Non-fluorinated polymer processing aids for die lip build-up mitigation in extrusion of compositions containing recycled polyethylene

Abstract

An extrudable polymeric composition and methods of making and using the extrudable polymeric composition are disclosed. The composition can include 5 wt.% to 99 wt.% of a recycled polyethylene, and 500 ppm to 5,000 ppm, based on the weight of the extrudable polymeric composition, of added polyether block amide. Also disclosed is a method of reducing die lip build-up during extrusion of polymeric compositions including recycled polyethylene.

Description

[0001] NON-FLUORINATED POLYMER PROCESSING AIDS FOR DIE LIP BUILD-UP MITIGATION IN EXTRUSION OF COMPOSITIONS CONTAINING RECYCLED POLYETHYLENE

[0002] TECHNICAL FIELD

[0003] The present disclosure generally relates to extruding polymeric compositions that include recycled polyethylene. In particular, the present disclosure is directed to polyether block amide polymers as a processing aid for reducing die lip build-up during extrusion of compositions including recycled polyethylene.

[0004] BACKGROUND ART

[0005] Extruding polyolefin polymers (e.g., polyethylene) oftentimes leads to die lip buildup (DLBU). DLBU generally refers to an unwanted material accumulation on the open faces of extrusion dies or at the lip of an extruder die exit. This DLBU issue can be particularly problematic when extruding polymeric compositions with recycled polyethylene (rPE) (e.g., post-consumer rPE) due to the presence of contaminants in the recycled resin. The contaminants can increase DLBU issues during the extrusion process. DLBU can lead to aesthetic and processing issues with the extruded polymeric composition. For instance, as the polymeric material buildup accumulates, it can create visible defects or gauge variations in the resulting polymeric products (e.g., extruded films and parts). DLBU can also reduce extrusion processing times and even lead to clogging of the die aperture / outlet. Ultimately, the extrusion process may need to be stopped to remove the DLBU material from the die plate surface and / or die outlet. This cleanup process can take hours to days before the extrusion process can be restarted, which can lead to inefficient manufacturing and cost-efficiency issues.

[0006] A current solution for reducing DLBU in virgin polyethylene is the use of fluorocontaining materials, such as, for example, fluoropolymer or fluoroelastomer copolymers of vinylidene difluoride and hexafluoropropylene. These fluoro-containing materials can be added to the polymeric compositions prior to extrusion. The fluoro-containing materials can help coat the surface of the extruder and die to prevent sticking of the polymeric compositions, which can reduce DLBU. A potential problem with the use of fluoro-containing materials, however, is the presence of fluorine. In particular, fluoro-containing materials can potentially be detrimental to the environment and / or are subject to a variety of governmental regulations.

[0007] While attempts have been made to use materials other than fluoro-containing materials to reduce DLBU, these materials can be complicated to use, costly, and / or can still result in DLBU issues. By way of example, U.S. Patent Application Publication No. 2023 / 0031000 to Ruocco et al., describes a material that is blend of at least two of a polyethylene glycol, a surfactant including a sorbitan ester or a polysorbate, and a metal salt of a fatty acid. Such a blend can be costly, and introduction of a multitude of components into the polymer resin can affect the properties of the resin.

[0008] There exists a need for improved solutions for reducing DLBU during extrusion of polymer compositions and particularly those containing recycled polyethylene.

[0009] SUMMARY OF INVENTION

[0010] A discovery has been made that provides a solution to at least one or more of the aforementioned problems associated with DEBU. In one aspect, the solution can include the use of a polyether block amide polymer as a processing aid to reduce DLBU issues when extruding polymeric compositions that include recycled polyethylene (e.g., post-consumer recycled polyethylene). Notably, while the recycled polyethylene may contain contaminants and previously added additives, which may include previously added fluoro-containing materials, and / or ethylene vinyl alcohol polymers, the present disclosure relies on the use of added polyether block amide to reduce DLBU. The newly added polyether block amide polymer is referred to throughout this specification as “added” polyether block amide. The newly added polyether block amide polymer can be added to the extrudable polymeric compositions as a masterbatch or concentrate. In one non-limiting embodiment, it was discovered that the use of added polyether block amide in polymeric compositions containing recycled polyethylene had better DLBU mitigation results when compared with the use of newly added polyvinylidene fluoride.

[0011] In one aspect, the present disclosure provides an extrudable polymeric composition including 5 wt.% to 99 wt.% of a recycled polyethylene, and 500 ppm to 5,000 ppm, based on the weight of the extrudable polymeric composition, of added polyether block amide. In some embodiments, the extrudable polymeric composition includes 1 wt.% to 95 wt.% of a virgin polyethylene. In some embodiments, the virgin polyethylene includes very low density polyethylene (VLDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), or any combination or blend thereof. In some embodiments, the virgin polyethylene is linear low density polyethylene.

[0012] In some embodiments, the extrudable polymeric composition can comprise less than 200 ppm, based on the weight of the extrudable polymeric composition, of a fluoropolymer or a copolymer thereof originating from the recycled polyethylene. In some embodiments, the fluoropolymer can be a polyvinylidene difluoride, a polyvinylidene fluoride-co- hexafluoropropylene, a polytetrafluoroethylene, or a combination thereof.

[0013] In some embodiments, the recycled polyethylene can include up to 5 wt.% polypropylene, based on the total weight of the recycled polyethylene. In some embodiments, the recycled polyethylene can include low density polyethylene (LDPE), linear low density polyethylene (LLDPE), or both. In some embodiments, the recycled polyethylene is from a mechanically recycled Polyethylene (PE) Clear Film Grade B. In some embodiments, the recycled polyethylene can include a melt index (h) of 0.5 to 5.0 grams per 10 minutes and a density of 0.910 to 0.940 g / cm3. In some embodiments, the recycled polyethylene can have a melt index (h) of 0.5 to 1.5 grams per 10 minutes and a density of 0.920 to 0.930 g / cm3.

[0014] In some embodiments, the extrudable polymeric composition can include, based on the total weight of the polymeric composition, 500 ppm to 3,000 ppm of the added polyether block amide and 0 to 1 wt.% additives. In some embodiments, the extrudable polymeric composition can include, based on the total weight of the polymeric composition, 500 ppm to 1,500 ppm of the added polyether block amide, and 0 to 1 wt.% additives. In some embodiments, the extrudable polymeric composition can include, based on the total weight of the polymeric composition, 800 ppm to 1,000 ppm of the added polyether block amide, and 0 to 1 wt.% additives.

[0015] In some embodiments, the extrudable polymeric composition is in a pellet form. In some embodiments, the extrudable polymeric composition, when extruded, can have a reduced die lip build-up when (1) compared to a reference composition that includes the same components in the same amounts but does not include the added polyether block amide or (2) compared to a reference composition that includes the same components in the same amounts but replaces the added poly ether block amide with poly vinylidene difluoride.

[0016] The present disclosure also provides a method of making the extrudable polymeric compositions disclosed herein. The method can include (a) melt compounding the recycled polyethylene and the added polyether block amide to produce a mixture and (b) extruding the mixture to obtain the polymeric composition.

[0017] The present disclosure also provides a method of extruding the extrudable polymeric compositions of the present invention. The method can include extruding the extrudable polymeric composition at a temperature of 160°C to 300°C, or between 200°C and 250°C.

[0018] Also disclosed is a method of reducing die lip build-up in an extrudable polymeric composition containing recycled polyethylene. The method includes adding 500 ppm to 5,000 ppm, based on the weight of the extrudable polymeric composition, of a polyether block amide to the extrudable polymeric composition prior to the extruding. Other components and / or parameters of the extrudable polymeric composition discussed above and throughout this specification are contemplated with this method of reducing die lip build-up. In some embodiments, the polyether block amide can be added by tumble blending. In some embodiments, the polyether block amide can be added as a masterbatch.

[0019] Other aspects of the invention are discussed throughout this specification. Any embodiments discussed with respect to one embodiments applies to other embodiments as well. Each aspect described herein is understood to be aspects of the invention that are applicable to other aspects of the invention. It is contemplated that any embodiments discussed herein can be combined with other embodiments discussed herein and / or implemented with respect to any method or composition of the invention, and vice versa. Furthermore, compositions of the invention can be used to achieve methods of the invention.

[0020] Other objects, features and advantages of the present invention will become apparent from the following figures, detailed description, and examples. It should be understood, however, that the figures, detailed description, and examples, while indicating specific embodiments of the invention, are given by way of illustration only and are not meant to be limiting. Additionally, it is contemplated that changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. In further embodiments, features from specific embodiments may be combined with features from other embodiments. For example, features from one embodiment may be combined with features from any of the other embodiments. In further embodiments, additional features may be added to the specific embodiments described herein.

[0021] BRIEF DESCRIPTION OF DRAWINGS

[0022] Advantages of the compositions and methods of the present disclosure may become apparent to those skilled in the art with the benefit of the following detailed description and upon reference to the accompanying drawings.

[0023] Figure 1 provides photographs of the die exit during extrusion of recycled polyethylene EX-PCR-NC4 (formerly sold by NOVA Chemicals) control sample (NC4), and two formulations containing fluoropolymer PPA KYNAR® 3121-50 at 250 (Cl) and 500 (C2) ppm loading levels (arrows point to DLBU).

[0024] Figure 2 provides photographs of the die exit during extrusion of recycled polyethylene EX-PCR-NC4 control sample (NC4), the fluoropolymer formulation (KYNAR @ 250 ppm, Cl) compared against PEBAX® MV 1074 @ 1,000 ppm (IE2) (arrows point to DLBU). Figure 3 provides photographs of the die exit during extrusion of recycled polyethylene EX-PCR-NC4 control sample (NC4), the polyether block amide -containing formulation (IE2), and an ethylene vinyl alcohol (EVOH) formulation (El) (arrows point to DLBU).

[0025] Figure 4 provides photographs of the die exit during extrusion of recycled polyethylene EX-PCR-NC4 control sample (NC4), and nylon 6 (C5) formulation (arrows point to DLBU).

[0026] Figure 5 provides photographs of the die exit during extrusion of recycled polyethylene EX-PCR-NC4 control sample (NC4), calcium stearate formulation (C6), and hydrotalcite (DHT-4V) formulation (C7) (arrows point to DLBU).

[0027] Figure 6 provides photographs of the die exit during extrusion of recycled polyethylene EX-PCR-NC4 control sample (NC4), and two formulations containing different PEG formulations (C3 and C4) (arrows point to DLBU).

[0028] Figure 7 provides photographs of the die exit during extrusion of Control sample 2 (98% recycled polyethylene EX-PCR-NC4) and Control sample 3 (75% recycled polyethylene EX-PCR-NC4) relative to the same polymer blends containing added polyether block amide (IE3 and IE4).

[0029] Figure 8 provides photographs of the die exit during extrusion of Control sample 4 (50% recycled polyethylene EX-PCR-NC4) and Control sample 5 (25% recycled polyethylene EX-PCR-NC4) relative to the same polymer blends containing added polyether block amide (IE5 and IE6).

[0030] While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings. The drawings may not be to scale.

[0031] DESCRIPTION OF EMBODIMENTS

[0032] A discovery has been made that provides a solution to at least one or more of the die lip build-up (DLBU) problems associated with extruding polymeric compositions that include recycled polyethylene resins. In one aspect, the solution includes incorporating added polyether block amide to the extrudable polymeric compositions prior to extruding the compositions. In one non-limiting embodiment, and as evidenced in the Examples of this specification, it was discovered that use of added polyether block amide in the extrudable polymeric compositions including recycled polyethylene had better DLBU mitigation results when compared with the use of newly added polyvinylidene fluoride. Without wishing to be bound by any particular theory, it is believed that the contaminants within the recycled polyethylene resin may act as antagonists for the newly added polyvinylidene fluoride (strong hydrogen bonding), thereby allowing the DLBU material to accumulate. By comparison, the reduced DLBU accumulation with the added polyether block amide is believed to be due to the comparatively lower hydrogen bonding strength (when compared with polyvinylidene fluoride), thereby allowing the added polyether block amide to coat the extruder and die lip surfaces to a sufficient extent to reduce DLBU. The compositions and methods disclosed herein provide an effective alternative to the use of fluoro-containing materials to reduce DLBU when extruding polymeric compositions containing recycled polyethylene, which may be advantageous from an environmental, regulatory, and / or manufacturing perspective.

