Polyethylene composition

Abstract

The present disclosure provides a composition. In one embodiment, there is provided a polyethylene composition comprising (A) at least 25% 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 further 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 / lOOC value of less than 0.015. The polyethylene composition has (1) a density of from 0.915 g / cm3 to 0.925 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 11.0, (4) a low M-SCBDI value of from 9.0 to 25.0, (5) a high M-SCBDI value of from-8.0 to-12.0, (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, the present invention relates to a polyethylene composition comprising: (1) a first polyethylene fraction having (a) at least one peak in a temperature range of 80 DEG C to 120 DEG C, and (b) having an average Mw of 100,000 g / mol to 200,000 g / mol, (7) a second polyethylene fraction having (a) at least one peak in a temperature range of 80 DEG C to 120 DEG C on an elution curve obtained via an improved iCCD analysis method, and (b) having an average Mw of 90,000 g / mol to 250,000 g / mol, 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 Art

[0001] Polyethylene compositions for packaging applications, films, multilayer structures and packaging products made therefrom are known. For packaging applications, polyethylene compositions require toughness to present a combination of good tear strength simultaneously. The abuse performance (e.g., impact resistance, puncture resistance and tear resistance) balance of achieving enhancement without sacrificing overall material rigidity remains a general challenge in the art. Along with packaging design developing to single material structure to support packaging sustainability efforts, it is increasingly necessary to realize this better balanced material of packaging performance.

[0002] The art recognizes that there is a continuing need for polyethylene compositions having a good balance of physical properties at a desired polymer composition density suitable for packaging applications. Summary of the invention

[0003] The present disclosure provides a composition. In one embodiment, a polyethylene composition is provided, the polyethylene composition comprising (A) at least 25 wt% of a high-density polyethylene having (i) 0.950 g / cm 3 Up to 0.970g / cm 3 (ii) a melt index of 0.2 g / 10 min to 2 g / 10 min (I 2 ), and (iii) a molecular weight distribution (M w(abs) / M n(abs) The polyethylene composition further comprises (B) a polyethylene reinforcing agent, wherein the polyethylene reinforcing agent is ethylene / C 4 -C 8 α-olefin copolymer having (i) 0.880 g / cm 3 Up to 0.910g / cm 3 The polyethylene composition has (1) a density of 0.915 g / cm 3 Up to 0.925g / cm 3 density, (2) a melt index (I) of 0.3 g / 10 min to 1.0 g / 10 min 2), (3) a Mw(abs) / Mn(abs) value of 5.0 to 11.0, (4) a low M-SCBDI value of 9.0 to 25.0, (5) a high M-SCBDI value of -8.0 to -12.0, (6) a first polyethylene fraction having (a) 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) having an average Mw(abs) value of 100,000 g / mol to 200,000 g / mol w , (7) a second polyethylene fraction, which (a) has at least one peak in the temperature range of 80° C. to 120° C. on an elution curve obtained by 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 The average M of the second polyethylene fraction w ratio.

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

[0005] Figure 1 A graph of the Short Chain Branching Distribution (SCBD) versus Molecular Weight (Log M) for Comparative Sample 1 and the value used to calculate the Molecular Weight Short Chain Branching Distribution Index (M-SCBDI) is provided.

[0006] Figure 2 A plot of the Short Chain Branching Distribution (SCBD) versus molecular weight (Log M) for Comparative Sample 3 and the value used to calculate M-SCBDI is provided.

[0007] Figure 3 A plot of the Short Chain Branching Distribution (SCBD) versus molecular weight (Log M) for Comparative Sample 4 and the value used to calculate M-SCBDI is provided.

[0008] Figures 4 to 5 is a graph of the Short Chain Branching Distribution (SCBD) versus molecular weight (Log M) for Example 1 of the present invention and the value used to calculate M-SCBDI.

[0009] Figure 6 A graph of the Short Chain Branching Distribution (SCBD) versus molecular weight (Log M) for Inventive Example 3 and the values ​​used to calculate M-SCBDI are provided.

[0010] definition

[0011] Any reference to the Periodic Table of the Elements is to the Periodic Table as published by CRC Press, Inc., 1990-1991. A group of elements in this table is referred to by a new notation for numbering the groups.

[0012] For purposes of U.S. patent practice, the contents of any referenced patent, patent application, or publication are incorporated by reference in their entirety (or their equivalent U.S. versions are incorporated by reference), particularly with respect to disclosure of definitions (to the extent not inconsistent with any definitions specifically provided in this disclosure).

[0013] The numerical range disclosed herein includes all values ​​from the lower limit to the upper limit, and includes the lower limit and the upper limit. For a range containing clear values ​​(e.g., 1 or 2, or 3 to 5, or 6, or 7), any sub-range between any two clear values ​​is included (e.g., the above range 1 to 7 includes 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.).

[0014] Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percentages are based on weight and all test methods are current as of the filing date of this disclosure.

[0015] The term "blend" or "polymer blend" as used refers to a mixture of two or more polymers. A blend may be miscible or immiscible (not phase separated at the molecular level). A blend may or may not be phase separated. A 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 may be achieved by physically mixing two or more polymers at a macroscopic level (e.g., melt blending resins or compounding) or a microscopic level (e.g., simultaneously formed in the same reactor).

[0016] The term "composition" refers to a mixture of materials comprising the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0017] 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 these components, steps, or procedures are specifically disclosed. For the avoidance of any doubt, all compositions claimed through the use of the term "comprising" may include any additional additives, adjuvants, or compounds, whether in polymeric form or otherwise, unless stated to the contrary. Conversely, the term "consisting essentially of excludes any other components, steps, or procedures (except those that are not essential to operability) from the scope of any subsequent statements. The term "consisting of" excludes any components, steps, or procedures that are not specifically described or listed. Unless otherwise stated, the term "or" refers to the listed members individually and in any combination.

[0018] An "ethylene-based polymer" is a polymer that contains more than 50 mole percent (wt%) of polymerized ethylene monomer (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-based polymer" and "polyethylene" are used interchangeably. Ethylene-based polymers may include ethylene homopolymers and ethylene copolymers (meaning units derived from ethylene and one or more comonomers). 3 -C 12 α-olefins or C 4 -C 8 α-olefins) and / or unsaturated esters copolymerized with ethylene.

[0019] 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 bonded to two hydrogen atoms, wherein the chemical unit is polymerized with other such chemical units to form an ethylene polymer composition.

[0020] A "heteroatom" is an atom other than carbon or hydrogen. A heteroatom can be a non-carbon atom from Group IV, Group V, Group VI, and Group VII of the periodic table. Non-limiting examples of heteroatoms include: F, N, O, P, B, S, and Si.

[0021] A "hydrocarbon" is a compound containing only hydrogen and carbon atoms. A "hydrocarbon group" (or "hydrocarbon group") is a hydrocarbon having a valence (usually a single valence). A hydrocarbon may have a straight chain structure, a cyclic structure, or a branched structure.

[0022] "Linear low density polyethylene" (or "LLDPE") is a linear ethylene / α-olefin copolymer containing a heterogeneous distribution of short chain branches, the copolymer comprising units derived from ethylene and units derived from at least one C 3 -C 10 α-olefin comonomer or at least one C 4 -C8 α-olefin comonomer or at least one C 6 -C 8 Units of α-olefin comonomers. LLDPE is characterized by minimal 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, each available from The Dow Chemical Company, TM Linear low density polyethylene resin and DOWLEX TM Polyethylene resin; and MARLEX TM Polyethylene (available from Chevron Phillips).

[0023] "Low density polyethylene" (or "LDPE") consists of ethylene homopolymer or ethylene copolymer with acrylate, vinyl acetate and / or vinyl silane as comonomers, 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 Company), LUPOLEN TM (LyondellBasell) and LDPE products from Borealis, Ineos, ExxonMobil, etc.

