WO2021216280A1 - Films de polyéthylène soufflés résistants à la déchirure - Google Patents

Films de polyéthylène soufflés résistants à la déchirure Download PDF

Info

Publication number
WO2021216280A1
WO2021216280A1 PCT/US2021/025933 US2021025933W WO2021216280A1 WO 2021216280 A1 WO2021216280 A1 WO 2021216280A1 US 2021025933 W US2021025933 W US 2021025933W WO 2021216280 A1 WO2021216280 A1 WO 2021216280A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyethylene
blown
hydrocarbon resin
layer
mol
Prior art date
Application number
PCT/US2021/025933
Other languages
English (en)
Inventor
Ge Yang
Zhen-yu ZHU
Petra M. DE WAEL
Linda M. Van Den Bossche
Li Shi
Chiao-Kiat Pey
Original Assignee
Exxonmobil Chemical Patents Inc.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Exxonmobil Chemical Patents Inc. filed Critical Exxonmobil Chemical Patents Inc.
Publication of WO2021216280A1 publication Critical patent/WO2021216280A1/fr

Links

Classifications

    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • 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
    • B32B2250/246—All polymers belonging to those covered by groups B32B27/32 and B32B27/30
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/02—Synthetic macromolecular particles
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal 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
    • B32B2307/582—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
    • B32B2307/732—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
    • 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
    • C08J2323/06—Polyethene
    • 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
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—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
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—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
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • 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
    • C08J2457/00—Characterised by the use of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C08J2457/02—Copolymers of mineral oil hydrocarbons

