WO2020014138A1 - Films coulés de polyéthylène et procédés de fabrication de tels films coulés de polyéthylène - Google Patents

Films coulés de polyéthylène et procédés de fabrication de tels films coulés de polyéthylène Download PDF

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WO2020014138A1
WO2020014138A1 PCT/US2019/040836 US2019040836W WO2020014138A1 WO 2020014138 A1 WO2020014138 A1 WO 2020014138A1 US 2019040836 W US2019040836 W US 2019040836W WO 2020014138 A1 WO2020014138 A1 WO 2020014138A1
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cast film
layer
composition
sub
polymer
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Carolina A. CATETO
Stefan B. Ohlsson
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Exxonmobil Chemical Patents Inc.
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/242—All polymers belonging to those covered by group B32B27/32
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/58—Cuttability
    • B32B2307/581—Resistant to cut
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/582—Tearability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/582—Tearability
    • B32B2307/5825—Tear resistant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/72—Density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging

Definitions

  • the invention relates to cast films prepared from polyolefin polymers, such as polyethylene polymers and compositions, and to methods for making the same.
  • Cast films have a wide variety of applications in broad fields such as packaging and food care. More specifically, cast films are used for stretch/cling wrap, flower wrapping, page protectors, transparent films, and much more.
  • cast films Compared to blown films, cast films typically have higher production quantities, more uniform thickness, superior optical properties including high transparency, make better gas and moisture barriers, and have quieter unwind. However, cast films also typically have poorer toughness, durability, and puncture resistance and are more materially wasteful than blown films due to the highly irregular edges which are often trimmed.
  • cast films are subject to tearing and puncturing forces.
  • cast films generally have poorer mechanical properties than blown films.
  • mechanical properties are more difficult to retain in the thinner and thinner films that are desired.
  • the invention provides for a cast film comprising: (a) an outer layer and a core layer, the outer layer and the core layer each independently comprising a first polyethylene composition including a linear low density polyethylene (LLDPE) polymer having a density from about 0.913 g/cm 3 to about 0.923 g/cm 3 and an MI (12) of from about 2.6 g/lO min to about 3.0 g/lO min; and (b) a sub-skin layer comprising a second polyethylene composition including an ethylene l-hexene copolymer having a density from about 0.917 g/cm 3 to about 0.919 g/cm 3 and an MI from about 0.9 g/lO min to about 1.1 g/lO min; wherein the sub-skin layer is disposed between the core layer and the outer layer.
  • LLDPE linear low density polyethylene
  • the invention provides for a method for producing a cast film as described above, the method comprising the steps of: (a) providing the core layer, a sub-skin layer, at least two of the outer layers; and (b) coextruding the at least two outer layers, the core layer, and the sub-skin layer to produce the cast film, wherein the sub-skin layer is disposed between the core layer and at least one outer layer.
  • FIG. 1A is a chart showing the Elmendorf tear in the machine direction (g) for the inventive and reference film formulations of Example I.
  • FIG. 1B is a chart showing the Elmendorf tear in the transverse direction (g) for the inventive and reference film formulations of Example I.
  • FIG. 2 is a chart showing the puncture energy at break (mJ) for the inventive and reference film formulations of Example I.
  • FIG. 3 is a chart showing elongation at break MD (%) for the inventive and reference film formulations of Example I.
  • FIG. 4 is a graph containing the tensile curves for the inventive and reference film formulations of Example I.
  • R 1 is hydrogen
  • R 2 is an alkyl group.
  • A“linear alpha-olefin” is an alpha-olefin defined in this paragraph wherein R 1 is hydrogen, and R 2 is hydrogen or a linear alkyl group.
  • a "catalyst system” as used herein may include one or more polymerization catalysts, activators, supports/carriers, or any combination thereof, and the terms “catalyst” and “catalyst system” are intended to be used interchangeably herein.
  • the term “supported” as used herein refers to one or more compounds that are deposited on, contacted with, vaporized with, bonded to, or incorporated within, adsorbed or absorbed in, or on, a support or carrier.
  • support or “carrier” for purposes of this specification are used interchangeably and are any support material, or a porous support material, including inorganic or organic support materials.
  • inorganic support materials include inorganic oxides and inorganic chlorides.
  • Other carriers include resinous support materials such as polystyrene, functionalized or crosslinked organic supports, such as polystyrene, divinyl benzene, polyolefins, or polymeric compounds, zeolites, talc, clays, or any other organic or inorganic support material and the like, or mixtures thereof.
  • CDBI composition distribution breadth index
  • the term,“composition distribution breadth index” or "CDBI” refers to the weight percent of the copolymer molecules having a comonomer content within 50% of the median total molar comonomer content.
  • the CDBI of any copolymer is determined utilizing known techniques for isolating individual fractions of a sample of the copolymer. Exemplary is Temperature Rising Elution Fraction (“TREF”), as described in Wild, et al. (1982) “Determination of Branching Distributions in Polyethylene and Ethylene Copolymers,” Jour. Poly. Sci., Poly. Phys. Ed., v.20, pp. 441-455, and as well as in U.S. Patent No. 5,008,204.
  • TREF Temperature Rising Elution Fraction
  • copolymer means polymers having more than one type of monomer, including interpolymers, terpolymers, or higher order polymers.
  • a“Cm” group or compound refers to a group or a compound with total number carbon atoms“n.”
  • a“Cm-Cn” group or compound refers to a group or compound having total number of carbon atoms in a range from m to n.
  • a C1-C50 alkyl group refers to an alkyl compound having 1 to 50 carbon atoms.
  • density refers to the density of the polymer independent of any additives, such as antiblocks, which may change the tested value.
  • olefin present in such polymer or copolymer is the polymerized form of the olefin.
  • a copolymer when a copolymer is said to have a“propylene” content of 35 wt% to 55 wt%, it is understood that the mer unit in the copolymer is derived from propylene in the polymerization reaction and said derived units are present at 35 wt% to 55 wt%, based upon the weight of the copolymer.
  • a copolymer can be terpolymers and the like.
  • LLDPE linear low density polyethylene
  • metallocene catalyzed linear low density polyethylene and "mLLDPE” means an LLDPE produced with a metallocene catalyst.