[0033] These and other non-limiting embodiments of the present invention are discussed in further detail in the following sections.

[0034] Definitions

[0035] The following includes definitions of various terms and phrases used throughout this specification.

[0036] “Virgin polyethylene” refers to manufactured polyethylene that has not been converted to a finished product. Virgin polyethylene is not recycled polyethylene and, thus, the term “virgin” is used herein to distinguish between the two.

[0037] “Recycled polyethylene” refers to polyethylene that has been obtained from, made from, and / or recovered from a polyethylene-containing waste stream. The recycled polyethylene can be post-consumer or post-industrial recycled polyethylene. Post-consumer recycled (PCR) polyethylene refers to polyethylene from a waste stream generated by a consumer after a polyethylene-containing article has been used for an original or previous purpose and disposed into the waste stream. Post-industrial recycled (PIR) polyethylene refers to polyethylene from a waste stream generated during a production process (such as for example, the manufacture of a polyethylene -containing product) or excess polyethylenecontaining material used in a production process (such as, for example, excess product packaging), or material diverted to the waste stream after a manufacturing process but before consumer use. It is to be understood that recycled polyethylene can contain non-polyethylene and non-polymeric components and / or contaminants. Non-limiting examples of such components and / or contaminants that can be present in recycled polyethylene include fluorinated polymers, nylon, ethylene vinyl alcohol, polyvinylidene chloride (PVDC), compatibilizers, inorganic pigments, and / or additives. Recycled polyethylene has been exposed to at least one heat history. It will be appreciated by those skilled in the art that “heat history” refers to the melting of polyethylene to form a finished good. “HDPE” refers to high density polyethylene, which generally has a density of greater or equal to 0.941 g / cm3, or for example, from 0.941 to 0.97 g / cm3. HDPE has a low degree of branching. HDPE may be produced using chromium / silica catalysts, Ziegler-Natta catalysts or metallocene catalysts. HDPE, and the other polyethylenes described herein, typically contain additives.

[0038] “LDPE” refers to low density polyethylene, which is a polyethylene with a high degree of long chain branching. Often, the density of a LDPE will range from 0.910 g / cm3to 0.940 g / cm3. LDPE is created by free radical polymerization under conditions of high ethylene pressure.

[0039] “LLDPE” refers to linear low density polyethylene, which is a polyethylene with significant numbers of short branches resulting from copolymerization of ethylene with at least one C3-12 a-olefin comonomer, e.g., butene, hexene, or octene. Typically, LLDPE has a density in the range of 0.915 g / cm3to 0.925 g / cm3. In some embodiments, the LLDPE is an ethylene hexene copolymer, or an ethylene octene copolymer, or an ethylene butene copolymer. The amount of comonomer incorporated can be from 0.5 to 12 mole %, or in some embodiments from 1.5 to 10 mole %, and in other embodiments from 2 to 8 mole % relative to ethylene. LLDPE may be produced using a wide variety of catalysts, including Ziegler-Natta catalysts and single site / metallocene catalysts, and in a wide variety of processes, including gas phase, slurry and solution processes. LLDPE is distinct from LDPE.

[0040] “MDPE” refers to medium density polyethylene, which is a polyethylene with some branching and a density in the range of 0.926 g / cm3to 0.940 g / cm3. MDPE can be produced using chromium / silica catalysts, Ziegler-Natta catalysts or single site / metallocene catalysts and in a wide variety of processes, including gas phase, slurry and solution processes.

[0041] “VLDPE” refers to very low density polyethylene, which is a polyethylene with high levels of short chain branching with a typical density in the range of 0.88 g / cm3to 0.915 g / cm3. In some embodiments, VLDPE is a substantially linear polymer. VLDPE is typically produced by copolymerization of ethylene with short-chain alpha-olefins (e.g., 1 -butene, 1- hexene, or 1 -octene). VLDPE is most commonly produced using metallocene catalysts in a solution process.

[0042] “Masterbatch” refers to a concentrated mixture of a polyether block amide, other additives, or a combination thereof, in a polymer carrier. The polymer carrier may include one or both of recycled polyethylene and virgin polyethylene. A masterbatch may be prepared by melt mixing the polyether block amide (and, optionally, other additives) with a small amount of the polymer carrier, such as for example virgin polyethylene. The terms “about” or “approximately” are defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment, the terms are defined to be within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.

[0043] The terms “wt.%”, “% by weight”, “vol.%”, “% by volume”, “mol.%”, or “% by mol.” refers to a weight percentage of a component, a volume percentage of a component, or molar percentage of a component, respectively, based on the total weight, the total volume of material, or total moles, which includes the component. In a non-limiting example, 10 grams of component in 100 grams of the material is 10 wt.% of component.

[0044] The terms “inhibiting” or “reducing” or “preventing” or “avoiding” or “mitigating” or any variation of these terms, when used in the claims and / or the specification includes any measurable decrease or complete inhibition to achieve a desired result.

[0045] The term “effective”, as that term is used in the specification and / or claims, means adequate to accomplish a desired, expected, or intended result.

[0046] The use of the words “a” or “an” when used in conjunction with any of the terms “comprising”, “including”, “containing”, or “having” in the claims, or the specification, may mean “one,” but it is also consistent with the meaning of “one or more”, “at least one”, and “one or more than one”.

[0047] The words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

[0048] The extrudable polymeric compositions of the present invention can “comprise”, “consist essentially of’, or “consist of’ particular ingredients, components, compositions, etc. disclosed throughout the specification. With respect to the transitional phrase “consisting essentially of’, in one non-limiting aspect, a basic and novel characteristic of the extrudable polymeric compositions of the present invention is that they can include an added polyether block amide polymer as a polymer processing aid to mitigate or reduce DLBU issues during extrusion of the polymeric compositions.

[0049] Extrudable Polymeric Compositions

[0050] The extrudable polymeric compositions of the present disclosure include recycled polyethylene and a polyether block amide. The extrudable polymeric compositions can include additional polymeric and non-polymeric components discussed throughout this specification and those known to people having skill in the art. For instance, the extrudable polymeric compositions can include virgin polyethylene and / or can include other thermoplastic polymers (e.g., polypropylene), and / or can include other additives. By way of example, the extrudable polymeric compositions can include non-polymeric components such as non-polymeric additives. By way of yet another example, the extrudable polymeric compositions can include contaminating materials, such as contaminants that may be present in recycled materials (for example, contaminants in the recycled polyethylene). For instance, and in some embodiments, the recycled polyethylene may include contaminants and previously added additives, which may include previously added fluoro-containing materials, and / or ethylene vinyl alcohol polymers.

[0051] In some embodiments, the extrudable polymeric compositions of the present invention can include, based on the total weight of the extrudable polymeric composition, at least 5 wt.%, at least 10 wt.%, at least 15 wt.%, at least 20 wt.%, at least 25 wt.%, at least 30 wt.%, at least 35 wt.%, at least 40 wt.%, at least 45 wt.%, at least 50 wt.%, at least 55 wt.%, at least 60 wt.%, at least 65 wt.%, at least 70 wt.%, at least 75 wt.%, at least 80 wt.%, at least 85 wt.%, at least 90 wt.%, at least 95 wt.%, at least 96 wt.%, at least 97 wt.%, at least 98 wt.%, or at least 99 wt.% of recycled polyethylene. In some embodiments, the extrudable polymeric compositions of the present invention can include, based on the total weight of the extrudable polymeric composition, at least 1 wt.%, at least 5 wt.%, at least 10 wt.%, at least 15 wt.%, at least 20 wt.%, at least 25 wt.%, at least 30 wt.%, at least 35 wt.%, at least 40 wt.%, at least 45 wt.%, at least 50 wt.%, at least 55 wt.%, at least 60 wt.%, at least 65 wt.%, at least 70 wt.%, at least 75 wt.%, at least 80 wt.%, at least 85 wt.%, at least 90 wt.%, or at least 95 wt.% of virgin polyethylene.

[0052] In some embodiments, the extrudable polymeric composition includes recycled polyethylene in an amount from about 5% to about 90% by weight of the composition. In some embodiments, the extrudable polymeric composition includes recycled polyethylene in an amount in the range from about 50% to about 90% by weight. In some embodiments, the extrudable polymeric composition may include recycled polyethylene in an amount from about 20% to about 80% by weight. In some embodiments, the extrudable polymeric composition includes recycled polyethylene in an amount from about 5% to about 20% by weight. In some embodiments, the extrudable polymeric composition includes recycled polyethylene in an amount from about 20% to about 50% by weight. In some embodiments, the extrudable polymeric composition includes recycled polyethylene in an amount from about 80% to about 90% by weight. In some embodiments, the extrudable polymeric composition includes recycled polyethylene in an amount of about 25% by weight. In some embodiments, the extrudable polymeric composition includes recycled polyethylene in an amount of about 50% by weight. In some embodiments, the extrudable polymeric composition includes recycled polyethylene in an amount of about 75% by weight.

[0053] In some embodiments, the extrudable polymeric composition includes about 25 wt.% recycled polyethylene and about 75 wt.% virgin polyethylene. In some embodiments, the extrudable polymeric composition includes about 50 wt.% recycled polyethylene and about 50 wt.% virgin polyethylene. In some embodiments, the extrudable polymeric composition includes about 75 wt.% recycled polyethylene and about 25 wt.% virgin polyethylene.

[0054] The extrudable polymeric compositions of the present disclosure can include 500 parts per million (ppm) to 5,000 ppm of the extrudable polymeric composition, based on the weight of the extrudable polymeric composition, of added polyether block amide. As used herein, “added polyether block amide” refers to an amount of polyether block amide that does not originate from the recycled polyethylene and / or the virgin polyethylene but rather is added to the recycled polyethylene and / or the virgin polyethylene to provide the disclosed extrudable polymeric composition.

[0055] In some embodiments, the amount of added polyether block amide is from 500 ppm to 3,500 ppm by weight, or from 500 ppm to 2,500 ppm by weight, or from 750 ppm to 4,000 ppm by weight, or from 750 ppm to 3,000 ppm by weight, or from 750 ppm to 2,500 ppm by weight, or from 1,000 ppm to 4,000 ppm by weight, or from 1,000 ppm to 3,000 ppm by weight, or from 1,000 ppm to 2,500 ppm by weight, or from 1,000 ppm to 2,250 ppm by weight, or from 1,000 ppm to 2,000 ppm by weight, or from 1,250 ppm to 1,750 ppm by weight, or from 500 ppm to 2,250 ppm by weight, or from 500 ppm to 2,000 ppm by weight (wherein “by weight” is based on the weight of the polymeric composition). In some embodiments, the extrudable polymeric composition can include, based on the total weight of the polymeric composition, 1,000 ppm to 2,000 ppm of the added polyether block amide.

[0056] In some embodiments, the extrudable polymeric composition can include, based on the total weight of the polymeric composition 500 ppm, 550 ppm, 600 ppm, 650 ppm, 700 ppm, 750 ppm, 800 ppm, 850 ppm, 900 ppm, 950 ppm, 1,000 ppm, 1,100 ppm, 1,200 ppm,

[0057] 1,300 ppm, 1,400 ppm, 1,500 ppm, 1,600 ppm, 1,700 ppm, 1,800 ppm, 1,900 ppm, 2,000 ppm, 2,100 ppm, 2,200 ppm, 2,300 ppm, 2,400 ppm, 2,500 ppm, 2,600 ppm, 2,700 ppm,

[0058] 2,800 ppm, 2,900 ppm, 3,000 ppm, 3,100 ppm, 3,200 ppm, 3,300 ppm, 3,400 ppm, 3,500 ppm, 3,600 ppm, 3,700 ppm, 3,800 ppm, 3,900 ppm, 4,000 ppm, 4,500 ppm, or 5,000 ppm of the added polyether block amide. Non-limiting examples of suitable polyether block amides are discussed later herein.