[0024] "Medium density polyethylene" (or "MDPE") is an ethylene homopolymer or a polymer comprising at least one C 3 -C 10 α-olefins or C 3 -C 4 An ethylene / alpha-olefin copolymer of an alpha-olefin having a density of 0.926 g / cc to 0.940 g / cc.

[0025] An "olefin" is an unsaturated aliphatic hydrocarbon having a carbon-carbon double bond.

[0026] "Olefin-based polymers" (interchangeably referred to as "polyolefins") are polymers containing a majority weight % polymerized olefin monomer (based on the total amount of polymerizable monomers) and optionally may contain at least one comonomer. Non-limiting examples of olefin-based polymers include ethylene-based polymers and propylene-based polymers.

[0027] As used herein, the term "polymer" or "polymeric material" refers to a compound prepared by polymerizing monomers, whether monomers of the same type or different types, which provide multiple and / or repeating "units" or "monomer units" constituting the polymer in a polymerized form. Therefore, the general term polymer covers the term homopolymer, which is usually used to refer to polymers prepared from only one type of monomer, and the term copolymer, which is usually used to refer to polymers prepared from at least two types of monomers. The general term also covers all forms of copolymers, such as random copolymers, block copolymers, etc. The terms "ethylene / α-olefin polymer" and "propylene / α-olefin polymer" represent copolymers prepared by polymerizing ethylene or propylene and one or more additional polymerizable α-olefin monomers, respectively, as described above. It should be noted that although polymers are generally referred to as "made of" one or more specified monomers, "based on" a specified monomer or monomer type, "containing" a specified monomer content, etc., in this context, the term "monomer" should be understood to refer to the polymerized residue of the specified monomer rather than the unpolymerized substance. In general, polymers are referred to herein as "units" based on the polymerized form of the corresponding monomers.

[0028] A "propylene-based polymer" is a polymer that contains more than 50 mole percent 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-based polymer" and "polypropylene" are used interchangeably. Non-limiting examples of propylene-based polymers (polypropylenes) are those having at least one C 2 or C 4 -C 10 Propylene / α-olefin copolymers with α-olefin comonomers.

[0029] Test Method

[0030] Coefficient of Friction (COF) The film samples to be tested are conditioned in an environment of 23°C (±2°C) and 50% RH (±10%) for at least 40 hours. According to ASTM standards, the standard test conditions are 23°C (±2°C) and 50% RH (±10%).

[0031] The metal-to-film COF was tested using an INSTRON 5564 universal testing machine. The sample of the film sample was cut to 3 inches by 6 inches. A B-type slide was used, which was 2.5 inches by 2.5 square inches and weighed 195g. The sample was tightly wrapped around the slide, aligning the longitudinal direction (MD) parallel to the direction of movement. This was aided by using a double-sided tape pre-attached to the top surface of the slide. Unless otherwise specified, all samples were single-layer films, so either side of the film could be wrapped onto the slide. In addition, it was ensured that there were no wrinkles on the surface of the film to be tested. A COF measuring fixture consisting of a rigid plate with a low-friction pulley was attached to the fixed base of the device. A metal plate was then placed on top of the above-mentioned rigid plate and subsequently used as a plane on which the slide was driven. The slide with the film sample attached was then placed on a metal plane and attached to a nylon tow rope, which was passed around the pulley and attached to the crosshead of the test frame. The crosshead was then driven a distance of 3 inches at a speed of 6 inches / minute. The force at which the sample begins to move (the initial peak in the load-displacement data) is the static force (FS). The average force calculated between 0.5 inches and 3 inches of movement is the dynamic force (FK). The static COF (μS) is the ratio of the static force (FS) to the normal force (= weight of the slide, W). Similarly, the dynamic COF (μK) is the ratio of the dynamic force (FK) to the normal force. Five replicates are performed for each sample and the average is reported. The coefficient of friction is dimensionless. The COF reported is the dynamic COF (interchangeably referred to as "power COF").

[0032] density Measured according to ASTM D792, Method B. Results are reported in grams per cubic centimeter (g / cc).

[0033] Improved comonomer content analysis method (iCCD)

[0034] An improved method for comonomer content analysis (iCCD) was developed in 2015 (Cong and Parrott et al., WO2017040127A1). iCCD testing was performed using a crystallization elution fractionation instrument (CEF) (PolymerChar, Spain) equipped with an IR-5 detector (PolymerChar, Spain) and a two-angle light scattering detector model 2040 (Precision Detectors, now Agilent Technologies). Ortho-dichlorobenzene (ODCB, 99% anhydrous or technical grade) was used. Silica gel 40 (particle size 0.2-0.5 mm, catalog number 10181-3) was obtained from EMD Chemicals (previously used for drying ODCB solvent). The CEF instrument was equipped with an automatic sampler with N2 sweep function. ODCB was bubbled with dry nitrogen (N2) for one hour before use. Sample preparation of membranes or pellets was performed with an autosampler at 160°C with shaking 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 equilibrium 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 were collected at a rate of one data point per second.

[0035] The iCCD column was filled with gold-plated nickel particles (Bright7GNM8-NiS, Nippon Chemical Industrial Co.) in a 15 cm (length) x 1 / 4 inch (ID) stainless steel tube. The column was filled and conditioned according to references (Cong, R.; Parrott, A.; Hollis, C.; Cheatham, M. WO2017040127A1). The final pressure of the TCB slurry filling was 150 bar.

[0036] The column temperature was calibrated by using a reference material, linear homopolymer polyethylene (with zero comonomer content, melt index (I2) of 1.0, polydispersity Mw / Mn of about 2.6 by conventional gel permeation chromatography, 1.0 mg / ml) and a mixture of ODCB containing eicosane (2 mg / ml). The iCCD temperature calibration consisted of four steps: (1) calculation of the delay volume, which was defined as the temperature offset between the measured peak elution temperature of eicosane minus 30.00°C; (2) subtraction of 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, so 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, according to reference (Cerk and Cong et al., US9,688,795), the elution temperature below 30.0°C is linearly extrapolated by using an elution heating rate of 3°C / min.

[0037] The relationship between the comonomer content and elution temperature of iCCD was constructed using 12 reference materials (ethylene homopolymers and ethylene-octene random copolymers prepared by single-site metallocene catalysts, with ethylene equivalent weight average molecular weights of 35,000 g / mol to 128,000 g / mol). All these reference materials were analyzed in the same manner as the previously specified 4 mg / mL. The elution peak temperature reported follows the elution temperature of iCCD at octene mole % to R2 of 0.984 in the figure.

[0038] The molecular weight of the polymer and the molecular weight of the polymer fractions were determined directly from the light scattering (LS) detector (90 degree angle) and the concentration detector (IR-5) by assuming a shape factor of 1 and all virial coefficients equal to zero according to the Rayleigh-Gans-Debys approximation (Striegel and Yau, Modern Size Exclusion Liquid Chromatogram, pp. 242 and 263). The baselines were subtracted from the LS and concentration detector chromatograms. The integration window was set to integrate the entire chromatogram over the elution temperature (temperature calibration specified above) range of 23.0°C to 120°C.

[0039] Calculation of molecular weight (Mw) from iCCD involves the following steps:

[0040] Measure the inter-detector offset. The offset is defined as the geometric volume offset between the LS detector and 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 into a temperature offset by using the elution heat rate and the elution flow rate. Linear high-density polyethylene (with zero comonomer content, melt index (I2) of 1.0, and a polydispersity Mw / Mn of about 2.6 by conventional gel permeation chromatography) is used. The same experimental conditions as the above-mentioned normal iCCD method are used, except for the following parameters: crystallization from 140°C to 137°C at 10°C / min, thermal equilibrium at 137°C for 1 minute as the soluble fraction elution time, the soluble fraction (SF) time is 7 minutes, and elution from 137°C to 142°C at 3°C / min. The flow rate during crystallization is 0.0mL / min. The flow rate during elution is 0.80mL / min. The sample concentration is 1.0mg / mL.

