Stretch films with post consumer resins

Abstract

According to one or more embodiments, a multilayer film may comprise two skin layers and one or more internal layers disposed between the skin layers. At least one of the one or more internal layers may comprise a polymer blend having a density from 0.910 g / cc to 0.935 g / cc. The polymer blend may comprise from 10 wt. % to 90 wt. % visbroken polyethylene post-consumer resin (PCR) and from 10 wt. % to 90 wt. % of virgin ethylene based polymer. The visbroken polyethylene PCR may have a density of 0.910 g / cc to 0.965 g / cc and a melt index (I2) from 1.5 dg / min to 9.0 dg / min.

Description

STRETCH FILMS WITH POST CONSUMER RESINSCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of, and priority to, U.S. Provisional Application No. 63 / 579105, filed August 28 2023, and U.S. Provisional Application No. 63 / 579167, filed August 28 2023, the entirety of which are incorporated herein by reference.BACKGROUND

[0002] Recycling of plastic waste is one of the most important sustainability issues of our time. Stretch films (e.g., cast stretch films) are an important application for recycled plastic, such as post-consumer resins (PCR). However, incorporation of present PCRs into stretch films is challenging as PCR based films have much higher gels and significantly reduce the mechanical properties (e.g., tear, stretch, puncture, etc.) of the film. This reduction in film mechanical properties can cause breakage of machine wrap films while wrapping the film around the pallet, resulting in substantial increases in operational expenses and user frustration.

[0003] Accordingly, multilayer film compositions suitable for use in stretch films and comprising substantial quantities of PCR while retaining mechanical properties are desired.BRIEF SUMMARY

[0004] Embodiments of the present disclosure meet this need by providing a multilayer film which utilizes visbroken polyethylene PCR. In embodiments, the visbroken polyethylene PCR is blended with virgin ethylene based polymers to achieve desirable blend properties.

[0005] According to one or more embodiments, a multilayer film may comprise two skin layers and one or more internal layers disposed between the skin layers. At least one of the one or more internal layers may comprise a polymer blend having a density from 0.910 g / cc to 0.935 g / cc. The polymer blend may comprise from 10 wt. % to 90 wt. % of visbroken polyethylene post-consumer resin (PCR) and from 10 wt. % to 90 wt. % of virgin ethylenebased polymer. The visbroken polyethylene PCR may have a density of 0.910 g / cc to 0.965 g / cc and a melt index (I2) from 1.5 dg / min to 9.0 dg / min.

[0006] These and other embodiments are described in more detail in the Detailed Description. It is to be understood that both the foregoing general description and the following detailed description present embodiments of the presently disclosed technology, and are intended to provide an overview or framework for understanding the nature and character of the technology as it is claimed. The accompanying drawings are included to provide a further understanding of the presently disclosed technology and are incorporated into and constitute a part of this specification. The drawings illustrate various embodiments and, together with the description, serve to explain the principles and operations of the presently disclosed technology. Additionally, the drawings and descriptions are meant to be merely illustrative, and are not intended to limit the scope of the claims in any manner.BRIEF DESCRIPTION OF THE DRAWINGS

[0007] The following detailed description of specific embodiments of the present disclosure can be best understood when read in conjunction with the following drawings, where like structure is indicated with like reference numerals and in which:

[0008] FIG. 1 depicts a cross section of a multilayer film, according to one or more embodiments described in this disclosure.

[0009] Reference will now be made in greater detail to various embodiments, some embodiments of which are illustrated in the accompanying drawings..DETAILED DESCRIPTION

[0010] "Polymer" refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type. The term polymer thus embraces the term homopolymer (employed to refer to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities can be incorporated into the polymer structure), 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 or a polymer blend.

[0011] “Copolymer” refers to a polymer formed by the polymerization reaction of at least two structurally different monomers. The term “copolymer” is inclusive of terpolymers. For example, ethylene copolymers, such as ethylene-propylene copolymers, include at least two structurally different monomers (e.g., ethylene-propylene copolymer includes copolymerized units of at least ethylene monomer and propylene monomer) and can optionally include additional monomers or functional materials or modifiers, such as acid, acrylate, or anhydride functional groups. Put another way, the copolymers described herein comprise at least two structurally different monomers, and although the copolymers may consist of only two structurally different monomers, they do not necessarily consist of only two structurally different monomers and may include additional monomers or functional materials or modifiers.

[0012] "Ethylene-based polymer" (also referred to herein as “polyethylene” or "polyethylene-based polymers”) refers to polymers comprising greater than 50% by weight of units, which have been derived from ethylene monomer. This includes 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).

[0013] The term “LLDPE” includes resins made using the traditional Ziegler-Natta catalyst systems as well as single-site catalysts such as metallocenes (sometimes referred to as “m- LLDPE”). LLDPEs contain less long chain branching than LDPEs and include the substantially linear ethylene polymers, which are further defined in U.S. Pat. No. 5,272,236, U.S. Pat. No. 5,278,272, U.S. Pat. No. 5,582,923 and U.S. Pat. No. 5,733,155; the homogeneously branched linear ethylene polymer compositions such as those in U.S. Pat. No. 3,645,992; the heterogeneously branched ethylene polymers such as those prepared according to the process disclosed in U.S. Pat. No. 4,076,698; and / or blends thereof (such as those disclosed in U.S. Pat. No. 3,914,342 or U.S. Pat. No. 5,854,045). The LLDPE can be made via gas-phase, solution-phase or slurry polymerization or any combination thereof,using any type of reactor or reactor configuration known in the art, including, but not limited to, gas and solution phase reactors.

[0014] “HDPE” generally refers to polyethylenes having densities greater than about 0.930 g / cm3and up to about 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).

[0015] The term “polypropylene,” as used herein, refers to a polymer that comprises, in polymerized form, greater than 50% by mole of units, which have been derived from propylene monomer. This includes propylene homopolymer, random copolymer polypropylene, impact copolymer polypropylene, propylene / a-olefin copolymer, and propylene / a-olefin copolymer.

