BIMODAL POLYETHYLENE COPOLYMER AND FILM THEREOF

Abstract

A bimodal ethylene-co-1-hexene copolymer consisting essentially of a higher molecular weight component and a lower molecular weight component, and, when in its molten state at 190 degrees Celsius, characterized by a unique cast property space defined by a combination of high-load melt flow index, melt flow ratio, and cast elasticity properties. A blown film consisting essentially of the bimodal ethylene-co-1-hexene copolymer. A method for synthesizing the bimodal ethylene-co-1-hexene copolymer. A method for manufacturing the blown film. A manufactured article comprising the bimodal ethylene-co-1-hexene copolymer.

Description

BIMODAL POLYETHYLENE COPOLYMER AND FILM THEREOF IVIA / a / ZUZU / Ul ZI 11 FIELD OF INVENTION Polyethylene copolymers, films, manufactured articles and related methods. BACKGROUND OF THE INVENTION Publications of patent applications in or about the field include US 2016 / 0068623 Al; US 2016 / 0297907 Al; and WO 2017 / 132092 Al. Patents in or about the field include US 5,332,706; US 5,882,750; US 6,989,344 B2; US 7,078,467 B1; US ​​7,090,927 B2; US 7,157,531 B2; US 7,223,825 B2; US 7,300,988 B2; US 8,227,552 B2 and US 8,497,329 B2. BRIEF DESCRIPTION OF THE INVENTION A bimodal ethylene-co-l-hexene copolymer consisting essentially of a higher molecular weight (HMW) component and a lower molecular weight (LMW) component, and, when in its molten form at 190 degrees Celsius (°C), characterized by a unique cast property space defined by a combination of high-load melt flow index, melt flow ratio, and cast elasticity properties (the bimodal ethylene-co-l-hexene copolymer). The bimodal ethylene-co-l-hexene copolymer consisting essentially of, is free from one-third or more of a component as determined by gel permeation chromatography (GPC) measured in accordance with the GPC Test Method. Ref. 313048 A method for synthesizing the bimodal ethylene-co-l-hexene copolymer, the method essentially comprising polymerizing ethylene (monomer) and 1-hexene (comonomer) with a single bimodal catalyst system in a single fluidized bed, gas-phase polymerization reactor (FB-GPP) under effective operating conditions, thereby producing the bimodal ethylene-co-l-hexene copolymer. Essentially, the method is free of Ziegler-Natta catalysts and chromium catalysts, and the polymerization is carried out in a single reactor (i.e., the FB-GPP reactor). The operating conditions are effective in imparting the unique combination of high loading melt flow index, melt flow ratio, and cast elasticity properties to the bimodal ethylene-co-l-hexene copolymer. Aside from this, the method is not particularly limited. A film consisting essentially of the bimodal copolymer of ethylene-co-l-hexene (the film). The film is characterized by enhanced toughness comprising enhanced tear strength and enhanced dart impact. While consisting essentially of, the film is free of other polyolefin polymers, but its constituents are not otherwise particularly restricted. A method for making a blown film, the method comprising melting the bimodal ethylene-co-1-hexene copolymer to provide a melt thereof, extruding the melt through a die configured to form a bubble to make a bubble of the bimodal ethylene-co-1-hexene copolymer, and blowing (inflating) the bubble with a film blowing machine, thereby making the blown film. A manufactured article comprising the bimodal copolymer of ethylene-co-l-hexene. DETAILED DESCRIPTION OF THE INVENTION The brief description and summary are included herein for reference. Certain modalities are described below as numbered aspects to facilitate cross-referencing. Aspect 1. A bimodal ethylene-co-l-hexene copolymer consisting essentially of a higher molecular weight (HMW) component and a lower molecular weight (LMW) component and, when in the molten form at 190 °C, is characterized by a cast property space defined by a combination of high loading melt index (HLMI or I21), I21 / I5 melt flow ratio (MFR5), and cast elasticity (G' / G at 0.1 rad / s) properties, wherein the HLMI is 7.0 to 11.0 grams per 10 minutes (g / 10 min), alternatively 7.3 to 10.0 g / 10 min, alternatively 