Polyethylene and recycled polyethylene blend compositions with improved toughness

Abstract

Polymeric compositions including recycled polyethylene, methods of making the compositions, and articles containing the compositions are described. In some embodiments, the polymeric compositions can contain 10 wt.% to 30 wt.% recycled polyethylene; 50 wt.% to 80 wt.% an ethylene alpha-olefin copolymer; and 5 wt.% to 25 wt.% high density polyethylene. In some embodiments, at least 70 wt.% of the article comprises the polymeric composition.

Description

[0001] POLYETHYLENE AND RECYCLED POLYETHYLENE BLEND COMPOSITIONS WITH IMPROVED TOUGHNESS

[0002] TECHNICAL FIELD

[0003] The present disclosure generally relates to polymeric compositions including recycled polyethylene and an ethylene alpha-olefin copolymer. The polymeric compositions disclosed herein may be used in molding applications, such as in rotomolding.

[0004] BACKGROUND ART

[0005] There is increasing interest in incorporating recycled polyethylene into products commonly formed from virgin polyethylene, such as rotomolded articles.

[0006] A traditional recycling method for plastics (for example, polyethylene) includes mechanical recycling. However, the mechanical properties (for example, tensile strength, tensile modulus, etc.) of recycled polyethylene can degrade during use and recycling. Thus, mechanical properties of an article of manufacture are often reduced with the incorporation of increasing amounts of recycled polymer.

[0007] The incorporation of recycled polyethylene into compositions suitable for rotomolding applications remains a challenge.

[0008] SUMMARY OF INVENTION

[0009] A solution to at least some of the aforementioned problems is disclosed herein. In some instances, the solution may be found in a combining recycled polyethylene with ethylene alpha-olefin copolymer having specific properties and high density polyethylene. In some instances, the recycled polyethylene, ethylene alpha-olefin copolymer, and high density polyethylene are combined in a particular ratio.

[0010] In one aspect, the solution can include combining a mixture of recycled polyethylene (rPE) with an ethylene alpha-olefin copolymer having a density from 0.933 g / cm3to 0.940 g / cm3, and high density polyethylene. This may result in a polymer composition and / or an article of manufacture that has improvement in toughness while maintaining acceptable tensile and flexural properties when compared to the base resin (such as a virgin polyethylene, commercial rotational molding grade). Therefore, articles of manufacture made from such compositions can have suitable properties and also be more sustainable.

[0011] One aspect of the present disclosure is directed to a polymeric resin composition. The polymeric composition includes 10 wt.% to 30 wt.% of recycled polyethylene; 50 wt.% to 80 wt.% of an ethylene alpha-olefin copolymer having a density from 0.933 g / cm3to 0.940 g / cm3and a zero-shear viscosity ZSV(A); and 5 wt.% to 25 wt.% of a high density polyethylene; wherein the polymeric composition has a zero-shear viscosity ZSV(B); wherein Izod impact performance at -40°C is greater than or equal to 6 ft-lb / in for a compression molded specimen of the polymeric composition, the compression molded specimen prepared in accordance with ASTM D-4703; and wherein a ratio of ZSV(B) to ZSV(A) is less than or equal to 1.9.

[0012] In some embodiments, the Izod impact performance at -40°C is greater than or equal to 9 ft-lb / in for the compression molded specimen of the polymeric composition.

[0013] In some embodiments, the recycled polyethylene may include a post-consumer recycled (PCR) polyethylene. In some embodiments, the recycled polyethylene may include a post-industrial recycled (PIR) polyethylene.

[0014] In some embodiments, the recycled polyethylene has a density of 0.910 g / cm3oto 0.940 g / cm3.

[0015] In some embodiments, the polymeric composition has a flexural secant modulus -1% between 640 MPa and 750 MPa.

[0016] In some embodiments, the polymeric composition has a melt flow index as measured under ASTM D-1238 at 190°C and 2.16 kilograms from 3.0 g / 10 min to 5.5 g / 10 min. In some embodiments, the polymeric composition has a melt flow index as measured under ASTM D-1238 at 190°C and 21.6 kilograms from 70 g / 10 min to 150 g / 10 min.

[0017] In some embodiments, the polymeric composition further includes 2 wt.%to 10 wt.% of one or both of a linear low density polyethylene and a very low density polyethylene.

[0018] In some embodiments the ethylene alpha-olefin copolymer has a melt flow index as measured under ASTM D-1238 at 190°C and 2.16 kilograms of between 3 g / 10 min and 7 g / 10 min. In some embodiments, the ethylene alpha-olefin copolymer has a melt flow index as measured under ASTM D-1238 at 190°C and 2.16 kilograms of between 3 g / 10 min and 5.5 g / 10 min.

[0019] In some embodiments, the ethylene alpha-olefin copolymer has a melt flow index as measured under ASTM D-1238 at 190°C and 21.6 kilograms ofbetween 80 g / 10 min and 170 g / 10 min. In some embodiments, the ethylene alpha-olefin copolymer has a melt flow index as measured under ASTM D-1238 at 190°C and 21.6 kilograms ofbetween 80 g / 10 min and 120 g / 10 min.

[0020] In some embodiments, the ethylene alpha-olefin copolymer has a zero-shear viscosity at 190°C of between 1,300 Pa-s and 2,700 Pa-s. In some embodiments, the ethylene alphaolefin copolymer has a zero-shear viscosity at 190°C of between 1,800 Pa-s and 2,200 Pa-s. In some embodiments, the ethylene alpha-olefin copolymer includes one or both of hexene and octene as a comonomer. In some embodiments, the recycled polyethylene includes more than one recycled polyethylene.

[0021] In some embodiments, the recycled polyethylene has a zero-shear viscosity at 190°C greater than or equal to 15,000 Pa-s. In some embodiments, the recycled polyethylene has a zero-shear viscosity at 190°C of 100,000 Pa-s to 1,000,000 Pa-s. In some embodiments, the recycled polyethylene has a zero-shear viscosity at 190°C of 15,000 Pa-s to 40,000 Pa-s.

[0022] In some embodiments, the recycled polyethylene has a melt flow index as measured under ASTM D-1238 at 190°C and 2.16 kilograms of between 0.4 g / 10 min and 2.0 g / 10 min.

[0023] In some embodiments, the recycled polyethylene has a melt flow index as measured under ASTM D-1238 at 190°C and 21.6 kilograms of between 20 g / 10 min to 70 g / 10 min. In some embodiments, a difference between the melt flow index as measured under ASTM D-1238 at 190°C and 2.16 kilograms of the ethylene alpha-olefin copolymer and the recycled polyethylene is less than 6.6 g / 10 min.

[0024] In some embodiments, a difference between the melt flow index as measured under ASTM D-1238 at 190°C and 21.6 kilograms of the ethylene alpha-olefin copolymer and the recycled polyethylene is less than 90 g / 10 min.

[0025] In some embodiments, the recycled polyethylene includes a low-density polyethylene (LDPE), a high-density polyethylene (HDPE), a medium-density polyethylene (MDPE), a linear low-density polyethylene (LLDPE), a very-low-density polyethylene (VLDPE), an ultra-high-molecular-weight polyethylene (UHMWPE), an ultra-low-molecular-weight polyethylene (ULMWPE), and / or a high-molecular- weight polyethylene (HMWPE).

[0026] In some embodiments, the high density polyethylene includes more than one high density polyethylene. In some embodiments, a most abundant high density polyethylene of the polymeric composition has a density from 0.945 g / cm3to 0.960 g / cm3. In some embodiments, a most abundant high density polyethylene of the polymeric composition has a melt flow index as measured under ASTM D-1238 at 190°C and 2.16 kilograms of between 25 and 65 g / 10 min. In some embodiments, a most abundant high density polyethylene of the polymeric composition has a melt flow index as measured under ASTM D-1238 at 190°C and 2.16 kilograms of between 40 and 60 g / 10 min. In some embodiments, a difference between the melt flow index as measured under ASTM D-1238 at 190°C and 2.16 kilograms of the ethylene alpha-olefin copolymer and a most abundant high density polyethylene of the polymeric composition is 30 to 50 g / 10 min.

[0027] In some embodiments, the polymeric composition is included in a film, a layer, or a sheet. In some embodiments, a molded article includes any one of the polymeric compositions disclosed herein. In some embodiments, at least 70 wt.% of the molded article includes the polymeric compositions disclosed herein.

[0028] The present disclosure also provides a method of making a molded article. In some embodiments, the method includes forming at least a portion of the molded article with the polymeric compositions disclosed herein. In some embodiments, at least 70 wt. % of the molded article includes the polymeric compositions disclosed herein.