[0016] “Recycled resins” refers to resins, which were incorporated into products and subsequently re-melted to form a recycled resin. The term “recycled resins” refers to mechanically recycled resins, where the resin is melted and reincorporated into a new product. “Recycled resins” does not include chemically recycled resins, where the polymer is broken down into constituent monomers and incorporated into a new virgin polymer. The term “recycled resins” embraces both pre-consumer recycled polymer and post-consumer resin. Recycled resins are defined in ISO 14021 7.8.1.1.

[0017] The terms “pre-consumer recycled polymer” and “post-industrial recycled polymer” refer to polymers, including blends of polymers, recovered from pre-consumer material, as defined by ISO- 14021. The generic term pre-consumer recycled polymer thus includes blends of polymers recovered from materials diverted from the waste stream during a manufacturing process. The generic term pre-consumer recycled polymer excludes the reutilization of materials, such as rework, regrind, or scrap, generated in a process and capable of being reclaimed within the same process that generated it. Pre-consumer recycled polymer is defined in ISO 14021 7.8.1.1.

[0018] The term “post-consumer resin” (or “PCR”), as used herein, refers to a polymeric material that includes materials previously used in a consumer or industry application (i.e., pre-consumer recycled polymer and post-industrial recycled polymer). PCR is typically collected from recycling programs and recycling plants. The PCR may include one or more of an ethylene-based polymer, such as LDPE, LLDPE, HDPE, a polyethylene, a polypropylene, a polyester, a poly(vinyl chloride), a polystyrene, an acrylonitrile butadiene styrene, a polyamide, an ethylene vinyl alcohol, an ethylene vinyl acetate, or a poly-vinyl chloride. The PCR may include one or more contaminants. The contaminants may be the result of the polymeric material’s use prior to being repurposed for reuse. For example, contaminants may include paper, ink, food residue, or other recycled materials in addition to the polymer, which may result from the recycling process. PCR is distinct from virgin polymeric material. A virgin polymeric material (such as a virgin polyethylene resin) does not include materials previously used in a consumer or industry application. Virgin polymeric material has not undergone, or otherwise has not been subject to, a heat process or a molding process, after the initial polymer manufacturing process. The physical, chemical, and flow properties of PCR resins differ when compared to virgin polymeric resin, which in turn can present challenges to incorporating PCR into formulations for commercial use. Postconsumer resin is defined in ISO 14021 7.8.1.1.

[0019] As used herein, the term “devolatilization” refers to a process by which undesired volatile contaminants (e.g., dissolved gasses, solvent, unreacted monomer, etc.) are removed from a polymer melt or solution.

[0020] Referring now to FIG. 1, a multilayer film 100 may comprise two skin layers 102 and one or more internal layers 104 disposed between the two skin layers 102. In some embodiments, the one or more internal layers 104 may comprise a core layer 106 disposed between two subskin layers 108. In some embodiments not depicted herein, more than two subskin layers 108 may be present.

[0021] At least one of the one or more internal layers 104 may comprise a polymer blend, further comprising a visbroken polyethylene PCR and a virgin ethylene based polymer, as described herein. In embodiments, the core layer 106, at least one of the subskin layers 108, or both comprises visbroken polyethylene PCR or the polymer blend. In specificembodiments, one or both of the subskin layers 108 may comprise the polymer blend. In embodiments, one or more of the internal layers 104 may independently comprise at least 50 wt. %, at least 60 wt. %, at least 70 wt. %, at least 80 wt. %, at least 90 wt. %, at least 95 wt. %, or even at least 99 wt. % of the polymer blend, on the basis of the total weight of that layer.

[0022] The polymer blend may comprise from 10 wt. % to 90 wt. % of a polyethylene postconsumer resin (PCR), such as from 10 wt. % to 20 wt. %, from 20 wt. % to 30 wt. %, from 30 wt. % to 40 wt. %, from 40 wt. % to 50 wt. %, from 50 wt. % to 60 wt. %, from 60 wt. % to 70 wt. %, from 70 wt. % to 80 wt. %, from 80 wt. % to 90 wt. %, from 10 wt. % to 50 wt. %, or any combination of two or more of these ranges of the polyethylene PCR, on the basis of the total weight of the polymer blend. In embodiments, the polymer blend may comprise from 10 wt. % to 90 wt.% of a virgin ethylene based polymer, such as from 10 wt. % to 20 wt. %, from 20 wt. % to 30 wt. %, from 30 wt. % to 40 wt. %, from 40 wt. % to 50 wt. %, from 50 wt. % to 60 wt. %, from 60 wt. % to 70 wt. %, from 70 wt. % to 80 wt. %, from 80 wt. % to 90 wt. %, or any combination of two or more of these ranges of the virgin ethylene based polymer, on the basis of the total weight of the polymer blend.

[0023] In embodiments, the polymer blend may have a density of from 0.910 g / cc to 0.935 g / cc, such as from 0.910 g / cc to 0.915 g / cc, from 0.915 g / cc to 0.920 g / cc, from 0.920 g / cc to 0.925 g / cc, from 0.925 g / cc to 0.930 g / cc, from 0.930 g / cc to 0.935 g / cc, or any combination of two or more of these ranges.

[0024] In embodiments, the polymer blend may have a melt index (I2) of from 2.0 dg / min to 9.0 dg / min, such as from 2.0 dg / min to 2.5 dg / min, from 2.5 dg / min to 3.0 dg / min, from 3.0 dg / min to 3.5 dg / min, from 3.5 dg / min to 4.0 dg / min, from 4.0 dg / min to 4.5 dg / min, from4.5 dg / min to 5.0 dg / min, from 5.0 dg / min to 5.5 dg / min, from 5.5 dg / min to 6.0 dg / min, from6.0 dg / min to 6.5 dg / min, from 6.5 dg / min to 7.0 dg / min, from 7.0 dg / min to 7.5 dg / min, from7.5 dg / min to 8.0 dg / min, from 8.0 dg / min to 8.5 dg / min, from 8.5 dg / min to 9.0 dg / min, or any combination of two or more of these ranges.