Definitions

  • the present disclosure relates to polyethylene films having improved tear resistance.
  • Polyethylene is a thermoplastic polymer used in a wide variety of applications, including packaging prepared from polyethylene films. Different properties are desirable for polyethylene films depending on type of packaging. For example, in food packaging, high oxygen and water barrier properties are preferred to mitigate food spoilage. For shopping bags, silage films, freeze films, and the like, tear resistance is desired to improve packaging strength and resistance to deformation under stress.
  • One strategy for increasing the tear resistance of polyethylene films includes the incorporation of metallocene -polyethylene (mPE) polymers into the polymer matrix because mPF tend to have highly defined microstructures, tacticity, and stereoregularity. Further, mPE polymers often have a moderate amount of polymer branching, which may enhance entanglement on a molecular level and prevent a tear from propagating through the film. Propagation tear resistance (or simply “tear resistance”) is measured as the force required to propagate a tear through a specified length of the polyethylene film after a tear has been started. Tear resistance is typically used as one indication of material strength.
  • MD machine direction
  • TD transverse direction
  • the present disclosure relates to polyethylene films having improved tear resistance in one orientation (e.g., TD or MD) while having a maintained or improved tear resistance in the perpendicular orientation.
  • the present disclosure includes a blown multilayer film that comprises: a first layer, a second layer, and a third layer, wherein the second layer is disposed between first layer and third layer, and wherein at least one of the first layer, second layer, and third layer comprises (or consists of) about 40 wt% to about 90 wt% of a first polyethylene, about 5 wt% to about 30 wt% of a second polyethylene, about 5 wt% to about 30 wt% of a hydrocarbon resin, and 0 wt% to about 15 wt% of an anti-drip additive.
  • the present disclosure includes a method of manufacturing a blown multilayer film comprising: compounding a composition comprising (or consisting of) about 40 wt% to about 90 wt% of a first polyethylene, about 5 wt% to about 30 wt% of a second polyethylene, about 5 wt% to about 30 wt% of a hydrocarbon resin, and 0 wt% to about 15 wt% of an anti-drip additive to form a polymer melt; and blowing the polymer melt with at least one additional polymer melt to form the blown multilayer film, wherein each polymer melt forms a layer of the blown multilayer film.
  • the present disclosure includes a blown monolayer film that comprises (or consists of): about 40 wt% to about 90 wt% of a first polyethylene, about 5 wt% to about 30 wt% of a second polyethylene, about 5 wt% to about 30 wt% of a hydrocarbon resin, and 0 wt% to about 15 wt% of an anti-drip additive.
  • the present disclosure includes a method of manufacturing a blown monolayer film comprising: blowing a polymer melt comprising (or consisting of) about 40 wt% to about 90 wt% of a first polyethylene, about 5 wt% to about 30 wt% of a second polyethylene, about 5 wt% to about 30 wt% of a hydrocarbon resin, and 0 wt% to about 15 wt% of an anti-drip additive to yield the blown monolayer film.
  • the present disclosure includes a bag comprising: an inner layer comprising (or consisting of) about 40 wt% to about 90 wt% of a first polyethylene, about 5 wt% to about 30 wt% of a second polyethylene, about 5 wt% to about 30 wt% of a hydrocarbon resin, and 0 wt% to about 15 wt% of an anti-drip additive; a core layer; and an outer layer.
  • the present disclosure includes a bag comprising: an inner layer; a core layer comprising (or consisting of) about 40 wt% to about 90 wt% of a first polyethylene, about 5 wt% to about 30 wt% of a second polyethylene, about 5 wt% to about 30 wt% of a hydrocarbon resin, and 0 wt% to about 15 wt% of an anti-drip additive; and an outer layer.
  • the present disclosure includes a bag comprising: an inner layer; a core layer; and an outer layer comprising (or consisting of) about 40 wt% to about 90 wt% of a first polyethylene, about 5 wt% to about 30 wt% of a second polyethylene, about 5 wt% to about 30 wt% of a hydrocarbon resin, and 0 wt% to about 15 wt% of an anti-drip additive.
  • Figure 1 is included to illustrate certain aspects of the embodiments, and should not be viewed as exclusive embodiments. The subject matter disclosed is capable of considerable modifications, alterations, combinations, and equivalents in form and function, as will occur to those skilled in the art and having the benefit of this disclosure [0015] Figure 1 provides data relating to the Elmendorf tear strength in the transverse direction of various films disclosed herein.
  • the films described herein are preferably blown films rather than cast films.
  • the method of production can cause the resultant film’s properties to be different.
  • cast films typically offer a higher transparency.
  • Cast and blown films prepared from the same ethylene polymer and to the same gauge can differ dramatically with respect to their haze and gloss properties.
  • blown films generally have a higher modulus than cast films.
  • blown films have a better tear resistance in the machine direction than cast films.
  • blown polyethylene films having improved tear resistance in one orientation (e.g., TD or MD) while having a maintained or improved tear resistance in the perpendicular orientation.
  • the present disclosure incorporates a hydrocarbon resin into polyethylene films to increase propagation tear resistance in one of the TD and MD orientations while retaining or improving propagation tear resistance in the other orientation. Therefore, packaging like shopping bags and freezer films produced from the polyethylene films described herein may, advantageously, be stronger and less susceptible to tearing.
  • 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.
  • the term “polymer” as used herein includes, but is not limited to, homopolymers, copolymers, terpolymers, etc.
  • the term “polymer” as used herein also includes impact, block, graft, random, and alternating copolymers.
  • the term “polymer” shall further include all possible geometrical configurations unless otherwise specifically stated. Such configurations may include isotactic, syndiotactic, and random symmetries.
  • copolymer(s) refers to polymers formed by the polymerization of at least two different monomers (/. ⁇ ? ., mer units).
  • 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 “propylene polymer” or “propylene copolymer” is a polymer or copolymer comprising at least 50 mole% propylene derived units, and so on.