[0029] The present disclosure also provides a method of making the polymeric composition is disclosed. In some embodiments, the method includes: combining a recycled polyethylene, an ethylene alpha-olefin copolymer, and a high density polyethylene to form the polymeric composition. In some embodiments, the combining includes heating the recycled polyethylene, the ethylene alpha-olefin copolymer, and the high density polyethylene to melt at least a portion of the recycled polyethylene, the ethylene alpha-olefin copolymer, and the high density polyethylene. In some embodiments, the combining includes extruding the polymeric composition.

[0030] Other objects, features and advantages of the present disclosure will become apparent from the following detailed description and examples. It should be understood, however, that the 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 disclosure 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.

[0031] BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Advantages 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. 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.

[0033] Figure 1 illustrates Izod impact versus melt flow index h for blend compositions comprising a post-consumer recycled polyethylene termed “PCR-B”. Figure 2 illustrates Izod impact versus melt flow index h for blend compositions comprising another post-consumer recycled polyethylene termed “PCR-C”.

[0034] Figure 3 illustrates Izod impact versus flexural secant modulus for blend compositions that used PCR-B.

[0035] Figure 4 illustrates Izod impact versus flexural secant modulus for blend compositions that used PCR-C.

[0036] Figure 5 illustrates melt flow index versus zero-shear viscosity measured from DMA frequency sweep for blend compositions that used PCR-B.

[0037] Figure 6 illustrates melt flow index versus zero-shear viscosity measured from DMA frequency sweep for blend compositions that used PCR-C.

[0038] DESCRIPTION OF EMBODIMENTS

[0039] A solution to at least some of the aforementioned problems is disclosed herein. In one non-limiting aspect, the solution can include a polymeric composition containing recycled polyethylene, an ethylene alpha-olefin copolymer having a density from 0.933 g / cm3to 0.940 g / cm3, and a high density polyethylene. This may result in an article of manufacture that has improved toughness, acceptable tensile properties, and acceptable flexural properties when compared to the base resin (such as a virgin polyethylene of a commercial rotational molding grade). In one aspect, it was found that a composition containing particular amounts of recycled polyethylene, ethylene alpha-olefin copolymer, and / or high density polyethylene can have excellent mechanical properties with recycle content. Therefore, articles of manufacture made from such compositions can have desirable properties and be more sustainable.

[0040] These and other non-limiting embodiments of the present disclosure are discussed in further detail in the following sections.

[0041] Definitions

[0042] The following includes definitions of various terms and phrases used throughout this specification.

[0043] “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.

[0044] “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 polyethylene (PCR) 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 polyethylene (PIR) 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, polypropylene, 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.

[0045] “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 g / cm3to 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 polyethylene described herein, may contain additives.

[0046] “LDPE” refers to low density polyethylene, which is a polyethylene with a high degree of branching with long chains. 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.

[0047] “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 alpha-olefin comonomer, for example butene, hexene, or octene. Typically, LLDPE has a density in the range of 0.915 g / cm3to 0.925 g / cm3. The LLDPE may be, for example, an ethylene hexene copolymer, or an ethylene octene copolymer, or an ethylene butene copolymer. The amount of comonomer incorporated can be from 0.5 mol % to 12 mol %, or in some embodiments from 1.5 mol % to 10 mol %, and in other embodiments from 2 mol% to 8 mol % 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.

[0048] “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.

[0049] “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 0.912 g / cm3. In some embodiments, VLDPE is a substantially linear polymer. VLDPE is typically produced by copolymerization of ethylene with short-chain alpha-olefins (for example, 1- butene, 1-hexene, or 1-octene). VLDPE is most commonly produced using metallocene catalysts in a solution process.

[0050] The terms “polymeric” or “polymeric composition” refers to a material or mixture of materials that comprises a polymer or a mixture of polymers. In some instances, the material or mixture of materials comprises components that are not polymers, such as impurities, residues, additives, metals, etc.

[0051] The term “ethylene alpha-olefin copolymer” refers to a random copolymer of ethylene with an a-olefin. The a-olefin of an ethylene alpha-olefin copolymer may be branched or linear. In some instances, the a-olefin may be butene, hexene, or octene.

[0052] “Masterbatch” refers to a concentrated mixture of a recycled polyethylene, ethylene alpha-olefin copolymer, high density polyethylene, low density polyethylene, very low density polyethylene, 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.

[0053] 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%.

[0054] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical values, however, inherently contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

[0055] In addition, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of “1 to 10” or “between 1 and 10” is intended to include all sub-ranges between and including the recited minimum value of 1 and the recited maximum value of 10; that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10. Because the disclosed numerical ranges are continuous, they include every value between the minimum and maximum values. Unless expressly indicated otherwise, the various numerical ranges specified in this application are approximations.

[0056] 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.

[0057] The terms “inhibiting” or “reducing” or “preventing” or “avoiding” or any variation of these terms, such as “inhibit”, “reduce”, “prevent”, “avoid”, etc., when used in the claims and / or the specification includes any measurable decrease or complete inhibition to achieve a desired result.

[0058] The term “effective”, as that term is used in the specification and / or claims, means adequate to accomplish a desired, expected, or intended result.

[0059] 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”.

[0060] 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.

[0061] The polymeric compositions of the present disclosure 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 polymeric compositions of the present disclosure is that they can include 10 wt.% to 30 wt.% of recycled polyethylene; 50 wt.% to 80 wt.% of an ethylene alpha-olefin copolymer; and 5 wt.% to 25 wt.% of a high density polyethylene.

[0062] The Polymeric Composition

[0063] The present disclosure provides a polymeric composition including i) 10 wt.% to 30 wt.% of a recycled polyethylene; ii) 50 wt.% to 85 wt.% of an ethylene alpha-olefin copolymer having a density from 0.933 g / cm3to 0.940 g / cm3and a zero-shear viscosity ZSV(A); and iii) 5 wt.% to 25 wt.% of a high density polyethylene, wherein the polymeric composition has a zero-shear viscosity ZSV(B); wherein Izod impact performance at -40°C is greater than or equal to 6 ft-lb / in for a compression molded specimen of the polymeric composition, the compression molded specimen prepared in accordance with ASTM D-4703; and wherein a ratio of ZSV(B) to ZSV(A) is less than or equal to 1.9.

[0064] In some embodiments, the polymeric composition includes 10 wt.%, 11 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, 15 wt.%, 16 wt.%, 17 wt.%, 18 wt.%, 19 wt.%, 20 wt.%, 21 wt.%, 22 wt.%, 23 wt.%, 24 wt.%, 25 wt.%, 26 wt.%, 27 wt.%, 28 wt.%, 29 wt.%, or 30 wt.% of the recycled polyethylene. In some embodiments, the recycled polyethylene includes more than one recycled polyethylene. Recycled polyethylene suitable for use in the present disclosure is described later herein.

[0065] In some embodiments, the polymeric composition includes 50 wt.%, 51 wt.%, 52 wt.%, 53 wt.%, 54 wt.%, 55 wt.%, 56 wt.%, 57 wt.%, 58 wt.%, 59 wt.%, 60 wt.%, 61 wt.%, 62 wt.%, 63 wt.%, 64 wt.%, 65 wt.%, 66 wt.%, 67 wt.%, 68 wt.%, 69 wt.%, 70 wt.%, 71 wt.%, 72 wt.%, 73 wt.%, 74 wt.%, 75 wt.%, 76 wt.%, 77 wt.%, 78 wt.%, 79 wt.%, 80 wt.%, 81 wt.%, 82 wt.%, 83 wt.%, 84 wt.%, or 85 wt.% of an ethylene alpha-olefin copolymer. Ethylene alpha-olefin copolymers suitable for use in the present disclosure are described later herein.

[0066] In some embodiments, the polymeric composition includes 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, 11 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, 15 wt.%, 16 wt.%, 17 wt.%, 18 wt.%, 19 wt.%, 20 wt.%, 21 wt.%, 22 wt.%, 23 wt.%, 24 wt.%, or 25 wt.% of a high density polyethylene. In some embodiments, the high density polyethylene is more than one high density polyethylene . High density polyethylene suitable for use in the present disclosure are described later herein.

[0067] In some embodiments, the polymeric composition further includes 2 wt.% to 10 wt.% of one or both of a linear low density polyethylene and a very low density polyethylene. In some embodiments, the polymeric composition includes 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, or 10 wt.% of one or both of a linear low density polyethylene and a very low density polyethylene.