[0025] As described herein, the polymer blend may comprise a visbroken polyethylene postconsumer resin (PCR). The visbroken polyethylene PCR may be formed from a base PCRethylene-based polymer by an extrusion visbreaking process. Extrusion visbreaking is a thermal cracking process conducted in an extruder under shear to reduce the viscosity of a polymer resin. Visbreaking process may produce a visbroken polyethylene PCR having a greater melt index (I2) than the base PCR ethylene-based polymer. In embodiments, the visbroken polyethylene PCR may be formed from a base PCR ethylene based polymer comprising linear low density polyethylene, high density polyethylene, or both. In embodiments, the visbroken polyethylene PCR may comprise at least 75 wt. %, at least 90 wt. %, at least 95 wt. %, at least 99 wt. %, or at least 99.9 wt. % of material formed from visbreaking the base PCR ethylene based polymer.

[0026] In embodiments, the visbroken polyethylene PCR may have a density of from 0.910 g / cc to 0.965 g / cc, such as from 0.910 g / cc to 0.915 g / cc, from 0.915 g / cc to 0.920 g / cc, from 0.920 g / cc to 0.925 g / cc, from 0.925 g / cc to 0.930 g / cc, from 0.930 g / cc to 0.935 g / cc, from 0.935 g / cc to 0.940 g / cc, from 0.940 g / cc to 0.945 g / cc, from 0.945 g / cc to 0.950 g / cc, from 0.950 g / cc to 0.955 g / cc, from 0.955 g / cc to 0.960 g / cc, from 0.960 g / cc to 0.965 g / cc, or any combination of two or more of these ranges. In embodiments, the visbroken polyethylene PCR may have a density greater than 0.945 g / cc. Prior to visbreaking, the base PCR ethylene based polymer may have had density greater than 0.910 g / cc, such as greater than 0.950 g / cc or greater than 0.961 g / cc. Generally, it may be preferable to use relatively high density material as the base PCR ethylene based polymer since it has the potential to have a relatively low gel count.

[0027] In embodiments, the visbroken polyethylene PCR may have a molecular weight distribution (Mw / Mn) of 2.5 to 9, such as from 2.5 to 3.0, from 3.0 to 4.0, from 4.0 to 5.0, from 5.0 to 6.0, from 6.0 to 7.0, from 7.0 to 8.0, from 8.0 to 9.0, or any combination of two or more of these ranges. .

[0028] In embodiments, the visbroken polyethylene PCR may have an I2 of at least 2 times greater, such as at least 3 times greater, at least 4 times greater, at least 5 times greater, at least 7 at least 8 times greater, at least 10 times greater, at least 12.5 times greater, at least 15 times greater, at least 17.5 times greater, at least 20 times greater, from 3 times to 50 times greater, from 5 times greater to 50 times greater, from 7 times greater to 50 times greater, from 10 times greater to 50 times greater, from 15 times greater to 50 times greater, from 18times greater to 50 times greater, or any subset thereof greater than the I2 of the base PCR ethylene-based polymer resin. Prior to visbreaking, the polyethylene PCR may have an I2 less than 1.0 dg / min, such as less than 0.9 dg / min, less than 0.8 dg / min, less than 0.7 dg / min, less than 0.6 dg / min, less than 0.5 dg / min, or less than 0.4 dg / min. In embodiments, the visbroken polyethylene PCR may have a melt index (I2) from 1.5 dg / min to 6.0 dg / min, such as from1.5 dg / min to 2.0 dg / min, from 2.0 dg / min to 2.5 dg / min, from 2.5 dg / min to 3.0 dg / min, from 3.0 dg / min to 3.5 dg / min, from 3.5 dg / min to 4.0 dg / min, from 4.0 dg / min to 4.5 dg / min, from4.5 dg / min to 5.0 dg / min, from 5.0 dg / min to 5.5 dg / min, from 5.5 dg / min to 6.0 dg / min, or any combination of two or more of these ranges.

[0029] In embodiments, the visbroken polyethylene PCR has an r|o.i / r|ioo of from 2 to 20, such as from 2 to 3, from 3 to 5, from 5 to 7, from 7 to 9, from 9 to 11, from 11 to 13, from 13 to 15, from 15 to 17, from 17 to 19, from 19 to 20, or any combination of two or more of these ranges. o.i is the shear viscosity measured at 0.1 radians / second and rpoo is the shear viscosity measured at 100 radians / second.

[0030] Suitable visbroken PCR ethylene-based polymers, and their methods of making, are disclosed in U.S. Patent Appln. No. 63 / 579,105, the entirety of which is incorporated herein by reference.

[0031] The visbroken PCR ethylene-based polymer may be produced by extrusion visbreaking the base PCR ethylene-based polymer resin in an extruder. The extruder may be a tandem system, a single screw extruder, a twin screw extruder, or the like. The extruder may be equipped with multilayer annular dies, flat film dies and feedblocks, multi-layer feedblocks, multi -vaned or multi-manifold dies such as a 3 -layer vane die. In embodiments, the extrusion visbreaking utilizes a twin screw extruder. The base PCR ethylene-based polymer resin may comprise at least 80 wt. % of polymers introduced into the extruder, such as at least 90 wt. %, at least 95 wt. %, at least 99 wt. %, or even at least 99.9 wt. %, on the basis of the total polymer weight introduced into the extruder. The base PCR ethylene-based polymer resin may comprise at least 80 wt. % of the material introduced into the extruder, such as at least 90 wt. %, at least 95 wt. %, at least 99 wt. %, at least 99.9 wt. %, or even at least 99.99 wt. % of all material introduced into the extruder.

[0032] Without being limited by theory, the extrusion visbreaking process may introduce heat and mechanical energy (through the extruder) into the base PCR ethylene-based polymer resin. Generally, this energy may cause chain scission of the ethylene-based polymers in the base PCR ethylene-based polymer resin. It is believed that the chain scission may cause the melt index of the resin to increase and the molecular weights and Mw / Mn to decrease. The total mechanical energy input may be referred to as the specific energy input (SEI). SEI may be calculated from according to the equation SEI has unitsof kW-hr / kg.

