EP4073154A1 - Films de polyéthylène orientés biaxialement et leur procédé de production - Google Patents

Films de polyéthylène orientés biaxialement et leur procédé de production

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Publication number
EP4073154A1
EP4073154A1 EP20839168.0A EP20839168A EP4073154A1 EP 4073154 A1 EP4073154 A1 EP 4073154A1 EP 20839168 A EP20839168 A EP 20839168A EP 4073154 A1 EP4073154 A1 EP 4073154A1
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EP
European Patent Office
Prior art keywords
film
psi
mil
polyethylene
ratio
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP20839168.0A
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German (de)
English (en)
Inventor
Nino RUOCCO
Matthew W. Holtcamp
Kevin A. STEVENS
Tamara L. BLANTON
Summer J. BERNHARDT
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Chemical Patents Inc
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ExxonMobil Chemical Patents Inc
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Publication of EP4073154A1 publication Critical patent/EP4073154A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene

Definitions

  • Biaxial orientation of polymer films can be used to improve the strength characteristics while reducing the thickness of films.
  • Packaging applications of biaxially oriented films is dominated by polypropylene. For example, over 60% of the biaxially oriented film market is represented by polypropylene and obtained with sequential tenter process. The strength and success of biaxially oriented polypropylene films is due an excellent processability (broad stretching temperature profile, slow crystallization), good overall properties, attractive costs (high production speed), and good yield (low density).
  • Polyethylene films are of recent interest in the field because polyethylene is more readily recycled. However, polyethylene tends to have a higher crystallinity than polypropylene, making it more difficult to down gauge and maintain a suitable balance of stiffness and toughness characteristics.
  • US 9,068,033 discloses ethylene hexene copolymers having, inter alia, a g' vis of less than 0.8, a melt index, I2, of 0.25 to 1.5 g/10min, that are converted into films.
  • the present disclosure relates to biaxially-oriented polyethylene films comprising polyethylene, such as linear low density polyethylene (LLDPE), with properties that improve processability while maintaining stiffness and high impact resistance.
  • This invention relates to biaxially-oriented polyethylene film comprising polyethylene having: (A) a melt index, I2, of 1.0 g/10 min or greater; (B) a density of 0.92 g/cm 3 to 0.94 g/cm 3 ; (C) a g'LCB of less than 0.8; (D) an Mz of 1,000,000 g/mol or more; (E) an Mw/Mn of 5 or more; (F) an Mw of 100,000 g/mol or more; (G) a ratio of the g'LCB to the g'Zave is greater than 1.0; and (H) a Strain Hardening Ratio of 4 or more, where the film has a 1% secant in the transverse direction of 60,000 p
  • compositions comprising: a biaxially-oriented film comprising a polyethylene having: (A) a melt index, I2, of 1.0 g/10 min or greater; (B) a density of 0.925 g/cm 3 to 0.945 g/cm 3 ; (C) a g' LCB of less than 0.8; (D) an Mz of 1,000,000 g/mol or more; (E) an Mw/Mn of 5 or more; (F) an Mw of 100,000 g/mol or more; (G) a ratio of the g' LCB to the g' Zave is greater than 1.0; and (H) a Strain Hardening Ratio of 4 or more, of 250 g/mil or more, and a ratio of 1% secant MD/1% secant TD is 0.65 or more.
  • the present disclosure also relates to methods comprising: producing a polymer melt comprising polymer described above; extruding a film from the polymer melt; and stretching the film in a machine direction to produce a machine direction oriented (MDO) polyethylene film; and stretching the MDO polyethylene film in a transverse direction to produce a biaxially-oriented polyethylene film.
  • MDO machine direction oriented
  • the present disclosure relates to biaxially-oriented polyethylene films comprising a LLDPE with well-defined properties that improve processability while maintaining mechanical properties such as stiffness, tensile strength, impact and puncture resistance.
  • the polyethylene of the present disclosure has: (A) a melt index, I 2 , of 1.0 g/10 min or greater; (B) a density of 0.925 g/cm 3 to 0.945 g/cm 3 ; (C) a g'LCB of less than 0.8; (D) an Mz of 1,000,000 g/mol or more; (E) an Mw/Mn of 5 or more; (F) an Mw of 100,000 g/mol or more; (G) a ratio of the g'LCB to the g'Zave is greater than 1.0; and (H) a Strain Hardening Ratio of 4 or more, where the film has a 1% secant in the transverse direction of 60,000 psi or more, a Dart Drop of 250 g/mil or more, and a ratio of 1% secant MD/1% secant TD is 0.65 or more.
  • the polyethylene may be further characterized by having: (A) a melt index, I 2 , of 1.5 g/10 min to 5 g/10 min; (B) a density of 0.925 g/cm 3 to 0.945 g/cm 3 ; (C) a g'LCB of less than 0.8 to 0.5; (D) an Mz of 1,200,000 g/mol or more; (E) an Mw/Mn of 5 to 10; (F) an Mw of 100,000 to 200,000 g/mol; (G) a ratio of the g'LCB to the g'Zave of 1.5 to 10; and (H) a Strain Hardening Ratio of 4.5 or more.
  • a melt index, I 2 of 1.5 g/10 min to 5 g/10 min
  • B a density of 0.925 g/cm 3 to 0.945 g/cm 3
  • C a g'LCB of less than 0.8 to 0.5
  • D an Mz of 1,200,000 g/mol or more
  • extruded polyethylene films can be stretched to a greater extent under a wider temperature window and achieve the physical properties like the toughness of thicker films produced with other LLDPEs.
  • room temperature is 25°C.
  • An “olefin,” alternatively referred to as “alkene,” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond.
  • a “polymer” has two or more of the same or different mer units.
  • a “homopolymer” is a polymer having mer units that are the same.
  • polymer as used herein includes, but is not limited to, homopolymers, copolymers, terpolymers, etc.
  • polymer as used herein also includes impact, block, graft, random, and alternating copolymers.
  • polymer shall further include all possible geometrical configurations unless otherwise symmetries.
  • copolymer(s) refers to polymers formed by the polymerization of at least two different monomers (i.e., mer units).
  • the term “copolymer” includes the copolymerization reaction product of propylene and an alpha-olefin, such as ethylene, 1-hexene.
  • a “terpolymer” is a polymer having three mer units that are different from each other.
  • copolymer is also inclusive terpolymers and tetrapolymers, such as, for example, the copolymerization product of a mixture of ethylene, propylene, 1-hexene, and 1-octene.
  • “Different” as used to refer to monomer mer units indicates that the mer units differ from each other by at least one atom or are different isomerically.
  • ethylene polymer or “ethylene copolymer” is a polymer or copolymer comprising at least 50 mole% ethylene derived units
  • a polyethylene is an ethylene polymer.
  • a polymer is referred to as “comprising, consisting of, or consisting essentially of” a monomer, the monomer is present in the polymer in the polymerized / derivative form of the monomer.
  • ethylene content of 35 wt% to 55 wt%
  • the mer unit in the copolymer is derived from ethylene in the polymerization reaction and said derived units are present at 35 wt% to 55 wt%, based upon the weight of the copolymer.
  • a “low density polyethylene,” LDPE, is an ethylene polymer having a density of more than 0.90 g/cm 3 to less than 0.94 g/cm 3 ; this class of polyethylene includes copolymers made using a heterogeneous catalysis process (often identified as linear low density polyethylene, LLDPE) and homopolymers or copolymers made using a high-pressure/free radical process (often identified as LDPE).
  • LLDPE linear low density polyethylene
  • LDPE high-pressure/free radical process
  • a “linear low density polyethylene,” LLDPE, is an ethylene polymer having a density of more than 0.90 g/cm 3 to less than 0.94 g/cm 3 , preferably from 0.910 to 0.935 g/cm 3 and typically having a g'LCB of 0.95 or more.
  • a “high density polyethylene” (“HDPE”) is an ethylene polymer having a density of 0.94 g/cm 3 or more.
  • Density reported in g/cm 3 , is determined in accordance with ASTM 1505-10 (the plaque is and molded according to ASTM D4703-10a, procedure C, plaque preparation, including that the plaque is conditioned for at least forty hours at 23°C to approach equilibrium crystallinity), where the measurement for density is made in a density gradient column.
  • molecular weight, and Mz is z-average molecular weight.
  • Polydispersity index (PDI) is defined to be Mw divided by Mn. Unless otherwise noted, all molecular weights (e.g., Mw, Mn, Mz) are reported in units of g/mol.
  • Gel Permeation Chromatography is a liquid chromatography technique used to measure, inter alia, the molecular weight and polydispersity of polymers.
  • the distribution and the moments of molecular weight e.g., Mw, Mn, Mz, Mw/Mn
  • the comonomer content e.g., C 2 , C 3 , C 6
  • a high temperature Gel Permeation Chromatography Polymer Char GPC-IR
  • IR5 multiple-channel band-filter based Infrared detector IR5
  • 18-angle light scattering detector and a viscometer.