  • MDPE linear medium density polyethylene
  • metallocene catalyst refers to a catalyst having at least one transition metal compound containing one or more substituted or unsubstituted Cp moiety (typically two Cp moieties) in combination with a Group 4, 5, or 6 transition metal.
  • a metallocene catalyst is considered a single site catalyst.
  • Metallocene catalysts generally require activation with a suitable co-catalyst, or activator, in order to yield an "active metallocene catalyst", i.e., an organometallic complex with a vacant coordination site that can coordinate, insert, and polymerize olefins.
  • Active catalyst systems generally include not only the metallocene complex, but also an activator, such as an alumoxane or a derivative thereof (preferably methyl alumoxane), an ionizing activator, a Lewis acid, or a combination thereof.
  • an activator such as an alumoxane or a derivative thereof (preferably methyl alumoxane), an ionizing activator, a Lewis acid, or a combination thereof.
  • Alkylalumoxanes typically methyl alumoxane and modified methylalumoxanes
  • the catalyst system can be supported on a carrier, typically an inorganic oxide or chloride or a resinous material such as, for example, polyethylene or silica.
  • the term“substituted” means that a hydrogen group has been replaced with a hydrocarbyl group, a heteroatom, or a heteroatom containing group.
  • methylcyclopentadiene is a Cp group substituted with a methyl group.
  • MI melt index
  • ASTM D-1238-E l90°C/2. l6 kg
  • melt index ratio is the ratio of I21/I2 and provides an indication of the amount of shear thinning behavior of the polymer and a parameter that might be correlated to the overall polymer mixture molecular weight distribution data obtained separately by using Gas Permeation Chromatography (“GPC”) and possibly in combination with another polymer analysis including TREF.
  • GPC Gas Permeation Chromatography
  • melt strength is a measure of the extensional viscosity and is defined as the maximum tension that can be applied to the melt without breaking. Extensional viscosity is the polymer’s ability to resist thinning at high draw rates and high draw ratios.
  • melt processing of polyolefins the melt strength is defined by two key characteristics that can be quantified in process-related terms and in rheological terms.
  • extrusion blow molding and melt phase thermoforming a branched polyolefin of the appropriate molecular weight can support the weight of the fully melted sheet or extruded portion prior to the forming stage. This behavior is sometimes referred to as sag resistance.
  • “M n ” is number average molecular weight
  • “M w ” is weight average molecular weight
  • “M z ” is z-average molecular weight.
  • all molecular weight units (e.g., M w , M n , M z ) including molecular weight data are in the unit of g mol 1 .
  • percent by mole is expressed as“mol%,” and percent by weight is expressed as“wt%.”
  • MWD Molecular weight distribution
  • PDI polydispersity index
  • m in the foregoing equations is the number fraction of molecules of molecular weight Mi.
  • Measurements of M w , M z , and M n are typically determined by Gel Permeation Chromatography as disclosed in Sun, T. et al. (2001)“Effect of Short Chain Branching on the Coil Dimensions of Poly olefins in Dilute Solution Macromolecules , v.34(l9), pg. 6812-6820. The measurements proceed as follows. Gel Permeation Chromatography (Agilent PL-220), equipped with three in-line detectors, a differential refractive index detector (“DRI”), a light scattering (LS) detector, and a viscometer, is used.
  • DRI differential refractive index detector
  • LS light scattering
  • Solvent for the experiment is prepared by dissolving 6 grams of butylated hydroxy toluene as an antioxidant in 4 liters of Aldrich reagent grade 1 ,2, 4-tri chlorobenzene (TCB). The TCB mixture is then filtered through a 0.1 pm Teflon filter. The TCB is then degassed with an online degasser before entering the GPC-3D. Polymer solutions are prepared by placing dry polymer in a glass container, adding the desired amount of TCB, then heating the mixture at l60°C with continuous shaking for about 2 hours. All quantities are measured gravimetrically.
  • the TCB densities used to express the polymer concentration in mass/volume units are 1.463 g/ml at about 2l°C and 1.284 g/ml at l45°C.
  • the injection concentration is from 0.5 to 2.0 mg/ml, with lower concentrations being used for higher molecular weight samples.
  • the DRI detector and the viscometer Prior to running each sample, the DRI detector and the viscometer are purged. The flow rate in the apparatus is then increased to 0.5 ml/minute, and the DRI is allowed to stabilize for 8 hours before injecting the first sample.
  • the LS laser is turned on at least 1 to 1.5 hours before running the samples.
  • the concentration, c, at each point in the chromatogram is calculated from the baseline-subtracted DRI signal, IQRI, using the following equation:
  • KDRJ is a constant determined by calibrating the DRI
  • (dn/dc) is the refractive index increment for the system.
  • the refractive index, n 1.500 for TCB at l45°C. Units on parameters throughout this description of the GPC-3D method are such that concentration is expressed in g/cm-C molecular weight is expressed in g/mole, and intrinsic viscosity is expressed in dL/g.
  • the LS detector is a Wyatt Technology High Temperature DAWN HELEOS.
  • M molecular weight at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering (M.B. Huglin, Light Scattering from Polymer Solutions, Academic Press, 1971):
  • AR(0) is the measured excess Rayleigh scattering intensity at scattering angle Q
  • c is the polymer concentration determined from the DRI analysis
  • A2 is the second virial coefficient
  • R(q) is the form factor for a monodisperse random coil
  • Ko is the optical constant for the system:
  • NA is Avogadro’s number
  • (dn/dc) is the refractive index increment for the system, which take the same value as the one obtained from DRI method.
  • a high temperature Viscotek Corporation viscometer which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers, can be used to determine specific viscosity. One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure.
  • the specific viscosity, h 5 for the solution flowing through the viscometer is calculated from their outputs.
  • the intrinsic viscosity, [h] at each point in the chromatogram is calculated from the following equation:
  • the branching index (gVis) is calculated using the output of the GPC-DRI-LS-VIS method as follows.
  • the average intrinsic viscosity, [rfiavg of the sample is calculated by:
  • the branching index gVis is defined as: g vis
  • M v is the viscosity-average molecular weight based on molecular weights determined by LS analysis.
  • the term“olefin” refers to a linear, branched, or cyclic compound comprising carbon and hydrogen and having a hydrocarbon chain containing at least one carbon-to-carbon double bond in the structure thereof, where the carbon-to-carbon double bond does not constitute a part of an aromatic ring.