7.4 to 9.5 g / 10 min and is measured in accordance with ASTM D1238-13 (190 °C, 21.6 kg); The MFR5 is from 22.0 to 35.0, alternatively from 25 to 32, alternatively from 26.6 to 30.6 where the I21 and I5 values ​​used to calculate the MFR5 are each in g / 10 min and are measured according to ASTM D1238-13 (190 °C, 21.6 kg, I21; and 190 °C, 5.0 kg, I5, respectively), and the casting elasticity is from 0.5 to 0.8 pascals (Pa), alternatively 0.50 to 0.70 Pa, alternatively 0.525 to 0.684 Pa, and wherein the cast elasticity = G' / G determined at 0.1 radians per second (rad / s) in accordance with the Cast Elasticity Test Method (described herein). The / signifies division. Cast elasticity characterizes the ratio between the cast storage modulus (G') and the loss modulus (G) at the dynamic frequency of 0.1 rad / s. This ratio is useful for evaluating polyethylene resins for film applications. Aspect 2. The bimodal ethylene-co-l-hexene copolymer of aspect 1 wherein the melt property space of the bimodal ethylene-co-l-hexene copolymer is further defined by any one of the following limitations (i) to (iii): (i) a melt flow index I2 of 0.05 to 0.10, alternatively 0.055 to 0.084, alternatively 0.060 to 0.080 g / 10 min measured in accordance with ASTM D1238-13 (190 °C, 2.16 kg, I2); (ii) a melt flow index I5 of 0.20 to 0.40, alternatively 0.25 to 0.35, alternatively 0.27 to 0.33 g / 10 min, measured in accordance with ASTM D1238-13 (190 °C, 5.0 kg, I5); and (iii) a flow rate ratio I21 / I2 (MFR2) of 80.0 to 150.0, alternatively 99 to 140.0, alternatively 101 to 139 wherein the I21 and I2 values ​​used to calculate MFR2 are each in g / 10 min and are measured in accordance with ASTM D1238-13 (190 °C, 21.6 kg, I21; and 190 °C, 2.16 kg, I2, respectively).In some respects, the foundry property space is further defined by any one of the limitations (iv) to (vii): (iv) both (i) and (ii); (v) both (i) and (iii); (vi) both (ii) and (iii); and (vii) each of (i) to (iii). Aspect 3. The bimodal ethylene-co-l-hexene copolymer of aspect 1 or 2 characterized by any one of the resin property limitations (i) to (iv): (i) a density of 0.9410 to 0.9550 grams per cubic centimeter (g / cm3), alternatively 0.9450 to 0.9530 g / cm3, alternatively 0.9480 to 0.9500 g / cm3, measured in accordance with ASTM D792-13, Method B; (ii) a split component fraction characterized by a weight fraction of the HMW component of 50.0 to 63 wt.%, alternatively 55 to 60.0 wt.%, alternatively 57.0 to 59.4 wt.%; and a weight fraction of the LWM component fraction is 50.0 to 37% by weight, alternatively 45 to 40.0% by weight, alternatively 43.0 to 40.6% by weight, respectively, of the combined weight of the HMW and LMW components, measured according to the Gel Permeation Chromatography (GPC) Test Method; (iii) a component molecular weight dispersion characterized by a ratio of the weighted average molecular weight of the HMW component (Mw-hmw) to the weighted average molecular weight of the LMW component (Mw-lmw) (i.e., Mw-hmw / Mw-lmw ratio) of 30.0 to 50.0, alternatively 40.0 to 45, alternatively 40.9 to 42.5, measured according to the GPC Test Method; and (iv) a molecular mass dispersion (Mw / Mn), Dm, of 30.0 to 40.0, alternatively from 34 to 39, alternatively from 34.8 to 38.6, wherein Mwy and Mn are measured according to the GPC Test Method.In some respects, the copolymer is further characterized by any one of the resin property limitations (v) to (xii): (v) both (i) and (ii); (vi) both (i) and (iii); (vii) both (i) and (iv); (viii) both (ii) and (iii); (ix) both (ii) and (iv); (x) both (iii) and (iv); (xi) any three of (i) to (iv); and (xii) each of (i) to (iv). In some respects, the bimodal ethylene-co-l-hexene copolymer may have a transition metal content, alternatively a Zr content, of less than 10 parts per million (ppm) as measured by inductively coupled plasma mass spectrometry (ICP-MS). Aspect 4. The bimodal ethylene-co-l-hexene copolymer of any one of aspects 1 to 3, which, when characterized in the form of a blown film and having a thickness of 0.0127 millimeters (mm, 12.7 micrometers (pm), 0.500 mil), is characterized by any one of the limitations (i) to (iv): (i) a