  • a polyethylene is an ethylene polymer.
  • a polymer when 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.
  • a copolymer when a copolymer is said to have an “ethylene” content of 35 wt% to 55 wt%, it is understood that 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.
  • metalocene polyethylene indicates that the polyethylene polymer was prepared using a transition metal catalyst activated by methods well known for such components, such as alumoxane or a non-coordinating anion.
  • Polyethylenes may be characterized by density and/or branching.
  • polyethylenes include very low-density polyethylene (VLDPE) having a density less than about 0.91 g/cm 3 , low-density polyethylene/linear low-density polyethylene (LDPE and LLDPE, respectively) having a density from about 0.91 g/cm 3 to about 0.93 g/cm 3 where LLDPE typically has a long chain branching index (g’ ViS ) of 0.95 or more, medium-density polyethylene (MDPE) having a from about 0.926 g/cm 3 to about 0.94 g/cm 3 , and high-density polyethylene (HDPE) having a density above 0.94 g/cm 3 .
  • VLDPE very low-density polyethylene
  • LDPE low-density polyethylene/linear low-density polyethylene
  • LDPE low-density polyethylene/linear low-density polyethylene
  • MDPE medium-density polyethylene
  • HDPE high-density polyethylene
  • LDPE generally has a high degree of short- and long-chain branching, whereas HDPE generally has a low degree of branching.
  • LLDPE has a moderate amount of short-chain branching, which can be controlled to some extent by the choice of olefin incorporated therein as well as through other process parameters.
  • Density reported in g/cm 3 , is determined in accordance with ASTM 1505-10 (the plaque is 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.
  • Mn is number average molecular weight
  • Mw is weight average molecular weight
  • 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.
  • GPC Gel Permeation Chromatography
  • the distribution and the moments of molecular weight (e.g., Mw, Mn, Mz, Mw/Mn) and the comonomer content (e.g., C2, C3, C6) is determined by using a high temperature Gel Permeation Chromatography (Polymer Char GPC-IR) equipped with a multiple-channel band-filter based Infrared detector IR5, an 18-angle light scattering detector and a viscometer. Three Agilent PLgel 10-pm Mixed-B LS columns are used to provide polymer separation.
  • TCB Aldrich reagent grade 1,2,4-trichlorobenzene
  • BHT butylated hydroxytoluene
  • the TCB mixture is filtered through a 0.1-mhi 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 qL.
  • 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-mu flow marker (heptane) added to it.
  • polymer 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 one hour for polyethylene samples or about two 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 the 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 CPp 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 1000 total carbons (CH3/IOOOTC) as a function of molecular weight.
  • the short-chain branch (SCB) content per lOOOTC (SCB/1000TC) can be then computed as a function of molecular weight by applying a chain-end correction to the CH3/IOOOTC function, assuming each chain to be linear and terminated by a methyl group at each end.
  • the bulk composition of the polymer from the GPC-IR and GPC-4D analyses is obtained by considering the entire signals of the Cft and C3 ⁇ 4 channels between the integration limits of the concentration chromatogram. First, the following ratio is obtained.
  • 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. B., Ed.; Academic Press, 1972):
  • AR(0) is the measured excess Rayleigh scattering intensity at scattering angle Q
  • c is the polymer concentration determined from the IR5 analysis
  • A2 is the second virial coefficient
  • R(q) is the form factor for a monodisperse random coil
  • a high temperature viscometer such as those made by Technologies, Inc. or 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 between the two sides of the bridge, measures a differential pressure.
  • s for the solution flowing through the viscometer is calculated from their outputs.
  • the average intrinsic viscosity, ([77]) of the sample is calculated by: where the summations are over the chromatographic slices, i, between the integration limits. [0035]
  • the long chain branching index (gYc B, also referred to as g'vis) is defined as where ( M ) is the viscosity average molecular weight calibrated with polystyrene standards, K and a are for the reference linear polymer, which are as calculated and published in literature (Sun, T. et al.
  • a 0.695 and K is 0.000579*(1- 0.0087*w2b+0.000018*(w2b)
  • a 0.695 and K is 0.000579*(l-0.0075*w2b) for ethylene- hexene copolymer where w2b is a bulk weight percent of hexene comonomer
  • a 0.695 and K is 0.000579*(l-0.0077*w2b) for ethylene-octene copolymer where w2b is a bulk weight percent of octene comonomer
  • w2b is a bulk weight percent of octene comonomer
  • Elmendorf tear strength in the MD and in the TD is measured by ASTM D 1922-09. Elmendorf tear strength may be reported as grams (g) (which is the measured value) or normalized to film thickness and reported as g/pm (which is the measured value divided by the thickness of the film).
  • Blown films described herein may have one or more layers.
  • a blown film described herein may be a blown monolayer film.
  • a blown film described herein may be a blown multilayer film that comprises from two layers to several hundred layers, with three to 12 layers being preferred.
  • a blown monolayer film may comprise or consist of a first polyethylene, a second polyethylene, about 5 wt% to about 50 wt% of a hydrocarbon resin, and optionally up to about 15 wt% of an anti-drip additive.
  • a blown multilayer polyethylene film may comprise a first layer, a second layer, and a third layer, wherein the second layer is disposed between the first layer and third layer. At least one of the first layer, second layer, and third layer may comprise or consist of about 5 wt% to about 30 wt% of the hydrocarbon resin. The balance of the layer may comprise or consist of about 40 wt% to about 90% of a first polyethylene and about 5 wt% to about 30 wt% of a second polyethylene.
  • an anti-drip additive may be included at a concentration from 0 wt% to about 15 wt%, which includes from 0 wt% to about 10 wt%, from about 5 wt% to about 15 wt%, and from about 5 wt% to about 10 wt%.
  • the additional layers which are those that do not include a hydrocarbon resin as described herein, may independently comprise any polymer and/or resin.
