Polyethylene blend compositions with high levels of recycled polyethylene

Abstract

The present disclosure provides a blend composition including 10 wt% to 60 wt.% of recycled polyethylene; and 40 wt.% to 90 wt.% of a virgin polyethylene, the virgin polyethylene having (a) a density less than 0.915 g / cm3 as measured according to ASTM D- 792, (b) a melt index, I2, less than 4 g / 10 min as measured according to ASTM D-1238 at 190°C using a 2.16 kg weight, (c) a Z-average molecular weight, Mz, between 120,000 g / mol and 300,000 g / mol as measured according to ASTM D6474-99, (d) a short chain branch frequency at Mz greater than 19 SCB / 1000C, and (e) a reverse comonomer distribution. The blend compositions disclosed herein are suitable for use in film applications.

Description

[0001] POLYETHYLENE BLEND COMPOSITIONS WITH HIGH LEVELS

[0002] OF RECYCLED POLYETHYLENE

[0003] TECHNICAL FIELD

[0004] The present disclosure generally relates to blend compositions that include recycled polyethylene and virgin polyethylene. The compositions disclosed herein may be used in film applications.

[0005] BACKGROUND ART

[0006] There is increasing interest in incorporation of recycled polyethylene into products commonly made from virgin polyethylene, such as films.

[0007] A traditional recycling method for plastics (for example, polyethylene) includes mechanical recycling, which may include bale de-wiring, bale breakup, shredding, screening, optical sorting, washing, drying, melt filtration, extrusion, devolatilization, and / or pelletizing. Although recycling of plastics is highly desirable it faces challenges for broader deployment. For instance, a decline in mechanical properties limits the applicability of recycled plastics partly due to the thermo-mechanical conditions of the recycling process that may lead to degradation of plastic polymer matrix. Highly branched polyolefins (for example, low density polyethylene, LDPE) exhibit increased susceptibility to thermo-mechanical degradation due to comparatively increased concentration of tertiary carbons surrounded by long carbon chains, which can generate radicals with longer lifetime due to stabilization provided by inductive effects. This prolonged lifetime can facilitate chain scission and oxidative reactions.

[0008] Consequently, mechanical properties of films are often reduced with the incorporation of recycled polyethylene.

[0009] Increasing the amount of recycled polyethylene in compositions suitable for film applications while maintaining good film properties is desirable.

[0010] SUMMARY OF INVENTION

[0011] The present disclosure provides a blend composition including 10 wt.%to 60 wt.% of recycled polyethylene; and 40 wt.% to 90 wt.% of a virgin polyethylene, the virgin polyethylene having (a) a density less than 0.915 g / cm3as measured according to ASTM D-792, (b) a melt index, L, less than 4 g / 10 min as measured according to ASTM D-1238 at 190°C using a 2.16 kg weight, (c) a Z-average molecular weight, Mz, between 120,000 g / mol and 300,000 g / mol as measured according to ASTM D6474-99, (d) a short chain branch frequency at Mzgreater than 19 SCB / 1000C, and (e) a reverse comonomer distribution.In some embodiments, the virgin polyethylene includes a first ethylene copolymer component having a first component density, and a first component weight average molecular weight, Mwi; and a second ethylene copolymer component having a second component density, and a second component weight average molecular weight, Mw2, that is less than the first component weight average molecular weight; wherein the difference between the second component density and the first component density is greater than 0.023 g / cm3.

[0012] In some embodiments, the first ethylene copolymer component has a first component short chain branch frequency of between 20 SCB / 1000C and 30 SCB / 1000C.

[0013] In some embodiments, the first ethylene copolymer component has a first component short chain branch frequency of between 31 SCB / 1000C and 38 SCB / 1000C.

[0014] In some embodiments, the Mzof the virgin polyethylene is between 120,000 g / mol and 250,000 g / mol.

[0015] In some embodiments, the density of the virgin polyethylene is between 0.905 g / cm3and 0.914 g / cm3.

[0016] In some embodiments, the density of the virgin polyethylene is between 0.905 g / cm3and 0.908 g / cm3.

[0017] In some embodiments, the virgin polyethylene has a number average molecular weight, Mn, between 20,000 g / mol and 40,000 g / mol as determined according to ASTM D6474-99.

[0018] In some embodiments, the virgin polyethylene has a polydispersity index, Mw / Mn, between 2.1 and 4.0.

[0019] In some embodiments, the first ethylene copolymer component is present in the virgin polyethylene in an amount of 30 wt.% to 45 wt.%.

[0020] In some embodiments, the first component weight average molecular weight is between 110,000 g / mol and 160,000 g / mol.

[0021] In some embodiments, the first ethylene copolymer component is present in the virgin polyethylene in an amount of 46 wt.% to 52 wt.% and the virgin polyethylene has a polydispersity index, Mw / Mn, between 4.1 and 4.5.

[0022] In some embodiments, the virgin polyethylene is an ethylene octene copolymer. In some embodiments, the recycled polyethylene has a density of 0.910 g / cm3to 0.940 g / cm3, as measured according to ASTM D-792.

[0023] In some embodiments, the recycled polyethylene has a melt flow index, h, as measured according to ASTM D-1238 at 190°C and using a 2.16 kg weight, between 0.4 g / 10 min and 2.0 g / 10 min.In some embodiments, the recycled polyethylene includes up to 5 wt.% polypropylene, based on the total weight of the recycled polyethylene.

[0024] In some embodiments, the recycled polyethylene contains LDPE in an amount of up to 10 wt.%.

[0025] In some embodiments, the blend composition includes the recycled polyethylene in an amount of 20 wt.% and the virgin polyethylene in an amount of 80 wt.%.

[0026] In some embodiments, the blend composition includes the recycled polyethylene in an amount of 30 wt.% and the virgin polyethylene in an amount of 70 wt.%.

[0027] In some embodiments, the blend composition includes the recycled polyethylene in an amount of 40 wt.% and the virgin polyethylene in an amount of 60 wt.%.

[0028] In some embodiments, the blend composition includes the recycled polyethylene and the virgin polyethylene in equal weight amounts.

[0029] In some embodiments, the blend composition is prepared by dry blending the virgin polyethylene and the recycled polyethylene.

[0030] The present disclosure also provides a blown fdm prepared from any of the blend compositions disclosed herein. In some embodiments, the blown film has a dart impact value of greater than 134 g / mil as measured according to ASTM D1709 using a 2.4 mil film. In some embodiments, the blown film has a machine direction tear value of at least 200 g / mil as measured according to ASTM D1922 using a 2.4 mil film.

[0031] Other objects, features and advantages of the present disclosure will become apparent from the following detailed description and examples.

[0032] DESCRIPTION OF EMBODIMENTS

[0033] In one aspect, the present disclosure provides a blend composition including 10 wt.% to 60 wt.% of recycled polyethylene; and 40 wt.% to 90 wt.% of a virgin polyethylene, the virgin polyethylene having: (a) a density less than 0.915 g / cm3as measured according to ASTM D-792; (b) a melt index, h, less than 4 g / 10 min as measured according to ASTM D-1238 at 190°C using a 2.16 kg weight; (c) a Z-average molecular weight, Mz, between 120,000 g / mol and 300,000 g / mol as measured according to ASTM D6474-99; (d) a branch frequency at Mz greater than 19 SCB / 1000C; and (e) a reverse comonomer distribution. The blend compositions of the present disclosure may result in fdms with a balance of film properties, including dart, machine direction tear, and machine direction elongation at break. Films made from the blend compositions of the present disclosure may be used in a wide range of flexible packaging applications, including flexible packaging, heavy-duty sacks, e-commerce mailers, stretch wrap, collation shrink, protective packaging, industrial films, can liners, and carry-out bags.

[0034] These and other non-limiting embodiments of the present disclosure are discussed in further detail in the following sections.

[0035] A, Definitions

[0036] The following includes definitions of various terms and phrases used throughout this specification.

[0037] “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. Herein, the term “virgin polyethylene” may be used interchangeably with the terms “virgin ethylene copolymer composition”, “virgin polyethylene resin”, or “virgin polyethylene composition”. It is known to the skilled person that one or more additives can be present in virgin polyethylene.

[0038] The term “ethylene copolymer” or “ethylene alpha-olefin copolymer” may be used interchangeably herein and 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.

[0039] “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, typically to form a finished good.“HDPE” refers to high density polyethylene, which generally has a density of greater or equal to 0.941 g / cm3, or for example, from 0.941 g / cm3to 0.970 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.

[0040] “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.

[0041] “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 (a-olefin) comonomer, for example butene, hexene, or octene. Typically, LLDPE has a density in the range of 0.910 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 % relative to ethylene, such as for example from 1.5 mol % to 10 mol %, or 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.