[0033] The specific energy input (SEI) may be from 0.4 kW-hr / kg polymer to 2.0 kW-hr / kg polymer. Without being limited by theory, it is believed that an SEI below this range may not cause sufficient chain scission to sufficiently increase the melt indices of the base ethylenebased polymer. Conversely, an SEI above this range may cause excessive chain scission and damage the mechanical properties of the base ethylene-based polymer. In embodiments, the SEI may be from 0.4 kW-hr / kg polymer to 1.8 kW-hr / kg polymer, from 0.4 kW-hr / kg polymer to 1.6 kW-hr / kg polymer, from 0.4 kW-hr / kg polymer to 1.4 kW-hr / kg polymer, from 0.4 kW-hr / kg polymer to 1.2 kW-hr / kg polymer, from 0.4 kW-hr / kg polymer to 1.0 kW- hr / kg polymer, from 0.4 kW-hr / kg polymer to 0.8 kW-hr / kg polymer, from 0.4 kW-hr / kg polymer to 0.6 kW-hr / kg polymer, from 0.6 kW-hr / kg polymer to 2.0 kW-hr / kg polymer, from 0.8 kW-hr / kg polymer to 2.0 kW-hr / kg polymer, from 1.0 kW-hr / kg polymer to 2.0 kW- hr / kg polymer, from 1.2 kW-hr / kg polymer to 2.0 kW-hr / kg polymer, from 1.4 kW-hr / kg polymer to 2.0 kW-hr / kg polymer, from 1.6 kW-hr / kg polymer to 2.0 kW-hr / kg polymer, from 1.8 kW-hr / kg polymer to 2.0 kW-hr / kg polymer, from 0.6 kW-hr / kg polymer to 1.8 kW- hr / kg polymer, from 0.8 kW-hr / kg polymer to 1.6 kW-hr / kg polymer, from 1.0 kW-hr / kg polymer to 1.4 kW-hr / kg polymer, or any subset thereof.

[0034] The extrusion visbreaking may occur at a temperature of at least 250 °C. Without being limited by theory, it is believed that if the visbreaking temperature is too low, such as less than 250 °C or less than 290 °C, it may be difficult for the extruder motor to add enough energy to the resin to accomplish the visbreaking. In embodiments, the extrusion visbreaking may occur at a temperature of at least 275 °C, at least 285 °C, at least 290 °C, at least 295°C, from 250 °C to 350 °C, from 275 °C to 350 °C, from 285 °C to 350 °C, from 295 °C to 350 °C, from 275 °C to 325 °C, from 285 °C to 325 °C, from 295 °C to 325 °C, from 295 °C to 315 °C, from 295 °C to 305 °C, or any subset thereof.

[0035] The extrusion visbreaking may occur in an extruder, such as a twin screw extruder, at a screw speed of at least 350 revolutions per minute (RPM). Without being limited by theory, it is believed that a screw speed below this range may not introduce enough energy to cause sufficient chain scission to sufficiently increase the melt indices of the base ethylenebased polymer. The extrusion visbreaking may occur at a screw speed of at least 400 RPM, at least 500 RPM, at least 600 RPM, at least 700 RPM, at least 800 RPM, from 400 RPM to1100 RPM, from 500 RPM to 1100 RPM, from 600 RPM to 1100 RPM, from 700 RPM to1100 RPM, from 800 RPM to 1100 RPM, from 900 RPM to 1100 RPM, from 350 RPM to1000 RPM, from 500 RPM to 1000 RPM, from 700 RPM to 1000 RPM from 800 RPM to1000 RPM, or any subset thereof.

[0036] The extrusion visbreaking may have a residence time of from 30 seconds (sec) to 200 sec. Without being limited by theory, the amount of energy input into the resin is a function of the temperature, the extruder motor power (as is defined by screw speed), and the amount of time the resin is exposed to these conditions (the residence time). The extrusion visbreaking may have a residence time of from 30 sec to 180 sec, from 30 sec to 160 sec, from 30 sec to 140 sec, from 30 sec to 120 sec, from 30 sec to 100 sec, from 30 sec to 80 sec, from 30 sec to 60 sec, from 50 sec to 200 sec, from 70 sec to 200 sec, from 90 sec to 200 sec, from 104 sec to 200 sec, from 130 sec to 200 sec, from 150 sec to 200 sec, from 170 sec to 200 sec, from 50 sec to 180 sec, from 70 sec to 160 sec, from 90 sec to 140 sec, from 104 sec to 130 sec, or any subset thereof.

[0037] The extrusion visbreaking may occur in the absence of oxygen. Without being limited by theory, it is believed that extrusion visbreaking in the absence of oxygen results in a lower percentage of aldehydes in the visbroken PCR ethylene-based polymer than extrusion visbreaking in the presence of oxygen. Aldehydes are organoleptic and can cause taste and odor issues in many applications. Accordingly, decreasing the production of aldehydes is a significant benefit. Generally, the concentration of oxygen may be reduced through the use of a vacuum or by replacing the oxygen with another gas, such an inert gas(e.g., nitrogen, helium, argon, krypton, neon, or xenon). The gas in the extruder may have an oxygen partial pressure of less than 3 psi, such as less than 2 psi, less than 1 psi, less than 0.5 psi, less than 0.1 psi, or even less than 0.01 psi. The gas in the extruder may be at least 80 mol. % of inert gas, such as at least 90 mol. %, at least 95 mol. %, at least 99 mol. %, at least 99.9 mol. %, at least 99.99 mol. %, or even at least 99.999 mol. % of inert gas, on the basis of the total moles of gas in the extruder.