  • Suitable hydrocarbon resins for use in compositions and methods of the present invention may include, but are not limited to, aliphatic hydrocarbon resins, hydrogenated aliphatic hydrocarbon resins, aliphatic/aromatic hydrocarbon resins, hydrogenated aliphatic aromatic hydrocarbon resins, cycloaliphatic hydrocarbon resins, hydrogenated cycloaliphatic resins, cycloaliphatic/aromatic hydrocarbon resins, hydrogenated cycloaliphatic/aromatic hydrocarbon resins, hydrogenated aromatic hydrocarbon resins, polyterpene resins, terpene- phenol resins, rosins and mixtures of two or more thereof.
  • rosin includes rosin esters and rosin acids, which may also be hydrogenated.
  • Examples of commercially available hydrocarbon resins may include, but are not limited to, OPPERATM PR 100, 101, 102, 103, 104, 105, 106, 111, 112, 115, 120, ECR-373, and ESCOREZ® 1000, 2000, and 5000 series hydrocarbon resins available from ExxonMobil Chemical Company; ARKONTM M90, M100, Ml 15 and M135 and SUPER ESTERTM rosin esters available from Arakawa Chemical Company of Japan; SYLVARESTM phenol modified styrene-a methyl styrene resins available from Kraton Corporation; styrenated terpene resins ZONATACTM available from Kraton Corporation; terpene phenolic resins available from Kraton Corporation; NORSOLENETM aliphatic aromatic resins available from Cray Valley of France; DERTOPHENETM terpene phenolic resins available from DRT Chemical Company of Austin, France; EASTOTACTM resins,
  • hydrocarbon resin used in compositions and methods of the present invention are not modified or reacted with an unsaturated acid or anhydride or derivative thereof.
  • the hydrocarbon resin may have an Mw of about 10,000 g/mol or less (e.g., about 1000 g/mol to about 10,000 g/mol, or about 1000 g/mol to about 5000 g/mol, or about 1000 g/mol to about 2500 g/mol, or about 1000 g/mol to about 2000 g/mol).
  • the hydrocarbon resin may have an Mn of about 10,000 g/mol or less (e.g. , about 400 g/mol to about 10,000 g/mol, or about 400 g/mol to about 5000 g/mol, or about 400 g/mol to about 2500 g/mol, or about 400 g/mol to about 1500 g/mol).
  • the hydrocarbon resin may have an Mz of about 10,000 g/mol or less (e.g., about 500 g/mol to about 10,000 g/mol, or about 500 g/mol to about 5000 g/mol, or about 500 g/mol to about 2500 g/mol, or about 500 g/mol to about 1500 g/mol).
  • the hydrocarbon resin may have a PDI of about 1 to about 4 (e.g. , about 1 to about
  • the hydrocarbon resin may have one or more of: (a) an Mw of about 10,000 g/mol or less (e.g., about 1000 g/mol to about 10,000 g/mol, or about 1000 g/mol to about 5000 g/mol, or about 1000 g/mol to about 2500 g/mol, or about 1000 g/mol to about 2000 g/mol), (b) an Mn of about 10,000 g/mol or less (e.g., about 400 g/mol to about 10,000 g/mol, or about 400 g/mol to about 5000 g/mol, or about 400 g/mol to about 2500 g/mol, or about 400 g/mol to about 1500 g/mol), (c) an Mz of about 10,000 g/mol or less (e.g.
  • a PDI of about 1 to about 4 e.g., about 1 to about 2.5, or about 2 to about 4.
  • a suitable hydrocarbon resin may have a softening point, as measured by ASTM D6493-ll(2015), of about 120°C to about 140°C (or about 120°C to about 130°C, or about 130°C to about 140°C).
  • layers in the blown polyethylene films described herein comprise or consist of a first polyethylene, a second polyethylene, and a hydrocarbon resin.
  • the first polyethylene and second polyethylene are different in at least one characteristic like comonomer presence, concentration, and/or composition; density; melt flow index; molecular weight; and the like.
  • a polyethylene suitable for use in a first polyethylene and/or second polyethylene may comprise one or more of an ethylene homopolymer and a copolymer of ethylene and one or more C3-C20 olefins.
  • a copolymer of ethylene and one or more of 1-butene, 1- hexene, and 1-octene may be suitable.
  • one or both of the first polyethylene and second polyethylene comprises an mPH comprising a copolymer of ethylene and 1 -hexene or comprising a copolymer of ethylene and 1 -butene.
  • the first polyethylene and second polyethylene may comprise one or more of any polyethylene type including, but not limited to, an HDPE, an MDPE, an LDPE, an LLDPE, and a VLDPE. Within each of these polyethylene types, there may be further polyethylene sub- types based on branching index (g’ ViS ), crystallinity, molecular weight, molecular weight distribution, method of preparation, or the like.
  • branching index g’ ViS
  • the first polyethylene and second polyethylene may be an MDPE, an LDPE, or an LLDPE, which may further optionally be a metallocene polyethylene (mPE).
  • mPE metallocene polyethylene
  • the first polyethylene may be an MDPE
  • second polyethylene may be an LDPE or an LLDPE.
  • the first polyethylene may be an LDPE
  • second polyethylene may be an LLDPE
  • the first polyethylene may be an MDPE or an LDPE having a g’ vis from 0.94 or less (e.g., from 0.81 to 0.94, or from 0.85 to 0.94, or from 0.90 to 0.94)
  • second polyethylene may be an LLDPE having a g’ ViS from 0.95 to 1.0.
  • the first polyethylene may be an MDPE having a g’ ViS from 0.81 to 1.0 (e.g., from 0.81 to 0.94, or from 0.85 to 0.94, or from 0.90 to 0.94, or from 0.95 to 1.0, or from 0.97 to 0.99), and second polyethylene may be an LDPE having a g’ ViS from 0.94 or less (e.g. , from 0.81 to 0.94, or from 0.85 to 0.94, or from 0.90 to 0.94) or an LLDPE having a g’ ViS from 0.95 to 1.0.
  • MDPE having a g’ ViS from 0.81 to 1.0
  • second polyethylene may be an LDPE having a g’ ViS from 0.94 or less (e.g. , from 0.81 to 0.94, or from 0.85 to 0.94, or from 0.90 to 0.94) or an LLDPE having a g’ ViS from 0.95 to 1.0.
  • One or both of the first polyethylene and the second polyethylene may have an Mw of about 100,000 g/mol to about 1,000,000 g/mol (e.g., about 100,000 g/mol to about 250,000 g/mol, or about 250,000 g/mol to about 500,000 g/mol, or about 500,000 g/mol to about 750,000 g/mol, or about 750,000 g/mol to about 1,000,000 g/mol).
  • One or both of the first polyethylene and the second polyethylene may have an Mn of about 50,000 g/mol to about 1,000,000 g/mol (e.g., about 50,000 g/mol to about 250,000 g/mol, or about 250,000 g/mol to about 500,000 g/mol, or about 500,000 g/mol to about 750,000 g/mol, or about 750,000 g/mol to about 1,000,000 g/mol).
  • One or both of the first polyethylene and the second polyethylene may have an Mz of about 50,000 g/mol to about 1,000,000 g/mol (e.g., about 50,000 g/mol to about 250,000 g/mol, or about 250,000 g/mol to about 500,000 g/mol, or about 500,000 g/mol to about 750,000 g/mol, or about 750,000 g/mol to about 1,000,000 g/mol).
