Polyethylene composition

Abstract

The present disclosure provides a composition. In one embodiment, there is provided a polyethylene composition comprising (A) at least 50% by weight of a high density polyethylene having (i) a density from 0.950 g / cm3 to 0.970 g / cm3, (ii) a melt index (I2) from 0.2 g / 10 minutes to 2 g / 10 minutes, and (iii) a molecular weight distribution (Mw (abs) / Mn (abs)) from greater than 4.0 to 30.0. The polyethylene composition comprises (B) a polyethylene enhancer which is an ethylene / C4-C8 alpha-olefin copolymer and has (i) a density of from 0.880 g / cm3 to 0.910 g / cm3, (ii) a melt index of from 0.2 g / 10 minutes to 2.0 g / 10 minutes, and (iii) an LCBf / 1000 C value of less than 0.015. The polyethylene composition has (1) a density of from 0.930 g / cm3 to 0.940 g / cm3, (2) a melt index (I2) of from 0.3 g / 10 minutes to 1.0 g / 10 minutes, (3) a Mw (abs) / Mn (abs) value of from 5.0 to 13.0, (4) a low M-SCBDI value of from 9.0 to 32.0, (5) a high M-SCBDI value of from-8.0 to-15.0, (6) a first polyethylene fraction on an elution curve obtained via an improved comonomer composition distribution (iCCD) analysis method (a) having at least one peak in a temperature range of from 40 DEG C to 79 DEG C, (7) a second polyethylene fraction having (a) at least one peak in the temperature range of from 80 DEG C to 120 DEG C and (b) an average Mw of from 90,000 g / mol to 250,000 g / mol on the elution curve obtained via an improved iCCD analysis method, (7) a second polyethylene fraction having (a) at least one peak in the temperature range of from 80 DEG C to 120 DEG C, and (b) an average Mw of from 90,000 g / mol to 250,000 g / mol, and (7) a second polyethylene fraction having (a) at least one peak in the temperature range of from 80 DEG C to 120 DEG C on the elution curve obtained via an improved iCCD analysis method; and (8) a ratio of the average Mw of the first polyethylene fraction to the average Mw of the second polyethylene fraction of 0.6 to 1.2. The present disclosure also provides a film made from the polyethylene composition.

Description

BACKGROUND OF THE INVENTION

[0001] Polyethylene compositions for packaging applications, films, multilayer structures, and packaging articles made therefrom are known. For packaging applications, polyethylene compositions require a combination of toughness while exhibiting good tear strength. Achieving a balance of enhanced abuse properties (e.g., impact resistance, puncture resistance, and tear resistance) without sacrificing overall material stiffness remains a common challenge in the art. As packaging design evolves towards single-material structures to support packaging sustainability efforts, there is an increasing need for materials that can achieve this better balance of packaging performance.

[0002] The art recognizes a continuing need for polyethylene compositions suitable for packaging applications that have a good balance of physical properties at a desired polymer composition density. SUMMARY OF THE INVENTION

[0003] The present disclosure provides a composition. In one embodiment, a polyethylene composition is provided that comprises (A) at least 50 wt% high density polyethylene having (i) a density of 0.950 g / cm 3 to 0.970 g / cm 3 , (ii) a melt index (I 2 ) of 0.2 g / 10 min to 2 g / 10 min, and (iii) a molecular weight distribution (M w(abs) / M n(abs) ) greater than 4.0 to 30.0. The polyethylene composition comprises (B) a polyethylene enhancer that is an ethylene / C 4 -C 8 alpha-olefin copolymer and has (i) a density of 0.880 g / cm 3 to 0.910 g / cm 3 , (ii) a melt index of 0.2 g / 10 min to 2.0 g / 10 min, and (iii) an LCBf / 1000C value of less than 0.015. The polyethylene composition has (1) a density of 0.930 g / cm 3 to 0.940 g / cm 3 , (2) a melt index (I 2), (3) an Mw(abs) / Mn(abs) value of 5.0 to 13.0, (4) a low M-SCBDI value of 9.0 to 32.0, (5) a high M-SCBDI value of -8.0 to -15.0, (6) a first polyethylene fraction that (a) has at least one peak in the temperature range of 40°C to 79°C on an elution curve obtained by an improved comonomer composition distribution (iCCD) analysis method, and (b) has an average M of 100,000 g / mol to 200,000 g / mol w , (7) a second polyethylene fraction that (a) has at least one peak in the temperature range of 80°C to 120°C on an elution curve obtained by the improved iCCD analysis method, and (b) has an average M of 90,000 g / mol to 250,000 g / mol w , and (8) a ratio of the average M of the first polyethylene fraction of 0.6 to 1.2 w to the average M of the second polyethylene fraction w .

[0004] The present disclosure also provides a film made from the polyethylene composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0005] Figure 1 A graph of the short-chain branching distribution (SCBD) on the molecular weight (Log M) of Comparative Sample 1 and values for calculating the molecular weight short-chain branching distribution index (M-SCBDI) are provided.

[0006] Figure 2 A graph of the short-chain branching distribution (SCBD) on the molecular weight (Log M) of Comparative Sample 2 and values for calculating the M-SCBDI are provided.

[0007] Figures 3 - 4 is a graph of the short-chain branching distribution (SCBD) on the molecular weight (Log M) of Example 1 of the present invention and values for calculating the M-SCBDI.

[0008] Figure 5 A graph of the short-chain branching distribution (SCBD) on the molecular weight (Log M) of Example 3 of the present invention and values for calculating the M-SCBDI are provided.

[0009] Definition

[0010] Any reference to the Periodic Table of the Elements is to the Periodic Table published by CRC Press, Inc. in 1990 - 1991. A group of elements in the table is referred to by a new notation for numbering the groups.

[0011] For the purposes of U.S. patent practice, the content of any referenced patent, patent application, or publication is incorporated by reference in its entirety (or its equivalent U.S. version is incorporated by reference), particularly with respect to the disclosure of definitions (to the extent not inconsistent with any definitions specifically provided in this disclosure).

[0012] The numerical ranges disclosed herein include all values from the lower value to the upper value, and include the lower and upper values. For ranges that contain definite values (e.g., 1 or 2, or 3 to 5, or 6, or 7), any sub-range between any two definite values is included (e.g., the above range 1 to 7 includes sub-ranges such as 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.).

[0013] Unless stated to the contrary, implied by the context, or customary in the art, all parts and percentages are by weight, and all test methods are current as of the filing date of this disclosure.

[0014] As used herein, the term "blend" or "polymer blend" refers to a mixture of two or more polymers. The blend can be miscible or can be immiscible (not phase-separating at the molecular level). The blend can be or can not be phase-separated. The blend may or may not contain one or more domain configurations, as determined by transmission electron spectroscopy, light scattering, x-ray scattering, and other methods known in the art. A blend can be achieved by physically mixing two or more polymers at the macro level (e.g., melt blending the resins or compounding) or at the micro level (e.g., forming simultaneously in the same reactor).

[0015] The term "composition" refers to a mixture of materials that comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0016] The terms "comprising," "including," "having," and their derivatives are not intended to exclude the presence of any additional components, steps, or procedures, whether or not specifically disclosed. To avoid any doubt, unless stated to the contrary, all compositions claimed by use of the term "comprising" may include any additional additives, adjuvants, or compounds, whether in polymeric form or otherwise. In contrast, the term "consisting essentially of" excludes any other components, steps, or procedures (except those that are not essential to the operability) from the scope of any subsequent statement. The term "consisting of" excludes any component, step, or procedure not specifically recited or listed. Unless otherwise stated, the term "or" refers to the listed members individually as well as in any combination.

[0017] "Ethylene-based polymers" are polymers that contain more than 50 mole % (weight %) of polymerized ethylene monomers (based on the total amount of polymerizable monomers) and optionally may contain at least one comonomer. Ethylene polymers include ethylene homopolymers and ethylene copolymers (meaning units derived from ethylene and one or more comonomers). The terms "ethylene polymer" and "polyethylene" are used interchangeably. Ethylene-based polymers can include ethylene copolymerized with α-olefins (e.g., C 3 -C 12 α-olefins or C 4 -C 8 α-olefins) and / or unsaturated esters.

[0018] As used herein, the term "ethylene monomer" or "ethylene" refers to a chemical unit having two carbon atoms with a double bond therebetween, and each carbon is bonded to two hydrogen atoms, where the chemical unit polymerizes with other such chemical units to form an ethylene-based polymer composition.

[0019] "Heteroatom" is an atom other than carbon or hydrogen. Heteroatoms can be non-carbon atoms from Groups IV, V, VI, and VII of the periodic table. Non-limiting examples of heteroatoms include: F, N, O, P, B, S, and Si.

[0020] "Hydrocarbon" is a compound containing only hydrogen atoms and carbon atoms. "Hydrocarbyl" (or "hydrocarbyl group") is a hydrocarbon having a valence (usually monovalent). Hydrocarbons can have a straight-chain structure, a cyclic structure, or a branched structure.

[0021] "Linear low density polyethylene" (or "LLDPE") is a linear ethylene / α-olefin copolymer containing a heterogeneous short chain branching distribution, the copolymer including units derived from ethylene and units derived from at least one C 3 -C 10 α-olefin comonomer or at least one C 4 -C 8 α-olefin comonomer or at least one C 6 -C 8 α-olefin comonomer. LLDPE is characterized by very little long chain branching (if any) compared to conventional LDPE. LLDPE has a density of 0.910 g / cc, or 0.915 g / cc, or 0.920 g / cc, or 0.925 g / cc to 0.930 g / cc, or 0.935 g / cc, or 0.940 g / cc. Non-limiting examples of LLDPE include TUFLIN TM linear low density polyethylene resins and DOWLEX TM polyethylene resins, each available from The Dow Chemical Company; and MARLEXTM Polyethylene (available from Chevron Phillips).