[0059] In some embodiments, the extrudable polymeric compositions of the present disclosure may include 0 to 1 wt.% of an additive or a combination of additives other than the added polyether block amide. Non-limiting examples of suitable additives are discussed later herein.

[0060] In some embodiments, the extrudable polymeric composition can include less than 200 ppm, based on the weight of the extrudable polymeric composition, of a fluoropolymer or a copolymer thereof originating from the recycled polyethylene. That is, the presence of fluoropolymer is not from adding fluoropolymer to the extrudable polymeric composition. In some embodiments, the fluoropolymer can be a polyvinylidene difluoride, a polyvinylidene fluoride-co-hexafluoropropylene, polytetrafluoroethylene, or a combination or blend thereof.

[0061] In some embodiments, the extrudable polymeric composition includes recycled polyethylene and polyether block amide added in the desired concentration. In some embodiments, the extrudable polymeric composition includes recycled polyethylene and a masterbatch of polyether block amide. In some embodiments, the masterbatch includes LLDPE as a carrier. In some embodiments, the extrudable polymeric composition is in a pellet form.

[0062] In some embodiments, when extruded, the extrudable polymeric composition has reduced die lip build-up when compared to a reference composition that includes the same components in the same amounts but does not include the added polyether block amide, or when compared to a reference composition that includes the same components in the same amounts but replaces the added polyether block amide with polyvinylidene difluoride.

[0063] In some embodiments, the extrudable polymeric composition is capable of producing an extrusion molded article, an injection molded article, a compression molded article, a rotational molded article, a blow molded article, an injection blow molded article, a 3-D printed article, a thermoformed article, a foamed article, a blown fdm, a cast film, or a writeable film.

[0064] The Recycled Polyethylene

[0065] The recycled polyethylene can include post-consumer recycled polyethylene, postindustrial recycled polyethylene, or a combination thereof. In some instances, both postconsumer recycled polyethylene and post-industrial recycled polyethylene materials can be purchased commercially. In some embodiments, the recycled polyethylene includes low density polyethylene (LDPE), linear low density polyethylene (LLDPE), or both.

[0066] In some embodiments, the recycled polyethylene is obtained from mechanical recycling of a baled commodity that is a mix of natural polyethylene fdm, primarily Linear Low Density Polyethylene (LLDPE) and Low Density Polyethylene (LDPE), predominantly clear or natural in colour, that has met its intended use generated from commercial sources. The fdms may be coded with ASTM D7611 resin identification code “#4, LDPE / LLDPE”. The bale composition includes a mix of retail-sourced packaging such as bags, shrink wrap, pouches, overwrap, and stretch films. Bales of this this feedstock may be referred to as “PE Clear film Grade B” in the industry. In some embodiments, the PE Clear Lilm Grade B bales are at least 80% clear or natural polyethylene film based on exterior visual inspection with up to 20% coloured / printed polyethylene film, moderate levels of HDPE film, and low levels of non-film contaminants.

[0067] In some instances, another source of recycled polyethylene is from used polyethylene parts that are first cleaned, next melted in an extruder, and then converted into pellets for sale. This source of recycled polyethylene may be exposed to at least two heat histories one in the original conversion process and another in the process to prepare recycled polyethylene pellets.

[0068] Recycling processes where materials experience heat histories will generally cause the formation of free radicals and hydroperoxides in the polyethylene. Most polyethylene is sold with an antioxidant system that contains a primary antioxidant (designed to trap free radicals) and a secondary antioxidant (designed to quench hydroperoxides). Hindered phenols are commonly used as the primary antioxidant (e.g., IRGANOX® 1010 and IRGANOX 1076, sold by BASE) and hindered phosphites are commonly used as the secondary antioxidant (e.g., IRGAPHOS® 168). These antioxidants may be oxidized during a heat history. It is known to measure the level of consumed antioxidants (oxidized antioxidants) in a polyethylene and to use this value of an indication of degradation, or the “wear and tear” that the polyethylene has been exposed to.

[0069] The recycled polyethylene may be provided in any suitable form, such as in the form of chips, pellets, powders, slurries, solutions, and the like.

[0070] The Added Polyether Block Amide

[0071] The added polyether block amide can include a copolymer having polyamide blocks and polyether blocks. Such a block copolymer, having polyamide blocks and polyether blocks, may also be called a “polyamide / polyether block copolymer”. In the present disclosure the term “poly(ether-block-amide) copolymer” can be abbreviated as “PEBA copolymer”. Similarly, the terms “poly(ether-block-amide)” and / or polyether block amide can be abbreviated as “PEBA”. The abbreviations “PEBA” and “PEBA copolymer” can be used interchangeably.

[0072] In some instances, a PEBA copolymer may be represented by the following general formula: where PA is a polyamide block, PE is a polyether block and p indicates the length of the PEBA copolymer and is indicative of the total number of polyamide and polyether blocks.

[0073] In some instances, a PEBA copolymer may be represented by the following general formula: where, EG is a first unspecified end group, B is unspecified bridging group, and EG* is second unspecified end group, where EG, B, and EG* are determined by the method of synthesis used to make the PEBA copolymer; and where n indicates the length of a polyamide block, x indicates the length of the amide component within a polyamide block, m indicates the length of a poly (ether) block, y indicates the length of the ether component within a poly (ether) block, and p indicates the length of the PEBA copolymer and is indicative of the total number of polyamide and polyether blocks.

[0074] In some instances, a PEBA copolymer may be represented by the following general formula: where n indicates the length of a polyamide block, x indicates the length of the amide component within a polyamide block, m indicates the length of a poly(ether) block, y indicates the length of the ether component within a poly(ether) block, and p indicates the length of the PEBA copolymer and is indicative of the total number of polyamide and poly ether blocks.

[0075] Suitable PEBA copolymers for use in some embodiments of the present disclosure are described in U.S. Pat. No. 5,986,005 which is incorporated herein in its entirety by reference. Suitable PEBA copolymers which may be used in some embodiments of the present disclosure, including methods for their preparation are further described by Malet, F.L. G. in The Handbook of Condensation Thermoplastic Elastomers, Chapter 9 30 (“Thermoplastic Poly(Ether-b-Amide) Elastomers: Synthesis”, 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, pages 243-262, and Eustache, R. P. in The Handbook of Condensation Thermoplastic Elastomers, Chapter 10 “Poly(Ether-b-Amide) Thermoplastic Elastomers: Structure, Properties, and Applications”, 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, pages 263-281, both of which are incorporated herein in their entirety by reference.

[0076] In some instances, a PEBA copolymer is the result of a copolycondensation reaction between one or more polyamide having reactive ends groups and one or more poly(oxyalkylene), such as for example, poly(oxyethylene), having reactive ends groups. Reactive end groups on a polyamide include for example, diamine chain ends, and dicarboxylic chain ends. Reactive end groups on a poly(oxyalkylene) include for example, dicarboxylic chain ends, diol chain ends, and diamine chain ends.

[0077] In some instances, a poly(oxyalkylene) having diamine chain ends is obtained by cyanoethylation and hydrogenation of alpha-omega-dihydroxy aliphatic poly(oxyalkylene)s, which are also known in the art as polyether diols.

[0078] In some instances, a polyamide having dicarboxylic chain ends is obtained by condensation of alpha-omega-aminocarboxylic acids of lactams (e.g., laurolactam), which is a bifunctional monomer or by condensation of dicarboxylic acids with diamines. Condensation polymerization may take place in the presence of a chain limiting dicarboxylic acid.

[0079] In some instances, a polyamide block in the PEBA copolymer is derived from polyamide-12 (PA-12), or polyamide-11 (PA-11), or polyamide-6 (PA-6), or polyamide-66 (PA-66).

[0080] In some instances, the number average molecular weight, Mn of the polyamide blocks in a PEBA copolymer will be from about 100 to about 15,000 g / mol, or about 300 to about 15,000 g / mol, or from about 600 to about 10,000 g / mol, or from about 600 to about 5,000 g / mol.

[0081] In some instances, the number average molecular weight, Mn of the polyether blocks in a PEBA copolymer will be from about 100 to about 15,000 g / mol, or from about 100 to about 10,000 g / mol, or from about 100 to about 6,000 g / mol, or from about 100 to about 3,000 g / mol, or from about 200 to about 6,000 g / mol, or from about 200 to about 3,000 g / mol, or from about 250 to about 2,000 g / mol, or from about 750 to about 3,500 g / mol, or from about 1,000 to about 3,000 g / mol.

[0082] In some instances, the number average molecular weight, Mn of a PEBA copolymer will be from 10,000 to 500,000 g / mol, including subranges within this range and any number within this range. For example, in some embodiments of the disclosure, the number average molecular weight, Mn of the PEBA copolymer may be from 10,000 to 400,000 g / mol, or from 10,000 to 300,000 g / mol, of from 10,000 to 250,000 g / mol, or from 15,000 to 300,000 g / mol, or from 20,000 to 300,000 g / mol, or from 15,000 to 200,000 g / mol, or from 20,000 to 200,000 g / mol, or from 30,000 to 250,000 g / mol, or from about 25,000 to about 75,000 g / mol, or from about 50,000 to about 75,000 g / mol, or from about 100,000 to about 150,000 g / mol.

[0083] In some instances, the weight average molecular weight, Mw of a PEBA copolymer will be from 25,000 to 500,000 g / mol, including subranges within this range and any number within this range. For example, in some embodiments of the disclosure, the weight average molecular weight, Mw of the PEBA copolymer may be from about 100,000 to about 250,000 g / mol, or from about 100,000 to about 150,000 g / mol, or from about 125,000 to about 150,000 g / mol.

[0084] In some instances, the blocks of the polyamide and the polyether within a PEBA copolymer may be randomly distributed.

[0085] In some instances, the PEBA copolymer includes polyamide blocks and polyether blocks, and the polyamide blocks make up at least 50 percent by weight of the copolymer. In some instances, the PEBA copolymer includes polyamide blocks and polyether blocks, and the polyether blocks make up at least 50 percent by weight of the copolymer. In further some instances, the PEBA copolymer includes polyamide blocks and polyether blocks, and the molar ratio of polyamide blocks to polyether blocks is in the range of from 1 : 3 to 3 : 1 , or from 1:2 to 2: 1, or from 3:2 to 1:3, or from 2:3 to 3: 1, or is about 1: 1.

[0086] In some instances, the PEBA copolymer having polyamide blocks and polyether blocks may be prepared by reaction of polyamide and polyether block precursors. For example, a lactam, a polyether diol, and a chain-limiting diacid may be reacted together in the presence of a small amount of water to give a PEBA copolymer having polyamide blocks and polyether blocks of variable length and a statistically random distribution within the block copolymer chain.

[0087] In some instances, polyether blocks may be derived from poly(oxyethylene), or from poly(oxypropylene), or from poly(tetramethylene ether) glycol, each in their natural state and copoly condensed with polyamide blocks containing carboxylic chain ends. Chain limiting agents may also be present during the polycondensation reaction to give PEBA copolymers containing polyamide blocks and polyether blocks which are randomly distributed within the block copolymer.

[0088] In some instances, polyether blocks may be derived from poly(oxyethylene), or from poly(oxypropylene), or from poly(tetramethylene ether) glycol, which are first converted into oly ether diamines by amination, and then copolycondensed with polyamide blocks containing carboxylic chain ends. Chain limiting agents may also be present during the polycondensation reaction to give PEBA copolymers containing polyamide blocks and polyether blocks which are randomly distributed within the block copolymer.

[0089] Suitable PEBA copolymers which may be used in some embodiments of the disclosure are described in, U.S. Pat. Nos 4,331,786; 4,115,475; 4,195,015; 4,839,441; 4,864,014; 4,230,838; 4,332,920; and 5,986,005 each of which is incorporated herein in its entirety by reference. Additional PEBA copolymers which may be used in some embodiments of the disclosure are described in U.S. Pat. No. 8,231,950, which is incorporated by reference in its entirety.