[0042] “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.

[0043] “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. VLDPE may be 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), and is most commonly produced using metallocene catalysts in a solution process.

[0044] 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 withinNotwithstanding 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.

[0045] 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.

[0046] 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.

[0047] 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”.

[0048] 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.

[0049] B, The Blend Composition

[0050] The present disclosure provides a blend composition including 10 wt. % to 60 wt. % of recycled polyethylene; and 40 wt.% to 90 wt.% of a virgin polyethylene, the virgin polyethylene having (a) a density less than 0.915 g / cm3as measured according to ASTM D-792, (b) a melt index, L, less than 4 g / 10 min as measured according to ASTM D-1238 at 190°C using a 2.16 kg weight, (c) a Z-average molecular weight, Mz, between 120,000 g / mol and 300,000 g / mol as measured according to ASTM D6474-99, (d) a branch frequency at Mzgreater than 19 SCB / 1000C, and (e) a reverse comonomer distribution. As used herein, the term “blend composition” refers to a composition provided by combining, mixing, or blending together the recycled polyethylene and the virgin polyethylene. The combining, mixing, or blending may be by any suitable means familiar to the person skilled in the art. In some embodiments the combining is by dry blending. In some embodiments, the blending is by melt blending.

[0051] In some embodiments, the blend composition includes the recycled polyethylene in an amount ranging from 15 wt.% to 50 wt.%, or 20 wt.% to 50 wt.%, or 20 wt.% to 40 wt.%, or 25 wt.% to 35 wt.%. In some embodiments, the blend composition includes the recycled polyethylene in an amount of 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, or 60 wt.%. In some embodiments, the recycled polyethylene includes more than one recycled polyethylene. Recycled polyethylene suitable for use in the blends of the present disclosure is described later herein.

[0052] In some embodiments, the blend composition includes the virgin polyethylene in an amount ranging from 50 wt.% to 85 wt.%, or 50 wt.% to 80 wt.%, or 60 wt.% to 80 wt.%, or 65 wt.% to 75 wt.%. In some embodiments, the blend composition includes virgin polyethylene in an amount of 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, 70 wt.%, 75 wt.%, 80 wt.%, 85 wt.%, or 90 wt.%. Virgin polyethylene suitable for use in the blends of the present disclosure is described later herein.

[0053] In some embodiments, the blend composition includes the recycled polyethylene in an amount of 20 wt.% and the virgin polyethylene in an amount of 80 wt.%. In some embodiments, the blend composition includes the recycled polyethylene in an amount of 30 wt.% and the virgin polyethylene in an amount of 70 wt.%. In some embodiments, the blend composition includes the recycled polyethylene in an amount of 40 wt.% and the virgin polyethylene in an amount of 60 wt.%. In some embodiments, the blend composition includes the recycled polyethylene and the virgin polyethylene in equal weight amounts.

[0054] In some embodiments, the blend composition contains one or more additives, including antioxidants, UV-stabilizers, heat stabilizers, nucleating agents, antistatic agents, or compatibilizers, which may be originally present in the virgin polyethylene and / or the recycled polyethylene.

[0055] In some embodiments, the blend composition is prepared by dry blending the virgin polyethylene and the recycled polyethylene. In some embodiments, the blend composition is prepared by combining, mixing, or blending the recycled polyethylene and the virgin polyethylene in a weight ratio of 1:5 recycled polyethylene: virgin polyethylene. In someembodiments, the blend composition is prepared by combining, mixing, or blending the recycled polyethylene and the virgin polyethylene in a weight ratio of 1:4 recycled polyethylene: virgin polyethylene. In some embodiments, the blend composition is prepared by combining, mixing, or blending the recycled polyethylene and the virgin polyethylene in a weight ratio of 1:3 recycled polyethylene: virgin polyethylene. In some embodiments, the blend composition is prepared by combining, mixing, or blending the recycled polyethylene and the virgin polyethylene in a weight ratio of 1 :2 recycled polyethylene: virgin polyethylene. In some embodiments, the blend composition is prepared by combining, mixing, or blending the recycled polyethylene and the virgin polyethylene in a weight ratio of 1:1. In some embodiments, the blend composition is prepared by combining, mixing, or blending the recycled polyethylene and the virgin polyethylene in a weight ratio of 2:1 recycled polyethylene : virgin polyethylene .

[0056] In some embodiments, the blend composition is prepared in situ at, for example, a fdm line. In some embodiments, the blend composition is isolated in a pellet form after melt blending the virgin polyethylene and the recycled polyethylene.

[0057] C. The Virgin Polyethylene

[0058] The virgin polyethylene in the blend compositions disclosed herein is virgin ethylene copolymer product. The ethylene copolymer product may include polymerized ethylene and one or more than one polymerized alpha-olefin comonomer selected from the group comprising C3-C12 alpha-olefins. In some embodiments, the alpha-olefin comonomer is 1-octene.

[0059] In some embodiments, the virgin polyethylene in the blend compositions of the present disclosure has a density of less than about 0.915 g / cm3, as measured according to ASTM D-792. In some embodiments, the virgin polyethylene has a density between 0.905 g / cm3and 0.914 g / cm3. In some embodiments, the virgin polyethylene has a density between 0.905 g / cm3and 0.908 g / cm3. In some embodiments, the virgin polyethylene has a density between 0.908 g / cm3and 0.914 g / cm3. In some embodiments, the virgin polyethylene has a density of 0.905 g / cm3, 0.906 g / cm3, 0.908 g / cm3, 0.910 g / cm3, 0.912 g / cm3, or 0.914 g / cm3.

[0060] In some embodiments, the virgin polyethylene used in the blend compositions of the present disclosure has a melt index, h, of less than 4 g / 10 min, as measured according to ASTM D-1238 (190°C, 2.16 kg weight). In some embodiments, the virgin polyethylene has a melt index, I2, between 0.5 g / 10 min and 3.5 g / 10 min. In some embodiments, the virgin polyethylene has a melt index, I2, between 0.4 g / 10 min and 2.0 g / 10 min. In some embodiments, the virgin polyethylene has a melt index, I2, between 0.8 g / 10 min and3 g / 10 min. In some embodiments, the virgin polyethylene has a melt index, h, of 0.8 g / 10 min, 0.9 g / 10 min, 1 g / 10 min, 2 g / 10 min, or 3 g / 10 min.

[0061] In some embodiments, the virgin polyethylene has a density of less than 0.914 g / cm3and a melt index, I2, of about 0.85 g / 10 min.

[0062] In some embodiments, the virgin polyethylene has a density of 0.914 g / cm3and a melt index, I2, of 0.85 g / 10 min. In some embodiments, the virgin polyethylene has a density of 0.908 g / cm3and a melt index, I2, of 0.85 g / 10 min. In some embodiments, the virgin polyethylene has a density of 0.908 g / cm3and a melt index, I2, of 3 g / 10 min.

[0063] The virgin polyethylene in the blend compositions of the present disclosure has a Z-average molecular weight, Mz, between 120,000 g / mol and 300,000 g / mol, as measured according to ASTM-D6474-99. In some embodiments, the virgin polyethylene has a Z-average molecular weight, Mz, between 120,000 g / mol and 250,000 g / mol. In some embodiments, the virgin polyethylene has a Z-average molecular weight, Mz, between 130,000 g / mol and 200,000 g / mol.

[0064] The presence of an alpha-olefin comonomer during polymerization produces “short chain branches” (SCB) in the virgin polyethylene, where short chain branching (also referred to as short chain branch frequency) is the number of short chain branches present per 1000 backbone carbon atoms The skilled person will appreciate that a comonomer of formula Cnkhn will produce a short chain branch that is a length of n-2. For example, 1 -octene produces a short chain branch having 6 carbon atoms. These short chain branches may reduce the crystallinity of the ethylene copolymer (in comparison to an ethylene homopolymer). Ethylene alpha-olefin copolymers produced using a Ziegler-Natta catalyst are sometimes referred to as being “heterogeneous” or “heterogeneously branched”, as the ethylene alphaolefin copolymer is typically a mixture of different polyethylene copolymer chains having significantly different molecular weights and alpha-olefin contents.