[0022] “Low density polyethylene” (or “LDPE”) consists of ethylene homopolymers or ethylene copolymers having acrylate, vinyl acetate, and / or vinyl silane in the form of comonomers, the LDPE having a density of 0.915 g / cc to 0.940 g / cc and containing long chain branching and a broad molecular weight distribution (MWD). LDPE is typically produced by high pressure free radical polymerization (tubular reactor or autoclave with free radical initiator). Non-limiting examples of LDPE include MarFlex TM (Chevron Phillips), LUPOLEN TM (LyondellBasell), and LDPE products from Borealis, Ineos, ExxonMobil, etc.

[0023] “Medium density polyethylene” (or “MDPE”) is an ethylene homopolymer or an ethylene / α-olefin copolymer including at least one C 3 -C 10 α-olefin or C 3 -C 4 α-olefin, having a density of 0.926 g / cc to 0.940 g / cc.

[0024] “Olefin” is an unsaturated aliphatic hydrocarbon having a carbon-carbon double bond.

[0025] “Olefin-based polymer” (alternatively referred to as “polyolefin”) is a polymer containing a majority weight % of polymerized olefin monomers (based on the total amount of polymerizable monomers) and optionally may contain at least one comonomer. Non-limiting examples of olefin polymers include ethylene polymers and propylene polymers.

[0026] As used herein, the term "polymer" or "polymeric material" refers to a compound prepared by polymerizing monomers, whether of the same type or different types, which in polymeric form provides multiple and / or repeating "units" or "monomer units" that make up the polymer. Thus, the general term polymer encompasses the term homopolymer, which is commonly used to refer to a polymer prepared from only one type of monomer, and the term copolymer, which is commonly used to refer to a polymer prepared from at least two types of monomers. This general term also encompasses all forms of copolymers, such as random copolymers, block copolymers, etc. The terms "ethylene / α-olefin polymer" and "propylene / α-olefin polymer" denote copolymers prepared as described above by polymerizing ethylene or propylene, respectively, and one or more additional polymerizable α-olefin monomers. It should be noted that although polymers are commonly referred to as being "made of", "based on", "containing" a specified monomer or monomer type, etc., in this context, the term "monomer" should be understood to refer to the polymerized residue of the specified monomer rather than the unpolymerized material. Generally, polymers herein are referred to as being based on "units" that are the polymerized form of the corresponding monomers.

[0027] A "propylene-based polymer" is a polymer containing more than 50 mole % of polymerized propylene monomer (based on the total amount of polymerizable monomers) and optionally may contain at least one comonomer. Propylene polymers include propylene homopolymers and propylene copolymers (meaning units derived from propylene and one or more comonomers). The terms "propylene polymer" and "polypropylene" are used interchangeably. Non-limiting examples of propylene-based polymers (polypropylene) are propylene / α-olefin copolymers having at least one C 2 or C 4 –C 10 α-olefin comonomer.

[0028] Test Method

[0029] Coefficient of Friction (COF) Condition the film sample to be tested for at least 40 hours in an environment of 23 °C (±2 °C) and 50% R.H. (±10%) according to ASTM standards. According to ASTM standards, the standard test conditions are 23 °C (±2 °C) and 50% R.H. (±10%).

[0030] The INSTRON 5564 universal testing machine was used to test the metal-to-film COF. The samples of the film samples were cut to 3 inches × 6 inches. A type B skid was used, which was 2.5 inches × 2.5 square inches and weighed 195 g. The sample was tightly wrapped around the skid with the longitudinal direction (MD) aligned parallel to the direction of movement. This was assisted by using double-sided tape pre-attached to the top surface of the skid. Unless otherwise specified, all samples were single-layer films, so either side of the film could be wrapped onto the skid. Additionally, ensure that there are no wrinkles on the surface of the film to be tested. A COF measurement fixture consisting of a rigid plate with low-friction pulleys was attached to the fixed base of the device. Then a metal plate was placed on top of the above-mentioned rigid plate and subsequently used as the plane on which the skid was driven. Then the skid with the film sample attached was placed on the metal plane and attached to a nylon towrope that passed around the pulley and was attached to the crosshead of the test frame. Then the crosshead was driven at a speed of 6 inches per minute for a distance of 3 inches. The force at the start of sample movement (the initial peak in the load-displacement data) was the static force (FS). The average force between 0.5 inches and 3 inches of movement was calculated as the dynamic force (FK). The static COF (μS) was the ratio of the static force (FS) to the normal force (= the weight of the skid, W). Similarly, the dynamic COF (μK) was the ratio of the dynamic force (FK) to the normal force. Five repetitions were performed for each sample and the average value was reported. The coefficient of friction is dimensionless. The reported COF is the dynamic COF (also interchangeably referred to as the "kinetic COF").

[0031] Density Measured according to ASTM D792 Method B. Results are reported in grams per cubic centimeter (g / cc).

[0032] Improved Comonomer Content Analysis (iCCD)

[0033] An improved method for the analysis of comonomer content (iCCD) was developed in 2015 (Cong and Parrott et al., WO2017040127A1). The iCCD test was performed using a crystallization elution fractionation instrument (CEF) (PolymerChar, Spain) equipped with an IR-5 detector (PolymerChar, Spain) and a dual-angle light scattering detector model 2040 (Precision Detectors, now Agilent Technologies). o-Dichlorobenzene (o-DCB, 99% anhydrous grade or technical grade) was used. Silica gel 40 (particle size 0.2 - 0.5 mm, catalog number 10181-3) was obtained from EMD Chemicals (which could be used previously for drying the o-DCB solvent). The CEF instrument was equipped with an autosampler with an N2 purge function. The o-DCB was bubbled with dry nitrogen (N2) for one hour before use. At 160 °C, with shaking, the sample preparation of the film or pellets was carried out with an autosampler at a target concentration of 4 mg / mL (unless otherwise specified) for 1 hour. The injection volume was 300 μL. The temperature profile of the iCCD was: crystallization from 105 °C to 30 °C at 3 °C / min, thermal equilibration at 30 °C for 2 minutes (including the elution time of the soluble fraction set to 2 minutes), and elution from 30 °C to 140 °C at 3 °C / min. The flow rate during crystallization was 0.0 mL / min. The flow rate during elution was 0.50 mL / min. Data was collected at a rate of one data point per second.

[0034] In a 15 cm (length) × 1 / 4 inch (ID) stainless steel tube, the iCCD column was packed with gold-plated nickel particles (Bright7GNM8-NiS, Nippon Chemical Industrial Co.). Column packing and conditioning were carried out according to the reference (Cong, R.; Parrott, A.; Hollis, C.; Cheatham, M. WO2017040127A1). The final pressure for the TCB slurry packing was 150 bar.

[0035] Column temperature calibration is performed by using a mixture of the reference material linear homopolymer polyethylene (with zero comonomer content, melt index (I2) of 1.0, polydispersity Mw / Mn of approximately 2.6 according to conventional gel permeation chromatography, 1.0 mg / mL) and eicosane (2 mg / mL) in ODCB. The iCCD temperature calibration consists of the following four steps: (1) Calculate the delay volume defined as the temperature offset between the measured peak elution temperature of eicosane minus 30.00 °C; (2) Subtract the temperature offset of the elution temperature from the iCCD raw temperature data. It should be noted that this temperature offset is a function of experimental conditions such as elution temperature, elution flow rate, etc.; (3) Create a linear calibration line to convert the elution temperature in the range of 30.00 °C to 140.00 °C such that the linear homopolymer polyethylene reference has a peak temperature at 101.0 °C and eicosane has a peak temperature at 30.0 °C; (4) For the soluble fraction measured isothermally at 30 °C, linearly extrapolate the elution temperature below 30.0 °C by using an elution heating rate of 3 °C / minute according to the reference (Cerk and Cong et al., US9,688,795).

[0036] The relationship between the comonomer content and the elution temperature of the iCCD is constructed using 12 reference materials (ethylene homopolymers and ethylene-octene random copolymers prepared by single-site metallocene catalysts, ethylene equivalent weight-average molecular weight from 35,000 to 128,000 g / mol). All of these reference materials are analyzed in the same manner as previously specified at 4 mg / mL. The reported elution peak temperatures follow the elution temperature of the iCCD with octene mole % versus R2 of 0.984 in the figure.

[0037] The molecular weight of the polymer and the molecular weight of the polymer fraction are directly determined from the light scattering (LS) detector (90-degree angle) and the concentration detector (IR-5) according to the Rayleigh-Gans-Debye approximation (Striegel and Yau, *Modern Size Exclusion Liquid Chromatogram*, pages 242 and 263) by assuming a shape factor of 1 and all virial coefficients equal to zero. Subtract the baseline from the LS and concentration detector chromatograms. Set the integration window to integrate all chromatograms with an elution temperature (temperature calibration specified above) in the range of 23.0 °C to 120 °C.

[0038] Calculating the molecular weight (Mw) from the iCCD includes the following steps:

[0039] Measure the offset between detectors. The offset is defined as the geometric volume offset of the LS detector relative to the concentration detector. It is calculated as the difference in the elution volume (mL) of the polymer peak between the concentration detector and the LS chromatogram. It is converted to a temperature offset by using the elution heat rate and the elution flow rate. Use linear high-density polyethylene (with zero comonomer content, melt index (I2) of 1.0, polydispersity Mw / Mn of approximately 2.6 by conventional gel permeation chromatography). Use the same experimental conditions as the normal iCCD method described above, except for the following parameters: Crystallize from 140 °C to 137 °C at 10 °C / min, thermally equilibrate at 137 °C for 1 minute as the soluble fraction elution time, the soluble fraction (SF) time is 7 minutes, elute from 137 °C to 142 °C at 3 °C / min. The flow rate during crystallization is 0.0 mL / min. The flow rate during elution is 0.80 mL / min. The sample concentration is 1.0 mg / mL.

[0040] Before integration, each LS data point in the LS chromatogram is shifted to correct for the inter-detector offset.

