Polyethylene compositions including recycled polyethylene

Abstract

Disclosed herein is a polyethylene composition, as well as injection molded articles made therefrom. The polyethylene composition includes a high density polyethylene and a recycled polyethylene composition. The recycled polyethylene composition molecular weight properties and others that when blended with a high density polyethylene results in a blend that can be used to form injected molded articles. The polyethylene composition can include at least 20 wt.% of the recycled polyethylene composition.

Description

POLYETHYLENE COMPOSITIONS INCLUDING RECYCLED POLYETHYLENE FIELD

[0001] The present invention relates to the field of polyethylene compositions including a high density polyethylene and a recycled polyethylene composition, processes for making the same, and articles comprising the same.BACKGROUND

[0002] High density polyethylene (HDPE) compositions are commonly used in packaging, such as bottles, jars, and their closures. The packaging can be molded using known techniques, such as injection molding, compression molding, and blow molding. Injection molding is commonly used for making complex shaped articles, such as caps, closures, threaded items, and hinged items.

[0003] Molding processes require the HDPE composition to provide an appropriate balance of easy processability and physical properties. For injection molding processes of caps and closures, the HDPE composition desirably has low melt viscosity at high shear rates so that it flows easily through the mold. Further, the HDPE composition desirably has good hinge resistance, mold shrinkage, and stiffness, so that it forms durable molded articles.

[0004] Adding recycled polyethylene such as post-consumer recycled (PCR) material as a blend partner to high-density polyethylene (HDPE) compositions for injection molded closures such as caps and closures can offer several benefits. It can reduce the environmental impact of materials by diverting plastic waste from landfills. This can help in conserving natural resources but also can lower the carbon footprint associated with manufacturing processes. Additionally, incorporating recycled polyethylene into HDPE can enhance the sustainability profile of the product, making it more appealing to environmentally conscious consumers and businesses. From a cost perspective, using recycled polyethylene can potentially lower material costs, as recycled plastics can be less expensive. However, incorporating recycled polyethylene into HDPE has its challenges. Recycled polyethylene, for example, can present variability in terms of flow and mechanical properties, contain different type of contaminants, and can have reduced mechanical properties. The way in which recycled polyethylene blends and interacts with HDPE is also less understood.

[0005] It is therefore desirable to develop polyethylene compositions of HDPE and recycled polyethylene that can include a significant amount of recycled polyethylene, and can have a good balance of processability and physical properties that can be useful in molding applications. The polyethylene compositions according to embodiments disclosed herein address one or more of the foregoing challenges by providing a polyethylene composition that can be processed for molding application, can have desirable properties such as melt flow, and can include significant amounts of recycled polyethylene composition.SUMMARY

[0006] Disclosed herein is a polyethylene composition. The polyethylene composition comprises a high density polyethylene having a density from 0.940 to 0.955 g / cm3and a melt index (I2) of at least 20.0 g / 10 min; and a recycled polyethylene composition having a density of at least 0.925 g / cm3, a melt index (I2) of at least 0.2 g / 10 min, a Mz(Abs) of at least 1,500,000 g / mol, and a Mw(Abs) / Mw(Conv) > 1.20; and wherein the polyethylene composition comprises at least 20 wt.% of the recycled polyethylene composition, based on the total weight of the polyethylene composition.

[0007] Disclosed herein is also an injection molded article. The injection molded article can be formed from the polyethylene composition according to embodiments disclosed herein.DETAILED DESCRIPTION

[0008] As used herein, the term “polymer” means a polymeric compound prepared by polymerizing monomers, whether of the same or a different type. The generic term polymer thus embraces the term homopolymer (employed to refer to polymers prepared from only one type of monomer), and the term copolymer or interpolymer. Trace amounts of impurities (for example, catalyst residues) may be incorporated into and / or within the polymer. A polymer may be a single polymer, a polymer blend, or a polymer mixture, including mixtures of polymers that are formed in situ during polymerization.

[0009] As used herein, the terms “polyethylene” or “ethylene-based polymer” shall mean polymers comprising a majority amount (>50 mol %) of units which have been derived from ethylene monomer. This includes polyethylene homopolymers and copolymers (meaning units derived from two or more comonomers). The terms “ethylene-based polymer” and “polyethylene”may be used interchangeably. Generally, polyethylene may be produced in gas-phase, fluidized bed reactors, liquid phase slurry process reactors, or liquid phase solution process reactors, using a heterogeneous catalyst system, such as Ziegler-Natta catalyst, a homogeneous catalyst system, comprising Group 4 transition metals and ligand structures such as metallocene, non-metallocene metal-centered, heteroaryl, heterovalent aryloxyether, phosphinimine, and others. Combinations of heterogeneous and / or homogeneous catalysts also may be used in either single reactor or dual reactor configurations.

[0010] As used herein, the terms “high density polyethylene” or “HDPE” refers to polyethylenes having densities of at least 0.935 g / cm3and up to 0.970 g / cm3, which are generally prepared with Ziegler-Natta catalysts, chrome catalysts, or single-site catalysts including, but not limited to, substituted mono- or bis-cyclopentadienyl catalysts (typically referred to as metallocene), constrained geometry catalysts, phosphinimine catalysts & polyvalent aryloxyether catalysts (typically referred to as bisphenyl phenoxy).

[0011] The term “composition,” as used herein, refers to a mixture of materials that comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition. The HDPE disclosed herein is a “composition” as it is a mixture of materials, as well as reaction products and decomposition products formed from the materials of the composition.

[0012] The term “recycled polyethylene composition,” as used herein, is a polyethylene that has been exposed to at least one heat history (e.g., via previous extrusion or conversion or melting into an article). Non-limiting examples of recycled polyethylene compositions include Post Consumer Recycled (“PCR”) compositions sold by The Dow Chemical Company (Midland, MI) (“Dow”).