[0065] The virgin polyethylene in the blend compositions of the present disclosure has a short chain branching frequency at Mzof greater than 19 short chain branches (SCB) per 1000 backbone carbon atoms ( / 1000 C), as determined using GPC-FTIR. In some embodiments, the virgin polyethylene has a short chain branching frequency at Mzof greater than or equal to 20 SCB / 1000 C. In some embodiments, the virgin polyethylene has a short chain branching frequency at Mzof greater than or equal to 22 SCB / 1000 C. In some embodiments, the virgin polyethylene has a short chain branching frequency at Mzof greater than or equal to 23 SCB / 1000 C. In some embodiments, the virgin polyethylene has a short chain branching frequency at Mzof greater than or equal to 24 SCB / 1000 C. Without being bound by anyparticular theory, it is believed that having a higher short chain (comonomer) content in the higher molecular weight portion (Mz), may create stronger and more entanglements in the longer chains and / or more tie chains, thereby increasing the strength of the disclosed blends when used for fdms.

[0066] Virgin polyethylene suitable for use in the blend compositions disclosed herein demonstrates a reverse comonomer distribution. The phrase “reverse comonomer distribution” means that on deconvolution of GPC-FTIR (or temperature raising elution fractionation, TREF) data profdes (typically using molecular weight distribution segments of not less than 10,000), there is one or more higher molecular weight component(s) having a higher comonomer incorporation than in one or more lower molecular weight segments. The that is, reverse comonomer distribution reflects an increased amount of a-olefm (comonomer) content with increasing molecular weight of the copolymer. If the comonomer incorporation rises with increasing molecular weight and then declines, the comonomer distribution is described as “partially reversed”.

[0067] In some embodiments, the virgin polyethylene has a number average molecular weight, Mn, between 20,000 g / mol and 40,000 g / mol as determined according to ASTM D6474-99. In some embodiments, the virgin polyethylene has a number average molecular weight, Mn, between 25,000 g / mol and 40,000 g / mol. In some embodiments, the virgin polyethylene has a number average molecular weight, Mn, between 27,000 g / mol and 40,000 g / mol.

[0068] In some embodiments, the virgin polyethylene has a polydispersity index (Mw / Mn) between 2.1 and 4.5. In some embodiments, the virgin polyethylene has a polydispersity index (Mw / Mn) between 2.1 and 4.0. In some embodiments, the virgin polyethylene has a polydispersity index (Mw / Mn) between 2.1 and 3.0. In some embodiments, the virgin polyethylene has a polydispersity index (Mw / Mn) between 2.5 and 4.0. In some embodiments, the virgin polyethylene has a polydispersity index (Mw / Mn) between 2.1 and 3.0. In some embodiments, the virgin polyethylene has a polydispersity index (Mw / Mn) between 4.1 and 4.5.

[0069] In some embodiments, the virgin polyethylene includes a first ethylene copolymer component having a first component density, and a first component weight average molecular weight, Mwi; and a second ethylene copolymer component having a second component density, and a second component weight average molecular weight, Mw2, that is less than the first average molecular weight; wherein the difference between the second component density and the first component density is greater than 0.023 g / cm3. That is to say, the density of theethylene copolymer component with the lower molecular weight minus the density of the ethylene copolymer component with the higher molecular weight is greater than 0.023 g / cm3. Density of the first and second ethylene copolymer components may be determined by deconvolution methods as described later herein. In some embodiments, the first component density is between 0.870 and 0.899 g / cm3. In some embodiments, the second component density is between 0.919 and 0.923 g / cm3.

[0070] In some embodiments, the first component weight average molecular weight of the first ethylene copolymer component is between 110,000 g / mol and 160,000 g / mol. In some embodiments, the first ethylene copolymer component has a branch frequency between 20 SCB / 1000C and 30 SCB / 1000C. In some embodiments, the first ethylene copolymer component has a branch frequency between 31 SCB / 1000C and 38 SCB / 1000C. In some embodiments, the first ethylene copolymer component is present in the virgin polyethylene in an amount of 30 wt.% to 45 wt.%. In some embodiments, the first ethylene copolymer component is present in the virgin polyethylene in an amount of 46 wt.% to 52 wt.%.

[0071] In some embodiments, the second component weight average molecular weight is between 40,000 g / mol and 70,000 g / mol. In some embodiments, the second ethylene copolymer component is present in an amount of 55 wt.% to 70 wt.%. In some embodiments, the second ethylene copolymer component is present in an amount of 48 wt.% to 54 wt.%.

[0072] In some embodiments, the virgin polyethylene is made by a solution polymerization process. In some embodiments, a single site catalyst is used to make the first ethylene copolymer component in a first reactor. In some embodiments a Ziegler-Natta catalyst is used to make the second ethylene copolymer component in a second reactor. Both single site catalysts and Ziegler-Natta catalysts are known to the person skilled in the art.

[0073] 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.

[0074] In some embodiments, the first ethylene copolymer component is prepared using at least one homogeneous catalyst formulation. One non-limiting example of a homogeneous catalyst formulation is a bridged metallocene catalyst formulation defined by Formula (I)

[0075]

[0076] In Formula (I): non-limiting examples of M include Group 4 metals (i.e. titanium, zirconium and hafnium); non-limiting examples of G include Group 14 elements, carbon, silicon, germanium, tin and lead; Ri, R2, R3, R4, and Rs are each independently selected from a hydrogen atom, a C1-20 hydrocarbyl radical, a C1-20 alkoxy radical, or a Ce-io aryl oxide radical.

[0077] In the art, a commonly used term for the Q group shown in Formula (I) is a “leaving group”, that is, any ligand that can be abstracted from Formula (I) forming a catalyst species capable of polymerizing one or more olefm(s). An equivalent term for the Q group is an “activatable ligand”. Non-limiting examples of activatable ligands include halides (e.g., chloride) or hydrocarbyl groups (e.g., methyl or benzyl groups). In some embodiments, each activatable ligand, Q, is a methyl group. In some embodiments, each activatable ligand, Q, is a benzyl group. In some embodiments, each activatable ligand, Q, is a chloride. Further nonlimiting examples of the Q group shown in Formula (I) include weak bases such as amines, phosphines, ethers, carboxylates and dienes.

[0078] As used herein, the terms “hydrocarbyl”, “hydrocarbyl radical”, or “hydrocarbyl group” refers to linear or branched, aliphatic, olefinic, acetylenic and aryl (aromatic) radicals comprising hydrogen and carbon that are deficient by one hydrogen. A hydrocarbyl group may be further specifically defined as being unsubstituted or substituted. As used herein the term “unsubstituted” means that hydrogen radicals are bounded to the molecular group that is referred to by the term unsubstituted. The term “substituted” means that the group referred to by this term possesses one or more moieties that have replaced one or more hydrogen radicals in any position within the group; non-limiting examples of moieties include halogen radicals (F, Cl, Br), an alkyl group, hydroxyl groups and combinations thereof.

[0079] As used herein, an “alkyl radical” or “alkyl group” includes linear, branched and cyclic paraffin radicals that are deficient by one hydrogen; non-limiting examples include methyl (-CH3) and ethyl (-CH2CH3) radicals.An “alkoxy group” is an oxy group having an alkyl group pendant there from; and includes for example a methoxy group, an ethoxy group, an iso-propoxy group, and the like.

[0080] An “aryloxy” group is an oxy group having an aryl group pendant there from; and includes for example a phenoxy group and the like. The term “aryl group” includes phenyl, naphthyl, pyridyl and other radicals whose molecules have an aromatic ring structure; nonlimiting examples include naphthalene, phenanthrene and anthracene.

[0081] In some embodiments, the single site catalyst used to make the first ethylene copolymer component is diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafhium dichloride having the molecular formula [(2,7-tBu2Flu)Ph2C(Cp)HfC12] . In some embodiments, the single site catalyst used to make the first ethylene copolymer component is diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafhium dimethyl having the molecular formula [(2,7-tBu2Flu)Ph2C(Cp)HfMe2] .

[0082] The polymerization catalyst or complex, requires activation by one or more co-catalytic or catalyst activator species in order to provide polymer from olefins. Hence, an unactivated polymerization catalyst or complex may be described as a “pre-polymerization catalyst”.

[0083] In embodiments, the pre-polymerization catalysts described and used in the present disclosure have improved activity when combined with a boron based catalyst activator, an alkylaluminoxane co-catalyst and a hindered phenol compound.

[0084] Accordingly, some embodiments, the olefin polymerization catalyst system used to prepare the virgin polyethylene compositions used in the blends disclosed herein includes: i) a pre-polymerization catalyst; ii) a boron based catalyst activator; iii) an alkyaluminoxane cocatalyst; and iv) a hindered phenol compound.

[0085] In some embodiments, the polymerization process includes polymerizing ethylene with one or more than one C3-C12 alpha-olefin in the presence of an olefin polymerization catalyst system that includes: i) a pre-polymerization catalyst; ii) a boron based catalyst activator; iii) an alkyaluminoxane co-catalyst; and iv) a hindered phenol compound.