  • TCB Aldrich reagent grade 1,2,4-trichlorobenzene
  • BHT butylated hydroxytoluene
  • the TCB mixture is filtered through a 0.1- ⁇ m Teflon filter and degassed with an online degasser before entering the GPC instrument.
  • the nominal flow rate is 1.0 mL/min, and the nominal injection volume is 200 ⁇ L.
  • the whole system including transfer lines, columns, and detectors is contained in an oven maintained at 145°C.
  • the polymer sample is weighed and sealed in a standard vial with 80- ⁇ L flow marker (heptane) added to it. After loading the vial in the autosampler, polymer is dissolved in the instrument with 8 mL added TCB solvent. The polymer is dissolved at 160°C with continuous shaking for about 1 hour for polyethylene samples or about 2 hours for polypropylene samples.
  • the TCB densities used in concentration calculation is 1.463 g/ml at room temperature and 1.284 g/mL at 145°C.
  • the sample solution concentration is from 0.2 to 2.0 mg/mL, with lower concentrations being used for higher molecular weight samples.
  • the mass recovery can be calculated from the ratio of the integrated area of the concentration chromatography over elution volume and the injection mass, which is equal to the pre-determined concentration multiplied by injection loop volume.
  • the conventional molecular weight (IR molecular weight) is determined by combining universal calibration relationship with the column calibration, which is performed with a series of monodispersed polystyrene (PS) standards ranging from 700 to 10,000,000 gm/mole.
  • PS monodispersed polystyrene
  • the comonomer composition is determined by the ratio of the IR5 detector intensity corresponding to CH2 and CH3 channel calibrated with a series of polyethylene and propylene homo/copolymer standards whose nominal value are predetermined by NMR or FTIR. In particular, this provides the methyls per 1,000 total carbons (CH 3 /1000TC) as a function of molecular weight.
  • the short-chain branch (SCB) content per 1,000TC (SCB/1000TC) can be then computed as a function of molecular weight by applying a chain-end correction to the CH3/1000TC function, assuming each chain to be linear and terminated by a methyl group at each end.
  • the LS detector is the 18-angle Wyatt Technology High Temperature DAWN HELEOSII.
  • the LS molecular weight (M) at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering (Light Scattering from Polymer Solutions; Huglin, M.
  • K c 1 ⁇ c is the polymer concentration determined from the IR5 analysis
  • a 2 is the second virial coefficient
  • P( ⁇ ) is the form factor for a monodisperse random coil
  • a high temperature viscometer such as those made by Technologies, Inc.
  • Viscotek Corporation which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers, is used to determine specific viscosity.
  • One transducer measures the total pressure drop across the detector, and the other, positioned ⁇ s , for the solution flowing through the viscometer is calculated from their outputs.
  • ⁇ 0.695 and K is 0.000579*(1-0.0075*w2b) for ethylene–hexene copolymer where w2b is a bulk weight percent of hexene comonomer
  • ⁇ 0.695 and K is 0.000579*(1-0.0077*w2b) for ethylene–octene copolymer where w2b is a bulk weight percent of octene comonomer
  • the g'Mz is determined by selecting the g' value at the Mz value on the GPC-4D trace produced by the GPC method described above.
  • the Mz value is obtained from the LS detector. For example, if the Mz-LS is 300,000 g/mol, the value on the g' trace on the GPC-4D graph at 300,000 g/mol is used.
  • the g' Mw is determined by selecting the g' value at the Mw value on the GPC-4D trace.
  • the Mw value is obtained from the LS detector. For example, if the Mw-LS is 100,000 g/mol, the value on the g' trace on the GPC-4D graph at 100,000 g/mol is used.
  • the g'Mn is determined by selecting the g' value at the Mn value on the GPC-4D trace.
  • the Mz value is obtained from the LS detector. For example, if the Mn-LS is 50,000 g/mol, the value on the g' trace on the GPC-4D graph at 50,000 g/mol is used.
  • Comonomer contents at the Mw, Mn, and Mz are determined by GPC-4D using the molecular weight values obtained by the LS detector. -8- Anton Paar MCR702 Rheometer. Samples were compression molded at 177°C for 15 minutes (including cool down under pressure). Then, a 25 mm testing disk specimen was die cut from the resulting plaques. Testing was conducted using a 25 mm parallel plate geometry.
  • the material Whenever the SHR is greater than 1, the material exhibits strain hardening.
  • DSC differential scanning calorimetry
  • Tm Melting point or melting temperature
  • Tc crystallization temperature
  • ⁇ H f or H f heat of fusion or heat flow
  • the melting temperature (Tm) and crystallization temperature (T c ) were calculated by integrating the melting and crystallization peaks (area below the curves).
  • the endothermic melting transition is analyzed for onset of transition and peak temperature and is considered to show a broad melting peak if at least 7°C are between the onset of transition and the peak temperature.
  • the melting temperature is defined to be the peak melting temperature (i.e., associated with the largest endothermic calorimetric response in that range of temperatures) from the DSC melting trace.
  • a “peak” occurs where the first derivative of the corresponding curve changes sign from positive value to negative value.
  • MFI Melt flow index
  • I 2 Melt flow index
  • ASTM 1238-13 Goettfert MI-4 Melt Indexer. Testing conditions were set at 190°C and 2.16 kg load. An amount of 5 g to 6 g of sample was loaded into the barrel of the instrument at 190°C and manually compressed. Afterwards, the material was automatically compacted into the barrel by lowering all available weights onto the piston to remove all air bubbles. Data acquisition was started after a 6 minute pre-melting time. Also, the sample was pressed through a die of 8 mm length and 2.095 mm diameter.
  • the terms “machine direction” and “MD” refer to the stretch direction in the plane of the film.
  • the terms “transverse direction” and “TD” refer to the perpendicular direction in the plane of the film relative to the MD.
  • extruding and grammatical variations thereof refer to processes that includes forming a polymer and/or polymer blend into a melt, such as by heating and/or sheer forces, and then forcing the melt out of a die in a form or shape such as in a film.
  • the yield is determined by a 2% off-set method.
  • Tensile at 100% Elongation is calculated as a function of the force at 100% elongation divided by the cross-sectional area of the specimen.
  • Tensile at 100% Elongation Force at 100% Elongation / Cross-Sectional Area.
  • Tensile at 200% Elongation is calculated as a function of the force at 200% elongation divided by the cross-sectional area of the specimen.
  • Tensile at 200% Elongation Force at 200% Elongation / Cross-Sectional Area.
  • the 1% secant modulus is measured of the material stiffness and is calculated as a function of the total force at 1% extension, divided by the cross-sectional area times 100 and reported in PSI units.
  • 1% Secant Modulus Load at 1% Elongation / (Average Thickness (Inches) x Width) x 100.
  • Clarity was determined by ASTM D1746-15.
  • Haze was determined by ASTM D1003-13.
  • Gloss was determined by ASTM D2457-13.
  • Dart drop was determined by phenolic Method A per ASTM D1709-16ae1.
  • Puncture properties including peak force, peak force per mil, break energy, and break energy per mil were determined by ASTM D5748, with the following modifications. Any film sample ⁇ 1 mil thick is placed in a circular clamp approximately 4 inches wide. A stainless steel custom-made plunger/probe with a 3/4” tip and two 0.25mil slip sheets are pressed through the specimen at a constant speed of 10in/min. Results are obtained after failure from five different locations chosen on the standard film strip and averaged. measurement by the value of the thickness of the film. For example, a 2 mil film having a peak force of 50 lbs has a peak force per mil of 25 lbs/mil.
  • Shrink in both Machine (MD) and Transverse (TD) directions was measured as the percentage decrease in length of a 100cm circle of film along the MD and TD, under a heat gun (Model HG-501A) set with an average temperature of 750°F (399°C). The heat gun was centered two inches over the sample and heat was applied until each specimen stopped shrinking.
  • WVTR Water vapor transmission rate
  • hydrocarbyl radical is an element from group 4 of the Periodic Table, e.g. Hf, Ti, or Zr.
  • hydrocarbyl group may be used interchangeably and are defined to mean a group consisting of hydrogen and carbon atoms only.
  • Preferred hydrocarbyls are C1-C100 radicals that may be linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic.
  • radicals include, but are not limited to, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, pentyl, iso-amyl, hexyl, octyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like, aryl groups, such as phenyl, benzyl naphthyl, and the like.
  • alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, pentyl, iso-amyl, hexyl, octyl cyclopropyl, cyclobutyl, cycl
  • a “metallocene” catalyst compound is a transition metal catalyst compound having one, two or three, typically one or two, substituted or unsubstituted cyclopentadienyl ligands bound to the transition metal, typically a metallocene catalyst is an organometallic compound containing two pi-bound cyclopentadienyl moieties (or substituted cyclopentadienyl moieties).