dart impact of 250 to 400 grams (g), alternatively 270 to 380 g, alternatively 275 to 376 g, measured according to the Dart Impact Test Method; (ii) an Elmendorf tear in the transverse direction (CD) of 60.0 to 190.0 grams-force (gf), alternatively 61 to 185 gf, alternatively 83 to 182 gf, measured in accordance with the Elmendorf Tear Test Method; (iii) an Elmendorf tear in the machine direction (MD) of 15 to 35 gf, alternatively 17 to 33 gf, alternatively 18 to 32 gf, measured in accordance with the Elmendorf Tear Test Method; and (iv) a gauge variation of 10.5% to 17%, alternatively 11.0% to 16.4%, alternatively 11.2% to 16.2%, measured in accordance with the Gauge Variation Test Method.In some respects the copolymer, when characterized in the form of a blown film, is further characterized by any one of the limitations (v) to (xii): (v) both (i) and (ii); (vi) both (i) and (iii); (vii) both (i) and (iv); (viii) both (ii) and (iii); (ix) both (ii) and (iv); (x) both (iii) and (iv); (xi) any three of (i) to (iv); and (xii) each of (i) to (iv). Aspect 5. A method for synthesizing the bimodal ethylene-co-l-hexene copolymer from any one of aspects 1 to 4, the method essentially comprising copolymerizing ethylene (monomer) and 1-hexene (comonomer) with a combination of a bimodal catalyst system and a cutting catalyst in the presence of molecular hydrogen gas (H2) and, optionally, an induced condensation agent (ICA) in a polymerization reactor (e.g., a fluidized bed gas-phase polymerization reactor (FB-GPP reactor)) under polymerization conditions effective to provide an initial bimodal ethylene-co-l-hexene copolymer, and optionally oxygen-adapted ethylene-co-l-hexene copolymer to provide an oxygen-adapted bimodal ethylene-co-l-hexene copolymer;wherein the bimodal catalyst system is prepared by contacting a first activator with bis(2-(pentamethylphenylamido)ethyl)aminezirconium dibenzyl and a bis(butylcyclopentadienyl)zirconium dihalide; wherein the cutting catalyst is prepared by contacting a second activator with bis(butylcyclopentadienyl)zirconium dialkyl; wherein the first and second activators are the same or different; and wherein the effective polymerization conditions comprise a reaction temperature of 80 degrees (°) to 110 °Celsius (°C), alternatively 83° to 106 °C, alternatively 83° to 87 °C, alternatively 91° to 100 °C, alternatively 101° to 106 °C; a molar ratio of molecular hydrogen gas to ethylene (H2 / C2 molar ratio) of 0.001 to 0.020, alternatively from 0.002 to 0.015, alternatively from 0.005 to 0.010;and a molar ratio of 1-hexene (Ce) to ethylene (molar ratio Ce / Cz) of 0.005 to 0.050, alternatively from 0.008 to 0.030, alternatively from 0.015 to 0.025. In some respects, bis(butylcyclopentadienyl)zirconium dihalide is bis(butylcyclopentadienyl)zirconium dichloride; and bis(butylcyclopentadienyl)zirconium dialkyl is bis(butylcyclopentadienyl)zirconium dimethyl or bis(butylcyclopentadienyl)zirconium diethyl, alternatively bis(butylcyclopentadienyl)zirconium dimethyl. In some respects, the first activator is an alkylaluminoxane (alkylalumoxane) and the second activator is independently an alkylaluminoxane compound or an alkylaluminum. Aspect 6. The method of aspect 5, which further essentially consists of removing the bimodal ethylene-co-1-hexene copolymer (initial and / or oxygen-adapted modes) from the reactor (e.g., the FB-GPP reactor) to provide a bimodal ethylene-co-1-hexene copolymer. In some aspects, the removed bimodal ethylene-co-1-hexene copolymer may be the initial bimodal ethylene-co-1-hexene copolymer, the oxygen-adapted bimodal ethylene-co-1-hexene copolymer, or both. In some aspects, the removed bimodal ethylene-co-1-hexene copolymer may be purged with an inert gas (e.g., N2) to remove trapped hydrocarbons and / or treated with a humidified nitrogen (N2) gas stream to in situ deactivate any residual amount of the bimodal catalyst system contained therein to provide a purged bimodal ethylene-co-1-hexene copolymer.In some aspects, the stripped or purged ethylene-co-l-hexene bimodal copolymer is degassed to remove volatile organic compounds, yielding a degassed ethylene-co-l-hexene bimodal