[0086] 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. In some embodiments, the second ethylene copolymer component synthesized using a first heterogeneous catalyst formulation. In some embodiments, the first heterogeneous catalyst formulation is an in-line Ziegler-Natta catalyst formulation. In someembodiments, the first heterogenous catalyst formulation is a batch Ziegler-Natta catalyst formulation.

[0087] Solution polymerization processes for the polymerization or copolymerization of olefins such as ethylene and alpha olefins are also 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 C5-12 hydrocarbons that 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).

[0088] 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.

[0089] In some embodiments, the virgin polyethylene disclosed herein and suitable for use in the blends of the present disclosure are made using solution polymerization.

[0090] In some embodiments, the virgin polyethylene is VPsK914-C04, sold by NOVA Chemicals (Canada). In some embodiments, the virgin polyethylene is QHsK908-A, sold by NOVA Chemicals (Canada).

[0091] D. The Recycled Polyethylene

[0092] The recycled polyethylene of the blend compositions disclosed herein can be postconsumer recycled polyethylene, post-industrial recycled polyethylene, or a combination thereof. In some embodiments, the blend composition includes more than one recycled polyethylene. Both post-consumer recycled polyethylene and post-industrial recycledpolyethylene materials can be purchased commercially. Post-consumer recycled polyethylene sourced from distribution centers can also be purchased commercially.

[0093] In some embodiments, the recycled polyethylene is obtained from mechanical recycling of a baled commodity that is a mix of natural polyethylene fdm, primarily linear low density polyethylene (LLDPE) and low density polyethylene (LDPE), predominantly clear or natural in colour, that has met its intended use generated from commercial sources. The fdms may be coded with ASTM D7611 resin identification code “#4, LDPE / LLDPE”. The bale composition includes a mix of retail-sourced packaging such as bags, shrink wrap, pouches, overwrap, and stretch films. Bales of this this feedstock may be referred to as “PE Clear Film Grade B” in the industry. In some embodiments, the PE Clear Film Grade B bales are at least 80% clear or natural polyethylene film based on exterior visual inspection with up to 20% coloured / printed polyethylene film, moderate levels of HDPE film, and low levels of non-film contaminants. In some embodiments, the recycled polyethylene is recycled polyethylene from stretch film.

[0094] In some embodiments, the recycled polyethylene is from used polyethylene parts that have been shredded, screened, optical sorted, washed, dried, melt filtered, extruded, devolatilized, and / or pelletized 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.

[0095] 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.

[0096] In some embodiments, the recycled polyethylene has a density between 0.910 g / cm3and 0.940 g / cm3, as measured according to ASTM D792. In some embodiments, the recycled polyethylene has a density between 0.910 and 0.930 g / cm3. In some embodiments, the recycled polyethylene has a density of 0.910 g / cm3, 0.911 g / cm3, 0.912 g / cm3, 0.913 g / cm3, 0.914 g / cm3, 0.915 g / cm3, 0.916 g / cm3, 0.917 g / cm3, 0.918 g / cm3, 0.919 g / cm3, 0.920 0.921g / cm3, 0.922 g / cm3, 0.923 g / cm3, 0.924 g / cm3, 0.925 g / cm3, 0.926 g / cm3, 0.927 g / cm3, 0.928 g / cm3, 0.929 g / cm3, or 0.930 g / cm3. In some embodiments, the recycled polyethylene has a density of between 0.918 g / cm3and 0.926 g / cm3.

[0097] In some embodiments, the recycled polyethylene has a melt flow index, h, as measured according to ASTM D-1238 at 190°C and 2.16 kilograms between 0.4 g / 10 min and 3.0 g / 10 min. In some embodiments, the recycled polyethylene has a melt flow index, h, as measured according to ASTM D-1238 at 190°C and 2.16 kilograms between 1 g / 10 min and 2.5 g / 10 min In some embodiments, the hofthe recycled polyethylene as measured under ASTM D-1238 at 190°C and 2.16 kilograms is 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, 2.0 g / 10 min, 2.1 g / 10 min, 2.2 g / 10 min, 2.3 g / 10 min, 2.4 g / 10 min, or 2.5 g / 10 min.

[0098] In some embodiments, the recycled polyethylene includes up to 5 wt.% polypropylene, based on the total weight of the recycled polyethylene. In some embodiments, the recycled polyethylene contains less than 10 wt.% LDPE. In some embodiments, the recycled polyethylene contains LDPE in amounts of up to 10 wt.%. In some embodiments, the recycled polyethylene contains 1 wt.% LDPE, 2 wt.% LDPE, 3 wt.% LDPE, 4 wt.% LDPE, 5 wt.% LDPE, 6 wt.% LDPE, 7 wt.% LDPE, 8 wt.% LDPE, 9 wt.% LDPE, or 10 wt.% LDPE.

[0099] In some embodiments, the amount of recycled polyethylene in the blend compositions disclosed herein is present in the range from about 10% to about 60% by weight of the blend composition. In some embodiments, the amount of recycled polyethylene present in the blend composition is in the range from 15% to 50% by weight of the blend composition. In some embodiments, the blend composition includes recycled polyethylene in an amount in the range from 20% to 50% by weight. In some embodiments, the blend composition may include recycled polyethylene in an amount in the range from 30% to 50% by weight.

[0100] The recycled polyethylene may be provided in any suitable form, such as in the form of chips, pellets, powders, slurries, solutions, and the like.

[0101] E, Films from the Blend Composition

[0102] The blend compositions disclosed herein are suitable for preparing films. In some embodiments, the film is a blown film. In some embodiments, the film is a cast film. In some embodiments, the blend compositions may be prepared by dry-blending the recycled polyethylene and the virgin polyethylene at a film line before extrusion.The blown film process is a well-known process for the preparation of plastic film. The process employs an extruder which heats, melts and conveys the molten plastic (e.g., the blend composition) and forces it through an annular die. Typical extrusion temperatures are from about 330 to about 500°F, or for example, about 350 to about 460°F.

[0103] The polyethylene film is drawn from the die and formed into a tube shape and eventually passed through a pair of draw or nip rollers. Internal compressed air is then introduced from a mandrel causing the tube to increase in diameter forming a “bubble” of the desired size. Thus, the blown film is stretched in two directions, namely in the axial direction (by the use of forced air which “blows out” the diameter of the bubble) and in the lengthwise direction of the bubble (by the action of a winding element which pulls the bubble through the machinery). External air is also introduced around the bubble circumference to cool the melt as it exits the die. Film width is varied by introducing more or less internal air into the bubble thus increasing or decreasing the bubble size. Film thickness is controlled primarily by increasing or decreasing the speed of the draw roll or nip roll to control the draw-down rate.

[0104] The bubble is then collapsed into two doubled layers of film immediately after passing through the draw or nip rolls. The cooled film can then be processed further by cutting or sealing to produce a variety of consumer products. While not wishing to be bound by theory, it is generally believed by those skilled in the art of manufacturing blown films that the physical properties of the finished films are influenced by both the molecular structure of a polyethylene copolymer and by the processing conditions. For example, the processing conditions are thought to influence the degree of molecular orientation (in both the machine direction and the axial or cross direction).

[0105] A balance of “machine direction” (“MD”) and “transverse direction” (“TD”, which is perpendicular to MD) molecular orientation is generally considered desirable for the films associated with this disclosure (for example, Dart Impact strength, Machine Direction and Transverse Direction tear properties). Thus, it is recognized that these stretching forces on the “bubble” can affect the physical properties of the finished film. In particular, it is known that the “blow up ratio” (i.e. the ratio of the diameter of the blown bubble to the diameter of the annular die) can have a significant effect upon the dart impact strength and tear strength of the finished film.

[0106] The above description relates to the preparation of monolayer films. Multilayer films may be prepared by 1) a “co-extrusion” process that allows more than one stream of moltenpolymer to be introduced to an annular die resulting in a multi-layered film membrane; or 2) a lamination process in which film layers are laminated together.

[0107] In some embodiments, the films disclosed herein are prepared using a blown film process. An alternative process is the so-called cast film process, wherein a polyethylene copolymer (or blend composition) is melted in an extruder, then forced through a linear slot die, thereby “casting” a thin flat film. The extrusion temperature for cast film is typically somewhat hotter than that used in the blown film process (with typically operating temperatures of from about 450°F to about 550°F). In general, cast film is cooled (quenched) more rapidly than blown film.

[0108] In some embodiments, the blown film prepared from the blend compositions disclosed herein have a dart impact value of greater than 134 g / mil as measured according to ASTM D1709 using a 2.4 mil film.

