Biaxially Oriented Polyethylene Films and Process for Production Thereof

Abstract

This invention relates to a biaxially-oriented polyethylene film comprising polyethylene having: (A) a melt index, I2, of 1.0 g/10 min or greater; (B) a density of 0.925 g/cm3 to 0.945 g/cm3; (C) a g′vis of less than 0.8; (D) an Mz of 1,000,000 g/mol or more; (E) an Mw/Mn of 5 or more; (F) an Mw of 100,000 g/mol or more; (G) a ratio of the g′LCB to the g′Zave is greater than 1.0; and (H) a Strain Hardening Ratio of 4 or more, where the film has a 1% secant in the transverse direction of 60,000 psi or more, a Dart Drop of 250 g/mil or more, and a ratio of 1% secant MD/1% secant TD is 0.65 or more.

Description

FIELD OF INVENTION

The present disclosure relates to biaxially-oriented polyethylene films.

BACKGROUND

Films with high strength characteristics, including tensile strength and impact toughness, are needed for packaging applications including food packaging and, stretch-wrap, shrink-wrap, and grocery bags. Films with increasingly thinner thickness that exhibit high strength requirements provide a better cost-performance relationship for the consumer. Biaxial orientation of polymer films can be used to improve the strength characteristics while reducing the thickness of films.

Packaging applications of biaxially oriented films is dominated by polypropylene. For example, over 60% of the biaxially oriented film market is represented by polypropylene and obtained with sequential tenter process. The strength and success of biaxially oriented polypropylene films is due an excellent processability (broad stretching temperature profile, slow crystallization), good overall properties, attractive costs (high production speed), and good yield (low density).

Polyethylene films are of recent interest in the field because polyethylene is more readily recycled. However, polyethylene tends to have a higher crystallinity than polypropylene, making it more difficult to down gauge and maintain a suitable balance of stiffness and toughness characteristics.

U.S. Pat. No. 9,068,033 discloses ethylene hexene copolymers having, inter alia, a g′_vis of less than 0.8, a melt index, I2, of 0.25 to 1.5 g/10 min, that are converted into films.

U.S. Pat. Nos. 5,955,625; 6,168,826; 6,225,426; 9,266,977; EP 2935367; US patent application publication numbers: US 2008/0233375; US 2016/0031191; US 2015/0258756; US 2009/0286024; US 2018/0237558; US 2018/0237559; US 2018/0237554; US 2018/0319907; US 2018/0023788; WIPO patent application publication numbers: WO 2017/127808; WO 2015/154253; WO 2015/138096; WO 1997/022470; Japanese Pat. App. Pub. No. 2016/147430; Kim, W. N. et al. (1994) “Morphology and Mechanical Properties of Biaxially Oriented Films of Polypropylene and HDPE Blends,” Appl. Polym. Sci., v. 54(11), pp. 1741-1750; Ratta, V. et al. (2001) “Structure-Property-Processing Investigations of the Tenter-Frame Process for Making Biaxially Oriented HDPE Film. I. Base Sheet and Draw Along the MD” Polymer, v. 42(21), pp. 9059-9071; Ajji, A. et al. (2004) “Biaxial Stretching and Structure of Various LLDPE Resins” Polym. Eng. Sci., v. 44(2), pp. 252-260; Ajji, A. et al. (2006) “Biaxial Orientation in LLDPE Films: Comparison of Infrared Spectroscopy, X-ray Pole Figures, and Birefringence Techniques,” Polym. Eng. Sci., v. 46(9), pp. 1182-1189; Uehara, H et al. (2004) “Stretchability and Properties of LLDPE Blends for Biaxially Oriented Film,” Intern. Polymer Processing, v. 19(2), pg. 163; Bobovitch, A. L. et al. (2006) “Mechanical Properties Stress-Relaxation, and Orientation of Double Bubble Biaxially Oriented Polyethylene Films,” J. Appl. Poly. Sci., v. 100(5), pp. 3545-3553; Sun, T. et al. (2001) Macromolecules, v. 34(19), pp. 6812-6820; Stadelhofer, J. et al. (1975) “Darstellung und Eigenschaften von Alkylmetallcyclo-Pentadienderivaten des Aluminiums, Galliums und Indiums,” Jrnl. Organometallic Chem., v. 84, pp. C1-C4 and Chen, Q. et al. (2019) “Structure Evolution of Polyethylene in Sequential Biaxial Stretching along the First Tensile Direction,” Ind. Eng. Chem. Res., V. 58, pp. 12419-12430.

SUMMARY OF THE INVENTION

The present disclosure relates to biaxially-oriented polyethylene films comprising polyethylene, such as linear low density polyethylene (LLDPE), with properties that improve processability while maintaining stiffness and high impact resistance.

This invention relates to biaxially-oriented polyethylene film comprising polyethylene having: (A) a melt index, I₂, of 1.0 g/10 min or greater; (B) a density of 0.92 g/cm³ to 0.94 g/cm³; (C) a g′_LCB of less than 0.8; (D) an Mz of 1,000,000 g/mol or more; (E) an Mw/Mn of 5 or more; (F) an Mw of 100,000 g/mol or more; (G) a ratio of the g′_LCB to the g′_Zave is greater than 1.0; and (H) a Strain Hardening Ratio of 4 or more, where the film has a 1% secant in the transverse direction of 60,000 psi or more, a Dart Drop of 250 g/mil or more, and a ratio of 1% secant MD/1% secant TD is 0.65 or more.

The present disclosure also relates to compositions comprising: a biaxially-oriented film comprising a polyethylene having: (A) a melt index, I₂, of 1.0 g/10 min or greater; (B) a density of 0.925 g/cm³ to 0.945 g/cm³; (C) a g′_LCB of less than 0.8; (D) an Mz of 1,000,000 g/mol or more; (E) an Mw/Mn of 5 or more; (F) an Mw of 100,000 g/mol or more; (G) a ratio of the g′_LCB to the g′_Zave is greater than 1.0; and (H) a Strain Hardening Ratio of 4 or more, where the film has a 1% secant in the transverse direction of 60,000 psi or more, a Dart Drop of 250 g/mil or more, and a ratio of 1% secant MD/1% secant TD is 0.65 or more.

The present disclosure also relates to methods comprising: producing a polymer melt comprising polymer described above; extruding a film from the polymer melt; and stretching the film in a machine direction to produce a machine direction oriented (MDO) polyethylene film; and stretching the MDO polyethylene film in a transverse direction to produce a biaxially-oriented polyethylene film.

DETAILED DESCRIPTION

The present disclosure relates to biaxially-oriented polyethylene films comprising a LLDPE with well-defined properties that improve processability while maintaining mechanical properties such as stiffness, tensile strength, impact and puncture resistance. More specifically, the polyethylene of the present disclosure has: (A) a melt index, I₂, of 1.0 g/10 min or greater; (B) a density of 0.925 g/cm³ to 0.945 g/cm³; (C) a g′_LCB of less than 0.8; (D) an Mz of 1,000,000 g/mol or more; (E) an Mw/Mn of 5 or more; (F) an Mw of 100,000 g/mol or more; (G) a ratio of the g′_LCB to the g′_Zave is greater than 1.0; and (H) a Strain Hardening Ratio of 4 or more, where the film has a 1% secant in the transverse direction of 60,000 psi or more, a Dart Drop of 250 g/mil or more, and a ratio of 1% secant MD/1% secant TD is 0.65 or more. The polyethylene may be further characterized by having: (A) a melt index, I₂, of 1.5 g/10 min to 5 g/10 min; (B) a density of 0.925 g/cm³ to 0.945 g/cm³; (C) a g′_LCB of less than 0.8 to 0.5; (D) an Mz of 1,200,000 g/mol or more; (E) an Mw/Mn of 5 to 10; (F) an Mw of 100,000 to 200,000 g/mol; (G) a ratio of the g′_LCB to the g′_Zave of 1.5 to 10; and (H) a Strain Hardening Ratio of 4.5 or more. Such a LLDPE is easier to process and stretch. As a result, the extruded polyethylene films can be stretched to a greater extent under a wider temperature window and achieve the physical properties like the toughness of thicker films produced with other LLDPEs.

Definitions and Test Methods

Unless otherwise indicated, room temperature is 25° C.

An “olefin,” alternatively referred to as “alkene,” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond.

A “polymer” has two or more of the same or different mer units. A “homopolymer” is a polymer having mer units that are the same. 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.

As used herein, unless specified otherwise, the term “copolymer(s)” refers to polymers formed by the polymerization of at least two different monomers (i.e., mer units). For example, the term “copolymer” includes the copolymerization reaction product of propylene and an alpha-olefin, such as ethylene, 1-hexene. A “terpolymer” is a polymer having three mer units that are different from each other. Thus, the term “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. An “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. For purposes of this invention, a polyethylene is an ethylene polymer.

As used herein, when a polymer is referred to as “comprising, consisting of, or consisting essentially of” a monomer, the monomer is present in the polymer in the polymerized/derivative form of the monomer. For example, 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.

A “low density polyethylene,” LDPE, is an ethylene polymer having a density of more than 0.90 g/cm³ to less than 0.94 g/cm³; this class of polyethylene includes copolymers made using a heterogeneous catalysis process (often identified as linear low density polyethylene, LLDPE) and homopolymers or copolymers made using a high-pressure/free radical process (often identified as LDPE). A “linear low density polyethylene,” LLDPE, is an ethylene polymer having a density of more than 0.90 g/cm³ to less than 0.94 g/cm³, preferably from 0.910 to 0.935 g/cm³ and typically having a g′_LCB of 0.95 or more. A “high density polyethylene” (“HDPE”) is an ethylene polymer having a density of 0.94 g/cm³ or more.

Density, reported in g/cm³, is determined in accordance with ASTM 1505-10 (the plaque is and molded according to ASTM D4703-10a, procedure C, plaque preparation, including that the plaque is conditioned for at least forty hours at 23° C. to approach equilibrium crystallinity), where the measurement for density is made in a density gradient column.

As used herein, Mn is number average molecular weight, Mw is weight average molecular weight, and Mz is z-average molecular weight. Polydispersity index (PDI) is defined to be Mw divided by Mn. Unless otherwise noted, all molecular weights (e.g., Mw, Mn, Mz) are reported in units of g/mol.

Gel Permeation Chromatography (GPC) is a liquid chromatography technique used to measure, inter alia, the molecular weight and polydispersity of polymers.

Unless otherwise indicated, 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-μm Mixed-B LS columns are used to provide polymer separation. Aldrich reagent grade 1,2,4-trichlorobenzene (TCB) with 300 ppm antioxidant butylated hydroxytoluene (BHT) is used as the mobile phase. The TCB mixture is filtered through a 0.1-μm 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 μL. 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-μL flow marker (heptane) added to it. After loading the vial in the autosampler, polymer is dissolved in the instrument with 8 mL added TCB solvent. The polymer is dissolved at 160° C. with continuous shaking for about 1 hour for polyethylene samples or about 2 hours for polypropylene samples. The TCB densities used in concentration calculation is 1.463 g/ml at room temperature and 1.284 g/mL at 145° C. The sample solution concentration is from 0.2 to 2.0 mg/mL, with lower concentrations being used for higher molecular weight samples. The concentration (c), at each point in the chromatogram is calculated from the baseline-subtracted IR5 broadband signal intensity (I), using the following equation: c=βI, where β is the mass constant. The mass recovery can be calculated from the ratio of the integrated area of the concentration chromatography over elution volume and the injection mass, which is equal to the pre-determined concentration multiplied by injection loop volume. The conventional molecular weight (IR molecular weight) is determined by combining universal calibration relationship with the column calibration, which is performed with a series of monodispersed polystyrene (PS) standards ranging from 700 to 10,000,000 gm/mole. The molecular weight at each elution volume is calculated with (1):

$\begin{array}{cc}\log M=\frac{\log \left(K_{\mathrm{PS}}/K\right)}{a+1}+\frac{a_{\mathrm{PS}}+1}{a+1}\log M_{\mathrm{PS}}& \mathrm{EQ}.1\end{array}$

where the variables with subscript “PS” stand for polystyrene while those without a subscript are for the test samples. In this method, α_PS=0.67 and K_PS=0.000175 while α and K for other materials are as calculated and published in literature (Sun, T. et al. (2001) Macromolecules, v. 34, pg. 6812), except that for purposes of this invention and claims thereto, α=0.705 and K=0.0002288 for linear propylene polymers, α=0.695 and K=0.000181 for linear butene polymers, α is 0.695 and K is 0.000579*(1-0.0087*w2b+0.000018*(w2b){circumflex over ( )}2) for ethylene-butene copolymer where w2b is a bulk weight percent of butene comonomer, α is 0.695 and K is 0.000579*(1-0.0075*w2b) for ethylene-hexene copolymer where w2b is a bulk weight percent of hexene comonomer, and α is 0.695 and K is 0.000579*(1-0.0077*w2b) for ethylene-octene copolymer where w2b is a bulk weight percent of octene comonomer, and α=0.695 and K=0.000579 for all other linear ethylene polymers. Concentrations are expressed in g/cm³, molecular weight is expressed in g/mole, and intrinsic viscosity (hence K in the Mark-Houwink equation) is expressed in dL/g, unless otherwise noted.

The comonomer composition is determined by the ratio of the IR5 detector intensity corresponding to CH₂ and CH₃ channel calibrated with a series of polyethylene and propylene homo/copolymer standards whose nominal value are predetermined by NMR or FTIR. In particular, this provides the methyls per 1,000 total carbons (CH₃/1000TC) as a function of molecular weight. The short-chain branch (SCB) content per 1,000 TC (SCB/1000TC) can be then computed as a function of molecular weight by applying a chain-end correction to the CH₃/1000TC function, assuming each chain to be linear and terminated by a methyl group at each end. The weight % comonomer can be then obtained from the following expression in which f is 0.3, 0.4, 0.6, 0.8, and so on for C₃, C₄, C₆, C₈, and so on co-monomers, respectively:

w2=f*SCB/1000 TC  EQ. 2

The bulk composition of the polymer from the GPC-IR and GPC-4D analyses is obtained by considering the entire signals of the CH₃ and CH₂ channels between the integration limits of the concentration chromatogram. First, the following ratio is obtained.

$\begin{array}{cc}\mathrm{Bulk}\mathrm{IR}\mathrm{ratio}=\frac{\mathrm{Area}\mathrm{of}{\mathrm{CH}}_3\mathrm{signal}\mathrm{within}\mathrm{integration}\mathrm{limits}}{\mathrm{Area}\mathrm{of}{\mathrm{CH}}_2\mathrm{signal}\mathrm{within}\mathrm{integration}\mathrm{limits}}& \mathrm{EQ}.3\end{array}$

Then the same calibration of the CH₃ and CH₂ signal ratio, as mentioned previously in obtaining the CH₃/1000TC as a function of molecular weight, is applied to obtain the bulk CH₃/1000TC. A bulk methyl chain ends per 1,000TC (bulk CH₃end/1000TC) is obtained by weight-averaging the chain-end correction over the molecular-weight range. Then,

w2b=f*bulk CH₃/1000TC  EQ. 4

bulk SCB/1000TC=bulk CH₃/1000TC−bulk CH₃end/1000TC  EQ. 5

and bulk SCB/1000TC are converted to bulk w2 in the same manner as described above.