copolymer. In some aspects, the stripped, purged, or degassed ethylene-co-l-hexene bimodal copolymer is pelletized to yield pellets (pelletized ethylene-co-l-hexene bimodal copolymer). The initial, oxygen-adapted, stripped, purged, degassed, and pelletized forms of the ethylene-co-l-hexene bimodal copolymer are collectively referred to as the ethylene-co-l-hexene bimodal copolymer, which may be that of any one of aspects 1 to 4. The ethylene-co-l-hexene bimodal copolymer may be combined with one or more film additives useful in polyethylene films. The combination may comprise mixing in a molten state one or more film additives into a melt of the bimodal ethylene-co-l-hexene copolymer.Alternatively, the combination may comprise soaking or injecting one or more film additives into pellets of the pelletized bimodal ethylene-co-l-hexene copolymer. Aspect 7. A manufactured article comprising the bimodal ethylene-co-l-hexene copolymer of any one of aspects 1 to 4. Aspect 8. A film consisting essentially of the bimodal ethylene-co-l-hexene copolymer of any one of Aspects 1 to 4 (the film). The transition phrase "consisting essentially of" means that the film is free of other polyolefin polymers, but otherwise its constituents are not particularly restricted. The film can be used in packaging applications to protect a substance that needs to be covered, wherein the film is disposed to at least partially cover the substance. Examples of substances that need to be covered are paper, paperboard (e.g., cardboard), food, pharmaceutical compounds, and a stack of cardboard boxes (e.g., where the film is shrink wrap used to wrap a pallet stacked with cardboard boxes). The film can be the blown film described below. Aspect 9. A method for making a blown film, the method comprising melting the bimodal ethylene-co-l-hexene copolymer of any one of Aspects 1 to 5 to provide a melt thereof, extruding the melt through a die configured to form a bubble to make a bubble of the bimodal ethylene-co-l-hexene copolymer, and blowing (inflating) the bubble with a film blowing machine, thereby making the blown film. The bubble is constrained in one dimension. The blown film may IVIA / a / ZUZU / Ul ZI 11 may be produced or manufactured without internal bubble cooling (IBC) by any suitable method, including IBC-free high-stem film blowing, such as using an active IBC-free high-stem film blowing manufacturing line. The blown film consists essentially of the bimodal ethylene-co-l-hexene copolymer of any of aspects 1 to 5 (the blown film). The transition phrase "consisting essentially of" means that the blown film is free of other polyolefin polymers, but its constituents are not otherwise particularly restricted. Aspect 10. A blown film manufactured by the method of aspect 9 and consisting essentially of the bimodal ethylene-co-l-hexene copolymer of any one of aspects 1 to 4 (the blown film). Whereas, the blown film consists essentially of, it is free of other polyolefin polymers, but its constituents are not otherwise particularly restricted. The blown film may be characterized by improved (increased) toughness (tear or dart impact) and / or improved gauge variation (reduced film thickness variability). The blown film may be used in packaging applications. Definitions Activator. A substance, other than the catalyst or one of the substrates, that increases the rate of a catalyzed reaction without being consumed. Activators typically contain aluminum and / or boron. Bimodal. Two, and only two, modalities or modes. Bimodal in reference to a copolymer (e.g., the ethylene-co-l-hexene copolymer) means a composition consisting essentially of a higher molecular weight component and a lower molecular weight component, wherein the higher molecular weight component consists of a first group of polymer macromolecules synthesized by a first catalyst in a first reactor under a first set of effective molecular weight polymerization process conditions (e.g., first reactor bed temperature, first molar ratio of H2 / C2 gas, first molar ratio of comonomer / monomer and / or use or non-use of oxygen adaptation) and the lower molecular weight component consists of a second group