  • One or both of the first polyethylene and the second polyethylene may have a PDI of about 1 to about 4 (e.g., about 1 to about 2.5, or about 2 to about 4).
  • first polyethylene and the second polyethylene may have one or more of: (a) an Mw of about 100,000 g/mol to about 1,000,000 g/mol (e.g., about 100,000 g/mol to about 250,000 g/mol, or about 250,000 g/mol to about 500,000 g/mol, or about 500,000 g/mol to about 750,000 g/mol, or about 750,000 g/mol to about 1,000,000 g/mol), (b) an Mn of about 50,000 g/mol to about 1,000,000 g/mol (e.g., about 50,000 g/mol to about 250,000 g/mol, or about 250,000 g/mol to about 500,000 g/mol, or about 500,000 g/mol to about 750,000 g/mol, or about 750,000 g/mol to about 1,000,000 g/mol), (c) an Mz of about 50,000 g/mol to about 1,000,000 g/mol (e.g., about 100,000 g/mol to about 250,000 g/mol, or about 250,000 g/mol
  • suitable polyethylenes available commercially include, but are not limited to, those sold under the brand name ENABLETM and EXCEEDTM by ExxonMobil Chemical.
  • EXCEED XPTM polyethylene polymers may prove particularly useful as they offer step-out performance with respect to, for example, dart drop impact strength, flex- crack resistance, and machine direction (MD) tear.
  • ENABLETM polyethylene polymers may prove particularly useful as they offer an outstanding balance between processing properties and film properties such as, but not limited to, tensile strength, impact strength, and puncture resistance.
  • a blown monolayer film described herein may be any thickness, for example, from about 15 pm to about 75 pm (or from about 50 pm to about 75 pm).
  • a blown multilayer film described herein may be prepared at any thickness, for example, from about 30 pm to about 160 pm (or from about 80 pm to about 120 pm, or from about 90 pm to about 110 pm).
  • a blown multilayer film may comprise from two layers to several hundred layers, with three to twelve layers being preferred.
  • the additional layers may comprise any polymer and/or resin compatible for forming a film with a layer comprising a hydrocarbon resin, as discussed above.
  • suitable polymers and/or resins for the additional layers include, but are not limited to, one or more of an HDPE, an MDPE, an LDPE, an LLDPE, and a VLDPE.
  • an additional layer may comprise a polyester, polyamide, polypropylene, ethylene vinyl alcohol, the like, or any blend thereof.
  • the additional layers may further comprise up to about 15 wt% of an anti-drip additive.
  • At least one of the additional layers comprises an LLDPE, which is optionally, but preferably, an mPE.
  • each of the first, second, and third layers include an LLDPE mPE resin.
  • the ratio of the thickness of a first layer to a second layer to a third layer in a multilayer film may range from about 1:1:1 to about 1:4:1. Alternatively, one layer may measure about 25%, about 50%, about 75%, or about 100% thicker than one or more of the other layers.
  • Suitable anti-drip additives include, but are not limited to, polystyrene, poly-a-alkylstyrene, polyalkyl acrylates, polyalkyl methacrylates, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyraldehyde, polybutadiene, styrene-acrylonitrile copolymers, alpha-alkylstyrene- acrylonitrile copolymer, an acrylonitrile-butadiene-styrene copolymer, styrene-butadiene rubber, sorbitan esters, ethoxylated sorbitan esters, glycerol esters, and fatty acid esters.
  • One or more anti-drip additive may be included at a concentration of up to about 15 wt%, which includes from 0 wt% to about 15 wt%, from 0 wt% to about 10 wt%, from about 5 wt% to about 15 wt%, and from about 5 wt% to about 10 wt%.
  • Additives not explicitly discussed above may optionally be included in one or more of the first, second and third layers. Suitable additives include, but are not limited to, pigments, plasticizers, tackifiers, anti-static agents, anti-fogging agents, and antioxidants.
  • a blown monolayer film comprising a first polyethylene, a second polyethylene, a hydrocarbon resin, and optionally an anti-drip additive may have increased tear resistance over a comparable blown monolayer film, for example, an Elmendorf TD tear strength at least about 60% higher than the TD tear strength of the comparable blown monolayer film.
  • the TD Elmendorf tear strength may measure at least about 100% higher than the TD Elmendorf tear strength of a comparable blown monolayer film.
  • a blown monolayer film comprising a hydrocarbon resin may retain its Elmendorf tear strength in both of the MD or TD orientations, thereby providing a blown monolayer film having an overall improved tear resistance compared to a comparable blown monolayer film.
  • the MD Elmendorf tear strength of a blown monolayer film comprising a hydrocarbon resin may measure higher or within about 1 % of the MD Elmendorf tear strength of a comparable blown monolayer film.
  • the blown monolayer films described herein may have (a) a TD Elmendorf tear strength of about 700 g to about 1500 g (or about 1000 g to about 1500 g) and (b) an MD Elmendorf tear strength of about 600 g to about 1600 g (or about 1000 g to about 1600 g).
  • the blown monolayer films described herein may have (a) a TD Elmendorf tear strength of about 14 g/pm to about 30 g/pm (or about 20 g/pm to about 30 g/pm) and (b) an MD Elmendorf tear strength of about 5 g/pm to about 17 g/pm (or 10 g/pm to about 17 g/pm).
  • the strength performance of a blown multilayer film wherein at least one layer comprises or consists of about 5 wt% to about 30 wt% of a hydrocarbon resin, a first polyethylene, a second polyethylene, and optionally an anti-drip additive may be improved over a comparable film absent an effective amount of the hydrocarbon resin.
  • the term “comparable film” refers to a film comprising or consisting of the first polyethylene, second polyethylene, optionally the anti-drip additive, and less than about 0.1 wt% of a hydrocarbon resin.
  • a blown multilayer film including a hydrocarbon resin may, for example, display enhanced Elmendorf tear strength in at least one of the MD and TD orientations.
  • Such a film may further retain or exhibit enhanced strength in the perpendicular orientation, thereby providing a blown multilayer film having an overall improved tear resistance over a comparable film.
  • a blown multilayer film comprising a hydrocarbon resin may have a TD Elmendorf tear strength of at least about 8% higher than the TD Elmendorf tear strength of a comparable film while at the same time, having an MD Elmendorf tear strength greater than or within about 1 % of the MD Elmendorf tear strength of the comparable film.
  • both the TD Elmendorf tear strength and the MD Elmendorf tear strength are at least about 8% higher than the TD and MD Elmendorf tear strength of a comparable film.