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):

$\begin{array}{cc}\frac{K_{o}c}{\Delta R\left(\theta \right)}=\frac{1}{\mathrm{MP}\left(\theta \right)}+2A_{2}c& \mathrm{EQ}.6\end{array}$

Here, ΔR(θ) is the measured excess Rayleigh scattering intensity at scattering angle θ, c is the polymer concentration determined from the IR5 analysis, A₂ is the second virial coefficient, P(O) is the form factor for a monodisperse random coil, and K_O is the optical constant for the system:

$\begin{array}{cc}{K}_o=\frac{4{\pi }^2{n^2\left(\mathrm{dn}/\mathrm{dc}\right)}^2}{{\lambda }^4{N}_A}{K}_o=\frac{4{\pi }^2{n^2\left(\mathrm{dn}/\mathrm{dc}\right)}^2}{{\lambda }^4{N}_A}& \mathrm{EQ}.7\end{array}$

where N_A is Avogadro's number, and (dn/dc) is the refractive index increment for the system, n=1.500 for TCB at 145° C., and λ=665 nm. For analyzing ethylene homopolymers, ethylene-hexene copolymers, and ethylene-octene copolymers, dn/dc=0.1048 ml/mg and A₂=0.0015; for analyzing ethylene-butene copolymers, dn/dc=0.1048*(1-0.00126*w2) ml/mg and A₂=0.0015 where w2 is weight percent butene comonomer, for all other ethylene polymers dn/dc=0.1048 ml/mg and A₂=0.0015.

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. The specific viscosity, η_S, for the solution flowing through the viscometer is calculated from their outputs. The intrinsic viscosity, [η], at each point in the chromatogram is calculated from the equation [η]=η_S/c, where c is concentration and is determined from the IR5 broadband channel output. The viscosity MW at each point is calculated as M=K_PSM^αPS+1/[η], where α_ps is 0.67 and K_PS is 0.000175. The average intrinsic viscosity, [η] of the sample is calculated by:

$\begin{array}{cc}\langle \left[\eta \right]\rangle =\frac{\sum {c_i\left[\eta \right]}_i}{\sum c_i}& \mathrm{EQ}.8\end{array}$

where the summations are over the chromatographic slices, i, between the integration limits.

The long chain branching index (g′_LCB, also referred to as g′_vis) is defined as

$\begin{array}{cc}{g}_{\mathrm{LCB}}^{\prime }=\frac{\langle \left[\eta \right]\rangle }{K{\langle M_{\mathrm{IR}}\rangle }^{\alpha }}& \mathrm{EQ}.9\end{array}$

where M_IR 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. (2001) Macromolecules, v. 34, pg. 6812), except that for purposes of this invention and claims thereto, α=0.705 and K=0.0002288 for linear propylene polymers, α=0.695 and K=0.000181 for linear butene polymers, α is 0.695 and K is 0.000579*(1-0.0087*w2b+0.000018*(w2b){circumflex over ( )}2) for ethylene-butene copolymer where w2b is a bulk weight percent of butene comonomer, α is 0.695 and K is 0.000579*(1-0.0075*w2b) for ethylene-hexene copolymer where w2b is a bulk weight percent of hexene comonomer, and α is 0.695 and K is 0.000579*(1-0.0077*w2b) for ethylene-octene copolymer where w2b is a bulk weight percent of octene comonomer, and α=0.695 and K=0.0005 for all other linear ethylene polymers.

The g′_Mz is determined by selecting the g′ value at the Mz value on the GPC-4D trace produced by the GPC method described above. The Mz value is obtained from the LS detector. For example, if the Mz-LS is 300,000 g/mol, the value on the g′ trace on the GPC-4D graph at 300,000 g/mol is used. The g′_Mw is determined by selecting the g′ value at the Mw value on the GPC-4D trace. The Mw value is obtained from the LS detector. For example, if the Mw-LS is 100,000 g/mol, the value on the g′ trace on the GPC-4D graph at 100,000 g/mol is used. The g′_Mn is determined by selecting the g′ value at the Mn value on the GPC-4D trace. The Mz value is obtained from the LS detector. For example, if the Mn-LS is 50,000 g/mol, the value on the g′ trace on the GPC-4D graph at 50,000 g/mol is used.

Comonomer contents at the Mw, Mn, and Mz are determined by GPC-4D using the molecular weight values obtained by the LS detector.

The small amplitude oscillatory shear (SAOS) measurements were made on the Anton Paar MCR702 Rheometer. Samples were compression molded at 177° C. for 15 minutes (including cool down under pressure). Then, a 25 mm testing disk specimen was die cut from the resulting plaques. Testing was conducted using a 25 mm parallel plate geometry. Amplitude sweeps were performed on all samples to determine the linear deformation regime. For amplitude sweep, the strain was set from 0.1% to 100% with a frequency of 6 rad/sec and temperature of 190° C. Once the linearity was established, frequency sweeps were performed to determine the complex viscosity profile from 0.01 rad/s to 500 rad/s at T=190° C. under 5% strain.

In order to quantify the shear-like rheological behavior, we define the degree of shear thinning (DST) parameter. The DST was measured by the following expression:

$\begin{array}{cc}\mathrm{DST}=\frac{\left[{\eta }_{0.01}-{\eta }_{50}\right]}{{\eta }_{0.01}}& \mathrm{EQ}.10\end{array}$

Where η_0.01 and η₅₀ are the complex viscosities at frequencies of 0.01 rad/s and 50 rad/s, respectively, measured at 190° C. The DST parameter helps to better differentiate and highlight the branching character of the samples.

The tensile evolution of the transient extensional viscosity was investigated by MCR501 rheometer available from Anton Paar with controlled operational speed. The linear viscoelastic envelope (LVE) is obtained from start-up steady shear experiments. Strain hardening is defined as a rapid and abrupt leveling-off of the extensional viscosity from the linear viscoelastic behavior. Therefore, this nonlinear behavior was quantified by the strain hardening ratio (SHR), which is defined as the ratio of the maximum transient extensional viscosity (η_E*) at 1 s⁻¹ over the respective value at 0.1 s⁻¹:

$\begin{array}{cc}\mathrm{SHR}=\frac{{\eta }_E^{*}\left(\epsilon =1s^{-1},t\right)}{{\eta }_E^{*}\left(\epsilon =0.1s^{-1},t\right)}& \mathrm{EQ}.11\end{array}$

The value at 0.1 s⁻¹ was preferred to LVE because of the choice to adopt only transient extensional and not start-up steady shear data in the treatment. Whenever the SHR is greater than 1, the material exhibits strain hardening.

Unless otherwise indicated, the differential scanning calorimetry (DSC) measurements were performed with TA Instruments' Discovery 2500. Melting point or melting temperature (Tm), crystallization temperature (Tc), and heat of fusion or heat flow (ΔH_f or H_f) were determined using the following DSC procedure. Samples weighing approximately 2 mg to 5 mg were sealed in aluminum hermetic pan. Heat flow was normalized with the sample mass. The DSC runs were ramped from 0° C. to 200° C. at a rate of 10° C./min. After equilibration for 45 sec, the samples were cooled down at 10° C./min to 0° C. Both first and second thermal cycles were recorded. Unless otherwise specified, DSC measurements are based on the 2^nd crystallization and melting ramps. The melting temperature (T_m) and crystallization temperature (T_c) were calculated by integrating the melting and crystallization peaks (area below the curves). The endothermic melting transition is analyzed for onset of transition and peak temperature and is considered to show a broad melting peak if at least 7° C. are between the onset of transition and the peak temperature. For samples displaying multiple peaks, the melting temperature is defined to be the peak melting temperature (i.e., associated with the largest endothermic calorimetric response in that range of temperatures) from the DSC melting trace.

As used herein, a “peak” occurs where the first derivative of the corresponding curve changes sign from positive value to negative value. As used herein, a “valley” occurs where the first derivative of the corresponding curve changes from a negative value to a positive value.

Melt flow index (MFI) or 12 was measured according to ASTM 1238-13 on a Goettfert MI-4 Melt Indexer. Testing conditions were set at 190° C. and 2.16 kg load. An amount of 5 g to 6 g of sample was loaded into the barrel of the instrument at 190° C. and manually compressed. Afterwards, the material was automatically compacted into the barrel by lowering all available weights onto the piston to remove all air bubbles. Data acquisition was started after a 6 minute pre-melting time. Also, the sample was pressed through a die of 8 mm length and 2.095 mm diameter.

As used herein, the terms “machine direction” and “MD” refer to the stretch direction in the plane of the film.

As used herein, the terms “transverse direction” and “TD” refer to the perpendicular direction in the plane of the film relative to the MD.

As used herein, the term “extruding” and grammatical variations thereof refer to processes that includes forming a polymer and/or polymer blend into a melt, such as by heating and/or sheer forces, and then forcing the melt out of a die in a form or shape such as in a film. Most any type of apparatus will be appropriate to effect extrusion such as a single or twin-screw extruder, or other melt-blending device as is known in the art and that can be fitted with a suitable die.

Gauge of a Film was Determined by ASTM D6988-13.

1% secant modulus and tensile properties, including yield strength, elongation at yield, tensile strength, and elongation at break, were determined by ASTM D882-10, with the following modifications: a jaw separation of 5 inches and a sample width of 1-inch is used. The index of stiffness of thin films is determined by manually loading the samples with slack and pulling the specimen at a rate of jaw separation (crosshead speed) of 0.5 inches per minute to a designated strain of 1% of its original length and recording the load at these points.

The calculation procedures are as follows:

Tensile strength is calculated as a function of the maximum force in pounds divided by the cross-sectional area of the specimen. Ultimate Tensile=Maximum Force/Cross-Sectional Area.

Yield strength is calculated as a function of the force at yield divided by the cross-sectional area of the specimen. Yield Strength=Force at Yield/Cross-Sectional Area.

Elongation is calculated as a function of the increase in length divided by the original length times 100. Elongation=Increase in Length/Original Length×100%.

Yield point is the first point in which there is an increase in strain (elongation) and none in stress (force). The yield is determined by a 2% off-set method.

Tensile at 100% Elongation is calculated as a function of the force at 100% elongation divided by the cross-sectional area of the specimen. Tensile at 100% Elongation=Force at 100% Elongation/Cross-Sectional Area.

Tensile at 200% Elongation is calculated as a function of the force at 200% elongation divided by the cross-sectional area of the specimen. Tensile at 200% Elongation=Force at 200% Elongation/Cross-Sectional Area.

The 1% secant modulus is measured of the material stiffness and is calculated as a function of the total force at 1% extension, divided by the cross-sectional area times 100 and reported in PSI units. 1% Secant Modulus=Load at 1% Elongation/(Average Thickness (Inches)×Width)×100.

Clarity was determined by ASTM D1746-15.

Haze was determined by ASTM D1003-13.

Gloss was determined by ASTM D2457-13.

Dart drop was determined by phenolic Method A per ASTM D1709-16ae1.

Puncture properties including peak force, peak force per mil, break energy, and break energy per mil were determined by ASTM D5748, with the following modifications. Any film sample ˜1 mil thick is placed in a circular clamp approximately 4 inches wide. A stainless steel custom-made plunger/probe with a ¾″ tip and two 0.25 mil slip sheets are pressed through the specimen at a constant speed of 10 in/min. Results are obtained after failure from five different locations chosen on the standard film strip and averaged.

As used herein, a measurement per mil is calculated by dividing the value of the measurement by the value of the thickness of the film. For example, a 2 mil film having a peak force of 50 lbs has a peak force per mil of 25 lbs/mil.

Shrink (in both Machine (MD) and Transverse (TD) directions) was measured as the percentage decrease in length of a 100 cm circle of film along the MD and TD, under a heat gun (Model HG-501A) set with an average temperature of 750° F. (399° C.). The heat gun was centered two inches over the sample and heat was applied until each specimen stopped shrinking.

Water vapor transmission rate (WVTR) performed on a MOCON Permatran W-700 and W3/61 obtained from MOCON, Inc. using ASTM F1249 at 100° F. (37.8° C.) and 100% relative humidity where samples were loaded without specific orientation.

Polyethylene Synthesis

For the purposes of this invention and the claims thereto, the new numbering scheme for the Periodic Table Groups is used as described in Chemical and Engineering News, v. 63(5), pg. 27 (1985). Therefore, a “group 4 metal” is an element from group 4 of the Periodic Table, e.g. Hf, Ti, or Zr.

The terms “hydrocarbyl radical,” “hydrocarbyl group,” or “hydrocarbyl” may be used interchangeably and are defined to mean a group consisting of hydrogen and carbon atoms only. Preferred hydrocarbyls are C₁-C₁₀₀ radicals that may be linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic. Examples of such radicals include, but are not limited to, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like, aryl groups, such as phenyl, benzyl naphthyl, and the like.

A “metallocene” catalyst compound is a transition metal catalyst compound having one, two or three, typically one or two, substituted or unsubstituted cyclopentadienyl ligands bound to the transition metal, typically a metallocene catalyst is an organometallic compound containing two π-bound cyclopentadienyl moieties (or substituted cyclopentadienyl moieties).

Substituted or unsubstituted cyclopentadienyl ligands include substituted or unsubstituted cyclopentadienyl, indenyl, fluorenyl, tetrahydro-s-indacenyl, tetrahydro-as-indacenyl, benz[f]indenyl, benz[e]indenyl, tetrahydrocyclopenta[b]naphthalene, tetrahydrocyclopenta[a]naphthalene, and the like.

Unless otherwise indicated, (e.g., the definition of “substituted hydrocarbyl,” etc.), the term “substituted” means that at least one hydrogen atom has been replaced with at least one non-hydrogen group, such as a hydrocarbyl group, a heteroatom, or a heteroatom containing group, such as halogen (such as Br, Cl, F or I) or at least one functional group such as —NR*₂, —OR*, —SeR*, —TeR*, —PR*₂, —AsR*₂, —SbR*₂, —SR*, —BR*₂, —SiR*₃, —GeR*₃, —SnR*₃, —PbR*₃, —(CH₂)q-SiR*₃, and the like, where q is 1 to 10 and each R* is independently hydrogen, a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted completely saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), or where at least one heteroatom has been inserted within a hydrocarbyl ring.

The term “substituted hydrocarbyl” means a hydrocarbyl radical in which at least one hydrogen atom of the hydrocarbyl radical has been substituted with at least one heteroatom (such as halogen, e.g., Br, Cl, F or I) or heteroatom-containing group (such as a functional group, e.g., —NR*₂, —OR*, —SeR*, —TeR*, —PR*₂, —AsR*₂, —SbR*₂, —SR*, —BR*₂, —SiR*₃, —GeR*₃, —SnR*₃, —PbR*₃, —(CH₂)q-SiR*₃, and the like, where q is 1 to 10 and each R* is independently hydrogen, a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted completely saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), or where at least one heteroatom has been inserted within a hydrocarbyl ring.