  • the term“olefin” is intended to embrace all structural isomeric forms of olefins, unless it is specified to mean a single isomer or the context clearly indicates otherwise.
  • 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.
  • A“copolymer” is a polymer having two or more mer units that are different from each other.
  • A“terpolymer” is a polymer having three mer units that are different from each other. “Different” in reference to mer units indicates that the mer units differ from each other by at least one atom or are different isomerically.
  • “shear thinning ratio” refers to the complex viscosity at l90°C at 0.01 rad/s over the complex viscosity at l90°C at 100 rad/s (or the nearest measured point).
  • substantially uniform comonomer distribution is used herein to mean that comonomer content of the polymer fractions across the molecular weight range of the ethylene- based polymer vary by ⁇ 10.0 wt.%.
  • a substantially uniform comonomer distribution refers to ⁇ 8.0 wt%, ⁇ 5.0 wt%, or ⁇ 2.0 wt%.
  • viscosity is a measure of resistance to shearing flow. Shearing is the motion of a fluid, layer-by-layer, like a deck of cards. When polymers flow through straight tubes or channels, they are sheared and the resistance is expressed by the viscosity.
  • Extensional or elongational viscosity is the resistance to stretching.
  • the elongational viscosity plays a role.
  • the resistance to stretching can be three times larger than in shearing.
  • the elongational viscosity can increase (tension stiffening) with the rate, although the shear viscosity decreased.
  • the bending stiffness is a measure of the resistance of film deformation when bent, and can be calculated the by following equation:
  • Sb is the bending stiffness, measured in mN*mm
  • M is the moment width
  • b is the width
  • R is the radius of the curvature.
  • Bending stiffness can be measured by applying opposing forces at various points on a beam and measuring the resulting curvature of the beam. For example, in the 3-point method, force is applied in one direction on the ends and in the opposite direction in the center, and the resulting radius of the curvature is measured.
  • Various measurements described herein are based on certain test standards. For example, measurements of tensile strength in the machine direction (MD) and transverse direction (TD) are based on ASTM D882. Measurements of Elmendorf tear strength in the machine direction and transverse direction are based on ASTM D 1922-09. Measurements for 1% Secant Modulus are based on ASTM D790A. Measurements for puncture resistance are based on ASTM D5748, which is designed to provide load versus deformation response under biaxial deformation conditions at a constant relatively low test speed (change from 250 mm/min to 5 mm/min after reach pre-load (0.1 N)). Measurements of dart-drop are made using ISO 7765-1, method "A".
  • Light transmission percent (or haze) measurements are based on ASTM D1003 using a haze meter Haze-Guard Plus AT-4725 from BYK Gardner and defined as the percentage of transmitted light passing through the bulk of the film sample that is deflected by more than 2.5
  • cast films having a core layer, a sub-skin layer and an outer layer.
  • the outer layer is adjacent to the sub-skin layer and the sub-skin layer is adjacent to the core layer.
  • the core layer is sandwiched between two sub-skin layers.
  • the sub-skin layer is sandwiched between the outer layer and the core layer.
  • the outer layer can be a cling outer layer or a non-cling outer layer.
  • the core layer comprises an LLDPE composition having a density of 0.918 g/cm 3 and an MI (E) of about 2.8 g/lO min, or an LLDPE composition blended with a polyethylene composition, the polyethylene composition comprising ethylene 1 -hexene copolymer having a density of about 0.918 g/cm 3 and MI of about 1.0 g/lO min, to provide a first polymer blend composition.
  • the core layer comprises the first polymer blend composition comprising about 80 wt% of the polyethylene composition having a density of about 0.918 g/cm 3 and MI of about 1.0 g/lO min and 20 wt% of the LLDPE composition having a density of 0.918 g/cm 3 and an MI of about 2.8 g/lO min.
  • the sub-skin layer comprises the polyethylene composition comprising ethylene l-hexene copolymer having a density of about 0.918 g/cm 3 and an MI of about 1.0 g/lO min, or the LLDPE composition having a density of 0.918 g/cm 3 and an MI of about 2.8 g/lO min blended with the polyethylene composition comprising ethylene l-hexene copolymer having a density of about 0.918 g/cm 3 and MI of about 1.0 g/lO min to provide a second polymer blend composition.
  • the sub-skin layer comprises the second polymer blend composition having about 40 wt% of the polyethylene composition and 60 wt% of the LLDPE composition.
  • the outer layer of the cast films provided herein comprises the LLDPE composition having a density of 0.918 g/cm 3 and an MI of about 2.8 g/lO min, or the LLDPE composition blended with a polypropylene composition, the propylene polymer composition comprising isotactic propylene repeat units with random ethylene distribution having a 0.862 g/cm 3 and an MI (L) of about 9.1 g/lO min and ethylene content of about 15 wt% to provide a third polymer blend composition.
  • the outer layer can be a non-cling layer or a cling layer.
  • the non-cling layer comprises the LLDPE composition having a density of 0.918 g/cm 3 and an MI of about 2.8 g/lO min.
  • the cling layer comprises the third polymer blend composition comprising the LLDPE composition having a density of 0.918 g/cm 3 and an MI of about 2.8 g/lO min and the propylene polymer composition comprising isotactic propylene repeat units with random ethylene distribution having a 0.862 g/cm 3 and an MI (I2) of about 9.1 g/lO min and ethylene content of about 15 wt%.
  • the cast film has 2n + 1 layers comprising either the core layer, two sub skin layers, and 2n - 2 outer layers or the core layer, 2n - 2 sub-skin layers, and two outer layers, wherein n is an integer greater than 0.
  • the cast film has three layers comprising either the core layer and the two outer layers or the core layer, one sub-skin layer, and one outer layer.
  • the cast film has five layers comprising the core layer, two sub-skin layers, and two outer layers.
  • the cast film has seven layers comprising either the core layer, two sub-skin layers, and four outer layers or the core layer, four sub-skin layers, and two outer layers.
  • the cast film has a layer thickness distribution of 10% for each of two outer layers, 35% for each of two sub-skin layers, and 10% for the core layer, wherein each percentage represents that layer’s thickness as a percentage of the total film thickness.