[0038] In some embodiments, the visbreaking process may comprise a devolatization step. This devolatilization may be carried out using any conventional devolatilization means and methods, including, in non-limiting embodiments, use of extruder reactors and / or kneader reactors, and methods including, for example, direct separation, main evaporation bulk evaporation, steam stripping, and / or direct devolatilization. In embodiments, the devolatization step may occur in the extruder during the extrusion visbreaking step or after the extrusion visbreaking step in a separate extruder. In embodiments, the devolatization process is driven by superheating the volatile component of the polymer melt, then subsequently exposing the melt to a rapid decompression. Devolatization may be performed on screw extruders, including single-screw or multi-screw extruders. A typical devolatization zone in a screw extruder consists of a portion of a screw that is partially filled, isolated by two sections that are filled with melt / solution. A stripping agent may be used in the extruder. In aspects, the stripping agent used in the extruder may be selected from the group consisting of water, carbon dioxide, nitrogen, and a hydrocarbon gas. The stripping agent used in the extruder may be selected from the group consisting of water and carbon dioxide. The stripping agent used in the extruder may be water.

[0039] Devolatilizing the visbroken PCR ethylene-based polymer may produce a devolatilized visbroken PCR ethylene-based polymer. The devolatilized visbroken PCR ethylene-based polymer may have a concentration of volatile organic compounds (VOCs) at least 50 % lower, such as at least 75 %, at least 80 %, at least 85 %, at least 90 %, at least 95 %, or even at least 99 % lower than the concentration of VOCs in the visbroken PCR ethylenebased polymer as the visbroken PCR ethylene-based polymer exits the extrusion visbreaking process. In embodiments, no properties of the visbroken PCR ethylene-based polymer, otherthan the VOC concentration, may change by more than 10 %, such as more than 5 %, more than 3 %, or more than 1 % during the devolatization process.

[0040] The extrusion visbreaking may occur without the presence of reaction aids (such as catalysts, peroxides, or radical initiators). The reaction aids may include metal salts, carboxylates (such as metal carboxylates, such as stearates), metal halides (such as chlorides), metal oxides and zeolites. Non-limiting examples include zinc, aluminum, manganese, cobalt, chromium, iron, calcium and magnesium, carboxylates thereof, chlorides thereof, and oxides thereof. The concentration of the reaction aids may be from 0 wt. % to 1 wt. %, from 0 wt. % to 0.5 wt. %, from 0 wt. % to 0.1 wt. %, from 0 wt. % to 0.01 wt. %, from 0 wt. % to 0.001 wt. %, from 0 wt. % to 0.0001 wt. %, from 0 wt. % to 0.000001 wt. %, or even from 0 wt. % to 0.0000000001 wt. % on the basis of the total polymer weight of the at least one base PCR ethylene-based polymer resin.

[0041] As described herein, the polymer blend may further comprise a virgin ethylene based polymer. The virgin ethylene based polymer may have a density of from 0.870 g / cc to 0.925 g / cc, such as from 0.870 g / cc to 0.875 g / cc, from 0.875 g / cc to 0.880 g / cc, from 0.880 g / cc to 0.885 g / cc, from 0.885 g / cc to 0.890 g / cc, from 0.890 g / cc to 0.895 g / cc, from 0.895 g / cc to 0.900 g / cc, from 0.900 g / cc to 0.905 g / cc, from 0.905 g / cc to 0.910 g / cc, from 0.910 g / cc to 0.915 g / cc, from 0.915 g / cc to 0.920 g / cc, from 0.920 g / cc to 0.925 g / cc, or any combination of two or more of these ranges. In embodiments, the virgin ethylene based polymer may be a linear low density polyethylene (LLDPE) or high density polyethylene (HDPE).

[0042] The virgin ethylene based polymer may have a melt index (I2) of from 2.5 dg / min to 5 dg / min, such as from 2.5 dg / min to 3.0 dg / min, from 3.0 dg / min to 3.5 dg / min, from 3.5 dg / min to 4.0 dg / min, from 4.0 dg / min to 4.5 dg / min, from 4.5 dg / min to 5.0 dg / min, or any combination of two or more of these ranges.

[0043] Generally, the properties of the virgin ethylene based polymer may be selected to balance the properties of the visbroken polyethylene PCR such that the desired properties of the polymer blend are within specifications. For example, the density of the virgin ethylenebased polymer may be selected to balance the density of the visbroken polyethylene PCR such that the density of the blend is within specifications.

[0044] Suitable virgin ethylene based polymers include ATTANE™, AFFINITY™, and ELITE™, available from The Dow Chemical Company Inc., Midland, MI.

[0045] Still referring to FIG. 1, the one or more internal layers 104 not comprising the polymer blend may comprise an ethylene based polymer, such as a virgin ethylene based polymer. The one or more of the internal layers 104 not comprising the polymer blend may comprise at least 50 wt. %, at least 75 wt. %, at least 85 wt. %, at least 90 wt. %, at least 95 wt. %, at least 99 wt. %, or at least 99 wt. % of the ethylene based polymer (e.g., a virgin ethylene based polymer).

[0046] The ethylene based polymer (e.g., a virgin ethylene based polymer) of the one or more internal layers 104 not comprising the polymer blend may have a density of from 0.910 g / cc to 0.935 g / cc, such as from 0.910 g / cc to 0.915 g / cc, from 0.915 g / cc to 0.920 g / cc, from 0.920 g / cc to 0.925 g / cc, from 0.925 g / cc to 0.930 g / cc, from 0.930 g / cc to 0.935 g / cc, or any combination of two or more of these ranges.

[0047] The ethylene based polymer (e.g., a virgin ethylene based polymer) of the one or more internal layers 104 not comprising the polymer blend may have a melt index (h) of from 2.0 dg / min to 6.0 dg / min, such as from 2.0 dg / min to 2.5 dg / min, from 2.5 dg / min to 3.0 dg / min, from 3.0 dg / min to 3.5 dg / min, from 3.5 dg / min to 4.0 dg / min, from 4.0 dg / min to 4.5 dg / min, from 4.5 dg / min to 5.0 dg / min, from 5.0 dg / min to 5.5 dg / min, from 5.5 dg / min to 6.0 dg / min, or any combination of two or more of these ranges.

[0048] Still referring to FIG. 1, the skin layers 102 may comprise ethylene-based polymer, propylene-based polymer, or combinations thereof.