[0090] In some embodiments of the present disclosure, a polyether block may be derived from a 25 poly (oxy ethylene), also known as a polyethylene glycol (PEG); or poly(oxypropylene), also known as polypropylene glycol (PPG). In some embodiments, a polyether block may be derived from poly(tetramethylene ether) glycol (PTMG), also known as polytetramethylene oxide (PTMEO) or polytetrahydrofuran (PTHF).

[0091] In some embodiments, the PEBA copolymer includes: i) polyamide blocks selected from polyamide-12 (PA-12), polyamide-11 (PA-11), polyamide-6 (PA-6), or mixtures thereof; and ii) polyether blocks selected from polyethylene glycol (PEG), polypropylene glycol (PPG), polytetrahydrofuran (PTHF), or mixtures thereof.

[0092] In some embodiments, the PEBA copolymer includes: i) polyamide blocks selected from polyamide-12 (PA-12), polyamide-11 (PA-11), polyamide-6 (PA-6), or mixtures thereof; and ii) polyether blocks which are polyethylene glycol (PEG).

[0093] In some embodiments, the PEBA copolymer includes: i) polyamide blocks which are polyamide-12 (PA- 12) and ii) poly ether 5 blocks which are polyethylene glycol (PEG).

[0094] In some embodiments, the PEBA copolymer includes from 10 to 20 polyamide blocks and from 10 to 20 polyether blocks.

[0095] In some embodiments, the PEBA copolymer includes only one type of polyamide block and only one type of polyether block.

[0096] In some embodiments, the PEBA copolymer includes: i) polyamide blocks which are polyamide-12 (PA-12) and ii) polyether blocks which are polyethylene glycol (PEG), wherein the polyamide-12 blocks represent about 30 to 70 weight percent of the copolymer, and the polyethylene glycol blocks represent about 70 to 30 weight percent of the copolymer.

[0097] In some embodiments, the PEBA copolymer includes: i) polyamide blocks which are polyamide-12 (PA-12) and ii) polyether blocks which are polyethylene glycol (PEG), wherein the polyamide-12 blocks represent about 40 to 50 weight percent of the copolymer, and the polyethylene glycol blocks represent about 60 to 40 weight percent of the copolymer.

[0098] In some embodiments, the PEBA copolymer includes: i) polyamide blocks which are polyamide-12 (PA-12) and ii) polyether blocks which are polyethylene glycol (PEG), wherein the polyamide-12 blocks represent about 45 weight percent of the copolymer, and the polyethylene glycol blocks represent about 55 weight percent of the copolymer.

[0099] In some embodiments, the PEBA copolymer includes: i) from 10 to 20 polyamide blocks which are polyamide-12 (PA- 12) and ii) from 10 to 20 polyether blocks which are polyethylene glycol (PEG).

[0100] In some embodiments, the PEBA copolymer includes: i) polyamide 30 blocks which are polyamide-12 (PA- 12) and ii) polyether blocks which are polyethylene glycol (PEG), and has a number average molecular weight, Mn of from about 25,000 to about 75,000 g / mol. In some embodiments, the PEBA copolymer includes: i) polyamide blocks which are polyamide-12 (PA-12) and ii) polyether blocks which are polyethylene glycol (PEG), and has a number average molecular weight, Mn of about 66,100 g / mol.

[0101] In some embodiments, the PEBA copolymer includes: i) polyamide blocks which are polyamide-12 (PA-12) and ii) polyether blocks which are polyethylene glycol (PEG), and has a weight average molecular weight, Mw of from about 100,000 to about 150,000 g / mol.

[0102] In some embodiments, the PEBA copolymer includes: i) polyamide blocks which are polyamide-12 (PA-12) and ii) polyether blocks which are polyethylene glycol (PEG), and has a weight average molecular weight, Mw of about 134,000 g / mol.

[0103] In some embodiments, the PEBA copolymer includes: i) polyamide blocks which are polyamide-6 (PA-6) and ii) polyether blocks which are polyethylene glycol (PEG).

[0104] In some embodiments, the PEBA copolymer includes: i) polyamide blocks which are polyamide-6 (PA-6) and ii) polyether blocks which are polyethylene glycol (PEG), wherein the polyamide-6 blocks represent about 30 to 60 weight percent of the copolymer, and the polyethylene glycol blocks represent about 70 to 40 weight percent of the copolymer.

[0105] In some embodiments, the PEBA copolymer includes: i) polyamide blocks which are polyamide-6 (PA-6) and ii) polyether blocks which are polyethylene glycol (PEG), wherein the polyamide-6 blocks represent about 50 to 35 weight percent of the copolymer, and the polyethylene glycol blocks represent about 50 to 65 weight percent of the copolymer.

[0106] In some embodiments, the PEBA copolymer includes: i) from 10 to 20 polyamide blocks which are polyamide-6 (PA-6) and ii) from 10 to 20 polyether blocks which are polyethylene glycol (PEG).

[0107] In some embodiments, the PEBA copolymer includes: i) polyamide blocks which are polyamide -11 (PA-11) and ii) poly ether blocks which are polyethylene glycol (PEG).

[0108] In some embodiments, the PEBA copolymer includes: i) polyamide blocks which are polyamide-12 (PA- 12) and ii) poly ether blocks which are polytetrahydrofuran (PTHF).

[0109] In some embodiments, the PEBA copolymer includes: i) polyamide blocks which are polyamide-12 (PA-12) and ii) polyether blocks which are polytetrahydrofuran (PTHF), wherein the polyamide-12 blocks represent about 75 to 10 weight percent of the copolymer, and the polytetrahydrofuran blocks represent about 25 to 90 weight percent of the copolymer.

[0110] In some embodiments, the PEBA copolymer includes: i) polyamide blocks which are polyamide-12 (PA-12) and ii) polyether blocks which are polytetrahydrofuran (PTHF), wherein the polyamide-12 blocks represent about 80 to 60 weight percent of the copolymer, and the polytetrahydrofuran blocks represent about 20 to 40 weight percent of the copolymer. In some embodiments, the PEBA copolymer includes: i) polyamide blocks which are polyamide-12 (PA-12) and ii) polyether blocks which are polytetrahydrofuran (PTHF), wherein the polyamide-12 blocks represent about 40 to 60 weight percent of the copolymer, and the polytetrahydrofuran blocks represent about 60 to 40 weight percent of the copolymer.

[0111] In some embodiments, the PEBA copolymer includes: i) polyamide blocks which are polyamide-12 (PA-12) and ii) polyether blocks which are polytetrahydrofuran (PTHF), wherein the polyamide-12 blocks represent about 30 to 10 weight percent of the copolymer, and the polytetrahydrofuran blocks represent about 70 to 90 weight percent of the copolymer.

[0112] In some embodiments, the PEBA copolymer includes: i) from 10 to 20 polyamide blocks which are polyamide-12 (PA- 12) and ii) from 10 to 20 polyether blocks which are polytetrahydrofuran (PTHF).

[0113] In some embodiments, the PEBA copolymer includes: i) polyamide blocks which are polyamide-12 (PA-12) and ii) polyether blocks which are polytetrahydrofuran (PTHF), and has a number average molecular weight, Mn of from about 25,000 to about 75,000 g / mol.

[0114] In some embodiments, the PEBA copolymer includes: i) polyamide blocks which are polyamide-12 (PA-12) and ii) polyether blocks which are polytetrahydrofuran (PTHF), and has a number average molecular weight, Mn of about 50,000 g / mol.

[0115] In some embodiments, the PEBA copolymer includes: i) polyamide blocks which are polyamide-6 (PA-6) and ii) polyether blocks which are polytetrahydrofuran (PTHF).

[0116] In some embodiments, the PEBA copolymer includes: i) polyamide blocks which are polyamide -11 (PA-11) and ii) poly ether blocks which are polytetrahydrofuran (PTHF).

[0117] In some embodiments, the PEBA copolymer is a commercially available elastomer and is sold under the trade name PEBAX®.

[0118] In some embodiments of the present disclosure, the PEBA copolymer is a commercially available elastomer selected from the group consisting of: PEBAX 2533 SA 01, PEBAX 2533 SA 01 MED, PEBAX 2533 SD 02, PEBAX 3533 SA 01, PEBAX 3533 SA 01 MED, PEBAX 3533 SP 01, PEBAX 4011, PEBAX 4033 SA 01, PEBAX 4033 SA 01 MED, PEBAX 4033 SP 01, PEBAX 4533 SA 01, PEBAX 4533 SA 01 MED, PEBAX 4533 SP 01, PEBAX 5513 SA 01, PEBAX 5513 SP 01, PEBAX 5533 SA 01, PEBAX 5533 SA 01MED, PEBAX 5533 SN 70 BLACK, PEBAX 5533 SP 01, PEBAX 6333 SA 01, PEBAX 6333 SA 01 MED, PEBAX 6333 SP01, PEBAX 7033 SA 01, PEBAX 7033 SA 01 MED, PEBAX 7033 SP 01, PEBAX 7233 SA 01, PEBAX 7233 SA 01 MED, PEBAX 7233 SP 01, PEBAX 7433 SA 01 MED, PEBAX Clear 1200, PEBAX ES 9002 UV, PEBAX MH 1657, PEBAX MH2030, PEBAX MV 1074 SA 01, PEBAX MV 1074 SA 01 MED, PEBAX MV 1074 SP 01, PEBAX MV 2080, PEBAX MV 3000 SP 01, PEBAX Rnew® 30R51 SA 01, PEBAX Rnew 35R53 SP 01, PEBAX Rnew 40 R53 SP 01, PEBAX Rnew 55R53 SP 01, PEBAX Rnew 63R53 SP 01, PEBAX Rnew 70R53 SP 01, PEBAX Rnew 72R53 SP 01, PEBAX Rnew 80R53 SP 02, and mixtures thereof. In some embodiments, the PEBA copolymer is an elastomer consistent with materials which are commercially available under the tradename PEBAX MV 1074. In some embodiments, the PEBA copolymer includes one or more of PEBAX MV 1074 SA 01, PEBAX MV 1074 SA 01 MED, and PEBAX MV 1074 SP 01.

[0119] In some embodiments, the PEBA copolymer is a commercially available elastomer and is sold under the tradename VESTAMID® or VESTAMID E.

[0120] In some embodiments, the PEBA copolymer is a commercially available elastomer selected from the group consisting of: VESTAMID D, VESTAMID DX, VESTAMID E, VESTAMID EX, VESTAMID Care, VESTAMID Care ML, VESTAMID Care ME, VESTAMID Care ME-B, VESTAMID L, VESTAMID LX, VESTAMID NRG, VESTAMID Terra, VESTAMID X, and mixtures thereof.

[0121] In some embodiments, the PEBA can include two polyether block amides of different number average molecular weight, Mn.

[0122] In some embodiments, the PEBA can include two polyether block amides of different number average molecular weight, Mn, and the two polyether block amides having different Mn, will be present in a mole ratio of from 1 : 99 to 99: 1 including any sub range encompassed within this range and any value within this range. For example, in some embodiments of the disclosure, the PEBA will include two polyether block amides of different number average molecular weight, Mn, in a mole ratio of from 5:95 to 95:5, or from 10:90 to 90: 10, or from 20:80 to 80:20, or from 25:75 to 75:25, or from 35:65 to 65:35, or from 40:60 to 60:40, or about 50:50.

[0123] The added PEBA copolymer may be used in the form of a semi solid or a viscous liquid, or as powders, pellets, or granules.

[0124] The Virgin Polyethylene

[0125] In some embodiments, the extrudable polymeric composition disclosed herein may include virgin polyethylene. The type, nature, and amount of virgin polyethylene may be chosen based on desired final properties of, or uses for, the extrudable polymeric composition.

[0126] In some embodiments, the virgin polyethylene is one or more of LDPE, LLDPE, MDPE, HDPE, or VLDPE, and may be in the form of powders, pellets, granules, or any other form suitable for preparing the extrudable polymeric composition. In some embodiments, the virgin polyethylene is a LLDPE.

[0127] In some embodiments, the virgin polyethylene is a LLDPE having a melt index, h, of from 0.1 g to 10.0 g / 10 min, or from 0.5 g to 5.0 g / 10 min as measured by ASTM D 1238, using conditions 190°C and a 2. 16 kg weight.