  • the cast film has a total thickness of 12 microns.
  • the present polyethylene compositions comprise from about 50.0 mol% to 100.0 mol% of units derived from ethylene and, generally, 80.0 mol% to 100.0 mol% of units derived from ethylene.
  • the lower limit on the range of ethylene content can be from 50.0 mol%, 75.0 mol%, 80.0 mol%, 85.0 mol%, 90.0 mol%, 92.0 mol%, 94.0 mol%, 95.0 mol%, 96.0 mol%, 97.0 mol%, 98.0 mol%, or 99.0 mol% based on the mol% of polymer units derived from ethylene.
  • the polyethylene composition can have an upper limit on the range of ethylene content of 80.0 mol%, 85.0 mol%, 90.0 mol%, 92.0 mol%, 94.0 mol%, 95.0 mol%, 96.0 mol%, 97.0 mol%, 98.0 mol%, 99.0 mol%, 99.5 mol%, or 100.0 mol%, based on polymer units derived from ethylene.
  • polyethylene compositions produced by polymerization of ethylene and, optionally, an alpha-olefin comonomer having from 3 to 10 carbon atoms.
  • Alpha-olefin comonomers are selected from monomers having 3 to 10 carbon atoms, such as C3-C 10 alpha-olefins.
  • Alpha-olefin comonomers can be linear or branched or may include two unsaturated carbon-carbon bonds, i.e., dienes.
  • suitable comonomers include linear C3-C 10 alpha-olefins and alpha-olefins having one or more C1-C3 alkyl branches or an aryl group.
  • Comonomer examples include propylene, l-butene, 3 -methyl- 1 -butene, 3,3- dimethy 1-1 -butene, l-pentene, l-pentene with one or more methyl, ethyl, or propyl substituents, 1 -hexene, 1 -hexene with one or more methyl, ethyl, or propyl substituents, 1- heptene, l-heptene with one or more methyl, ethyl, or propyl substituents, l-octene, l-octene with one or more methyl, ethyl, or propyl substituents, l-nonene, l-nonene with one or more methyl, ethyl, or propyl substituents, ethyl, methyl, or dimethyl-substituted l-decene, 1- dodecene,
  • Exemplary combinations of ethylene and comonomers include: ethylene l-butene, ethylene l-pentene, ethylene 4-methyl- l-pentene, ethylene 1 -hexene, ethylene l-octene, ethylene decene, ethylene dodecene, ethylene l-butene 1 -hexene, ethylene l-butene l-pentene, ethylene l-butene 4-methyl- l-pentene, ethylene l-butene l-octene, ethylene 1 -hexene 1- pentene, ethylene 1 -hexene 4-methyl- l-pentene, ethylene 1 -hexene l-octene, ethylene 1- hexene decene, ethylene 1 -hexene dodecene, ethylene propylene l-octene, ethylene l-octene l-butene,
  • the foregoing list of comonomers and comonomer combinations are merely exemplary and are not intended to be limiting.
  • the comonomer is 1 -butene, 1 -hexene, or l-octene.
  • monomer feeds are regulated to provide a ratio of ethylene to comonomer, e.g., alpha-olefin, so as to yield a polyethylene having a comonomer content, as a bulk measurement, of from about 0.1 mol% to about 20 mol% comonomer.
  • the comonomer content is from about 0.1 mol% to about 4.0 mol%, or from about 0.1 mol% to about 3.0 mol%, or from about 0.1 mol% to about 2.0 mol%, or from about 0.5 mol% to about 5.0 mol%, or from about 1.0 mol% to about 5.0 mol%.
  • reaction temperature may be regulated so as to provide desired polyethylene compositions.
  • molecular weight control agent such as Eh
  • the amount of comonomers, comonomer distribution along the polymer backbone, and comonomer branch length will generally delineate the density range.
  • Comonomer content is based on the total content of all monomers in the polymer.
  • the polyethylene copolymer has minimal long chain branching (i.e., less than 1.0 long-chain branch/lOOO carbon atoms, preferably particularly 0.05 to 0.50 long-chain branch/lOOO carbon atoms). Such values are characteristic of a linear structure that is consistent with a branching index (as defined below) of gVis > 0.980, 0.985, > 0.99, > 0.995, or 1.0.
  • long chain branches can be present (i.e., less than 1.0 long-chain branch/lOOO carbon atoms, preferably less than 0.5 long-chain branch/lOOO carbon atoms, particularly 0.05 to 0.50 long-chain branch/lOOO carbon atoms).
  • the present polyethylene compositions comprise ethylene-based polymers which include LLDPE produced by gas-phase polymerization of ethylene and, optionally, an alpha-olefin with a catalyst having as a transition metal component a bis(n-C3-4 alkyl cyclopentadienyl) hafnium compound, wherein the transition metal component comprises from about 95 to about 99 mol% of the hafnium compound.
  • polyethylene can be polymerized in any catalytic polymerization process, including solution phase processes, gas phase processes, slurry phase processes, and combinations of such processes.
  • An exemplary process used to polymerize ethylene-based polymers, such as LLDPEs, is as described in U.S. Patent Nos. 6,936,675 and 6,528,597.
  • Polyethylene compositions provided herein can be blends of LLDPE and other polymers, such as additional polymers prepared from ethylene monomers.
  • additional polymers are LLDPE, non-linear LDPE, very low density polyethylene (“VLDPE”), MDPE, high density polyethylene (“HDPE”), differentiated polyethylene (“DPE”), and combinations thereof.
  • DPE copolymers include EVA, EEA, EMA, EBA, and other specialty copolymers.
  • the additional polymers contemplated in certain aspects include ethylene homopolymers and/or ethylene-olefin copolymers.
  • the polyethylene composition comprising a blend of LLDPE and one or more other polymers is referred to a polymer blend composition.
  • polyethylene compositions provided herein include polymer blend compositions which include at least 0.1 wt% and up to 99.9 wt% of LLDPE, and at least 0.1 wt% and up to 99.9 wt% of one or more additional polymers, with these wt% based on the total weight of the polyethylene composition.
  • Alternative lower limits of LLDPE can be 5%, 10%, 20%, 30%, 40%, or 50% by weight.