[0049] In embodiments, one of the skin layers 102 may serve as a release layer 114. A release layer, for example, may have non-cling characteristics or may exhibit lower cling characteristics than a cling layer. The release layer may comprise any material suitable for use as a release layer. The other skin layer 102 may be a cling layer 116. Cling layers, forexample, may enable the multilayer film 100 to cling to itself when the film is wrapped on a load. The cling layer 116 may comprise any material suitable for use as a cling layer.

[0050] In embodiments, one or both of the skin layers 102 (e.g., the release layer 114, the cling layer 116, or both) may comprise ethylene-based polymer, such LLDPE, having a density of from 0.860 g / cc to 0.920 g / cc. In embodiments, the one or both of the skin layers 102 may comprise at least 50 wt.%, such as at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, or even at least 99 wt.% of LLDPE. In some embodiments, the ethylene-based polymer of each of the skin layers 102 can independently comprise from 0.1 wt.% to 30 wt.% of LDPE, based on the total weight of the respective layer.

[0051] In embodiments, the cling layer 116 may comprise a base resin (such as LLDPE) and a cling additive. The cling additive may be present in an amount from 0.1 wt. % to 10 wt. %, based on the total polymer weight of the cling layer 116. In embodiments, the cling layer 116 comprising the cling additive may have a density of from 0.912 g / cm3to 0.925 g / cm3and a melt index (I2) of from 0.5 g / 10 min to 3.0 g / 10 min.

[0052] Suitable resins for use in the cling layer 116 may include ATTANE™4601, an ethylene-hexene copolymer, available from The Dow Chemical Company Inc., Midland, ML In embodiments, the cling layer 116 may comprise the polyethylene and a cling additive. Suitable cling additives may include polyisobutylene, VERSIFY™ available from Dow™ Inc., Midland, MI, VISTAMAXX™ available from ExxonMobil, and CLEARFLEX™ CL DO available from Versalis S.p.A.

[0053] Suitable resins for use in the release layer 114 may include ELITE™ 5230 GC, an ethylene-octene copolymer, available from Dow™ Inc., Midland, MI.

[0054] It should be understood that any of the foregoing layers can further comprise one or more additives as known to those of skill in the art such as, for example, antioxidants, ultraviolet light stabilizers, thermal stabilizers, slip agents, antiblock agents, antistatic agents, pigments or colorants, processing aids, crosslinking catalysts, flame retardants, fillers and foaming agents. The layer may contain any amounts of such additives, such as from 0 wt.% to 10 wt.%, from 0 wt.% to 5 wt.%, from 0 wt.% to 1 wt.%, from 0 wt.% to 0.1 wt.%, from 0 wt.% to 0.001 wt.%, or any subset thereof, based on a weight of the layer.

[0055] The multilayer film 100 may have a thickness of less than 5 mil. In embodiments, the multilayer film 100 may have a thickness of less than 4 mil, less than 3 mil, less than 2 mil, less than 1 mil, from 0.1 mil to 0.25 mil, from 0.25 mil to 0.50 mil, from 0.50 mil to 0.75 mil, from 0.75 mil to 1.0 mil, from 1.0 mil to 1.5 mil, from 1.5 mil to 2.0 mil, from 2.0 mil to 2.5 mil, from 2.5 mil to 3.0 mil, from 3.0 mil to 4.0 mil, from 4.0 mil to 5.0 mil, or any combination of two or more of these ranges.

[0056] It should be understood that the multilayer film 100 may comprise 3 or more layers. In embodiments, the multilayer film may comprise more than 5 layers, such as 5, 7, 9, or 11 layers.

[0057] The multilayer film 100 may be a stretch film. In embodiments, the multilayer film 100 may have an ultimate stretch of at least 300 %, such as at least 310 %, at least 320 %, at least 330 %, at least 350 %, at least 375 %, or at least 400 %. In embodiments, the multilayer film 100 may have an Engineering & Solutions for Transport & Logistics (ESTL) tear of at least 5 seconds, such as at least 5.5 seconds, at least 6 seconds, at least 7 seconds, at least 8 seconds, at least 9 seconds, or even at least 10 seconds, when ESTL tear is measured at 0.6 mil thickness and 20 in film width. In embodiments, the multilayer film 100 may have an on pallet puncture of at least 10 lbs, such as at least 11 lbs, at least 12 lbs, at least 13 lbs, at least 14 lbs, or at least 15 lbs. On pallet puncture is measured at 0.6 mil film thickness and 20 in film width.

[0058] An article, such as a roll of stretch film, may be formed from the multilayer film 100.

[0059] In embodiments, a method of making the multilayer film 100 may comprise visbreaking polyethylene PCR having a melt index (h) of 0.4 to 2.5 dg / min, such as from 0.4 to 0.6 dg / min, from 0.6 to 0.8 dg / min, from 0.8 to 1.0 dg / min, from 1.0 to 1.5 dg / min, from 1.5 to 2.0 dg / min, from 2.0 to 2.5 dg / min, or any combination of two or more of these ranges. Visbreaking the polyethylene PCR may increase the melt index (I2) of the polymer and thereby produce the visbroken polyethylene PCR having the properties described herein.

[0060] The process may further comprise blending the visbroken polyethylene PCR with virgin ethylene based polymer to produce the polymer blend; and then producing themultilayer film by extruding the two skin layers 102 and one or more internal layers 104 disposed between the skin layers 102. In embodiments, the extrusion process is cast film extrusion.TEST METHODSDensity

[0061] Density is measured in accordance with ASTM D792, and expressed in grams / cubic centimeter (g / cc).Melt Index

[0062] Melt Index (I2) is measured in accordance with ASTM D 1238-10 at 190 °C and 2.16 kg, Method B, and is expressed in dg / min eluted.Gel Permeation Chromatography

[0063] The chromatographic system utilized a PolymerChar GPC-IR (Valencia, Spain) high temperature GPC chromatograph equipped with an internal IR5 infra-red detector (IR5). The autosampler oven compartment was set at 160° Celsius and the column compartment was 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 tri chlorobenzene 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.

