

[0146] Bottle Fabrication

[0147] 14 oz Boston Round-shaped bottles with a target bottle weight of 26±0.5 grams are made using a Bekum H-111 continuous extrusion blow molding machine equipped with a 50 mm extruder and MACO 6500*digital readout controller. The blow molding equipment is run using parison programming to ensure that a consistent uniform wall thickness distribution is maintained in the bottles produced. The extruder barrel temperatures are maintained at 350°F. The extrusion rate is approximately 120 to 140 g / min. For samples that do not have enough melt strength, lower extruder barrier temperatures are used to improve the melt strength and reduce the sagging. Head weight is used to adjust the weight throughout the parison. This can be used to compensate for the added weight of profiling the bottle. A higher head weight is correlated with a wider die gap and vice versa. Detail processing conditions are listed in Table 5. The target bottle weight for each produced bottle was 26 grams. The properties of the produced bottles are listed in Table 6. Table 6: Bottle Fabrication Processing Conditions84904-WO-PCT / DOW 84904 WOTable 7: Bottle properties84904-WO-PCT / DOW 84904 WO

Claims

84904-WO-PCT / DOW 84904 WO CLAIMS 1. A blow molded article comprising an 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 breadth index (CDBI) greater than or equal to 55%; a CDFLS; and a LCBf; wherein the CDFLS × LCBf × 100 is greater than 0.5, and wherein the CDFLSis calculated by measuring an area fraction of a molecular weight distribution obtained from absolute molecular weights from low angle light scattering greater than 500,000 g / mol using GPC molecular weight distribution, and the LCBf is measured as described in the specification.

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

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

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

5. The blow molded article of any preceding claim, wherein the ethylene / alpha-olefin interpolymer has a V0.1 / V100 value, as determined by Dynamic Mechanical Spectroscopy, of greater than or equal to 5.

5.

6. The blow molded article of any preceding claim, wherein the ethylene / alpha-olefin interpolymer has a V0.1 / V100 value, as determined by Dynamic Mechanical Spectroscopy, of from 5.5 to 20.

7. The blow molded article of any preceding claim, wherein the ethylene / alpha-olefin interpolymer has a melt strength (MS), wherein the MS and I2 meets 4 ^^ > 8 − × ^2 384904-WO-PCT / DOW 84904 WO ^ Or, ^^ > 10 −^× ^2 ^ Or, ^^ > 14.5 −^× ^2 and wherein the I2 is expressed in g / 10 minutes and MS is expressed in cN.

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

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

10. The blow molded article of any preceding claim, wherein the ethylene / alpha-olefin interpolymer has a hexane extractables value of less than 1 wt.% based on the weight of the ethylene / alpha-olefin interpolymer.

11. The blow molded article of any preceding claim wherein the ethylene / alpha-olefin interpolymer has a clarity greater than or equal to 65%.

12. The blow molded article of any preceding claim, wherein the ethylene / alpha-olefin interpolymer has a melting peak temperature measured by DSC of from 115°C to 126°C.

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

14. The blow molded article of any preceding claim, wherein the ethylene / alpha-olefin interpolymer has a Mw(abs) / Mn(abs) of from 4.0 to 7.0, wherein the Mw(abs) and Mn(abs) are measured by Triple Detector Gel Permeation Chromatography.

15. The blow molded article of any preceding claim, wherein the ethylene / alpha-olefin interpolymer has a comonomer distribution breadth index greater than or equal to 55%.84904-WO-PCT / DOW 84904 WO 16. The blow molded article of any preceding claim, wherein the ethylene / alpha-olefin interpolymer has a CDFLS × LCBf × 100 of from 0.5 to 10, wherein the CDFLS and LCBf are measured as described in the specification.

17. The blow molded article of any preceding claim, wherein the ethylene / alpha-olefin interpolymer has a MWSCBDI of from -1.0 to 1.0.

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