  • Alternative upper limits of LLDPE can be 95%, 90%, 80%, 70%, 60%, and 50% by weight. Ranges from any lower limit to any upper limit are within the scope of the invention.
  • Polymer blend compositions include compositions having more than about 90% LLDPE, and preferably more than about 95% LLDPE.
  • the polymer blend composition includes from 5-85%, alternatively from 10-50% or from 10-30% by weight of the LLDPE.
  • the balance of the weight percentage is the weight of the additional and/or other type of polymers, e g., different LLDPE, LDPE, VLDPE, MDPE, HDPE, DPE such as EVA, EEA, EMA, EBA, and combinations thereof.
  • the polyethylene composition can have a density > about 0.900 g/cm 3 , > about 0.905 g/cm 3 , > about 0.910 g/cm 3 , > about 0.915 g/cm 3 , > about 0.920 g/cm 3 , > about 0.925 g/cm 3 , > about 0.930 g/cm 3 , > about 0.935 g/cm 3 , > about 0.940 g/cm 3 , > about
  • polyethylene compositions can have a density ⁇ about 0.960 g/cm 3 , ⁇ about 0.945 g/cm 3 , ⁇ about 0.940 g/cm 3 , ⁇ about 0.935 g/cm 3 , ⁇ about 0.930 g/cm 3 , ⁇ about 0.925 g/cm 3 , ⁇ about
  • 0.920 g/cm 3 ⁇ about 0.915 g/cm 3 , ⁇ about 0.910 g/cm 3 , ⁇ about 0.905 g/cm 3 , and ⁇ about 0.900 g/cm 3 .
  • ranges include, but are not limited to, ranges formed by combinations of any of the above-enumerated values, e.g., from about 0.930 to about 0.945 g/cm 3 , 0.930 to about 0.935 g/cm 3 , 0.9350 to 0.940 g/cm 3 , 0.935 to 0.950 g/cm 3 , etc.
  • Density is determined using chips cut from plaques compression molded in accordance with ASTM D-1928-C, aged in accordance with ASTM D-618 Procedure A, and measured as specified by ASTM D-1505.
  • the polyethylene composition can have an MI (E,) according to ASTM D-1238-E (l90°C/2. l6 kg) and reported in grams per 10 minutes (g/lO min), of > about 0.50 g/lO min, > about 0.60 g/lO min, > about 0.70 g/lO min, > about 0.80 g/lO min, > about 0.90 g/lO min, > about 1.00 g/lO min, > about 1.10 g/lO min, > about 1.20 g/lO min, > about 1.30 g/lO min, > about 1.40 g/lO min, and > about 1.50 g/lO min.
  • MI MI
  • the polyethylene composition can have an MI (b) ⁇ about 3.0 g/lO min, ⁇ about 2.0 g/lO min, ⁇ about 1.5 g/lO min, ⁇ about 1.0 g/lO min, ⁇ about 0.75 g/lO min, ⁇ about 0.50 g/lO min, ⁇ about 0.40 g/lO min, ⁇ about 0.30 g/lO min, ⁇ about 0.25 g/lO min, ⁇ about 0.22 g/lO min, ⁇ about 0.20 g/lO min, ⁇ about 0.18 g/lO min, or ⁇ about 0.15 g/lO min.
  • ranges include, but are not limited to, ranges formed by combinations any of the above- enumerated values, for example: from about 0.1 to about 3.0; about 0.2 to about 2.0; about 0.2 to about 0.5 g/lO min, etc.
  • the polyethylene composition can have at least a first peak and a second peak in a comonomer distribution analysis, wherein the first peak has a maximum at a log(M w ) value of 4.0 to 5.4, 4.3 to 5.0, or 4.5 to 4.7; and a TREF elution temperature of 70.0°C to l00.0°C, 80.0°C to 95.0°C, or 85.0°C to 90.0°C.
  • the second peak in the comonomer distribution analysis has a maximum at a log(M w ) value of 5.0 to 6.0, 5.3 to 5.7, or 5.4 to 5.6; and a TREF elution temperature of 5.0°C to 60.0°C or l0.0°C to 60.0°C.
  • a description of the TREF methodology is described in U.S. Patent Nos. 8,431,661 B2 and US 6,248,845 Bl.
  • the polyethylene composition can have a broad orthogonal comonomer distribution.
  • the term“broad orthogonal comonomer distribution” is used herein to mean across the molecular weight range of the ethylene polymer, comonomer contents for the various polymer fractions are not substantially uniform and a higher molecular weight fraction thereof generally has a higher comonomer content than that of a lower molecular weight fraction.
  • Both a substantially uniform and an orthogonal comonomer distribution may be determined using fractionation techniques such as gel permeation chromatography-differential viscometry (GPC-DV), temperature rising elution fraction-differential viscometry (TREF-DV) or cross fractionation techniques.
  • the present polyethylene compositions typically have a broad composition distribution as measured by CDBI or solubility distribution breadth index (“SDBI”).
  • CDBI solubility distribution breadth index
  • Polymers produced using a catalyst system described herein have a CDBI less than 50%, or less than 40%, or less than 30%.
  • the polymers have a CDBI of from 20% to less than 50%.
  • the polymers have a CDBI of from 20% to 35%.
  • the polymers have a CDBI of from 25% to 28%.
  • Polyethylene composition are produced using a catalyst system described herein and have a SDBI greater than l5°C, or greater than l6°C, or greater than l7°C, or greater than l8°C, or greater than 20°C.
  • the polymers have a SDBI of from l8°C to 22°C.
  • the polymers have a SDBI of from l8.7°C to 2l.4°C.
  • the polymers have a SDBI of from 20°C to 22°C.
  • ENABLE® mPE metallocene polyethylene compositions
  • ENABLE® mPE metallocene polyethylene compositions
  • ASTM® mPE metallocene polyethylene compositions
  • Applications for ENABLE® products include food packaging, form fill and seal packaging, heavy duty bags, lamination film, stand up pouches, multilayer packaging film, and shrink film.
  • ENABLETM 20-10CB is an ethylene l-hexene copolymer comprising a thermal stabilizer and having a density of 0.920 g/cm 3 and an MI (E) of 1.0 g/lO min.