[0013] The molecular weights of the compositions disclosed herein can be measured by conventional GPC and measured by absolute GPC. Conventional GPC measurements recited here can be recognized as, for example, “Mn(Conv)” or “Mw(Conv)” or “Mz(Conv),” whereas Absolute GPC measurements can be recognized as, for example, “Mn(Abs)” or “Mw(Abs)” or “Mz(Abs).” Conventional and absolute GPC measurements are well known to those skilled in the art and are carried out in accordance with the test methods described below.

[0014] A polyethylene composition is disclosed. The polyethylene composition comprises a high density polyethylene and a recycled polyethylene composition. The polyethylene composition comprises at least 20 wt.% of the recycled polyethylene composition, based on the total weight of the polyethylene composition. In some embodiments, the polyethylene composition comprises a lower limit of 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, or 40 wt.% to an upper limit of 60 wt.%, 55 wt.%, 50 wt.%, 45 wt.%, 40 wt.%, 35 wt.%, 30 wt.%, or 25 wt.%, based on the total weight of the polyethylene composition. In some embodiments, the polyethylene composition comprises from 40 to 80 wt.% of the high density polyethylene, and from 20 to 60 wt.% of the recycled polyethylene composition, where weight percent (wt.%) is based on the total weight the high density polyethylene and recycled polyethylene composition. In some embodiments, the polyethylene composition consists of the high density polyethylene and recycled polyethylene composition according to embodiments disclosed herein.

[0015] HDPE

[0016] The polyethylene composition comprises a high density polyethylene (HDPE) having a density from 0.940 to 0.955 g / cm3and a melt index (I2) of at least 20.0 g / 10 min. The HDPE can have a density of a lower limit of 0.941, 0.943, 0.945, 0.947, 0.949, or 0.951 g / cm3to an upper limit of 0.955, 0.953, 0.951, 0.949, 0.947, 0.945, or 0.943 g / cm3. The HDPE can have a melt index (I2) of at least 20.0 g / 10 min, 25.0 g / 10 min, 30.0 g / 10 min, 35.0 g / 10 min or 40.0 g / 10 min, or can be in a range of from 20.0 to 80.0 g / 10 min, or 30.0 to 70.0 g / 10 min, or 35.0 to 60.0 g / 10 min or 35.0 to 55.0 g / 10 min.

[0017] In some embodiments, the HDPE has a molecular weight distribution, Mw / Mn(Conv) of less than 7.0, or in a range of 1.0 to 6.0, or 2.0 to 6.0, as measured by conventional GPC. As known by those skilled in the art, the molecular weight distribution of the polyethylene composition can be indicative of the modality and / or catalyst system employed in making the composition. The HDPE can have a weight average molecular weight (Mw) in the ranges of 30,000 to 100,000 g / mol, or 40,000 to 80,000 g / mol; and can have a number average molecular weight (Mn) of 5,000 to 20,000 g / mol, as measured by conventional GPC.

[0018] Examples of suitable comonomers used to make the HDPE may include alpha-olefins. Suitable alpha-olefins may include those containing from 3 to 20 carbon atoms (C3-C20). For example, the alpha-olefin may be a C4-C20 alpha-olefin, a C4-C12 alpha-olefin, a C3-C10 alpha-olefin, a C3-C8 alpha-olefin, a C4-C8 alpha-olefin, or a C6-C8alpha-olefin. In some embodiments, the alpha-olefin is selected from the group consisting of propylene, 1 -butene, 1 -pentene, 1 -hexene, 4-methyl-l -pentene, 1 -heptene, 1 -octene, 1 -nonene and 1 -decene. In other embodiments, the alpha-olefin is selected from the group consisting of propylene, 1 -butene, 1 -hexene, and 1 -octene. In further embodiments, the alpha-olefin is selected from the group consisting of 1 -hexene and 1-octene.

[0019] In some embodiments, the HDPE comprises at least 95 weight percent repeating units derived from ethylene, or at least 96 weight percent or at least 97 weight percent or at least 98 weight percent or at least 99 weight percent or at least 99.5 weight percent, with the remaining repeating units derived from unsaturated comonomers. In some embodiments, an HDPE comprises less than 4 weight percent, or less than 3 weight percent, or less than 2 weight percent, or less than 1 weight percent, or less than 0.5 weight percent, repeating units derived from alphaolefin comonomers, or at least 3 weight percent or at least 2 weight percent or at least 1 weight percent or at least 0.5 weight percent, with the remaining repeating units derived from ethylene monomer. It is well known how to select comonomers and comonomer content to obtain the desired density or molecular weight and other properties for an HDPE.

[0020] In some embodiments, the HDPE has a unimodal molecular weight distribution. A unimodal HDPE, as used herein, has molecular weight profile that has a single peak in a GPC chromatogram; in contrast to a multimodal HDPE, which as a molecular weight profile that has multiple peaks that represent a distinct fraction having a different weight average molecular weight from the main fraction. In some embodiments, the HDPE is a gas-phase Ziegler-Natta HDPE. In such embodiments, the HDPE is made in a gas-phase reactor with a Ziegler-Natta catalyst for polymerization of ethylene and an alpha-olefin comonomer to achieve the requisite density and melt index (I2).Recycled Polyethylene Composition

[0021] The polyethylene composition of the present invention comprises a recycled polyethylene composition having a density of at least 0.930 g / cm3, a melt index (I2) of at least 0.2 g / 10 min, a Mz(Abs) of at least 1,500,000 g / mol, and a Mw(Abs) / Mw(Conv) > 1.20. The polyethylene composition comprises at least 20 wt.% of the recycled polyethylene composition, based on the total weight of the polyethylene composition.

[0022] In some embodiments, the recycled polyethylene composition is a pre-consumer / post-industrial recycled polyethylene. The terms “pre-consumer recycled composition” and “postindustrial recycled composition” refer to polymers and blends recovered from pre-consumer material, as defined by ISO- 14021, such as scraps and waste from manufacturing facilities or from fabricators. The term recycled polyethylene composition can include blends of HDPE resins (optionally with other polymers) recovered from materials diverted to the waste stream during a manufacturing process.