  • Substituted or unsubstituted cyclopentadienyl ligands include substituted or unsubstituted cyclopentadienyl, indenyl, fluorenyl, tetrahydro-s-indacenyl, tetrahydro-as- indacenyl, benz[f]indenyl, benz[e]indenyl, tetrahydrocyclopenta[b]naphthalene, tetrahydrocyclopenta[a]naphthalene, and the like.
  • substituted means that at least one hydrogen atom has been replaced with at least one non-hydrogen group, such as a hydrocarbyl group, a heteroatom, or a heteroatom as -NR* 2 , -OR*, -SeR*, -TeR*, -PR* 2 , -AsR* 2 , -SbR* 2 , -SR*, -BR* 2 , -SiR* 3 , -GeR* 3 , -SnR* 3 , -PbR* 3 , -(CH 2 )q-SiR* 3 , and the like, where q is 1 to 10 and each R* is independently hydrogen, a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted completely
  • substituted hydrocarbyl means a hydrocarbyl radical in which at least one hydrogen atom of the hydrocarbyl radical has been substituted with at least one heteroatom (such as halogen, e.g., Br, Cl, F or I) or heteroatom-containing group (such as a functional group, e.g., -NR* 2 , -OR*, -SeR*, -TeR*, -PR* 2 , -AsR* 2 , -SbR* 2 , -SR*, -BR* 2 , -SiR* 3 , -GeR* 3 , -SnR* 3 , -PbR* 3 , -(CH 2 )q-SiR* 3 , and the like, where q is 1 to 10 and each R* is independently hydrogen, a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted
  • substituted means that a hydrogen group has been replaced with a hydrocarbyl group, a heteroatom, or a heteroatom containing group, such as halogen (such as Br, Cl, F or I) or at least one functional group such as -NR* 2 , -OR*, -SeR*, -TeR*, -PR* 2 , -AsR* 2 , -SbR* 2 , -SR*, -BR* 2 , -SiR* 3 , -GeR* 3 , -SnR* 3 , -PbR* 3 , -(CH 2 )q-SiR* 3 , and the like, where q is 1 to 10 and each R* is independently hydrogen, a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted or unsubstitute
  • halogen such as Br, Cl, F or I
  • inventive ethylene-based copolymers useful herein are preferably made in a process comprising contacting ethylene and of one or more C 3 to C 20 olefins in at least one gas phase reactor at a temperature in the range of from 60°C to 90°C and at a reactor pressure of from 70 kPa to 7,000 kPa, in the presence of a metallocene catalyst system.
  • Preferred metallocene catalyst systems include an activator and a bridged metallocene compound.
  • Particularly useful bridged metallocene compounds include those represented by the following formula:
  • M is a group 4 metal, especially zirconium or hafnium
  • T is a group 14 atom, preferably Si or C
  • D is hydrogen, methyl, or a substituted or unsubstituted aryl group, most preferably phenyl
  • R a and R b are independently, hydrogen, halogen, or a C 1 to C 20 substituted or unsubstituted rocarbyl, and R a and R b can form a cyclic structure including substituted or unsubstituted aromatic, p d, or saturated cyclic or fused ring system
  • each X 1 and X 2 is independently selected from the group consisting of C 1 to C 20 substituted or unsub uted hydrocarbyl groups, hydrides, amides, amines, alkoxides, sulfides, phosphides, halides, dienes, phosphines, and ethers, and X 1 and X 2 can form a cyclic
  • aliphatic, hydrocarbyl refers to hydrocarbyls that have at least one heteroatom bound thereto such as carboxyl, methoxy, phenoxy, BrCH 3 —, NH 2 CH 3 —, etc.
  • Preferred metallocene compounds may be represented by the following formula: wherein R 1 , R 2 , ed above; and R 10 , R 11 , R 12 , R 13 , and R 14 are each independently H or a C 1 to C 40 substituted or unsubstituted hydrocarbyl.
  • Particularly preferred metallocene compounds useful herein are represented by the formula:
  • metallocene compounds useful herein may be represented by the following structure: wh a useful embodiment, R 1 , R 2 , R 3 , R 4 , and R 5 are H, and R a , R b , X 1 , X 2 , T, and M are as defined above.
  • Examples of preferred metallocene compounds include: dimethylsilylene(3- phenyl-1-indenyl)(2,3,4,5-tetramethyl-1-cyclopentadienyl)zirconium dichloride; methyl; bis(n-propyl ccyclopentadienyl)Hf dimethyl bis(n-propyl cyclopentadienyl)Hf dichloride; and the like.
  • the metallocene compound is dimethylsilylene(3- phenyl-1-indenyl)(2,3,4,5-tetramethyl-1-cyclopentadienyl)zirconium dichloride.
  • the polymerization process of the present invention may be carried out using any suitable process, such as, for example, solution, slurry, high pressure, and gas phase.
  • a particularly desirable method for producing polyolefin polymers according to the present invention is a gas phase polymerization process preferably utilizing a fluidized bed reactor.
  • gas phase polymerization processes are such that the polymerization medium is either mechanically agitated or fluidized by the continuous flow of the gaseous monomer and diluent.
  • Other gas phase processes contemplated by the process of the invention include series or multistage polymerization processes.
  • the metallocene catalyst is used with an activator in the polymerization process to produce the inventive polyethylenes.
  • activator is used herein to be any compound which can activate any one of the metallocene compounds described above by converting the neutral catalyst compound to a catalytically active metallocene compound cation.
  • the catalyst system comprises an activator.
  • Activators useful herein include alumoxanes or “non-coordinating anion” activators such as boron-based compounds (e.g., tris(perfluorophenyl)borane, or ammonium tetrakis(pentafluorophenyl)borate).
  • the catalyst systems useful herein can include at least one non-coordinating anion (NCA) activator, such as NCA activators represented by the formula below: Z d + (A d- ) where: Z is (L-H) or a reducible Lewis acid; L is a neutral Lewis base; H is hydrogen; (L-H) is a Bronsted acid; A d- is a boron containing non-coordinating anion having the charge d-; d is 1, 2, or 3.
  • NCA activators represented by the formula below: Z d + (A d- ) where: Z is (L-H) or a reducible Lewis acid; L is a neutral Lewis base; H is hydrogen; (L-H) is a Bronsted acid; A d- is a boron containing non-coordinating anion having the charge d-; d is 1, 2, or 3.
  • the cation component, Z d + may include Bronsted acids such as protons or protonated Lewis bases or reducible Lewis acids capable of protonating or abstracting a moiety, such as an alkyl or aryl, from the bulky ligand metallocene containing transition metal catalyst precursor, resulting in a cationic transition metal species.
  • the activating cation Z d + may also be a moiety such as silver, tropylium, carboniums, ferroceniums and mixtures, preferably carboniums and ferroceniums. Most preferably Z d + is triphenyl carbonium.
  • Preferred reducible Lewis acids can be any triaryl formula: (Ar 3 C + ), where Ar is aryl or aryl substituted with a heteroatom, a C1 to C40 hydrocarbyl, or a substituted C 1 to C 40 hydrocarbyl), preferably the reducible Lewis acids in formula (14) above as "Z" include those represented by the formula: (Ph 3 C), where Ph is a substituted or unsubstituted phenyl, preferably substituted with C1 to C40 hydrocarbyls or substituted a C 1 to C 40 hydrocarbyls, preferably C 1 to C 20 alkyls or aromatics or substituted C1 to C20 alkyls or aromatics, preferably Z is a triphenylcarbonium.
  • Z d + is the activating cation (L-H) d + , it is preferably a Bronsted acid, capable of donating a proton to the transition metal catalytic precursor resulting in a transition metal cation, including ammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof, preferably ammoniums of methylamine, aniline, dimethylamine, diethylamine, N- methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine, triphenylphosphine, and diphenylphosphine, oxomiuns from ethers such as dimethyl ether diethyl ether,
  • each Q is a fluorinated hydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q is a fluorinated aryl group, and most preferably each Q is a pentafluoryl aryl group.
  • suitable A d- also include diboron compounds as disclosed in U.S. Patent No.5,447,895, which is fully incorporated herein by reference.
  • Illustrative, but not limiting examples of boron compounds which may be used as an activating cocatalyst are the compounds described as (and particularly those specifically listed as) activators in US 8,658,556 , which is incorporated by reference herein.
  • the activator Z d + (A d- ) is one or more of N,N-dimethylanilinium tetra(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N- dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-
  • preferred activators may include alumoxane compounds (or “alumoxanes”) and modified alumoxane compounds.
  • Alumoxanes are generally oligomeric compounds containing -Al(R 1 )-O- sub-units, where R 1 is an alkyl group.
  • alumoxanes examples include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane, isobutylalumoxane, and mixtures thereof.
  • Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, particularly when the abstractable ligand is an alkyl, halide, alkoxide, or amide. Mixtures of different alumoxanes and modified alumoxanes may also be used. It may be preferable to use a visually clear methylalumoxane.
  • a cloudy or gelled alumoxane can be filtered to produce a clear solution or clear alumoxane can be decanted from the cloudy solution.