[0128] In some embodiments, the virgin polyethylene has a density of from about 0.910 g / cm3to about 0.936 g / cm3as measured by ASTM D 792.

[0129] In some embodiments, the virgin polyethylene has a density from about 0.915 g / cm3to about 0.925 g / cm3as measured by ASTM D 792, and a melt index, h, of from 0.1 g to 10.0 g / 10 min, or from 0.5 g to 5.0 g / 10 min as measured by ASTM D 1238, using conditions 190°C and a 2.16 kg weight.

[0130] The virgin polyethylene may be a commercially available polyethylene. A nonlimiting example of a virgin polyethylene suitable for the extrudable polymeric compositions including recycled polyethylene disclosed herein is LP120-A, commercially available from NOVA Chemicals (Canada). LP120-A has a melt index, I2, of 1.0 g / 10 minutes and a density of 0.920 g / cm3.

[0131] Additives

[0132] The extrudable polymeric compositions of the present invention can include an additive or multiple additives that are not the polyether block amide. Non-limiting examples of additives include an antioxidant, a light stabilizer, an ultra-violet (UV), stabilizer, a polyamide stabilizer, a co-stabilizer, a nucleating agent, a metal deactivator, a slip agent, an anti-blocking agent, a colorant, an antistatic agent, or a mixture thereof. The polymeric composition can include an amount of additives, based on the total weight of the composition, of 0 and 1 wt.%, preferably 0.01 wt.% and less than 1 wt.% or between 0.5 wt.% and less than 1 wt.%, or 0 wt.%, 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, or 1 wt.% or any range or value therebetween.

[0133] Non-limiting examples of antioxidants include alkylated mono-phenols (also described herein as “hindered phenol primary antioxidants”). Non-limiting examples of hindered phenols include 2,6-di-tert-butyl-4-methylphenol; 2-tert-butyl-4,6-dimethylphenol; 2,6-di-tert- butyl-4-ethylphenol; 2,6-di-tert-butyl-4-n-butylphenol; 2,6-di-tert-butyl-4- isobutylphenol; 2,6-dicyclopentyl-4-methylphenol; 2-(alpha.-methylcyclohexyl)-4,6 dimethylphenol; 2,6-di- octadecyl-4-methylphenol; 2,4,6,-tricyclohexyphenol; and 2,6-di- tert-butyl-4- methoxy methylphenol. Suitable hindered phenolic antioxidants which can be used in embodiments of the disclosure, are sold under the trademarks IRGANOX® 1010 (CAS Registry number 6683-19-8) and IRGANOX 1076 (CAS Registry number 2082-79-3) by BASF Corporation.

[0134] In some embodiments, antioxidants can include alkylated hydroquinones. Nonlimiting examples of alkylated hydroquinones include 2,6-di-tert-butyl-4-methoxyphenol; 2,5-di-tert- butylhydroquinone; 2,5-di-tert-amyl-hydroquinone; and 2,6-diphenyl-4- octadecyloxyphenol .

[0135] Other non-limiting examples of antioxidants include thiodiphenyl ethers. Nonlimiting examples of thiodiphenyl ethers include: 2,2'-thio-bis-(6-tert-butyl-4- methylphenol); 2,2'-thio-bis-(4-octylphenol); 4,4'-thio-bis-(6-tertbutyl-3-methylphenol); and 4, 4'-thio-bis-(6-tert-butyl-2 -methylphenol).

[0136] In embodiments of the present invention, an antioxidant can include alkylidenebisphenols. Non-limiting examples of alkylidenebisphenols can include 2,2'- methylene-bis-(6-tert-butyl-4-methylphenol); 2,2'- methylene-bis-(6-tert-butyl-4- ethylphenol); 2,2'-methylene-bis-(4-methyl-6-(alpha- methylcyclohexyl)phenol); 2,2'- methylene-bis-(4-methyl-6-cyclohexylphenol); 2,2'- methylene-bis-(6-nonyl-4- methylphenol); 2,2'-methylene-bis-(6-nonyl-4-methylphenol); 2,2'-methylene-bis-(6-(alpha- methylbenzyl)-4-nonylphenol); 2,2'-methylene-bis-(6-(alpha, alpha-dimethylbenzyl)-4- nonyl -phenol); 2,2'-methylene-bis-(4,6-di-tert-butylphenol); 2,2'-ethylidene-bis-(6-tert- butyl-4-isobutylphenol); 4,4'-methylene-bis-(2,6-di-tert-butylphenol); 4,4'-methylene-bis-(6- tert-butyl-2-methylphenol); l,l-bis-(5-tert-butyl-4-hydroxy-2- methylphenol)butane 2,6-di- (3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol; l,l,3-tris-(5-tert-butyl-4-hydroxy- 2-methylphenyl)butane; l,l-bis-(5-tert-butyl-4-hydroxy-2- methylphenyl)-3-dodecyl- mercaptobutane; ethylene glycol-bis-(3,3,-bis-(3'-tert-butyl-4'- hydroxyphenyl)-butyrate)-di- (3 -tert-butyl -4-hydroxy-5 -methylpenyl) -dicyclopentadiene ; di- (2-(3 '-tert-butyl -2 'hydroxy- 5'methylbenzyl)-6-tert-butyl-4-methylphenyl)terephthalate; and other phenolics such as monoacrylate esters of bisphenols such as ethylidene bis-2,4-di-t- butylphenol monoacrylate ester.

[0137] In certain aspects, antioxidants can include benzyl compounds. Non-limiting examples of benzyl compounds include: l,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6- trimethylbenzene; bis-(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide; isooctyl 3,5-di-tert-butyl- 4-hydroxybenzyl-mercaptoacetate; bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol- terephthalate; l,3,5-tris-(3,5-di-tert-butyl-4,10 hydroxybenzyl)isocyanurate; l,3,5-tris-(4- tert- butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate; dioctadecyl 3,5-di-tert-butyl-4- hydroxybenzylphosphonate; calcium salt of monoethyl 3,5-di-tertbutyl-4- hydroxybenzylphosphonate; and l,3,5-tris-(3,5-dicyclohexyl-4- hydroxybenzyl)isocyanurate.

[0138] Non-limiting examples of an acvlaminophenol antioxidant can include: 4-hydroxy- lauric acid anilide; 4-hydroxy-stearic acid anilide; 2,4-bis-octyhnercapto-6-(3,5-tert-butyl-4- hydroxyanilino)-s-triazine; and octyl- N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate.

[0139] Non-limiting examples of other antioxidants can include esters of beta-(5 -tert-butyl - 4-hydroxy-3-methylphenyl)-propionic acid with monohydric or polyhydric alcohols. Nonlimiting examples of such compounds include: methanol; diethyleneglycol; octadecanol; triethyleneglycol; 1,6-hexanediol; pentaerythritol; neopentylglycol; tris -hydroxy ethyl isocyanurate; tridiethyleneglycol; and dihydroxy ethyl oxalic acid diamide. In embodiments of the disclosure, a primary antioxidant is selected from amides of beta-(3,5-di-tert-butyl-4- hydroxyphenol)-propionic acid, such as for example, N,N'-di-(3,5- di-tert-butyl-4- hydroxyphenylpropionyl)-hexamethylendiamine ; N,N'-di-(3 ,5 -di-tert-butyl- 4- hydroxyphenylpropionyl) trimethylenediamine; and N,N'-di(3,5-di-tert-butyl-4- hy droxypheny Iprop iony 1) -hydrazine .

[0140] Non-limiting examples of other antioxidants can include phosphites and phosphonites (also described herein as “phosphorus containing secondary antioxidants”), such as, for example, triphenyl phosphite; diphenylalkyl phosphites; phenyldialkyl phosphites; tris (nonyl -phenyl)phosphite [WESTON® 399, available from SI Group]; phosphorous acid, mixed 2,4-bis(l,l-dimethylpropyl)phenyl and 4-( 1 , 1- dimethylpropyl)phenyl triesters [WESTON 705, CAS Reg. No. 939402-02-5, available from SI Group]; trilauryl phosphite; trioctadecyl phosphite; distearyl pentaerythritol diphosphite; tris(2,4-di-tert- butylphenyl)phosphite [IRGAFOS 168, available from BASF]; diisodecyl pentaerythritol diphosphite; 2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-l,3-propanediol phosphite; bis(2,4-di- tert-butyl-6-methylphenyl) ethyl phosphite [IRGAFOS 38, available from BASF]; 2, 2', 2"- nitrilo[triethyltris(3,3'5,5'-tetra-tert-butyl-l,r-biphenyl- 2,2'-diyl) phosphite [IRGAFOS 12, available from BASF]; bis(2,4-di-tert- butylphenyl)pentaerythritol diphosphite tristearyl sorbitol triphosphite; tetrakis(2,4-di-tert- butylphenyl)4,4'-biphenylene diphosphonate; 6-[3- (3 -tert-butyl -4-hydroxy-5- methylphenyl)propoxy]-2,4,8, 10-tetra-tert-butyldibenzo[d,f] [1,3,2] dioxaphospepin [SUMILIZER® GP]; bis(2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphate; bis(2,4- dicumylphenyl)pentaerythritol diphosphate; distearyl pentaerythritol diphosphate; diisodecyl pentaerythritol diphosphate; bis(2,4 di-tert-butylphenyl) pentaerythritol diphosphite [ULTRANOX® 626, available from SI Group]; bis(2,6-di-tert- butyl-4-methylpenyl) pentaerythritol diphosphite; bisisodecyloxy-pentaerythritol diphosphite; bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite; bis(2,4,6-tri- tert- butylphenyl) pentaerythritol diphosphite; tetrakis(2,4-di-tert-butylphenyl)4,4'- bipheylene-diphosphonite [IRGAFOS P-EPQ, available from BASF]; bis(2,4- dicumylphenyl)pentaerythritol diphosphite [DOVERPHOS® S9228-T or DOVERPHOS S9228-CT] and P-EPQ® (CAS Reg. No. 119345-01-06) a commercially available diphosphonate; or a mixture thereof. In embodiments of the disclosure, a secondary antioxidant is selected from DOVERPHOS LGP-11, DOVERPHOS LGP-12 and DOVERPHOS LGP-12LV. In some embodiments, alkylphenol free, polymeric polyphosphites, can be used. Non-limiting examples of which are disclosed in U.S. Pat. No. 8,563,637.

[0141] Antioxidants can also include hydroxylamines and amine oxides. Non-limiting examples of hydroxylamines and amine oxides can include N,N-dibenzylhydroxylamine; N,N- diethylhydroxylamine; N,N-dioctylhydroxylamine; N,N-dilaurylhydroxylamine; N,N- ditetradecylhydroxylamine; N,N-dihexadecylhydroxylamine; N,N- dioctadecylhydroxylamine; N-hexadecy- 1 -N-octadecylhydroxylamine; N-heptadecyl-N- octadecylhydroxylamine; and N,N-dialkylhydroxylamine derived from hydrogenated tallow amine. The analogous amine oxides are also suitable. A commercially available example of hydroxylamine which may be used in embodiments of the disclosure is the N,N- di(alkyl)hydroxylamine sold as IRGASTAB® 042 (by BASF) and which is reported to be prepared by the direct oxidation of N,N - di (hydrogenated) tallow amine.

[0142] In some embodiments, an antioxidant can include a nitrone. Non-limiting examples of nitrones include N-benzyl-alpha-phenyl nitrone; N-ethyl-alpha- methyl nitrone; N- octyl- alpha-heptyl nitrone; N-lauryl-alpha-undecyl nitrone; N-tetradecyl-alpha-tridecyl nitrone; N- hexadecyl-alpha-pentadecyl nitrone; N-octadecyl-alpha-heptadecylnitrone; N- hexadecyl- alpha-heptadecyl nitrone; N-octadecyl-alpha-pentadecyl nitrone; N-heptadecyl- alphaheptadecyl nitrone; N-octadecyl- alpha-hexadecyl nitrone; and nitrone derived from N, N- dialkylhydroxylamine derived from hydrogenated tallow amine.