[0041] Integrate the baseline-subtracted LS and concentration chromatograms over the entire elution temperature range of step (1). The MW detector constant is calculated by using known MW HDPE samples in the range of 100,000 Mw to 140,000 Mw and the area ratio of the LS and concentration integration signals.

[0042] Calculate the Mw of the polymer by using the ratio of the integrated light scattering detector (90-degree angle) to the concentration detector and using the MW detector constant. Using the measured MW detector constant, NIST NBS1475a analyzed by the same method as specified in (1) above gives a molecular weight of 58,000 g / mol.

[0043] Instrumented Dart Impact (IDI) . The Instrumented Dart Impact (IDI) test follows and conforms to ASTM D7192. Condition the film according to ASTM standards at 23 °C (+ / -2 °C) and 50% R.H. (+ / -10%) for at least 40 hours. According to ASTM standards, the standard test conditions are 23 °C (+ / -2 °C) and 50% R.H. (+ / -10%). The probe used is stainless steel polished to a mirror finish and impacts the film at 3.3 m / s. The force-displacement curve, peak force, peak energy, displacement, and total energy are reported. The IDI energy results are reported in joules (J).

[0044] Melt Index . As used herein, the term "melt index" or "MI" refers to a measure of the ease with which a thermoplastic polymer flows in the molten state. The melt index or I 2Measured according to ASTM D 1238 Method A, condition 190 °C / 2.16 kg, and reported as grams eluted per 10 minutes (g / 10 min). I10 is measured according to ASTM D 1238 Method A, condition 190 °C / 10 kg, and reported as grams eluted per 10 minutes (g / 10 min). The melt flow rate ratio is calculated from these individual values by taking the ratio of I10 to I2. The melt flow rate ratio is dimensionless.

[0045] Puncture Strength . The puncture test determines the resistance of the film to probe penetration at a standard low rate and a single test speed.

[0046] Condition the film according to ASTM standards at 23 °C (+ / - 2 °C) and 50% R.H (+ / - 10%) for at least 40 hours. According to ASTM standards, the standard test conditions are 23 °C (+ / - 2 °C) and 50% R.H (+ / - 10%).

[0047] Measure puncture on a tensile testing machine. Cut square samples from the sheet to approximately 6 inches x 6 inches in size. Clamp the sample in a 4-inch diameter circular sample holder and push a puncture probe into the center of the clamped film at a crosshead speed of 10 inches / minute. The probe used is a 0.5-inch diameter polished steel ball on a 0.25-inch diameter support rod. Make a single thickness measurement at the center of the sample. For each sample, determine the maximum force, breaking force, penetration distance, breaking energy, and puncture strength (energy per unit volume of the sample). Test a total of 5 samples to determine the average puncture value. Clean the puncture probe with a "Kim-wipe" after each sample. The puncture value is reported in ft-lbf / in 3 Report.

[0048] 2% Secant Modulus . Measure the secant modulus as described herein. Condition the film sample according to ASTM standards at 23 °C (±2 °C) and 50% R.H (±10%) for at least 40 hours before testing according to ASTM standards at 23 °C (±2 °C) and 50% R.H (±10%). Cut film strips 1 inch wide x 8 inches long from the film in the desired directions (machine direction (MD) and cross direction (CD)). Load the sample onto a tensile testing frame using line clamps with a gauge length set to 4 inches (flat rubber on one side of the jaws and line clamps on the other). Then strain the sample at a crosshead speed of 2 inches / minute until 5% nominal strain. The secant modulus is measured at a specific strain and is the ratio of the stress at a specific strain to the specific strain, as determined from the load-elongation curve. Typically, calculate the secant modulus at 1% and 2% strain. Typically, perform five replicate tests on each sample. The secant modulus results are reported in ksi (1000 psi).

[0049] Tear Resistance - Machine Direction (MD) and Cross Direction (CD) The Elmendorf tear test determines the average force required to propagate a tear through a specified length of plastic film or non-rigid sheet after the tear has initiated, using an Elmendorf-type tear tester.

[0050] Condition the film for at least 40 hours at 23 °C (+ / - 2 °C) and 50% R.H. (+ / - 10%) according to ASTM standards. The standard test conditions according to ASTM standards are 23 °C (+ / - 2 °C) and 50% R.H. (+ / - 10%).

[0051] The force required to propagate a tear across the film or sheet sample was measured using a precisely calibrated pendulum device, in grams. Acting by gravity, the pendulum swings in an arc, thus tearing the sample from a pre-cut slit. One side of the sample is held by the pendulum and the other side is held by a fixed member. The energy loss of the pendulum is indicated by a pointer or an electronic scale. The scale indication is a function of the force required to tear the sample. The samples used are of the "constant radius geometry" as specified in D1922. Samples cut from the MD and CD directions are typically tested. Before testing, the sample thickness is measured at the center of the sample. A total of 15 samples are tested for each direction and the average tear strength is reported. Samples torn at an angle greater than 60° to the vertical are described as "tilted" tears - such tears should be noted, although the strength values are included in the average strength calculation. The tear resistance results are reported in gf.

[0052] Triple Detection Gel Permeation Chromatography (TDGPC) The chromatography system consists of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5) and a 4-capillary viscometer (DV) coupled to a Precision Detectors (now Agilent Technologies) 2-angle laser light scattering (LS) detector model 2040. For all absolute light scattering measurements, a 15-degree angle is used for measurement. The autosampler oven chamber is set to 160 degrees Celsius and the column and detector chambers are set to 150 degrees Celsius. The columns used are 4 Agilent "Mixed A" 30 cm 20 micron linear mixed-bed columns. The chromatography solvent used is 1,2,4-trichlorobenzene and contains 200 ppm of butylated hydroxytoluene (BHT). The solvent source is nitrogen-sparged. The injection volume used is 200 microliters and the flow rate (FR) is 1.0 ml / min.

[0053] The total plate count of the GPC column set is carried out with decane, and decane is introduced into the blank sample via a micro pump controlled by the PolymerChar GPC-IR system. For 4 Agilent "Mixed A" 30 cm 20 micron linear mixed bed columns, the plate count of the chromatographic system should be greater than 18,000.

[0054] Samples are prepared semi-automatically using PolymerChar "Instrument Control" software, where the target weight of the pellet or film sample is set at 2 mg / mL, and the solvent (containing 200 ppm BHT) is added to a septum-capped vial pre-bubbled with nitrogen through the PolymerChar high-temperature auto sampler. The sample is dissolved at 160 °C for 2 hours with "low-speed" shaking.

[0055] To monitor the deviation over time, a flow rate marker (decane) is introduced into each sample via a micro pump controlled by the PolymerChar GPC-IR system. This flow rate marker (FM) is used to linearly correct the pump flow rate (FR 标称 ) of each sample by the following method: comparing the retention volume (RV) (RV FM样品 ) of the corresponding decane peak in the sample with the retention volume (RV FM校准 ) of the decane peak in the narrow standard calibration. Then, it is assumed that any change in the decane marker peak time is related to the linear change in the flow rate (FR 有效 ) throughout the run. After calibrating the system based on the flow marker peak, the effective flow rate (relative to the narrow standard calibration) is calculated according to Equation 1. The processing of the flow marker peak is completed by PolymerChar GPCOne TM software. An acceptable flow rate correction results in the effective flow rate being within + / - 0.5% of the nominal flow rate.

[0056] FR 有效 = FR 标称 × (RV FM校准 / RV FM样品 ) (Equation 1)

[0057] To determine the offsets of the viscometer and light scattering detector relative to the IR5 detector, a systematic method for determining multi-detector offsets is performed in a manner consistent with that published by Balke, Mourey, et al. (Mourey and Balke, Chromatography Polym., Chapter 12, (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym., Chapter 13, (1992)), thus using PolymerChar GPCOne TM software to optimize the triple detector log molecular weight and intrinsic viscosity results from a linear homopolymer polyethylene reference with a molecular weight range of 115,000 g / mol to 125,000 g / mol (3.5 > M w / M n > 2.2) with the narrow standard column calibration results from the narrow standard calibration curve.

[0058] Absolute molecular weight data is obtained using PolymerChar GPCOne TM software in a manner consistent with that published as follows: Zimm (Zimm, B.H., J. Chem. Phys., 16, 1099 (1948)) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987)). The total injection concentration for determining molecular weight is obtained from the mass detector area and the mass detector constant, which is from one of a suitable linear polyethylene homopolymer or a polyethylene standard of known weight-average molecular weight. The calculated molecular weight (using GPCOne TM ) is obtained using the light scattering constant from one or more of the polyethylene standards mentioned below and the refractive index concentration coefficient dn / dc of -0.104 mL / g. Typically, the mass detector response (IR5) and the light scattering constant (determined using GPCOne TM ) should be determined using a linear homopolymer polyethylene reference with a molecular weight in the range of 115,000 g / mol to 125,000 g / mol (3.5 > M w / M n > 2.2). Viscometer calibration (using GPCOne TMThe determination can be done using the method described by the manufacturer or, alternatively, by using the published values of suitable linear standards such as Standard Reference Material (SRM) 1475 (available from the National Institute of Standards and Technology, NIST). Calculate the viscometer constant (using GPCOne TM obtained), which will be used to calibrate the specific viscosity area and injection mass of the standard to its intrinsic viscosity. Assume that the chromatographic concentration is low enough to eliminate the effect of solving the second virial coefficient (the effect of concentration on molecular weight).