[0064] 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. Thepolystyrene 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)).:

[0065] ^polyethylene A X Mpolystyrene)' (EQI)

[0066] where M is the molecular weight, A has a value of 0.4049 and B is equal to 1.0.

[0067] A fifth order polynomial was used to fit the respective polyethylene-equivalent calibration points.

[0068] The total plate count of the GPC column set was performed with 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.

[0069] 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 2 hours at 160° Celsius under “low speed” shaking.

[0070] The calculations of Mn, Mw, and Mz were based on GPC results using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph according to Equations 2-4, 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.

[0074] In order to monitor the deviations over time, a flowrate marker (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)) 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 Equation 5. 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.

[0075] Flowrate(effective) = Flowrate(nominal) * (RV(FM Calibrated) / RV(FM Sample)) (EQ 5)DMS Viscosity

[0076] r|o.i andrpoo are determined according to the DMS viscosity test. For preparation, test samples are initially placed into a 1.5 in. diameter chase of thickness 3.10 mm and compression molded at a pressure of 25,000 lbs for 6.5 min. at 190 °C with a hydraulic press. After cooling to room temperature, the samples are extracted to await dynamic mechanical spectroscopy.

[0077] The DMS (dynamic mechanical spectroscopy) frequency sweep is conducted using 25 mm parallel plates at frequencies ranging from 0.1 to 100 rad / s. The test gap separating the plates is 1.8 mm. A strain that satisfies linear viscoelastic conditions is utilized. Each test is conducted under nitrogen atmosphere and isothermal conditions at 190 °C. To initiate the DMS test, the rheometer oven is first allowed to equilibrate at the desired testing temperature 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 1.8 mm,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 are measured.

[0078] All DMS frequency tests are conducted on either ARES-G2 or DHR-3 rheometers, both of which are manufactured by TA Instruments. Data analyses are conducted via TA Instruments TRIOS software.Ultimate Stretch (US)

[0079] Ultimate stretch is measured using an ESTL film performance tester (ESTL, Deerlijk, Belgium) - FPT-750 Film Property Tester. The ultimate stretch test is selected from the test menu and the W-wrap method is then selected. Table A provides the settings for the equipment used in this method. The unwind force, wind force, peel off force, stretch force, peel angle and sound level are measured as a function of the pre-stretch. The pre-stretch is increased until a breaking point. The wind speed during the test is constant at 360 feet / min. The test is repeated 3 times and an average ultimate stretch (US) is reported as a percentage (%) ultimate stretch.Table AOn Pallet Puncture - Type B Load (OPP-B)

[0080] If a unitized pallet is not uniform in shape with limited irregularities, it’s defined as Type “B-Load”. This test uses a Bruceton staircase method to determine the maximum force to load at which the film can be passed over a test probe for three overlapping wraps with no failures. The test probe is inserted into the test stand at the desired protrusion distance. All films were tested by 2 inch x 2 inch blunt metal probe extending 6 inches out. The film ispositioned such that the test probe is aligned with the center of the film. The film is attached to the test stand and the wrapper started. Once the wrapper reaches 250% pre-stretch, the film is allowed to pass over the probe for a maximum of three wraps. The film is wrapped three times starting with post stretch film tension / force to load (F2) of 7 lbs. If the film is not punctured by the probe, the test is repeated at an increased F2 force at increments of 0.5 lbs. until failure. Any breakage of the film during any of the wrap is considered a failure at that force to load setting. Once the F2 force reaches a point where failures start to happen the test is repeated for 6 times at one force setting. If the film passes 4 of the 6 tests the film F2 force is increased. If the film fails 4 of the 6 tests then the test is stopped and this is considered the failure point of the film. Depending on the performance of the film at the load setting (z.e., passed or failed), the force to load is increased / decreased and the test is repeated at the new load setting. This test continues until the maximum force at which failure is greater than 50% is found. The highest passing F2 force is reported as On Pallet Puncture (OPP) value. Standard variation for this test is observed to be + / - 1 lb. It should be understood that Type B Load Test is commonly used in pallet packing that a person of ordinary skill in the art would recognize its meaning as used herein. Table B below provides the equipment and settings used in this method.Table BESTL Tear propagation

[0081] This test was executed on ESTL FPT-750 equipment. The film is stretched to a certain pre-defined pre-stretch level (250%). Next the film is clamped with a frame and counter frame, so a sharp blade can travel with a fixed pre-defined speed until it reaches the film. After the incision is made, the clamp is opened and the forces in the film are monitored.If the tear does not propagate, the wind drum will start to slowly pull until the film completely breaks.EXAMPLES

[0082] The following examples are provided to illustrate embodiments described in this disclosure and are not intended to limit the scope of this disclosure or its appended claims.Materials:

[0083] The following materials were used in the examples.

[0084] Envision Ecoprime™ is a food safe, recycled resin with a density of 0.961 g / cc and a melt index (h) of about 0.6, commercially available from Envision Plastics.

[0085] Avangard 100 (also referred to herein as "AVI 00) is a recycled resin with a density of 0.917 g / cc and a melt index (I2) of 2.32 dg / minutes, commercially available from Avangard Innovative.

[0086] DMDA™ 1270 is a virgin ethylene based polymer resin with a density of 0.955 g / cc and a melt index (I2) of 2.5 dg / min, commercially available from The Dow Chemical Company Inc., Midland MI.

[0087] ATTANE™ 4404G is an ultra-low density polyethylene having a density of 0.904 g / cc and a melt index (12) of 4.0 dg / min, commercially available from the Dow Chemical Company Inc., Midland MI.

[0088] AFFINITY™ KC8852 is an ethylene alpha-olefin plastomer having a density of 0.875 g / cc and a melt index (12) of 3.0 dg / min, commercially available from the Dow Chemical Company Inc., Midland MI.