[0068] In some embodiments, the polymeric composition has a zero shear viscosity, ZSV(B), at 190°C of between about 1,900 Pa-s to about 5,700 Pa-s as determined by Dynamic Mechanical Analysis (DMA) frequency sweep using a Carreau-Yasuda Model. In some embodiments, the polymeric composition has a ZSV(B) at 190°C between about 2,100 Pa-s to about 2,800 Pa-s. In some embodiments, the polymeric composition has aZSV(B) at 190°C between about 2,100 Pa-s, about 2,200 Pa-s, about 2,300 Pa-s, about 2,400 Pa-s, about 2,500 Pa-s, about 2,600 Pa-s, about 2,700 Pa-s, or about 2,800 Pa-s. In some embodiments, the polymeric composition has a ZSV(B) at 190°C between about 3,000 Pa-s and about 4,000 Pa- s. In some embodiments, the polymeric composition has a ZSV(B) at 190°C between about 3,000 Pa-s, about 3,100 Pa-s, about 3,200 Pa-s, about 3,300 Pa-s, about 3,400 Pa-s, about 3,500 Pa-s, about 3,600 Pa-s, about 3,700 Pa-s, about 3,800 Pa-s, about 3,900 Pa-s, or about 4,000 Pa-s.

[0069] In some embodiments, the polymeric composition of the present disclosure can have any one of, any combination of, or all of the following properties: a flexural secant modulus -1% between 640 MPa and 750 MPa, such as for example 640 MPa, 650 MPa, 660 MPa, 670 MPa, 680 MPa, 690 MPa, 700 MPa, 710 MPa, 720 MPa, 730 MPa, or 740 MPa at 23°C, as measured in accordance with ASTM D638; a melt flow index, h, as measured under ASTM D-1238 at 190°C and 2.16 kilograms from 3.0 g / 10 min to 5.5 g / 10 min such as, for example,

[0070] 3.1 g / 10 min, 3.2 g / 10 min, 3.3 g / 10 min, 3.5 g / 10 min, 3.6 g / 10 min, 3.7 g / 10 min, 3.8 g / 10 min, 3.9 g / 10 min, 4 g / 10 min, 4.1 g / 10 min, 4.2 g / 10 min, 4.3 g / 10 min, 4.4 g / 10 min, 4.5 g / 10 min, 4.6 g / 10 min, 4.7 g / 10 min, 4.8 g / 10 min, 4.9 g / 10 min, 5 g / 10 min, 5.1 g / 10 min,

[0071] 5.2 g / 10 min, 5.3 g / 10 min, 5.4 g / 10 min, or 5.5 g / 10 min; and / or a melt flow index, hi, as measured under ASTM D-1238 at 190°C and 21.6 kilograms, from 70 g / 10 min to 150 g / 10 min such as for example 70 g / 10 min, 75 g / 10 min, 80 g / 10 min, 85 g / 10 min, 90 g / 10 min, 95 g / 10 min, 100 g / 10 min, 105 g / 10 min, 110 g / 10 min, 115 g / 10 min, 120 g / 10 min, 125 g / 10 min, 130 g / 10 min, 135 g / 10 min, 140 g / 10 min, 145 g / 10 min, or 150 g / 10 min.

[0072] In some embodiments, the polymeric composition has an Izod impact performance at -40°C greater than or equal to 6 ft-lb / in for a compression molded specimen of the polymeric composition, the compression molded specimen prepared in accordance with ASTM D-4703. In some embodiments, the polymeric composition has an Izod impact performance at -40°C of 6 ft-lb / in, 7 ft-lb / in, 8 ft-lb / in, 9 ft-lb / in, 10 ft-lb / in, 11 ft-lb / in, 12 ft-lb / in, 13 ft-lb / in, 14 ft-lb / in, 15 ft-lb / in, 16 ft-lb / in, 17 ft-lb / in, 18 ft-lb / in, 19 ft-lb / in, or 20 ft-lb / in for a compression molded specimen of the polymeric composition, the compression molded specimen prepared in accordance with ASTM D-4703. In certain embodiments, the polymeric composition has an Izod impact performance at -40°C greater than or equal to 9 ft-lb / in.

[0073] In some embodiments, the polymeric composition can further contain one or more additives selected from pigments, plasticizers, antioxidants, UV-stabilizers, heat stabilizers, dye enhancing agents, lubricant, mold release agents, crystal nucleating agents, fluidability- improving agents, antistatic agents, compatibilizers, or anti -drip agents. In some embodiments, the polymeric composition can contain pigments and plasticizer.

[0074] The Recycled Polyethylene

[0075] The recycled polyethylene of the polymeric compositions disclosed herein is postconsumer recycled polyethylene, post-industrial recycled polyethylene, or a combination thereof. In some embodiments, the polymeric composition comprises more than one recycled polyethylene. In some embodiments, both post-consumer recycled polyethylene and postindustrial recycled polyethylene materials can be purchased commercially. For instance, EX- rPE-0418, sold by NOVA Chemicals Corporation, is 100% post-consumer recycled resin sourced from white agricultural and irrigation film. Post-consumer recycled polyethylene sourced from distribution centers can also be purchased commercially.

[0076] In some embodiments, 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.

[0077] Recycling processes where materials experience heat histories will generally cause the formation of free radicals and hydroperoxides in the polyethylene. Many polyethylene resins are 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 BASF) 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.

[0078] In some embodiments, the recycled polyethylene has a melt flow index, h, as measured under ASTM D-1238 at 190°C and 2.16 kilograms between 0.4 g / 10 min and 2.0 g / 10 min. In some embodiments, the recycled polyethylene has a melt flow index as measured under ASTM D-1238 at 190°C and 2.16 kilograms of 0.4 g / 10 min, 0.5 g / 10 min, 0.6 g / 10 min, 0.7 g / 10 min, 0.8 g / 10 min, 0.9 g / 10 min, 1.0 g / 10 min, 1.1 g / 10 min, 1.2 g / 10 min, 1.3 g / 10 min, 1.4 g / 10 min, 1.5 g / 10 min, 1.6 g / 10 min, 1.7 g / 10 min, 1.8 g / 10 min, 1.9 g / 10 min, or 2.0 g / 10 min. In some embodiments, the recycled polyethylene has a melt flow index, I21, as measured under ASTM D-1238 at 190°C and 21.6 kilograms between 20 g / 10 min and 70 g / 10 min. In some embodiments, the I21 of the recycled polyethylene is 20 g / 10 min, 21 g / 10 min, 22 g / 10 min, 23 g / 10 min, 24 g / 10 min, 25 g / 10 min, 26 g / 10 min, 27 g / 10 min, 28 g / 10 min, 29 g / 10 min, 30 g / 10 min, 31 g / 10 min, 32 g / 10 min, 33 g / 10 min, 34 g / 10 min, 35 g / 10 min, 36 g / 10 min, 37 g / 10 min, 38 g / 10 min, 39 g / 10 min, 40 g / 10 min, 41 g / 10 min, 42 g / 10 min, 43 g / 10 min, 44 g / 10 min, 45 g / 10 min, 46 g / 10 min, 47 g / 10 min, 48 g / 10 min, 49 g / 10 min, 50 g / 10 min, 51 g / 10 min, 52 g / 10 min, 53 g / 10 min, 54 g / 10 min, 55 g / 10 min, 56 g / 10 min, 57 g / 10 min, 58 g / 10 min, 59 g / 10 min, 60 g / 10 min, 61 g / 10 min, 62 g / 10 min, 63 g / 10 min, 64 g / 10 min, 65 g / 10 min, 66 g / 10 min, 67 g / 10 min, 68 g / 10 min, 69 g / 10 min, or 70 g / 10 min.

[0079] In some embodiments, the recycled polyethylene has a zero-shear viscosity at 190°C greater than or equal to 10,000 Pa-s as determined by Dynamic Mechanical Analysis (DMA) frequency sweep using a Carreau-Yasuda Model. In some embodiments, the zero-shear viscosity of the recycled polyethylene is greater than 15,000 Pa-s, 30,000 Pa-s, 40,000 Pa-s, 50,000 Pa-s, 70,000 Pa-s, 90,000 Pa-s, 100,000 Pa-s, 150,000 Pa-s, 200,000 Pa-s, 300,000 Pa-s, 400,000 Pa-s, 500,000 Pa-s, 600,000 Pa-s, 700,000 Pa-s, 800,000 Pa-s, 900,000 Pa-s, 1,000,000 Pa-s, 1,500,000 Pa-s, 2,000,000 Pa-s, or 3,000,000 Pa-s. In some embodiments, the recycled polyethylene has a zero-shear viscosity at 190°C between 10,000 Pa-s to 3,000,000 Pa-s, 10,000 Pa-s to 1,000,000 Pa-s, 15,000 Pa-s to 3,000,000 Pa-s, 15,000 Pa-s to 2,000,000 Pa-s, 10,000 Pa-s to 40,000 Pa-s, 15,000 Pa-s to 40,000 Pa-s, 10,000 Pa-s to 100,000 Pa-s, 15,000 Pa-s to 100,000 Pa-s, 100,000 Pa-s to 3,000,000 Pa-s, 100,000 Pa-s to 1,000,000 Pa- s, 40,000 Pa-s to 100,000 Pa-s, 50,000 Pa-s to 100,000 Pa-s, 30,000 Pa-s to 300,000 Pa-s, or 30,000 Pa-s to 150,000 Pa-s. In some embodiments, the recycled polyethylene has a zeroshear viscosity at 190°C of 1,000,000 Pa-s.