[0041] Prior to integration, each LS data point in the LS chromatogram was shifted to correct for inter-detector offset.

[0042] The baseline subtracted LS and concentration chromatograms were integrated over the entire elution temperature range of step (1). The MW detector constant was calculated using known MW HDPE samples in the range of 100,000 Mw to 140,000 Mw and the area ratios of the LS and concentration integrated signals.

[0043] The Mw of the polymer was calculated 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 in the same manner as specified in (1) above gave a molecular weight of 58,000 g / mol.

[0044] Instrumented Dart Impact (IDI) . The instrumented dart impact (IDI) test follows and complies with ASTM D7192. The membrane is conditioned at 23°C (+ / -2°C) and 50% RH (+ / -10) for at least 40 hours according to ASTM standards. The standard test conditions are 23°C (+ / -2°C) and 50% RH (+ / -10) according to ASTM standards. The probe used is stainless steel polished to a mirror finish and impacts the membrane at 3.3m / s. The force versus displacement curve, peak force, peak energy, displacement, and total energy are reported. IDI energy results are reported in Joules (J).

[0045] 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 a molten state. 2Melt flow rate ratio is measured according to ASTM D 1238, Method A, Condition 190°C / 2.16 kg, and is reported in grams eluted per 10 minutes (g / 10 min). I10 is measured according to ASTM D 1238, Method A, Condition 190°C / 10 kg, and is reported in 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.

[0046] Puncture strength The puncture test determines the resistance of a membrane to penetration by a probe at a standard low rate, single test speed.

[0047] The membranes were conditioned at 23°C (+ / -2°C) and 50% RH (+ / -10%) for at least 40 hours according to ASTM standards.According to ASTM standards, standard test conditions are 23°C (+ / -2°C) and 50% RH (+ / -10%).

[0048] Puncture is measured on a tensile testing machine. Square samples are cut from sheets to a size of approximately 6 inches by 6 inches. The samples are clamped in a 4-inch diameter round sample holder and the puncture probe is pushed 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. A single thickness measurement is made in the center of the sample. For each sample, the maximum force, breaking force, penetration distance, breaking energy, and puncture strength (energy per unit volume of the sample) are determined. A total of 5 samples are tested to determine the average puncture value. The puncture probe is cleaned after each sample using a "Kim-wipe". The puncture value is reported in ft-lbf / in 3 Report.

[0049] 2% secant modulus . Secant modulus is measured as described herein. Before testing at 23°C (±2°C) and 50% RH (±10%) according to ASTM standards, the film samples are conditioned at 23°C (±2°C) and 50% RH (±10%) for at least 40 hours according to ASTM standards. Film strips with a size of 1 inch wide × 8 inches long are cut from the film in the desired direction (longitudinal (MD) and transverse (CD)). The sample is loaded onto the tensile test frame using a wire clamp jaw (flat rubber on one side of the jaw and wire clamp on the other side) with a gauge length set to 4 inches. The sample is then strained to a nominal strain of 5% at a crosshead speed of 2 inches / minute. Secant modulus is measured at a specific strain and is the ratio of stress at a specific strain to a specific strain, as determined from a load-extension curve. Typically, the secant modulus at 1% and 2% strain is calculated. Typically five replicates are tested for each sample. Secant modulus results are reported in ksi (1000psi).

[0050] Tear resistance - machine direction (MD) and cross direction (CD) The Elmendorf Tear Test uses an Elmendorf-type tear tester to determine the average force required to propagate a tear through a specified length of plastic film or nonrigid sheet material after the tear has been initiated.

[0051] The membranes were conditioned at 23°C (+ / -2°C) and 50% RH (+ / -10%) for at least 40 hours according to ASTM standards.According to ASTM standards, standard test conditions are 23°C (+ / -2°C) and 50% RH (+ / -10%).

[0052] The force required to propagate tearing across a film or sheet sample is measured in grams using a precisely calibrated pendulum device. Acting by gravity, the pendulum swings in an arc, thereby tearing the sample from the pre-cut slit. One side of the sample is fixed by the pendulum and the other side is fixed 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 sample used is a "constant radius geometry" as specified in D1922. Samples cut from the MD and CD directions are usually 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° from the vertical are described as "oblique" tearing-this tear should be noted, although the strength value is included in the average strength calculation. Tear resistance results are reported in gf.

[0053] Triple Detection Gel Permeation Chromatography (TDGPC) . The chromatographic system consisted of a PolymerCharGPC-IR (Valencia, Spain) high temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5) and 4 capillary viscometers (DV) connected to a Precision Detectors (now Agilent Technologies) 2-angle laser scattering (LS) detector model 2040. For all absolute light scattering measurements, a 15 degree angle was used for measurement. The autosampler oven chamber was set to 160 degrees Celsius, and the column and detector chambers were set to 150 degrees Celsius. The columns used were 4 Agilent "Mixed A" 30 cm 20 micron linear mixed bed columns. The chromatographic solvent used was 1,2,4 trichlorobenzene and contained 200 ppm of butylated hydroxytoluene (BHT). The solvent source was nitrogen sparged. The injection volume used was 200 microliters, and the flow rate (FR) was 1.0 ml / min.

[0054] Total plate counts for the GPC column set were performed with decane, which was introduced into the blank sample via a micro pump controlled by the PolymerChar GPC-IR system. The plate count of the chromatography system should be greater than 18,000 for 4 Agilent "Mixed A" 30 cm 20 micron linear mixed bed columns.

[0055] The samples were prepared semi-automatically using the PolymerChar "Instrument Control" software, where the target weight of the pellet or film sample was set to 2 mg / mL and the solvent (containing 200 ppm BHT) was added to a septum-capped vial previously sparged with nitrogen by the PolymerChar high temperature autosampler. The samples were dissolved at 160°C for 2 hours under "slow" shaking.

[0056] To monitor the deviation over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly calibrate the pump flow rate (FR) for each sample by the following method: 标称 ): The retention volume (RV) of the corresponding decane peak in the sample (RV FM样品 ) and the retention volume (RV FM校准 ). It is then assumed that any changes in the decane marker peak time are related to the flow rate (FR) during the entire run. 有效 ). 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. TM The software completes the processing of the flow marker peaks. An acceptable flow rate correction is such that the effective flow rate should be within + / - 0.5% of the nominal flow rate.

[0057] FR 有效 =FR 标称 ×(RV FM校准 / RV FM样品 ) (Equation 1)

[0058] To determine the offset of the viscometer and light scattering detectors relative to the IR5 detector, a systematic method for determining multi-detector offset was 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)) using the PolymerChar GPCOne TM The software optimizes the molecular weight range from 115,000 g / mol to 125,000 g / mol for a linear homopolymer polyethylene reference (3.5>M w / M n >2.2) with the narrow standards column calibration results from the narrow standards calibration curve.

[0059] Absolute molecular weight data using PolymerChar GPCOne TM The software was obtained in a manner consistent with that published by Zimm (Zimm, BH, Chem. Phys., 16, 1099 (1948)) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987)). The total injected concentration used to determine the molecular weight is obtained from the mass detector area and the mass detector constant, which is derived from a suitable linear polyethylene homopolymer or one of the polyethylene standards 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 a refractive index concentration coefficient dn / dc of -0.104 mL / g. Typically, the mass detector response (IR5) and the light scattering constant (using GPCOne TM The molecular weight of the polyethylene reference (3.5>M w / M n >2.2). Viscometer calibration (using GPCOne TMThe viscometer constant (measured using GPCOne TM Obtained), which relates the specific viscosity area and injected mass used for calibration standards to their intrinsic viscosity. The chromatographic concentrations were assumed to be low enough to eliminate the effects of the resolved 2nd Virial coefficient (the effect of concentration on molecular weight).