  • some of the blown multilayer films may display even stronger properties and have one or more of a TD Elmendorf tear strength at least about 50% higher and an MD Elmendorf tear strength at least about 40% higher than the TD and MD Elmendorf tear strength, respectively, of the comparable film.
  • the blown multilayer films described herein may have (a) a TD Elmendorf tear strength of the about 2000 g to about 2500 g (or about 2000 g to about 2250 g) and (b) an MD Elmendorf tear strength of about 600 g to about 1600 g (or about 1000 g to about 1600 g).
  • the blown multilayer films described herein may have (a) a TD Elmendorf tear strength of about 20 g/pm to about 25 g/pm (or about 20 g/pm to about 23 g/pm) and (b) an MD Elmendorf tear strength of about 5 g/pm to about 17 g/pm (or 10 g/pm to about 17 g/pm).
  • a monolayer film may be prepared by blowing a composition comprising or consisting of a first polyethylene, a second polyethylene, from about 5 wt% to about 50 wt% of a hydrocarbon resin, and optionally up to about 15 wt% of an anti-drip additive.
  • a composition comprising or consisting of a first polyethylene, a second polyethylene, from about 5 wt% to about 50 wt% of a hydrocarbon resin, and optionally up to about 15 wt% of an anti-drip additive.
  • Suitable hydrocarbons, suitable first and second polyethylenes, and suitable anti-drip additives are described above.
  • Extrusion by blowing methods to form a film may be carried out by any method known to one of ordinary skill in the art. Examples of blown film forming methods are provided in US Patent Nos. 5,569,693, 9,126,269, 10,124,528, which are incorporated herein by reference.
  • the composition comprising or consisting of a first polyethylene, a second polyethylene, from about 5 wt% to about 50 wt% of a hydrocarbon resin, and optionally up to about 15 wt% of an anti-drip additive can be extruded in a molten state through an annular die and then blown and cooled/quenched to form a tubular, blown film, which can then be axially slit and unfolded to form a flat film.
  • blown films can be prepared wherein the polymer composition is introduced into the feed hopper of an extruder.
  • the film can be produced by extruding one or more of the polymer compositions through a die into a film cooled by blowing air onto the surface of the film.
  • the film is drawn from the die typically forming a cylindrical film that is cooled/quenched, collapsed and, optionally, subjected to a desired auxiliary process, such as slitting, treating, sealing, surface treatment, and/or printing.
  • melt temperatures are from 175°C to 225 °C.
  • Blown film rates are generally from 5 to 30 lbs per hour per inch of die circumference.
  • the finished film can be wound into rolls for later processing, or can be fed into a bag machine and converted into bags.
  • a polymer melt described herein (comprising or consisting of a first polyethylene, a second polyethylene, and from about 5 wt% to about 50 wt% of a hydrocarbon resin) may then be co-extruded via blowing methods with at least one additional polymer melt, which forms at least one additional layer in a multilayer film.
  • the additional polymers and/or resins may independently comprise an HDPE, an MDPE, an LDPE, an LLDPE, and a VLDPE, a polyethylene, a polyester, polyamide, polypropylene, ethylene vinyl alcohol, the like, or any blend thereof and may optionally include up to about 15 wt% of an anti-drip additive.
  • any additional layer may comprise or consist of two different types of polyethylene and about 10 wt% of an anti-drip additive.
  • two different types of LLDPE each of which are optionally, but preferably, an mPE are employed in one or more additional layers.
  • the hydrocarbon resin may be included in any of the layers.
  • a blown three-layer film may have a composition such that a first layer is a composition suitable for an outer layer of a packaging, a second layer is a composition suitable for a core layer of the packaging, and a third layer is a composition suitable for an inner layer of the packaging.
  • any of the outer, core, or inner layers may be the compositions described herein comprising or consisting of: about 40 wt% to about 90 wt% of a first polyethylene, about 5 wt% to about 30 wt% of a second polyethylene, about 5 wt% to about 30 wt% of a hydrocarbon resin, and 0 wt% to about 15 wt% of an anti-drip additive.
  • a nonlimiting example embodiment of the present disclosure is a blown multilayer film that comprises: a first layer, a second layer, and a third layer, wherein the second layer is disposed between first layer and third layer, and wherein at least one of the first layer, second layer, and third layer comprises about 40 wt% to about 90 wt% of a first polyethylene, about 5 wt% to about 30 wt% of a second polyethylene, about 5 wt% to about 30 wt% of a hydrocarbon resin, and 0 wt% to about 15 wt% of an anti-drip additive.
  • Said blown multilayer film may further include: Element 1: wherein at least one of the first layer, second layer, and third layer consists of about 40 wt% to about 90 wt% of the first polyethylene, about 5 wt% to about 30 wt% of the second polyethylene, about 5 wt% to about 30 wt% of the hydrocarbon resin, and 0 wt% to 15 wt% of the anti-drip additive; Element 2: wherein the first polyethylene is an MDPE, and wherein the second polyethylene is an LDPE or an LLDPE; Element 3: wherein the first polyethylene is an LDPE, and wherein the second polyethylene is an LLDPE; Element 4: wherein the first polyethylene is an MDPE having a g’ ViS from 0.94 or less or an LDPE having a g’ ViS from 0.94 or less, and wherein the second polyethylene is an LLDPE; Element 5: wherein the first polyethylene is a medium-density polyethylene (
  • Examples of combinations include, but are not limited to, Element 1 and one of Elements 2-5 in combination; Element 1 in combination with one or more of Elements 6-13; two or more of Elements 6-13 in combination; and one or more of Elements 6-13 in combination with one of Elements 2-5 and optionally in further combination with Element 1.
  • Another nonlimiting example embodiment of the present disclosure is a method of manufacturing a blown multilayer film comprising: compounding a composition comprising about 40 wt% to about 90 wt% of a first polyethylene, about 5 wt% to about 30 wt% of a second polyethylene, about 5 wt% to about 30 wt% of a hydrocarbon resin, and 0 wt% to about 15 wt% of an anti-drip additive to form a polymer melt; and blowing the polymer melt with at least one additional polymer melt to form the blown multilayer film, wherein each polymer melt forms a layer of the blown multilayer film.