[0080] In some embodiments, the amount of recycled polyethylene present in the polymeric composition can be in the range from about 10% to about 30% by weight of the composition. In some embodiments, the amount of recycled polyethylene present in the composition is in the range from about 10% to about 15% by weight of the composition. In some embodiments, the polymeric composition includes recycled polyethylene in an amount in the range from about 15% to about 25% by weight. In some embodiments, the polymeric composition may include recycled polyethylene in an amount in the range from about 20% to about 30% by weight. In some embodiments, the polymeric composition may include recycled polyethylene in an amount in the range from about 10% to about 15% by weight. In some embodiments, the polymeric composition may include recycled polyethylene in an amount in the range from about 20% to about 25% by weight. In some embodiments, the polymeric composition may include recycled polyethylene in an amount in the range from about 25% to about 30% by weight.

[0081] The recycled polyethylene may be provided in any suitable form, such as in the form of chips, pellets, powders, slurries, solutions, and the like.

[0082] The Ethylene Alpha-Olefin Copolymer

[0083] In some embodiments, the ethylene alpha-olefin copolymer includes polymerized ethylene and one or more than one polymerized alpha-olefin selected from the group comprising C3-C12 alpha-olefins.

[0084] In some embodiments, the ethylene alpha-olefin copolymer includes polymerized ethylene and one or more than one polymerized alpha olefin selected from the group comprising C3-C12 alpha-olefins, and the polymerized ethylene comprises at least 85 weight percent of the ethylene alpha-olefin copolymer.

[0085] In some embodiments, the ethylene alpha-olefin copolymer includes polymerized ethylene and one or more than one polymerized alpha olefin selected from the group comprising C3-C12 alpha olefins, and the polymerized ethylene comprises at least 90 weight percent of the ethylene alpha-olefin copolymer.

[0086] In some embodiments, the ethylene alpha-olefin copolymer includes polymerized ethylene and one or more than one polymerized alpha-olefin selected from the group includes propylene, 1 -butene, 1 -hexene, 1 -octene, 1 -decene, 4-methyl-l -pentene, and 1 -octadecene.

[0087] In some embodiments, the ethylene alpha-olefin copolymer includes polymerized ethylene and one or more than one alpha-olefin selected from the group comprising 1-butene, 1 -hexene, and 1 -octene.

[0088] In some embodiments, the ethylene alpha-olefin copolymer includes polymerized ethylene and 1 -hexene.

[0089] In some embodiments, the ethylene alpha-olefin copolymer includes polymerized ethylene and one or more than one alpha-olefin selected from the group comprising 1-butene, 1-hexene, and 1-octene, and polymerized ethylene comprises at least 85 weight percent of the ethylene alpha-olefin copolymer.

[0090] In some embodiments, the ethylene alpha-olefin copolymer includes polymerized ethylene and one or more than one polymerized alpha olefin selected from the group comprising 1-butene, 1-hexene, and 1-octene, and polymerized ethylene comprises at least 90 weight percent of the ethylene alpha-olefin copolymer. In some embodiments, the ethylene alpha-olefin copolymer includes polymerized ethylene and 1 -hexene, and polymerized ethylene comprises at least 85 weight percent of the ethylene alpha-olefin copolymer.

[0091] In some embodiments, the ethylene alpha-olefin includes polymerized ethylene and 1 -hexene and polymerized ethylene comprises at least 90 weight percent of the ethylene alpha-olefin copolymer.

[0092] Suitable polymerization catalysts which may be employed to make the polyethylene copolymer include so-called heterogeneous catalysts and so-called single site catalysts.

[0093] Heterogeneous catalysts, also known as “multi-site catalysts”, include Ziegler-Natta catalysts, and chromium -based catalysts (e.g. Phillips catalyst), both of which are well known to persons skilled in the art.

[0094] Single site catalysts, include metallocene catalysts, constrained geometry catalysts, and phosphinimine catalysts, all of which are well known to persons skilled in the art. So called, “post-metallocene” catalysts, such as for example, those having tetradentate ligands are also examples of single site catalysts which are well known to persons skilled in the art.

[0095] The ethylene alpha-olefin copolymers may be prepared by using one or more polymerization catalysts in any conventionally known processes, such as gas phase polymerization, slurry phase polymerization, or solution phase polymerization, and using one or more suitable polymerization reactors. In an embodiment, the ethylene alpha-olefin copolymer is prepared by gas phase polymerization.

[0096] In a gas phase polymerization process, a transition metal polymerization catalyst may be immobilized on a suitable support material, and the resulting particulate catalyst may be employed in a fluidized bed polymerization process. In general, a fluidized bed gas phase polymerization reactor employs a “bed” of polymer and catalyst particles which is fluidized by a flow of monomer and other optional components which are at least partially gaseous. Heat is generated by the enthalpy of polymerization of the monomer (and optional comonomer(s)) flowing through the bed. Unreacted monomer and other optional gaseous components exit the fluidized bed and are contacted with a cooling system to remove this heat. The cooled gas stream, including monomer, and optional other components (such as condensable liquids), is then re-circulated through the polymerization zone, together with “make-up” monomer to replace that which was polymerized on the previous pass. Simultaneously, polymer product is withdrawn from the reactor. As will be appreciated by those skilled in the art, the “fluidized” nature of the polymerization bed helps to evenly distribute / mix the heat of reaction and thereby minimize the formation of localized temperature gradients.

[0097] In a slurry phase polymerization process, a transition metal polymerization catalyst may be immobilized on a suitable support material, and the resulting particulate catalyst may be employed in a slurry phase polymerization process. Slurry phase polymerization processes are conducted in the presence of a hydrocarbon diluent such as an alkane (including for example isoalkanes), an aromatic or a cycloalkane. The diluent may also be the alpha olefin comonomer used in copolymerizations. Some non-limiting alkane diluents include propane, butanes, (i.e., normal butane and / or isobutane), pentanes, hexanes, heptanes and octanes. The monomers may be soluble in (or miscible with) the diluent, but the polymer is not (under polymerization conditions). In some embodiments, the polymerization temperature is from about 5°C to about 200°C, or less than about 120°C, or from about 10°C to about 100°C. The reaction temperature is selected so that an ethylene or alpha-olefin homopolymer or copolymer is produced in the form of solid particles. The reaction pressure is influenced by the choice of diluent and reaction temperature. For example, in embodiments, the pressures may range from 15 to 45 atmospheres (about 220 to 660 psi or about 1,500 to about 4,600 kPa) when isobutane is used as diluent to approximately twice that (i.e., from 30 to 90 atmospheres - about 440 to 1,300 psi or about 3,000-9,100 kPa) when propane is used. The pressure in a slurry process must be kept sufficiently high to keep at least part of the ethylene and / or alpha olefin to be polymerized in the liquid phase. The reaction typically takes place in a jacketed closed loop reactor having an internal stirrer (e.g., an impeller) and at least one settling leg. Catalyst, monomers and diluents are fed to the reactor as liquids or suspensions. The slurry circulates through the reactor and the jacket is used to control the temperature of the reactor. Through a series of letdown valves the slurry enters a settling leg and then is let down in pressure to flash the diluent and unreacted monomers and recover the polymer generally in a cyclone. The diluent and unreacted monomers are recovered and recycled back to the reactor.

[0098] Solution polymerization processes for the polymerization or copolymerization of olefins such as ethylene and alpha olefins are well known in the art. Solution processes are generally conducted in the presence of an inert hydrocarbon solvent in which the resultant polyolefin is soluble under the polymerization conditions employed. In some embodiments, the solvent used in a solution phase polymerization process is selected from the group consisting of C5-12 hydrocarbons which may be unsubstituted or substituted by C1-4 alkyl group, and include hydrocarbon solvents such as pentane, methyl pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane and hydrogenated naphtha. Another example of a suitable solvent for use in embodiments of the present disclosure and which is commercially available is “ISOPAR® E” (C8-12 aliphatic solvent, Exxon Chemical Co.). The polymerization temperature in a conventional solution process may be from about 80°C to about 300°C. The polymerization pressure in a solution process may be a “medium pressure process”, meaning that the pressure in the reactor is less than about 6,000 psi (about 42,000 kiloPascals or kPa).