[0143] Non-limiting examples of UV absorbers and / or light stabilizers include 2-(2'- hydroxyphenyl)-benzotriazoles, such as, for example, the 5'-methyl-; 3',5'-di-tert- butyl-; 5'- tert-butyl-; 5'(l,l,3,3-tetramethylbutyl)-; 5-chloro-3',5'-di-tert-butyl-; 5-chloro-3'- tert-butyl- 5'-methyl-; 3'-sec-butyl-5'-tert-butyl-; 4'-octoxy-3',5'-di-tert-amyl-; and 3',5'-bis- (alpha, alpha - dimethylbenzyl) derivatives.

[0144] Other UV absorber or light stabilizer can include 2 -hydroxy-benzophenones. Nonlimiting examples of benzophenones include: the 4-hydroxy-; 4-methoxy-; 4-octoxy; 4- decyloxy-; 4-dodecyloxy-; 4-benzyloxy-; 4,2',4'-trihydroxy-; and 2'-hydroxy-4,4'- dimethoxy derivative.

[0145] In some embodiments, a UV absorber or light stabilizer can be a sterically hindered amines. Non-limiting examples of sterically hindered amines include: bis (2, 2,6,6- tetramethylpiperidyl)-sebacate; bis-5(l,2,2,6,6-pentamethylpiperidyl)-sebacate; n-butyl-3,5- di-tert-butyl-4- hydroxybenzyl malonic acid bis(l,2,2,6,6,-pentamethylpiperidyl)ester; condensation product of l-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidine and succinic acid; condensation product of N,N'-(2,2,6,6-tetramethylpiperidyl)- hexamethylendiamine and 4- tert-octylamino-2,6-dichloro-l,3,5-s-triazine; tris-(2, 2,6,6- tetramethylpiperidyl)- nitrilotriacetate, tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)- l,2,3,4butane-tetra-arbonic acid; and l,l'(l,2-ethanediyl)-bis-(3, 3,5,5- tetramethylpiperazinone). These amines are typically called HALS (Hindered Amines Light Stabilizing) and include butane tetracarboxylic acid 2,2,6,6-tetramethyl piperidinol esters. Such amines include hydroxylamines derived from hindered amines, such as di(l -hydroxy- 2, 2, 6, 6-tetramethylpiperidin-4-yl) sebacate; 1- hydroxy 2,2,6,6-tetramethyl-4- benzoxypiperidine; 1 -hydroxy -2, 2, 6, 6-tetramethyl-4-(3,5-di- tert-butyl -4-hydroxy hydrocinnamoyloxy)-piperdine; and N-(l-hydroxy-2, 2,6,6- tetramethyl-piperidin-4-yl)- epsiloncaprolactam. Suitable commercially available HALS which may be used in embodiments ofthe disclosure include those sold underthe trademarks CHIMASSORB® 119; CHIMASSORB 944; CHIMASSORB 2020; TINUVIN® 622 and TINUVIN 770 from BASF, and CYASORB® UV 3346, CYASORB UV 3529, CYASORB UV 4801, and CYASORB UV 4802 from Solvay. In other embodiments, the use of mixtures of more than one HALS are also contemplated.

[0146] Other examples of a UV absorber or light stabilizer are substituted and unsubstituted benzoic acids. Non-limiting examples of benzoic acids can include: phenyl salicylate; 4- tertbutylphenyl-salicylate; octylphenyl salicylate; dibenzoylresorcinol; bis-(4-tert- butylbenzoyl)-resorcinol; benzoylresorcinol; 2, 4-di -tert-butyl -phenyl-3, 5 -di -tert-butyl-4- hydroxybenzoate; and hexadecyl-3, 5-di-tert-butyl-4-hydroxybenzoate.

[0147] In some embodiments, a UV absorber or light stabilizer can be an acrylates. Nonlimiting examples of acrylates can include: alpha-cyano-beta,beta-diphenylacrylic acid-ethyl ester or isooctyl ester; alpha-carbomethoxy-cinnamic acid methyl ester; alpha-cyano-beta- methyl-p- methoxy-cinnamic acid methyl ester or butyl ester; alpha-carbomethoxy-p- methoxy-cinnamic acid methyl ester; and N-(beta-carbomethoxy-beta-cyano-vinyl)-2- methyl- indoline. Non-limiting examples of co-stabilizers can include melamine; polyvinylpyrrolidone; dicyandiamide; triallyl cyanurate; urea derivatives; hydrazine derivatives; amines; polyurethanes; alkali metal salts and alkaline earth metal salts of higher fatty acids, for example, Ca stearate, calcium stearoyl lactate, calcium lactate, Zn stearate, Mg stearate, Na ricinoleate and K palmitate; antimony pyrocatecholate or zinc pyrocatecholate, including neutralizers such as hydrotalcites and synthetic hydrotalcites; and Li, Na, Mg, Ca, Al hydroxy carbonates. Hydrotalcites which may be used in embodiments of the present invention can, include materials commercially available under the general tradenames DHT-4® (A, C, or V), ZHT-4V®, HYCITE® 713, and AC-207™.

[0148] Non-limiting examples of nucleating agents can include 4-tert-butylbenzoic acid; adipic acid; diphenylacetic acid; sodium salt of methylene bis-2,4-dibutylphenyl; cyclic phosphate esters; sorbitol tris-benzaldehyde acetal; and sodium salt of bis(2,4-di-t- butylphenyl) phosphate or Na salt of ethylidene bis(2,4-di-t-butyl phenyl)phosphate. Nucleating agents may improve stiffness of a rotomolded part.

[0149] In some embodiments, slip agents can be used. Non-limiting examples of slip agents can include oleamide; erucamide; stearamide; and behenamide.

[0150] In some embodiments, metal deactivators can be used. Non-limiting examples of metal activators can include N,N'-diphenyloxalic acid diamide, N-salicylal-N'- salicyloylhydrazine, N,N'-bis-salicyloylhydrazine, N,N'-bis-(3,5-di-tert-butyl-4- hydrophenylpropionyl)-2 -hydrazine, salicyloylamino-I,2,4-triazole, and bis-benzyliden- oxalic acid dihydrazide.

[0151] Non-limiting examples of polyamide stabilizers copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.

[0152] Other additives can include plasticizers, epoxidized vegetable oils, such as epoxidized soybean oils, lubricants, emulsifiers, pigments, optical brighteners, flameproofing agents, anti-static agents, blowing agents and thiosynergists, such as dilaurythiodipropionate or distearylthiodipropionate .

[0153] Non-limiting examples of fillers and reinforcing agents can include calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, and graphite.

[0154] Method of Making the Extrudable Polymeric Composition

[0155] The extrudable polymeric compositions of the present disclosure can be made using known compounding methodology. In some embodiments, the polyether block amide may be dry blended in the required weight ratio with the recycled polyethylene, and optionally the virgin polyethylene and / or other additives, in a suitable device such as a tumble blender. The resulting dry blend can then be melted in a suitable compounding equipment (e.g., an extruder).

[0156] The recycled polyethylene and / or virgin polyethylene can be provided in the form of powders, pellets, granules, or in any other extrudable form to prepare the extrudable polymeric composition.

[0157] In some embodiments, a masterbatch can be prepared, added to the recycled polyethylene, melt blended, and extruded. In some embodiments of the present disclosure, a polyether block amide is added to the extrudable polymeric composition using a masterbatch formulation containing the polyether block amide and a virgin polyethylene carrier. In some embodiments, the virgin polyethylene carrier is an LLDPE.

[0158] In some embodiments of the present disclosure, from about 0.1 to about 15.0 weight percent, or from about 0.5 to about 15.0 weight percent, or from about 0.5 to about 10.0 weight percent, or from about 0.1 to about 10.0 weight percent, or from about 0.1 to about

[0159] 7.5 weight percent, or from about 0.5 to about 7.5 weight percent or from about 0.5 to about 5.0 weight percent, or from about 0.1 to about 5.0 weight percent, or from about 1.0 to about 15.0 weight percent, or from about 1.0 to about 5.0 weight percent, or from about 1.0 to about

[0160] 7.5 weight percent, or from about 1.0 to about 5.0 weight percent, or from about 0.1 to about

[0161] 2.5 weight percent, or from about 0.5 to about 2.5 weight percent of a masterbatch can be added to the extrudable polymeric composition, where weight percent of the masterbatch is based on the total weight of the extrudable polymeric composition.

[0162] In some embodiments of the present disclosure, a masterbatch may contain an amount of polyether block amide (PEBA copolymer) from 10,000 ppm to 300,000 ppm based on the weight of the masterbatch (1 wt.% to 30 wt.%) including subranges within this range and any number within this range. In some embodiments, a masterbatch may contain an amount of polyether block amide from 50,000 ppm to 300,000 ppm by weight based on the weight of the masterbatch (5 wt.% to 30 wt.%) including subranges within this range and any number within this range. For example, in some embodiments of the disclosure, a masterbatch may contain an amount of polyether block amide, based on the weight of the masterbatch, in the range of from 10,000 ppm to 50,000 ppm, or from 10,000 ppm to 45,000 ppm, or from 10,000 ppm to 35,000 ppm, or from or from 15,000 ppm to 50,000 ppm, or from 17,500 ppm to 50,000 ppm, or from 20,000 ppm to 50,000 ppm, or from 30,000 ppm to 50,000 ppm, or from 40,000 ppm to 50,000 ppm, or from 50,000 ppm to 250,000 ppm, or from 50,000 to 200,000 ppm, or from 50,000 ppm to 100,000 ppm, or from 75,000 ppm to 250,000 ppm, or from 75,000 ppm to 200,000 ppm, or from 75,000 ppm to 150,000 ppm, or from 75,000 ppm to 100,000 ppm, or from 100,000 ppm to 300,000 ppm, or from 100,000 ppm to 250,000 ppm, or from 100,000 ppm, to 200,000 ppm, or from 100,000 ppm to 150,000 ppm. In some embodiments, the masterbatch contains PEBA copolymer in an amount of 2,500 ppm, or 2.5 wt.%, based on the weight of the masterbatch. In some embodiments, the masterbatch contains polyether block amide in an amount of 5,000 ppm, or 5 wt.%, based on the weight of the masterbatch. In some embodiments, the masterbatch contains polyether block amide in an amount of 100,000 ppm, or 10 wt.%, based on the weight of the masterbatch. In some embodiments, the masterbatch contains polyether block amide in an amount of 150,000 ppm, or 15 wt.%, based on the weight of the masterbatch. In some embodiments, the masterbatch contains polyether block amide in an amount of 200,000 ppm, or 20 wt.%, based on the weight of the masterbatch. In some embodiments, the masterbatch contains polyether block amide in an amount of 250,000 ppm, or 25 wt.%, based on the weight of the masterbatch. In some embodiments, the masterbatch contains polyether block amide in an amount of 300,000 ppm, or 30 wt.%, based on the weight of the masterbatch.

[0163] In some embodiments, the dry components of the blend may be metered directly into an extruder.

[0164] Extruders for thermoplastic polyolefins (e.g., recycled polyethylene and blends of recycled polyethylene and virgin polyethylene) and extrusion processes which employ these extrudes are well known to those skilled in the art. A typical extruder contains one (or two) flighted screws which rotate within a cylinder or “barrel”. The polyolefin can be sheared between the barrel and the screw by the stresses caused by the rotation of the screw. In addition, the barrel of the extruder may be heated. The shear and / or heat cause the plastic to melt and the action of the flighted screw transports it along the length of the extruder. The molten polyolefin composition extrudate can then be forced through a die to form the desired plastic part. The extruder used for the final extrusion may also be a single or twin-screw extruder. The die may be a slot die or it may be an annular ring die extruding a film of the polymer blend about a stable bubble of air. The film can be collapsed after passing over or about the bubble.