[0059] The absolute molecular weight (M i ) in each chromatographic slice is (using GPCOne TM ) obtained by: dividing the area of the light scattering (LS) integrated chromatogram (taking into account the light scattering constant) by the mass recovered from the mass constant and the area of the mass detector (IR5) obtained from the IR chromatogram by subtracting the baseline at each equally spaced data acquisition point (IR i ). At the chromatographic end where the signal-to-noise ratio (using GPCOne TM ) becomes low, linearly extrapolate the M i and intrinsic viscosity (IV i ) values, but the extrapolation must be done in such a way that EQ3 equals the bulk molecular weight measured by light scattering (Ortin, A., Lopez, E., Hierro, P., Sancho-Tello, J., Yau., W., Macromol. Symp., 377, 1700044 (2018)). The absolute molecular weight moments M n , M w and M z are calculated as follows:

[0060]

[0061] LCB frequency (LCB f ) calculation . Calculate the long-chain branching frequency based on the difference between g’, which is the ratio of the intrinsic viscosity of the polymer sample to the intrinsic viscosity of a linear polymer reference with the same molecular weight. In TDGPC practice, at the start of each run queue, inject a reference polyethylene homopolymer that contains no detectable LCB or SCB and has an Mw of approximately 120,000 g / mol and a polydispersity of approximately 3.0 to create a Mark-Houwink linear reference line. Apply a first-order linear fit to the logarithms of the intrinsic viscosity and the logarithms of the molecular weight data obtained within the logarithm of the molecular weight range from 4.5 g / mol to 5.8 g / mol to provide the linear reference K and α values.

[0062] The polyethylene samples of interest were analyzed to obtain the intrinsic viscosity, molecular weight values, and g was calculated in each chromatographic slice (i) according to Equation 5. i ' value:

[0063] g i '=(IV 样品，i / IV 线性参考，i )(Equation 5),

[0064] The calculation uses IV values ​​equal to the linear reference in the logarithmic molecular weight range of 4.5 g / mol to 5.8 g / mol and at the same SCB content values. 样品，i If there is a difference in SCB content, the IV is shifted vertically by adjusting the K value from the Mark-Houwink plot. 线性参考，i line to illustrate with IV 样品，i The linear reference line was moved until it formed a single point of contact to form a tangent line to the sample Mark-Houwink line at a log molecular weight of 4.5.

[0065] The Zimm-Stockmayer branching coefficient g is calculated from g', g' = g e , using an ε factor of 0.5. The number of branches (B) along the polymer sample at each data slice (i) n ) can be determined by using Equation 6 (BH Zimm and WH Stockmayer, J. Chem. Phys. 17, 1301 (1949)):

[0066]

[0067] Finally, the average LCBf amount per 1000 carbons in the polymer for all slices (i) can be determined using Equation 7:

[0068]

[0069] TDGPC and Absolute Molecular Weight Weighted Short Chain Branching Distribution Index (M - SCBDI) Calibration for IR5 detector dosing is performed using at least ten ethylene-based polymer references (octene as comonomer) with narrow short chain branching (SCB) distribution and known comonomer content (e.g., by 13Prepared in a solution process (polyethylene homopolymer and ethylene / octene copolymer) from a single reactor via a single-site metallocene catalyst as measured by 13C NMR, Qiu et al., Anal. Chem. 2009, 81, 8585 - 8589), the known comonomer content ranges from homopolymer (0 SCB / 1000 total C) to about 40 SCB / 1000 total C, where total C = carbon in the main chain + carbon in the branches (Cong, R., de Groot, W., Parrott, A., Yau, W., Hazlitt, L., Brown, R., Miller, M., Zhou, Z., Macromolecules, 44, 3062 - 3072 (2011)). Each reference has a weight-average molecular weight of 36,000 g / mol to 126,000 g / mol measured by GPC and a molecular weight distribution (M w / M n )(Karjala, T., Sammler, R., Mangnus, M., Hazlitt, L., Johnson, M., Wang, J., Hagen, C., Huang, J., Reichek, K., J. Appl. Polym. Sci., 119, 636 - 646 (2011)). The polymer properties of the SCB standards are shown in Table A.

[0070] Table A: "SCB" Standards

[0071] Comonomer Weight % SCB / 1000 Total C <![CDATA[M w > <![CDATA[M w / M n > 23.1 28.9 37,300 2.22 14.0 17.5 36,000 2.19 0.0 0.0 38,400 2.20 35.9 44.9 42,200 2.18 5.4 6.8 37,400 2.16 8.6 10.8 36,800 2.20 39.2 49.0 125,600 2.22 1.1 1.4 107,000 2.09 14.3 17.9 103,600 2.20 9.4 11.8 103,200 2.26

[0072] Calculate the "IR5 area ratio (or "IR5 甲基通道面积 / IR5 测量通道面积 ")" of the "area response of the IR5 methyl channel sensor minus the baseline" to the "area response of the IR5 measurement channel sensor minus the baseline" for each of the "SCB" standards (including the standard filter and filter wheel supplied by PolymerChar (Perlimocha Corporation): part number IR5_FWM01 as part of the GPC-IR instrument). The linear fit of the SCB frequency to the "IR5 area ratio" is constructed in the form of Equation 8:

[0073] SCB / 1000 total C = A 0 + [A 1 × (IR5 甲基通道面积 / IR5 测量通道面积 )] (Equation 8)

[0074] where A 0The intercept of "SCB / 1000 total C" at a "IR5 area ratio" of zero, and A 1 is the slope of "SCB / 1000 total C" with respect to "IR5 area ratio" and represents the increase in SCB / 1000 total C as a function of "IR5 area ratio". For narrow PDI and narrow SCBD standard materials, the IR5 area ratio is equal to the IR5 height ratio.

[0075] A "series of linear baseline-subtracted chromatographic heights" of the chromatogram generated by the "IR5 methyl channel sensor" is established as a function of column elution volume to produce a baseline-corrected chromatogram (methyl channel). A "series of linear baseline-subtracted chromatographic heights" of the chromatogram generated by the "IR5 measurement channel" is established as a function of column elution volume to produce a baseline-corrected chromatogram (measurement channel).

[0076] The "IR5 height ratio" of the "baseline-corrected chromatogram (methyl channel)" to the "baseline-corrected chromatogram (measurement channel)" is calculated at each column elution volume index within the sample integration range (each equally spaced index representing 1 data point per second at an elution flow rate of 1 mL / min). Multiply the "IR5 height ratio" by coefficient A 1 , and add coefficient A 0 to this result to produce the predicted SCB frequency of the sample.

[0077] Thus, the comonomer composition values are reported as octene comonomer equivalent SCB / 1000 total C at each index i and plotted as a function of the absolute molecular weight (M i ) at the corresponding index i. The absolute molecular weight values measured by light scattering are also plotted as the molecular weight distribution of dWf / dLog(M i ) versus Log(M i ), where the increment of Log(M i ) is 0.01. Thus, two distributions are defined.

[0078] The absolute molecular weight values measured by light scattering are obtained from a light scattering detector with a minimum signal-to-noise ratio (S / N) of 300. S / N is defined as:

[0079]

[0080] where LS 峰最大 is the maximum light scattering signal located at the polymer peak, LS 基线 is the average of consecutive, equally spaced baseline data points eluting before the polymer peak and consists of at least 10% of the entire GPC run time length, and LS 噪声 is the standard deviation of the same data array used in the calculation of LS 基线 .

[0081] Copolymer distribution of SCB / 1000 total C (function of Log(M i )) is divided into two parts: high molecular weight region and low molecular weight region. These regions are defined near the maximum peak of the SCB / 1000 total C distribution (SCB / 1000C peak) and its corresponding Log(M i ) value (denoted as Log(M SCB峰 ))

[0082] For the calculation of the high absolute molecular weight SCB distribution index (high M-SCBDI), the Log(M SCB峰 ) values in the range of [Log(M SCB峰 ) + 0.1] to [Log(M i ) + 0.6] define "high LogM 范围 ", that is, the region 0.5 LogM higher than Log(M SCB峰 ). The calculation of the high M-SCBDI value requires at least 51 non-zero data points equally spaced at 0.01 increments on the x-axis. The EXCEL linear regression function (LINETT) for the corresponding SCB / 1000 total C (y-axis) and Log(M i )(x-axis) within this defined range generates the slope value defined as the high M-SCBDI value.

[0083] For the calculation of the low absolute molecular weight SCB distribution index (low M-SCBDI), the Log(M SCB峰 ) values in the range of [Log(M SCB峰 ) - 0.6] to [Log(M i ) - 0.1] define "low LogM 范围 ", that is, the region 0.5 LogM lower than Log(M SCB峰 ). The calculation of the low M-SCBDI value requires at least 51 non-zero data points equally spaced at 0.01 increments on the x-axis. The EXCEL linear regression function (LINEST) for the SCB / 1000 total (y-axis) and Log(M i )(x-axis) values within this defined range generates the slope value defined as the low M-SCBDI value.

[0084] If the non-zero Log(M 范围 ) values in the high or low Log M i do not meet the requirement that they are higher or lower than Log(M SCB峰) If the minimum requirement of the value is not met, the LINETT fitting cannot be applied to calculate M-SCBDI. In addition, to ensure data quality, all SCB / 1000C values used in the calculation must exceed 4.0 so that no false peaks are identified from low signal-to-noise data. Further, all Log(M i ) values used in the linear regression for low and high M-SCBDI calculations must have corresponding dWf / dLogM values from the absolute molecular weight distribution, and these corresponding values must be greater than 10% of the maximum dWf / dLogM value (i.e., dWf / LogM p ) at the peak of the curve (LogM p ). Detailed Embodiments

[0085] The present disclosure provides a polyethylene composition. In one embodiment, the polyethylene composition comprises (A) at least 50 wt% of high density polyethylene having (i) a density of 0.950 g / cm 3 to 0.970 g / cm 3 , (ii) a melt index (I 2 ) of 0.2 g / 10 min to 2.0 g / 10 min, and (iii) a molecular weight distribution (M w(abs) / M n(abs) ) greater than 4.0 to 30.0. The polyethylene composition further comprises (B) a polyethylene enhancer which is an ethylene / C 4 -C 8 α-olefin copolymer and has (i) a density of 0.880 g / cm 3 to 0.910 g / cm 3 , (ii) a melt index of 0.2 g / 10 min to 2.0 g / 10 min, and (iii) an LCBf / 1000C value less than 0.015. The polyethylene composition has (1) a density of 0.930 g / cm 3 to 0.940 g / cm 3 , (2) a melt index (I 2 ) of 0.3 g / 10 min to 1.0 g / 10 min, (3) an Mw(abs) / Mn(abs) value of 5.0 to 13.0, (4) a low M-SCBDI value of 9.0 to 32.0, (5) a high M-SCBDI value of -8.0 to -15.0, (6) a first polyethylene fraction which (a) has at least one peak in the temperature range of 40 °C to 79 °C on an elution curve obtained by an improved comonomer composition distribution (iCCD) analysis method, and (b) has an average M w, (7) a second polyethylene fraction that (a) has at least one peak in the temperature range of 80 °C to 120 °C on an elution curve obtained via an improved iCCD analysis method, and (b) has an average M of 90,000 g / mol to 250,000 g / mol w , and (8) an average M of the first polyethylene fraction of 0.6 to 1.2 w to the average M of the second polyethylene fraction w ratio.