  • EXCEED XP® metallocene polyethylene compositions
  • EXCEED XPTM metallocene polyethylene compositions
  • EXCEED XPTM compositions offer step-out performance with respect to, for example, dart drop impact strength, flex-crack resistance, and machine direction (MD) tear, as well as maintaining stiffness at lower densities.
  • EXCEED XPTM compositions also offer optimized solutions for a good balance of melt strength, toughness, stiffness, and sealing capabilities which makes this family of polymers well-suited for blown film/sheet solutions.
  • EXCEEDTM 3518 polyethylene composition comprises ethylene l-hexene copolymers and has a density of about 0.918 g/cm 3 and an MI (I2) of about 3.5 g/lO min.
  • EXCEEDTM 8318 polyethylene composition comprises ethylene l-hexene copolymers and has a density of about 0.918 g/cm 3 and an MI (I2) of about 1.0 g/lO min.
  • the linear low density polyethylene composition, ExxonMobilTM LLDPELL LL1004YB is an LLDPE composition having a density of 0.918 g/cm 3 , and an MI (I2) of about 2.8 g/lO min.
  • VISTAMAXXTM 6202 composition is a propylene polymer composition comprising isotactic propylene repeat units with random ethylene distribution having a density of about
  • VISTAMAXXTM 6000 composition is a propylene polymer composition comprising isotactic propylene repeat units with random ethylene distribution having a density of about 0.889 g/cm 3 and an MI (b) of about 3.7 g/lO min.
  • Conventional catalysts refer to Ziegler Natta catalysts or Phillips-type chromium catalysts. Examples of conventional-type transition metal catalysts are discussed in U.S. Patent Nos. 4,115,639, 4,077,904 4,482,687, 4,564,605, 4,721,763, 4,879,359 and 4,960,741.
  • the conventional catalyst compounds that may be used in the processes disclosed herein include transition metal compounds from Groups 3 to 10, preferably 4 to 6 of the Periodic Table of Elements.
  • M is a metal from Groups 3 to 10, or Group 4, or titanium; R is a halogen or a hydrocarbyloxy group; and x is the valence of the metal M, preferably x is 1, 2, 3 or 4, or x is 4.
  • R include alkoxy, phenoxy, bromide, chloride and fluoride.
  • Non- limiting examples of conventional-type transition metal catalysts where M is titanium include TiCl3, TiCl4, TiBr4, Ti(OC2H5)3Cl, Ti(OC2H5)Cl3, Ti(OC4H9)3Cl, Ti(OC3H7)2Cl2, Ti(OC2H5)2Br2, TiCl3. l/3AlCl3 and Ti(OCl2H25)Cl3.
  • Conventional chrome catalysts may include Cr03, chromocene, silyl chromate, chromyl chloride (Cr02Cl2), chromium-2-ethyl-hexanoate, chromium acetylacetonate (Cr(AcAc)3).
  • Cr02Cl2 chromocene
  • Cr(AcAc)3 chromium acetylacetonate
  • Non-limiting examples are disclosed in U.S. Patent Nos. 2,285,721, 3,242,099 and 3,231,550.
  • many conventional-type catalysts require at least one cocatalyst. A detailed discussion of cocatalyst may be found in U.S. Patent No. 7,858,719, Col. 6, line 46, to Col. 7, line 45.
  • Metallocene catalysts are generally described as containing one or more ligand(s) and one or more leaving group(s) bonded to at least one metal atom, optionally with at least one bridging group.
  • the ligands are generally represented by one or more open, acyclic, or fused ring(s) or ring system(s) or a combination thereof. These ligands, the ring(s) or ring system(s), can comprise one or more atoms selected from Groups 13 to 16 atoms of the Periodic Table of
  • the atoms are selected from the group consisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorous, germanium, boron and aluminum or a combination thereof.
  • the ring(s) or ring system(s) comprise carbon atoms such as, but not limited to, those cyclopentadienyl ligands or cyclopentadienyl-type ligand structures or other similar functioning ligand structures such as a pentadiene, a cyclooctatetraendiyl, or an imide ligand.
  • the metal atom can be selected from Groups 3 through 15 and the lanthanide or actinide series of the Periodic Table of Elements. The metal is a transition metal from Groups 4 through 12,
  • Exemplary metallocene catalysts and catalyst systems are described in, for example, U.S. Patent Nos. 4,530,914, 4,871,705, 4,937,299, 5,017,714, 5,055,438, 5,096,867, 5,120,867, 5,124,418, 5,198,401, 5,210,352, 5,229,478, 5,264,405, 5,278,264, 5,278,119, 5,304,614,
  • the catalysts described above are suitable for use in any olefin pre-polymerization or polymerization process or both.
  • Suitable polymerization processes include solution, gas phase, slurry phase, and a high-pressure process, or any combination thereof.
  • a desirable process is a gas phase polymerization of one or more olefin monomers having from 2 to 30 carbon atoms, from 2 to 12 carbon atoms in an aspect, and from 2 to 8 carbon atoms in an aspect.
  • Other monomers useful in the process include ethylenically unsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers and cyclic olefins.
  • Non-limiting monomers may also include norbomene, norbomadiene, isobutylene, isoprene, vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethybdene norbomene, dicyclopentadiene and cyclopentene.
  • a copolymer of ethylene derived units and one or more monomers or comonomers is produced.
  • the one or more comonomers are an a-olefin having from 4 to 15 carbon atoms in an aspect, from 4 to 12 carbon atoms in an aspect, and from 4 to 8 carbon atoms in an aspect.
  • the comonomer can be 1 -hexene.
  • Hydrogen gas is often used in olefin polymerization to control the final properties of the polyolefin, such as described in Polypropylene Handbook, Hanser Publishers, (1996) pp. 76-78. Increasing concentrations (partial pressures) of hydrogen increase the melt flow rate
  • MFR MFR
  • MI MFR
  • the MFR or MI can thus be influenced by the hydrogen concentration.
  • the amount of hydrogen in the polymerization can be expressed as a mole ratio relative to the total polymerizable monomer, for example, ethylene, or a blend of ethylene and hexane or propene.
  • the amount of hydrogen used in the polymerization process is an amount necessary to achieve the desired MFR or MI of the final polyolefin composition.