[0060] The absolute molecular weight (M) in each chromatographic slice i )Yes (Using GPCOne TM ) is obtained by dividing the area of ​​the integrated light scattering (LS) chromatogram (taking into account the light scattering constant) by the mass recovered from the mass constant and the mass from each equally spaced data acquisition point (IR i ) minus the baseline from the mass detector (IR5) area of ​​the IR chromatogram. TM ) Linear extrapolation of the end of the chromatogram where the signal-to-noise ratio becomes low i and intrinsic viscosity (IV i ) value, but the extrapolation must be performed in such a way that EQ3 is equal to 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 moment M measured by light scattering n 、M w and M z It is calculated as follows:

[0061]

[0062] LCB frequency (LCB f ) . The long chain branching frequency is calculated 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 having the same molecular weight. In TDGPC practice, a reference polyethylene homopolymer containing no detectable LCB or SCB and having an Mw of approximately 120,000 g / mol and a polydispersity of approximately 3.0 is injected at the beginning of each run train to create a Mark-Houwink linear reference line. A first order linear fit is applied to the logarithm of the intrinsic viscosity and the logarithm of the molecular weight data obtained over the logarithm of the molecular weight range of 4.5 g / mol to 5.8 g / mol to provide linear reference K and α values.

[0063] 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:

[0064] g i '=(IV 样品,i / IV 线性参考,i )(Equation 5),

[0065] 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.

[0066] 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)):

[0067]

[0068] Finally, the average LCBf amount per 1000 carbons in the polymer for all slices (i) can be determined using Equation 7:

[0069]

[0070] 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 13The comonomer content of the copolymers is in the range of 0 SCB / 1000 total C for homopolymers to about 40 SCB / 1000 total C, where total C = carbon in the backbone + carbon in the branches (Cong, R., deGroot, W., Parrott, A., Yau, W., Hazlitt, L., Brown, R., Miller, M., Zhou, Z., Macromolecules, 44, 3062-3072 (2011)), measured by C NMR method, Qiu et al., Anal. Chem. 2009, 81, 8585-8589). Each reference has a weight average molecular weight of 36,000 g / mole to 126,000 g / mole and a molecular weight distribution (M) of 2.0 to 2.5 as measured by GPC. 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 SCB standard polymer properties are shown in Table A.

[0071] Table A: "SCB" Standards

[0072] Comonomer weight % SCB / 1000Total 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

[0073] The “IR5 Area Ratio” (or “IR5 Area Response”) of the “Baseline-Subtracted Area Response of the IR5 Methyl Channel Sensor” to the “Baseline-Subtracted Area Response of the IR5 Measurement Channel Sensor” was calculated for each of the “SCB” standards. 甲基通道面积 / IR5 测量通道面积 ”)” (including standard filters and filter wheels supplied by PolymerChar: Part No. IR5_FWM01 as part of the GPC-IR instrument). A linear fit of SCB frequency to “IR5 area ratio” was constructed in the form of Equation 8 below:

[0074] SCB / 1000Total C=A 0 +[A 1 ×(IR5 甲基通道面积 / IR5 测量通道面积 )] (Equation 8)

[0075] Among them A 0 is the "SCB / 1000 Total C" intercept at the "IR5 Area Ratio" of zero, and A1 is the slope of "SCB / 1000 Total C" versus "IR5 Area Ratio" and represents the increase in SCB / 1000 Total C as a function of "IR5 Area Ratio". For the narrow PDI and narrow SCBD standard materials, the IR5 Area Ratio is equal to the IR5 Height Ratio.

[0076] A "series of linear, baseline-subtracted chromatogram heights" of the chromatogram produced by the "IR5 methyl channel sensor" was established as a function of the column elution volume to produce a baseline-corrected chromatogram (methyl channel). A "series of linear, baseline-subtracted chromatogram heights" of the chromatogram produced by the "IR5 measurement channel" was established as a function of the column elution volume to produce a baseline-corrected chromatogram (measurement channel).

[0077] 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 (each equally spaced index represents 1 data point per second at an elution flow rate of 1 mL / min) within the sample integration range. The "IR5 height ratio" is multiplied by the factor A. 1 , and the coefficient A 0 Add to this result to produce the predicted SCB frequency for the sample.

[0078] The comonomer composition values ​​are therefore reported as octene comonomer equivalent SCB / 1000 Total C at each index i and plotted as absolute molecular weight (M) at the corresponding i index. i The absolute molecular weight values ​​measured by light scattering are also plotted as dWf / dLog(M i ) for Log(M i ) molecular weight distribution, where Log(M i ) with an increment of 0.01. Thus, two distributions are defined.

[0079] 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:

[0080]

[0081] Among them LS 峰值最大值 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 consisting of at least 10% of the total GPC run time length, and LS 噪声 It is in LS 基线 Calculate the standard deviation of the same data array used.

[0082] SCB / 1000 Total C Comonomer Distribution (Log(M i ) function) is divided into two parts: high molecular weight region and low molecular weight region. These regions are limited to the maximum peak of the SCB / 1000 total C distribution (SCB / 1000C peak) and its corresponding Log (M i ) value (expressed as Log(M SCB峰 ))nearby.

[0083] For the calculation of high absolute molecular weight SCB distribution index (high M-SCBDI), in [Log(M SCB峰 )+0.1] to [Log(M SCB峰 )+0.6] in the range of Log(M i ) value defines the "high LogM 范围 ", that is, higher than Log(M SCB峰 )0.5LogM region. Calculation of high M-SCBDI values ​​requires at least 51 non-zero data points equally spaced in 0.01 increments on the x-coordinate. The corresponding SCB / 1000 total C (y-axis) and Log(M) within this defined range are i The EXCEL linear regression function (LINETT) performed on (x-axis) produced a slope value defined as the high M-SCBDI value.

[0084] For the calculation of low absolute molecular weight SCB distribution index (low M-SCBDI), in [Log(M SCB峰 )-0.6] to [Log(M SCB峰 )-0.1] range Log(M i ) value defines the "low LogM 范围 ", that is, lower than Log(M SCB峰 )0.5LogM region. The calculation of the low M-SCBDI value requires at least 51 non-zero data points equally spaced in 0.01 increments on the x-coordinate. The EXCEL linear regression function (LINEST) within this limited range SCB / 1000 total C (y axis) and Log (M i ) (x-axis) values ​​yield slope values ​​defined as low M-SCBDI values.

[0085] If high or low Log M is not met 范围 Non-zero Log(M i ) value is higher or lower than Log(M SCB峰) values, 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 false peaks are not identified from low signal-to-noise data. In addition, all Log(M) used in the linear regression for low and high M-SCBDI calculations i ) values ​​must have corresponding dWf / dLogM values ​​from the absolute molecular weight distribution that are greater than the peak (LogM p ) at the maximum dWf / dLogM value (i.e., dWf / LogM p ) of 10%. DETAILED DESCRIPTION

[0086] The present disclosure provides a polyethylene composition. In one embodiment, the polyethylene composition comprises (A) at least 25 wt% of a high-density polyethylene having (i) 0.950 g / cm 3 Up to 0.970g / cm 3 (ii) a melt index (I) of 0.2 g / 10 min to 2.0 g / 10 min 2 ), and (iii) a molecular weight distribution (M w(abs) / M n(abs) The polyethylene composition further comprises (B) a polyethylene reinforcing agent, wherein the polyethylene reinforcing agent is ethylene / C 4 -C 8 α-olefin copolymer having (i) 0.880 g / cm 3 Up to 0.910g / cm 3 The polyethylene composition has (1) a density of 0.915 g / cm 3 Up to 0.925g / cm 3 density, (2) a melt index (I) of 0.3 g / 10 min to 2.0 g / 10 min 2 ), (3) a Mw(abs) / Mn(abs) value of 5.0 to 11.0, (4) a low M-SCBDI value of 9.0 to 25.0, (5) a high M-SCBDI value of -8.0 to -12.0, (6) a first polyethylene fraction having (a) 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) having an average Mw(abs) value of 100,000 g / mol to 200,000 g / mol w, (7) a second polyethylene fraction, which (a) has at least one peak in the temperature range of 80° C. to 120° C. on an elution curve obtained by 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 The average M of the second polyethylene fraction w ratio.