[0109] In some embodiments, the blown film prepared from the blend compositions disclosed herein has a machine direction tear value of at least 200 g / mil as measured according to ASTM D1922 using a 2.4 mil film.

[0110] In an embodiment, the films disclosed herein are prepared using a cast film process. It should be understood 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.

[0111] EXAMPLES

[0112] Methods

[0113] Density

[0114] Virgin polyethylene densities were determined using ASTM D792-13 (November 1, 2013).

[0115] Melt Index

[0116] Virgin polyethylene melt index values were determined using ASTM D1238 (August 1, 2013). Melt indexes, h, k, and hi were measured at 190°C, using weights of 2.16 kg, 6.48 kg, and 21.6 kg, respectively.GPC

[0117] Virgin polyethylene molecular weights Mw, Mn, and Mz(g / mol), as well as polydispersity index (PDI; Mw / Mn), were determined by size exclusion chromatography (SEC) analysis with either Gel Permeation Chromatography with differential refractive index (GPC-DRI) detection or with polymer char GPC-IR5 as indicated, each according to ASTM D6474.

[0118] GPC-DRI

[0119] Polymer sample solutions ( 1 to 2 mg / mL) were prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) and rotating on a wheel for 4 hours at 150°C in an oven. Antioxidant 2,6-di-tert-butyl-4-methylphenol (BHT) was added to the mixture to stabilize the polymer against oxidative degradation. The BHT concentration was 250 ppm. Sample solutions were chromatographed at 140°C on a PL 220 high-temperature chromatography unit equipped with four Shodex columns (HT803, HT804, HT805, and HT806) using 1,2,4-trichlorobenzene (TCB) as the mobile phase with a flow rate of 1.0 mL / minute, with a differential refractive index (DRI) as the concentration detector. BHT was added to the mobile phase at a concentration of 250 ppm to protect SEC columns from oxidative degradation. The sample injection volume was 200 pL. The SEC raw data were processed with the Cirrus GPC software, to produce molar mass averages (Mn, Mw, Mz) and molar mass distribution (e.g., Polydispersity, Mw / Mn). In the polyethylene art, a commonly used term that is equivalent to SEC is GPC, i.e., Gel Permeation Chromatography. The SEC columns were calibrated with narrow distribution polystyrene standards. The polystyrene molecular weights were converted to polyethylene molecular weights using the Mark-Houwink equation, as described in the ASTM standard test method D6474.

[0120] GPC-IR5

[0121] A polymer sample (about 15 mg) was weighed into the sample vial and loaded onto the auto-sampler of the Polymer Char SEC-IR5 unit. The vial was filled with 8 mb of 1,2,4-trichlorobenzene (TCB), heated to the desired dissolution temperature (e.g. 160°C) with a shaking for 120 minutes. Antioxidant 2, 6-di -tert-butyl -4-methylphenol (BHT) was added to TCB in order to stabilize the polymer against oxidative degradation. The BHT concentration was 250 ppm. Sample solutions were chromatographed at 140°C on a Polymer Char GPC-IR5 chromatography unit equipped with four Shodex SEC columns (HT803, HT804, HT805 and HT806) using TCB as the mobile phase with a flow rate of 1.0 mL / minute, with an Infrared IR5 as the concentration detector. BHT was added to the mobile phase at a concentration of 250 ppm to protect SEC columns from oxidative degradation. The sampleinjection volume was 200 pL. The GPC columns were calibrated with narrow distribution polystyrene standards. The polystyrene molecular weights were converted to polyethylene molecular weights using the Mark-Houwink equation, as described in the ASTM standard test method D6474.

[0122] Comonomer Content

[0123] The quantity of comonomer in the virgin ethylene alpha-olefin copolymer product (i.e., the virgin polyethylene) was determined as follows and reported as the Short Chain Branching (SCB) content having dimensions of CH3# / 1000C (number of methyl branches per 1000 carbon atoms).

[0124] A polymer sample (20 to 25 mg) was weighed into the sample vial and loaded onto the auto-sampler of the Polymer Char GPC-IR4 unit. The vial was fdled with 6 mb 1,2,4-trichlorobenzene (TCB), heated to the desired dissolution temperature (e.g. 160°C) with shaking for 160 minutes. Sample solutions were chromatographed at 140°C on a Polymer Char GPC-IR4 chromatography unit equipped with four Shodex columns (HT803, HT804, HT805 and HT806) using TCB as the mobile phase with a flow rate of 1.0 mL / minute, with a Bruker TENSOR 27 FTIR spectrophotometer and a heated FTIR flow through cell coupled with the chromatography unit through a heated transfer line as the detection system. Antioxidant 2,6-di-tert-butyl-4-methylphenol BHT was added to the mobile phase at a concentration of 250 ppm to protect SEC columns from oxidative degradation. The sample injection volume was 300 pL. The raw FTIR spectra were processed with OPUS FTIR software and the polymer concentration and methyl content were calculated in real time with the Chemometric Software (PLS technique) associated with the OPUS. Then the polymer concentration and methyl content were acquired with Polymer Char GPC-IR4 instrument control software. The SEC columns were calibrated with narrow distribution polystyrene standards. The polystyrene molecular weights were converted to polyethylene molecular weights using the Mark-Houwink equation, as described in the ASTM standard test method D6474. The comonomer content was calculated based on the polymer concentration and methyl content predicted by the PLS technique as described in the published work by Paul J. DesLauriers [Polymer 43 (2002) 159-170], This provides the methyl (CH3) per 1000 carbons (1000C) as a function of molecular weight. A chain-end correction can be applied to methyl (CH3) per 1000 carbons (1000C) by assuming each chain to be linear and terminated by a methyl group at one or both ends.

[0125] Alternatively, for instances using GPC-IR5, the comonomer content was determined by the ratio of the IR5 detector intensity corresponding to the CH3 and CH2 channelscalibrated with a series of PE standards whose nominal value are predetermined by NMR or FTIR. This provided the methyl (CH3) per 1000 carbons (1000C) as a function of molecular weight. A chain-end correction can be applied to methyl (CH3) per 1000 carbons (1000C) by assuming each chain to be linear and terminated by a methyl group at one or both ends. Deconvolution

[0126] Polyethylene Composition Deconvolution

[0127] Mathematical deconvolutions were performed to determine the relative amounts of each of the first and second ethylene copolymer components present in the virgin polyethylene composition, as well as the molecular weights (Mw, Mn, Mz), and comonomer content (the SCB frequency per 1000 polymer backbone carbon atoms) of each of the first and second ethylene copolymer components made in the first and second reactors (R1 and R2). Examples of the virgin polyethylene (ethylene alpha-olefin copolymer compositions) were produced in a dual reactor solution polymerization process in which the contents of the first reactor flow into the second reactor. This in-series “dual reactor” process produces an “in-situ” polyethylene blend (i.e. the polyethylene composition). Note that when an in-series reactor configuration is used, unreacted ethylene monomer, and unreacted alpha-olefin comonomer present in the first reactor will flow into the downstream second reactor for further polymerization.

[0128] The melt index, h, and density of the first and second ethylene copolymer components were estimated by GPC and GPC-FTIR deconvolutions as discussed further below.

[0129] High temperature GPC equipped with an online FTIR detector (GPC-FTIR) was used to measure the comonomer content as a function of molecular weight. In order to deconvolute the virgin polyethylene (an ethylene copolymer product from the use of a single site catalyst (SSC) in R1 and a Ziegler-Natta catalyst in R2), into components the mathematical deconvolution model. See, for example, Alfred Rudin, in The Elements of Polymer Science and Engineering, 2nd edition, Academic Press, 1999 and U.S. Pat. No. 8,022,143. Modifications to find the properties of the Ziegler-Natta component (as made in R2) are described further below.

[0130] Here, in the mathematical deconvolution of the GPC and GPC-FTIR data, the molecular weight distribution of the first ethylene copolymer component (the SSC component made in Rl) which was made using a single site catalyst was modeled using at least one Schultz Flory distribution (where the Mw / Mnwas assumed to be 2; the Mnwas Mw / 2 and the Mzwas I.5xMw) as described in U.S. Pat. No. 8,022,143, while the molecular weight distribution of the second polyethylene which was made using a multi-site Ziegler-Nattacatalyst in R2, is considered to have at least two catalyst sites for the sake of the model, and hence was modeled using at least two Shultz -Flory distributions (each of which had a Mw / Mnof 2; and where Mnwas Mw / 2 and Mzwas 1.5 / Mwfor each site).