of polymer macromolecules synthesized by a second catalyst in a second reactor under a second set of effective molecular weight polymerization process conditions (e.g., second reactor bed temperature, second molar ratio of theH2 / C2 gas, second comonomer / monomer molar ratio, and / or use or non-use of oxygen adaptation), wherein at least one of the following differences is present: (a) the first catalyst differs in catalytic metal and / or ligand composition from that of the second catalyst(s); (b) the first reactor differs from the second reactor, or the first and second reactors are the same reactor, but the polymerization reaction producing the higher molecular weight component occurs at a different time than the polymerization reaction producing the lower molecular weight component; (c) at least one of the first set of molecular weight-effective polymerization process conditions differs from that of the second set of molecular weight-effective polymerization process conditions. Bimodal polymer compositions include post-reactor blends and reactor blends (where the lower and higher molecular weight components are synthesized).in the same reactor). The bimodal copolymer can be characterized by two peaks separated by a distinguishable local minimum between them on a plot of dW / dLog (MW) on the y-axis as opposed to Log (MW) on the x-axis to give a gel permeation chromatography (GPC) chromatogram, wherein Log (MW) and dW / dLog (MW) are as defined herein and measured by the Gel Permeation Chromatography (GPC) Test Method described herein. Bimodal, when referring to a catalyst system, means a catalyst system containing two different catalysts to catalyze the same polymerization process (e.g., olefin polymerization) and produce a bimodal polymer composition. Two catalysts IVIA / a / XUXU / Ul XI 11 are different if they differ from each other in at least one of the following characteristics: (a) their catalytic metals are different (Ti vs Zr, Zr vs Hf, Ti vs Hf; non-activating metals such as Al); (b) one catalyst has a functional ligand covalently bonded to its catalytic metal and the other catalyst is free of functional ligands bonded to its catalytic metal; (c) both catalysts have functional ligands covalently bonded to their catalytic metal and the structure of at least one of the functional ligands of one of the catalysts is different from the structure of each of the functional ligands of the other catalyst (e.g., cyclopentadienyl vs propylcyclopentadienyl or butylcyclopentadienyl vs (pentamethylphenylamido)ethyl)amine); and (d) for catalysts disposed on a support material, the compositions of the support materials are different.Functional ligands do not include leaving groups X as defined below. Two catalysts of a bimodal catalyst system can be disposed on the same support material, either on the same particles of the same support material or each on different particles of the same support material. The same catalyst, in terms of catalytic metal and ligands, where one part is disposed on a support material and a different part is dissolved in an inert solvent, does not in itself constitute a bimodal catalyst system. Catalyst. A material that enhances the rate of a reaction (e.g., the polymerization of ethylene and 1-hexene) and is not completely consumed. Catalytic system. A combination of a catalyst per se and a complementary material such as a modifying compound to attenuate the reactivity of the catalyst, a support material on which the catalyst is disposed, a carrier material in which the catalyst is disposed, or a combination of any two of these, or a reaction product of a reaction of these. That consists essentially of, consists essentially of, and similar expressions. Partially closed expressions that exclude anything that would affect the basic and novel characteristics of what they describe, but that otherwise permit anything else. In some respects, any one, alternatively, each that comprises or comprises can be replaced by that consists essentially of or consists essentially of, respectively; alternatively, by that consists of or consists of, respectively. That consists of and consists of. Closed expressions