  • Another useful alumoxane is a modified methylalumoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A, disclosed in US 5,041,584).
  • MMAO modified methylalumoxane
  • the activator is an alkylalumoxane, preferably methylalumoxane or isobutylalumoxane, most preferably methylalumoxane.
  • the activator is supported on a support material prior to contact with the metallocene compound.
  • the activator may be combined with the metallocene compound prior to being placed upon a support material.
  • the activator may be combined with the metallocene compound in the absence of a support material.
  • cocatalysts may be used.
  • Aluminum alkyl or organometallic compounds which may be utilized as cocatalysts (or scavengers) include, for example, triethylaluminum, tri-isobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethyl aluminum chloride, dibutyl zinc, diethyl zinc, and the like.
  • the catalyst system comprises an inert support material.
  • the supported material is a porous support material, for example, talc, and inorganic oxides.
  • Other support materials include zeolites, clays, organoclays, or any other organic or inorganic support material, or mixtures thereof.
  • the support material is an inorganic oxide in a finely divided form.
  • Suitable inorganic oxide materials for use in metallocene compounds herein include Groups 2, 4, 13, and 14 metal oxides such as silica, alumina, and mixtures thereof.
  • Other inorganic oxides that may be employed, either alone or in combination, with the silica or alumina are magnesia, titania, zirconia, and the like.
  • suitable support materials can be employed, for -19- Particularly useful supports include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolites, talc, clays, and the like.
  • support materials may be used, for example, silica-chromium, silica-alumina, silica-titania, and the like.
  • Preferred support materials include Al 2 O 3 , ZrO 2 , SiO 2 , and combinations thereof, more preferably SiO 2 , A l 2 O 3 , or SiO 2 /A catalyst system may be suspended in a paraffinic agent, such as mineral oil
  • a paraffinic agent such as mineral oil
  • the polyethylene may be an ethylene homopolymer or an ethylene copolymer, such as ethylene-alpha-olefin (preferably C 3 to C 20 alpha-olefin) copolymers (such as ethylene- butene copolymers, ethylene-hexene copolymers, and/or ethylene-octene copolymers) having an Mw/Mn of 5 or more (preferably 5 to 10).
  • ethylene-alpha-olefin preferably C 3 to C 20 alpha-olefin
  • copolymers such as ethylene-butene copolymers, ethylene-hexene copolymers, and/or ethylene-octene copolymers having an Mw/Mn of 5 or more (preferably 5 to 10).
  • Mw/Mn ethylene-octene copolymers
  • the comonomer content (cumulatively if more than one comonomer is used) of the polyethylene can be 0 mol% (i.e., a homopolymer) to 25 mol% (or 0.5 mol% to 20 mol%, or 1 mol% to 15 mol %, or 3 mol% to 10 mol%, or 6 to 10 mol %) with the balance being ethylene.
  • the ethylene content of the polyethylene can be 75 mol% or more ethylene (or 75 mol% to 100 mol%, or 80 mol% to 99.5 mol%, or 85 mol% to 99 mol%, or 90 mol% to 97 mol%, or 4 to 90 mol%).
  • the comonomer content (cumulatively if more than one comonomer is used) in the polyethylene can be 0 wt% (i.e., a homopolymer) to 25 wt% (or 0.5 wt% to 20 wt%, or 1 wt% to 15 wt %, or 3 wt% to 10 wt%, or 6 to 10 wt %) and the ethylene content of the polyethylene can be 75 wt% or more ethylene (or 75 wt% to 100 wt%, or 80 wt% to 99.5 wt%, or 85 wt% to 99 wt%, or 90 wt% to 97 wt%, or 4 to 90 wt%).
  • the comonomer is present at 6 to 10 wt%, and is preferably a C 3 to C 12 alpha-olefin (preferably one or more of propylene, butene, hexene, and octene).
  • the comonomer can be one or more C 3 to C 20 olefin comonomer (preferably C 3 to C12 alpha-olefin; more preferably propylene, butene, hexene, octene, decene, and/or dodecene; most preferably propylene, butene, hexene, and/or octene).
  • the monomer is ethylene and the comonomer is hexene, preferably from 1 mol% to 15 mol% hexene, or 1 mol% to 10 mol% hexene, or 5 mol% to 15 mol% hexene, or 7 mol% to 11 mol% hexene.
  • A a melt index, I2, of 1.0 g/10 min or greater (or 1.5 to 5 g/10 min, or 1.8 to 4 g/10min, or 1.9 to 3 g/10 min);
  • B a density of 0.925 g/cm 3 to 0.945 g/cm 3 (0.927 g/cm 3 to 0.942 g/cm 3 , or 0.93 g/cm 3 to 0.941 g/cm 3 , or 0.931 g/cm 3 to 0.94 g/cm 3 );
  • C a g'LCB of less than 0.8 (or from 0.78 to 0.5, alternately from 0.75 to 0.5),
  • D an Mz of 1,000,000 g/mol or more, alternately 1,200,000 g/mol or more, alternately 1,300,000 g/mol or more, alternately from 1,200,000 to 3,000,000 g/mol;
  • E an Mw/Mn of 5 or more, alternately 5.5 or more, alternately from 5.5 to 10;
  • F
  • the polyethylene used in films of the present disclosure can have: (A) a melt index, I 2 , of 1.0 g/10 min or greater (or 1.5 to 5 g/10 min, or 1.8 to 4 g/10min, or 1.9 to 3 g/10 min); (B) a density of 0.925 g/cm 3 to 0.945 g/cm 3 (0.927 g/cm 3 to 0.942 g/cm 3 , or 0.93 g/cm 3 to 0.941 g/cm 3 , or 0.931 g/cm 3 to 0.94 g/cm 3 ); (C) a g'LCB of less than 0.8 (or from 0.78 to 0.5, alternately from 0.75 to 0.5), (D) an Mz of 1,000,000 g/mol or more, alternately 1,200,000 g/mol or more, alternately 1,300,000 g/mol or more, alternately from 1,200,000 to 3,000,000 g/mol; (E) an Mw/Mn of 5 or more
  • the polyethylene (including any of the foregoing) used in films of the present disclosure can have an Mz-LS/Mn-Ls of 15 or more, alternately 20 or more.
  • the polyethylene (including any of the foregoing) used in films of the present disclosure can have an Mz-LS/Mw-LS of 6 or more, alternately 8 or more, alternately 10 or more.
  • the polyethylene described herein has at least 7°C (alternately at least 10°C, alternately at least 15°C) between the onset of transition and the melting peak, as shown in the DSC trace.
  • the polyethylene described herein has at least 10°C (alternately at least 15°C, alternately at least 20°C) between the melting peak and the crystallization peak values.
  • Blends [0102] In another embodiment, the polyethylene composition produced herein is combined with one or more additional polymers in a blend prior to being formed into a film.
  • a “blend” may refer to a dry or extruder blend of two or more different polymers, and in-reactor blends, including blends arising from the use of multi or mixed catalyst systems in a single reactor zone, and blends that result from the use of one or more catalysts in one or more reactors under the same or different conditions (e.g., a blend resulting from in series reactors (the same or different) each running under different conditions and/or with different catalysts).
  • Useful additional polymers include other polyethylenes, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random copolymer of propylene and ethylene, and/or butene, and/or hexene, polybutene, ethylene vinyl acetate, LDPE, LLDPE, HDPE, ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethylmethacrylate or any other polymers polymerizable by a high-pressure free radical process, polyvinylchloride, polybutene-1, isotactic polybutene, ABS resins, ethylene- copolymers, polyamides, polycarbonates, PET resins, cross linked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as polystyrene, poly-1 esters, polyacetal, polyvinylidine fluoride, polyethylene glycols, and
  • the polyethylene prepared by the process described herein are preferably formed into films, particularly oriented films, such as biaxially oriented films.
  • the present disclosure relates to oriented polyethylene films comprising a LLDPE with properties that improve processability while providing a good balance between machine and transverse direction stiffness while providing high toughness (or impact resistance).
  • the invention relates to biaxially oriented films comprising polyethylene having: (A) a melt index, I 2 , of 1.0 g/10 min or greater (or 1.5 to 5 g/10 min, or 1.8 to 4 g/10min, or 1.9 to 3 g/10 min); (B) a density of 0.925 g/cm 3 to 0.945 g/cm 3 (0.927 g/cm 3 to 0.942 g/cm 3 , or 0.93 g/cm 3 to 0.941 g/cm 3 , or 0.931 g/cm 3 to 0.94 g/cm 3 ); (C) a g' LCB of less than 0.8 (or from 0.78 to 0.5, alternately from 0.75 to 0.5), (D) an Mz of 1,000,000 g/mol or more, alternately 1,200,000 g/mol or more, alternately 1,300,000 g/mol or more, alternately from 1,200,000 to 3,000,000 g/mol; (E) an Mz of 1,000,000 g
  • the films described herein may also have a gloss of 60% or less, such as 20 to 55%.