[0165] In methods that involve an extruder, the extruder can be a twin or single screw extruder. If it is a twin screw extruder it can be operated in a co-rotating mode (i.e., both screws turning in the same direction) or in a counter rotating mode (i.e., the screws rotate in opposite directions). Specific conditions for operation of any extruder will differ from that of any other extruder. Variations between machines can usually be resolved by non-inventive testing. The extruder can extrude the polymer composition as strands which are then cooled and cut into pellets for subsequent use, typically fdm extrusion.

[0166] For polyolefin compounding, conditions can include temperature and pressure. Temperatures can range from 160°C to 315°C. In some embodiments, the temperature may be 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, 310°C, or 315°C or any value or range therebetween. In some embodiments, the temperature may be between 215°C and 225 °C. Pressures can range from 0. 1 MPa to 65 MPa. In some embodiments, the extrusion pressure is 0.1 MPa, 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa, 10 MPa, 20 MPa, 30 MPa, 40 MPa, 50 MPa, 60 MPa, 65 MPa, or any value or range therebetween, depending on the compounding method. In some embodiments, the extrusion is at a pressure between 3 and 7 MPa.

[0167] Articles Made from the Extrudable Polymeric Composition

[0168] The extrudable polymeric compositions of the present invention can be shaped into a variety of articles and shapes (e.g., pellets, powder, molded parts, films, etc.) by using a variety of methods (e.g., injection molding, extrusion molding, rotation molding, foam molding, calendar molding, blow molding, blow-film molding, thermoforming, compaction, melt spinning, and the like). Non-limiting examples of articles include consumer goods, packaging products, pharmaceutical containers, bottles, caps, closures, liners, trash bags, food packaging film and / or materials, laminations, toys, tanks, wire sheathing, cable sheathing, pipes, hoses, or fittings. In some embodiments, the article of manufacture can include printed or written graphics, lettering, or the like. In some embodiments, the polymeric compositions can be formed into blow molded films. In some embodiments, the polymeric compositions can be used as a monolayer in a film or as a skin or a multilayer package.

[0169] Additionally, the extrudable polymeric compositions (with or without additives) can also be formed into films or sheets as well as components of stacked polymeric materials (e.g., laminates). The sheet can be a foam sheet, paper sheet, or fabric sheet. Articles include, for example, fibers, sheets, films, multilayer sheets, multilayer films, molded parts, and extruded profiles.

[0170] Examples

[0171] The present disclosure will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes only and are not intended to be limiting in any manner. Those of skill in the art will readily recognize a variety of noncritical parameters which can be changed or modified to yield essentially the same results.

[0172] DLBU Assessment Method

[0173] To measure the effectiveness of added polyether block amide to mitigate DLBU issues when extruding post-consumer recycled polyethylene, a single-screw extruder was used. The manufacturer of the single-screw extruder is OCS Optical Control Systems GmbH (Germany), model number ME20 / 26 single screw extruder. The die assembly was a 3 mm filament. A polymer formulation was continually extruded over a period of minutes to hours and pictures taken periodically of the die exits where the strands were being extruded to observe the formation of the DLBU. Extrusion conditions are provided in Tables 2 and 3. Extrudable Polymeric Compositions

[0174] Compositions of recycled polyethylene (EX-PCR-NC4) and different polymer processing aids (see Table 1) were pre -compounded on a Leistritz twin-screw extrusion line. EX-PCR-NC4 is a recycled polyethylene from PE Clear Film Grade B bale that was formerly commercially available from NOVA Chemicals (Canada). EX-PCR-NC4 has a melt index (Condition 190°C / 2.16 kg ASTM D 1238) of 1.0 g / 10 minutes and a density of 0.925 g / cm3, as measured by ASTM D 792.

[0175] Blends of recycled polyethylene and virgin polyethylene were tumble blended prior to feeding via the ME20 / 26 single-screw extruder. The blends are shown in Table 1 and included one or more the following components:

[0176] Recycled Polyethylene: rPE (EX-PCR-NC4).

[0177] Virgin Polyethylene: FP120-A, a commercially available polyethylene from NOVA Chemicals (Canada). FP120-A has a melt index (Condition 190°C / 2.16 kg ASTM D 1238) of 1.0 g / 10 minutes and a density of 0.920 g / cm3, as measured by ASTM D 792.

[0178] PEBA Concentrate Masterbatch: (PEBA MB) A pre-compounded PEBA concentrate containing 95 wt.% FP120-A (a commercially available polyethylene from NOVA Chemicals (Canada)) and 5 wt.% PEBA (PEBAX MV 1074 from Arkema) prepared on a Leistritz twin- screw extrusion line. rPE / virgin PE / PEBA Blend: A pre-compounded polymer blend containing 50% EX- PCR-NC4, 49.7% FP120-A, and 3,000 ppm of PEBA (PEBAX MV 1074 from Arkema), prepared on a Leistritz twin-screw extrusion line. Table 1 provides the formulations used in the DLBU mitigation studies.

[0179] TABLE 1 Formerly sold by NOVA Chemicals (Canada). EX-PCR-NC4 (“NC4”) has a melt index (190°C / 2.16 kg) of .0 g / 10 min, as determined by ASTM D 1238 and a density of 0.925 g / cm3as determined by ASTM D 792. It greater than 99 wt.% post-consumer recycled LLDPE / LDPE resin sourced from distribution centers.2KYNAR FLEX® 3121-50 is a pelletized flexible, semi-crystalline VF2 based copolymer. It is a PVDF additive that can be molded or extruded and has a useful temperature range from -40°C - 150°C. KYNAR FLEX 3120-50 has a UL RTI of 150°C.

[0180] 3EVOH has an ethylene content of 32 (mol %), a density (g / cm3at 20°C) of 1.19, and a MFR (g / 10 min at 190°C, 2,160 g) of 1.6.

[0181] 4PEBA has a density (g / cm3, ISO 1183) of 1.07, and a melting point of 158°C.

[0182] 5PEG 3350 has average molar mass 3350 g / mol.

[0183] 6ZnO is zinc oxide (ZnO), powdered solid with a particle size of 0.31 microns and surface area of 3.5 m2 / g with minimum purity of 99.9 wt.%.

[0184] ’Mixed MW PEG is a blend of PEG 3350 and PEG 35,000 where the latter has an average molar mass of 35,000 g / mol.

[0185] 8Nylon 1030FDX34 is a nucleated, high viscosity polyamide 6 homopolymer with a melting point of 220°C (ISO 11357) and density of 1.14 g / cm3 (DIN 53479).

[0186] 9Calcium stearate has a melting point range of 150 - 160°C, and ash content of 9.2 - 10.2 %.

[0187] 10Hydrotalcite is an acid scavenger mineral with particle size range of 0.3 - 0.6 microns and specific surface area of 5 - 15 m2 / g.

[0188] 11Sold by NOVA Chemicals (Canada). FP120-A has a melt index (190°C / 2.16 kg) of 1.0 g / 10 min, as determined by ASTM D 1238 and a density of 0.920 g / cm3as determined by ASTM D 792.

[0189] 12The PEBA Masterbatch is a concentrate pre-compounded on a Leistritz extruder containing 95 wt.% FP120- A (a commercially available polyethylene from NOVA Chemicals (Canada)) and 5 wt.% PEBA (PEBAX MV 1074 from Arkema).

[0190] Tables 2 and 3 provide extrusion conditions during DLBU mitigation studies.

[0191] TABLE 2

[0192] TABLE 3

[0193] DLBU Data

[0194] Figure 1 provides photographs of die exit for EX-PCR-NC4 control sample (NC4), and two formulations containing fluoropolymer PPA KYNAR 3121-50 at 250 (Cl) and 500 (C2) ppm loading levels. The DLBU is clearly evident in the control as the dark grey irregular shaped material at the top of the extruding strand (arrows point to DLBU). The DLBU for the KYNAR samples is similar in magnitude, with a possible slight improvement at the 250 ppm loading level.

[0195] Figure 2 provides photographs of die exit for EX-PCR-NC4 control sample (NC4), the fluoropolymer formulation (KYNAR @ 250 ppm, Cl) compared against PEBAX MV 1074 @ 1,000 ppm (IE2) (arrows point to DLBU). There is very little DLBU present in the PEBAX formulation, even after 120 min.

[0196] Figure 3 provides photographs of die exit for EX-PCR-NC4 control sample (NC4), PEBA formulation (IE2), and EVOH formulation (El) (arrows point to DLBU). Both the PEBA and EVOH samples demonstrated very little DLBU after 60 minutes. However, there does appear to be slightly more build up for the EVOH sample.

[0197] Figure 4 provides photographs of die exit for EX-PCR-NC4 control sample (NC4), and nylon 6 (C5) formulation (arrows point to DLBU). Clearly there is significant DLBU present in the nylon formulation and notably worse than the control.

[0198] Figure 5 provides of die exit for EX-PCR-NC4 control sample (NC4), calcium stearate formulation (C6), and hydrotalcite (DHT-4V) formulation (C7) (arrows point to DLBU). Both the calcium stearate and hydrotalcite samples demonstrated very little up to 15 minutes. However, there does appear to be more build up after 30 minutes for both the calcium stearate and hydrotalcite samples.

[0199] Figure 6 provides of die exit for EX-PCR-NC4 control sample (NC4), and two formulations containing different PEG formulations (C3 and C4) (arrows point to DLBU). However, there does appear to be more build up for both the PEG samples.

[0200] Figure 7 provides photographs of die exit for Control sample 2 (98% NC4) and Control sample 3 (75% NC4) relative to the same polymer blends containing PEBA (IE3 and IE4). Clearly, there is significant DLBU present in the control samples, which are notably worse than the inventive examples containing PEBA.

[0201] Figure 8 provides photographs of die exit for Control sample 4 (50% NC4) and Control sample 5 (25% NC4) relative to the same polymer blends containing PEBA (IE5 and IE6). Clearly, there is significant DLBU present in the control samples, which are notably worse than the inventive examples containing PEBA.

[0202] The PEBAX formulation (Figures 2 and 3) significantly reduced the formation of the DLBU that forms with the control sample (Figure 1). Further, a reduction in gels was observed. Without wishing to be bound by a particular theory, it is believed that reduction of gels is a result of a reduced amount of DLBU material sloughing off into the extruded material. The EVOH formulation follows as an effective DLBU suppressant (Figure 3). The polyether block amide formulation also reduced die lip build-up in the extrusion of blends of rPE and virgin polyethylene. The efficacy of the fluoropolymer PPA is surprisingly poor (Figure 1) at loading levels that would be expected to give positive results in virgin polyethylene formulations. The effectiveness of the other non-fluorinated PPAs such as nylon formulation (Figure 4), calcium stearate formulation and hydrotalcite formulation (Figure 5), and PEG formulations (Figure 6) seems not as promising as PEBA to reduce DLBU in the recycled polyethylene compositions.

[0203] Without wishing to be bound by theory, it is believed that the contaminants within the PCR resin may be antagonists for the fluoropolymers (strong hydrogen bonding) to effectively coat the extruder surfaces, thereby allowing the build-up to accumulate to a similar extent as the barefoot PCR-NC4. The ability of PEBA to be effective for DLBU mitigation may be due to lower hydrogen bonding strength, allowing the PEBA to coat the extruder surfaces to a sufficient extent.

[0204] Non-limiting embodiments of the present disclosure include the following:

[0205] Embodiment A. An extrudable polymeric composition comprising: 5 wt.%to 99 wt.% of a recycled polyethylene; and 500 ppm to 5,000 ppm, based on the weight of the extrudable polymeric composition, of added polyether block amide.

[0206] Embodiment B. The extrudable polymeric composition of Embodiment A, comprising 1 wt.% to 95 wt.% of a virgin polyethylene.

[0207] Embodiment C. The extrudable polymeric composition of Embodiment B, wherein the virgin polyethylene comprises, very low density polyethylene (VLDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), or any combination thereof.

[0208] Embodiment D. The extrudable polymeric composition of Embodiment B, wherein the virgin polyethylene is a linear low density polyethylene.

[0209] Embodiment E. The extrudable polymeric composition Embodiment A, B, C, or D, comprising less than 200 ppm, based on the weight of the extrudable polymeric composition, of a fluoropolymer or a copolymer thereof originating from the recycled polyethylene.