  • the mole ratio of hydrogen to total monomer is in a range of from greater than 0.0001 in an aspect, from greater than 0.0005 in an aspect, from greater than 0.001 in an aspect, to less than 10 in an aspect, less than 5 in an aspect, less than 3 in an aspect, and less than 0.10 in an aspect, wherein a desirable range may comprise any combination of any upper mole ratio limit with any lower mole ratio limit described herein.
  • the amount of hydrogen in the reactor at any time may range to up to 5,000 ppm, up to 4,000 ppm in an aspect, up to 3,000 ppm in an aspect, between 50 ppm and 5,000 ppm in an aspect, and between 100 ppm and 2,000 ppm in an aspect.
  • a continuous cycle is often employed where one part of the cycle of a reactor system, a cycling gas stream, otherwise known as a recycle stream or fluidizing medium, is heated in the reactor by the heat of polymerization. This heat is removed from the recycle composition in another part of the cycle by a cooling system external to the reactor.
  • a gas fluidized bed process for producing polymers a gaseous stream containing one or more monomers is continuously cycled through a fluidized bed in the presence of a catalyst under reactive conditions. The gaseous stream is withdrawn from the fluidized bed and recycled back into the reactor. Simultaneously, polymer product is withdrawn from the reactor and fresh monomer is added to replace the polymerized monomer.
  • the ethylene partial pressure can vary between 80 and 300 psia, or between 100 and 280 psia, or between 120 and 260 psia, or between 140 and 240 psia. More importantly, a ratio of comonomer to ethylene in the gas phase can vary from 0.0 to 0.10, or between 0.005 and 0.05, or between 0.007 and 0.030, or between 0.01 and 0.02.
  • Reactor pressure typically varies from 100 psig (690 kPa) to 500 psig (3448 kPa). In an aspect, the reactor pressure is maintained within the range of from 200 psig (1,379 kPa) to 500 psig (3,448 kPa). In an aspect, the reactor pressure is maintained within the range of from 250 psig (1,724 kPa) to 400 psig (2,759 kPa).
  • Cast film extrusion generally involves the steps of melting and extruding a resin, delivered as solid pellets through a gravimetric feeding system, through a flat linear die onto a series of large chilling rollers. To form a film comprising multiple layers, several resins are coextruded to form a coextrudate, which is then sent onto the series of large chilling rollers.
  • Components of the cast film extrusion process comprise a gravimetric feeding system, an extruder, a filtration system, a flat die system, a cooling unit, a corona treatment, a winder, and a computerized control system.
  • a common issue in cast film extrusion is premature pellet melting, especially in cases of small pellets or with materials having low melting temperature. This issue can be solved by vibration or cooling of feeding hoppers (not shown). Another common issue is introduction of moisture into the system which can create bubbles in the film. Drying, which may be built in to the feeding system, can eliminate moisture in the feed.
  • the gravimetric feeding system controls the amount of material that is fed into the extruders by weight.
  • solid pellets of polyethylene composition are fed into the feeding system to start production of a film.
  • An extruder melts and mixes the fed pellets by conveying the pellets along a heated barrel (not shown) with a rotating screw (not shown) having a screw shape with a gap between the barrel and screw.
  • the screw shape is tailored to the desired characteristics of the film.
  • the screw is typically maintained at a near-constant rotation speed to ensure constant film thickness in the machine direction.
  • the gap between the screw and barrel is maintained at a relatively constant value to ensure constant film thickness.
  • a melt pump (not shown) is used downstream of the extruder.
  • the melt pump is a positive displacement pump, which ensures near-constant flow and alleviates pressure in the extruder, in turn reducing wear on the barrel and screw.
  • the number of extruders depends on the number of different materials being extruded and not necessarily on the number of layers.
  • Current feedblock technology allows fluid flow from one extruder to be split into two or more layers in the coextrudate.
  • a filtration system having one or more filters (not shown) of a metallic mesh can be used.
  • the filtration system filters impurities present in the melt and other gels that may form during the extrusion process.
  • the filtration system must be able to withstand the pressure of the polymer flow leaving the extruder.
  • a die system (not shown) comprises a coextrusion feedblock (not shown), a flat die (not shown), and melt transfer adapters (not shown) that transport the different molten polymers from the extruders to the feedblock inlet ports.
  • the die system forms a multi-layered film that can be uniformly distributed across the width of the die with thickness variations of the film (and each layer) that conform to specified tolerances.
  • the present cast film is coextruded through an extrusion die having a diameter of about 0.6 mm.
  • a coextrusion feedblock arranges the different melt streams in a predetermined layer sequence and generates a melt stream for each layer. Each melt stream then meets its neighboring layers and a final planar coextrudate is formed.
  • the coextrusion feedblock can be fixed or have variable geometry blocks.
  • a flat die, and the synergy between the die and the feedblock, are crucial to high quality film production.
  • the die must spread the coextrudate received from the feedblock while maintaining flatness of the film.
  • the die requires a sufficiently short residence time in order to prevent heat transfer between layers or polymer degradation.
  • the die must also be sufficiently strong so as to resist deformation when subjected to high pressures inherent in thin film processes.
  • a cooling unit typically includes a primary quenching roll (not shown), a secondary roll (not shown), a motorized roll positioning system (not shown) for proper vertical and cross machine direction alignment of the rolls, and a vacuum box (not shown).
  • the cooling unit allows the line to operate at high speeds. As the line speed increases, so does the diameter of the roll.
  • the cast film is coextruded at a line speed of about 400 meters of film per minute.
  • coextrudate exiting the die first enters the primary quenching roll.
  • the rolls are chrome-plated with water circulating within the rolls as a cooling agent. The primary quenching roll must be properly aligned with the coextrudate and have controlled angular velocity so as to maintain thickness and uniformity in all directions.
  • a vacuum box can enhance the efficiency of the cooling unit by applying a vacuum to the coextrudate.
  • the applied vacuum removes air and other gases between the coextrudate and the rolls, increasing the rate of heat transfer.
  • Vacuum strength can affect the position of a frost line of a film.
  • the frost line marks the position where the molten coextrudate solidifies. Lowering the vacuum lowers the frost line, and the coextrudate will solidify farther downstream of the die.
  • a surface treatment particularly a corona treatment (not shown) can be used to apply a coating onto the cast film. Electrodes apply high frequency energy to the film surface (not shown), raising the surface tension of the film and aiding adhesion between the coating and the film. If corona treatment is performed inline, the potential generation of toxic ozone may warrant additional ventilation.