[0087] The polyethylene composition of the present invention comprises (A) at least 25 wt% of a high-density polyethylene. As used herein, "high-density polyethylene" is an ethylene homopolymer or an ethylene / C 4 -C 8 The α-olefin copolymer 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) ).

[0088] In one embodiment the high density polyethylene has

[0089] (i) a density of 0.950 g / cc to 0.970 g / cc, or 0.955 g / cc to 0.970 g / cc;

[0090] (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

[0091] (iii) M 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.

[0092] In one embodiment, the high-density polyethylene is high-density polyethylene post-consumer resin, or "HDPE-PCR". The term "post-consumer resin" (or "PCR") refers to polymeric materials that were previously used as consumer packaging or industrial packaging. In other words, PCR is waste plastic. PCR is typically collected from recycling programs and recycling plants. PCR typically requires additional cleaning and / or treatment before it can be reintroduced into the production line. PCR may contain 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 may contain one or more contaminants. Contaminants may be the result of the use of polymeric materials before they are reused for reuse. In some embodiments, contaminants may include paper, ink, food residues, or other recycled materials other than polymers, which may be generated from the recycling process. It should be understood that PCR differs from post-industrial recycled (PIR) resins in that the latter have not been exposed to consumers. It should be understood that similar principles described herein for PCR also apply to PIR resins.

[0093] PCR is different from virgin polymeric material. 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 a heat treatment or molding process other than that associated with the initial manufacture of pellets or granules. The physical, chemical and flow properties of PCR resins are different when compared to virgin polymeric resins.

[0094] 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:

[0095] (i) a density of 0.950 g / cc to 0.970 g / cc, or 0.955 g / cc to 0.970 g / cc;

[0096] (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

[0097] (iii) M 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)).

[0098] Non-limiting examples of suitable HDPE-PCR include those manufactured 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, KWR102-8812BLK, KWR102, KWR105-7525, KWR-105M2 and KWR105M4.

[0099] The polyethylene composition comprises (B) a polyethylene reinforcing agent. As used herein, a "polyethylene reinforcing agent" is an ethylene-based polymer from the group of single-site catalyzed linear low-density polyethylenes, including both linear low-density resins and substantially linear low-density resins (m-LLDPE); ethylene-based plastomers (POPs) and ethylene-based elastomers (POEs). The polyethylene reinforcing agent is an ethylene / C 4 -C 8 α-olefin copolymer having (i) 0.880 g / cm 3 Up to 0.910g / cm 3 The present invention relates to a polyurethane elastomer having a density of (i) 0.2 g / 10 min to 2.0 g / 10 min, (ii) a melt index of 0.2 g / 10 min to 2.0 g / 10 min, and (iii) a LCBf / 1000C value of less than 0.015.

[0100] In one embodiment, the polyethylene composition consists of

[0101] (A) at least 25% by weight of high-density polyethylene having

[0102] (i) a density of 0.950 g / cc to 0.970 g / cc, or 0.955 g / cc to 0.970 g / cc;

[0103] (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

[0104] (iii) M 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) )

[0105] and

[0106] (B) a polyethylene reinforcing agent, the polyethylene reinforcing agent being ethylene / C 4 -C 8 α-olefin copolymer having

[0107] (i) 0.880 g / cm 3 Up to 0.910g / cm 3 density; and

[0108] (ii) a melt index of 0.2 g / 10 minutes to 2.0 g / 10 minutes, and

[0109] (iii) an LCBf / 1000C value of less than 0.015, and

[0110] The polyethylene composition has

[0111] (1) 0.915 g / cm 3 Up to 0.925g / cm 3 The density of

[0112] (2) Melt index (I) of 0.3 g / 10 min to 1.0 g / 10 min 2 ),

[0113] (3) Mw(abs) / Mn(abs) values ​​of 5.0 to 11.0,

[0114] (4) Low M-SCBDI values ​​of 9.0 to 25.0,

[0115] (5) High M-SCBDI values ​​ranging from -8.0 to -12.0,

[0116] (6) a first polyethylene fraction having an elution curve obtained by an improved comonomer composition distribution (iCCD) analysis method.

[0117] (a) having at least one peak in the temperature range of 40°C to 79°C, and

[0118] (b) having an average M of 100,000 g / mol to 200,000 g / mol w ,

[0119] (7) a second polyethylene fraction having an elution curve obtained by the improved iCCD analysis method.

[0120] (a) having at least one peak in the temperature range of 80°C to 120°C, and

[0121] (b) having an average M of 90,000 g / mol to 250,000 g / mol w ,and

[0122] (8) The average M of the first polyethylene fraction is 0.6 to 1.2 w The average M of the second polyethylene fraction w ratio.

[0123] The polyethylene composition has a thickness of 0.915 g / cm 3 Up to 0.925g / cm 3 density, a melt index (I 2 ) and Mw(abs) / Mn(abs) values ​​of 5.0 to 11.0.

[0124] The polyethylene composition has a low M-SCBDI value of 9.0 to 25.0 and a high M-SCBDI value of -8.0 to -12.0.

[0125] 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 corresponding temperature ranges in the elution curves obtained via an improved comonomer composition distribution (iCCD) analysis method (hereinafter interchangeably referred to as "iCCD").

[0126] The first polyethylene fraction is located in the first polyethylene fraction region defined by the temperature range of 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 of 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 below 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 below the single peak of the second polyethylene fraction in the iCCD elution curve, the second polyethylene fraction having 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 corresponding single peak. The polyethylene composition has an 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 wThe average M of the second polyethylene fraction w ratio.

[0127] In one embodiment, the polyethylene composition comprises

[0128] (A) 25 to 75 wt%, or 30 to 60 wt%, or 30 to 40 wt%, or 31 to 36 wt% of a high-density polyethylene having

[0129] (i) 0.950 g / cm 3 Up to 0.970g / cm 3 , or 0.955g / cm 3 Up to 0.970g / cm 3 The density of

[0130] (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

[0131] (iii) a molecular weight distribution of greater than 4.0 to 30.0, or greater than 6.0 to 25

[0132] (M w(abs) / M n(abs) );

[0133] (B) 75 wt % to 25 wt %, or 70 wt % to 40 wt %, or 70 wt % to 60 wt %, or 69 wt % to 64 wt % of a polyethylene reinforcing agent, the polyethylene reinforcing agent being ethylene / C 4 -C 8 α-olefin copolymer having

[0134] (i) 0.880 g / cm 3 Up to 0.910g / cm 3 , or 0.880g / cm 3 To less than 0.900g / cm 3 The density of

[0135] (ii) 0.2 g / 10 min to 2.0 g / 10 min, or 0.3 g / 10 min to 1.0 g / 10 min,

[0136] or a melt index of 0.4 g / 10 min to 0.9 g / 10 min,

[0137] (iii) an LCBf / 1000C value of less than 0.020, or from 0.001 to 0.020, or from 0.001 to 0.015, or from 0.001 to 0.010, and

[0138] The polyethylene composition has

[0139] (1) 0.915 g / cm 3 Up to 0.925g / cm 3 , or 0.918g / cm 3 To 0.921g / cm 3 The density of

[0140] (2) a melt index (I) of 0.3 g / 10 min to 1.0 g / 10 min, or 0.35 g / 10 min to 0.9 g / 10 min. 2 ),

[0141] (3) Mw(abs) / Mn(abs) values ​​of 5.0 to 11.0,

[0142] (4) Low M-SCBDI values ​​of 9.0 to 25.0,

[0143] (5) High M-SCBDI values ​​ranging from -8.0 to -12.0,

[0144] (6) a first polyethylene fraction, the first polyethylene fraction being

[0145] (a) has a single peak in the temperature range of 40°C to 79°C, and

[0146] (b) having 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 ,

[0147] (7) A second polyethylene fraction, which is in the iCCD

[0148] (a) has a single peak in the temperature range of 80°C to 120°C, and

[0149] (b) having 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

[0150] (8) The average M of the first polyethylene fraction is from 0.4 to 1.4, or from 0.6 to 1.3, or from 0.7 to less than 1.0 w The average M of the second polyethylene fraction w The ratio of (hereinafter interchangeably referred to as "Composition 1").