[0131] To improve the deconvolution accuracy and consistency, as a constraint, the melt index, h, of the modeled composition (i.e. the virgin polyethylene) was set and the following relationship was satisfied during the deconvolution:

[0132] log10(Melt Index I2) = 7.900 - 3.909 [log10] - 0.2799 (Equation 1),

[0133]

[0134] where the experimentally measured overall melt index (i.e. of the virgin polyethylene), h, was used on the left side of the equation.

[0135] At least three sites (at least one for the SSC, i=l (or 2, etc.); and at least two for the ZN catalyst, i=2 to 5) were used to deconvolute the virgin ethylene alpha-olefin copolymer. The w(i) and Mn(i), i=l to at least 3 (e.g., 1 to 3, 1 to 4, 1 to 5), were obtained while Mw(i) and Mz(i) of each site were calculated using the above relationships using Mn(i) for each site. Note that the sum of w(i), i=l to at least 3, is equal to unity. During the deconvolution, the overall Mn, Mwand Mz were calculated with the following relationships: Mn = l / (wi / (Mn)i), Mw = (wi x (Mw)i), Mz = (wi x (Mz)i2 / (wi x (Mzi), where i represents the i-th component and wi represents the relative weight of the i-th component in the composition from the above deconvolution.

[0136] The GPC-FTIR chromatograph fraction profile was subsequently deconvoluted using the w(i) results to obtain the short chain branching in short chain branches per 1000 carbons (the SCB / 1000C) for each site: SCB(i), i=l to 5.

[0137] To obtain the overall characteristics of the second polyethylene made with the Ziegler-Natta catalyst in R2, the weight fraction, wi of each of the modeled Ziegler-Natta sites from the above overall deconvolution was normalized first (i.e. the weight fraction wiof each ZN site was divided by the total weight of the four sites for the ZN components). The overall Mn, Mw, Mz and SCB / 1000C of the second polyethylene made with the ZN catalyst in R2 were then calculated using the above relationships, with the above data of Mn(i), Mw(i), Mz(i), SCB(i) and the newly normalized w(i) for each ZN site.

[0138] In order to calculate the melt index, h of each of the first and the second ethylene copolymer components of the virgin polyethylene, Equation 1 above was used.

[0139] The density of the ethylene copolymer component made using a single site catalyst was calculated using the following density model:p1= 0.978863 - 5.94808 X 10“3(j^)°65- 3.83133 X 10“4[log10(Mn)]3- 5.77986 X + 5.57395 X 10“3(Equation 2)

[0140]

[0141]

[0142] where the Mn, Mwand Mzwere the deconvoluted values of the first polyethylene as obtained from the results of the above GPC deconvolution and the SCB / 1000C was obtained from the GPC-FTIR deconvolution described herein.

[0143] The density of the ethylene copolymer component, made using a Ziegler-Natta catalyst, was calculated using the following equation:

[0144] j°2=(J°— WIJ°I) / W2 (Equation 3) where p is the density of the virgin polyethylene composition determined experimentally.

[0145] Deconvolution results are shown in Table 7.

[0146] Film Dart Impact

[0147] Film dart impact strength was determined using ASTM DI 709-09 Method A (May 1, 2009). In this disclosure the dart impact test employed a 1.5 inch (38 mm) diameter hemispherical headed dart.

[0148] Film Puncture

[0149] Film “puncture”, the energy (J / mm) required to break the film was determined using ASTM D5748-95 (originally adopted in 1995, reapproved in 2012).

[0150] The virgin polyethylene products used in the following examples are listed in Table 1.

[0151] Table 1: Virgin Polyethylene Used in Blends

[0152]

[0153] For Examples 3 to 6 and Comparative 2, the following single site catalyst components were used to prepare the first ethylene / a-olefm copolymer in the first reactor (Rl): component A, diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafhium dimethide [(2,7-tBu2Flu)Ph2C(Cp)HfMe2]; component M, methylaluminoxane (MMAO-07); component B, trityl tetrakis(pentafluoro-phenyl)borate (trityl borate); and component P, 2,6-di-tert-butyl-4-ethylphenol (BHEB). Methylaluminoxane (MMAO-07); and 2,6-di-tert-butyl-4-ethylphenol were premixed in-line and then combined with diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafhium dimethide and trityl tetrakis(pentafluoro-phenyl)borate just before entering the polymerization reactor (Rl). The following catalyst component solvents were used: methylpentane for components M and P; and xylene for component A and B. The efficiency of the single site catalyst formulation was optimized by adjusting the quantity of component A added to Rl [Rl catalyst (ppm) as recited in Table 2], the mole ratios of the catalyst components — i.e., [M] / [A], [P] / [M] and [B] / [A] — and the Rl catalyst inlet temperature as tabulated in Table 2.

[0154] For Example 3 and Comparative 2, in-line Ziegler-Natta catalyst formulation catalyst was used to prepare the second ethylene / a-olefm copolymer in the second reactor (R2). The in-line Ziegler-Natta catalyst formulation had the following components: butyl ethyl magnesium [component v]; tertiary butyl chloride [component vi]; titanium tetrachloride [component vii]; diethyl aluminum ethoxide [component viii]; and triethyl aluminum [component ix] . Methylpentane was used as the catalyst component solvent and the in-line Ziegler-Natta catalyst formulation was prepared using the following steps and then injected into the second reactor (R2). In step one, a solution of triethylaluminum and butyl ethyl magnesium (Mg:Al = 20, mol:mol) was combined with a solution of tertiary butyl chloride and allowed to react for about 30 seconds to produce a MgCh support. In step two, a solution of titanium tetrachloride was added to the mixture formed in step one and allowed to react for about 14 seconds prior to injection into second reactor (R2). The in-line Ziegler-Natta catalyst was activated in the reactor by injecting a solution of diethyl aluminum ethoxide into R2. The efficiency of the in-line Ziegler-Natta catalyst formulation was optimized by adjusting the quantity of titanium tetrachloride added to the reactor — recited as R2 catalyst (ppm) in Table 2, the mole ratios of the catalyst components — i.e., [vi] / [v], [viii] / [vii] and [ix] / [vii] — and R2 catalyst inlet temperature as tabulated in Table 2.

[0155] In operating the continuous solution polymerization process shown in Table 2, the total amount of ethylene supplied to the process were portioned or split between the reactors Rl and R2. In Table 2, this operational variable was called the ethylene split (ES), i.e., ESRIand ESR2 referred to the weight percent of ethylene injected in R1 and R2, respectively; with the proviso that ESRI + ESR2 = 100%. For Comparative 2 in Table 2, ethylene was added to the third reactor and ESRI + ESR2 + ESR3 = 100%.

[0156] Octene- 1 was also added to the continuous solution polymerization process and was proportioned or split between R1 and R2. In Table 2, this operational variable was called the octene-1 split (OS), i.e., OSR1 and OSR2 referred to the weight percent of octene-1 comonomer that was injected in R1 and R2, respectively; with the proviso that OSR1 + OSR2 = 100%.

[0157] For Examples 3 to 6, no fresh ethylene, octene-1, hydrogen and catalyst were pumped into the third reactor.

[0158] In operating the continuous solution polymerization process shown in Table 2, the total amount of ethylene converted in each reactor is monitored. The term QR1 referred to the percent of the ethylene added to R1 that was converted into a first ethylene a-olefin copolymer by the catalyst formulation. Similarly, QR2 represented the percent of the ethylene added to R2 that was converted into the second ethylene a-olefin copolymer.

[0159] In Table 2, the term QT represented the total or overall ethylene conversion across the entire continuous solution polymerization plant, i.e., QT = 100 x [weight of ethylene in the ethylene a-olefin copolymer composition] / ([weight of ethylene in the ethylene a / olefin copolymer composition] + [weight of unreacted ethylene]).

[0160] Polymerization in the continuous solution polymerization process was terminated by adding a catalyst deactivator to the third exit stream exiting the tubular reactor (R3). The catalyst deactivator used was octanoic acid (caprylic acid), commercially available from P&G Chemicals, Cincinnati, OH, U.S.A. The catalyst deactivator was added such that the moles of fatty acid added were 50% of the total molar amount of catalytic metal and aluminum added to the polymerization process; to be clear, the moles of octanoic acid added = 0.5 x (moles hafnium + moles aluminum).