[0023] In some embodiments, the recycled polyethylene composition is a post-consumer recycled (PCR) HDPE resin. The term “post-consumer recycled” (or “PCR”) HDPE resin refers to HDPE resins and blends that were previously used in a consumer application such as packaging and were recycled after their use was completed. PCR polyethylene is typically collected from recycling programs and recycling plants. Sources of PCR HDPE resin can include, for example, bottle caps and closures, milk, water or orange juice containers, detergent bottles, office automation equipment (printers, computers, copiers), white goods (refrigerators, washing machines), consumer electronics (televisions, video cassette recorders, stereos), automotive shredder residue (the mixed materials remaining after most of the metals have been sorted from shredded automobiles and other metal-rich products “shredded” by metal recyclers), packaging waste, household waste, rotomolded parts (kayaks / coolers), building waste and industrial molding and extrusion scrap. In some embodiments, the recycled polyethylene composition comprises recycled milk containers or recycled caps made from high density polyethylene.

[0024] The recycled polyethylene composition has a density of at least 0.925 g / cm3. In some embodiments, the recycled polyethylene composition has a density of at least 0.927 g / cm3, at least 0.929 g / cm3, at least 0.935 g / cm3, at least 0.940 g / cm3, at least 0.945 g / cm3, at least 0.950 g / cm3, or at least 0.955 g / cm3. The recycled polyethylene composition can have a density in a range of 0.925 to 0.965 g / cm3, or 0.930 to 0.965 g / cm3, or 0.930 to 0.950 g / cm3, or 0.940 to 0.965 g / cm3, 0.950 to 0.965 g / cm3. The recycled polyethylene composition has a melt index (h) of at least 0.2 g / 10 min. The recycled polyethylene composition can have a melt index in a range of 0.2 to 10.0 g / 10 min, or 0.2 to 5.0 g / 10 min. Recycled polyethylene compositions according to embodiments disclosed herein are commercially available and can be provided with specification on density and melt index due to often variable conditions of recycled polyethylene compositions.

[0025] The recycled polyethylene composition has a Mz(Abs) of at least 1,500,000 g / mol, and a Mw(Abs) / Mw(Conv) > 1.20. In some embodiments, the recycled polyethylene composition can have a Mz(Abs) of at least 1,500,000 g / mol, or at least 1,600,000 g / mol, or at least 1,700,000 g / mol, or at least 1,800,000 g / mol, or in the range of 1,500,000 g / mol to 2,500,000 g / mol, or 1,500,000 g / mol to 2,300,000 g / mol, or 1,600,000 g / mol to 2,200,000 g / mol. In some embodiments, the recycled polyethylene composition can have a Mw(Abs) / Mw(Conv) > 1.20, or > 1.25, or >1.30, or >1.35, or >1.40, or >1.42. Without being bound by theory, the combination of the specific HDPE and recycled polyethylene composition, including its Mw(Abs) / Mw(Conv) > 1.20 and high Mz(Abs) value (at least 1,500,000 g / mol), can result in a polyethylene composition particularly suitable for injection molding and with significant amounts (>20 wt.%) of recycled polyethylene composition. As is known by those skilled in the art, the Mw(Abs) / Mw(Conv) > 1.20 calculation is a measurement in relation to long chain branching of the composition, where, without being bound by theory, the high Mz(Abs) and Mw(Abs) / Mw(Conv) of the recycled composition serves as a desirable blend partner with the HDPE for injected molding performance properties.

[0026] The recycled polyethylene composition can have conventional GPC measurements as follows: a Mn of 10,000 to 30,000 g / mol; a Mw of 100,000 to 250,000 g / mol; a Mz of 1,500,000 to 3,000,000 g / mol; or Mw / Mn of 7 to 25. The recycled polyethylene can have absolute GPC measurements as follows: a Mn of 10,000 to 30,000 g / mol; or a Mw of 100,000 to 300,000 g / mol. In some embodiments, the recycled polyethylene composition has a Mw(Abs) greater than 150,000 g / mol.

[0027] In some embodiments, the recycled polyethylene composition comprises less than 25 wt.% polypropylene, based on the total weight of the recycled polyethylene composition. The recycled polyethylene composition can comprise less than 22 wt.% polypropylene, less than 20 wt.% polypropylene, or less than 18 wt.% polypropylene (from homo-polypropylene), or from 5 to 30 wt.% or from 5 to 25 wt.% of polypropylene, based on the total weight of the recycled polyethylene composition. In some embodiments, the recycled polyethylene composition comprises less than 2 wt.% or less than 1 wt.% propylene (from ethylene / propylene copolymer), based on the total weight of the recycled polyethylene composition. The recycled polyethylene composition can comprise at least 65 wt.%, at least 70 wt.%, at least 75 wt.%, at least 80 wt.% ofpolyethylene (from ethylene / butene and ethylene / hexene). Weight percents of polypropylene, propylene, and polyethylene can be measured by the NMR test methods below.Polyethylene Composition

[0028] The polyethylene composition can have a density in a range of from 0.945 to 0.965 g / cm3, or 0.950 to 0.960 g / cm3, or 0.950 to 0.957 g / cm3. The polyethylene composition can have a melt index (h) in a range of 5.0 to 25.0 g / 10 min or 5.0 to 20.0 g / 10 min. The Mw / Mn (Conv) can be in the range of 4.0 to 10.0, or 4.0 to 8.0.

[0029] The polyethylene composition according to embodiments disclosed herein can have desirable rheology, stiffness, hinge resistance, and mold shrinkage, such that the composition can be suitable for injection molding. The polyethylene composition can have a viscosity at 9,000 s-1 of less than 50 Pa.s, or less than 45 Pa.s, or less than 40 Pa.s. The polyethylene composition can have a viscosity at 5,000 s-1 of less than 60 Pa.s, less than 55 Pa.s, or less than 50 Pa.s. The polyethylene composition can have a viscosity at 1,000 s-1 of less than 165 Pa.s, less than 155 Pa.s, less than 150 Pa.s, or less than 145 Pa.s. The lower viscosity at higher shear rates can be advantageous for injection molded articles.