[0086] The polyethylene composition of the present invention comprises (A) at least 50% by weight of high-density polyethylene. As used herein, "high-density polyethylene" is a homopolymer of ethylene or an ethylene / C 4 -C 8 α-olefin copolymer and has a density of 0.95 g / cc to 0.97 g / cc, a melt index of 0.2 g / 10 min to 2.0 g / 10 min, and (iii) an M of greater than 4.0 to 30.0 w(abs) / M n(abs) ).

[0087] In one embodiment, the high-density polyethylene has

[0088] (i) a density of 0.950 g / cc to 0.970 g / cc, or 0.955 g / cc to 0.970 g / cc;

[0089] (ii) a melt index of 0.2 g / 10 min to 2.0 g / 10 min, or 0.3 g / 10 min to 1.2 g / 10 min; and

[0090] (iii) an M of greater than 4.0 to 30.0, or 4.2 to 30.0, or 4.5 to 25.0, or 5.0 to 23.0 w(abs) / M n(abs) . Non-limiting examples of high-density polyethylene are disclosed in WO2021 / 076357 and WO2021 / 242384, the contents of each of which are incorporated herein by reference.

[0091] In one embodiment, the high-density polyethylene is post-consumer high-density polyethylene resin, or "HDPE-PCR". The term "post-consumer resin" (or "PCR") refers to polymeric materials that were previously used for consumer packaging or industrial packaging. In other words, PCR is waste plastic. PCR is typically collected from recycling programs and recycling plants. PCR generally requires additional cleaning and processing before it can be re-introduced into the production line. PCR can include one or more of ethylene-based polymers, propylene-based polymers, polyesters, polyvinyl chloride, polystyrene, acrylonitrile butadiene styrene, polyamides, ethylene vinyl alcohol, ethylene vinyl acetate, or polyvinyl chloride. PCR can contain one or more contaminants. The contaminants may be the result of the use of the polymeric material before it is reused. In some embodiments, the contaminants can include paper, ink, food residues, or other recycled materials other than polymers, which can result from the recycling process. It should be understood that PCR is different from post-industrial recycled (PIR) resin in that the latter has not been in contact with consumers. It should be understood that the similar principles described herein for PCR also apply to PIR resin.

[0092] PCR is different from virgin polymeric materials. Since PCR has undergone an initial heating and molding process; PCR is not a "virgin" polymeric material. "Virgin polymeric material" is a polymeric material that has not undergone or otherwise been subjected to heat treatment or molding processes other than those related to the initial manufacture of pellets or granules. When compared to virgin polymeric resins, the physical, chemical, and flow characteristics of PCR resins are different.

[0093] PCR is high-density polyethylene-PCR ("HDPE-PCR"). Non-limiting examples of sources of HDPE-PCR include rigid HDPE packaging (such as bottles (baby bottles, juice containers)) and flexible HDPE packaging (such as stand-up pouches and vest bags). HDPE-PCR also includes residues from its original use, such as residues of paper, adhesives, inks, ethylene vinyl alcohol (EVOH), polyamide (PA), polyethylene terephthalate (PET), and other odor-causing agents. HDPE-PCR has:

[0094] (i) a density of 0.950 g / cc to 0.970 g / cc, or 0.955 g / cc to 0.970 g / cc;

[0095] (ii) a melt index of 0.2 g / 10 min to 2.0 g / 10 min, or 0.3 g / 10 min to 1.2 g / 10 min; and

[0096] (iii) an M w(abs) / M n(abs) )

[0097] Non-limiting examples of suitable HDPE-PCR include those sold by Envision Plastics, North Carolina, USA under the name EcoPrime TM , PRISMA TM , natural HDPE PCR resin, mixed color and black HDPE PCR resin; PCR sold by KW Plastics, Alabama, USA under the following names: KWR101-150, KWR102-8812 BLK, KWR102, KWR105-7525, KWR-105M2 and KWR105M4.

[0098] The polyethylene composition comprises (B) a polyethylene enhancer. As used herein, "polyethylene enhancer" is an ethylene-based polymer from the group of linear low density polyethylenes from single-site catalysis, including both linear low density resins and substantially linear low density resins (m-LLDPE); ethylene-based plastomers (POP) and ethylene-based elastomers (POE). The polyethylene enhancer is an ethylene / C 4 -C 8 α-olefin copolymer and has (i) a density of 0.880 g / cm 3 to 0.910 g / cm 3 , (ii) a melt index of 0.2 g / 10 min to 2.0 g / 10 min, and (iii) an LCBf / 1000C value of less than 0.015.

[0099] In one embodiment, the polyethylene composition consists of

[0100] (A) at least 50 wt% of high density polyethylene having

[0101] (i) a density of 0.950 g / cc to 0.970 g / cc, or 0.955 g / cc to 0.970 g / cc;

[0102] (ii) a melt index of 0.2 g / 10 min to 2.0 g / 10 min, or 0.3 g / 10 min to 1.2 g / 10 min; and

[0103] (iii) an M w(abs) / M n(abs) )

[0104] and

[0105] (B) A polyethylene enhancer, which is an ethylene / C 4 -C 8 α-olefin copolymer and has

[0106] (i) A density of 0.880 g / cm 3 to 0.910 g / cm 3 ; and

[0107] (ii) A melt index of 0.2 g / 10 min to 2.0 g / 10 min, and

[0108] (iii) An LCBf / 1000C value less than 0.015, and

[0109] The polyethylene composition has

[0110] (1) A density of 0.930 g / cm 3 to 0.940 g / cm 3 ;

[0111] (2) A melt index (I 2 ) of 0.3 g / 10 min to 1.0 g / 10 min,

[0112] (3) An Mw(abs) / Mn(abs) value of 5.0 to 13.0,

[0113] (4) A low M-SCBDI value of 9.0 to 32.0,

[0114] (5) A high M-SCBDI value of -8.0 to -15.0,

[0115] (6) A first polyethylene fraction, which has at least one peak in the temperature range of 40°C to 79°C on the elution curve obtained by the improved comonomer composition distribution (iCCD) analysis method, and

[0116] (a) has at least one peak in the temperature range of 40°C to 79°C, and

[0117] (b) has an average M of 100,000 g / mol to 200,000 g / mol w ,

[0118] (7) A second polyethylene fraction, which has at least one peak in the temperature range of 80°C to 120°C on the elution curve obtained by the improved iCCD analysis method, and

[0119] (a) has at least one peak in the temperature range of 80°C to 120°C, and

[0120] (b) has an average M of 90,000 g / mol to 250,000 g / molw , and

[0121] (8) The average M of the first polyethylene fraction from 0.6 to 1.2 w and the average M of the second polyethylene fraction w .

[0122] The polyethylene composition has a density of 0.930 g / cm 3 to 0.940 g / cm 3 and a melt index (I 2 ) of 0.3 g / 10 min to 1.0 g / 10 min and an Mw(abs) / Mn(abs) value of 5.0 to 13.0.

[0123] The polyethylene composition has a low M-SCBDI value of 9.0 to 32.0 and a high M-SCBDI value of -8.0 to -15.0.

[0124] The polyethylene composition has a first polyethylene fraction and a second polyethylene fraction. A polyethylene "fraction" refers to a portion of the total polyethylene composition. The first polyethylene fraction and the second polyethylene fraction are each quantified by their respective temperature ranges in the elution curve obtained via the improved comonomer composition distribution (iCCD) analysis method (hereinafter interchangeably referred to as "iCCD").

[0125] The first polyethylene fraction is located in the first polyethylene fraction region defined by the temperature range from 40 °C to 79 °C in the elution curve obtained via iCCD. The second polyethylene fraction is located in the second polyethylene fraction region defined by the temperature range from 80 °C to 120 °C in the elution curve obtained via iCCD. In one embodiment, the first polyethylene fraction area is the area between 40 °C and 79 °C under the single peak of the first polyethylene fraction in the iCCD elution curve, and the first polyethylene fraction has an average M of 100,000 g / mol to 200,000 g / mol, or 100,000 g / mol to 150,000 g / mol w , and the second polyethylene fraction area is the area between 80 °C and 120 °C under the single peak of the second polyethylene fraction in the iCCD elution curve, and the second polyethylene fraction has an average M of 90,000 g / mol to 250,000 g / mol, or 90,000 g / mol to 180,000 g / mol w . Each peak includes an upward-sloping region, followed by a downward-sloping region to form each respective single peak. The polyethylene composition has a ratio of the average M w of the first polyethylene fraction to the average M w of the second polyethylene fraction of 0.4 to 1.4, or 0.6 to 1.3, or 0.7 to less than 1.0.