[0151] The polyethylene composition may include one or more optional additives. Non-limiting examples of suitable additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, fillers (e.g., TiO 2 or CaCO 3 ), opacifiers, nucleating agents, processing aids, pigments, primary antioxidants, secondary antioxidants, UV stabilizers, anti-caking agents, slip agents, tackifiers, flame retardants, antimicrobial agents, deodorants, antifungal agents and combinations thereof. Based on the total weight of the polyethylene composition containing such additives, the polyethylene composition of the present invention may include 0.001 wt % to 10 wt %, or 0.01 wt % to 1 wt %, or 0.1 wt % to 0.5 wt % of the combined weight of such additives.

[0152] The present disclosure provides a film. In one embodiment, the film is composed of a polyethylene composition.

[0153] The polyethylene composition consists of the following

[0154] (A) at least 25% by weight of high-density polyethylene having

[0155] (i) a density of 0.950 g / cc to 0.970 g / cc, or 0.955 g / cc to 0.970 g / cc;

[0156] (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

[0157] (iii) M 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) )

[0158] and

[0159] (B) a polyethylene reinforcing agent, the polyethylene reinforcing agent being ethylene / C 4 -C 8 α-olefin copolymer having

[0160] (i) 0.880 g / cm 3 Up to 0.910g / cm 3 density; and

[0161] (ii) a melt index of 0.2 g / 10 minutes to 2.0 g / 10 minutes, and

[0162] (iii) an LCBf / 1000C value of less than 0.015, and

[0163] The polyethylene composition has

[0164] (1) 0.915 g / cm 3 Up to 0.925g / cm 3 The density of

[0165] (2) Melt index (I) of 0.3 g / 10 min to 2.0 g / 10 min 2 ),

[0166] (3) Mw(abs) / Mn(abs) values ​​of 5.0 to 11.0,

[0167] (4) Low M-SCBDI values ​​of 9.0 to 25.0,

[0168] (5) High M-SCBDI values ​​ranging from -8.0 to -12.0,

[0169] (6) a first polyethylene fraction having an elution curve obtained by an improved comonomer composition distribution (iCCD) analysis method.

[0170] (a) having at least one peak in the temperature range of 40°C to 79°C, and

[0171] (b) having an average M of 100,000 g / mol to 200,000 g / mol w ,

[0172] (7) a second polyethylene fraction having an elution curve obtained by the improved iCCD analysis method.

[0173] (a) having at least one peak in the temperature range of 80°C to 120°C, and

[0174] (b) having an average M of 90,000 g / mol to 250,000 g / mol w ,and

[0175] (8) The average M of the first polyethylene fraction is 0.6 to 1.2 w The average M of the second polyethylene fraction w ratio.

[0176] In one embodiment, the film consists of composition 1.

[0177] 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.

[0178] In one embodiment, the film is a monolayer film.

[0179] In one embodiment, the film is a layer of a multilayer film. The multilayer film may have 2, 3, or 4, or 5, or 6, or 7, or 8, or 9, or 10, or 11 layers.

[0180] The films of the present disclosure can have various 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.

[0181] It should be understood that any of the aforementioned films / layers may also include one or more additives. Non-limiting examples of suitable additives include antioxidants, UV stabilizers, heat stabilizers, slip agents, anti-caking agents, pigments or colorants, processing aids, cross-linking catalysts, flame retardants, fillers and foaming agents. In one embodiment, based on the gross weight of the film, the film comprises 0 wt %, or greater than 0 wt %, or 1 wt % to 1.5 wt %, or 2 wt %, or 2.5 wt %, or 3 wt % of total additives.

[0182] In one embodiment, the film is laminated to another film and comprises a layer formed from the polyethylene composition of the present invention.

[0183] The films of the present invention may be corona treated and / or printed (eg, reverse or surface printed).

[0184] In one embodiment, the films of the present invention are uniaxially oriented (eg, in the machine direction) or biaxially oriented (eg, in the machine direction and the transverse direction).

[0185] In one embodiment, the film has a thickness of 1.5 mils to 2.5 mils, or 1.7 mils to 2.3 mils.The film is composed of a polyethylene composition.

[0186] In one embodiment, the film is composed of a polyethylene composition. The polyethylene composition comprises

[0187] (A) 25 to 75 wt%, or 30 to 60 wt%, or 30 to 40 wt%, or 31 to 36 wt% of a high-density polyethylene having

[0188] (i) 0.950 g / cm 3 Up to 0.970g / cm 3 , or 0.955g / cm 3 Up to 0.970g / cm 3 The density of

[0189] (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

[0190] (iii) a molecular weight distribution (M) of greater than 4.0 to 30.0, or greater than 6.0 to 25 w(abs) / M n(abs) );

[0191] (B) 75 wt % to 25 wt %, or 70 wt % to 40 wt %, or 70 wt % to 60 wt %, or 69 wt % to 64 wt % of a polyethylene reinforcing agent, the polyethylene reinforcing agent being ethylene / C 4 -C 8 α-olefin copolymer having

[0192] (i) 0.880 g / cm 3 Up to 0.910g / cm 3 , or 0.880g / cm 3 To less than 0.900g / cm 3 The density of

[0193] (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,

[0194] (iii) an LCBf / 1000C value of less than 0.020, or from 0.001 to 0.020, or from 0.001 to 0.015, or from 0.001 to 0.010, and

[0195] The polyethylene composition has

[0196] (1) 0.915 g / cm 3 Up to 0.925g / cm 3 , or 0.918g / cm 3 To 0.921g / cm 3 The density of

[0197] (2) a melt index (I) of 0.3 g / 10 min to 1.0 g / 10 min, or 0.35 g / 10 min to 0.9 g / 10 min. 2 ),

[0198] (3) Mw(abs) / Mn(abs) values ​​of 5.0 to 11.0,

[0199] (4) Low M-SCBDI values ​​of 9.0 to 25.0,

[0200] (5) High M-SCBDI values ​​ranging from -8.0 to -12.0,

[0201] (6) a first polyethylene fraction, the first polyethylene fraction being

[0202] (a) has a single peak in the temperature range of 40°C to 79°C, and

[0203] (b) having 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 being

[0204] (a) has a single peak in the temperature range of 80°C to 120°C, and

[0205] (b) having 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

[0206] (8) The average M of the first polyethylene fraction is from 0.4 to 1.4, or from 0.6 to 1.3, or from 0.7 to less than 1.0 w The average M of the second polyethylene fraction w ratio, and

[0207] The film has one, some or all of the following properties:

[0208] (i) an instrumented dart impact energy of 2.5 J to 6 J; and / or

[0209] (ii) a longitudinal tear strength of 400 gf to 800 gf; and / or

[0210] (iii) a transverse tear strength of 800 gf to 1300 gf; and / or

[0211] (iv) 90 ft-lbf / in 3 Up to 190 ft-lbf / in 3 puncture resistance; and / or

[0212] (v) a 2% modulus in the longitudinal direction of 37 ksi to 41 ksi; and / or

[0213] (vi) a transverse direction 2% modulus of 41 ksi to 44 ksi; and / or

[0214] (vii) A dynamic friction coefficient of 0.5 to 0.65.