[0099] In solution polymerization, the monomers are dissolved / dispersed in the solvent either prior to being fed to the reactor (or for gaseous monomers the monomer may be fed to the reactor so that it will dissolve in the reaction mixture). Prior to mixing, the solvent and monomers are generally purified to remove potential catalyst poisons such as water, oxygen or metal impurities. The feedstock purification follows standard practices in the art, e.g., molecular sieves, alumina beds and oxygen removal catalysts are used for the purification of monomers. The solvent itself as well (e.g., methyl pentane, cyclohexane, hexane or toluene) may be treated in a similar manner.

[0100] In some embodiments a Ziegler-Natta catalyst is used to make the ethylene alphaolefin copolymer.

[0101] In some embodiments a Ziegler-Natta catalyst is used to make the ethylene alphaolefin copolymer in a gas phase polymerization process.

[0102] The presence of an alpha-olefin comonomer within the ethylene copolymer produces “short chain branches” (SCB) in the copolymer, where short chain branching is the number of short chain branches present per 1000 backbone carbon atoms (for example, 1 -hexene, produces a short chain branch having 4 carbon atoms). These short chain branches may reduce the crystallinity of the ethylene copolymer (in comparison to an ethylene homopolymer) and the ethylene copolymers may have improved impact resistance as a result (in comparison to ethylene homopolymers). Ethylene alpha-olefin copolymers produced using a Ziegler-Natta catalyst are sometimes referred to as being “heterogeneous” or “heterogeneously branched”, as the ethylene alpha-olefin copolymer is typically a mixture of different polyethylene copolymer chains having significantly different molecular weights and alpha-olefin contents.

[0103] In some embodiments, the ethylene alpha-olefin copolymer has a density between 0.926 g / cm3to 0.940 g / cm3. In some embodiments, the density of the alpha-olefin copolymer is 0.926 g / cm3, 0.927 g / cm3, 0.928 g / cm3, 0.929 g / cm3, 0.930 g / cm3, 0.931 g / cm3, 0.932 g / cm3, 0.933 g / cm3, 0.934 g / cm3, 0.935 g / cm3, 0.936 g / cm3, 0.937 g / cm3, 0.938 g / cm3, 0.939 g / cm3, or 0.940 g / cm3. In some embodiments, the ethylene alpha-olefin copolymer is an ethylene hexene copolymer.

[0104] In some embodiments, an ethylene alpha-olefin copolymer is characterized by its melt index, I2, as determined by ASTM D1238, at 190°C. In some embodiments, the ethylene alpha-olefin copolymer has amelt index, h, between 0. 1 g / 10 min and 20.0 g / 10 min. In some embodiments, the ethylene alpha-olefin copolymer has a melt index, I2, between 0. 1 g / 10 min and 15.0 g / 10 min, or between 0.1 g / 10 min and 10.0 g / 10 min, or between 0.3 g / 10 min and 15.0 g / 10 min, or between 0.3 g / 10 min to 10.0 g / 10 min, or between 0.1 g / 10 min and 5.0 g / 10 min, or between 0.3 g / 10 min and 5.0 g / 10 min, or between 0.5 g / 10 min and 15.0 g / 10 min, or between 0.5 g / 10 min and 10.0 g / 10 min, or between 0.5 g / 10 min and 5.0 g / 10 min, or betweenl.O g / 10 min and 10.0 g / 10 min, or between 2.0 g / 10 min and 10.0 g / 10 min, or between 1.0 g / 10 min and 8.0 g / 10 min, or between 2.0 g / 10 min and 8.0 g / 10 min, or between 3.0 g / 10 min and 7.0 g / 10 min, or between 3.0 g / 10 min and 5.5 g / 10 min.

[0105] In some embodiments, the ethylene alpha-olefin copolymer has a melt index, I2 of from 2 g / 10 min to 10 g / 10 min and a density of from 0.930 to 0.940 g / cm3. In some embodiments, the ethylene alpha-olefin copolymer has a melt index, I2, from 3 g / 10 min to 7 g / 10 min and a density of from 0.933 g / cm3to 0.940 g / cm3. In some embodiments, the ethylene alpha-olefin copolymer has a melt index, I2, from 3 g / 10 min to 5.5 g / 10 min and a density of 0.933 g / cm3to 0.940 g / cm3.

[0106] In some embodiments, the difference between the melt flow index, I2, of the ethylene alpha-olefin copolymer and the recycled polyethylene as measured under ASTM D-1238 at 190°C and 2.16 kilograms is less than or equal to 6.6 g / 10 min such as, for example, 0.5 g / 10 min, 1 g / 10 min, 1.5 g / 10 min, 2 g / 10 min, 2.5 g / 10 min, 3 g / 10 min, 3.5 g / 10 min, 4 g / 10 min, 4.5 g / 10 min, 5 g / 10 min, 5.5 g / 10 min, 6 g / 10 min, 6.5 g / 10 min, or 6.6 g / 10 min. In some embodiments, the difference between the melt flow index, I21, of the ethylene alphaolefin copolymer and the recycled polyethylene as measured under ASTM D-1238 at 190°C and 21.6 kilograms is less than or equal to 90 g / 10 min such as, for example, 5 g / 10 min, 10 g / 10 min, 15 g / 10 min, 20 g / 10 min, 25 g / 10 min, 30 g / 10 min, 35 g / 10 min, 40 g / 10 min, 45 g / 10 min, 50 g / 10 min, 55 g / 10 min, 60 g / 10 min, 65 g / 10 min, 70 g / 10 min, 75 g / 10 min, 80 g / 10 min, 85 g / 10 min, or 90 g / 10 min.

[0107] In some embodiments, the ethylene alpha-olefin copolymer has a zero shear viscosity, ZSV(A), at 190°C between about 1,000 Pa-s to about 3,000 Pa-s as determined from a Dynamic Mechanical Analysis (DMA) frequency sweep and using a Carreau-Yasuda model. In some embodiments, the ZSV(A) of the alpha-olefin copolymer at 190°C is between about 1,300 Pa-s to about 2,700 Pa-s. In some embodiments, the ZSV(A) of the alpha-olefin copolymer at 190°C is between about 1,300 Pa-S and about 1,400 Pa-s. In some embodiments, the ZSV(A) of the ethylene alpha-olefin copolymer at 190°C is about 1,300 Pa-s, about 1,310 Pa-s, about 1,320 Pa-s, about 1,330 Pa-s, about 1,340 Pa-s, about 1,350 Pa-s, about 1,360 Pa- s, about 1,370 Pa-s, about 1,380 Pa-s, about 1,390 Pa-s, or about 1,400 Pa-s. In some embodiments, the ethylene alpha-olefin copolymer has a ZSV(A) at 190°C between about 2,000 Pa-s and about 2,700 Pa-s. In some embodiments, the ethylene alpha-olefin copolymer has a ZSV(A) at 190°C of about 2,000 Pa-s, about 2,100 Pa-s, about 2,200 Pa-s, about 2,300 Pa-s, about 2,400 Pa-s, about, 2,500 Pa-s, or about 2,600 Pa-s.

[0108] In some embodiments, the polymeric composition has a zero-shear viscosity ZSV(B) as described above, and the alpha-olefin copolymer has a zero-shear viscosity ZSV(A) as described above, wherein a ratio of ZSV(B) to ZSV(A) is less than or equal to 1.9. In some embodiments, the polymeric composition has a zero-shear viscosity ZSV(B) as described above, and the alpha-olefin copolymer has a zero-shear viscosity ZSV(A) as described above, wherein a ratio of ZSV(B) to ZSV(A) is 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, or 1.9.

[0109] Non-limiting examples of ethylene alpha-olefin copolymers which may be used in embodiments of the disclosure are sold by NOVA Chemicals Corporation under the tradenames TRx-0338-U, TRx-0338-UG, TR-0338-UI, TR-0338-UIG, TRx0535-U, TRx0535-UG, TR-0535-UI, TR-0535-UIG, TR-0735-U, TR-735-UG, TR-0740-U.

[0110] The High Density Polyethylene

[0111] In some embodiments, the high density polyethylene included in the compositions disclosed herein comprises a comonomer. In some embodiments, the comonomer is butene.