For purposes of the present disclosure, in relation to metallocene compounds, the term “substituted” means that a hydrogen group has been replaced with a hydrocarbyl group, a heteroatom, or a heteroatom containing group, such as halogen (such as Br, Cl, F or I) or at least one functional group such as —NR*₂, —OR*, —SeR*, —TeR*, —PR*₂, —AsR*₂, —SbR*₂, —SR*, —BR*₂, —SiR*₃, —GeR*₃, —SnR*₃, —PbR*₃, —(CH₂)q-SiR*₃, and the like, where q is 1 to 10 and each R* is independently hydrogen, a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted completely saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), or where at least one heteroatom has been inserted within a hydrocarbyl ring.

The inventive ethylene-based copolymers useful herein are preferably made in a process comprising contacting ethylene and of one or more C₃ to C₂₀ olefins in at least one gas phase reactor at a temperature in the range of from 60° C. to 90° C. and at a reactor pressure of from 70 kPa to 7,000 kPa, in the presence of a metallocene catalyst system.

Preferred metallocene catalyst systems include an activator and a bridged metallocene compound.

Particularly useful bridged metallocene compounds include those represented by the following formula:

wherein:

M is a group 4 metal, especially zirconium or hafnium;

T is a group 14 atom, preferably Si or C;

D is hydrogen, methyl, or a substituted or unsubstituted aryl group, most preferably phenyl;

R^a and R^b are independently, hydrogen, halogen, or a C₁ to C₂₀ substituted or unsubstituted hydrocarbyl, and R^a and R^b can form a cyclic structure including substituted or unsubstituted aromatic, partially saturated, or saturated cyclic or fused ring system;

each X¹ and X² is independently selected from the group consisting of C₁ to C₂₀ substituted or unsubstituted hydrocarbyl groups, hydrides, amides, amines, alkoxides, sulfides, phosphides, halides, dienes, phosphines, and ethers, and X¹ and X² can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system;

each of R¹, R², R³, R⁴, and R⁵ is, independently, hydrogen, halide, alkoxide or a C₁ to C₂₀ or C₄₀ substituted or unsubstituted hydrocarbyl group, and any of adjacent R², R³, R⁴, and/or R⁵ groups may form a fused ring or multicenter fused ring systems, where the rings may be substituted or unsubstituted, and may be aromatic, partially unsaturated, or unsaturated; and

each of R⁶, R⁷, R⁸, and R⁹ is, each independently, hydrogen or a C₁ to C₂₀ or C₄₀ substituted or unsubstituted hydrocarbyl group, most preferably methyl, ethyl or propyl; and

further provided that at least two of R⁶, R⁷, R⁸, and R⁹ are C₁ to C₄₀ substituted or unsubstituted hydrocarbyl groups; wherein “hydrocarbyl” (or “unsubstituted hydrocarbyl”) refers to carbon-hydrogen radicals such as methyl, phenyl, iso-propyl, napthyl, etc. (aliphatic, cyclic, and aromatic compounds consisting of carbon and hydrogen), and “substituted hydrocarbyl” refers to hydrocarbyls that have at least one heteroatom bound thereto such as carboxyl, methoxy, phenoxy, BrCH₃—, NH₂CH₃—, etc.

Preferred metallocene compounds may be represented by the following formula:

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R^a, R^b, X¹, X², T, and M are as defined above; and R¹⁰, R¹¹, R¹², R¹³, and R¹⁴ are each independently H or a C¹ to C⁴⁰ substituted or unsubstituted hydrocarbyl.

Particularly preferred metallocene compounds useful herein are represented by the formula:

wherein R¹, R², R³, R⁴, R⁵, R^a, R^b, X¹, X², T, D, and M are as defined above.

In particularly preferred embodiments, metallocene compounds useful herein may be represented by the following structure:

wherein R¹, R², R³, R⁴, R⁵, R^a, R^b, X¹, X², T, and M are as defined above. In a useful embodiment, R¹, R², R³, R⁴, and R⁵ are H, and R^a, R^b, X¹, X², T, and M are as defined above.

Examples of preferred metallocene compounds include: dimethylsilylene(3-phenyl-1-indenyl)(2,3,4,5-tetramethyl-1-cyclopentadienyl)zirconium dichloride; dimethylsilylene(3-phenyl-1-indenyl)(2,3,4,5-tetramethyl-1-cyclopentadienyl) zirconium methyl; bis(n-propyl ccyclopentadienyl)Hf dimethyl bis(n-propyl cyclopentadienyl)Hf dichloride; and the like.

In a preferred embodiment, the metallocene compound is dimethylsilylene(3-phenyl-1-indenyl)(2,3,4,5-tetramethyl-1-cyclopentadienyl)zirconium dichloride.

The polymerization process of the present invention may be carried out using any suitable process, such as, for example, solution, slurry, high pressure, and gas phase. A particularly desirable method for producing polyolefin polymers according to the present invention is a gas phase polymerization process preferably utilizing a fluidized bed reactor. Desirably, gas phase polymerization processes are such that the polymerization medium is either mechanically agitated or fluidized by the continuous flow of the gaseous monomer and diluent. Other gas phase processes contemplated by the process of the invention include series or multistage polymerization processes.

The metallocene catalyst is used with an activator in the polymerization process to produce the inventive polyethylenes. The term “activator” is used herein to be any compound which can activate any one of the metallocene compounds described above by converting the neutral catalyst compound to a catalytically active metallocene compound cation. Preferably the catalyst system comprises an activator. Activators useful herein include alumoxanes or “non-coordinating anion” activators such as boron-based compounds (e.g., tris(perfluorophenyl)borane, or ammonium tetrakis(pentafluorophenyl)borate).

The catalyst systems useful herein can include at least one non-coordinating anion (NCA) activator, such as NCA activators represented by the formula below:

Z_d⁺(A^d−)

where: Z is (L-H) or a reducible Lewis acid; L is a neutral Lewis base; H is hydrogen; (L-H) is a Bronsted acid; A^d− is a boron containing non-coordinating anion having the charge d−; d is 1, 2, or 3.

The cation component, Z_d⁺ may include Bronsted acids such as protons or protonated Lewis bases or reducible Lewis acids capable of protonating or abstracting a moiety, such as an alkyl or aryl, from the bulky ligand metallocene containing transition metal catalyst precursor, resulting in a cationic transition metal species.

The activating cation Z_d⁺ may also be a moiety such as silver, tropylium, carboniums, ferroceniums and mixtures, preferably carboniums and ferroceniums. Most preferably Z_d⁺ is triphenyl carbonium. Preferred reducible Lewis acids can be any triaryl carbonium (where the aryl can be substituted or unsubstituted, such as those represented by the formula: (Ar₃C⁺), where Ar is aryl or aryl substituted with a heteroatom, a C₁ to C₄₀ hydrocarbyl, or a substituted C₁ to C₄₀ hydrocarbyl), preferably the reducible Lewis acids in formula (14) above as “Z” include those represented by the formula: (Ph₃C), where Ph is a substituted or unsubstituted phenyl, preferably substituted with C₁ to C₄₀ hydrocarbyls or substituted a C₁ to C₄₀ hydrocarbyls, preferably C₁ to C₂₀ alkyls or aromatics or substituted C₁ to C₂₀ alkyls or aromatics, preferably Z is a triphenylcarbonium.

When Z_d⁺ is the activating cation (L-H)_d⁺, it is preferably a Bronsted acid, capable of donating a proton to the transition metal catalytic precursor resulting in a transition metal cation, including ammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof, preferably ammoniums of methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine, triphenylphosphine, and diphenylphosphine, oxomiuns from ethers such as dimethyl ether diethyl ether, tetrahydrofuran and dioxane, sulfoniums from thioethers, such as diethyl thioethers, tetrahydrothiophene, and mixtures thereof.

The anion component A^d− includes those having the formula [M^k+Q_n]^d− wherein k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6 (preferably 1, 2, 3, or 4); n−k=d; M is an element selected from Group 13 of the Periodic Table of the Elements, preferably boron or aluminum, and Q is independently a hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, said Q having up to 20 carbon atoms with the proviso that in not more than 1 occurrence is Q a halide. Preferably, each Q is a fluorinated hydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q is a fluorinated aryl group, and most preferably each Q is a pentafluoryl aryl group. Examples of suitable A^d− also include diboron compounds as disclosed in U.S. Pat. No. 5,447,895, which is fully incorporated herein by reference.

Illustrative, but not limiting examples of boron compounds which may be used as an activating cocatalyst are the compounds described as (and particularly those specifically listed as) activators in U.S. Pat. No. 8,658,556, which is incorporated by reference herein.

Most preferably, the activator Z_d⁺ (A^d−) is one or more of N,N-dimethylanilinium tetra(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or triphenylcarbenium tetra(perfluorophenyl)borate.

Alternately, preferred activators may include alumoxane compounds (or “alumoxanes”) and modified alumoxane compounds. Alumoxanes are generally oligomeric compounds containing —Al(R¹)—O— sub-units, where R¹ is an alkyl group. Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane, isobutylalumoxane, and mixtures thereof. Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, particularly when the abstractable ligand is an alkyl, halide, alkoxide, or amide. Mixtures of different alumoxanes and modified alumoxanes may also be used. It may be preferable to use a visually clear methylalumoxane. A cloudy or gelled alumoxane can be filtered to produce a clear solution or clear alumoxane can be decanted from the cloudy solution. Another useful alumoxane is a modified methylalumoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A, disclosed in U.S. Pat. No. 5,041,584). Preferably of this invention, the activator is an alkylalumoxane, preferably methylalumoxane or isobutylalumoxane, most preferably methylalumoxane.

Preferably, the activator is supported on a support material prior to contact with the metallocene compound. Also, the activator may be combined with the metallocene compound prior to being placed upon a support material. Preferably, the activator may be combined with the metallocene compound in the absence of a support material.

In addition to activator compounds, cocatalysts may be used. Aluminum alkyl or organometallic compounds which may be utilized as cocatalysts (or scavengers) include, for example, triethylaluminum, tri-isobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethyl aluminum chloride, dibutyl zinc, diethyl zinc, and the like.

Preferably, the catalyst system comprises an inert support material. Preferably, the supported material is a porous support material, for example, talc, and inorganic oxides. Other support materials include zeolites, clays, organoclays, or any other organic or inorganic support material, or mixtures thereof.

Preferably, the support material is an inorganic oxide in a finely divided form. Suitable inorganic oxide materials for use in metallocene compounds herein include Groups 2, 4, 13, and 14 metal oxides such as silica, alumina, and mixtures thereof. Other inorganic oxides that may be employed, either alone or in combination, with the silica or alumina are magnesia, titania, zirconia, and the like. Other suitable support materials, however, can be employed, for example, finely divided functionalized polyolefins such as finely divided polyethylene. Particularly useful supports include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolites, talc, clays, and the like. Also, combinations of these support materials may be used, for example, silica-chromium, silica-alumina, silica-titania, and the like. Preferred support materials include Al₂O₃, ZrO₂, SiO₂, and combinations thereof, more preferably SiO₂, Al₂O₃, or SiO₂/Al₂O₃.

The supported catalyst system may be suspended in a paraffinic agent, such as mineral oil Processes and catalyst compounds useful in making the polyethylene useful herein are further described in U.S. Pat. Nos. 9,266,977, 9,068,033, 6,225,426, and US 2018/0237554, all of which are incorporated herein by reference.

Polyethylene

The polyethylene may be an ethylene homopolymer or an ethylene copolymer, such as ethylene-alpha-olefin (preferably C₃ to C₂₀ alpha-olefin) copolymers (such as ethylene-butene copolymers, ethylene-hexene copolymers, and/or ethylene-octene copolymers) having an Mw/Mn of 5 or more (preferably 5 to 10). Unless otherwise specified, the term “polyethylene” encompasses both ethylene homopolymers and ethylene copolymers.

The comonomer content (cumulatively if more than one comonomer is used) of the polyethylene can be 0 mol % (i.e., a homopolymer) to 25 mol % (or 0.5 mol % to 20 mol %, or 1 mol % to 15 mol %, or 3 mol % to 10 mol %, or 6 to 10 mol %) with the balance being ethylene. Accordingly, the ethylene content of the polyethylene can be 75 mol % or more ethylene (or 75 mol % to 100 mol %, or 80 mol % to 99.5 mol %, or 85 mol % to 99 mol %, or 90 mol % to 97 mol %, or 4 to 90 mol %).

Alternately, the comonomer content (cumulatively if more than one comonomer is used) in the polyethylene can be 0 wt % (i.e., a homopolymer) to 25 wt % (or 0.5 wt % to 20 wt %, or 1 wt % to 15 wt %, or 3 wt % to 10 wt %, or 6 to 10 wt %) and the ethylene content of the polyethylene can be 75 wt % or more ethylene (or 75 wt % to 100 wt %, or 80 wt % to 99.5 wt %, or 85 wt % to 99 wt %, or 90 wt % to 97 wt %, or 4 to 90 wt %). In a preferred embodiment, the comonomer is present at 6 to 10 wt %, and is preferably a C₃ to C₁₂ alpha-olefin (preferably one or more of propylene, butene, hexene, and octene).

The comonomer can be one or more C₃ to C₂₀ olefin comonomer (preferably C₃ to C₁₂ alpha-olefin; more preferably propylene, butene, hexene, octene, decene, and/or dodecene; most preferably propylene, butene, hexene, and/or octene). Preferably, the monomer is ethylene and the comonomer is hexene, preferably from 1 mol % to 15 mol % hexene, or 1 mol % to 10 mol % hexene, or 5 mol % to 15 mol % hexene, or 7 mol % to 11 mol % hexene.

The polyethylene used in films of the present disclosure can have:

(A) a melt index, I₂, of 1.0 g/10 min or greater (or 1.5 to 5 g/10 min, or 1.8 to 4 g/10 min, or 1.9 to 3 g/10 min);

(B) a density of 0.925 g/cm³ to 0.945 g/cm³ (0.927 g/cm³ to 0.942 g/cm³, or 0.93 g/cm³ to 0.941 g/cm³, or 0.931 g/cm³ to 0.94 g/cm³);

(C) a g′_LCB of less than 0.8 (or from 0.78 to 0.5, alternately from 0.75 to 0.5),

(D) an Mz of 1,000,000 g/mol or more, alternately 1,200,000 g/mol or more, alternately 1,300,000 g/mol or more, alternately from 1,200,000 to 3,000,000 g/mol;

(E) an Mw/Mn of 5 or more, alternately 5.5 or more, alternately from 5.5 to 10;

(F) an Mw of 100,000 g/mol or more, or 120,000 g/mol or more, or 130,000 g/mol or more, or 140,000 g/mol or more such as 100,000 to 200,000 g/mol, alternately from 130,000 to 155,000 g/mol;

(G) a ratio of the g′_LCB to the g′_Zave of greater than 1.0, or from 1.5 to 10, or from 2.0 to 5; and

(H) a Strain Hardening Ratio of 4 or more, such as 4.5 or more, such as 5.0 or more, such as 6 or more, such as 6.5 to 10, preferably where the film has a 1% secant in the transverse direction of 60,000 psi or more, a Dart Drop of 250 g/mil or more, and a ratio of 1% secant MD/1% secant TD is 0.65 or more.