  • the films described herein may also have Dart Drop A of 250 g/mil to 1,350 g/mil (alternately 275 g/mil to 1,300 g/mil, or 300 g/mil to 1,250 g/mil).
  • the films of the present disclosure are biaxially stretched in the machine direction (MD) and the transverse direction (TD) and comprise the polyethylene described herein.
  • the films of the present disclosure comprise polyethylene in an amount of at least 90 wt% (or 90 wt% to 100 wt%, or 90 wt% to 99.9 wt%, or 95 wt% to 99 wt%).
  • the polyethylene described herein does not need to be mixed with another polymer to achieve good processability and film properties.
  • the films may comprise additives.
  • additives include, but are not limited to, stabilization agents (e.g., antioxidants or other heat or light stabilizers), anti-static agents, crosslink agents or co-agents, crosslink promoters, release agents, adhesion promoters, plasticizers, anti-agglomeration agents (e.g., oleamide, stearamide, erucamide or other derivatives with the same activity), and fillers.
  • stabilization agents e.g., antioxidants or other heat or light stabilizers
  • anti-static agents e.g., anti-static agents, crosslink agents or co-agents, crosslink promoters, release agents, adhesion promoters, plasticizers, anti-agglomeration agents (e.g., oleamide, stearamide, erucamide or other derivatives with the same activity), and fillers.
  • stabilization agents e.g., antioxidants or other heat or light stabilizers
  • anti-static agents e.g., crosslink agents or co-agent
  • Nonlimiting examples of antioxidants include, but are not limited to, IRGANOX® 1076 (a high molecular weight phenolic antioxidant, available from BASF), IRGAFOS® 168 (tris(2,4-di-tert-butylphenyl) phosphite, available from BASF), and tris(nonylphenyl)phosphite.
  • IRGANOX® 1076 a high molecular weight phenolic antioxidant, available from BASF
  • IRGAFOS® 168 tris(2,4-di-tert-butylphenyl) phosphite, available from BASF)
  • tris(nonylphenyl)phosphite tris(nonylphenyl)phosphite.
  • a nonlimiting example of a processing aid is DYNAMAR® FX-5920 (a free-flowingfluropolymer based processing additive, available from 3M).
  • Methods of producing a biaxially-oriented polyethylene film can comprise: producing a polymer melt comprising a polyethylene described herein; extruding a film from the polymer melt; stretching the film in a machine direction at a temperature below the melting film; and stretching the MDO polyethylene film in a transverse direction to produce the biaxially-oriented polyethylene film.
  • Stretching in the machine direction can be achieved by threading the film through a series of rollers where the temperature and speed of the individual rollers are controlled to achieve a desired film thickness and the stretch ratio of MD stretching.
  • this series of rollers are called MDO rollers or part of the MDO stage of the film production.
  • MDO may include, but are not limited to, pre-heat rollers, various stretching stages with or without annealing rollers between stages, one or more conditioning and annealing rollers, and one or more chill rollers. Stretching of the film in the MDO stage is accomplished by inducing a speed differential between two or more adjacent rollers.
  • the stretch ratio for MD stretching can be used to describe the degree of stretching of the film.
  • the stretch ratio is the speed of the fast roller divided by the speed of the slow roller. For example, stretching a film using an apparatus where the slow roller speed is 1 m/min and fast roller speed is 7 m/min means the stretch ratio was 7 (also referred to herein as 7 times or 7x).
  • the physical amount of stretching of the film is close to but not exactly the stretch ratio because relaxation of the film can occur after stretching.
  • Greater stretch ratios for MD stretching result in thinner films with greater orientation in the MD.
  • the stretch ratio in the machine direction can be 1x to 10x (or 3x to 7x, or 5x to 9x, or 7x to 10x).
  • Stretching in the transverse direction can be achieved by pulling the film from the edges in a tenter frame, which is a series of mobile clips, as the film passes through a stretching zone of a TDO stage oven.
  • the TDO stage oven typically has three zones: (1) a preheat zone that softens the film, (2) a stretch zone that stretches the film in the transverse direction, and (3) an annealing zone where the stretched film cools and relaxes.
  • the stretch ratio for TD stretching can be used to describe the degree of stretching of the film using the tenter frame (as compared to the roller speeds when stretching in the MD).
  • the stretch ratio for TD stretching is increase in width of the tenter from beginning to end of stretching and calculated as end-stretched tenter width divided by the initial tenter width and can be reported a number or number times or numbers as is the case with MD stretching. Greater stretch ratios for TD stretching result in thinner films with greater orientation in the TD.
  • the stretch ratio when stretching the polyethylene films described herein in the transverse undo experimentation can determine suitable temperatures and tenter frame operating parameters in a given TDO stage of film production for producing the desired stretch ratios.
  • the polyethylene descried herein can be stretched in the transverse and or machine direction over a large range of temperatures.
  • the polyethylene can be stretched in the machine direction over a temperature range of at least 3°C, preferably at least 6°C, preferably at least 7°C, preferably at least 8°C, preferably at least 10°C, preferably at least 12°C, alternately from 3 to 20°C, alternately from 5 to 15°C.
  • polyethylene can be stretched in the transverse direction over a temperature range of at least 3°C, at least 5°C, preferably at least 6°C, preferably at least 7°C, preferably at least 8°C, preferably at least 10°C, preferably at least 12°C, alternately from 3 to 20°C, alternately from 3 to 15°C, alternately from 3 to 10°C, alternately from 3 to 6°C.
  • the film can be stretched in the transverse direction without tearing the web and creating gauge inhomogeneities, over an temperature range of at least 3°C, at least 5°C, preferably at least 6°C, preferably at least 7°C, preferably at least 8°C, preferably at least 10°C, preferably at least 12°C, alternately from 3 to 20°C, alternately from 3 to 15°C, alternately from 3 to 10°C, alternately from 3 to 6°C.
  • the film can be stretched in the machine direction without web instability and large gauge variations, over an temperature range of at least 3°C, preferably at least 6°C, preferably at least 7°C, preferably at least 8°C, preferably at least 10°C, preferably at least 12°C, alternately from 3 to 20°C, alternately from 5 to 15°C.
  • the broader stretching temperature range in both MD and TD section allows to have more flexibility in operating the machinery in terms of accessible line speed and stretch ratios.
  • the biaxially-oriented polyethylene films described herein can have a thickness of 3 mils or less (or 0.1 mils to 3 mils, or 0.5 mils to 2 mils, or 0.5 mils to 1.5 mils, or 0.5 mils to 1 mils).
  • the biaxially-oriented polyethylene films described herein may have (i) a 1% secant in the transverse direction of 60,000 psi or more (alternately 70,000 psi to 150,000 psi, or 75,000 psi to 140,000 psi, or 80,000 psi to 130,000 psi) and (ii) a Dart Drop A of 250 g/mil to 1,350 g/mil (alternately 275 g/mil to 1,300 g/mil, or 300 g/mil to 1,250 g/mil).
  • the biaxially-oriented polyethylene films described herein may have (I) a 1% secant in the transverse direction of 60,000 psi or more (alternately 70,000 psi or more, alternately 75,000 psi to 150,000 psi, or 80,000 psi to 140,000 psi, or 90,000 psi to 130,000 psi); (II) a 1% secant in the machine direction of 50,000 psi or more (alternately 60,000 psi or 130,000 psi), and (III) ratio of 1% secant MD/1% secant TD is 0.65 or more, alternately 0.7 more, alternately 0.75 or more, alternately 0.75 to 1, alternately 0.75 to 0.95.
  • the biaxially-oriented polyethylene films described herein can have (I) , (II) and (III) above and one or more of the following properties: (IV) a yield strength in the machine direction of 2,000 psi to 5,000 psi (or 2,200 psi to 4,000 psi) and a yield strength in the transverse direction of 4,000 psi to 15,000 psi (or 5,000 psi to 11,000 psi); (V) a tensile strength in the machine direction of 6,000 psi to 15,000 psi (or 7,500 psi to 14,500 psi, or 8,000 psi to 11,000 psi) and a tensile strength in the transverse direction of 10,000 psi to 30,000 psi (or 11,000 psi to 25,000 psi, or 12,000 psi to 20,000 psi); (VI) a peak force per mil of 10 lbs/mil to
  • the biaxially-oriented polyethylene films described herein have (I) and (II) and one or more of the following properties: (III), (IV), (V), and (VII).
  • the biaxially-oriented polyethylene films described herein have (I) and (II) and one or more of the following properties: (IV) and (V).