[0112] In some embodiments, the high density polyethylene comprises more than one high density polyethylene. In some embodiments, the most abundant high density polyethylene of the polymeric composition has a density between 0.945 g / cm3and 0.960 g / cm3. In some embodiments, the density of the most abundant high density polyethylene is 0.945 g / cm3, 0.946 g / cm3, 0.947 g / cm3, 0.948 g / cm3, 0.949 g / cm3, 0.950 g / cm3, 0.951 g / cm3, 0.952 g / cm3, 0.953 g / cm3, 0.954 g / cm3, 0.955 g / cm3, 0.956 g / cm3, 0.957 g / cm3, 0.958 g / cm3, 0.959 g / cm3, or 0.960 g / cm3.

[0113] In some embodiments, the most abundant high density polyethylene of the polymeric composition has a melt flow index, h, as measured under ASTM D-1238 at 190°C and 2.16 kilograms of between 25 g / 10 min and 65 g / 10 min. In some embodiments, the h of the most abundant high density polyethylene is 25 g / 10 min, 26 g / 10 min, 27 g / 10 min, 28 g / 10 min, 29 g / 10 min, 30 g / 10 min, 31 g / 10 min, 32 g / 10 min, 33 g / 10 min, 34 g / 10 min, 35 g / 10 min, 36 g / 10 min, 37 g / 10 min, 38 g / 10 min, 39 g / 10 min, 40 g / 10 min, 41 g / 10 min, 42 g / 10 min,

[0114] 43 g / 10 min, 44 g / 10 min, 45 g / 10 min, 46 g / 10 min, 47 g / 10 min, 48 g / 10 min, 49 g / 10 min,

[0115] 50 g / 10 min, 51 g / 10 min, 52 g / 10 min, 53 g / 10 min, 54 g / 10 min, 55 g / 10 min, 56 g / 10 min,

[0116] 57 g / 10 min, 58 g / 10 min, 59 g / 10 min, 60 g / 10 min, 61 g / 10 min, 62 g / 10 min, 63 g / 10 min,

[0117] 64 g / 10 min, or 65 g / 10 min.

[0118] In some embodiments, the difference between the melt flow index as measured under ASTM D-1238 at 190°C and 2.16 kilograms of the ethylene alpha-olefin copolymer and a most abundant high density polyethylene of the polymeric composition is between 30 g / 10 min and 50 g / 10 min. In some embodiments, the difference between the melt flow index as measured under ASTM D-1238 at 190°C and 2.16 kilograms of the ethylene alpha-olefin copolymer and a most abundant high density polyethylene of the polymeric composition is 30 g / 10 min, 31 g / 10 min, 32 g / 10 min, 33 g / 10 min, 34 g / 10 min, 35 g / 10 min, 36 g / 10 min,

[0119] 37 g / 10 min, 38 g / 10 min, 39 g / 10 min, 40 g / 10 min, 41 g / 10 min, 42 g / 10 min, 43 g / 10 min,

[0120] 44 g / 10 min, 45 g / 10 min, 46 g / 10 min, 47 g / 10 min, 48 g / 10 min, 49 g / 10 min, or 50 g / 10 min.

[0121] Non-limiting examples of high density polyethylene which may be used in embodiments of the present disclosure include 2712, 2712CC, and 2714 sold by NOVA Chemicals Corporation.

[0122] Additives

[0123] The polymeric compositions of the present disclosure can include an additive or multiple additives, fillers, pigments, and the like. Non-limiting examples of additives include an antioxidant, a light stabilizer, an ultra-violet (UV), stabilizer, a polyamide stabilizer, a costabilizer, 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.

[0124] 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.

[0125] 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 .

[0126] 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).

[0127] In embodiments of the present disclosure, 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.

[0128] In some embodiments, 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.

[0129] 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.

[0130] 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 .

[0131] 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.

[0132] 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-l-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.

[0133] 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.

[0134] 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. 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.

[0135] 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.

[0136] 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.

[0137] 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.

[0138] 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 can, include materials commercially available under the general tradenames DHT®-4 (A, C, or V), ZHT-4V® HYCITE® 713, and AC-207™.

[0139] 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.

[0140] In some embodiments, slip agents can be used. Non-limiting examples of slip agents can include oleamide; erucamide; stearamide; and behenamide.

[0141] 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.

[0142] Non-limiting examples of polyamide stabilizers copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.

[0143] 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 .

[0144] 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. If present, then in some embodiments, fillers may be incorporated into the composition in amounts up to about 50 weight percent, or up to about 30 weight percent, or up to about 20 weight percent, or up to about 10 weight percent (based on the weight of the composition).

[0145] Methods for Making the Polymeric Compositions

[0146] The polymeric compositions of the present disclosure can be made using known compounding methodology. For example, all the components may be dry blended in the required weight ratio in a suitable device such as a tumble blender. The resulting dry blend can then be melted in a suitable compounding equipment (for example, an extruder). In another example, a masterbatch can be prepared with some of the recycled polyethylene and the other ingredients. The masterbatch can then be fed to an extruder and melt blended. In another example, the dry components of the blend may be metered directly into an extruder.

[0147] Extruders for thermoplastic polyolefins (for example, 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.

[0148] 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 (both screws turning in the same direction) or in a counter rotating mode (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 film extrusion.

[0149] For compounding, conditions can include temperature and pressure. Temperatures can range from 160°C to 315°C, or 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. Pressures can range from 0.1 MPa to 65 MPa, or 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. Articles Comprising the Polymeric Composition

[0150] The polymeric compositions of the present disclosure can be shaped into a variety of articles and shapes by using a variety of methods (for example, rotational molding, injection molding, extrusion molding, foam molding, powder coating, blow molding, thermoforming, melt spinning, and the like). In some embodiments, the polymeric compositions of the present disclosure are particularly suitable for rotational molding applications. Non-limiting examples of articles include consumer goods, toys, personal watercraft, intermediate bulk containers (IBCs), general purpose custom molding, agricultural storage tanks, marine parts, septic tanks, chemical containers, mailboxes, home and garden items, liners, cable sheathing, wire sheathing, pipes, hoses, conduits. In some embodiments, the article of manufacture can include printed or written graphics, lettering, or the like.

[0151] EXAMPLES

[0152] 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 limit 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.

[0153] Table 1 provides non-limiting ASTM assays used.

[0154] Table 1 : ASTM Assays

[0155] Table 2 provides select characteristics for resins used in the examples.

[0156] Table 2: Individual Resin Characteristics

[0157] 1PEI is a medium density ethylene a-olefin copolymer from NOVA Chemicals under the name TRx-0535.

[0158] 2PCR-B is a post-consumer recycled PE previously sold by NOVA Chemicals under the name EX-PCR-

[0159] WR3. PCR-B is sourced from closed-loop agricultural and irrigation film.

[0160] 3PCR-C is a post-consumer recycled PE sourced from distribution centers. 4 PE2 is commercially manufactured (NOVA Chemicals) under the name QPsK905.

[0161] 5PE3 is a commercial LLDPE manufactured under the name VPs412-A (NOVA Chemicals)

[0162] 6PE4 is a commercial HDPE product from NOVA Chemicals under the name SCLAIR 2714.

[0163] Example Polymeric Resin Compositions

[0164] Blend formulations shown in Tables 3 and 4 were prepared by melt compounding using a Leistritz twin-screw extruder. Blend characteristics and performance of select compositions containing PCR-B and PCR-C are found in Tables 5 and 6, respectively.

[0165] Table 3 : Comparative (B 1 to B6) and Example Blend Formulations According to the

[0166] Present Disclosure (B7 to B12) using PCR-B. Table 4: Comparative (Cl to C4) and Example Blend Formulations According to the

[0167] Present Disclosure (C5 and C6) using PCR-C.

[0168] Table 5: Blend Characteristics and Performance of Select Compositions Containing PCR-B,

[0169] Table 6: Blend Characteristics and Performance of Select Compositions Containing PCR-C.

[0170] The Izod impact versus melt flow index h for some blend compositions that used PCR-B is shown in Figure 1. The Izod impact versus melt flow index h for blend compositions that used PCR-C is shown in Figure 2. The Izod impact versus flexural secant modulus for blend compositions that used PCR-B is shown in Figure 3. The Izod impact versus flexural secant modulus for blend compositions that used PCR-C is shown in Figure 4. The melt flow index versus zero-shear viscosity measured from DMA frequency sweep for blend compositions that used PCR-B is shown in Figure 5. The melt flow index versus zeroshear viscosity measured from DMA frequency sweep for blend compositions that used PCR- C is shown in Figure 6. The results show that the disclosed compositions have improved toughness while maintaining tensile and flexural properties as compared to a virgin polyethylene rotomolding grade.

[0171] Although embodiments of the present application and their advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the embodiments as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the above disclosure, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein can be utilized. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.