The polyethylene used in films of the present disclosure can have:

(A) a melt index, I₂, of 1.0 g/10 min or greater (or 1.5 to 5 g/10 min, or 1.8 to 4 g/10 min, or 1.9 to 3 g/10 min);

(B) a density of 0.925 g/cm³ to 0.945 g/cm³ (0.927 g/cm³ to 0.942 g/cm³, or 0.93 g/cm³ to 0.941 g/cm³, or 0.931 g/cm³ to 0.94 g/cm³);

(C) a g′_LCB of less than 0.8 (or from 0.78 to 0.5, alternately from 0.75 to 0.5),

(D) an Mz of 1,000,000 g/mol or more, alternately 1,200,000 g/mol or more, alternately 1,300,000 g/mol or more, alternately from 1,200,000 to 3,000,000 g/mol;

(E) an Mw/Mn of 5 or more, alternately 5.5 or more, alternately from 5.5 to 10;

(F) an Mw of 100,000 g/mol or more, or 120,000 g/mol or more, or 130,000 g/mol or more, or 140,000 g/mol or more such as 100,000 to 200,000 g/mol, alternately from 130,000 to 155,000 g/mol;

(G) a ratio of the g′_LCB to the g′_Zave of greater than 1.0, or from 1.5 to 10, or from 2.0 to 5;

(H) a Strain Hardening Ratio of 4 or more, such as 4.5 or more, such as 5.0 or more, such as 6 or more, such as 6.5 to 10; and one, two, three, four or five of the following:

(I) a DST of 0.85 to 0.95 (or 0.86 to 0.90, or 0.87),

(K) a melting temperature of 122° C. or greater (or 122° C. to 127° C., or 123° C. to 125° C.),

(L) a crystallization temperature of 110° C. or greater (or 110° C. to 115° C., or 110° C. to 113° C.),

(M) heat of fusion (Hf) of about 100 to about 175 J/g, and

(N) at least 7° C. (alternately at least 10° C., alternately at least 15° C.) between the onset of transition and the melting peak, as shown in the DSC trace.

Further, the polyethylene (including any of the foregoing) used in films of the present disclosure can have an Mz-LS/Mn-Ls of 15 or more, alternately 20 or more.

Further, the polyethylene (including any of the foregoing) used in films of the present disclosure can have an Mz-LS/Mw-LS of 6 or more, alternately 8 or more, alternately 10 or more.

In a preferred embodiment, the polyethylene described herein has at least 7° C. (alternately at least 10° C., alternately at least 15° C.) between the onset of transition and the melting peak, as shown in the DSC trace.

In a preferred embodiment, the polyethylene described herein has at least 10° C. (alternately at least 15° C., alternately at least 20° C.) between the melting peak and the crystallization peak values.

Blends

In another embodiment, the polyethylene composition produced herein is combined with one or more additional polymers in a blend prior to being formed into a film. As used herein, a “blend” may refer to a dry or extruder blend of two or more different polymers, and in-reactor blends, including blends arising from the use of multi or mixed catalyst systems in a single reactor zone, and blends that result from the use of one or more catalysts in one or more reactors under the same or different conditions (e.g., a blend resulting from in series reactors (the same or different) each running under different conditions and/or with different catalysts).

Useful additional polymers include other polyethylenes, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random copolymer of propylene and ethylene, and/or butene, and/or hexene, polybutene, ethylene vinyl acetate, LDPE, LLDPE, HDPE, ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethylmethacrylate or any other polymers polymerizable by a high-pressure free radical process, polyvinylchloride, polybutene-1, isotactic polybutene, ABS resins, ethylene-propylene rubber (EPR), vulcanized EPR, EPDM, block copolymer, styrenic block copolymers, polyamides, polycarbonates, PET resins, cross linked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as polystyrene, poly-1 esters, polyacetal, polyvinylidine fluoride, polyethylene glycols, and/or polyisobutylene.

Films and Methods

The polyethylene prepared by the process described herein are preferably formed into films, particularly oriented films, such as biaxially oriented films.

The present disclosure relates to oriented polyethylene films comprising a LLDPE with properties that improve processability while providing a good balance between machine and transverse direction stiffness while providing high toughness (or impact resistance).

For example, the invention relates to biaxially oriented films comprising polyethylene having:

(A) a melt index, I₂, of 1.0 g/10 min or greater (or 1.5 to 5 g/10 min, or 1.8 to 4 g/10 min, or 1.9 to 3 g/10 min);

(B) a density of 0.925 g/cm³ to 0.945 g/cm³ (0.927 g/cm³ to 0.942 g/cm³, or 0.93 g/cm³ to 0.941 g/cm³, or 0.931 g/cm³ to 0.94 g/cm³);

(C) a g′_LCB of less than 0.8 (or from 0.78 to 0.5, alternately from 0.75 to 0.5),

(D) an Mz of 1,000,000 g/mol or more, alternately 1,200,000 g/mol or more, alternately 1,300,000 g/mol or more, alternately from 1,200,000 to 3,000,000 g/mol;

(E) an Mw/Mn of 5 or more, alternately 5.5 or more, alternately from 5.5 to 10;

(F) an Mw of 100,000 g/mol or more, or 120,000 g/mol or more, or 130,000 g/mol or more, or 140,000 g/mol or more such as 100,000 to 200,000 g/mol, alternately from 130,000 to 155,000 g/mol;

(G) a ratio of the g′_LCB to the g′_Zave of greater than 1.0, or from 1.5 to 10, or from 2.0 to 5;

(H) a Strain Hardening Ratio of 4 or more, such as 4.5 or more, such as 5.0 or more, such as 6 or more, such as 6.5 to 10;

(I) at least 10° C. between the melting peak and the crystallization peak values; and

(J) optionally, at least 7° C. (alternately at least 10° C., alternately at least 15° C.) between the onset of transition and the melting peak, as shown in the DSC trace;

wherein the film has (I) a 1% secant in the transverse direction of 60,000 psi or more (alternately 70,000 psi to 150,000 psi, or 75,000 psi to 140,000 psi, or 80,000 psi to 130,000 psi) and (II) a 1% secant in the machine direction of 50,000 psi or more (alternately 60,000 psi or more, alternately 75,000 psi to 150,000 psi, or 80,000 psi to 140,000 psi, or 90,000 psi to 130,000 psi)

wherein the ratio of 1% secant MD/1% secant TD is 0.65 or more, alternately 0.7 more, alternately 0.75 or more, alternately 0.75 to 1, alternately 0.75 to 0.95, and or

wherein the ratio of Yield strength MD/Yield strength TD is 0.20 or more, alternately 0.3 or more, alternately 0.4 or more, alternately 0.2 to 0.95, alternately 0.3 to 0.85, and or

wherein the ratio of Tensile strength MD/Tensile strength TD is 0.30 or more, alternately 0.35 or more, alternately 0.4 or more, alternately 0.30 to 1.1, alternately 0.35 to 1.

The films described herein may also have a gloss of 60% or less, such as 20 to 55%.

The films described herein may also have Dart Drop A of 250 g/mil to 1,350 g/mil (alternately 275 g/mil to 1,300 g/mil, or 300 g/mil to 1,250 g/mil).

The films of the present disclosure are biaxially stretched in the machine direction (MD) and the transverse direction (TD) and comprise the polyethylene described herein. Preferably, the films of the present disclosure comprise polyethylene in an amount of at least 90 wt % (or 90 wt % to 100 wt %, or 90 wt % to 99.9 wt %, or 95 wt % to 99 wt %). Advantageously, the polyethylene described herein does not need to be mixed with another polymer to achieve good processability and film properties.

In addition to the polyethylene, the films may comprise additives. Examples of additives include, but are not limited to, stabilization agents (e.g., antioxidants or other heat or light stabilizers), anti-static agents, crosslink agents or co-agents, crosslink promoters, release agents, adhesion promoters, plasticizers, anti-agglomeration agents (e.g., oleamide, stearamide, erucamide or other derivatives with the same activity), and fillers.

Nonlimiting examples of antioxidants include, but are not limited to, IRGANOX®1076 (a high molecular weight phenolic antioxidant, available from BASF), IRGAFOS® 168 (tris(2,4-di-tert-butylphenyl) phosphite, available from BASF), and tris(nonylphenyl)phosphite. A nonlimiting example of a processing aid is DYNAMAR® FX-5920 (a free-flowing fluropolymer based processing additive, available from 3M).

When present, the amount of the additives cumulatively may range from 0.01 wt % to 1 wt % (or 0.01 wt % to 0.1 wt %, or 0.1 wt % to 1 wt %).

Methods of producing a biaxially-oriented polyethylene film can comprise: producing a polymer melt comprising a polyethylene described herein; extruding a film from the polymer melt; stretching the film in a machine direction at a temperature below the melting temperature of the polyethylene to produce a machine direction oriented (MDO) polyethylene film; and stretching the MDO polyethylene film in a transverse direction to produce the biaxially-oriented polyethylene film.

Stretching in the machine direction can be achieved by threading the film through a series of rollers where the temperature and speed of the individual rollers are controlled to achieve a desired film thickness and the stretch ratio of MD stretching. Typically, this series of rollers are called MDO rollers or part of the MDO stage of the film production. Examples of MDO may include, but are not limited to, pre-heat rollers, various stretching stages with or without annealing rollers between stages, one or more conditioning and annealing rollers, and one or more chill rollers. Stretching of the film in the MDO stage is accomplished by inducing a speed differential between two or more adjacent rollers.

The stretch ratio for MD stretching can be used to describe the degree of stretching of the film. The stretch ratio is the speed of the fast roller divided by the speed of the slow roller. For example, stretching a film using an apparatus where the slow roller speed is 1 m/min and fast roller speed is 7 m/min means the stretch ratio was 7 (also referred to herein as 7 times or 7×). The physical amount of stretching of the film is close to but not exactly the stretch ratio because relaxation of the film can occur after stretching.

Greater stretch ratios for MD stretching result in thinner films with greater orientation in the MD. The stretch ratio in the machine direction can be 1× to 10× (or 3× to 7×, or 5× to 9×, or 7× to 10×). One skilled in the art without undo experimentation can determine suitable temperatures and roller speeds for each roller in a given MDO stage of film production for producing the desired stretch ratios.

Stretching in the transverse direction can be achieved by pulling the film from the edges in a tenter frame, which is a series of mobile clips, as the film passes through a stretching zone of a TDO stage oven. The TDO stage oven typically has three zones: (1) a preheat zone that softens the film, (2) a stretch zone that stretches the film in the transverse direction, and (3) an annealing zone where the stretched film cools and relaxes.

The stretch ratio for TD stretching can be used to describe the degree of stretching of the film using the tenter frame (as compared to the roller speeds when stretching in the MD). The stretch ratio for TD stretching is increase in width of the tenter from beginning to end of stretching and calculated as end-stretched tenter width divided by the initial tenter width and can be reported a number or number times or numbers as is the case with MD stretching. Greater stretch ratios for TD stretching result in thinner films with greater orientation in the TD. The stretch ratio when stretching the polyethylene films described herein in the transverse direction can be 1× to 12× (or 3× to 7×, or 5× to 9×, or 8× to 12×). One skilled in the art without undo experimentation can determine suitable temperatures and tenter frame operating parameters in a given TDO stage of film production for producing the desired stretch ratios.

In embodiments of the invention, the polyethylene descried herein can be stretched in the transverse and or machine direction over a large range of temperatures. For example, the polyethylene can be stretched in the machine direction over a temperature range of at least 3° C., preferably at least 6° C., preferably at least 7° C., preferably at least 8° C., preferably at least 10° C., preferably at least 12° C., alternately from 3 to 20° C., alternately from 5 to 15° C.

Likewise, polyethylene can be stretched in the transverse direction over a temperature range of at least 3° C., at least 5° C., preferably at least 6° C., preferably at least 7° C., preferably at least 8° C., preferably at least 10° C., preferably at least 12° C., alternately from 3 to 20° C., alternately from 3 to 15° C., alternately from 3 to 10° C., alternately from 3 to 6° C.

Preferably the film, can be stretched in the transverse direction without tearing the web and creating gauge inhomogeneities, over an temperature range of at least 3° C., at least 5° C., preferably at least 6° C., preferably at least 7° C., preferably at least 8° C., preferably at least 10° C., preferably at least 12° C., alternately from 3 to 20° C., alternately from 3 to 15° C., alternately from 3 to 10° C., alternately from 3 to 6° C.

Preferably the film, can be stretched in the machine direction without web instability and large gauge variations, over an temperature range of at least 3° C., preferably at least 6° C., preferably at least 7° C., preferably at least 8° C., preferably at least 10° C., preferably at least 12° C., alternately from 3 to 20° C., alternately from 5 to 15° C. The broader stretching temperature range in both MD and TD section allows to have more flexibility in operating the machinery in terms of accessible line speed and stretch ratios.

The biaxially-oriented polyethylene films described herein can have a thickness of 3 mils or less (or 0.1 mils to 3 mils, or 0.5 mils to 2 mils, or 0.5 mils to 1.5 mils, or 0.5 mils to 1 mils).

The biaxially-oriented polyethylene films described herein may have (i) a 1% secant in the transverse direction of 60,000 psi or more (alternately 70,000 psi to 150,000 psi, or 75,000 psi to 140,000 psi, or 80,000 psi to 130,000 psi) and (ii) a Dart Drop A of 250 g/mil to 1,350 g/mil (alternately 275 g/mil to 1,300 g/mil, or 300 g/mil to 1,250 g/mil).

The biaxially-oriented polyethylene films described herein may have (I) a 1% secant in the transverse direction of 60,000 psi or more (alternately 70,000 psi or more, alternately 75,000 psi to 150,000 psi, or 80,000 psi to 140,000 psi, or 90,000 psi to 130,000 psi); (II) a 1% secant in the machine direction of 50,000 psi or more (alternately 60,000 psi or more, alternately 75,000 psi to 150,000 psi, or 80,000 psi to 140,000 psi, or 90,000 psi to 130,000 psi), and (III) ratio of 1% secant MD/1% secant TD is 0.65 or more, alternately 0.7 more, alternately 0.75 or more, alternately 0.75 to 1, alternately 0.75 to 0.95.

The biaxially-oriented polyethylene films described herein can have (I), (II) and (III) above and one or more of the following properties:

(IV) a yield strength in the machine direction of 2,000 psi to 5,000 psi (or 2,200 psi to 4,000 psi) and a yield strength in the transverse direction of 4,000 psi to 15,000 psi (or 5,000 psi to 11,000 psi);

(V) a tensile strength in the machine direction of 6,000 psi to 15,000 psi (or 7,500 psi to 14,500 psi, or 8,000 psi to 11,000 psi) and a tensile strength in the transverse direction of 10,000 psi to 30,000 psi (or 11,000 psi to 25,000 psi, or 12,000 psi to 20,000 psi);

(VI) a peak force per mil of 10 lbs/mil to 40 lbs/mil (or 12 lbs/mil to 35 lbs/mil, or 15 lbs/mil to 25 lbs/mil); and

(VII) a Dart Drop A of 250 g to 1,350 g (or 275 g to 1,300 g, or 300 g to 1,250 g).