[0126] In one embodiment, the polyethylene composition comprises

[0127] (A) 50 wt% to 80 wt%, or 51 wt% to 75 wt%, or 52 wt% to 70 wt%, or 53 wt% to 65 wt% of high-density polyethylene, the high-density polyethylene having

[0128] (i) a density of 0.950 g / cm 3 to 0.970 g / cm 3 or 0.955 g / cm 3 to 0.970 g / cm 3 ,

[0129] (ii) a melt index of 0.2 g / 10 min to 2.0 g / 10 min, or 0.3 g / 10 min to 1.0 g / 10 min

[0130] (iii) a molecular weight distribution greater than 4.0 to 30.0, or greater than 6.0 to 25

[0131] (M w(abs) / M n(abs) )

[0132] (B) 50 wt% to 20 wt%, or 49 wt% to 25 wt%, or 48 wt% to 30 wt%, or 47 wt% to 35 wt% of a polyethylene enhancer, the polyethylene enhancer being an ethylene / C 4 -C 8 α-olefin copolymer and having

[0133] (i) a density of 0.880 g / cm 3 to 0.910 g / cm 3 or 0.880 g / cm 3 to less than 0.900 g / cm 3 ,

[0134] (ii) a melt index of 0.2 g / 10 min to 2.0 g / 10 min, or 0.3 g / 10 min to 1.0 g / 10 min, or 0.4 g / 10 min to 0.9 g / 10 min,

[0135] (iii) an LCBf / 1000C value less than 0.020, or 0.001 to 0.020, or 0.001 to 0.015, or 0.001 to 0.010, and

[0136] the polyethylene composition has

[0137] (1) 0.930 g / cm 3from 0.940 g / cm to 3 or 0.932 g / cm 3 to 0.938 g / cm 3 in density,

[0138] (2) a melt index (I 2 ) of from 0.3 g / 10 min to 1.0 g / 10 min, or from 0.35 g / 10 min to 0.9 g / 10 min,

[0139] (3) an Mw(abs) / Mn(abs) value of from 5.0 to 13.0,

[0140] (4) a low M-SCBDI value of from 9.0 to 32.0,

[0141] (5) a high M-SCBDI value of from -8.0 to -15.0,

[0142] (6) a first polyethylene fraction which in iCCD

[0143] (a) has a single peak in the temperature range from 40 °C to 79 °C, and

[0144] (b) has an average M w of from 100,000 g / mol to 200,000 g / mol, or from 100,000 g / mol to 150,000 g / mol, or from 110,000 g / mol to 130,000 g / mol,

[0145] (7) a second polyethylene fraction which in iCCD

[0146] (a) has a single peak in the temperature range from 80 °C to 120 °C, and

[0147] (b) has an average M w of from 90,000 g / mol to 250,000 g / mol, or from 90,000 g / mol to 180,000 g / mol, or from 100,000 g / mol to 160,000 g / mol, and

[0148] (8) a ratio of the average M w of the first polyethylene fraction to the average M w of the second polyethylene fraction of from 0.4 to 1.4, or from 0.6 to 1.3, or from 0.7 to less than 1.0 (hereinafter interchangeably referred to as "Composition 1").

[0149] The polyethylene composition may comprise one or more optional additives. Non-limiting examples of suitable additives include, but are not limited to, antistatic agents, colorants, dyes, lubricants, fillers (such as TiO2 or CaCO 3 ), light stabilizers, nucleating agents, processing aids, pigments, primary antioxidants, secondary antioxidants, UV stabilizers, anti-caking agents, slip agents, tackifiers, flame retardants, anti-microbial agents, deodorants, anti-fungal agents, and combinations thereof. Based on the total weight of the polyethylene composition comprising such additives, the polyethylene composition of the present invention may comprise from 0.001 wt% to 10 wt%, or from 0.01 wt% to 1 wt%, or from 0.1 wt% to 0.5 wt% of the combined weight of such additives.

[0150] The present disclosure provides a film. In one embodiment, the film consists of a polyethylene composition.

[0151] The polyethylene composition consists of

[0152] (A) at least 50 wt% of high density polyethylene having

[0153] (i) a density of from 0.950 g / cc to 0.970 g / cc, or from 0.955 g / cc to 0.970 g / cc;

[0154] (ii) a melt index of from 0.2 g / 10 min to 2.0 g / 10 min, or from 0.3 g / 10 min to 1.2 g / 10 min; and

[0155] (iii) an M of greater than 4.0 to 30.0, or 4.2 to 30.0, or 4.5 to 25.0, or 5.0 to 23.0 w(abs) / M n(abs) )

[0156] and

[0157] (B) a polyethylene enhancer, which is an ethylene / C 4 -C 8 α-olefin copolymer and has

[0158] (i) a density of from 0.880 g / cm 3 to 0.910 g / cm 3 ; and

[0159] (ii) a melt index of from 0.2 g / 10 minutes to 2.0 g / 10 minutes, and

[0160] (iii) an LCBf / 1000C value of less than 0.015, and

[0161] the polyethylene composition has

[0162] (1) from 0.930 g / cm 3 to 0.940 g / cm3 Density,

[0163] (2) A melt index (I 2 ) of 0.3 g / 10 minutes to 1.0 g / 10 minutes,

[0164] (3) An Mw(abs) / Mn(abs) value of 5.0 to 13.0,

[0165] (4) A low M-SCBDI value of 9.0 to 32.0,

[0166] (5) A high M-SCBDI value of -8.0 to -15.0,

[0167] (6) A first polyethylene fraction that has at least one peak in the elution curve obtained via an improved comonomer composition distribution (iCCD) analysis method and

[0168] (a) has a peak in the temperature range of 40 °C to 79 °C, and

[0169] (b) has an average M of 100,000 g / mol to 200,000 g / mol w ,

[0170] (7) A second polyethylene fraction that has at least one peak in the elution curve obtained via the improved iCCD analysis method and

[0171] (a) has a peak in the temperature range of 80 °C to 120 °C, and

[0172] (b) has an average M of 90,000 g / mol to 250,000 g / mol w , and

[0173] (8) A ratio of the average M of the first polyethylene fraction to the average M of the second polyethylene fraction of 0.6 to 1.2. w of the first polyethylene fraction to the average M w of the second polyethylene fraction.

[0174] In one embodiment, the film consists of Composition 1.

[0175] The film is a blown film or a cast film. The film is a single-layer film, or one or more layers of a multi-layer film.

[0176] In one embodiment, the film is a single-layer film.

[0177] In one embodiment, the film is one layer of a multi-layer film. The multi-layer film can have 2, 3, or 4, or 5, or 6, or 7, or 8, or 9, or 10, or 11 layers.

[0178] The films of the present disclosure can have a variety of thicknesses. In one embodiment, the film is a blown film, and the blown film has a thickness of 0.25 mil, or 0.5 mil, or 0.7 mil, or 1.0 mil, or 1.75 mil, or 2.0 mil to 4.0 mil, or 6.0 mil, or 8.0 mil, or 10 mil, or 15 mil.

[0179] It should be understood that any of the foregoing films / layers may also contain one or more additives. Non-limiting examples of suitable additives include antioxidants, ultraviolet light stabilizers, heat stabilizers, slip agents, anti-caking agents, pigments or colorants, processing aids, crosslinking catalysts, flame retardants, fillers, and blowing agents. In one embodiment, based on the total weight of the film, the film contains 0 wt%, or greater than 0 wt%, or 1 wt% to 1.5 wt%, or 2 wt%, or 2.5 wt%, or 3 wt% total additives.

[0180] In one embodiment, the film is laminated to another film and contains a layer formed from the polyethylene composition of the present invention.

[0181] The films of the present invention can be corona treated and / or printed (e.g., reverse or surface printing).

[0182] In one embodiment, the film of the present invention is uniaxially oriented (e.g., along the longitudinal direction) or biaxially oriented (e.g., along the longitudinal and transverse directions).

[0183] In one embodiment, the film has a thickness of 1.5 mil to 2.5 mil, or 1.7 mil to 2.3 mil. The film consists of a polyethylene composition.

[0184] In one embodiment, the film consists of a polyethylene composition. The polyethylene composition comprises

[0185] (A) 50 wt% to 80 wt%, or 51 wt% to 75 wt%, or 52 wt% to 70 wt%, or 53 wt% to 65 wt% of high density polyethylene, the high density polyethylene having

[0186] (i) 0.950 g / cm 3 to 0.970 g / cm 3 、or 0.955 g / cm 3 to 0.970 g / cm 3 of density,

[0187] (ii) 0.2 g / 10 min to 2.0 g / 10 min, or 0.3 g / 10 min to 1.0 g / 10 min melt index

[0188] (iii) greater than 4.0 to 30.0, or greater than 6.0 to 25 molecular weight distribution

[0189] (M w(abs) / M n(abs) );

[0190] (B) 50 wt% to 20 wt%, or 49 wt% to 25 wt%, or 48 wt% to 30 wt%, or 47 wt% to 35 wt% of a polyethylene enhancer, the polyethylene enhancer being an ethylene / C 4 -C 8 α-olefin copolymer and having

[0191] (i) 0.880 g / cm 3 to 0.910 g / cm 3 , or 0.880 g / cm 3 to less than 0.900 g / cm 3 of density,

[0192] (ii) 0.2 g / 10 min to 2.0 g / 10 min, or 0.3 g / 10 min to 1.0 g / 10 min, or 0.4 g / 10 min to 0.9 g / 10 min of melt index,

[0193] (iii) less than 0.020, or 0.001 to 0.020, or 0.001 to 0.015, or 0.001 to 0.010 of LCBf / 1000C value, and

[0194] the polyethylene composition has

[0195] (1) 0.930 g / cm 3 to 0.940 g / cm 3 , or 0.932 g / cm 3 to 0.938 g / cm 3 of density,

[0196] (2) 0.3 g / 10 min to 1.0 g / 10 min, or 0.35 g / 10 min to 0.9 g / 10 min of melt index (I 2 ),

[0197] (3) 5.0 to 13.0 of Mw(abs) / Mn(abs) value,

[0198] (4) 9.0 to 32.0 of low M-SCBDI value,

[0199] (5) -8.0 to -15.0 of high M-SCBDI value,

[0200] (6) A first polyethylene fraction, the first polyethylene fraction in iCCD

[0201] (a) has a single peak in the temperature range of 40 °C to 79 °C, and

[0202] (b) has an average M of 100,000 g / mol to 200,000 g / mol, or 100,000 g / mol to 150,000 g / mol, or 110,000 g / mol to 130,000 g / mol w , (7) a second polyethylene fraction, the second polyethylene fraction in the iCCD

[0203] (a) has a single peak in the temperature range of 80 °C to 120 °C, and

[0204] (b) has an average M of 90,000 g / mol to 250,000 g / mol, or 90,000 g / mol to 180,000 g / mol, or 100,000 g / mol to 160,000 g / mol w , and

[0205] (8) the ratio of the average M of the first polyethylene fraction of 0.4 to 1.4, or 0.6 to 1.3, or 0.7 to less than 1.0 w to the average M of the second polyethylene fraction w , and

[0206] the film has one, some, or all of the following properties:

[0207] (i) an instrumented dart impact energy of 0.3 J to 0.6 J; and / or

[0208] (ii) a longitudinal tear strength of 200 gf to 800 gf; and / or

[0209] (iii) a transverse tear strength of 1200 gf to 1700 gf; and / or

[0210] (iv) a puncture resistance of 50 ft-lbf / in 3 to 130 ft-lbf / in 3 ; and / or

[0211] (v) a longitudinal 2% modulus of 60 ksi to 75 ksi; and / or

[0212] (vi) a transverse 2% modulus of 70 ksi to 85 ksi; and / or

[0213] (vii) a dynamic coefficient of friction of 0.3 to 0.8.