[0030] The polyethylene composition can have a tensile modulus sec. 2% of at least 120 MPa. The polyethylene composition can have a stress at break of at least 3,000 psi or 3,500 psi. The polyethylene composition can have a stress at yield of at least 2,000 psi, at least 2,200 psi, at least 2,400 psi, at least 2,600 psi, or at least 2,800 psi. The polyethylene composition can have a shrinkage in LD between 1.50% and 2.50% and can have a shrinkage in the TD between 0.75 and 1.50%. The polyethylene composition can have an isotropic index in a range of 1.00 to 2.20. When the polyethylene composition is formed into a hinged closure, the closure can have a cycle to failure of greater than 500 cycles, or greater than 750 cycles, or greater 900 cycles.

[0031] The polyethylene composition can be formed known methods such as melt blending of the HDPE and recycled polyethylene composition. The polyethylene composition can be fabricated to make molded articles after it is blended while still molten, such as by feeding from the extruder into an injection molding, blow-molding, or compression molding or other end use process. The polyethylene composition is particularly suitable for formed a closure with desirable properties. The polyethylene composition can be made into pellets or other intermediate form for convenient storage and shipping, such as by extruding, chopping, and cooling the composition.Shaped Articles and Their Production

[0032] The polyethylene compositions of this invention can be used in conventional fabrication processes to make shaped articles, such as injection molding, compression molding, and blow molding. Each of these processes is well-known and described in many publications, and equipment to practice it is commercially available.

[0033] An injection molding process generally comprises the steps of: (1) injecting the polyethylene composition according to embodiments disclosed herein into a mold; (2) cooling the polyethylene composition in the mold until solidified to form the molded article.

[0034] In a compression molding process, a two-piece mold provides a cavity having the shape of a desired molded article. The mold is heated, and an appropriate amount of polyethylene composition is loaded into the lower half of the mold. The two parts of the mold are brought together under pressure. The composition, softened by heat, is thereby welded into a continuous mass having the shape of the cavity. The continuous mass may be hardened via chilling under pressure in the mold and released from the mold.

[0035] In an extrusion blow molding process, the polyethylene composition is melted and extruded as a hollow tube, called a parison. The parison is enclosed in a cooled metal mold for a shaped article such as a bottle, container, or part. Air or a neutral gas such as nitrogen is then blown into the parison, inflating it into the shape of the mold. After the polyethylene composition has cooled sufficiently, the mold is opened, and the part is ejected.

[0036] In an injection blow molding process, the polyethylene composition is melted and injected into a metal mold for a shaped article such as a bottle, container, or part. Air or a neutral gas such as nitrogen is then blown into the mold, inflating the polyethylene composition into the shape of the mold. After the polyethylene composition has cooled sufficiently, the mold is opened, and the part is ejected.

[0037] In an injection stretch blow molding process, a preform of the polyethylene composition is made by injection molding. In some embodiments, the final neck features for the final molded item (such as threading on a bottle neck) are made on the preform. Next, the molten preform is placed in a mold. Air or a neutral gas such as nitrogen is then blown into the preform, inflating it into the shape of the mold. After the polyethylene composition has cooled sufficiently,the mold is opened, and the part is ejected. The preform may be blown immediately after it is formed, or it may be cooled and then reheated and blown later.

[0038] Each of these processes makes a molded or shaped article comprising the composition of the present invention. Shaped articles can come in a variety of shapes and sizes, from small articles such as pill bottles, to medium articles such as drink bottles, to large items such as outdoor furniture, trash cans and auto parts. In some embodiments, the polyethylene composition of the present invention may be the only polymer in an article. In some embodiments, the shaped article may contain layers or zones of different polymers to serve different purposes in the article. In some embodiments, the injection molded article is a closure for a container. In some embodiments, the injection molded article is a closure having a tethered portion connecting a cap to a retainer portion.

[0039] ASPECTSASPECT 1 - A polyethylene composition comprising:a high density polyethylene having a density from 0.940 to 0.955 g / cm3and a melt index (I2) of at least 20.0 g / 10 min; anda recycled polyethylene composition having a density of at least 0.925 g / cm3, a melt index (I2) of at least 0.2 g / 10 min, a Mz(Abs) of at least 1,500,000 g / mol, and a Mw(Abs) / Mw(Conv) > 1.20;andwherein the polyethylene composition comprises at least 20 wt.% of the recycled polyethylene composition, based on the total weight of the polyethylene composition.ASPECT 2 - The polyethylene composition of aspect 1, wherein the polyethylene composition has a viscosity at 9,000 s-1 of less than 50 Pa.s.ASPECT 3 - The polyethylene composition of any one of aspect 1 or 2, wherein the polyethylene composition has a viscosity at 5,000 s-1 of less than 60 Pa.s.ASPECT 4 - The polyethylene composition of any one of aspect 1 or 2 or 3, wherein the high density polyethylene has a molecular weight distribution (Mw / Mn) of less than 7.0, as measured by conventional GPC in the description.ASPECT 5 - The polyethylene composition of any one of aspect 1, 2, 3, or 4, wherein the polyethylene composition has a viscosity at 1,000 s-1 of less than 165 Pa.s.APSECT 6 - The polyethylene composition of any one of aspect 1, 2, 3, 4, or 5, wherein the recycled polyethylene composition comprises less than 30 wt.% polypropylene.ASPECT 7 - The polyethylene composition of any one of aspect 1, 2, 3, 4, 5, or 6, wherein the recycled polyethylene composition has a Mw(Abs) greater than 150,000 g / mol.ASPECT 8 - The polyethylene composition of any one of aspect 1, 2, 3, 4, 5, 6, or 7, wherein the polyethylene composition comprises from 40 to 80 wt.% of the high density polyethylene, and from 20 to 60 wt.% of the recycled polyethylene composition, where weight percent (wt.%) is based on the total weight of the polyethylene composition.ASPECT 9 - The polyethylene composition of any one of aspect 1, 2, 3, 4, 5, 6, 7, or 8, wherein the high density polyethylene is a gas-phase Ziegler-Natta HDPE.ASPECT 10 - The polyethylene composition of any one of aspect 1, 2, 3, 4, 5, 6, 7, 8, or 9, wherein the polyethylene composition has a tensile modulus sec. 2% of at least 120 MPa.ASPECT 11 - The polyethylene composition of any one of aspect 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, wherein when the polyethylene composition is formed into a closure, the closure has a cycle to failure of greater than 500 cycles.ASPECT 12 - The polyethylene composition of any one of aspect 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11, wherein the recycled polyethylene composition is a pre-consumer / post-industrial recycled polyethylene composition.ASPECT 13 - An injection molded article formed from the composition of any of aspect 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11.ASPECT 14 - The injection molded article of aspect 13, wherein the article is a closure.ASPECT 15 - The injection molded article of aspect 13, wherein the article is a closure having a tethered portion.