[0089] ELITE™ 5230 is a linear low density metallocene copolymer polyethylene resin having a density of 0.916 g / cc and a melt index (12) of 4.0 dg / min, commercially available from the Dow Chemical Company Inc., Midland MLVisbreaking Process

[0090] Envision Ecoprime was used as the starting material in an extrusion visbreaking process. The properties of Envision Ecoprime are given in Tables.Table 1 |I

[0091] The visbreaking extrusion process is conducted on ZSK 26mm Twin Screw Extruder. Below at the conditions given in Table 2. The mechanical properties of the resulting resin, denominated as VI are given in Table 3a. GPC characterization of the base Envision Ecoprime resin and VI are given in Table 3b.Table 2Table 3aTable 3b

[0092] Avangard AVI 00 was also used as the starting material for the visbreaking extrusion process. The visbreaking parameters, properties of the base AVI 00 resin, and the visbrokenAV100 resins are all given in Table 4. Extruder flowrate is given in pounds of substrate per hour.Table 4Multilayer Films

[0093] Three layer and five layers cast stretch films are fabricated on a 5 layer Egan Davis Standard coextrusion cast film line. The cast line includes three 2-12” and two 2” 30: 1 L / D Egan Davis Standard MAC extruders which are air cooled. All extruders have moderate work DSB (Davis Standard Barrier) type screws. A microprocessor monitors and controls the operations. The extrusion process is monitored by pressure transducers located before and after the breaker plate as well as four heater zones on each barrel, one each at the adapter and the block, and two zones on the die. The microprocessor also tracks the extruder RPM, %FLA, HP, rate, line speed, % draw, primary and secondary chill roll temperatures, gauge deviation, layer ratio, rate / RPM, and melt temperature for each extruder.

[0094] Equipment specifications include a Cloeren 5 layer dual plane feed block and a Cloeren 36” Epoch III auto gauge 5.1 die. The primary chill roll has a matte finish and is 40” O.D. x 40” long with a 30-40 RMS surface finish for improved release characteristics. The secondary chill roll is 20” O.D. x 40” long with a 2-4 RMS surface for improved web tracking. Both the primary and secondary chill roll has chilled water circulating through it to provide quenching. There is an X-ray gauge sensor from Scantech for gauge thickness and automatic gauge control if needed. Rate is measured by five Barron weigh hoppers with load cells on each hopper for gravimetric control. Samples are finished on the two position single turret Horizon winder on 3” I.D. cores with center wind automatic roll changeover and slitterstation. The maximum throughput rate for the line is 600 pounds per hour and maximum line speed is 1200 feet per minute.

[0095] Samples C-A to C-C and E-l were produced according to the process conditions given in Table 5.Table 5

[0096] Films C-A to C-C and E-l were produced as described in Table 6. The material properties of the films are given in Table 7. As can be seen from Table 7, Example E-l was able to achieve an Ultimate Stretch, ESTL Tear, and On-Pallet Puncture substantially greater than comparative example C-B, which used a similar amount of the polyethylene PCR. The percentages given in the second row are the percent of overall thickness.Table 6Table 7

Claims

CLAIMS1. A multilayer film comprising two skin layers and one or more internal layers disposed between the skin layers, wherein: at least one of the one or more internal layers comprises a polymer blend having a density from 0.910 g / cc to 0.940 g / cc, and comprising: from 10 wt. % to 90 wt. % visbroken polyethylene post-consumer resin (PCR) having a density of 0.910 g / cc to 0.965 g / cc and a melt index (h) from 1.5 dg / min to 9.0 dg / min; and from 10 wt. % to 90 wt. % of virgin ethylene based polymer.

2. The multilayer film of claim 1, wherein the polymer blend has a melt index (I2) of from 2.0 dg / min to 6 dg / min.

3. The multilayer film of claim 1 or 2, wherein the visbroken polyethylene PCR has a density greater than 0.945 g / cc.

4. The multilayer film of any one of claims 1 to 3, wherein the visbroken polyethylene PCR has an r|o.i / r|ioo of from 2 to 20, wherein r|o.i is the shear viscosity measured at 0.1 radians / second and rpoo was measured at 100 radians / second.

5. The multilayer film of any one of claims 1 to 4, wherein the virgin ethylene based polymer has a density of from 0.870 g / cc to 0.925 g / cc.

6. The multilayer film of any one of claims 1 to 5, wherein the virgin ethylene based polymer has a melt index (I2) of from 2.5 dg / min to 5 dg / min.

7. The multilayer film of any one of claims 1 to 6, wherein the polymer blend has a density of from 0.910 g / cc to 0.935 g / cc.

8. The multilayer film of any one of claims 1 to 7, wherein: the one or more internal layers comprise two subskin layers and a core layer disposed between the subskin layers; andthe core layer, at least one of the subskin layers, or both comprises the visbroken polyethylene PCR.

9. The multilayer film of claim 8, wherein the subskin layers comprise the polymer blend.

10. The multilayer film of any one of claims 1 to 9, wherein the visbroken polyethylene PCR is formed from linear low density polyethylene, high density polyethylene, or both.

11. The multilayer film of any one of claims 1 to 10, wherein the multilayer film has at least one of the following: an ultimate stretch of at least 300 %; an ESTL Tear of at least 5 seconds, as measured at 0.6 mil thickness an 20 in film width; and an on pallet puncture of at least 10 lbs measured at 0.6 mil film thickness and 20 in film width.

12. An article comprising the multilayer film of any one of claims 1 to 11.

13. A method of making the multilayer film of any one of claims 1 to 11 comprising: visbreaking polyethylene PCR having a starting melt index (h) of 0.3 to 2.5 dg / min to increase the melt index (I2) and thereby produce the visbroken polyethylene PCR with a melt index (I2) greater than the melt index of the polyethylene PCR; blending the visbroken polyethylene PCR with virgin ethylene based polymer to produce the polymer blend; and producing the multilayer film by extruding the two skin layers and one or more internal layers disposed between the skin layers, wherein at least one of the one or more internal layers comprise the polymer blend.

14. The method of claim 13, wherein the polyethylene PCR prior to visbreaking has a density greater than 0.910 g / cc and I2 less than 1.0 dg / min.

15. The method of claim 13 or 14, wherein the extrusion is cast film extrusion.

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