  • the polymer melt may consist of about 40 wt% to about 90 wt% of a first polyethylene, about 5 wt% to about 30 wt% of a second polyethylene, about 5 wt% to about 30 wt% of a hydrocarbon resin, and 0 wt% to about 15 wt% of an anti-drip additive to yield the blown monolayer film.
  • the nonlimiting example embodiment may incorporate one or more of Elements 2-13 including in the foregoing combinations.
  • Yet another nonlimiting example embodiment of the present disclosure is a blown monolayer film that comprises: about 40 wt% to about 90 wt% of a first polyethylene, about 5 wt% to about 30 wt% of a second polyethylene, about 5 wt% to about 30 wt% of a hydrocarbon resin, and 0 wt% to about 15 wt% of an anti-drip additive.
  • Said blown monolayer film may further include: Element 14: wherein the blown monolayer film consisting of: about 40 wt% to about 90 wt% of a first polyethylene, about 5 wt% to about 30 wt% of a second polyethylene, about 5 wt% to about 30 wt% of a hydrocarbon resin, and 0 wt% to about 15 wt% of an anti drip additive; Element 15: wherein the first polyethylene is an MDPE, and wherein the second polyethylene is an LDPE or an LLDPE; Element 16: wherein the first polyethylene is an LDPE, and wherein the second polyethylene is an LLDPE; Element 17: wherein the first polyethylene is an MDPE having a g’ ViS from 0.94 or less or an LDPE having a g’ ViS from 0.94 or less, and wherein the second polyethylene is an LLDPE; Element 18: wherein the first polyethylene is an MDPE having a g’ ViS from 0.81 to
  • Examples of combinations include, but are not limited to, Element 14 and one of Elements 15-19 in combination; Element 14 in combination with one or more of Elements 20-25; two or more of Elements 20-25 in combination; and one or more of Elements 20-25 in combination with one of Elements 15-19 and optionally in further combination with Element 14.
  • Another nonlimiting example embodiment of the present disclosure is a method of manufacturing a blown monolayer film comprising: blowing a polymer melt comprising about 40 wt% to about 90 wt% of a first polyethylene, about 5 wt% to about 30 wt% of a second polyethylene, about 5 wt% to about 30 wt% of a hydrocarbon resin, and 0 wt% to about 15 wt% of an anti-drip additive to yield the blown monolayer film.
  • the polymer melt may consist of about 40 wt% to about 90 wt% of a first polyethylene, about 5 wt% to about 30 wt% of a second polyethylene, about 5 wt% to about 30 wt% of a hydrocarbon resin, and 0 wt% to about 15 wt% of an anti-drip additive to yield the blown monolayer film.
  • the nonlimiting example embodiment may incorporate one or more of Elements 15-25 including in the foregoing combinations.
  • Yet another nonlimiting example embodiment of the present disclosure is a bag comprising: an inner layer comprising (or consisting of) about 40 wt% to about 90 wt% of a first polyethylene, about 5 wt% to about 30 wt% of a second polyethylene, about 5 wt% to about 30 wt% of a hydrocarbon resin, and 0 wt% to about 15 wt% of an anti-drip additive; a core layer; and an outer layer.
  • Yet another nonlimiting example embodiment of the present disclosure is a bag comprising: an inner layer; a core layer comprising (or consisting of) about 40 wt% to about 90 wt% of a first polyethylene, about 5 wt% to about 30 wt% of a second polyethylene, about 5 wt% to about 30 wt% of a hydrocarbon resin, and 0 wt% to about 15 wt% of an anti-drip additive; and an outer layer.
  • Yet another nonlimiting example embodiment of the present disclosure is a bag comprising: an inner layer; a core layer; and an outer layer comprising (or consisting of) about 40 wt% to about 90 wt% of a first polyethylene, about 5 wt% to about 30 wt% of a second polyethylene, about 5 wt% to about 30 wt% of a hydrocarbon resin, and 0 wt% to about 15 wt% of an anti-drip additive.
  • Example 1 Different types of polyethylene polymers were compounded with varying amounts of hydrocarbon resin to generate a hydrocarbon resin master batch (HR-MB). The HR-MB was then compounded with a second polyethylene and blown to form a monolayer film. [0083] Table 1 lists the types of polyethylene that were utilized in each film and, for simplicity for further data reporting, designates a polyethylene (PE) letter to each for further reference. Each is available from ExxonMobil Chemical.
  • PE polyethylene
  • Table 2 lists each experimental composition as well as a TD and MD Elmendorf tear strength measured for each.
  • HR- MB compositions were prepared with 60 wt% OPPERATM PR120, available from ExxonMobil Chemical, and 40 wt% of the polyethylene noted in the first row. In each composition, each masterbatch was compounded with ENABLETM 4002MC at the HR-MB:PE ratio listed in the second row of Table 2. Two control compositions were tested. Reference film #1 was absent the OPPERATM resin. Reference film #2 reflects a film wherein a masterbatch was not first prepared, but where 10 wt% OPPERATM PR120 was compounded directly with the polyethylene. Films of each were prepared having a 50 pm thickness.
  • each of films 1-8 having 20 wt% or 30 wt% of the OPPERATM hydrocarbon resin, has a TD tear strength higher than both of the reference films.
  • Data presented in Table 2 may be visualized graphically in Figure 1. Though the data is not shown, there was no significant loss in the MD tear strength of films 1-8 when compared to the reference films.
  • Example 2 Three-layer films (100 pm thick) were prepared using OPPERATM hydrocarbon resin in one of a first layer, a second layer, and a third. The thickness ratio of first to second to third layers in the films was about 1:1:1, though any ratio could be used.
  • An HR- MB was prepared by compounding OPPERATM PR100 and an LLDPE resin, EXXONMOBILTM LLDPE 1002AY, both sold by ExxonMobil Chemical, at a 50:50 ratio.
  • Table 3 lists the composition of each layer as a ratio of polyethylene (using the letter designations listed in Table 1) to the HR-MB to a surfactant anti-drip additive (“anti-drip”). Table 3 also reports the TD and MD Elmendorf tear strengths of each three-layer film. This data is also shown graphically in Figure 1.
  • incorporation of the OPPERATM hydrocarbon resin generates films having a high MD tear strength that also show improvement in TD tear strength, and vice versa.
  • the films generated are surprising in spite of the general trend that improvement in tear strength in one orientation reduces the tear strength in the opposite orientation.
  • tear strength in both orientations was improved, leading to an overall stronger film than previously available.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Wrappers (AREA)
  • Laminated Bodies (AREA)