[0040] Test MethodsParameters described in this application can be measured using the following measurements:Parameter TestMeasurements are made within one hour of sample pressing and in accordance with ASTM D792, Density Method B. Values are reported in grams per cubic centimeter (g / cc). Samples are prepared according to ASTM D4703 Annex A.1 Procedure C (controlled cooling at 15°C / min).ASTM D1238, Procedure B, Condition 190°C. Measured with 2.16 kg weight (I₂), 10 kg (I₁₀), or Melt Index21.6 kg (I₂₁). Values are reported in decigram / minute (dg / min) or grams / 10 minute (g / 10 min). Molecular Weight and MolecularWeight Distribution See below for Conventional and Absolute GPC test measurementsTensile properties are measured according to ASTM D638 employing Type IV Specimen with Tensile properties: Breaking 0.0725” nominal thickness. The measurement is conducted at a strain rate of either 2 inch / minute (50 Stress, Breaking Strain, Yield mm / minute) or 20 in / minute (500 mm / minute). The samples used for tensile property measurement is Stress, Yield Strain molded according to ASTM D4706 Annex A.1 Procedure C (controlled cooling at 15°C / min). The measurement requires at least 5 replicates.Capillary Rheometry Carried out at 190°C, with corrected shear rates ranging from 200 s-1 up to 15,000 s-1Carried out using an in-house automated test equipment that acquires the number of cycles to failure Hinge cycle test at the hinge area of each individual sample. Cycle tests were performed at frequency of 1 complete (open-close) hinge cycle / second.ISO 294-4: 2018; using standard test specimen Type D2 (60 mm x 60 mm x 2 mm), measured after Mold Shrinkage48 hours.Standard hinged caps were molded in a 110-ton press equipped with a 32 mm diameter single-screw Injection molding plasticator and L / D ratio of 20: 1.Measures composition of PCR (post-consumer recycled material) through a method comprising three steps: (i) Sample Preparation, (ii) Data Acquisition and (iii) Data Analysis.Sample Preparation: The sample was prepared by adding approximately 2.84g of 75:25 mixture of proteo & deutero tetrachloroethane containing 0.025 M Cr (AcAc)3 to 0.1g sample in a Norell 1001-7 10mm NMR tube. Oxygen was removed by manually purging tubes with nitrogen using a Pasteur pipette for 30s. The sample was dissolved and homogenized by heating the tube and its contents to ~135°C using a heating block with minimal use of heat gun. Each sample was visually inspected to ensure homogeneity. Sample was thoroughly mixed immediately prior to analysis, and not allowed to cool before insertion into the heated NMR probe. This is necessary to ensure the sample is homogeneous and representative of the whole.NMR Data Acquisition Parameters: The data were collected using a Bruker 600 MHz spectrometer equipped with a Bruker cryoprobe. The data were acquired using 1280 transients a 6 sec pulse repetition delay with a sample temperature of 120°C. All measurements were made on non-spinning sample in locked mode. Sample was allowed to thermally equilibrate for 7 minutes prior to data acquisition. The 13C NMR chemical shifts were internally referenced to the EEE triad at 30 ppm. Data Analysis: The whole spectrum was normalized to 1000 carbons. Moles of butene, hexene and propylene were measured using resonances unique for C2, C4 and Cl branches respectively. Relative mass was calculated using MW for each comonomer. The rest of the contribution was attributed to ethylene. Wt% of each comonomer is expressed as a percentage of total polymer sample weight. All wt% values are on the basis of polymer weight and do not account for any insoluble material, if present. Chemical shifts documented in NMR spectra of polymers and polymer additives by AnitaBrandolini were utilized as a reference to look for PET.

[0041] Gel Permeation Chromatography (GPC)

[0042] The chromatographic system consisted of a PolymerChar GPC-IR (Valencia, Spain) 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 was set at 160° Celsius and the column and detector compartment were set at 150° Celsius. The columns used were 4 Agilent “Mixed A” 30cm 20-micron linear mixed-bed columns. The chromatographic solvent used was 1,2,4 trichlorobenzene and contained 200 ppm of butylated hydroxytoluene (BHT). The solvent source was nitrogen sparged. The injection volume used was 200 microliters and the flow rate was 1.0 milliliters / minute.

[0043] Calibration of the GPC column set was performed with 21 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000 and were arranged in 6 “cocktail” mixtures with at least a decade of separation between individual molecular weights. The standards were purchased from Agilent Technologies. The polystyrene standards were prepared at 0.025 grams in 50 milliliters of solvent for molecular weights equal to or greater than 1,000,000, and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000. The polystyrene standards were pre-dissolved at 80 °C with gentle agitation for 30 minutes then cooled and the room temperature solution is transferred cooled into the autosampler dissolution oven at 160°C for 30 minutes. The polystyrene standard peak molecular weights were converted to polyethylene molecular weights using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)).:^polyethylene = A × (M_polystyrene)^B (EQ1)

[0044] where M is the molecular weight, A has a value of 0.405 and B is equal to 1.0.