[0210] Embodiment F. The extrudable polymeric composition of Embodiment E, wherein the fluoropolymer is a polyvinylidene difluoride, a polyvinylidene fluoride-co- hexafluoropropylene, a polytetrafluoroethylene, or a combination thereof.

[0211] Embodiment G. The extrudable polymeric composition of Embodiment A, B, C, D, E, or F, wherein the recycled polyethylene comprises up to 5 wt.% polypropylene, based on the total weight of the recycled polyethylene. Embodiment H. The extrudable polymeric composition Embodiment A, B, C, D, E, F, or G, wherein the recycled polyethylene comprises low density polyethylene (LDPE), linear low density polyethylene (LLDPE), or both.

[0212] Embodiment L The extrudable polymeric composition of Embodiment A, B, C, D, E, F, or G, wherein the recycled polyethylene is from a mechanically recycled PE Clear Film Grade B.

[0213] Embodiment J. The extrudable polymeric composition of Embodiment A, B, C, D, E, F, or G, wherein the recycled polyethylene has: a melt index (h) of 0.5 to 5.0 grams per 10 minutes; and a density of 0.910 to 0.940 g / cm3.

[0214] Embodiment K. The extrudable polymeric composition of Embodiment A, B, C, D, E, F, or G, wherein the recycled polyethylene has: a melt index (h) of 0.5 to 1.5 grams per 10 minutes; and a density of 0.920 to 0.930 g / cm3.

[0215] Embodiment L. The extrudable polymeric composition of Embodiment A, B, C, D, E, F, G, H, I, J, or K, comprising, based on the total weight of the polymeric composition: 500 ppm to 3,000 ppm of the added polyether block amide; and 0 to 1 wt.% additives.

[0216] Embodiment M. The extrudable polymeric composition of Embodiment A, B, C, D, E, F, G, H, I, J, or K, comprising, based on the total weight of the polymeric composition: 500 ppm to 1,500 ppm of the added polyether block amide; and 0 to 1 wt.% additives.

[0217] Embodiment N. The extrudable polymeric composition of Embodiment A, B, C, D, E, F, G, H, I, J, or K, comprising, based on the total weight of the polymeric composition: 800 ppm to 1,000 ppm of the added polyether block amide; and 0 to 1 wt.% additives.

[0218] Embodiment O. The extrudable polymeric composition of Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, or N, wherein the extrudable polymeric composition is in a pellet form.

[0219] Embodiment P. A method of making the extrudable polymeric composition A, B, C, D, E, F, G, H, I, J, K, L, M, N, or O, the method comprising: (a) melt compounding the recycled polyethylene and the polyether block amide to produce a mixture; and (b) extruding the mixture to obtain the polymeric composition.

[0220] Embodiment Q. A method of extruding the extrudable polymeric composition of A, B, C, D, E, F, G, H, I, J, K, L, M, N, or O, the method comprising extruding the polymeric composition at a temperature of 160°C to 300°C.

[0221] Embodiment R. The method of Embodiment Q, wherein the temperature is between 200°C and 250°C. Embodiment S. A method of reducing die lip build-up when extruding an extrudable polymeric composition comprising recycled polyethylene, the method comprising adding 500 ppm to 5,000 ppm of a polyether block amide to the extrudable polymeric composition prior to extruding.

[0222] Embodiment T. The method according to Embodiment S, wherein the extrudable polymeric composition comprises 5 wt.% to 99 wt.% of the recycled polyethylene.

[0223] Embodiment U. The method according to Embodiment S or T, wherein the extrudable polymeric composition comprises 1 wt.% to 95 wt.% of a virgin polyethylene.

[0224] Embodiment V. The method according to Embodiment U, wherein the virgin polyethylene comprises, very low density polyethylene (VLDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), or any combination thereof.

[0225] Embodiment W. The method according Embodiment U, wherein the virgin polyethylene is linear low density polyethylene.

[0226] Embodiment X. The method according to Embodiment S, T, U, V, or W, wherein the extrudable polymeric composition comprises less than 200 ppm, based on the weight of the extrudable polymeric composition, of a fluoropolymer or a copolymer thereof.

[0227] Embodiment Y. The method according to Embodiment S, T, U, V, W, or X, wherein the recycled polyethylene comprises low density polyethylene (LDPE), linear low density polyethylene (LLDPE), or both.

[0228] Embodiment Z. The method according to Embodiment S, T, U, V, W, or X, wherein the recycled polyethylene has: a melt index (h) of 0.5 to 5.0 grams per 10 minutes; and a density of 0.910 to 0.940 g / cm3.

[0229] Embodiment AA. The method according to Embodiment S, T, U, V, W, or X, wherein the recycled polyethylene has: a melt index (h) of 0.5 to 1.5 grams per 10 minutes; and a density of 0.920 to 0.930 g / cm3.

[0230] Embodiment AB. The method according to Embodiment S, T, U, V, W, X, Y, Z, or AA, wherein 500 ppm to 3,000 ppm of the polyether block amide is added.

[0231] Embodiment AC. The method according to Embodiment S, T, U, V, W, X, Y, Z, or

[0232] AA, wherein 500 ppm to 1,500 ppm of the polyether block amide is added.

[0233] Embodiment AD. The method according to Embodiment S, T, U, V, W, X, Y, Z, AA,

[0234] AB, or AC, further comprising adding up to 1 wt.% of an additive to the composition prior to extruding the composition. Embodiment AE. The method according to Embodiment S, T, U, V, W, X, Y, Z, AA, AB, AC, or AD, wherein die lip build-up is reduced when extruding the extrudable polymeric composition as: compared to a reference composition that includes the same components in the same amounts but does not include the added polyether block amide; or compared to a reference composition that includes the same components in the same amounts but replaces the added poly ether block amide with poly vinylidene difluoride.

[0235] Embodiment AF. The method according to Embodiment S, T, U, V, W, X, Y, Z, AA, AB, AC, AD, or AE, wherein the polyether block amide is added to the extrudable polymeric composition as a masterbatch. Embodiment AG. The method according to Embodiment S, T, U, V, W, X, Y, Z, AA,

[0236] AB, AC, AD, or AE, wherein the polyether block amide is added by tumble blending.

[0237] Embodiment AH. The method according to Embodiment R, S, T, U, V, W, X, Y, Z, AA, AB, AC, AD, AE, AF, or AG, wherein the extruding is at a temperature of 160°C to 250°C.

Claims

CLAIMS1. An extrudable polymeric composition comprising:5 wt.% to 99 wt.% of a recycled polyethylene; and500 ppm to 5,000 ppm, based on the weight of the extrudable polymeric composition, of added polyether block amide.

2. The extrudable polymeric composition of claim 1, comprising 1 wt.% to 95 wt.% of a virgin polyethylene.

3. The extrudable polymeric composition of claim 2, wherein the virgin polyethylene comprises, very low density polyethylene (VLDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HD PE), or any combination thereof.

4. The extrudable polymeric composition of claim 2, wherein the virgin polyethylene is a linear low density polyethylene.

5. The extrudable polymeric composition of any one of claims 1 to 4, comprising less than 200 ppm, based on the weight of the extrudable polymeric composition, of a fluoropolymer or a copolymer thereof originating from the recycled polyethylene.

6. The extrudable polymeric composition of claim 5, wherein the fluoropolymer is a polyvinylidene difluoride, a polyvinylidene fluoride-co-hexafluoropropylene, a polytetrafluoroethylene, or a combination thereof.

7. The extrudable polymeric composition of any one of claims 1 to 6, wherein the recycled polyethylene comprises up to 5 wt.% polypropylene, based on the total weight of the recycled polyethylene.

8. The extrudable polymeric composition of any one of claims 1 to 7, wherein the recycled polyethylene comprises low density polyethylene (LDPE), linear low density polyethylene (LLDPE), or both.

9. The extrudable polymeric composition of any one of claims 1 to 7, wherein the recycled polyethylene is from a mechanically recycled PE Clear Film Grade B.

10. The extrudable polymeric composition of any one of claims 1 to 7, wherein the recycled polyethylene has: a melt index, h, of 0.5 to 5.0 grams per 10 minutes; and a density of 0.910 to 0.940 g / cm3.

11. The extrudable polymeric composition of any one of claims 1 to 7, wherein the recycled polyethylene has: a melt index, h, of 0.5 to 1.5 grams per 10 minutes; anda density of 0.920 to 0.930 g / cm3.

12. The extrudable polymeric composition of any one of claims 1 to 11, comprising, based on the total weight of the polymeric composition:500 ppm to 3,000 ppm of the added polyether block amide; and0 to 1 wt.% additives.

13. The extrudable polymeric composition of any one of claims 1 to 11 , comprising, based on the total weight of the polymeric composition:500 ppm to 1,500 ppm of the added polyether block amide; and0 to 1 wt.% additives.

14. The extrudable polymeric composition of any one of claims 1 to 11, comprising, based on the total weight of the polymeric composition:800 ppm to 1,000 ppm of the added polyether block amide; and0 to 1 wt.% additives.

15. The extrudable polymeric composition of any one of claims 1 to 14, wherein the extrudable polymeric composition is in a pellet form.

16. A method of making the extrudable polymeric composition of any one of claims 1 to 15, the method comprising:(a) melt compounding the recycled polyethylene and the polyether block amide to produce a mixture; and(b) extruding the mixture to obtain the polymeric composition.

17. A method of extruding the extrudable polymeric composition of any one of claims 1 to 15, the method comprising extruding the polymeric composition at a temperature of 160°C to 300°C.

18. The method of claim 17, wherein the temperature is between 200°C and 250°C.

19. A method of reducing die lip build-up when extruding an extrudable polymeric composition comprising recycled polyethylene, the method comprising adding 500 ppm to 5,000 ppm, based on the weight of the extrudable polymeric composition, of a polyether block amide to the extrudable polymeric composition prior to extruding.

20. The method according to claim 19, wherein the extrudable polymeric composition comprises 5 wt.% to 99 wt.% of the recycled polyethylene.

21. The method according to claim 19 or 20, wherein the extrudable polymeric composition comprises 1 wt.% to 95 wt.% of a virgin polyethylene.

22. The method according to claim 21, wherein the virgin polyethylene comprises, very low density polyethylene (VLDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), or any combination thereof.

23. The method according to claim 21, wherein the virgin polyethylene is linear low density polyethylene.

24. The method according to any one of claims 19 to 23, wherein the extrudable polymeric composition comprises less than 200 ppm, based on the weight of the extrudable polymeric composition, of a fluoropolymer or a copolymer thereof.

25. The method according to any one of claims 19 to 24, wherein the recycled polyethylene comprises low density polyethylene (LDPE), linear low density polyethylene (LLDPE), or both.

26. The method according to any one of claims 19 to 24, wherein the recycled polyethylene has: a melt index, h, of 0.5 to 5.0 grams per 10 minutes; and a density of 0.910 to 0.940 g / cm3.

27. The method according to any one of claims 19 to 24, wherein the recycled polyethylene has: a melt index, h, of 0.5 to 1.5 grams per 10 minutes; and a density of 0.920 to 0.930 g / cm3.

28. The method according to any one of claims 19 to 27, wherein 500 ppm to 3,000 ppm of the poly ether block amide is added.

29. The method according to any one of claims 19 to 27, wherein 500 ppm to 1,500 ppm of the poly ether block amide is added.

30. The method according to any one of claims 19 to 29, further comprising adding up to 1 wt.% of an additive to the composition prior to extruding the composition.

31. The method according to any one of claims 19 to 30, wherein die lip build-up is reduced when extruding the extrudable polymeric composition as: compared to a reference composition that includes the same components in the same amounts but does not include the added polyether block amide; or compared to a reference composition that includes the same components in the same amounts but replaces the added polyether block amide with polyvinylidene difluoride.

32. The method according to any one of claims 19 to 31, wherein the polyether block amide is added to the extrudable polymeric composition as a masterbatch.

33. The method according to any one of claims 19 to 31, wherein the polyether block amide is added by tumble blending.

34. The method according to any one of claims 19 to 33, wherein the extruding is at a temperature of 160°C to 250°C.

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