[0161] A two-stage devolatilization process was employed to recover the ethylene a-olefin copolymer composition from the process solvent, i.e., two vapor / liquid separators were used, and the second bottom stream (from the second V / L separator) was passed through a gear pump / pelletizer combination. The gear pump was a VACOREX® 45 / 45 pump with 191 liter per hour capacity which was steam jacketed with 270# steam. The ethylene a-olefin copolymer composition leaving the gear pump was then passed through a 4” diameter static mixer before entering the pelletizer where the ethylene / a-olefin copolymer composition was forced through the holes in the die plate top down. There were 32 holes on the die with a holediameter of 0.125”. The aspect ratio (i.e., length-to-diameter ratio) for each hole was 6.3:1 and the die had a thickness of 1.63” and a diameter of 12”. There were 6 cutter knives — 8.6878” OD sweep and 6.2418 ID sweep — located on the side of the die that faced the cooling water system. There were internal heating channels within the die plate and die body and plate were heated with 600# or 270# steam. Cooling water system had a temperature range of from 10 to 80°C and a flow of 7500-9500 kg / h. DHT®-4V (hydrotalcite), supplied by Kyowa Chemical Industry Co. LTD, Tokyo, Japan may be used as a passivator, or acid scavenger, in the continuous solution process. A slurry of DHT-4V in process solvent may be added prior to the first V / L separator. Prior to pelletization, the ethylene / a-olefin copolymer composition was stabilized by adding 500 ppm of IRGANOX® 1076 (a primary antioxidant) and 500 ppm of IRGAFOS® 168 (a secondary antioxidant), based on weight of the ethylene a-olefin copolymer composition. Antioxidants were dissolved in process solvent and added between the first and second V / L separators.

[0162] Table 2 provides the conditions for preparing the virgin ethylene a-olefin copolymer composition (i.e., the virgin polyethylene used in the blends herein) of Example 3, Example 4, Example 5, Example 6, and Comparative 2.

[0163] Table 2

[0164]

[0165]

[0166] *(2,7-tBu2Flu)Ph2C(Cp)Hf e2; and1' concentration of component vii.

[0167] Tables 3-7 provide select properties of the virgin polyethylene used in the blend compositions of the present disclosure, and Tables 8-12 provide select properties of the virgin polyethylene used in comparative blend examples.Table 3: Select Properties of the Virgin Polyethylene Resins used in Blend Compositions of the Present Disclosure

[0168]

[0169] Table 4: Molecular Weight Distribution from GPC of Virgin Polyethylene Resins used in Blend Compositions of the Present Disclosure

[0170]

[0171] “Determined using Polymer Char GPC-IR5

[0172] Table 5: Branch Frequency (BrF) by GPC-FTIR of Virgin Polyethylene Resins used in Blend Compositions of the Present Disclosure

[0173]

[0174] Table 6: Select FTIR Data of Virgin Polyethylene Resins used in Blend Compositions of the Present Disclosure

[0175]

[0176] Table 7: Resin Deconvolution Results of Virgin Polyethylene Resins used in Blend Compositions of the Present Disclosure

[0177]

[0178] Table 8: Select Properties of the Virgin Polyethylene Resins

[0179] used in Comparative Blend Compositions

[0180]

[0181] Table 9: Molecular Weight Distribution from GPC of Virgin Polyethylene Resins used in Comparative Blends

[0182]

[0183] “Determined using Polymer Char GPC-IR5

[0184] Table 10: Branch Frequency (BrF) by GPC-FTIR of Virgin Polyethylene Resins used in Comparative Blends

[0185]

[0186] Table 11: Select FTTR Data of Virgin Polyethylene Resins used in Comparative Blends

[0187]

[0188] Table 12: Resin Deconvolution Results for Virgin Polyethylene Resins used in Comparative Blends

[0189]

[0190] For blends using virgin polyethylene Examples 1, 2, and 3, as well as the Comparative virgin polyethylene, the recycled polyethylene used was EX-PCR-NC4, formerly sold by NOVA Chemicals (Canada). EX-PCR-NC4 is a recycled polyethylene from PE Clear Film Grade B bale (LLDPE / LDPE recycled resin) that has a melt index (ASTM D 1238; 190°C and 2.16 kg) of 1.0 g / 10 minutes and a density of 0.925 g / cm3, as measured by ASTM D 792. For blends using virgin polyethylene Examples 4 to 7, the recycled polyethylene used wasEX-PCR-IN4 sold by NOVA Chemicals (Canada). EX-PCR-IN4 is an experimental postconsumer mechanically recycled rLLDPE / LDPE that has a melt index (ASTM D 1238; 190°C and 2.16 kg) of 1.0 g / 10 minutes and a density of 0.924 g / cm3, as measured by ASTM D 792.

[0191] Blends were prepared by dry-blending the recycled polyethylene and virgin polyethylene at the indicated weight percentage at the fdm line before extrusion. Blown fdms were prepared as follows: Monolayer blown fdms were produced on a monolayer blown fdm line (Gloucester Blown Film Line). This line was equipped with a Gloucester extruder, 2.5-inch (6.45 cm) barrel diameter, 24 / 1 L / D (barrel Length / barrel Diameter) equipped with: a barrier screw; a low pressure 4 inch (10.16 cm) diameter die with a 35 mil (0.089 cm) die gap; and a Western Polymer Air ring. The extruder was equipped with the following screen pack: 20 / 40 / 60 / 80 / 20 mesh. Blown fdms, of about 1.0 to 2.5 mil (25.4 pm) thick at 2.5:1 Blow Up Ratio (BUR), were produced at a constant output rate of 100 Ib / hr (45.4 kg / hr) by adjusting extruder screw speed; and the frost line height was maintained at 15-18 inch (38.1-45.72 cm) by adjusting the cooling air.

[0192] The fdm physical properties were evaluated on the resultant fdms. Blown fdm performance is shown in Tables 13 to 15 for different levels of recycled polyethylene incorporation for examples using EX-PCR-NC4. Tables 16 to 18 show blown fdm performance for different levels of recycled polyethylene incorporation for examples using EX-PCR-IN4.

[0193] Table 13: Monolayer Blown Film Performance of Disclosed and Comparative Resins with Recycled Polyethylene, EX-PCR-NC4, at 15 wt.%

[0194]

[0195] Table 14: Monolayer Blown Film Performance of Disclosed and Comparative Resins with Recycled Polyethylene, EX-PCR-NC4 (NC4), at 25-35 wt.%

[0196]

[0197] Table 15: Monolayer Blown Film Performance of Disclosed and Comparative Resins with Recycled Polyethylene, EX-PCR-NC4, at 50 wt.%

[0198]

[0199] Table 16: Monolayer Blown Film Performance of Disclosed Resins with Recycled Polyethylene, EX-PCR-IN4, at 20 wt.%

[0200]

[0201] Table 17: Monolayer Blown Film Performance of Disclosed Resins with Recycled Polyethylene, EX-PCR-IN4, at 30 wt.%

[0202]

[0203] Table 18: Monolayer Blown Film Performance of Disclosed Resins with Recycled Polyethylene, EX-PCR-IN4, at 50 wt.%

[0204]

[0205] As can been seen, the disclosed recycled polyethylene and ethylene alpha-olefin copolymer (virgin polyethylene) blends were found to demonstrate superior balance of film physical properties, including dart, MD tear, puncture, and MD elongation at break.

[0206] 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.

[0207] Non-limiting embodiments of the present disclosure include the following:

[0208] Embodiment A. A blend composition comprising: 10 wt.% to 60 wt.% of recycled polyethylene; and 40 wt.% to 90 wt.% of a virgin polyethylene, the virgin polyethylene having (a) a density less than 0.915 g / cm3as measured according to ASTM D-792, (b) amelt index, h, less than 4 g / 10 min as measured according to ASTM D-1238 at 190°C using a 2.16 kg weight, (c) a Z-average molecular weight, Mz, between 120,000 g / mol and 300,000 g / mol as measured according to ASTM D6474-99, (d) a short chain branch frequency at Mzgreater than 19 SCB / 1000C, and (e) a reverse comonomer distribution.

[0209] Embodiment B. The blend composition of Embodiment A, wherein the virgin polyethylene comprises a first ethylene copolymer component having a first component density, and a first component weight average molecular weight, Mwi; and a second ethylene copolymer component having a second component density, and a second component weight average molecular weight, Mw2, that is less than the first component weight average molecular weight; wherein the difference between the second component density and the first component density is greater than 0.023 g / cm3.

[0210] Embodiment C. The blend composition of Embodiment B, wherein the first ethylene copolymer component has a first component short chain branch frequency of between 20 SCB / 1000C and 30 SCB / 1000C.Embodiment D. The blend composition of Embodiment B, wherein the first ethylene copolymer component has a first component short chain branch frequency of between 31 SCB / 1000C and 38 SCB / 1000C.

[0211] Embodiment E. The blend composition of Embodiment A, B, C, or D, wherein the Mz is between 120,000 g / mol and 250,000 g / mol.

[0212] Embodiment F. The blend composition of Embodiment A, B, C, D, or E, wherein the density of the virgin polyethylene is between 0.905 g / cm3and 0.914 g / cm3.