  • a winder converts the film into a roll of material while maintaining the film’s properties and dimensions. Winder size and winder speed depend on film properties and process conditions.
  • a turret winder can be used (not shown).
  • film tension decreases as the roll diameter increases.
  • a randomizer (not shown) can move the film back and forth in order to achieve a more uniform thickness distribution in the film.
  • the computerized control system typically operates the above-mentioned components.
  • the computerized control system can control startup, shutdown, speed, temperatures and pressures throughout various components, and more functions.
  • the control system includes a gauge control system, which monitors the distribution of thickness in the extrudate by measuring absorption of radiation across the coextrudate.
  • Cast films (referred to herein also as“film formulations” or“films”) were produced in a five layer coextrusion cast line having four extruders and a 2 m width die.
  • the air gap and die gap were 25 mm and 0.6 mm, respectively.
  • the films were produced at a line speed of 400 m/min.
  • the films were subjected to vacuums of varying strength while cooling; the“Vacuum Box Setting” percentages refer to arbitrary values that are positively correlated with the strength of the applied vacuum.
  • the film formulations and processing details for this example are presented immediately below in Tables 1A, 1B and 1C.
  • the sub-skin layer of Reference Sample 1 comprises a fourth polymer blend composition comprising a second polyethylene composition having a density of 0.920 g/cm 3 and an MI (b) of 1.0 g/lO min blended with the LLDPE composition, wherein the fourth polymer blend composition comprises 40% second polyethylene composition and 60% LLDPE composition.
  • the sub-skin layer of Reference Sample 2 comprises a fifth polymer blend composition comprising a third polyethylene composition having a density of about 0.918 g/cm 3 and an MI (I2) of about 3.5 g/lO min blended with the second polyethylene composition, wherein the fifth polymer blend composition comprises 90% third polyethylene composition and 10% second polyethylene composition.
  • the core layer of Reference Sample 1 comprises a sixth polymer blend composition comprising the second polyethylene composition blended with the LLDPE composition, wherein the sixth polymer blend composition comprises 80% second polyethylene composition and 20% LLDPE composition.
  • the core layer of Reference Sample 2 comprises the third polyethylene composition.
  • the non-cling outer layer of Reference Sample 1 comprises the LLDPE composition.
  • the non-cling outer layer of Reference Sample 2 comprises a second propylene polymer composition having a density of about 0.889 g/cm 3 and an MI (I2) of about 3.7 g/lO min.
  • the inventive films have a significantly higher Elmendorf tear in the machine direction than the reference films.
  • the strength of the applied vacuum appears to have little relation to Elmendorf tear in MD.
  • the Elmendorf tear in the transverse direction was approximately constant for all the inventive films and the 12 micron reference film.
  • Reference Sample 2 provides approximately 10% higher Elmendorf tear in TD direction than the other inventive and reference films. Vacuum strength appears to have minimal impact on Elmendorf tear in TD.
  • inventive films have puncture energies at break similar to the reference films. Vacuum strength appears to have a negative correlation with puncture energy at break for the inventive films, but the higher puncture energy of Inventive Sample 4 suggests that composition is more important to puncture energy, as Inventive Sample 4 overall comprises significantly more LLDPE composition and less polyethylene composition than the other inventive films.
  • inventive films have percentages of elongation at break (MD) comparable to the reference films.
  • vacuum strength appears to have a negative correlation with percent elongation at break for the inventive films.
  • Inventive Sample 4 overall comprising significantly more LLDPE composition and less polyethylene composition than the other inventive films, has a percent elongation at break lower than all of the inventive and reference films.
  • FIG. 4 shows similar trends for strain as FIG. 2 and FIG. 3. Vacuum strength appears to have a positive correlation with the force needed to strain the inventive films to a given length.
  • Inventive Sample 4 overall comprising significantly more LLDPE composition and less polyethylene composition than the other inventive films, requires a higher force to strain the film to a certain length than the other inventive samples.
  • FIGS. 2, 3, and 4 suggest that a stronger applied vacuum yields weaker and stiffer films and that higher LLDPE compositions/lower polyethylene compositions yield tougher, stiffer films.
  • Inventive Samples 1, 2, and 3 as vacuum strength increases, puncture resistance decreases, percent elongation in the machine direction at break decreases, and force needed to strain the films to a given length increased.
  • Inventive Sample 4 Comparing Inventive Sample 4 to the other inventive films, a higher LLDPE composition/lower polyethylene composition yields higher puncture resistance, lower percent elongation in the machine direction at break, and higher force needed to strain the films to a given length.
  • FIG. 1A and FIG. 2 demonstrate that the inventive films achieve significantly higher Elmendorf tear in MD while maintaining comparable puncture resistance.
  • the inventive films provide an improved Elmendorf tear in MD direction combined with excellent puncture resistance.
  • the elongation of these films can be tailored by changing the frost line position.
  • the data is particularly useful for the cast stretch film applications, but also for other applications where high Elmendorf tear in MD direction is required, such as hygiene back sheet, cast silage film and cast PE film applications in general.
  • ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited.
  • ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited.
  • within a range includes every point or individual value between its end points even though not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.

Abstract

L'invention concerne des films coulés comprenant : (a) une couche externe et une couche centrale, chaque couche comprenant une composition de LLDPE ayant une densité d'environ 0,913 g/cm3 à environ 0,923 g/cm3 et un MI (I2) d'environ 2,6 g/10 min à environ 3,0 g/10 min ; et (b) une couche sous-jacente comprenant une composition de polyéthylène, la composition de polyéthylène comprenant un copolymère d'éthylène 1-hexène et ayant une densité d'environ 0,917 g/cm3 à environ 0,919 g/cm3 et un MI d'environ 0,9 g/10 min à environ 1,1 g/10 min. L'invention porte également sur des procédés de production des films coulés.
PCT/US2019/040836 2018-07-09 2019-07-08 Films coulés de polyéthylène et procédés de fabrication de tels films coulés de polyéthylène WO2020014138A1 (fr)

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CN112356543A (zh) * 2020-10-28 2021-02-12 中国石油化工股份有限公司 一种高光泽高透明聚乙烯流延膜及其制备方法

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