[0045] A fifth order polynomial was used to fit the respective polyethylene-equivalent calibration points.

[0046] In order to monitor the deviations over time, a flowrate marker (n-decane) was introduced into each sample via a micropump controlled with the PolymerChar GPC-IR system. This flowrate marker (FM) was used to linearly correct the pump flowrate (Flowrate(nominal)) foreach sample by retention volume (RV) alignment of the respective n-decane peak within the sample (RV(FM Sample)) to that of the n-decane peak within the narrow standards calibration (RV(FM Calibrated)). Any changes in the time of the n-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 Equation 2. Processing of the flow marker peak was done via the PolymerChar GPCOne™ Software. Acceptable flowrate correction is such that the effective flowrate should be within + / -0.5% of the nominal flowrate.

[0047] Flowrate(effective) = Flowrate(nominal) * (RV(FM Calibrated) / RV(FM Sample))(EQ2)

[0048] The total plate count of the GPC column set was performed with n-decane which was introduced into blank sample via a micropump controlled with the PolymerChar GPC-IR system. The 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.

[0049] Samples were prepared in a semi-automatic manner with the PolymerChar “Instrument Control” Software, wherein the samples were weight-targeted at 2 mg / ml, and the solvent (contained 200ppm BHT) was added to a pre nitrogen-sparged septa-capped vial, via the PolymerChar high temperature autosampler. The samples were dissolved for 3 hours at 160° Celsius under “low speed” shaking.

[0050] The calculations of Mn(GPC), MW(GPC), and MZ(GPC) were based on GPC results using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph according to Equations 3-5, using PolymerChar GPCOne™ software, the baseline-subtracted IR chromatogram at each equally-spaced data collection point (i), and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve for the point (i) from Equation 1. The baseline was drawn using PolymerChar GPCOne™ software in a straight line from a point just prior to sample retention volume to a point after sample retention volume but before the n-decane peak, where this point is located at minimum IR5 detector measurement channel signal value. The two integration limits to bound the baseline-subtracted chromatogram are located at, 1) the intercept of the baseline with the IR5 detector measurement channel signal prior to peak retention volume and at, 2) the retention volume point that corresponds to a value,according to ASTM-D6474-99, of PE equivalent MW of 500 g / mol determined from Equation 1 using the polystyrene narrow standard molecular weight calibration curve.Mn(Conv) =v(EQ 3)y / ^polyethylene^ J IX l?(jRi*Mpolyethylene^..Mw(Conv) = — * - —; - (EQ 4)X y.l(jRi*Mpolyethylene{Z)Mz(Conv) = —7 - (EQ 5)Ri*^polyethylene 0

[0051] Triple Detector GPC (TDGPC)

[0052] For the determination of the viscometer and light scattering detector offsets from the IR5 detector, the Systematic Approach for the determination of multi-detector offsets is done 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.

[0053] The absolute molecular weight data was 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, was 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 known weight-average molecular weight. The calculated molecular weights (using GPCOne™) were 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 thepublished values of suitable linear standards, such as Standard Reference Materials (SRM) 1475a (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).

[0054] 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 be calculated according to equations 8-10 as follows:Mn(Abs) = — IRi / / M Absolute!Mw(Abs) = (EQ 9)Mz(Abs) = (EQ io)Yl^^i*^Absolutei)EXAMPLES

[0055] Materials:

[0056] HDPE 1 - A unimodal, gas phase, Ziegler-Natta resin, having approximately 1.8% wt. of comonomer hexene, density specification 0.951 g / cm3, melt index (190°C / 2.16 kg) specification 40.0 to 48.0 g / 10 min. Molecular characteristics as measured through Conventional GPC are: Mn = 11,332 g / mol, Mw = 46,689 g / mol, Mz = 205,734 g / mol and Mw / Mn = 4.12. Absolute GPC: Mn = 11,147 g / mol, Mw = 60,725 g / mol, Mz = 2,189,360 g / mol, Mw / Mn = 5.45 and Mw(Abs) / Mw(Conv) = 1.30.

[0057] HDPE 2 - A bimodal, gas phase, Ziegler-Natta resin, having approximately 1.7% wt. of comonomer hexene, density specification 0.955g / cm3, melt index (190°C / 2.16 kg) specification 1.20 to 1.80 g / 10 min. Molecular characteristics as measured through Conventional GPC are: Mn = 11,346 g / mol, Mw = 123,599 g / mol, Mz = 728,318 g / mol and Mw / Mn = 10.89. Absolute GPC: Mn = 11,338 g / mol, Mw = 138,332 g / mol, Mz = 1,028,636 g / mol, Mw / Mn = 12.20 and Mw(Abs) / Mw(Conv) = 1.12.

[0058] HDPE 3 - A unimodal, gas phase, Ziegler-Natta resin, having approximately 1.7% wt. of comonomer hexene, density specification 0.952g / cm3, melt index (190°C / 2.16 kg) specification 13.0 to 17.0 g / 10 min. Molecular characteristics as measured through Conventional GPC are: Mn = 11,746 g / mol, Mw = 92,720 g / mol, Mz = 3,002,154 g / mol and Mw / Mn = 7.89. Absolute GPC: Mn = 10,736 g / mol, Mw = 92,063 g / mol, Mz = 2,134,592 g / mol, Mw / Mn = 8.58 and Mw(Abs) / Mw(Conv) = 0.99.

[0059] HDPE 4 - A unimodal, solution, Ziegler-Natta resin, having approximately 2.0% wt. of comonomer octene, density specification 0.950g / cm3, melt index (190°C / 2.16 kg) specification 14.0 to 20.0 g / 10 min. Molecular characteristics as measured through Conventional GPC are: Mn = 16,254 g / mol, Mw = 57,115 g / mol, Mz = 209,400 g / mol and Mw / Mn = 3.51. Absolute GPC: Mn = 17,604 g / mol, Mw = 58,723 g / mol, Mz = 278,497 g / mol, Mw / Mn = 3.34 and Mw(Abs) / Mw(Conv) = 1.03.