[0213] Embodiment G. The blend composition of Embodiment A, B, C, D, or E, wherein the density of the virgin polyethylene is between 0.905 g / cm3and 0.908 g / cm3.

[0214] Embodiment H. The blend composition of Embodiment A, B, C, D, E, F, or G, wherein the virgin polyethylene has a number average molecular weight (Mn) between 20,000 g / mol and 40,000 g / mol as determined according to ASTM D6474-99.

[0215] Embodiment L The blend composition of Embodiment A, B, C, D, E, F, G, or H, wherein the virgin polyethylene has a polydispersity index, Mw / Mn, between 2.1 and 4.0.

[0216] Embodiment J. The blend composition of Embodiment B, C, D, E, F, G, H, or I, wherein the first ethylene copolymer component is present in the virgin polyethylene in an amount of 30 wt.% to 45 wt.%.

[0217] Embodiment K. The blend composition of Embodiment B, C, D, E, F, G, H, I, or J, wherein the first component weight average molecular weight is between 110,000 g / mol and 160,000 g / mol.

[0218] Embodiment L. The blend composition of Embodiment B, C, D, E, F, G, or H, wherein the first ethylene copolymer component is present in the virgin polyethylene in an amount of 45 wt.% to 52 wt.% and the virgin polyethylene has a polydispersity index, Mw / Mn, between 4.1 and 4.5.

[0219] Embodiment M. The blend composition of Embodiment A, B, C, D, E, F, G, H, I, J, K, or L, wherein the virgin polyethylene is an ethylene octene copolymer.

[0220] Embodiment N. The blend composition of Embodiment A, B, C, D, E, F, G, H, I, J, K, L, or M, wherein the recycled polyethylene has a density of 0.910 g / cm3to 0.940 g / cm3, as measured according to ASTM D-792.

[0221] Embodiment O. The blend composition of Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, or N, wherein the recycled polyethylene has a melt index, h, as measured according to ASTM D-1238 at 190°C and using a 2.16 kg weight, between 0.4 g / 10 min and 2.0 g / 10 min.Embodiment P. The blend composition of Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, or O, wherein the recycled polyethylene comprises up to 5 wt.% polypropylene, based on the total weight of the recycled polyethylene.

[0222] Embodiment Q. The blend composition of Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, wherein the recycled polyethylene is present in an amount of 20 wt.% and the virgin polyethylene is present in an amount of 80 wt.%.

[0223] Embodiment R. The blend composition of Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, wherein the recycled polyethylene is present in an amount of 30 wt.% and the virgin polyethylene is present in an amount of 70 wt.%.

[0224] Embodiment S. The blend composition of Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, wherein the recycled polyethylene is present in an amount of 40 wt.% and the virgin polyethylene is present in an amount of 60 wt.%.

[0225] Embodiment T. The blend composition of Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, or P, wherein the recycled polyethylene and the virgin polyethylene are present in equal weight amounts.

[0226] Embodiment U. The blend composition of Embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, or T, prepared by dry blending the virgin polyethylene and the recycled polyethylene.

[0227] Embodiment V. The blend 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 the recycled polyethylene contains LDPE in an amount of up to 10 wt.%.

[0228] Embodiment W. A blown fdm prepared from the blend 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.

[0229] Embodiment X. The blown film of Embodiment U, having a dart impact value of greater than 134 g / mil as measured according to ASTM D1709 using a 2.4 mil film.

[0230] Embodiment Y. The blown film of Embodiment W or X, having a machine direction tear value of at least 200 g / mil as measured according to ASTM DI 922 using a 2.4 mil film.

[0231] Embodiment Z. A cast film prepared form the blend 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.

[0232] Other implementations are also within the scope of the following claims.

[0233] INDUSTRIAL APPLICABILITY

[0234] Blend compositions containing recycled polyethylene and that are suitable for film applications.

Claims

CLAIMS1. A blend composition comprising:10 wt.% to 60 wt.% of recycled polyethylene; and40 wt.% to 90 wt.% of a virgin polyethylene, the virgin polyethylene having(a) a density less than 0.915 g / cm3as measured according to ASTM D-792, (b) a melt index, h, less than 4 g / 10 min as measured according to ASTM D- 1238 at 190°C using a 2.16 kg weight,(c) a Z-average molecular weight, Mz, between 120,000 g / mol and 300,000 g / mol as measured according to ASTM D6474-99,(d) a short chain branch frequency at Mzgreater than 19 SCB / 1000C, and (e) a reverse comonomer distribution.

2. The blend composition of claim 1, wherein the virgin polyethylene comprises a first ethylene copolymer component having a first component density, and a first component weight average molecular weight, Mwi; anda second ethylene copolymer component having a second component density, and a second component weight average molecular weight, Mwi, that is less than the first component weight average molecular weight;wherein the difference between the second component density and the first component density is greater than 0.023 g / cm3.

3. The blend composition of claim 2, wherein the first ethylene copolymer component has a first component short chain branch frequency of between 20 SCB / 1000C and 30 SCB / 1000C.

4. The blend composition of claim 2 wherein the first ethylene copolymer component has a first component short chain branch frequency of between 31 SCB / 1000C and 38 SCB / 1000C.

5. The blend composition of any one of claims 1 to 4, wherein the Mzof the virgin polyethylene is between 120,000 g / mol and 250,000 g / mol.

6. The blend composition of any one of claims 1 to 5, wherein the density of the virgin polyethylene is between 0.905 g / cm3and 0.914 g / cm3.

7. The blend composition of any one of claims 1 to 5, wherein the density of the virgin polyethylene is between 0.905 g / cm3and 0.908 g / cm3.

8. The blend composition of any one of claims 1 to 7, wherein the virgin polyethylene has a number average molecular weight (Mn) between 20,000 and 40,000 g / mol as determined according to ASTM D6474-99.

9. The blend composition of any one of claims 1 to 8, wherein the virgin polyethylene has a poly dispersity index, Mw / Mn, between 2.1 and 4.0.

10. The blend composition of any one of claims 2 to 9, wherein the first ethylene copolymer component is present in the virgin polyethylene in an amount of 30 wt.% to 45 wt.%.

11. The blend composition of any one of claims 2 to 10, wherein the first component weight average molecular weight is between 110,000 g / mol and 160,000 g / mol.

12. The blend composition of any one of claims 2 to 8, wherein the first ethylene copolymer component is present in the virgin polyethylene in an amount of 46 wt.% to 52 wt.% and the virgin polyethylene has a polydispersity index, Mw / Mn, between 4.1 and 4.5.

13. The blend composition of any one of claims 1 to 12, wherein the virgin polyethylene is an ethylene octene copolymer.

14. The blend composition of any one of claims 1 to 13, wherein the recycled polyethylene has a density of 0.910 g / cm3to 0.940 g / cm3, as measured according to ASTM D-792.

15. The blend composition of any one of claims 1 to 14, wherein the recycled polyethylene has a melt index, h, as measured according to ASTM D-1238 at 190°C and using a 2.16 kg weight, between 0.4 g / 10 min and 2.0 g / 10 min.

16. The blend composition of any one of claims 1 to 15, wherein the recycled polyethylene comprises up to 5 wt. % polypropylene, based on the total weight of the recycled polyethylene.

17. The blend composition of any one of claims 1 to 16, wherein the recycled polyethylene is present in an amount of 20 wt.% and the virgin polyethylene is present in an amount of 80 wt.%.

18. The blend composition of any one of claims 1 to 16, wherein the recycled polyethylene is present in an amount of 30 wt.% and the virgin polyethylene is present in an amount of 70 wt.%.

19. The blend composition of any one of claims 1 to 16, wherein the recycled polyethylene is present in an amount of 40 wt.% and the virgin polyethylene is present in an amount of 60 wt.%.

20. The blend composition of any one of claims 1 to 16, wherein the recycled polyethylene and the virgin polyethylene are present in equal weight amounts.

21. The blend composition of any one of claims 1 to 20, prepared by dry blending the virgin polyethylene and the recycled polyethylene.

22. The blend composition of any one of claims 1 to 21, wherein the recycled polyethylene contains LDPE in an amount of up to 10 wt.%.

23. A blown fdm prepared from the blend composition of any one of claims 1 to 22.

24. The blown fdm of claim 23, having a dart impact value of greater than 134 g / mil as measured according to ASTM D1709 using a 2.4 mil fdm.

25. The blown fdm of claim 23 or 24, having a machine direction tear value of at least 200 g / mil as measured according to ASTM DI 922 using a 2.4 mil fdm.

26. A cast fdm prepared from the blend composition of any one of claims 1 to 22.

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