[0215] By way of example and not limitation, some embodiments of the present disclosure will now be described in detail in the following examples.

[0216] Example

[0217] The materials used in the comparative samples (CS) and the inventive examples (IE) are provided in Table 1A and Table 1B below.

[0218] Table 1A - Relevant properties of reference resins

[0219]

[0220] A. High-density polyethylene

[0221] Table 1B - Relevant properties of high density polyethylene component (A)

[0222]

[0223]

[0224] B. Polyethylene reinforcement and polymerization

[0225] All raw materials (ethylene and 1-octene) and process solvents (narrow boiling range high purity isoparaffin solvent, Isopar-E) were purified with molecular sieves before introduction into the reaction environment. Hydrogen was supplied under pressure in high purity grades without further purification. The reactor monomer feed stream was pressurized to greater than the reaction pressure via a mechanical compressor. Solvent and comonomer feeds were pressurized to greater than the reaction pressure via a pump. Individual catalyst components were manually diluted in batches with purified solvents and pressurized to greater than the reaction pressure. All reaction feed streams were measured with mass flow meters and independently controlled with computer automated valve control systems.

[0226] Use single reactor system.Continuous solution polymerization reactor is made up of non-adiabatic isothermal circulation loop reactor full of liquid that imitates the continuous stirred tank reactor (CSTR) with heat removal.All fresh solvents, monomers, comonomers, hydrogen and catalyst component feeds can be controlled independently.By making the feed stream pass through heat exchanger, the total fresh feed stream (solvent, monomer, comonomer and hydrogen) to reactor is temperature controlled to maintain single solution phase.The total fresh feed to polymerization reactor is injected into reactor at two positions, wherein the reactor volume between each injection position is roughly equal.Control fresh feed with half of the total fresh feed mass flow rate received by each injector.Catalyst component and cocatalyst are provided in table 2 below.

[0227] Table 2

[0228]

[0229] The catalyst components are injected into the polymerization reactor by injection insertion tube. The computer controls the main catalyst component feed to maintain the reactor monomer conversion under the specified target. The co-catalyst component is fed based on the calculated specified molar ratio with the main catalyst component. Immediately after the reactor feed injection position, the feed stream is mixed with the circulating polymerization reactor contents with a static mixing element. The contents of the reactor are continuously circulated through a heat exchanger, which is responsible for removing a large amount of reaction heat, and the temperature of 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.

[0230] The reactor effluent enters a zone where it is deactivated by adding and reacting with a suitable reagent (water). At this 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-hydroxyhydrocinnamate))methane and tris(2,4-di-tert-butyl-phenyl)phosphite.

[0231] After catalyst deactivation and addition of additives, the reactor effluent enters a devolatilization system in which ethylene / octene copolymer is removed from a non-polymer stream. The separated ethylene / octene copolymer melt is pelletized 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 removed from the process. The polymerization conditions of the polyethylene enhancer are provided in Table 3 below.

[0232] Table 3

[0233]

[0234]

[0235] The properties of the polyethylene reinforcement ("Reinforcement") are provided in Table 4 below.

[0236] Table 4 - Properties of polyethylene reinforcement component (B)

[0237]

[0238] C. Polyethylene Composition

[0239] Each pellet component is fed into the hopper with 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 to the blown film die. The LTE feed throat is set to 193°C, and the remaining barrel, conveying section and die temperatures are set and maintained at 215°C. A single-layer blown film is produced by a 2-inch die diameter blown film production line with a 1.0 mm die gap. In order to produce the film, the film bubble is inflated to a blow-up ratio of 2.5 with pressurized ambient air as the target with an output rate of 2.4 lb / hr / in die circumference. A double-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 for film thickness is 2 mils and is controlled within ±10% by adjusting the roller speed. The film is wound into rolls.

[0240]

[0241]

[0242] The polyethylene composition of the present invention has a unique SCBD curve shape over polymer molecular weight. This unique SCBD shape is defined by a peak and two slope calculations on each side of the peak (referred to as "low M-SCBDI" and "high M-SCBDI").

[0243] Figure 1 is a graph showing the SCBD over molecular weight (Log M) for Comparative Sample 1 (CS1). A linear regression using the excelLINEST function or similar function is applied to the x-coordinate absolute Log M values ​​and their corresponding y-coordinate SCB / 1000C values ​​over the molecular weight range of Log M = 4.17-5.17 (15,000 g / mol-150,000 g / mol). The resulting fitted slope value, called the molecular weight short chain branching distribution index (M-SCBDI), describes the magnitude of the comonomer variation as a function of molecular weight and whether the incorporation is positive, negative, or uniform. CS1 lacks the key features that characterize the compositions of the present invention in the SCBD vs. log M graph. In this case, a single slope value of -1.3 would adequately describe the comonomer incorporation over Log M.

[0244] Figure 2 CS3 shows that the necessary calculation conditions are not met to produce low M-SCBDI and high M-SCBDI values ​​(i.e., only low M-SCBDI calculations are possible). The molecular weight peak at the SCB / 1000C peak (Log(M SCB峰)) is 5.36. SCB峰 )-0.6] to [Log(M SCB峰 )-0.1]. In this case, the calculation range for low M-SCBDI spans from LogM=4.76 to LogM=5.26. CS3 meets the calculation criteria of requiring 51 consecutive equally spaced data points within the defined 0.5LogM calculation range for low M-SCBDI. SCB峰 )+0.1] to [Log(M SCB峰 )+0.6]. In this case, the calculation range for high M-SCBDI spans from LogM=5.46 to LogM=5.96. CS3 does not meet the calculation criteria of requiring 51 consecutive equally spaced data points within the defined 0.5LogM calculation range for high M-SCBDI. Therefore, high M-SCBDI cannot be calculated, and CS3 does not meet the requirements of the composition of the present invention.

[0245] Figure 3 CS4 is a graph showing the SCBD over molecular weight (Log M) of CS4. CS4 shows that the data quality parameters necessary for the calculation conditions of low M-SCBDI and high M-SCBDI are not met. In this case, there are a sufficient number of data points on either side of the SCB / 1000C peak to calculate both low M-SCBDI and high M-SCBDI. However, the requirement of a "minimum dWf ratio" of 10.0% or more determined by the ratio of the lowest value of either "dWf low" or "dWf high" to the value of "dWf at Mp" is not met, 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 at Mp is the dWf / dLogM at the peak of the molecular weight (Log M) distribution. In the case of CS4, dWf low = 0.672, dWf high = 0.055, and dWf at Mp = 0.93. Therefore, the minimum dWf ratio = 0.055 / 0.93*100 = 5.9%, which is below the requirement of 10% minimum data quality. This means that the data used in the high M-SCBDI calculations are from the tail of the MWD distribution with a low signal-to-noise ratio (S / N).

[0246] Figures 4 to 5 is a graph showing the SCBD on the molecular weight (Log M) of IE1. Figure 4 The relevant details of the high M-SCBDI calculation are shown for IE1. The calculation of high M-SCBDI first requires the identification of the SCB / 1000C peak and its corresponding Log(MSCB峰 ) value. For IE1, Log(M SCB峰 )=5.05. The calculation range for high M-SCBDI values ​​is limited to [Log(M SCB峰 )+0.1] to [Log(M SCB峰 )+0.6]. For IE1, the upper and lower limits for the high M-SCBDI calculation range are LogM=5.65 and LogM=5.15, respectively. A linear regression using the LINEST function in Excel or a similar function is applied to the x-coordinate LogM values ​​and the corresponding y-coordinate SCB / 1000C values ​​within this range to generate a slope value that 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 calculation. The "dWf High Ratio" uses the dWfLogM p =0.85 (i.e., the dWf / dLogM value at the molecular weight peak of the Abs MWD curve) and dWfhigh = 0.198 (corresponding to the lowest dWf / dLogM value in the high M-SCBDI calculation). In this case, dWfhigh ratio = 0.198 / 0.85*100 = 23.3%. Since the dWfhigh ratio exceeds 10.0%, the lower S / N data at the higher molecular weight tail of the MWD are not used for the high M-SCBDI calculation.