[0060] PCR 1 - Post consumer recycled resin, sourced from a blow molding HDPE stream, with density specification 0.955 to 0.963 g / cm3, melt index (190°C / 2.16 kg) specification 0.20 to 0.50 g / 10 min. Molecular characteristics are noted in table below.

[0061] PCR 2 - Post consumer recycled resin, sourced from HDPE beverage caps stream, with density specification 0.930 to 0.950 g / cm3, melt index (190°C / 2.16 kg) specification 1.0 to 3.0 g / 10 min. Molecular characteristics as measured through Conventional GPC are noted in the table below. Contains about 15.1 wt.% of polypropylene (from homopolymer), 0.1 wt.% of propylene (from ethylene / propylene copolymer), and 87.3 wt.% polyethylene (from ethylene / butene and ethylene / hexene).

[0062] Table 1 below provide the GPC measurements of Conventional and Absolute for the compositions.Table 1 - Conventional and Absolute GPC MeasurementsConventional GPC Absolute GPCMw(Abs) Identification Mn Mw Mz Mw / Mn Mn Mw Mz Mw / Mn / Mw(GPC) HDPE 1 11,332 46,689 205,734 4.12 11,147 60,725 2,189,360 5.45 1.30 HDPE 2 11,346 123,599 728,319 10.89 11,338 138,332 1,028,636 12.20 1.12 HDPE 3 11,746 92,720 3,002,154 7.89 10,736 92,063 2,134,592 8.58 0.99 HDPE 4 16,254 57,115 209,400 3.51 17,604 58,723 278,497 3.34 1.03 PCR 1 > 10.0 > 11.0 > 1.2011,000 140,000 1,500,000 12,500 180,000 1,500,000PCR2 14,303 127,340 777,560 8.90 16,227 184,961 1,848,437 9.99 1.45

[0063] Blend formulations of HDPE / PCR were prepared through melt mixing in a Haake Polylab OS Single Screw Mixer / Extrusion, Rheomex 19 / 25 OS model, with a screw diameter of 19 mm and L / D ratio of 25. Extrusion parameters: Barrel temperature = 190°C, die temperature = 190°C, screw speed = 80 rpm. Inventive and comparative polyethylene compositions and their properties are listed below in Tables 2 and 3.Table 2 - Inventive CompositionsHOPE 1 / PCR 1 HOPE 1 / PCR 1 HOPE 1 / PCR 2 (75 / 25) (60 / 40) (60 / 40)IE#1 IE#2 IE#3Density (g / cc) 0.955 0.955 0.952Melt Flow Rate 15.2 7.5 13.8Mn(Conv) (g / mol) 11,350 11,566 12,641 Mw(Conv) (g / mol) 74,237 89,921 76,067Mz(Conv) (g / mol) 659,977 837,852 487,582Mw / Mn (Conv) 6.54 7.77 6.02Mn(Abs) (g / mol) 12,778 13,232 14,308Mw(Abs) (g / mol) 106,811 126,109 109,944Mz(Abs) (g / mol) 1,977,074 1,938,121 2,028,079Mw / Mn (Abs) 8.36 9.53 7.68 Mw(Abs) / Mw(Conv) 1.44 1.38 1.45Viscosity at 300 s-1 (Pa.s) 233 294 238Viscosity at 1,000 s-1 (Pa.s) 120 138 116Viscosity at 5,000 s-1 (Pa.s) 53 57 47Viscosity at 9,000 s-1 (Pa.s) 39 42 35Stress at Break (50 mm / min) (psi) 3562 + / - 98 3556 + / - 118 3500 + / - 194Stress at Yield (50 mm / min) (psi) 3566 + / - 102 3262 + / - 275 2946 + / - 109 Tensile Modulus Sec.2% (50 mm / min) (ksi) 122.7 + / - 9.5 120.7 + / - 2.2 122.7 + / - 9.5 Shrinkage in LD (%) 1.95 2.24 1.88 Shrinkage in TD (%) 1.22 1.08 1.03 Isotropic Index (Ratio LD / TD) 1.59 2.07 1.83Hinge cycles to failure 584 + / - 39 >1000 >1000Table 3 Comparative CompositionsHOPE 3 / HOPE 3 / HOPE 3 / HOPE 3 / HOPE 3 / HOPE 3 / HOPE 4 / HOPE 4 / HOPE 4 / HOPE 1 HOPE 2 HOPE 3 PCR 1 PCR 1 PCR 1 PCR 2 PCR 2 PCR 2 HOPE 4 PCR 1 PCR 1 PCR 1 (90 / 10) (70 / 30) (50 / 50) (90 / 10) (70 / 30) (50 / 50) (90 / 10) (70 / 30) (50 / 50) CE#1 CE#2 CE#3 CE#4 CE#5 CE#6 CE#7 CE#8 CE#9 CE#10 CE#11 CE#12 CE#13 Density (g / cc) 0.953 0.952 0.951 0.953 0.954 0.958 0.953 0.952 0.951 0.951 0.952 0.953 0.957 Melt Flow Rate(190°C / 2.16 kg) (g / 10 40.2 1.6 14.2 10.7 2.5 2.4 12.0 8.1 5.5 10.0 11.5 12.0 2.7 min)Mn(Conv) (g / mol) 11,332 11,346 11,746 11,942 12,244 13,032 11,987 12,482 13,241 16,254 16,186 15,896 15,661 Mw(Conv) (g / mol) 46,689 123,599 92,720 98,082 114,061 129,791 96,452 103,067 110,186 57,115 68,871 88,422 114,885 Mz(Conv) (g / mol) 205,734 728,319 3,002,154 2,498,112 2,035,467 1,933,947 2,683,962 2,179,585 1,477,761 209,400 439,277 731,739 1,067,879 Mw / Mn (Conv) 4.12 10.89 7.89 8.21 9.32 9.96 8.05 8.26 8.32 3.51 4.25 5.56 7.34 Mn(Abs) (g / mol) 11,147 11,338 10,736 10,777 12,463 14,367 11,641 12,840 13,273 17,604 17,403 14,144 16,201 Mw(Abs) (g / mol) 60,725 138,332 92,063 105,740 132,232 158,126 104,957 118,986 135,022 58,723 79,058 108,463 143,800 Mz(Abs) (g / mol) 2,189,360 1,028,636 2,134,592 2,394,455 2,295,270 2,409,139 2,407,547 2,346,984 1,942,513 278,497 917,093 1,557,265 1,913,038 Mw / Mn (Abs) 5.45 12.20 8.58 9.81 10.61 11.01 9.02 9.27 10.17 3.34 4.54 7.67 8.88 Mw(Abs) / Mw(Conv) 1.30 1.12 0.99 1.08 1.16 1.22 1.09 1.15 1.23 1.03 1.15 1.23 1.25 Viscosity at 300 s-1 153 415 232 257 318 393 243 275 316 259 284 348 420 (Pa.s)Viscosity at 1,000 s-191 153 123 130 149 167 124 132 145 140 147 164 183 (Pa.s)Viscosity at 5,000 s-1 44 53 56 57 62 64 55 57 61 57 60 67 70 (Pa.s)Viscosity at 9,000 s-133 37 43 42 47 47 42 43 46 41 44 49 50 (Pa.s)Stress at Break (503720+ / - 75 3334 + / - 520 2880+ / - 891 3516 + / - 68 2206+ / - 690 2740 + / - 791 3210 + / - 889 2824 + / - 861 3452 + / - 144 2852 + / - 874 2516 + / - 860 2424 + / - 732 2476 + / - 671 mm / min) (psi)Stress at Yield (503638 + / - 254 3562 + / - 88 3572 + / - 158 3554 + / - 184mm / min) (psi) 3174+ / - 96 3708 + / - 131 3128 + / - 307 3504+ / - 157 3516 + / - 223 3508 + / - 149 3166 + / - 243 3470+ / - 207 3496 + / - 71 Tensile ModulusSec.2% (50 mm / min) 127.4 + / - 4.3 128.3 + / - 7.9 121.5 + / - 3.9 122.8 + / - 6.9 114.4 + / _ 4.3 116.9 + / - 3.5 123.9+ / - 5.3 120.6 + / - 1.8 124.0 + / - 3.6 110.2 + / - 7.1 116.5 + / - 2.9 110.5 + / - 8.7 110.4 + / - 2.4 (ksi)Shrinkage in LD (%) 1.92 3.50 2.19 2.18 2.73 2.92 2.32 2.45 2.34 2.26 2.71 3.03 Shrinkage in TD (%) 1.52 1.21 1.55 1.31 1.06 0.86 ----- 1.19 1.04 1.62 1.39 1.07 0.89 Isotropic Index (Ratio 1.42 1.94 1.44 2.54 3.42 LD / TD) 1.26 2.89 1.66 2.57 3.38 2.35 1.63Hinge cycles to failure 221 + / - 77 >1000 442 + / - 66 887+ / - 109 >1000 >1000 834 + / - 49 >1000 >1000 421 + / - 19 522 + / - 74 >1000 >1000