Preferably, the biaxially-oriented polyethylene films described herein have (I) and (II) and one or more of the following properties: (III), (IV), (V), and (VII). Preferably, the biaxially-oriented polyethylene films described herein have (I) and (II) and one or more of the following properties: (IV) and (V).

The biaxially-oriented polyethylene films described herein can have (I) and (II), one or more of (III)-(VIII), and one or more of the following properties:

(IX) an average density of 0.925 g/cm³ to 0.945 g/cm³ (0.927 g/cm³ to 0.942 g/cm³, or 0.93 g/cm³ to 0.941 g/cm³, or 0.931 g/cm³ to 0.94 g/cm³);

(X) an elongation at yield in the machine direction of 5% to 15% (or 6% to 10%) and an elongation at yield in the transverse direction of 9% to 17% (or 10% to 15%);

(XI) an elongation at break in the machine direction of 140% to 250% (or 150% to 240%, or 160% to 230%) and an elongation at break in the transverse direction of 30% to 120% (or 40% to 110%, or 50% to 100%);

(XII) a haze of 5% to 35% (or 10% to 31%);

(XIII) a clarity of 30% to 80% (or 45% to 75%); and

(IX) a break energy of 5 lbs*in to 25 lbs*in (or 7 lbs*in to 25 lbs*in, or 9 lbs*in to 15 lbs*in) and/or a break energy per mil of 5 lbs*in/mil to 19 lbs*in/mil (or 6 lbs*in/mil to 18 lbs*in/mil, or 9 lbs*in/mil to 16 lbs*in/mil).

Preferably, the biaxially-oriented polyethylene films described herein have (I) and (II), one or more of (III)-(VIII), and one or more of the following properties: (IX), (X), (XI), (XII), and (XIII).

In any embodiment herein, the biaxially-oriented polyethylene films described herein may have a yield strength in the machine direction of 2,000 psi to 5,000 psi (or 2,200 psi to 4,000 psi) and a yield strength in the yield strength in the transverse direction of 4,000 psi to 15,000 psi (or 5,000 psi to 11,000 psi) and a ratio of Yield strength MD/Yield strength TD is 0.20 or more, alternately 0.3 or more, alternately 0.4 or more, alternately 0.2 to 0.95, alternately 0.3 to 0.85.

In any embodiment herein, the biaxially-oriented polyethylene films described herein may have a tensile strength in the machine direction of 6,000 psi to 15,000 psi (or 7,500 psi to 14,500 psi, or 8,000 psi to 11,000 psi) and a tensile strength in the transverse direction of 10,000 psi to 30,000 psi (or 11,000 psi to 25,000 psi, or 12,000 psi to 20,000 psi) and a ratio of Tensile strength MD/Tensile strength TD is 0.30 or more, alternately 0.35 or more, alternately 0.4 or more, alternately 0.30 to 1.1, alternately 0.35 to 1.

In any embodiment herein, the biaxially-oriented polyethylene films described herein may have a shrink in the machine direction of 50% to 75% (or 55% to 70%) and a shrink in the transverse direction of 60% to 90% (or 70% to 87%, or 72% to 83%).

In any embodiment herein, the biaxially-oriented polyethylene films described herein may have a peak force per mil of 10 lbs/mil to 40 lbs/mil (or 12 lbs/mil to 35 lbs/mil, or 15 lbs/mil to 25 lbs/mil).

In any embodiment herein, the biaxially-oriented polyethylene films described herein may have a Dart Drop A of 250 g to 1,350 g (or 275 g to 1,300 g, or 300 g to 1,250 g) and/or a Dart Drop A of 250 g/mil to 1,350 g/mil (alternately 275 g/mil to 1,300 g/mil, or 300 g/mil to 1,250 g/mil).

In any embodiment herein, the biaxially-oriented polyethylene films described herein may have an average density of 0.925 g/cm³ to 0.945 g/cm³ (0.927 g/cm³ to 0.942 g/cm³, or 0.93 g/cm³ to 0.941 g/cm³, or 0.931 g/cm³ to 0.94 g/cm³).

In any embodiment herein, the biaxially-oriented polyethylene films described herein may an elongation at yield in the machine direction of 5% to 15% (or 6% to 10%) and an elongation at yield in the transverse direction of 9% to 17% (or 10% to 15%).

In any embodiment herein, the biaxially-oriented polyethylene films described herein may an elongation at break in the machine direction of 140% to 250% (or 150% to 240%, or 160% to 230%) and an elongation at break in the transverse direction of 30% to 120% (or 40% to 110%, or 50% to 100%).

In any embodiment herein, the biaxially-oriented polyethylene films described herein may have a haze of 5% to 35% (or 10% to 31%).

In any embodiment herein, the biaxially-oriented polyethylene films described herein may have a clarity of 30% to 80% (or 45% to 75%).

In any embodiment herein, the biaxially-oriented polyethylene films described herein may have a break energy of 5 lbs*in to 25 lbs*in (or 7 lbs*in to 25 lbs*in, or 9 lbs*in to 15 lbs*in) and/or a break energy per mil of 5 lbs*in/mil to 19 lbs*in/mil (or 6 lbs*in/mil to 18 lbs*in/mil, or 9 lbs*in/mil to 16 lbs*in/mil).

End Uses

The biaxially-oriented polyethylene films described herein may be used as monolayer films or as one or more layers of a multilayer film. Examples of other layers include, but are not limited to, unstretched polymer films, MDO polymer films, and other biaxially-oriented polymer films of polymers like polyethylene, polypropylene, polyethylene terephthalate, polystyrene, polyamide, and the like.

Specific end use films include, for example, blown films, cast films, stretch films, stretch/cast films, stretch cling films, stretch hand wrap films, machine stretch wrap, shrink films, shrink wrap films, green house films, laminates, and laminate films. Exemplary films are prepared by any conventional technique known to those skilled in the art, such as for example, techniques utilized to prepare blown, extruded, and/or cast stretch and/or shrink films (including shrink-on-shrink applications).

The biaxially-oriented polyethylene films described herein (alone or as part of a multilayer film) are useful end use applications that include, but are not limited to, film-based products, shrink film, cling film, stretch film, sealing films, snack packaging, heavy-duty bags, grocery sacks, baked and frozen food packaging, diaper back-sheets, house wrap, medical packaging (e.g., medical films and intravenous (IV) bags), industrial liners, membranes, and the like.

In one embodiment, multilayer films or multiple-layer films may be formed by methods well known in the art. The total thickness of multilayer films may vary based upon the application desired. A total film thickness of about 5-100 μm, more typically about 10-50 μm, is suitable for most applications. Those skilled in the art will appreciate that the thickness of individual layers for multilayer films may be adjusted based on desired end-use performance, resin or copolymer employed, equipment capability, and other factors. The materials forming each layer may be coextruded through a coextrusion feed block and die assembly to yield a film with two or more layers adhered together but differing in composition. Coextrusion can be adapted for use in both cast film or blown film processes. Exemplary multilayer films have at least two, at least three, or at least four layers. In one embodiment, the multilayer films are composed of five to ten layers.

To facilitate discussion of different film structures, the following notation is used herein. Each layer of a film is denoted “A” or “B”. Where a film includes more than one A layer or more than one B layer, one or more prime symbols (′, ″, ′″, etc.) are appended to the A or B symbol to indicate layers of the same type that can be the same or can differ in one or more properties, such as chemical composition, density, melt index, thickness, etc. Finally, the symbols for adjacent layers are separated by a slash (/). Using this notation, a three-layer film having an inner layer disposed between two outer layers would be denoted A/B/A′. Similarly, a five-layer film of alternating layers would be denoted A/B/A′/B′/A″. Unless otherwise indicated, the left-to-right or right-to-left order of layers does not matter, nor does the order of prime symbols; e.g., an A/B film is equivalent to a B/A film, and an A/A′/B/A″ film is equivalent to an A/B/A′/A″ film, for purposes described herein. The relative thickness of each film layer is similarly denoted, with the thickness of each layer relative to a total film thickness of 100 (dimensionless) indicated numerically and separated by slashes; e.g., the relative thickness of an A/B/A′ film having A and A′ layers of 10 μm each and a B layer of 30 μm is denoted as 20/60/20.

The thickness of each layer of the film, and of the overall film, is not particularly limited, but is determined according to the desired properties of the film. Typical film layers have a thickness of from about 1 to about 1,000 μm, more typically from about 5 to about 100 μm, and typical films have an overall thickness of from about 10 to about 100 μm.

In some embodiments, and using the nomenclature described above, the present invention provides for multilayer films with any of the following exemplary structures: (a) two-layer films, such as A/B and B/B′; (b) three-layer films, such as A/B/A′, A/A′/B, B/A/B′ and B/B′/B″; (c) four-layer films, such as A/A′/A″/B, A/A′/B/A″, A/A′/B/B′, A/B/A′/B′, A/B/B′/A′, B/A/A′/B′, A/B/B′/B″, B/A/B′/B″ and B/B′/B″/B′″; (d) five-layer films, such as A/A′/A″/A′/B, A/A′/A″/B/A′″, A/A′/B/A″/A′″, A/A′/A″/B/B′, A/A′/B/A″/B′, A/A′/B/B′/A″, A/B/A′/B′/A″, A/B/A′/A″/B, B/A/A′/A″/B′, A/A′/B/B′/B″, A/B/A′/B′/B″, A/B/B′/B″/A′, B/A/A′/B′/B″, B/A/B′/A′/B″, B/A/B′/B″/A′, A/B/B′/B″/B′″, B/A/B′/B″/B′″, B/B′/A/B″/B′″, and B/B′/B″/B″/B″″; and similar structures for films having six, seven, eight, nine, twenty-four, forty-eight, sixty-four, one hundred, or any other number of layers. It should be appreciated that films having still more layers.

In any of the embodiments above, one or more A layers can be replaced with a substrate layer, such as glass, plastic, paper, metal, etc., or the entire film can be coated or laminated onto a substrate. Thus, although the discussion herein has focused on multilayer films, the films may also be used as coatings for substrates such as paper, metal, glass, plastic, and other materials capable of accepting a coating.

The films can further be embossed, or produced or processed according to other known film processes. The films can be tailored to specific applications by adjusting the thickness, materials and order of the various layers, as well as the additives in or modifiers applied to each layer.

EXAMPLE EMBODIMENTS

This invention further relates to:

1. A biaxially-oriented polyethylene film comprising polyethylene having:

(A) a melt index, I₂, of 1.0 g/10 min or greater;

(B) a density of 0.925 g/cm³ to 0.945 g/cm³;

(C) a g′_LCB of less than 0.8;

(D) an Mz of 1,000,000 g/mol or more;

(E) an Mw/Mn of 5 or more;

(F) an Mw of 100,000 g/mol or more;

(G) a ratio of the g′_LCB to the g′_Zave is greater than 1.0; and

(H) a Strain Hardening Ratio of 4 or more,

where the film has a 1% secant in the transverse direction of 60,000 psi or more, a Dart Drop of 250 g/mil or more, and a ratio of 1% secant MD/1% secant TD is 0.65 or more.

2. The film of paragraph 1, wherein the ratio of Yield strength MD/Yield strength TD of the film is 0.20 or more, and or the ratio of Tensile strength MD/Tensile strength TD of the film is 0.30 or more.3. The film of paragraph 1 or 2, wherein the polyethylene described herein has at least 10° C. between the onset of transition and the melting peak, as shown in the DSC trace.4. The film of paragraph 1, 2 or 3, wherein the polyethylene described herein has at least 10° C. between the melting peak and the crystallization peak values.5. The film of paragraph 1 to 4, wherein the polyethylene is present at 90 wt % to 100 wt % of the biaxially-oriented film.6. The film of any of paragraphs 1 to 5, wherein the biaxially-oriented film further comprises an additive at 0.01 wt % to 1 wt % of biaxially-oriented film.7. The film of any of paragraphs 1 to 6, wherein the biaxially-oriented film has a thickness of 0.1 to 3 mils or less.8. The film of any preceding paragraph, wherein the polyethylene has:

(A) a melt index, I₂, of 1.9 to 3 g/10 min or greater;

(B) a density of 0.925 g/cm³ to 0.945 g/cm³;

(C) a g′_LCB of 0.78 to 0.5;

(D) an Mz of 1,300,000 g/mol or more; and

(F) an Mw of 155,000 g/mol or more.

9. The film of any preceding paragraph, wherein the biaxially-oriented film has one or more of the following properties:

(IV) a yield strength in the machine direction of 2,000 psi to 5,000 psi and a yield strength in the transverse direction of 4,000 psi to 15,000 psi;

(V) a tensile strength in the machine direction of 6,000 psi to 15,000 psi and a tensile strength in the transverse direction of 10,000 psi to 30,000 psi;

(VI) a peak force per mil of 10 lbs/mil to 40 lbs/mil; and

(VII) a Dart Drop A of 250 g/mil to 1350 g/mil.

10. The film of paragraph 9, wherein the biaxially-oriented film also has one or more of the following properties:

(IX) an average density of 0.925 g/cm³ to 0.945 g/cm³;

(X) an elongation at yield in the machine direction of 5% to 15% and an elongation at yield in the transverse direction of 9% to 17%);

(XI) an elongation at break in the machine direction of 140% to 250% and an elongation at break in the transverse direction of 30% to 120%;

(XII) a haze of 5% to 35%;

(XIII) a clarity of 30% to 80%; and

(IX) a break energy of 5 lbs*in to 25 lbs*in and/or a break energy per mil of 5 lbs*in/mil to 19 lbs*in/mil.

11. The film of any of paragraphs 1 to 10, wherein the biaxially-oriented film has a thickness of 0.3 mils to 2 mils.12. The film of paragraph 10 or 11, wherein the film was stretched in the machine direction at a stretch ratio of 1 to 10, and stretched in the transverse direction at a stretch ratio of 1 to 12.13. A method comprising:

producing a polymer melt comprising a polyethylene having:

• • (A) a melt index, I₂, of 1.0 g/10 min or greater;
  • (B) a density of 0.925 g/cm³ to 0.945 g/cm³;
  • (C) a g′_LCB of less than 0.8;
  • (D) an Mz of 1,000,000 g/mol or more;
  • (E) an Mw/Mn of 5 or more;
  • (F) an Mw of 100,000 g/mol or more;
  • (G) a ratio of the g′_LCB to the g′_Zave is greater than 1.0; and
  • (H) a Strain Hardening Ratio of 4 or more,

extruding a film from the polymer melt;

stretching the film in a machine direction to produce a machine direction oriented (MDO) polyethylene film; and

stretching the MDO polyethylene film in a transverse direction to produce a biaxially-oriented polyethylene film, where the film has a 1% secant in the transverse direction of 60,000 psi or more, a Dart Drop of 250 g/mil or more, and a ratio of 1% secant MD/1% secant TD is 0.65 or more.