that exclude anything not specifically described by the limitation they modify. In some respects, any one, alternatively, each expression that consists essentially of or consists essentially of can be replaced by the expression that consists of or consists of, respectively. Dry. Generally, a moisture content of 0 to less than 5 parts per million based on the total parts by weight. The materials fed into the reactor(s) during a polymerization reaction are dry. Feed. The amount of reactant or reagent added to a reactor. In continuous polymerization, each feed can be either continuous or batch. Feeds can be measured, for example, by counting, to monitor the quantities and relative amounts of the various reactants and reagents in the reactor at any given time. Feed line. A pipe or conduit structure for transporting a feed. Film: an article restricted in one dimension. The restricted dimension may be called a film thickness, and the thickness (gauge variation) is substantially uniform in this. The stated properties of the film are measured on single-layer films 13 (12.7) micrometers thick. Inert. Generally, non-reactive (perceptibly) or non-interfering (perceptibly) in the inventive polymerization reaction. The term inert applied to ethylene feed or purge gas means a molecular oxygen (O2) content of 0 to less than 5 parts per million based on the total parts by weight of the ethylene feed or purge gas. Internal bubble cooling or IBC is an aspect of film blowing performed actively using special purpose IBC auxiliary equipment, such as that of US 2002 / 0150648 Al to RE Cree. Metallocene catalyst. Homogeneous or heterogeneous material containing a cyclopentadienyl ligand-metal complex that enhances the reaction rates of olefin polymerization. Substantially single-site or dual-site. Each metal is a transition metal (Ti, Zr, or Hf). Each cyclopentadienyl ligand is independently an unsubstituted cyclopentadienyl group or a hydrocarbyl-substituted cyclopentadienyl group. In some respects, the metallocene catalyst has two cyclopentadienyl ligands, and at least one, or alternatively both, of the cyclopentadienyl ligands are independently hydrocarbyl-substituted cyclopentadienyl groups. Each hydrocarbyl-substituted cyclopentadienyl group can independently have 1, 2, 3, 4, or 5 hydrocarbyl substituents. Each hydrocarbyl substituent can independently be a (C1-C4) alkyl group. Clipping catalyst. A quantity of a metallocene catalyst that is identical, except for group X described below, to the metallocene catalyst of the bimodal catalyst system. The clipping catalyst is normally fed (e.g., to the FB-GPP reactor) as a solution of the catalyst dissolved in an inert liquid (nonpolar, aprotic, e.g., hydrocarbon solvent). The clipping catalyst is used with the bimodal catalyst system to modify at least one property of the copolymer thus produced. Examples of at least one such property are density, melt flow index I2, melt flux I2i, melt flux ratio (I21 / I2), and molecular weight dispersion (Mw / Mn), BM. Ziegler-Natta catalysts. Heterogeneous materials that improve the reaction rates of olefin polymerization and are prepared by contacting inorganic titanium compounds, such as titanium halides supported on a magnesium chloride support, with an activator. Reactor and polymerization method In an illustrative pilot plant process for producing the bimodal ethylene-co-1-hexene copolymer, a fluidized bed gas-phase polymerization reactor (FB-GPP reactor) is used, having a reaction zone dimensioned as 304.8 mm (12 in) in internal diameter and a straight-side height of 2.4384 meters (8 ft), and containing a fluidized bed of granules of the bimodal ethylene-co-1-hexene copolymer. The FB-GPP reactor is configured with a recycled gas line to circulate a recycled gas stream. The FB-GPP reactor is fitted with gas feed inlets and a polymer product outlet. Gas feed streams of ethylene and hydrogen, along with any comonomer (e.g., 1-hexene), are introduced below the bed of the FB-GPP reactor in the recycled gas line. Polymerization operating conditions are any variable or combination of variables that may affect a polymerization reaction in the GPP reactor or a