[0214] By way of example and not limitation, some embodiments of the present disclosure will now be described in detail in the following examples.

[0215] Example

[0216] The materials used in the Comparative Sample (CS) and the Invention Examples (IE) are provided in Tables 1A and 1B below.

[0217] Table 1A - Related Properties of Reference Resin

[0218]

[0219] A. High - Density Polyethylene

[0220] Table 1B - Related Properties of High - Density Polyethylene Component (A)

[0221]

[0222] B. Polyethylene Reinforcer and Polymerization

[0223] All raw materials (ethylene and 1-octene) and process solvents (narrow-boiling high-purity isoparaffinic solvent, Isopar-E) were purified with molecular sieves before being introduced into the reaction environment. Hydrogen was supplied pressurized in a high-purity grade and was not further purified. The reactor monomer feed stream was pressurized to greater than the reaction pressure via a mechanical compressor. The solvent and comonomer feeds were pressurized to greater than the reaction pressure via a pump. The individual catalyst components were manually batch-diluted with the purified solvent and pressurized to greater than the reaction pressure. All reaction feed streams were measured with mass flow meters and independently controlled with a computerized automated valve control system.

[0224] A single reactor system was used. The continuous solution polymerization reactor consisted of a liquid-filled non-adiabatic isothermal recycle loop reactor mimicking a continuous stirred tank reactor (CSTR) with heat removal. All fresh solvent, monomer, comonomer, hydrogen, and catalyst component feeds could be controlled independently. The total fresh feed stream (solvent, monomer, comonomer, and hydrogen) to the reactor was temperature-controlled to maintain a single solution phase by passing the feed stream through a heat exchanger. The total fresh feed to the polymerization reactor was injected into the reactor at two locations, where the reactor volume between each injection location was approximately equal. The fresh feed was controlled by receiving half of the total fresh feed mass flow rate with each injector. The catalyst components and cocatalyst are provided in Table 2 below.

[0225] Table 2

[0226]

[0227] The catalyst components are injected into the polymerization reactor through an injection insertion tube. A computer controls the feed of the main catalyst component to maintain the reactor monomer conversion rate under a specified target. The cocatalyst component is fed based on a calculated specified molar ratio with the main catalyst component. Immediately following the reactor feed injection location, a static mixing element is used to mix the feed stream with the recycled polymerization reactor contents. The contents of the reactor are continuously circulated through a heat exchanger, which is responsible for removing a large amount of reaction heat, and where the temperature on the coolant side is responsible for maintaining the isothermal reaction environment at a specified temperature. The circulation around the reactor loop is provided by a pump.

[0228] The reactor effluent enters a zone where it is deactivated by adding a suitable reagent (water) and reacting with it. At the same reactor outlet location, other additives are added for polymer stabilization. The additives are octadecyl 3,5 - di - tert - butyl - 4 - hydroxyhydrocinnamate, tetrakis(methylene(3,5 - di - tert - butyl - 4 - hydroxycinnamate))methane, and tris(2,4 - di - tert - butyl - phenyl)phosphite.

[0229] After the catalyst is deactivated and the additives are added, the reactor effluent enters a devolatilization system where the ethylene / octene copolymer is removed from the non - polymer stream. The separated ethylene / octene copolymer melt is granulated and collected. The non - polymer stream passes through various devices that separate most of the ethylene removed from the system. Most of the solvent and unreacted comonomer are recycled back to the reactor after passing through a purification system. A small amount of solvent and comonomer are purged from the process. The polymerization conditions for the polyethylene enhancer are provided in Table 3 below.

[0230] Table 3

[0231]

[0232]

[0233] The properties of the polyethylene enhancer (“enhancer”) are provided in Table 4 below.

[0234] Table 4 - Properties of Polyethylene Reinforcer Component (B)

[0235]

[0236] C. Polyethylene Composition

[0237] Each pellet component is fed into the hopper using a gravimetric feeder. The gravimetric feeder meters the resin formulation into a Labtech LTE20-32 twin-screw extruder at a rate of 15 lb / h. The resin formulation is conveyed from the extruder into a blown film die. The LTE feed throat is set at 193 °C, and the remaining barrel, transfer section, and die temperatures are set and maintained at 215 °C. A single-layer blown film is produced by a blown film line with a 2-inch die diameter and a die gap of 1.0 mm. To produce the film, the film bubble is inflated to a blow-up ratio of 2.5 using pressurized ambient air targeting a die circumference output rate of 2.4 lb / hr / in. A dual-lip air ring driven by a variable-speed blower is used for all experiments. The frost line height (FLH) is maintained between 9.3 inches and 10.3 inches. The target film thickness is 2 mils and is controlled within ±10% by adjusting the roll speed. The film is wound into a roll.

[0238]

[0239]

[0240]

[0241] The polyethylene composition of the present invention has a unique SCBD curve shape in terms of polymer molecular weight. This unique SCBD shape is defined by a peak and two slopes on each side of the peak (referred to as "low M-SCBDI" and "high M-SCBDI") calculated therefrom.

[0242] Figure 1It is a graph showing the SCBD on the molecular weight (Log M) of Comparative Sample 1 (CS1). Linear regression using the Excel LINEST function or a similar function is applied to the absolute Log M values of the x - coordinates within the molecular weight range of LogM = 4.17 - 5.17 (15,000 g / mol - 150,000 g / mol) and their corresponding y - coordinate SCB / 1000C values. The resulting fitted slope value (referred to as the Molecular Weight Short Chain Branching Distribution Index (M - SCBDI)) describes the variation amplitude of the comonomer as a function of the molecular weight and whether the incorporation is positive, negative, or uniform. The parameters characterizing the SCBD of the compositions of the present invention cannot accurately define or calculate CS1 due to poor data quality (see the method description of TDGPC and the Absolute Molecular Weight - weighted Short Chain Branching Distribution Index (M - SCBDI)). Although there is a SCB / 1000C peak at LogM = 4.06, all SCB / 1000C values in the possible high and low M - SCBDI calculation ranges are below 4.0, which is not conducive to the accuracy of the calculation. Therefore, two characteristic slope values cannot be established on either side. In this case, a single slope value would better describe the comonomer incorporation on Log M.

[0243] Figure 2 It is a graph showing the SCBD on the molecular weight (Log M) of CS2. CS2 shows additional required data quality parameters that are not met for the calculation conditions to generate low M - SCBDI and high M - SCBDI values (i.e., only low M - SCBDI calculation is possible). For these calculations, the sample must meet two key data quality parameters within the corresponding calculation range, particularly regarding the minimum number of data points and the minimum signal intensity used for M - SCBDI calculation, such that the minimum dWf ratio exceeds 10%. For CS2, the molecular weight (Log(M SCB峰 )) at the SCB / 1000C peak is 5.64. The low M - SCBDI is calculated in the region defined by [Log(M SCB峰 ) - 0.6] to [Log(M SCB峰 ) - 0.1]. In this case, the calculation range of the low M - SCBDI spans LogM = 5.04 to LogM = 5.54. The high M - SCBDI is calculated in the region defined by [Log(M SCB峰 ) + 0.1] to [Log(M SCB峰 ) + 0.6]. In this case, the calculation range of the high M - SCBDI spans LogM = 5.74 to LogM = 6.24. CS2 does not meet the minimum data quality criteria, i.e., for both calculations of low and high M - SCBDI values, at least 51 consecutive equally - spaced non - zero data points are required within the defined 0.5 LogM range.

[0244] The minimum data quality standard for signal strength is represented by a "minimum dWf ratio" (min dWf ratio) of 10.0% or greater. The minimum dWf ratio is determined by the ratio of the lowest value of either "dWf low" or "dWf high" to the value of "dWf LogM" p ", where dWf low is the lowest dWf / dLogM value in the calculation region for low M-SCBDI, dWf high is the lowest dWf / dLogM value in the calculation region for high M-SCBDI, and dWf LogM p is dWf / dLogM at the peak of the molecular weight (Log M) distribution. In the case of CS2, dWf low = 0.73, dWf high = 0.01, and dWf LogM p = 0.77. Thus, the minimum dWf ratio = 0.01 / 0.77 * 100 = 1.30%, which is below the 10% minimum data quality requirement. This means that the data used in the high M-SCBDI calculation comes from the tail of the MWD distribution with a low signal-to-noise ratio (S / N). Therefore, the quality of the data is insufficient for calculating high M-SCBDI values, and CS2 does not meet the requirements of the compositions of the present invention.