  • the biaxially-oriented polyethylene films described herein can have (I) and (II), one or more of (III)-(VIII), and one or more of the following properties: (IX) an average density of 0.925 g/cm 3 to 0.945 g/cm 3 (0.927 g/cm 3 to 0.942 g/cm 3 , or 0.93 g/cm 3 to 0.941 g/cm 3 , or 0.931 g/cm 3 to 0.94 g/cm 3 ); (X) an elongation at yield in the machine direction of 5% to 15% (or 6% to 10%) and an elongation at yield in the transverse direction of 9% to 17% (or 10% to 15%); (XI) an elongation at break in the machine direction of 140% to 250% (or 150% to 240%, or 160% to 230%) and an elongation at break in the transverse direction of 30% to 120% (or 40% to 110%, or 50% to 100%); (XX) an
  • the biaxially-oriented polyethylene films described herein may have a yield strength in the machine direction of 2,000 psi to 5,000 psi (or 2,200 psi to 4,000 psi) and a yield strength in the yield strength in the transverse direction of 4,000 psi to 15,000 psi (or 5,000 psi to 11,000 psi) and a ratio of Yield strength MD/Yield strength TD is 0.20 or more, alternately 0.3 or more, alternately 0.4 or more, alternately 0.2 to 0.95, alternately 0.3 to 0.85.
  • the biaxially-oriented polyethylene films described herein may have a tensile strength in the machine direction of 6,000 psi to 15,000 psi (or 7,500 psi to 14,500 psi, or 8,000 psi to 11,000 psi) and a tensile strength in the transverse direction of 10,000 psi to 30,000 psi (or 11,000 psi to 25,000 psi, or 12,000 psi to 20,000 psi) and a ratio of Tensile strength MD/Tensile strength TD is 0.30 or more, alternately 0.35 or more, alternately 0.4 or more, alternately 0.30 to 1.1, alternately 0.35 to 1.
  • the biaxially-oriented polyethylene films described herein may have a shrink in the machine direction of 50% to 75% (or 55% to 70%) and a shrink in the transverse direction of 60% to 90% (or 70% to 87%, or 72% to 83%).
  • the biaxially-oriented polyethylene films described herein may have a peak force per mil of 10 lbs/mil to 40 lbs/mil (or 12 lbs/mil to 35 lbs/mil, or 15 lbs/mil to 25 lbs/mil).
  • the biaxially-oriented polyethylene films described herein may have a Dart Drop A of 250 g to 1,350 g (or 275 g to 1,300 g, or 300 g to 1,250 g) and/or a Dart Drop A of 250 g/mil to 1,350 g/mil (alternately 275 g/mil to 1,300 g/mil, or 300 g/mil to 1,250 g/mil).
  • the biaxially-oriented polyethylene films described herein may have an average density of 0.925 g/cm 3 to 0.945 g/cm 3 (0.927 g/cm 3 to 0.942 g/cm 3 , or 0.93 g/cm 3 to 0.941 g/cm 3 , or 0.931 g/cm 3 to 0.94 g/cm 3 ).
  • the biaxially-oriented polyethylene films described herein may an elongation at yield in the machine direction of 5% to 15% (or 6% to 10%) and an elongation at yield in the transverse direction of 9% to 17% (or 10% to 15%).
  • the biaxially-oriented polyethylene films described herein may an elongation at break in the machine direction of 140% to 250% (or 150% to (or 40% to 110%, or 50% to 100%). [0138] In any embodiment herein, the biaxially-oriented polyethylene films described herein may have a haze of 5% to 35% (or 10% to 31%). [0139] In any embodiment herein, the biaxially-oriented polyethylene films described herein may have a clarity of 30% to 80% (or 45% to 75%).
  • the biaxially-oriented polyethylene films described herein may have a break energy of 5 lbs*in to 25 lbs*in (or 7 lbs*in to 25 lbs*in, or 9 lbs*in to 15 lbs*in) and/or a break energy per mil of 5 lbs*in/mil to 19 lbs*in/mil (or 6 lbs*in/mil to 18 lbs*in/mil, or 9 lbs*in/mil to 16 lbs*in/mil).
  • the biaxially-oriented polyethylene films described herein may be used as monolayer films or as one or more layers of a multilayer film.
  • Examples of other layers include, but are not limited to, unstretched polymer films, MDO polymer films, and other biaxially-oriented polymer films of polymers like polyethylene, polypropylene, polyethylene terephthalate, polystyrene, polyamide, and the like.
  • Specific end use films include, for example, blown films, cast films, stretch films, stretch/cast films, stretch cling films, stretch hand wrap films, machine stretch wrap, shrink films, shrink wrap films, green house films, laminates, and laminate films.
  • Exemplary films are prepared by any conventional technique known to those skilled in the art, such as for example, techniques utilized to prepare blown, extruded, and/or cast stretch and/or shrink films (including shrink-on-shrink applications).
  • biaxially-oriented polyethylene films described herein are useful end use applications that include, but are not limited to, film-based products, shrink film, cling film, stretch film, sealing films, snack packaging, heavy-duty bags, grocery sacks, baked and frozen food packaging, diaper back-sheets, house wrap, medical packaging (e.g., medical films and intravenous (IV) bags), industrial liners, membranes, and the like.
  • multilayer films or multiple-layer films may be formed by methods well known in the art.
  • the total thickness of multilayer films may vary based upon the application desired. A total film thickness of about 5-100 ⁇ m, more typically about 10-50 ⁇ m, is suitable for most applications.
  • the thickness of individual layers for multilayer films may be adjusted based on desired end-use performance, resin or copolymer employed, equipment capability, and other factors.
  • Exemplary multilayer films have at least two, at least three, or at least four layers. In one embodiment, the multilayer films are composed of five to ten layers. [0145] To facilitate discussion of different film structures, the following notation is used herein. Each layer of a film is denoted "A" or "B".
  • a film includes more than one A layer or more than one B layer
  • one or more prime symbols are appended to the A or B symbol to indicate layers of the same type that can be the same or can differ in one or more properties, such as chemical composition, density, melt index, thickness, etc.
  • the symbols for adjacent layers are separated by a slash (/). Using this notation, a three-layer film having an inner layer disposed between two outer layers would be denoted A/B/A'. Similarly, a five-layer film of alternating layers would be denoted A/B/A'/B'/A".
  • each film layer is similarly denoted, with the thickness of each layer relative to a total film thickness of 100 (dimensionless) indicated numerically and separated by slashes; e.g., the relative thickness of an A/B/A' film having A and A' layers of 10 ⁇ m each and a B layer of 30 ⁇ m is denoted as 20/60/20.
  • each layer of the film, and of the overall film is not particularly limited, but is determined according to the desired properties of the film.
  • Typical film layers have a thickness of from about 1 to about 1,000 ⁇ m, more typically from about 5 to about 100 ⁇ m, and typical films have an overall thickness of from about 10 to about 100 ⁇ m.
  • the present invention provides for multilayer films with any of the following exemplary structures: (a) two-layer films, such as A/B and B/B'; (b) three-layer films, such as A/B/A', A/A'/B, B/A/B' and B/B'/B"; (c) four-layer films, such as A/A'/A"/B, A/A'/B/A", A/A'/B/B', A/B/A'/B', A/B/B'/A', B/A/A'/B', A/B/B'/B", B/A/B'/B" and B/B'/B"/B'"; (d) five-layer films, such as A/A'/A"/A'"/B, A/A'/A"/B/A'", A/A'/B/A"/A'", A/A'/A"/B/B
  • one or more A layers can be replaced with a substrate layer, such as glass, plastic, paper, metal, etc., or the entire film can be coated or laminated onto a substrate.
  • a substrate layer such as glass, plastic, paper, metal, etc.
  • the films may also be used as coatings for substrates such as paper, metal, glass, plastic, and other materials capable of accepting a coating.
  • the films can further be embossed, or produced or processed according to other known film processes.
  • the films can be tailored to specific applications by adjusting the thickness, materials and order of the various layers, as well as the additives in or modifiers applied to each layer.
  • Example Embodiments [0150] This invention further relates to: 1.
  • a biaxially-oriented polyethylene film comprising polyethylene having: (A) a melt index, I2, of 1.0 g/10 min or greater; (B) a density of 0.925 g/cm 3 to 0.945 g/cm 3 ; (C) a g'LCB of less than 0.8; (D) an Mz of 1,000,000 g/mol or more; (E) an Mw/Mn of 5 or more; (F) an Mw of 100,000 g/mol or more; (G) a ratio of the g'LCB to the g'Zave is greater than 1.0; and (H) a Strain Hardening Ratio of 4 or more, where the film has a 1% secant in the transverse direction of 60,000 psi or more, a Dart Drop of 250 g/mil or more, and a ratio of 1% secant MD/1% secant TD is 0.65 or more.
  • the polyethylene has: (A) a melt index, I2, of 1.9 to 3 g/10 min or greater; (B) a density of 0.925 g/cm 3 to 0.945 g/cm 3 ; (C) a g'LCB of 0.78 to 0.5; (D) an Mz of 1,300,000 g/mol or more; and (F) an Mw of 155,000 g/mol or more.