[0172] Non-limiting embodiments of the present disclosure include the following:

[0173] Embodiment A. A polymeric composition comprising: 10 wt.% to 30 wt.% of recycled polyethylene; 50 wt.% to 80 wt.% of an ethylene alpha-olefin copolymer having a density from 0.933 g / cm3to 0.940 g / cm3and a zero-shear viscosity ZSV(A); and 5 wt.% to 25 wt.% of a high density polyethylene; wherein the polymeric composition has a zero-shear viscosity ZSV(B); wherein Izod impact performance at -40°C is greater than or equal to 6 ft- Ib / in for a compression molded specimen of the polymeric composition, the compression molded specimen prepared in accordance with ASTM D-4703; and wherein a ratio of ZSV(B) to ZSV(A) is less than or equal to 1.9.

[0174] Embodiment B. The polymeric composition of Embodiment A, wherein the Izod impact performance at -40°C is greater than or equal to 9 ft-lb / in for the compression molded specimen of the polymeric composition.

[0175] Embodiment C. The polymeric composition of Embodiment A or B, wherein the recycled polyethylene comprises a post-consumer recycled (PCR) polyethylene.

[0176] Embodiment D. The polymeric composition of Embodiment A or B, wherein the recycled polyethylene comprises a post-industrial recycled (PIR) polyethylene.

[0177] Embodiment E. The polymeric composition of Embodiment A, B, C, or D, wherein the recycled polyethylene has a density of 0.910 g / cm3to 0.940 g / cm3.

[0178] Embodiment F. The polymeric composition of Embodiment A, B, C, D, or E, wherein the polymeric composition has a flexural secant modulus -1% between 640 MPa and 750 MPa.

[0179] Embodiment G. The polymeric composition of Embodiment A, B, C, D, E, or F, having a melt flow index as measured under ASTM D-1238 at 190°C and 2.16 kilograms from 3.0 g / 10 min to 5.5 g / 10 min; and / or a melt flow index as measured under ASTM D- 1238 at 190°C and 21.6 kilograms from 70 g / 10 min to 150 g / 10 min.

[0180] Embodiment H. The polymeric composition of Embodiment A, B, C, D, E, F, or G, further comprising 2 wt.% to 10 wt.% of one or both of a linear low density polyethylene and a very low density polyethylene.

[0181] Embodiment !. The polymeric composition of Embodiment A, B, C, D, E, F, G, orH, wherein the ethylene alpha-olefin copolymer has a melt flow index as measured under ASTM D-1238 at 190°C and 2.16 kilograms of between 3 g / 10 min and 7 g / 10 min.

[0182] Embodiment J. The polymeric composition of Embodiment A, B, C, D, E, F, G, H, or I, wherein the ethylene alpha-olefin copolymer has a melt flow index as measured under ASTM D-1238 at 190°C and 2.16 kilograms of between 3 g / 10 min and 5.5 g / 10 min.

[0183] Embodiment K. The polymeric composition of Embodiment A, B, C, D, E, F, G, H, I, or J, wherein the ethylene alpha-olefin copolymer has a melt flow index as measured under ASTM D-1238 at 190°C and 21.6 kilograms of between 80 g / 10 min and 170 g / 10 min. Embodiment L. The polymeric composition of Embodiment A, B, C, D, E, F, G, H, I, J, or K, wherein the ethylene alpha-olefin copolymer has a melt flow index as measured under ASTM D-1238 at 190°C and 21.6 kilograms of between 80 g / 10 min and 120 g / 10 min.

[0184] Embodiment M. The polymeric composition of Embodiment A, B, C, D, E, F, G, H, I, J, K, or L, wherein the ethylene alpha-olefin copolymer has a zero-shear viscosity at 190°C of between 1,300 Pa-s and 2,700 Pa-s.

[0185] Embodiment N. The polymeric composition of Embodiment A, B, C, D, E, F, G, H, I, J, K, L, or M, wherein the ethylene alpha-olefin copolymer has a zero-shear viscosity at 190°C of between 1,800 Pa-s and 2,200 Pa-s.

[0186] Embodiment O. The polymeric composition of Embodiment A, B, C, D, E, F, G, H,

[0187] I, J, K, L, M, or N, wherein the recycled polyethylene comprises more than one recycled polyethylene.

[0188] Embodiment P. The polymeric composition of Embodiment A, B, C, D, E, F, G, H, I,

[0189] J, K, L, M, N, or O, wherein the recycled polyethylene has a zero-shear viscosity at 190°C greater than or equal to 15,000 Pa-s.

[0190] Embodiment Q. The polymeric composition of Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, wherein the recycled polyethylene has a zero-shear viscosity at 190°C of 100,000 Pa-s to 1,000,000 Pa-s.

[0191] Embodiment R. The polymeric composition of Embodiment A, B, C, D, E, F, G, H,

[0192] I, J, K, L, M, N, O, or P, wherein the recycled polyethylene has a zero-shear viscosity at 190°C of 15,000 Pa-s to 40,000 Pa-s.

[0193] Embodiment S. The polymeric composition of Embodiment A, B, C, D, E, F, G, H, I,

[0194] J, K, L, M, N, O, P, Q, or R, wherein the recycled polyethylene has a melt flow index as measured under ASTM D-1238 at 190°C and 2.16 kilograms of between 0.4 g / 10 min and 2.0 g / 10 min.

[0195] Embodiment T. The polymeric composition of Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, or S, wherein recycled polyethylene has a melt flow index as measured under ASTM D-1238 at 190°C and 21.6 kilograms of between 20 g / 10 min to 70 g / 10 min.

[0196] Embodiment U. The polymeric composition of Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, or T, wherein a difference between a melt flow index as measured under ASTM D-1238 at 190°C and 2.16 kilograms of the ethylene alpha-olefin copolymer and the recycled polyethylene is less than 6.6 g / 10 min. Embodiment V. The polymeric composition of Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, or U, wherein a difference between a melt flow index as measured under ASTM D-1238 at 190°C and 21.6 kilograms of the ethylene alpha-olefin copolymer and the recycled polyethylene is less than 90 g / 10 min.

[0197] Embodiment W. The polymeric composition of Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, or V, wherein the high density polyethylene comprises more than one high density polyethylene.

[0198] Embodiment X. The polymeric composition of Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, or W, wherein a most abundant high density polyethylene of the polymeric composition has a density from 0.945 g / cm3to 0.960 g / cm3.

[0199] Embodiment Y. The polymeric composition of Embodiment A, B, C, D, E, F, G, H,

[0200] I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W, or X, wherein a most abundant high density polyethylene of the polymeric composition has a melt flow index as measured under ASTM D-1238 at 190°C and 2.16 kilograms of between 25 g / 10 min and 65 g / 10 min.

[0201] Embodiment Z. The polymeric composition of Embodiment A, B, C, D, E, F, G, H, I,

[0202] J, K, L, M, N, O, P, Q, R, S, T, U, V, W, X, or Y, wherein a most abundant high density polyethylene of the polymeric composition has a melt flow index as measured under ASTM D-1238 at 190°C and 2.16 kilograms of between 40 g / 10 min and 60 g / 10 min.

[0203] Embodiment AA. The polymeric composition of Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, or Z, wherein a difference between the melt flow index as measured under ASTM D-1238 at 190°C and 2.16 kilograms of the ethylene alpha-olefin copolymer and a most abundant high density polyethylene of the polymeric composition is 30 to 50 g / 10 min.

[0204] Embodiment AB. The polymeric composition of Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, or AA, wherein: (i) the ethylene alphaolefin copolymer comprises hexene and / or octene as a comonomer; and / or (ii) the high density polyethylene comprises butene as a comonomer.

[0205] Embodiment AC. The polymeric composition of Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, AA, or AB, wherein the recycled polyethylene comprises a low-density polyethylene (LDPE), a high-density polyethylene (HDPE), a medium-density polyethylene (MDPE), a linear low-density polyethylene (LLDPE), a very-low-density polyethylene (VLDPE), an ultra-high-molecular-weight polyethylene (UHMWPE), an ultra-low-molecular-weight polyethylene (ULMWPE), and / or a high-molecular-weight polyethylene (HMWPE). Embodiment AD. The polymeric composition of Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, AA, AB, or AC, wherein the polymeric composition is comprised in a film, a layer, or a sheet.

[0206] Embodiment AE. The polymeric composition of Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, AA, AB, or AC, wherein the polymeric composition is comprised in a rotational molded article.

[0207] Embodiment AF. A molded article comprising the polymeric composition of Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, AA, AB, or AC.

[0208] Embodiment AG. The molded article of Embodiment AF, wherein at least 70 wt. % of the molded article comprises the polymeric composition.