14. The method of paragraph 13 wherein the polyethylene has a ratio of Yield strength MD/Yield strength TD of the film of 0.20 or more, and or a ratio of Tensile strength MD/Tensile strength TD of the film of 0.30 or more.15. The method of paragraph 13 wherein the polyethylene has at least 10° C. between the onset of transition and the melting peak, as shown in the DSC trace.16. The method of paragraph 13, 14 or 15, wherein stretching in the machine direction is at a stretch ratio of 1 to 10, and wherein stretching in the transverse direction is at a stretch ratio of 1 to 12.17. The method of any of paragraphs 13-16, wherein the film can be stretched in the transverse direction without web breakage or tearing, over an 8° C. range and stretched in the transverse direction without web breakage or tearing, over a 5° C. range.18. The method of any of paragraphs 13-17, wherein the polyethylene has:

(I) a degree of shear thinning of 0.85 to 0.95,

(J) a strain hardening ratio of 4 or greater,

(K) a melting temperature of 122° C. or greater,

(L) a crystallization temperature of 110° C. or greater,

(M) a Mw of 100,000 g/mol to 155,000 g/mol, and

(N) a Mw/Mn of 5 to 10.

19. The method of any of paragraphs 13-18, wherein the polyethylene is present at 90 wt % to 100 wt % of the polymer melt.20. The method of any of paragraphs 13-19, wherein polymer melt further comprises an additive at 0.01 wt % to 1 wt % of the polymer melt.21. The method of any of paragraphs 13-20, wherein the biaxially-oriented film has a thickness of 0.1 to 3 mils.22. The method of any of paragraphs 13-21, wherein the biaxially-oriented film has one or more of the following properties:

(IV) a yield strength in the machine direction of 2,000 psi to 5,000 psi and a yield strength in the transverse direction of 5,000 psi to 11,000 psi;

(V) a tensile strength in the machine direction of 6,000 psi to 15,000 psi and a tensile strength in the transverse direction of 10,000 psi to 30,000 psi;

(VI) a peak force per mil of 10 lbs/mil to 40 lbs/mil; and

(VII) a Dart Drop A of 250 g/mil to 1350 g/mil.

23. The method of paragraph 18, wherein the biaxially-oriented film also has one or more of the following properties:

(IX) an average density of 0.925 g/cm³ to 0.945 g/cm³;

(X) an elongation at yield in the machine direction of 5% to 15% and an elongation at yield in the transverse direction of 9% to 17%);

(XI) an elongation at break in the machine direction of 140% to 250% and an elongation at break in the transverse direction of 30% to 120%;

(XII) a haze of 5% to 35%

(XIII) a clarity of 30% to 80%; and

(IX) a break energy of 5 lbs*in to 25 lbs*in and/or a break energy per mil of 5 lbs*in/mil to 19 lbs*in/mil.

24. A polyethylene having:

(A) a melt index, I₂, of 1.0 g/10 min or greater;

(B) a density of 0.925 g/cm³ to 0.945 g/cm³;

(C) a g′_LCB of less than 0.8;

(D) an Mz of 1,000,000 g/mol or more;

(E) an Mw/Mn of 5 or more;

(F) an Mw of 100,000 g/mol or more;

(G) a ratio of the g′_LCB to the g′_Zave is greater than 1.0; and

(H) a Strain Hardening Ratio of 4 or more,

that when the polyethylene is formed into a biaxially oriented 1 mil thick film, the film has a 1% secant in the transverse direction of 60,000 psi or more, a Dart Drop of 250 g/mil or more, and a ratio of 1% secant MD/1% secant TD is 0.65 or more.

25. The polyethylene of paragraph 24, further comprising that when the polyethylene is formed into a biaxially oriented 1 mil thick film, the ratio of Yield strength MD/Yield strength TD of the film is 0.20 or more, and or the ratio of Tensile strength MD/Tensile strength TD of the film is 0.30 or more.26. The polyethylene of paragraph 24 or 25, wherein the polyethylene has:

(I) a degree of shear thinning of 0.85 to 0.95,

(J) a strain hardening ratio of 4 or greater,

(K) a melting temperature of 122° C. or greater,

(L) a crystallization temperature of 110° C. or greater,

(M) a Mw of 100,000 g/mol to 155,000 g/mol, and

(N) a Mw/Mn of 5 to 10.

This invention further relates to:

1A. A biaxially-oriented polyethylene film comprising polyethylene having:

(A) a melt index, I₂, of 1.0 g/10 min or greater;

(B) a density of 0.925 g/cm³ to 0.945 g/cm³;

(C) a g′_LCB of less than 0.8;

(D) an Mz of 1,000,000 g/mol or more;

(E) an Mw/Mn of 5 or more;

(F) an Mw of 100,000 g/mol or more;

(G) a ratio of the g′_LCB to the g′_Zave is greater than 1.0; and

(H) a Strain Hardening Ratio of 4 or more,

where the film has a 1% secant in the transverse direction of 60,000 psi or more, a Dart Drop of 250 g/mil or more, and a ratio of 1% secant MD/1% secant TD is 0.65 or more.

2A. The film of paragraph 1A, wherein the ratio of Yield strength MD/Yield strength TD of the film is 0.20 or more, and or the ratio of Tensile strength MD/Tensile strength TD of the film is 0.30 or more.3A. The film of paragraph 1A, wherein the polyethylene described herein has at least 10° C. between the onset of transition and the melting peak, as shown in the DSC trace.4A. The film of paragraph 1A, wherein the polyethylene described herein has at least 10° C. between the melting peak and the crystallization peak values.5A. The film of paragraph 1A, wherein the polyethylene is present at 90 wt % to 100 wt % of the biaxially-oriented film.6A. The film of paragraph 1A, wherein the biaxially-oriented film further comprises an additive at 0.01 wt % to 1 wt % of biaxially-oriented film.7A. The film of paragraph 1A, wherein the biaxially-oriented film has a thickness of 0.1 to 3 mils or less.8A. The film of paragraph 1A, wherein the polyethylene has:

(A) a melt index, I₂, of 1.9 to 3 g/10 min or greater;

(B) a density of 0.925 g/cm³ to 0.945 g/cm³;

(C) a g′_LCB of 0.78 to 0.5;

(D) an Mz of 1,300,000 g/mol or more; and

(F) an Mw of 155,000 g/mol or more.

9A. The film of paragraph 1A, wherein the biaxially-oriented film has one or more of the following properties:

(IV) a yield strength in the machine direction of 2,000 psi to 5,000 psi and a yield strength in the transverse direction of 4,000 psi to 15,000 psi;

(V) a tensile strength in the machine direction of 6,000 psi to 15,000 psi and a tensile strength in the transverse direction of 10,000 psi to 30,000 psi;

(VI) a peak force per mil of 10 lbs/mil to 40 lbs/mil; and

(VII) a Dart Drop A of 250 g/mil to 1350 g/mil.

10A. The film of paragraph 9A, wherein the biaxially-oriented film also has one or more of the following properties:

(IX) an average density of 0.925 g/cm³ to 0.945 g/cm³;

(X) an elongation at yield in the machine direction of 5% to 15% and an elongation at yield in the transverse direction of 9% to 17%);

(XI) an elongation at break in the machine direction of 140% to 250% and an elongation at break in the transverse direction of 30% to 120%;

(XII) a haze of 5% to 35%

(XIII) a clarity of 30% to 80%; and

(IX) a break energy of 5 lbs*in to 25 lbs*in and/or a break energy per mil of 5 lbs*in/mil to 19 lbs*in/mil.

11A. The film of paragraph 1A, wherein the biaxially-oriented film has a thickness of 0.3 mils to 2 mils.12A. The film of paragraph 10A, wherein the film was stretched in the machine direction at a stretch ratio of 1 to 10, and stretched in the transverse direction at a stretch ratio of 1 to 12.13A. A method comprising:

producing a polymer melt comprising a polyethylene having:

(A) a melt index, I₂, of 1.0 g/10 min or greater;

(B) a density of 0.925 g/cm³ to 0.945 g/cm³;

(C) a g′_LCB of less than 0.8;

(D) an Mz of 1,000,000 g/mol or more;

(E) an Mw/Mn of 5 or more;

(F) an Mw of 100,000 g/mol or more;

(G) a ratio of the g′_LCB to the g′_Zave is greater than 1.0; and

(H) a Strain Hardening Ratio of 4 or more,

extruding a film from the polymer melt;

stretching the film in a machine direction to produce a machine direction oriented (MDO) polyethylene film; and

stretching the MDO polyethylene film in a transverse direction to produce a biaxially-oriented polyethylene film, where the film has a 1% secant in the transverse direction of 60,000 psi or more, a Dart Drop of 250 g/mil or more, and a ratio of 1% secant MD/1% secant TD is 0.65 or more.

14A. The method of paragraph 13A, wherein the polyethylene has a ratio of Yield strength MD/Yield strength TD of the film of 0.20 or more, and or a ratio of Tensile strength MD/Tensile strength TD of the film of 0.30 or more.15A. The method of paragraph 13A, wherein the polyethylene has at least 10° C. between the onset of transition and the melting peak, as shown in the DSC trace.16A. The method of paragraph 13A, wherein stretching in the machine direction is at a stretch ratio of 1 to 10, and wherein stretching in the transverse direction is at a stretch ratio of 1 to 12.17A. The method of paragraph 13A, wherein the film can be stretched in the transverse direction without web breakage or tearing, over an 8° C. range and stretched in the transverse direction without web breakage or tearing, over a 5° C. range.18A. The method of paragraph 13A, wherein the polyethylene has:

(I) a degree of shear thinning of 0.85 to 0.95,

(J) a strain hardening ratio of 4 or greater,

(K) a melting temperature of 122° C. or greater,

(L) a crystallization temperature of 110° C. or greater,

(M) a Mw of 100,000 g/mol to 155,000 g/mol, and

(N) a Mw/Mn of 5 to 10.

19A. The method of paragraph 13A, wherein the polyethylene is present at 90 wt % to 100 wt % of the polymer melt.20A. The method of paragraph 13A, wherein polymer melt further comprises an additive at 0.01 wt % to 1 wt % of the polymer melt.21A. The method of paragraph 13A, wherein the biaxially-oriented film has a thickness of 0.1 to 3 mils.22A. The method of paragraph 13A, wherein the biaxially-oriented film has one or more of the following properties:

(IV) a yield strength in the machine direction of 2,000 psi to 5,000 psi and a yield strength in the transverse direction of 5,000 psi to 11,000 psi);

(V) a tensile strength in the machine direction of 6,000 psi to 15,000 psi and a tensile strength in the transverse direction of 10,000 psi to 30,000 psi;

(VI) a peak force per mil of 10 lbs/mil to 40 lbs/mil; and

(VII) a Dart Drop A of 250 g/mil to 1350 g/mil.

23A. The method of paragraph 18A, wherein the biaxially-oriented film also has one or more of the following properties:

(IX) an average density of 0.925 g/cm³ to 0.945 g/cm³;

(X) an elongation at yield in the machine direction of 5% to 15% and an elongation at yield in the transverse direction of 9% to 17%);

(XI) an elongation at break in the machine direction of 140% to 250% and an elongation at break in the transverse direction of 30% to 120%;

(XII) a haze of 5% to 35%

(XIII) a clarity of 30% to 80%; and

(IX) a break energy of 5 lbs*in to 25 lbs*in and/or a break energy per mil of 5 lbs*in/mil to 19 lbs*in/mil.

24A. A polyethylene having:

(A) a melt index, I₂, of 1.0 g/10 min or greater;

(B) a density of 0.925 g/cm³ to 0.945 g/cm³;

(C) a g′_LCB of less than 0.8;

(D) an Mz of 1,000,000 g/mol or more;

(E) an Mw/Mn of 5 or more;

(F) an Mw of 100,000 g/mol or more;

(G) a ratio of the g′_LCB to the g′_Zave is greater than 1.0; and

(H) a Strain Hardening Ratio of 4 or more,

that when the polyethylene is formed into a biaxially oriented 1 mil thick film, the film has a 1% secant in the transverse direction of 60,000 psi or more, a Dart Drop of 250 g/mil or more, and a ratio of 1% secant MD/1% secant TD is 0.65 or more.

25A. The polyethylene of paragraph 24A, further comprising that when the polyethylene is formed into a biaxially oriented 1 mil thick film, the ratio of Yield strength MD/Yield strength TD of the film is 0.20 or more, and or the ratio of Tensile strength MD/Tensile strength TD of the film is 0.30 or more.26A. The polyethylene of paragraph 24A, wherein the polyethylene has:

(I) a degree of shear thinning of 0.85 to 0.95,

(J) a strain hardening ratio of 4 or greater,

(K) a melting temperature of 122° C. or greater,

(L) a crystallization temperature of 110° C. or greater,

(M) a Mw of 100,000 g/mol to 155,000 g/mol, and

(N) a Mw/Mn of 5 to 10.

To facilitate a better understanding of the embodiments of the present invention, the following examples of preferred or representative embodiments are given. In no way should the following examples be read to limit, or to define, the scope of the invention.

EXPERIMENTAL

Catalyst A is Me₂Si[Me₄Cp][3-Ph-Ind]ZrCl₂, dimethylsilyl (tetramethyl-cyclopentadienyl)(3-phenylindenyl)zirconium dichloride and was prepared as generally described in U.S. Pat. No. 9,266,977 (see Metallocene 1).

Preparation of Me₂Si[Me₄Cp][3-Ph-Ind]ZrCl₂ Supported Catalyst

Activation and supportation of Me₂Si[Me₄Cp][3-Ph-Ind]ZrCl₂ was prepared as follows. In a 4 L stirred vessel in the drybox a 687 g amount of methylaluminoxane (MAO) (30 wt % in toluene) was added along with a 1504 g amount of toluene. A 15.7 g amount of the metallocene dissolved in 200 mL of toluene was added. This solution was then stirred at 60 rpm for 5 minutes. Another 165 g amount of toluene was added. The solution was stirred for 30 minutes at 120 rpm. The stir rate was reduced to 8 rpm. ES-70™ silica (PQ Corporation, Conshohocken, Pa.) that had been calcined at 875° C. was added to the vessel. This slurry with another 154 grams of toluene for rinse was stirred for 30 minutes before drying under vacuum at room temperature for twenty-two hours. After emptying the vessel and sieving the supported catalyst, a 763 gram amount was collected.

Polymerization

Polymerization was performed in a 22 foot tall gas-phase fluidized bed reactor with a 13 inch straight section inner diameter and a wider conical expanded section above. Cycle and feed gases were fed into the reactor body through a perforated distributor plate, and the reactor was controlled at 290 psig and 64 mol % ethylene. The reactor temperature was controlled by manipulating the temperature of the cycle gas loop.