[0245] Figures 3 - 4 is a graph showing SCBD on the molecular weight (Log M) of IE1. In Figure 3 , the relevant details of the high M-SCBDI calculation are shown for IE1. The calculation of high M-SCBDI first requires identifying the SCB / 1000C peak and its corresponding Log(M SCB峰 ) value. For IE1, Log(M SCB峰 ) = 5.08. The calculation range for the high M-SCBDI value is defined as [Log(M SCB峰 ) + 0.1] to [Log(M SCB峰 ) + 0.6]. For IE1, the upper and lower limits of the high M-SCBDI calculation range are LogM = 5.68 and LogM = 5.18, respectively. Linear regression using the LINEST function or a similar function in Excel is applied to the x-coordinate LogM values and the corresponding y-coordinate SCB / 1000C values within this range to generate a slope value, which is equal to the high M-SCBDI. IE1 has the required 51 non-zero data points spaced 0.01 apart on the LogM scale for the calculation. The "dWf high ratio" uses dWfLogM p= 0.73 (i.e., the dWf / dLogM value at the molecular weight peak of the Abs MWD curve) and dWf high = 0.17 (corresponding to the lowest dWf / dLogM value in the high M-SCBDI calculation). In this case, the dWf high ratio = 0.17 / 0.73 * 100 = 23.29%. Since the dWf high ratio exceeds 10.0%, the lower S / N data at the higher molecular weight tail of the MWD is not used for the high M-SCBDI calculation.

[0246] In Figure 4 the relevant details of the low M-SCBDI calculation are shown for IE1. The calculation of low M-SCBDI first requires the identification of the SCB / 1000C peak and its corresponding Log(M SCB峰 ) value. For IE1, Log(M SCB峰 ) = 5.08. The calculation range for the low M-SCBDI value is limited to [Log(M SCB峰 ) - 0.6] to [Log(M SCB峰 ) - 0.1]. For IE1, the upper and lower limits of the low M-SCBDI calculation range are LogM = 4.98 and LogM = 4.48 respectively. Linear regression using the LINEST function or a similar function in Excel is applied to the x-coordinate LogM values and the corresponding y-coordinate SCB / 1000C values within this range to generate a slope value, which is equal to the low M-SCBDI. IE1 has the required 51 non-zero data points spaced 0.01 apart on the LogM scale for the calculation. The "dWf low ratio" is calculated using dWf LogM p = 0.73 (i.e., the dWf / dLogM value at the molecular weight peak of the Abs MWD curve) and dWf low = 0.54 (the corresponding lowest dWf / dLogM value in the low M-SCBDI calculation). For IE1, the dWf low ratio = 0.54 / 0.73 * 100 = 74.0%. Since the dWf low ratio exceeds 10.0%, the lower S / N data at the lower molecular weight tail of the MWD is not used for the low M-SCBDI calculation.

[0247] Figure 5 shows a graph of SCBD versus the molecular weight (Log M) of IE3. IE3 meets all the requirements for performing both low and high M-SCBDI calculations. It contains sufficient SCB / 1000C data points on either side of Log(M SCB峰 ) = 4.98 and also meets the minimum dWf ratio requirement.

[0248]

[0249]

[0250] Compared with the commercially available resin (CS1), the compositions (IE1 - IE3) of the present invention exhibit a better balance of abuse and stiffness properties (Table 7). These compositions IE1 - IE3 of the present invention are achieved through specific design features of each component. It has been found that the HDPE component with a broad molecular weight distribution Mw(abs) / Mn(abs) > 4 is a key feature for providing a better balance of properties. However, this HDPE component with a broad molecular weight distribution needs to be combined with a suitable polyethylene reinforcing resin to maximize the performance provided by the polyethylene composition. Specifically, it has been found that both density and long chain branching frequency (LCBf) are key design elements of the polyethylene reinforcing component. When comparing the properties of the compositions (CS3 - CS6) containing Reinforcer 3 with a density of 0.868 g / cc and the compositions (CS7 - CS10) containing Reinforcer 2 with a density of 0.898 g / cc in Table 7, an increase in MD tear resistance and MD / CD modulus was observed for the formulations containing Reinforcer 2, while the CD tear resistance, puncture resistance, and IDI energy remained relatively unchanged. When comparing the properties of the polyethylene compositions (IE1 - IE3) containing Reinforcer 1 with the compositions (CS7 - CS10) containing Reinforcer 2 in Table 7, where both reinforcers have a density of 0.898 g / cc but the LCBf / 1000C values are 0.001 and 0.026 respectively, an increase in both IDI and puncture resistance was observed while still maintaining the tear resistance and modulus properties achieved with Reinforcer 2.

[0251] Further comparison of the properties of IE1 - IE3 and CS11 in Table 7 reinforces the need for the HDPE component with a broad molecular weight distribution in the composition, which provides a material with a better balance of IDI energy, tear resistance, puncture resistance, and stiffness.

[0252] IE1 contains PCR. It is known that PCR has contaminants that can reduce mechanical properties. Nevertheless, IE1 still provides a way to produce a material that provides performance comparable to the commercially available virgin resin (CS1).

[0253] In particular, it is desirable that the present disclosure is not limited to the embodiments and descriptions contained herein, but includes modifications of those embodiments, which include combinations of parts of the embodiments and elements of different embodiments that fall within the scope of the following claims.

Claims

1. A polyethylene composition, the polyethylene composition comprising: (A) at least 50 wt% of high-density polyethylene, the high-density polyethylene having (i) 0.950 g / cm 3 to 0.970 g / cm 3 of density, (ii) A melt index (I 2 ) of from 0.2 g / 10 minutes to 2 g / 10 minutes (iii) A molecular weight distribution (M w(abs) / M n(abs) ) greater than 4.0 to 30.0; (B) Polyethylene reinforcing agent, the polyethylene reinforcing agent being an ethylene / C 4 -C 8 α-olefin copolymer and having (i) A density of 0.880 g / cm 3 to 0.910 g / cm 3 and (ii) a melt index of 0.2 g / 10 min to 2.0 g / 10 min, and (iii) an LCBf / 1000C value of less than 0.015; wherein the polyethylene composition has (1) A density of 0.930 g / cm 3 to 0.940 g / cm 3 and (2) Melt index (I 2 ) of 0.3 g / 10 min to 1.0 g / 10 min (3) an Mw(abs) / Mn(abs) value of 5.0 to 13.0, (4) a low M-SCBDI value of 9.0 to 32.0, (5) a high M-SCBDI value of -8.0 to -15.0, (6) a first polyethylene fraction, the first polyethylene fraction having on an elution curve obtained by an improved comonomer composition distribution (iCCD) analysis method (a) at least one peak in the temperature range of 40 °C to 79 °C, and (b) having an average M of 100,000 g / mol to 200,000 g / mol w , (7) a second polyethylene fraction, the second polyethylene fraction having on the elution curve obtained by the improved iCCD analysis method (a) at least one peak in the temperature range of 80 °C to 120 °C, and (b) having an average M of 90,000 g / mol to 250,000 g / mol w and (8) The average M of the first polyethylene fraction of 0.6 to 1.2 w to the average M of the second polyethylene fraction w ratio.

2. The composition according to claim 1, wherein the composition comprises (A) 50 wt% to 80 wt% of the high-density polyethylene; and (B) 50 wt% to 20 wt% of the polyethylene enhancer.

3. The composition according to any one of claims 1 to 2, wherein the composition has a molecular weight distribution (M w(abs) / M n(abs) ) greater than 5.

0.

4. The composition according to any one of claims 1 to 3, wherein the high density polyethylene has a molecular weight distribution (M w(abs) / M n(abs) ) greater than 4.

5. The composition according to any one of claims 1 to 4, wherein the high-density polyethylene is post-consumer recycled high-density polyethylene.

6. The composition according to any one of claims 1 to 5, the composition further comprising additives.

7. A film, the film comprising: (A) at least 50 wt% of high-density polyethylene, the high-density polyethylene having (i) a density of 0.950 g / cm 3 to 0.970 g / cm 3 ; (ii) A melt index (I 2 ) of from 0.2 g / 10 minutes to 2 g / 10 minutes (iii) A molecular weight distribution (M w(abs) / M n(abs) ) greater than 4.0 to 30.0; (B) Polyethylene reinforcing agent, the polyethylene reinforcing agent being an ethylene / C 4 -C 8 α-olefin copolymer and having (i) A density of 0.880 g / cm 3 to 0.910 g / cm 3 and (ii) a melt index of 0.2 g / 10 min to 2.0 g / 10 min, and (iii) an LCBf / 1000C value of less than 0.015; wherein the polyethylene composition has (1) A density of 0.930 g / cm 3 to 0.940 g / cm 3 , (2) Melt index (I 2 ) of 0.3 g / 10 min to 1.0 g / 10 min (3) an Mw(abs) / Mn(abs) value of 5.0 to 13.0, (4) a low M-SCBDI value of 9.0 to 32.0, (5) a high M-SCBDI value of -8.0 to -15.0, (6) a first polyethylene fraction, the first polyethylene fraction having on an elution curve obtained by an improved comonomer composition distribution (iCCD) analysis method (a) at least one peak in the temperature range of 40 °C to 79 °C, and (b) having an average M of from 100,000 g / mol to 200,000 g / mol w , (7) a second polyethylene fraction, the second polyethylene fraction having on the elution curve obtained by the improved iCCD analysis method (a) at least one peak in the temperature range of 80 °C to 120 °C, and (b) having an average M of 90,000 g / mol to 250,000 g / mol w and (8) The average M of the first polyethylene fraction of 0.6 to 1.2 w and the average M of the second polyethylene fraction w ratio.

8. The film according to claim 7, wherein the film has properties selected from the group consisting of an instrumented dart impact energy of 0.3 J to 0.6 J; a longitudinal tear strength of 200 gf to 800 gf; a transverse tear strength of 1200 gf to 1700 gf; 50 ft-lbf / in 3 to 130 ft-lbf / in 3 of puncture resistance; a longitudinal 2% modulus of 60 ksi to 75 ksi; a transverse 2% modulus of 70 ksi to 85 ksi; a dynamic coefficient of friction of 0.3 to 0.8; and combinations thereof.

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