[0209] Embodiment AH. A method of making a molded article, the method comprising forming at least a portion of the molded article with the polymeric composition of Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, AA, AB, or AC.

[0210] Embodiment AE The method of Embodiment AH, wherein at least 70 wt.% of the molded article comprises the polymeric composition.

[0211] Embodiment AJ. A method of making the polymeric composition of Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, AA, AB, or AC, the method comprising: combining a recycled polyethylene, an ethylene alpha-olefin copolymer, and a high density polyethylene to form the polymeric composition.

[0212] Embodiment AK. The method of Embodiment AJ, wherein the combining comprises heating the recycled polyethylene, the ethylene alpha-olefin copolymer, and the high density polyethylene to melt at least a portion of the recycled polyethylene, the ethylene alpha-olefin copolymer, and the high density polyethylene.

[0213] Embodiment AL. The method of Embodiment A J or AK, wherein the combining comprises extruding the polymeric composition.

[0214] INDUSTRIAL APPLICABILITY

[0215] Compositions including recycled polyethylene suitable for rotomolding applications.

Claims

CLAIMS1. A polymeric composition comprising:10 wt.% to 30 wt.% of recycled polyethylene;50 wt.% to 80 wt.% of an ethylene alpha-olefin copolymer having a density from 0.933 g / cm3to 0.940 g / cm3and a zero-shear viscosity ZSV(A); and5 wt.% to 25 wt.% of a high density polyethylene; wherein the polymeric composition has a zero-shear viscosity ZSV(B); wherein Izod impact performance at -40°C is greater than or equal to 6 ft-lb / in for a compression molded specimen of the polymeric composition, the compression molded specimen prepared in accordance with ASTM D-4703; and wherein a ratio of ZSV(B) to ZSV(A) is less than or equal to 1.9.

2. The polymeric composition of claim 1, wherein the Izod impact performance at -40°C is greater than or equal to 9 ft-lb / in for the compression molded specimen of the polymeric composition.

3. The polymeric composition of claim 1 or 2, wherein the recycled polyethylene comprises a post-consumer recycled polyethylene4. The polymeric composition of claim 1 or 2, wherein the recycled polyethylene comprises a post-industrial recycled polyethylene.

5. The polymeric composition of any one of claims 1 to 4, wherein the recycled polyethylene has a density of 0.910 g / cm3to 0.940 g / cm3.

6. The polymeric composition of claim 1 or 5, wherein the polymeric composition has a flexural secant modulus -1% between 640 MPa and 750 MPa.

7. The polymeric composition of any one of claims 1 to 6, wherein the polymeric composition has a melt flow index, h, as measured under ASTM D-1238 at 190°C and 2.16 kilograms from 3.0 g / 10 min to 5.5 g / 10 min; and a melt flow index, hi, as measured under ASTM D-1238 at 190°C and 21.6 kilograms from 70 g / 10 min to 150 g / 10 min.

8. The polymeric composition of any one of claims 1 to 7, further comprising 2 wt.% to 10 wt.% of one or both of a linear low density polyethylene and a very low density polyethylene.

9. The polymeric composition of any one of claims 1 to 8, wherein the ethylene alphaolefin copolymer has a melt flow index, h, as measured under ASTM D-1238 at 190°C and 2.16 kilograms of between 3 g / 10 min and 7 g / 10 min.

10. The polymeric composition of any one of claims 1 to 8, wherein the ethylene alphaolefin copolymer has a melt flow index, h, as measured under ASTM D-1238 at 190°C and 2.16 kilograms of between 3 g / 10 min and 5.5 g / 10 min.

11. The polymeric composition of any one of claims 1 to 10, wherein the ethylene alphaolefin copolymer has a melt flow index, hi, as measured under ASTM D-1238 at 190°C and 21.6 kilograms of between 80 g / 10 min and 170 g / 10 min.

12. The polymeric composition of any one of claims 1 to 10, wherein the ethylene alphaolefin copolymer has a melt flow index, hi, as measured under ASTM D-1238 at 190°C and 21.6 kilograms of between 80 g / 10 min and 120 g / 10 min.

13. The polymeric composition of any one of claims 1 to 12, wherein the ethylene alphaolefin copolymer has a zero-shear viscosity at 190°C of between 1,300 Pa-s and 2,700 Pa-s.

14. The polymeric composition of any one of claims 1 to 12, wherein the ethylene alphaolefin copolymer has a zero-shear viscosity at 190°C of between 1,800 Pa-s and 2,200 Pa-s.

15. The polymeric composition of any one of claims 1 to 14, wherein the recycled polyethylene comprises more than one recycled polyethylene.

16. The polymeric composition of any one of claims 1 to 15, wherein the recycled polyethylene has a zero-shear viscosity at 190°C greater than or equal to 15,000 Pa-s.

17. The polymeric composition of any one of claims 1 to 16, wherein the recycled polyethylene has a zero-shear viscosity at 190°C of 100,000 Pa-s to 1,000,000 Pa-s.

18. The polymeric composition of any one of claims 1 to 16, wherein the recycled polyethylene has a zero-shear viscosity at 190°C of 15,000 Pa-s to 40,000 Pa-s.

19. The polymeric composition of any one of claims 1 to 18, wherein the recycled polyethylene has a melt flow index, h, as measured under ASTM D-1238 at 190°C and 2.16 kilograms of between 0.4 g / 10 min and 2.0 g / 10 min.

20. The polymeric composition of any one of claims 1 to 19, wherein recycled polyethylene has a melt flow index, hi, as measured under ASTM D-1238 at 190°C and 21.6 kilograms of between 20 g / 10 min to 70 g / 10 min.

21. The polymeric composition of any one of claims 1 to 20, wherein a difference between a melt flow index, h, as measured under ASTM D-1238 at 190°C and 2.16 kilograms of the ethylene alpha-olefin copolymer and the recycled polyethylene is less than 6.6 g / 10 min.

22. The polymeric composition of any one of claims 1 to 21, wherein a difference between a melt flow index, hi, as measured under ASTM D-1238 at 190°C and 21.6 kilograms of the ethylene alpha-olefin copolymer and the recycled polyethylene is less than 90 g / 10 min.

23. The polymeric composition of any one of claims 1 to 22, wherein the high density polyethylene comprises more than one high density polyethylene.

24. The polymeric composition of any one of claims 1 to 23, wherein a most abundant high density polyethylene of the polymeric composition has a density from 0.945 g / cm3to 0.960 g / cm3.

25. The polymeric composition of any one of claims 1 to 23, wherein a most abundant high density polyethylene of the polymeric composition has a melt flow index, h, as measured under ASTM D-1238 at 190°C and 2.16 kilograms of between 25 g / 10 min and 65 g / 10 min.

26. The polymeric composition of any one of claims 1 to 23, wherein a most abundant high density polyethylene of the polymeric composition has a melt flow index, h, as measured under ASTM D-1238 at 190°C and 2. 16 kilograms of between 40 g / 10 min and 60 g / 10 min.

27. The polymeric composition of any one of claims 1 to 23, wherein a difference between the melt flow index, h, as measured under ASTM D-1238 at 190°C and 2.16 kilograms of the ethylene alpha-olefin copolymer and a most abundant high density polyethylene of the polymeric composition is 30 g / 10 min to 50 g / 10 min.

28. The polymeric composition of any one of claims 1 to 27, wherein:(i) the ethylene alpha-olefin copolymer comprises hexene and / or octene as a comonomer; and / or(ii) the high density polyethylene comprises butene as a comonomer.

29. The polymeric composition of any one of claims 1 to 28, wherein the polymeric composition is comprised in a film, a layer, or a sheet.

30. The polymeric composition of any one of claims 1 to 28, wherein the polymeric composition is comprised in a rotational molded article.

31. A molded article comprising the polymeric composition of any one of claims 1 to 28.

32. The molded article of claim 31, wherein at least 70 wt.% of the molded article comprises the polymeric composition.

33. A method of making a molded article, the method comprising forming at least a portion of the molded article with the polymeric composition of any one of claims 1 to 28.

34. The method of claim 34, wherein at least 70 wt.% of the molded article comprises the polymeric composition.

35. A method of making the polymeric composition of any one of claims 1 to 28, the method comprising: combining a recycled polyethylene, an ethylene alpha-olefin copolymer, and a high density polyethylene to form the polymeric composition.

36. The method of claim 35, wherein the combining comprises heating the recycled polyethylene, the ethylene alpha-olefin copolymer, and the high density polyethylene to melt at least a portion of the recycled polyethylene, the ethylene alpha-olefin copolymer, and the high density polyethylene.

37. The method of any one of claims 35 or 36, wherein the combining comprises extruding the polymeric composition.

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