Catalyst was fed to the reactor as a dry powder with N₂ carrier gas. Continuity additive (CA-300, from Univation) was co-fed into the reactor by a second carrier nozzle to reactor bed, and the feed rate of continuity additive was adjusted to maintain a weight concentration in the bed of between 20 ppm and 40 ppm. Good reactor operability was observed for all conditions. The polymer processing conditions can be found in Table A.

	TABLE A
	Polymer Product	Product A	Product B
	Catalyst (—)	Catalyst A	Catalyst A
	Bed Temperature (° F.)	185.0	185.0
	Reactor Pressure (psig)	289.1	290.0
	Ethylene Concentration	63.8	63.9
	(mol %)
	H2/C2 = Gas Ratio (ppm/mol %)	5.60	5.28
	C6/C2 = Flow Ratio (lb/lb)	0.079	0.062
	iC5 Composition (mol %)	3.7	3.9
	Settled Bulk Density (g/cm3)	0.3343	0.3632
	Residence Time (hr)	2.1	2.4

The polymers were characterized and results reported in Tables 1, 2, and 3.

TABLE 1
GPC4D structural parameters
					Comonomer	Branching
Sample	Mw (LS)	Mz (LS)	Mn (LS)	PDI (LS)	content, C6	index, LCB-g′
name	[g/mol]	[g/mol]	[g/mol]	[−]	[wt %]	[−]
Product A	152,000	1,482,000	26,000	5.8	6.93	0.706
Product B	141,000	1,417,000	24,000	5.9	4.96	0.734

TABLE 2
DSC structural parameters
	Melt,	Cryst.	Melt. Heat	Cryst. Heat
	temperature,	temperature,	flow, ΔHm	flow, ΔHc
Sample name	Tm [° C.]	Tc [° C.]	[J/g]	[J/g]
Product A	125.2	110.4	155	153
Product B	125.4	112.4	170	169

TABLE 3
Structural and rheological parameters
			Strain	Degree
			Hardening	of Shear
	Melt		Ratio,	Thinning,	Ratio
	Index, MI	Density,	SHR	DST	(LCB-g′)
Sample name	[g/10 min]	ρ[g/cc]	[—]	[—]	[—]
Product A	1.9	0.928	6.78	0.893	2.188
Product B	2.8	0.933	7.2	0.844	2.369

Testing Procedures for Properties

Melt index (MI) measurements were made on the Goettfert MI-4 Melt Indexer (ASTM D1238). Testing conditions for the MI were set at 190° C. and 2.16 kg load. An amount of ˜3 g of sample was loaded into the barrel of the instrument at 190° C. and manually compressed. Afterwards, the material was automatically compacted into the barrel by lowering all available weights onto the piston to remove all air bubbles. Data acquisition was started after a 6 minute pre-melting time. Also, the sample was pressed through a die of 8 mm length and 2.095 mm diameter. The gradient density of the samples was measured according the standard test method for plastics (ASTM D1505-10) and molded by following ASTM D4703-10a test method.

Differential Scanning Calorimetry (DSC)

The DSC runs were performed with TA Instruments' Discovery 2500. Peak melting point or melting temperature (Tm), peak crystallization temperature or crystallization temperature (Tc) and heat of fusion or heat flow (ΔHf or Hf) were determined using the following DSC procedure. Samples weighing approximately 2-5 mg were carefully sealed in aluminum hermetic pan. Heat flow was normalized with the sample mass. The DSC runs were ramped up from 0° C. to 200° C. at a rate of at 10° C./min, after equilibration, the samples were cooled down at 10° C./min to 0° C. Both first and second thermal cycles were recorded. The melting (Tm) was calculated by integrating the melting peak (area below the curve) over a range of approximately 5° C. to approximately 135° C. (baseline).

Film Production

Biaxially oriented polyethylene films were produced on a BIAX lab pilot line by Parkinson Technologies Inc, which is a scaled-down version of commercial line. The BIAX lab pilot line has 5 main sections: extrusion, casting, MD, TD, and winding.

The uniaxial stretching along MD was obtained by increasing speed between two intermediate rollers. The MD orientation section was operated off-line directly from roll-stock to produce a uniaxially oriented film over heated and cooled rollers. The MD orientation is linked to the TD orientation section's downstream tenter frame to fabricate biaxially oriented films.

In the following trial, the BIAX lab pilot line was operated to produce unoriented cast films and combined with the other sections for biaxially (MD-TD) oriented films. Also, we used a single screw extruder (monolayer) and the main parameters are reported in Table B. The MDO section was operated to produce a uniaxially oriented film over heated and cooled rollers. This section is linked to the TD downstream tenter frame to fabricate biaxially oriented films. The MDO section is vertically designed and has six rollers with diameter of 18″ (457 mm) and 30″ (762 mm) face width. The draw section gap was set at 0.035″ (0.889 mm) and kept constant for all biaxially oriented films. Temperature and speed were accurately and independently controlled.

TABLE B
extruder parameters
					Zone
	Zone	Zone	Zone	Zone	5	Head	Screw	Die	Melt
Sample	1	2	3	4	(Die)	Pressure	Speed	Pressure	Torque
Unit	[° C.]	[° C.]	[° C.]	[° C.]	[° C.]	[psig]	[rpm]	[psig]	[%]
Sample A	232	238	249	249	249	549	36	370	40.1
(Product A)
3 × 7.25
Sample B	232	238	249	249	249	591	39.9	390	43.5
(Product A)
4 × 7
Sample C	232	238	249	249	249	636	47	418	47.3
(Product A)
4 × 8
Sample D	232	238	249	249	249	631	46.9	413	47.3
(Product A)
3 × 9
Sample E	232	238	249	249	249	633	46.9	415	47.1
(Product A)
3.5 × 9
Sample F	232	238	249	249	249	670	49.9	425	50.2
(Product A)
5 × 6
Sample G	232	238	249	249	249	680	49.9	427	49.6
(Product A)
4 × 8
Sample H	232	238	249	249	249	539	39.9	337	41.6
(Product B)
4 × 7

In the TDO section, films were biaxially oriented by heating up the pre-stretched MDO material (hot air oven) and pulling the web along TD from the edges in a tenter frame (series of mobile clips). The film orientation was tuned and adjusted through a pair of diverging rails. The preheat, stretch and annealing temperatures were set in the TDO section. The oven is composed by three heated and independently controlled zones.

Both MDO and TDO processing conditions are reported in Table C including cast sheet size and line speed. Also, the web was allowed to relax in the annealing zone at about 5% per side in order to partially remove the accumulated stress. After the TDO, the film was trimmed at the edges and the gauge was measured before the winding section.

During the trial for all the samples, we were able to reach a reliable and stable line with speed up to 76.5 ft/min.

TABLE C
MDP and TDO parameters
	Sample	Sample	Sample	Sample	Sample	Sample	Sample	Sample
	A	B	C	D	E	F	G	H
	(Prod.	(Prod.	(Prod.	(Prod.	(Prod.	(Prod.	(Prod.	(Prod.
	A)	A)	A)	A)	A)	A)	A)	B)
	3 × 7.25	4 × 7	4 × 8	3 × 9	3.5 × 9	5 × 6	4 × 8	4 × 7
Sample ID	289264	289267	289265	289266	289268	289269	289270	289271
(BCT)
Cast Width	10 ⅝	10 ⅝	10 ⅝	10 ¾	10 ¾	10 ⅞	10 ⅞	10 ⅞
(in)
Cast	23	23	30	30	30	31.5	31.5	29
Thickness
(mil)
MDO Exit	8 ¾	8 ½	8 ⅝	8 ¾	8 ¾	8 ¾	9	9
Width (in)
MDO Exit	8	7	8	10	10	7	8	9
Thickness
(mil)
TDO Exit	48 ¾	47	53 ¾	60 ¼	60 ¼	40 ½	55 ½	47 ¾
Width (in)
TDO Exit	40	40	40	48	48	37	41	41
Trimmed
Width (in)
TDO Exit	1	1	1	1.1	1.1	0.8	0.8	0.8
Thickness
(mil)
MDO Ratio	3	4	4	3	3.5	5	4	4
(−)
TDO Ratio	7.25	7	8	9	9	6	8	7
(−)
TDO Relax	5% + 5%	5% + 5%	5% + 5%	5% + 5%	5% + 5%	5% + 5%	5% + 5%	6% + 6%
(% + %)
Roll 1-	15	15	15	15	15	15	15	13
Preheat I
(fpm)
Roll 2-	15	15	15	15	15	15	15	13
Preheat II
(fpm)
Roll 3-Slow	15.3	15.3	15.3	15.3	15.3	15.3	15.3	13.3
draw (fpm)
Roll 4-Fast	45.9	61.2	61.2	45.9	53.5	76.5	61.2	53
draw (fpm)
Roll 5-	45.7	61	61	45.7	53.4	76.2	61	52.9
Annealing
(fpm)
Roll 6-	45.7	60.9	60.9	45.7	53.3	76.1	60.9	52.8
Cooling
(fpm)
Roll 1-	66	66	66	66	66	66	66	66
Preheat I
(dg C.)
Roll 2-	104	104	104	100	100	100	113	121
Preheat II
(dg C.)
Roll 3-Slow	107	107	107	110	110	110	116	124
Draw (dg C.)
Roll 4-Fast	104	104	104	100	100	100	110	118
Draw (dg C.)
Roll 5-	66	66	66	66	66	66	66	66
Annealing
(dg C.)
Roll 6-	32	32	32	32	32	32	32	32
Cooling
(dg C.)
TDO Master	45.9	61.2	61.2	45.9	53.5	76.5	61.2	53
Chain (fpm)
Preheat	116	121	124	118	118	121	121	121
Zone (dg C.)
Stretch Zone	116	118	118	116	113	116	116	113
(dg C.)
Annealing	102	102	102	102	102	99	99	93
Zone (dg C.)

Product: BOPE Film Properties

Film characterization was performed on the 8 samples and is reported in Table 4. All samples were measured along MD and TD. Prior to the testing, all samples were conditioned for 40 hours at 230±2° C. and 50±10% relative humidity (ASTM D618-08).

It was noted that some of the films had bands along the machine and transverse direction. These bands imparted inhomogeneities and gauge variations across the web. Therefore, we only targeted film properties at ˜1 mil and excluded values out of the +/−0.2 range. The bands at the TDO clips were probably due to the necking formation (longitudinal bands). The transversal bands (along MD) were developed downstream the equipment at the die aperture of the extruder.

TABLE 4
Film Properties
	Sample	Sample	Sample	Sample	Sample	Sample	Sample	Sample
	A	B	C	D	E	F	G	H
	(Product	(Product	(Product	(Product	(Product	(Product	(Product	(Product
	A)	A)	A)	A)	A)	A)	A)	B)
	3 × 7.25	4 × 7	4 × 8	3 × 9	3.5 × 9	5 × 6	4 × 8	4 × 7
Sample ID	289264	289267	289265	289266	289268	289269	289270	289271
(BCT)
Stretch Ratio	3 × 7.25	4 × 7	4 × 8	3 × 9	3.5 × 9	5 × 6	4 × 8	4 × 7
(MD × TD)
Gauge (mil)	1.0	1.0	1.0	1.0	1.0	0.9	0.8	1.0
Film Density	0.933	0.932	0.932	0.934	0.934	0.933	0.933	0.940
(g/cc)
1% Sec.	66	55	59	77	77	58	59	90
Modulus
(kpsi) MD
1% Sec.	85	73	66	98	94	72	68	102
Modulus
(kpsi) TD
Yield Strength	2.8	2.7	2.6	2.9	3.2	3.2	2.6	3.9
(kpsi) MD
Yield Strength	7.9	5.0	5.1	8.9	10.5	5.3	7.4	6.8
(kpsi) TD
Elongation @	6.1	6.3	5.9	5.8	8.5	6.5	5.6	6.1
Yield (%) MD
Elongation @	9.6	8.1	8	9.7	10.1	8.1	8.7	7.5
Yield (%) TD
Tensile	7.4	8.8	8.3	6.9	8.3	11.4	8.6	9.7
Strength (kpsi)
MD
Tensile	15.8	11.0	10.7	18.5	20.2	11.9	15.4	15.1
Strength (kpsi)
TD
Elongation @	385	335	357	421	302	218	316	241
Break (%)
MD
Elongation @	77	95	81	67	54	82	64	69
Break (%) TD
Haze (%)	10.4	25.4	30.8	11.7	12.3	31	18.6	24.1
Clarity (%)	74.6	56.8	48.6	72.6	70.9	48.1	56.3	59.1
Gloss (GU)	50.6	26.2	24.7	53.3	47.5	20.8	28.6	36.9
MD
Peak Force	22.61	16.34	16.43	22.4	22.8	17.53	15.73	20.58
(lbs)
Peak Force	22.21	16.88	15.83	22.09	23.6	19.18	19.64	20.81
Norm.
(lbs/mil)
Break Energy	16	11.47	11.96	12.33	11.78	10.14	9.12	10.92
(in-lbs)
Break Energy	15.72	11.85	11.52	12.16	12.19	11.1	11.39	11.04
Norm, (in-
lbs/mil)
Dart Ph Met.	463	307	355	565	529	376	367	493
A (g)
Dart Ph Met.	455	317	342	557	548	411	458	498
A Norm.
(g/mil)
Shrink (%)	61	63	59	57	63	67	62	65
MD
Shrink (%)	79	73	76	81	82	76	78	76
TD
1% Sec.	0.78	0.75	0.89	0.79	0.82	0.81	0.87	0.88
Modulus Ratio
(−) MD/TD
Yield Strength	0.35	0.54	0.51	0.33	0.30	0.60	0.35	0.57
Ratio (−)
MD/TD
Tensile	0.47	0.80	0.78	0.37	0.41	0.96	0.56	0.64
Strength Ratio
(−) MD/TD

The present invention may at first blush appear similar to a concurrently filed application (related application U.S. Ser. No. 62/945,760, entitled “Biaxially Oriented Polyethylene Films” (attorney docket number 2019EM494)), but note the below comparison in Table 5 between the U.S. Ser. No. 62/945,760 samples and the present samples.