Claims

CLAIMSWe claim:

1. A polyethylene composition comprising:a high density polyethylene having a density from 0.940 to 0.955 g / cm3and a melt index (E) of at least 20.0 g / 10 min; anda recycled polyethylene composition having a density of at least 0.925 g / cm3, a melt index (I2) of at least 0.2 g / 10 min, a Mz(Abs) of at least 1,500,000 g / mol, and a Mw(Abs) / Mw(Conv) > 1.20;andwherein the polyethylene composition comprises at least 20 wt.% of the recycled polyethylene composition, based on the total weight of the polyethylene composition.

2. The polyethylene composition of any one of the preceding claim, wherein the polyethylene composition has a viscosity at 9,000 s-1 of less than 50 Pa.s.

3. The polyethylene composition of any one of the preceding claim, wherein the polyethylene composition has a viscosity at 5,000 s-1 of less than 60 Pa.s.

4. The polyethylene composition of any one of the preceding claims, wherein the high density polyethylene has a molecular weight distribution (Mw / Mn) of less than 7.0, as measured by conventional GPC in the description.

5. The polyethylene composition of any one of the preceding claims, wherein the polyethylene composition has a viscosity at 1,000 s-1 of less than 165 Pa.s.

6. The polyethylene composition of any one of the preceding claims, wherein the recycled polyethylene composition comprises less than 30 wt.% polypropylene.

7. The polyethylene composition of any one of the preceding claims, wherein the recycled polyethylene composition has a Mw(Abs) greater than 150,000 g / mol.

8. The polyethylene composition of any one of the preceding claims, wherein the polyethylene composition comprises from 40 to 80 wt.% of the high density polyethylene, and from 20 to 60 wt.% of the recycled polyethylene composition, where weight percent (wt.%) is based on the total weight of the polyethylene composition.

9. The polyethylene composition of any one of the preceding claims, wherein the high density polyethylene is a gas-phase Ziegler-Natta HDPE.

10. The polyethylene composition of any preceding claim, wherein the polyethylene composition has a tensile modulus sec. 2% of at least 120 MPa.

11. The polyethylene composition of any one of the preceding claims, wherein when the polyethylene composition is formed into a closure, the closure has a cycle to failure of greater than 500 cycles.

12. The polyethylene composition of any one of the preceding claims, wherein the recycled polyethylene composition is a pre-consumer / post-industrial recycled polyethylene composition.

13. An injection molded article formed from the polyethylene composition of any preceding claim.

14. The injection molded article of claim 13, wherein the article is a closure.

15. The injection molded article of claim 13, wherein the article is a closure having a tethered portion.

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