  • the biaxially-oriented film has one or more of the following properties: (IV) a yield strength in the machine direction of 2,000 psi to 5,000 psi and a yield strength in the transverse direction of 4,000 psi to 15,000 psi; (V) a tensile strength in the machine direction of 6,000 psi to 15,000 psi and a tensile strength in the transverse direction of 10,000 psi to 30,000 psi; (VI) a peak force per mil of 10 lbs/mil to 40 lbs/mil; and (VII) a Dart Drop A of 250 g/mil to 1350g/mil. 10.
  • the biaxially-oriented film also has one or more of the following properties: (IX) an average density of 0.925 g/cm 3 to 0.945 g/cm 3 ; (X) an elongation at yield in the machine direction of 5% to 15% and an elongation at yield in the transverse direction of 9% to 17%); (XI) an elongation at break in the machine direction of 140% to 250% and an elongation at break in the transverse direction of 30% to 120%; (XII) a haze of 5% to 35%; (XIII) a clarity of 30% to 80%; and (IX) a break energy of 5 lbs*in to 25 lbs*in and/or a break energy per mil of 5 lbs*in/mil to 19 lbs*in/mil.
  • a method comprising: (A) a melt index, I2, of 1.0 g/10 min or greater; (B) a density of 0.925 g/cm 3 to 0.945 g/cm 3 ; (C) a g'LCB of less than 0.8; (D) an Mz of 1,000,000 g/mol or more; (E) an Mw/Mn of 5 or more; (F) an Mw of 100,000 g/mol or more; (G) a ratio of the g'LCB to the g'Zave is greater than 1.0; and (H) a Strain Hardening Ratio of 4 or more, extruding a film from the polymer melt; stretching the film in a machine direction to produce a machine direction oriented (MDO) polyethylene film; and stretching the MDO polyethylene film in a transverse direction to produce a biaxially- oriented polyethylene film, where the film has a 1% secant in the transverse direction of 60,000 psi or more, a Dart Drop
  • the polyethylene has a ratio of Yield strength MD/Yield strength TD of the film of 0.20 or more, and or a ratio of Tensile strength MD/Tensile strength TD of the film of 0.30 or more.
  • the polyethylene has at least 10°C between the onset of transition and the melting peak, as shown in the DSC trace.
  • stretching in the machine direction is at a stretch ratio of 1 to 10
  • stretching in the transverse direction is at a stretch ratio of 1 to 12. 17.
  • any of paragraphs 13-16 wherein the film can be stretched in the transverse direction without web breakage or tearing, over an 8°C range and stretched in the transverse direction without web breakage or tearing, over a 5°C range.
  • the polyethylene has: (I) a degree of shear thinning of 0.85 to 0.95, (J) a strain hardening ratio of 4 or greater, (K) a melting temperature of 122°C or greater, (L) a crystallization temperature of 110°C or greater, (M) a Mw of 100,000 g/mol to 155,000 g/mol, and (N) a Mw/Mn of 5 to 10. to 100 wt% of the polymer melt. 20.
  • polymer melt further comprises an additive at 0.01 wt% to 1 wt% of the polymer melt.
  • the biaxially-oriented film has a thickness of 0.1 to 3 mils. 22.
  • the biaxially-oriented film has one or more of the following properties: (IV) a yield strength in the machine direction of 2,000 psi to 5,000 psi and a yield strength in the transverse direction of 5,000 psi to 11,000 psi; (V) a tensile strength in the machine direction of 6,000 psi to 15,000 psi and a tensile strength in the transverse direction of 10,000 psi to 30,000 psi; (VI) a peak force per mil of 10 lbs/mil to 40 lbs/mil; and (VII) a Dart Drop A of 250 g/mil to 1350 g/mil. 23.
  • the biaxially-oriented film also has one or more of the following properties: (IX) an average density of 0.925 g/cm 3 to 0.945 g/cm 3 ; (X) an elongation at yield in the machine direction of 5% to 15% and an elongation at yield in the transverse direction of 9% to 17%); (XI) an elongation at break in the machine direction of 140% to 250% and an elongation at break in the transverse direction of 30% to 120%; (XII) a haze of 5% to 35% (XIII) a clarity of 30% to 80%; and (IX) a break energy of 5 lbs*in to 25 lbs*in and/or a break energy per mil of 5 lbs*in/mil to 19 lbs*in/mil.
  • a polyethylene having: (A) a melt index, I 2 , of 1.0 g/10 min or greater; (B) a density of 0.925 g/cm 3 to 0.945 g/cm 3 ; (C) a g' LCB of less than 0.8; (D) an Mz of 1,000,000 g/mol or more; (E) an Mw/Mn of 5 or more; (F) an Mw of 100,000 g/mol or more; (G) a ratio of the g' LCB to the g' Zave is greater than 1.0; and (H) a Strain Hardening Ratio of 4 or more, has a 1% secant in the transverse direction of 60,000 psi or more, a Dart Drop of 250 g/mil or more, and a ratio of 1% secant MD/1% secant TD is 0.65 or more.
  • This invention further relates to: 1A.
  • a biaxially-oriented polyethylene film comprising polyethylene having: (A) a melt index, I2, of 1.0 g/10 min or greater; (B) a density of 0.925 g/cm 3 to 0.945 g/cm 3 ; (C) a g'LCB of less than 0.8; (D) an Mz of 1,000,000 g/mol or more; (E) an Mw/Mn of 5 or more; (F) an Mw of 100,000 g/mol or more; (G) a ratio of the g'LCB to the g'Zave is greater than 1.0; and (H) a Strain Hardening Ratio of 4 or more, where the film has a 1% secant in the transverse direction of 60,000 psi or more, a Dart Drop of 250 g/mil or more, and a ratio of 1% secant MD/1% secant TD is 0.65 or more.
  • the film of paragraph 1A, wherein the polyethylene has: (A) a melt index, I2, of 1.9 to 3 g/10 min or greater; (B) a density of 0.925 g/cm 3 to 0.945 g/cm 3 ; (C) a g'LCB of 0.78 to 0.5; (D) an Mz of 1,300,000 g/mol or more; and (F) an Mw of 155,000 g/mol or more.
  • the film of paragraph 9A, wherein the biaxially-oriented film also has one or more of the following properties: (IX) an average density of 0.925 g/cm 3 to 0.945 g/cm 3 ; (X) an elongation at yield in the machine direction of 5% to 15% and an elongation at yield in the transverse direction of 9% to 17%); (XI) an elongation at break in the machine direction of 140% to 250% and an elongation at break in the transverse direction of 30% to 120%; (XII) a haze of 5% to 35% (XIII) a clarity of 30% to 80%; and (IX) a break energy of 5 lbs*in to 25 lbs*in and/or a break energy per mil of 5 lbs*in/mil to 19 lbs*in/mil.
  • a method comprising: producing a polymer melt comprising a polyethylene having: (A) a melt index, I 2 , of 1.0 g/10 min or greater; (B) a density of 0.925 g/cm 3 to 0.945 g/cm 3 ; (C) a g' LCB of less than 0.8; (D) an Mz of 1,000,000 g/mol or more; (E) an Mw/Mn of 5 or more; (F) an Mw of 100,000 g/mol or more; (G) a ratio of the g' LCB to the g' Zave is greater than 1.0; and (H) a Strain Hardening Ratio of 4 or more, extruding a film from the polymer melt; stretching the film in a
  • the method of paragraph 13A wherein the film can be stretched in the transverse direction without web breakage or tearing, over an 8°C range and stretched in the transverse direction without web breakage or tearing, over a 5°C range.
  • 18A The method of paragraph 13A, wherein the polyethylene has: (I) a degree of shear thinning of 0.85 to 0.95, (J) a strain hardening ratio of 4 or greater, (K) a melting temperature of 122°C or greater, (L) a crystallization temperature of 110°C or greater, (N) a Mw/Mn of 5 to 10. 19A.
  • the method of paragraph 13A, wherein the polyethylene is present at 90 wt% to 100 wt% of the polymer melt. 20A.
  • polymer melt further comprises an additive at 0.01 wt% to 1 wt% of the polymer melt. 21A.
  • the method of paragraph 13A, wherein the biaxially-oriented film has a thickness of 0.1 to 3 mils. 22A.
  • the biaxially-oriented film has one or more of the following properties: (IV) a yield strength in the machine direction of 2,000 psi to 5,000 psi and a yield strength in the transverse direction of 5,000 psi to 11,000 psi); (V) a tensile strength in the machine direction of 6,000 psi to 15,000 psi and a tensile strength in the transverse direction of 10,000 psi to 30,000 psi; (VI) a peak force per mil of 10 lbs/mil to 40 lbs/mil; and (VII) a Dart Drop A of 250 g/mil to 1350 g/mil. 23A.
  • the biaxially-oriented film also has one or more of the following properties: (IX) an average density of 0.925 g/cm 3 to 0.945 g/cm 3 ; (X) an elongation at yield in the machine direction of 5% to 15% and an elongation at yield in the transverse direction of 9% to 17%); (XI) an elongation at break in the machine direction of 140% to 250% and an elongation at break in the transverse direction of 30% to 120%; (XII) a haze of 5% to 35% (XIII) a clarity of 30% to 80%; and (IX) a break energy of 5 lbs*in to 25 lbs*in and/or a break energy per mil of 5 lbs*in/mil to 19 lbs*in/mil.