TABLE 5
Property differences between the related invention the and the instant invention
		Instant Invention
Document	USSN 62/945760 Samples	Sample	Sample	Sample	Sample	Sample	Sample	Sample	Sample
Sample	I-1	I-1	I-1	I-2	I-2	I-2	I-2	I-2	A	B	C	D	E	F	G	H
name	4 × 7	4 × 8	5 × 8	4 × 7	4 × 8	5 × 8	5 × 9	5 × 10	3 × 7.25	4 × 7	4 × 8	3 × 9	3.5 × 9	5 × 6	4 × 8	4 × 7
1% secant	0.6	0.6	0.6	0.6	0.5	0.5	0.5	0.5	0.8	0.8	0.9	0.8	0.8	0.8	0.9	0.9
modulus
MD/TD
ratio
Yield	0.3	0.2	0.2	0.2	0.2	0.2	0.2	0.1	0.4	0.5	0.5	0.3	0.3	0.6	0.4	0.6
strength
MD/TD
ratio
Elongation	0.6	0.6	0.6	0.6	0.5	0.6	0.5	0.5	0.6	0.8	0.7	0.6	0.8	0.8	0.6	0.8
at yield
MD/TD
ratio
Tensile	0.6	0.4	0.6	0.6	0.5	0.6	0.5	0.4	0.5	0.8	0.8	0.4	0.4	1.0	0.6	0.6
strength
MD/TD
ratio
Elongation	0.2	0.2	0.3	0.2	0.2	0.3	0.2	0.2	5.0	3.5	4.4	6.3	5.6	2.7	4.9	3.5
at break
MD/TD
ratio
Norm.	0.4	0.4	0.5	0.5	0.4	0.5	0.4	0.5	4.3	1.1	0.8	5.6	3.7	0.5	1.9	2.0
Elmendorf
tear
MD/TD
ratio
Shrink	0.8	0.8	0.8	0.8	0.7	0.8	0.8	0.7	0.8	0.9	0.8	0.7	0.8	0.9	0.8	0.9
MD/TD
ratio
Gloss (−)	59	61	63	57	57	63	68	64	51	26	25	53	48	21	29	37

Film Characterization Methods

Gauge of a film was determined by ASTM D6988-13.

1% secant modulus and tensile properties, including yield strength, elongation at yield, tensile strength, and elongation at break, were determined by ASTM D882-10, with the following modifications: a jaw separation of 5 inches and a sample width of 1-inch is used. The index of stiffness of thin films is determined by manually loading the samples with slack and pulling the specimen at a rate of jaw separation (crosshead speed) of 0.5 inches per minute to a designated strain of 1% of its original length and recording the load at these points. The calculation procedures are as follows:

• • Tensile strength is calculated as a function of the maximum force in pounds divided by the cross-sectional area of the specimen. Ultimate Tensile=Maximum Force/Cross-Sectional Area.
  • Yield strength is calculated as a function of the force at yield divided by the cross-sectional area of the specimen. Yield Strength=Force at Yield/Cross-Sectional Area.
  • Elongation is calculated as a function of the increase in length divided by the original length times 100. Elongation=Increase in Length/Original Length×100%. Yield point is the first point in which there is an increase in strain (elongation) and none in stress (force). The yield is determined by a 2% off-set method.
  • Tensile at 100% Elongation is calculated as a function of the force at 100% elongation divided by the cross-sectional area of the specimen. Tensile at 100% Elongation=Force at 100% Elongation/Cross-Sectional Area.
  • Tensile at 200% Elongation is calculated as a function of the force at 200% elongation divided by the cross-sectional area of the specimen. Tensile at 200% Elongation=Force at 200% Elongation/Cross-Sectional Area.

The 1% secant modulus is measured of the material stiffness and is calculated as a function of the total force at 1% extension, divided by the cross-sectional area times 100 and reported in PSI units. 1% Secant Modulus=Load at 1% Elongation/(Average Thickness (Inches)×Width)×100.

Clarity was determined by ASTM D1746-15.

Haze was determined by ASTM D1003-13.

Gloss was determined by ASTM D2457-13.

Dart drop was determined by phenolic Method A per ASTM D1709-16ae1.

Puncture properties including peak force, peak force normalized to a thickness of 1 mil (peak force divided by thickness), break energy, and break energy normalized to a thickness of 1 mil (break energy divided by thickness) were determined by ASTM D5748, with the following modifications. Any film sample ˜1 mil thick is placed in a circular clamp approximately 4 inches wide. A stainless steel custom-made plunger/probe with a ¾″ tip and two 0.25 mil slip sheets are pressed through the specimen at a constant speed of 10 in/min. Results are obtained after failure from five different locations chosen on the standard film strip and averaged.

Shrink (in both Machine (MD) and Transverse (TD) directions) was measured as the percentage decrease in length of a 100 cm circle of film along the MD and TD, under a heat gun (Model HG-501A) set with an average temperature of 750° F. (399° C.). The heat gun was centered two inches over the sample and heat was applied until each specimen stopped shrinking.

Water vapor transmission rate (WVTR) was performed on a MOCON Permatran W-700 and W3/61 obtained from MOCON, Inc. ASTM F1249 at 100° F. (37.8° C.) and 100% relative humidity where samples were loaded without specific orientation.

SAOS: The small amplitude oscillatory shear (SAOS) measurements were made on the Anton Paar MCR702 Rheometer. Samples were compression molded at 177° C. for 15 minutes (including cool down under pressure) and 25 mm testing disk specimen were die cut from the resulting plaques. Testing was conducted using a 25 mm parallel plate geometry. Amplitude sweeps were performed on all samples to determine the linear deformation regime. For amplitude sweep, the strain was set from 0.1 to 100% with a frequency of 6 rad/sec and temperature of 190° C. Once the linearity was established, frequency sweeps were performed to determine the complex viscosity profile. Tests were run from 0.01 to 500 rad/s and carried out at T=190° C. under 5% strain.

In order to quantify the shear-like rheological behavior, we defined the degree of shear thinning (DST) parameter. The DST was measured by the following expression:

$\mathrm{DST}=\frac{\left[{\eta }^{*}\left(0.01\mathrm{rad}/s\right)-{\eta }^{*}\left(50\mathrm{rad}/s\right)\right]}{{\eta }^{*}\left(0.01\mathrm{rad}/s\right)}$

Where η*(0.01 rad/s) and η*(50 rad/s) are the complex viscosities at frequencies of 0.01 and 50 rad/s, respectively, measured at 190° C. The DST parameter helps to better differentiate and highlight the branching character of the samples. In fact, the higher is the DST parameter, the higher is the degree of shear thinning.

SER: The Sentmanat Extensional Rheometer (SER) testing platform and transient uniaxial extensional viscosity testing are described in detail in US 2018/0319907. The tensile evolution of the transient extensional viscosity was investigated by MCR501 (Anton Paar) rheometer with controlled operational speed. The linear viscoelastic envelope (LVE) is obtained from start-up steady shear experiments.

For all samples, the tensile stress growth exhibit deviations from LVE for extension rate between 0.1 and 10 s⁻¹ at T=150° C. In the nonlinear regime, branching and high molecular weight polymers present strain hardening profiles in extensional viscosity testing. Strain hardening is defined as a rapid and abrupt leveling-off of the extensional viscosity from the linear viscoelastic behavior. Therefore, this nonlinear behavior was quantified by the strain hardening ratio (SHR), which is defined as the ratio of the maximum transient extensional viscosity at 1 s⁻¹ over the respective value at 0.1 s⁻¹:

$\mathrm{SHR}=\frac{{\eta }_E^{*}\left(\stackrel{.}{\epsilon }=1s^{-1},t\right)}{{\eta }_E^{*}\left(\stackrel{.}{\epsilon }=0.1s^{-1},t\right)}$

The value at 0.1 s⁻¹ was preferred to LVE because of the choice to adopt only transient extensional and not start-up steady shear data in the treatment. Whenever the ratio is greater than 1, the material exhibit strain hardening.

All documents described herein are incorporated by reference herein, including any priority documents and/or testing procedures to the extent they are not inconsistent with this text. As is apparent from the foregoing general description and the specific embodiments, while forms of the invention have been illustrated and described, various modifications can be made without departing from the spirit and scope of the invention. Accordingly, it is not intended that the invention be limited thereby. Likewise, the term “comprising” is considered synonymous with the term “including.” Likewise whenever a composition, an element or a group of elements is preceded with the transitional phrase “comprising”, it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of”, “selected from the group of consisting of,” or “is” preceding the recitation of the composition, element, or elements and vice versa.

Claims

1. A biaxially-oriented polyethylene film comprising polyethylene having: (A) a melt index, I2, of 1.0 g/10 min or greater;(B) a density of 0.925 g/cm3 to 0.945 g/cm3;(C) a g′LCB of less than 0.8;(D) an Mz of 1,000,000 g/mol or more;(E) an Mw/Mn of 5 or more;(F) an Mw of 100,000 g/mol or more;(G) a ratio of to g′LCB to g′Mz greater than 1.0; and(H) a Strain Hardening Ratio of 4 or more,where the film has a 1% secant in the transverse direction of 60,000 psi or more, a Dart Drop of 250 g/mil or more, and a ratio of 1% secant MD/1% secant TD is 0.65 or more.

2. The film of claim 1, wherein the ratio of Yield strength MD/Yield strength TD of the film is 0.20 or more, and or the ratio of Tensile strength MD/Tensile strength TD of the film is 0.30 or more.

3. The film of claim 1, wherein the polyethylene has at least 10° C. between the onset of transition and the melting peak, as shown in a DSC trace.

4. The film of claim 1, wherein the polyethylene described herein has at least 10° C. between the melting peak and the crystallization peak values.

5. The film of claim 1, wherein the polyethylene is present at 90 wt % to 100 wt % of the biaxially-oriented film.

6. (canceled)

7. The film of claim 1, wherein the biaxially-oriented film has a thickness of 0.1 to 3 mils.

8. The film of claim 1, wherein the polyethylene has: (A′) a melt index, I2, of 1.9 to 3 g/10 min or greater;(B′) a density of 0.925 g/cm3 to 0.945 g/cm3;(C′) a g′LCB of 0.78 to 0.5;(D′) an Mz of 1,300,000 g/mol or more; and(F′) an Mw of 155,000 g/mol or more.

9. The film of claim 1, wherein the biaxially-oriented film has one or more of the following properties: (IV) a yield strength in the machine direction of 2,000 psi to 5,000 psi and a yield strength in the transverse direction of 4,000 psi to 15,000 psi;(V) a tensile strength in the machine direction of 6,000 psi to 15,000 psi and a tensile strength in the transverse direction of 10,000 psi to 30,000 psi;(VI) a peak force per mil of 10 lbs/mil to 40 lbs/mil; and(VII) a Dart Drop A of 250 g/mil to 1350 g/mil.

10. The film of claim 9, wherein the biaxially-oriented film also has one or more of the following properties: (IX) an average density of 0.925 g/cm3 to 0.945 g/cm3;(X) an elongation at yield in the machine direction of 5% to 15% and an elongation at yield in the transverse direction of 9% to 17%);(XI) an elongation at break in the machine direction of 140% to 250% and an elongation at break in the transverse direction of 30% to 120%;(XII) a haze of 5% to 35%(XIII) a clarity of 30% to 80%; and(IX) a break energy of 5 lbs*in to 25 lbs*in and/or a break energy per mil of 5 lbs*in/mil to 19 lbs*in/mil.

11. (canceled)

12. (canceled)

13. A method comprising: producing a polymer melt comprising a polyethylene having: (A) a melt index, I2, of 1.0 g/10 min or greater;(B) a density of 0.925 g/cm3 to 0,945 g/cm3;(C) a g′LCB of less than 0.8;(D) an Mz of 1,000,000 g/mol or more;(E) an Mw/Mn of 5 or more;(F) an Mw of 100,000 g/mol or more;(G) a ratio of g′LCB to g′Mz greater than 1.0; and(H) a Strain Hardening Ratio of 4 or more,extruding a film from the polymer melt;stretching the film in a machine direction to produce a machine direction oriented (MDO) polyethylene film; andstretching the MDO polyethylene film in a transverse direction to produce a biaxially-oriented polyethylene film, where the film has a 1% secant in the transverse direction of 60,000 psi or more, a Dart Drop of 250 g/mil or more, and a ratio of 1% secant MD/1% secant TD is 0.65 or more.

14. The method of claim 13 wherein the polyethylene has a ratio of Yield strength MD/Yield strength TD of the film of 0.20 or more, and or a ratio of Tensile strength MD/Tensile strength TD of the film of 0.30 or more.

15. (canceled)

16. The method of claim 13, wherein stretching in the machine direction is at a stretch ratio of 1 to 10, and wherein stretching in the transverse direction is at a stretch ratio of 1 to 12.

17. The method of claim 13, wherein the film can be stretched in the transverse direction without web breakage or tearing, over an 8° C. range and stretched in the transverse direction without web breakage or tearing, over a 5° C. range.

18. The method of claim 13, wherein the polyethylene has: (I) a degree of shear thinning of 0.85 to 0.95,(J) a strain hardening ratio of 4 or greater,(K) a melting temperature of 122° C. or greater,(L) a crystallization temperature of 110° C. or greater,(M) a Mw of 100,000 g/mol to 155,000 g/mol, and(N) a Mw/Mn of 5 to 10.

19. (canceled)

20. (canceled)

21. The method of claim 13, wherein the biaxially-oriented film has a thickness of 0.1 to 3 mils.

22. The method of claim 13, wherein the biaxially-oriented film has one or more of the following properties: (IV) a yield strength in the machine direction of 2,000 psi to 5,000 psi and a yield strength in the transverse direction of 5,000 psi to 11,000 psi;(V) a tensile strength in the machine direction of 6,000 psi to 15,000 psi and a tensile strength in the transverse direction of 10,000 psi to 30,000 psi;(VI) a peak force per mil of 10 lbs/mil to 40 lbs/mil; and(VII) a Dart Drop A of 250 g/mil to 1350 g/mil.

23. The method of claim 18, wherein the biaxially-oriented film also has one or more of the following properties: (IX) an average density of 0.925 g/cm3 to 0.945 g/cm3;(X) an elongation at yield in the machine direction of 5% to 15% and an elongation at yield in the transverse direction of 9% to 17%);(XI) an elongation at break in the machine direction of 140% to 250% and an elongation at break in the transverse direction of 30% to 120%;(XII) a haze of 5% to 35%;(XIII) a clarity of 30% to 80%; and(IX) a break energy of 5 lbs*in to 25 lbs*in and/or a break energy per mil of 5 lbs*in/mil to 19 lbs*in/mil.

24. A polyethylene having: (A) a melt index, I2, of 1.0 g/10 min or greater;(B) a density of 0.925 g/cm3 to 0.945 g/cm3;(C) a g′LCB of less than 0.8;(D) an Mz of 1,000,000 g/mol or more;(E) an Mw/Mn of 5 or more;(F) an Mw of 100,000 g/mol or more;(G) a ratio of g′LCB to g′Mz greater than 1.0; and(H) a Strain Hardening Ratio of 4 or more,that when the polyethylene is formed into a biaxially oriented 1 mil thick film, the film has a 1% secant in the transverse direction of 60,000 psi or more, a Dart Drop of 250 g/mil or more, and a ratio of 1% secant MD/1% secant TD is 0.65 or more.

25. The polyethylene of claim 24, wherein, when the polyethylene is formed into a biaxially oriented 1 mil thick film, the ratio of Yield strength MD/Yield strength TD of the film is 0.20 or more, and/or the ratio of Tensile strength MD/Tensile strength TD of the film is 0.30 or more.

26. The polyethylene of claim 24, wherein the polyethylene has: (I) a degree of shear thinning of 0.85 to 0.95,(J) a strain hardening ratio of 4 or greater,(K) a melting temperature of 122° C. or greater,(L) a crystallization temperature of 110° C. or greater,(M) a Mw of 100,000 g/mol to 155,000 g/mol, and(N) a Mw/Mn of 5 to 10.