Abstract

Les films soufflés peuvent être monocouche ou multicouche, une couche comprenant (ou consistant en) environ 40 % en poids à environ 90 % en poids d'un premier polyéthylène, environ 5 % en poids à environ 30 % en poids d'un second polyéthylène, environ 5 % en poids à environ 30 % en poids d'une résine hydrocarbonée, et 0 % en poids à environ 15 % en poids d'un additif anti-goutte.
PCT/US2021/025933 2020-04-22 2021-04-06 Films de polyéthylène soufflés résistants à la déchirure WO2021216280A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202063013966P 2020-04-22 2020-04-22
US63/013,966 2020-04-22

Publications (1)

Publication Number Publication Date
WO2021216280A1 true WO2021216280A1 (fr) 2021-10-28

Family

ID=75675014

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2021/025933 WO2021216280A1 (fr) 2020-04-22 2021-04-06 Films de polyéthylène soufflés résistants à la déchirure

Country Status (1)

Country Link
WO (1) WO2021216280A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5569693A (en) 1995-06-05 1996-10-29 Borden Inc. High stretch film for pallet wrapping
WO2014144397A2 (fr) * 2013-03-15 2014-09-18 Univation Technologies, Llc Films de polyéthylène catalysé par un hafnocène ayant un développement d'adhérence rapide
US9126269B2 (en) 2010-10-26 2015-09-08 Exxonmobil Chemical Patents Inc. Multilayer polyolefin blown film
US10124528B2 (en) 2014-05-29 2018-11-13 Exxonmobil Chemical Patents Inc. Cyclic-diene additives in polyethylene films and enhanced film orientation balance in production thereof
WO2019022801A1 (fr) * 2017-07-24 2019-01-31 Exxonmobil Chemical Patents Inc. Films de polyéthylène et leurs procédés de production
WO2020068497A1 (fr) * 2018-09-25 2020-04-02 Exxonmobil Chemical Patents Inc. Films multicouches et leurs procédés de fabrication
WO2021034400A1 (fr) * 2019-08-20 2021-02-25 Exxonmobil Chemical Patents Inc. Films et leurs procédés de fabrication

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5569693A (en) 1995-06-05 1996-10-29 Borden Inc. High stretch film for pallet wrapping
US9126269B2 (en) 2010-10-26 2015-09-08 Exxonmobil Chemical Patents Inc. Multilayer polyolefin blown film
WO2014144397A2 (fr) * 2013-03-15 2014-09-18 Univation Technologies, Llc Films de polyéthylène catalysé par un hafnocène ayant un développement d'adhérence rapide
US10124528B2 (en) 2014-05-29 2018-11-13 Exxonmobil Chemical Patents Inc. Cyclic-diene additives in polyethylene films and enhanced film orientation balance in production thereof
WO2019022801A1 (fr) * 2017-07-24 2019-01-31 Exxonmobil Chemical Patents Inc. Films de polyéthylène et leurs procédés de production
WO2020068497A1 (fr) * 2018-09-25 2020-04-02 Exxonmobil Chemical Patents Inc. Films multicouches et leurs procédés de fabrication
WO2021034400A1 (fr) * 2019-08-20 2021-02-25 Exxonmobil Chemical Patents Inc. Films et leurs procédés de fabrication

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Light Scattering from Polymer Solutions", 1972, ACADEMIC PRESS
SUN, T. ET AL., MACROMOLECULES, vol. 34, 2001, pages 6812

Similar Documents

Publication Publication Date Title
US8889794B2 (en) Resin compositions for extrusion coating
KR102037561B1 (ko) 에틸렌-기재 중합체 및 그의 제조 방법
EP2064057B1 (fr) Film moulticouche
EP1276611B1 (fr) Composition et films associes
US5102955A (en) Broad distribution, high molecular weight low density polyethylene and method of making thereof
EP2718365B1 (fr) Compositions de resine ameliorees pour revetement par extrusion
KR20120096405A (ko) 에틸렌계 중합체 조성물
KR20150065750A (ko) 에틸렌-기재 중합체 및 그의 제조 방법
AU2001234711A1 (en) Polyethylene films having improved optical properties
KR20190052684A (ko) 다중 모드 폴리에틸렌 필름
JP6419718B2 (ja) エチレン系ポリマーおよびその製造プロセス
EP3344454B1 (fr) Films multicouches et procédés associés
KR101043187B1 (ko) 압출 코팅용 중합체 조성물
EP1957547B1 (fr) Polymère
CN114096414A (zh) 多层吹塑膜
JP2020514507A (ja) 改善された光学を有するエチレン系ポリマー
US20200231791A1 (en) Blends of linear low density polyethylenes
WO2021216280A1 (fr) Films de polyéthylène soufflés résistants à la déchirure
EP2746320A1 (fr) Composition de polyéthylène ayant des propriétés mécaniques élevées
JP2021503036A (ja) エチレン／ｃｏインターポリマー及びその製造プロセス
WO2023076818A1 (fr) Films de polyéthylène à basse densité linéaire hautement orientés ayant une aptitude au traitement et des propriétés mécaniques exceptionnelles
JP2022544361A (ja) 酸コポリマー樹脂をブレンドすることにより、アルミニウム箔への接着性が強化された低密度ポリエチレン
CN118284565A (zh) 多层膜

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21721751

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21721751

Country of ref document: EP

Kind code of ref document: A1