  • a polyethylene having: (A) a melt index, I 2 , of 1.0 g/10 min or greater; (B) a density of 0.925 g/cm 3 to 0.945 g/cm 3 ; (C) a g' LCB of less than 0.8; (D) an Mz of 1,000,000 g/mol or more; (E) an Mw/Mn of 5 or more; (F) an Mw of 100,000 g/mol or more; (H) a Strain Hardening Ratio of 4 or more, that when the polyethylene is formed into a biaxially oriented 1 mil thick film, the film has a 1% secant in the transverse direction of 60,000 psi or more, a Dart Drop of 250 g/mil or more, and a ratio of 1% secant MD/1% secant TD is 0.65 or more.
  • the polyethylene of paragraph 24A wherein the polyethylene has: (I) a degree of shear thinning of 0.85 to 0.95, (J) a strain hardening ratio of 4 or greater, (K) a melting temperature of 122°C or greater, (L) a crystallization temperature of 110°C or greater, (M) a Mw of 100,000 g/mol to 155,000 g/mol, and (N) a Mw/Mn of 5 to 10. [0152] To facilitate a better understanding of the embodiments of the present invention, the following examples of preferred or representative embodiments are given. In no way should the following examples be read to limit, or to define, the scope of the invention.
  • Catalyst A is Me2Si[Me4Cp][3-Ph-Ind]ZrCl2, dimethylsilyl (tetramethyl- cyclopentadienyl)(3-phenylindenyl)zirconium dichloride and was prepared as generally described in US 9,266,977 (see Metallocene 1). Preparation of Me2Si[Me4Cp][3-Ph-Ind]ZrCl2 Supported Catalyst [0154] Activation and supportation of Me2Si[Me4Cp][3-Ph-Ind]ZrCl2 was prepared as follows.
  • a 687g amount of methylaluminoxane (MAO) (30 wt % in toluene) was added along with a 1504g amount of toluene.
  • MAO methylaluminoxane
  • a 15.7g amount of the metallocene dissolved in 200mL of toluene was added. This solution was then stirred at 60 rpm for 5 minutes. Another 165g amount of toluene was added. The solution was stirred for 30 minutes at 120 rpm. The stir rate was reduced to 8 rpm.
  • ES-70TM silica (PQ Corporation, Conshohocken, Pennsylvania) that had been calcined at 875°C was added to the vessel.
  • Continuity additive (CA-300, from Univation) was co-fed into the reactor by a second carrier nozzle to reactor bed, and the feed rate of continuity additive was adjusted to maintain a weight concentration in the bed of between 20 ppm and 40 ppm. Good reactor operability was observed for all conditions.
  • the polymer processing conditions can be found in Table A.
  • Table A Table 1: GPC4D structural parameters S l M (LS) M (LS) M (LS) PDI (LS) Comonomer Branching -40- [0157] Melt index (MI) measurements were made on the Goettfert MI-4 Melt Indexer (ASTM D1238). Testing conditions for the MI were set at 190°C and 2.16kg load.
  • Peak melting point or melting temperature (Tm), peak crystallization temperature or crystallization temperature (Tc) and heat of fusion or heat flow ( ⁇ Hf or Hf) were determined using the following DSC procedure. Samples weighing approximately 2-5mg were carefully sealed in aluminum hermetic pan. Heat flow was normalized with the sample mass. The DSC runs were ramped up from 0°C to 200°C at a rate of at 10°C/min, after equilibration, the samples were cooled down at 10°C/min to 0°C. Both first and second thermal cycles were recorded. The melting (Tm) was calculated by integrating the melting peak (area below the curve) over a range of approximately 5°C to approximately 135°C (baseline).
  • Biaxially oriented polyethylene films were produced on a BIAX lab pilot line by Parkinson Technologies Inc, which is a scaled-down version of commercial line.
  • the BIAX lab pilot line has 5 main sections: extrusion, casting, MD, TD, and winding.
  • the uniaxial stretching along MD was obtained by increasing speed between two intermediate rollers.
  • the MD orientation section was operated off-line directly from roll-stock to produce a uniaxially oriented film over heated and cooled rollers.
  • the MD orientation is linked to the TD orientation section’s downstream tenter frame to fabricate biaxially oriented films. cast films and combined with the other sections for biaxially (MD - TD) oriented films.
  • the MDO section was operated to produce a uniaxially oriented film over heated and cooled rollers. This section is linked to the TD downstream tenter frame to fabricate biaxially oriented films.
  • the MDO section is vertically designed and has six rollers with diameter of 18” (457 mm) and 30” (762 mm) face width.
  • the draw section gap was set at 0.035” (0.889 mm) and kept constant for all biaxially oriented films. Temperature and speed were accurately and independently controlled.
  • Table B extruder parameters MDO material (hot air oven) and pulling the web along TD from the edges in a tenter frame (series of mobile clips).
  • the film orientation was tuned and adjusted through a pair of diverging rails.
  • the preheat, stretch and annealing temperatures were set in the TDO section.
  • the oven is composed by three heated and independently controlled zones.
  • Both MDO and TDO processing conditions are reported in Table C including cast sheet size and line speed.
  • the web was allowed to relax in the annealing zone at about 5% per side in order to partially remove the accumulated stress.
  • the film was trimmed at the edges and the gauge was measured before the winding section.
  • Yield point is the first point in which there is an increase in strain (elongation) and none in stress (force). The yield is determined by a 2% off-set method.
  • Tensile at 100% Elongation is calculated as a function of the force at 100% elongation divided by the cross-sectional area of the specimen.
  • Tensile at 100% Elongation Force at 100% Elongation / Cross-Sectional Area.
  • Tensile at 200% Elongation is calculated as a function of the force at 200% elongation divided by the cross-sectional area of the specimen.
  • Tensile at 200% Elongation Force at 200% Elongation / Cross-Sectional Area.
  • the 1% secant modulus is measured of the material stiffness and is calculated as a function of the total force at 1% extension, divided by the cross-sectional area times 100 and reported in PSI units.
  • 1% Secant Modulus Load at 1% Elongation / (Average Thickness (Inches) x Width) x 100.
  • Clarity was determined by ASTM D1746-15.
  • Haze was determined by ASTM D1003-13.
  • Gloss was determined by ASTM D2457-13.
  • Dart drop was determined by phenolic Method A per ASTM D1709-16ae1.
  • Puncture properties including peak force, peak force normalized to a thickness of 1 mil (peak force divided by thickness), break energy, and break energy normalized to a thickness of 1 mil (break energy divided by thickness) were determined by ASTM D5748, with the following modifications. Any film sample ⁇ 1 mil thick is placed in a circular clamp approximately 4 inches wide. A stainless steel custom-made plunger/probe with a 3/4” tip and two 0.25mil slip sheets are pressed through the specimen at a constant speed of 10in/min. and averaged.
  • Shrink in both Machine (MD) and Transverse (TD) directions was measured as the percentage decrease in length of a 100cm circle of film along the MD and TD, under a heat gun (Model HG-501A) set with an average temperature of 750°F (399°C). The heat gun was centered two inches over the sample and heat was applied until each specimen stopped shrinking.
  • WVTR Water vapor transmission rate
  • DST degree of shear thinning
  • the tensile evolution of the transient extensional viscosity was investigated by MCR501 (Anton Paar) rheometer with controlled operational speed.
  • the linear viscoelastic envelope (LVE) is obtained from start-up steady shear experiments.
  • branching and high molecular hardening is defined as a rapid and abrupt leveling-off of the extensional viscosity from the linear viscoelastic behavior.
  • SHR strain hardening ratio
  • compositions, an element or a group of elements are preceded with the transitional phrase “comprising”, it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of”, “selected from the group of consisting of,” or “is” preceding the recitation of the composition, element, or elements and vice versa.

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Abstract

La présente invention concerne un film de polyéthylène orienté biaxialement comprenant du polyéthylène ayant : (A) un indice de fluidité à chaud, I2, supérieur ou égal à 1,0 g/10 min ; (B) une masse volumique de 0,925 g/cm3 à 0,945 g/cm3 ; (C) un g'vis inférieur à 0,8 ; (D) un Mz supérieur ou égal à 1 000 000 g/mol ; (E) un rapport Mw/Mn supérieur ou égal à 5 ; (F) un Mw supérieur ou égal à 100 000 g/mol ; (G) un rapport entre le g'LCB et le g'Zave supérieur à 1,0 ; et (H) un rapport de rhéodurcissement supérieur ou égal à 4, le film ayant une sécante à 1 % dans la direction transversale supérieure ou égale à 60 000 psi, un impact à masse tombante supérieur ou égal à 250 g/mil et un rapport entre la sécante MD à 1 % et la sécante TD à 1 % supérieur ou égal à 0,65.
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