[0247] exist Figure 5 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 )=5.05. The calculation range for low M-SCBDI values ​​is limited to [Log(M SCB峰 )-0.6] to [Log(M SCB峰 )-0.1]. For IE1, the upper and lower limits for the low M-SCBDI calculation range are LogM=4.95 and LogM=4.45, respectively. A linear regression using the LINEST function in Excel or a similar function is applied to the x-coordinate LogM values ​​and the corresponding y-coordinate SCB / 1000C values ​​within this range to generate a slope value that 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 calculation. The "dWf Low Ratio" uses the dWfLogM p=0.85 (i.e., the dWf / dLogM value at the molecular weight peak of the Abs MWD curve) and dWflow = 0.464 (the corresponding lowest dWf / dLogM value in the low M-SCBDI calculation). For IE1, dWflow ratio = 0.464 / 0.85*100 = 54.6%. Since the dWflow ratio exceeds 10.0%, the lower S / N data at the lower molecular weight tail of the MWD are not used for the low M-SCBDI calculation.

[0248] Figure 6 A plot of SCBD over molecular weight (Log M) of IE3 is shown. IE3 meets all requirements for performing low and high M-SCBDI calculations. It has a high molecular weight (Log M) and a low molecular weight (Log M). SCB峰 )=4.95 contains enough SCB / 1000C data points on either side and also meets the minimum dWf ratio requirement.

[0249]

[0250] Compared with commercially available resins (CS1-CS3), the compositions of the present invention (IE1-IE3) show a better balance of abuse and stiffness properties (Table 7). These compositions of the present invention IE1-IE3 are achieved by specific design features of each component. It is found that the HDPE component with a wide molecular weight distribution Mw (abs) / Mn (abs)> 4 is a key feature that provides a better balance of properties. However, this HDPE component with a wide molecular weight distribution needs to be combined with a suitable polyethylene reinforcing agent resin to maximize the performance provided by the polyethylene composition. Specifically, it is found that both density and long chain branching frequency (LCBf) are key design factors for polyethylene reinforcing agent components. When comparing the performance of the compositions (IE1-IE3) containing reinforcing agent 1 or the compositions (CS8-CS11) containing reinforcing agent 2 with a density of 0.898 g / cc in Table 7 and the compositions (CS4-CS7) containing reinforcing agent 3 with a density of 0.868 g / cc, a significant decrease in the IDI energy of CS4-CS7 and lower MD tear resistance and puncture resistance are observed. When comparing the performance of polyethylene compositions containing Reinforcement Agent 1 (IE1-IE3) with an LCBf / 1000C of 0.001 to compositions containing Reinforcement Agent 2 (CS8-CS11) with an LCBf / 1000C of 0.026 in Table 7, a significant drop in the IDI energy of CS8-CS11 is observed.

[0251] Further comparison of the performance of IE1-IE3 with CS12 in Table 7 reinforces the need for a 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. PCR is known to have contaminants that can degrade mechanical properties. Nevertheless, IE1 provides a way to produce a material that provides comparable performance to several commercially available virgin resins (CS1-CS3).

[0253] It is particularly intended that the present disclosure is not limited to the embodiments and descriptions contained herein, but includes modifications of those embodiments including parts of the embodiments and combinations of elements of different embodiments as appear within the scope of the following claims.

Claims

1. A polyethylene composition, comprising: (A) at least 25% by weight of high-density polyethylene, the high-density polyethylene having (i) 0.950 g / cm 3 Up to 0.970g / cm 3 The density of (ii) a melt index (I) of 0.2 g / 10 min to 2 g / 10 min 2 ), (iii) a molecular weight distribution (M) of greater than 4.0 to 30.0 w(abs) / M n(abs) ); (B) a polyethylene reinforcing agent, wherein the polyethylene reinforcing agent is ethylene / C 4 -C 8 α-olefin copolymer having (i) 0.880 g / cm 3 Up to 0.910g / cm 3 The density of (ii) a melt index of 0.2 g / 10 minutes to 2.0 g / 10 minutes, and (iii) an LCBf / 1000C value of less than 0.015; The polyethylene composition has (1) 0.915 g / cm 3 Up to 0.925g / cm 3 The density of (2) Melt index (I) of 0.3 g / 10 min to 1.0 g / 10 min 2 ), (3) Mw(abs) / Mn(abs) values ​​of 5.0 to 11.0, (4) Low M-SCBDI values ​​of 9.0 to 25.0, (5) High M-SCBDI values ​​ranging from -8.0 to -12.0, (6) a first polyethylene fraction, wherein the first polyethylene fraction has an elution curve obtained by an improved comonomer composition distribution (iCCD) analysis method. (a) having 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, wherein the second polyethylene fraction has an elution curve obtained by the improved iCCD analysis method. (a) having 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 is 0.6 to 1.2 w The average M of the second polyethylene fraction w ratio.

2. The composition according to claim 1, wherein the composition comprises (A) 30 wt% to 60 wt% of said high density polyethylene; and (B) 40 to 70 wt% of the polyethylene reinforcing agent.

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

0. w(abs) / M n(abs) ).

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

5. The composition of 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, further comprising an additive.

7. A film comprising: (A) at least 25% by weight of high-density polyethylene, the high-density polyethylene having (i) 0.950 g / cm 3 Up to 0.970g / cm 3 The density of (ii) a melt index (I) of 0.2 g / 10 min to 2 g / 10 min 2 ), (iii) a molecular weight distribution (M) of greater than 4.0 to 30.0 w(abs) / M n(abs) ); (B) a polyethylene reinforcing agent, wherein the polyethylene reinforcing agent is ethylene / C 4 -C 8 α-olefin copolymer having (i) 0.880 g / cm 3 Up to 0.910g / cm 3 The density of (ii) a melt index of 0.2 g / 10 minutes to 2.0 g / 10 minutes, and (iii) an LCBf / 1000C value of less than 0.015; The polyethylene composition has (1) 0.915 g / cm 3 Up to 0.925g / cm 3 The density of (2) Melt index (I) of 0.3 g / 10 min to 1.0 g / 10 min 2 ), (3) Mw(abs) / Mn(abs) values ​​of 5.0 to 11.0, (4) Low M-SCBDI values ​​of 9.0 to 25.0, (5) High M-SCBDI values ​​ranging from -8.0 to -12.0, (6) a first polyethylene fraction, wherein the first polyethylene fraction has an elution curve obtained by an improved comonomer composition distribution (iCCD) analysis method. (a) having 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, wherein the second polyethylene fraction has an elution curve obtained by the improved iCCD analysis method. (a) having 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 is 0.6 to 1.2 w The average M of the second polyethylene fraction w ratio.

8. The film of claim 7, wherein the film has a property selected from the group consisting of Instrumented dart impact energy of 2.5J to 6J; 400gf to 800gf longitudinal tear strength; 800gf to 1300gf transverse tear strength; 90ft-lbf / in 3 Up to 190 ft-lbf / in 3 Puncture resistance; 2% modulus in the longitudinal direction of 37 ksi to 41 ksi; 2% transverse modulus of 41 ksi to 44 ksi; A dynamic coefficient of friction between 0.5 and 0.65; and A combination of them.

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