composition or property of a bimodal ethylene-co-l-hexene copolymer product made in that manner.Variables may include reactor design and size, catalyst composition and quantity; reactant composition and quantity; molar ratio of two different reactants; presence or absence of feed gases such as H2 and / or O2; molar ratio of feed gases to reactants; absence or concentration of interfering materials (e.g., H2O); presence or absence of an induced condensation agent (ICA); average polymer residence time in the reactor; constituent partial pressures; monomer feed rates; reactor bed temperature (e.g., fluidized bed temperature); nature or sequence of process steps; and transition times between steps. Variables other than those described or modified by the method or application may be kept constant. In the operation of the polymerization method, the individual flow rates of ethylene (C2), hydrogen (H2), and 1-hexene (Ce or Cx, where x is 6) are controlled to maintain a fixed comonomer-to-ethylene gas monomer molar ratio (Cx / C2, e.g., C6 / C2) equal to a specified value (e.g., 0.0050), a constant hydrogen-to-ethylene gas molar ratio (H2 / C2) equal to a specified value (e.g., 0.0020), and a constant ethylene partial pressure (C2) equal to a specified value (e.g., 1,000 kPa). Gas concentrations are measured using an online gas chromatograph to understand and maintain the composition in the recycled gas stream. A reaction bed of growing polymer particles is maintained in a fluidized state by continuously flowing a makeup feed and recycling the gas through the reaction zone. Use a surface gas velocity of 0.49 to 0.67 meters per second (m / s) (1.6 to 2.2 feet per second (ft / s)). Operate the FB-GPP reactor at a total pressure of approximately 2344 to approximately 2413 kilopascals (kPa) (approximately 340 to approximately 350 pounds per square inch (psig)) and at a first temperature described. IVIA / a / ZUZU / Ul ZI 11 of the RBT reactor bed. Maintain the fluidized bed at a constant height by removing a portion of the bed at a rate equal to the particle production rate of the bimodal ethylene-co-l-hexene copolymer, which can be 10 to 20 kilograms per hour (kg / h), or alternatively, 13 to 18 kg / h. Remove the bimodal ethylene-co-l-hexene copolymer product semi-continuously through a series of valves into a fixed-volume chamber, where the removed bimodal ethylene-co-l-hexene copolymer is purged to remove trapped hydrocarbons and treated with a humidified nitrogen (N2) gas stream to deactivate any residual catalysts. See the polymerization method described herein. The bimodal catalyst system can be fed to the polymerization reactors in either dry or wet mode. Dry mode uses a dry powder or granules. Wet mode uses a suspension in an inert liquid such as mineral oil. The molar ratio of comonomer / ethylene gas Cx / C2 of comonomer (1-hexene / ethylene or Ce / C2) and ethylene fed to the gas phase polymerization (GPP) reactor can be from 0.0001 to 0.1, alternatively from 0.0002 to 0.05, alternatively from 0.0004 to 0.02. The comonomer gas molar ratio to ethylene (Cx / C2 gas molar ratio) is the amount of all alpha-olefin comonomers (e.g., 1-hexene Ce), in moles, fed in gaseous or vaporous form into the GPP reactor divided by the amount of ethylene monomer (C2), in moles, fed in gaseous form into the GPP reactor. The comonomer moles and ethylene moles are measured using gas flow meters or other suitable means. Partial pressure of ethylene (e.g., C2P) in the GPP reactor. From 690 to 2070 kilopascals (kPa, i.e., from 100 to 300 psia (pounds per square inch absolute)); alternatively from 830 to 1655 kPa (120 to 240 psia), alternatively from 1300 to 1515 kPa (190 to 220 psia). Alternatively, the partial pressure of ethylene can be from 690 to 3450 kilopascals (kPa, from 100 to 500 pounds per square inch absolute (psia), alternatively, from 1030 to 2070 kPa (from 150 to 300 psia), alternatively, from 1380 to 1720 kPa (from 200 to 250 psia), alternatively, from 1450 to 1590 kPa (from 210 to 230 psia), for example, 1520 kPa (220 psia). 1000 psia = 6.8948 kPa. Hydrogen to ethylene (H2 / C2) the molar ratio of gas in the GPP reactor is from 0.010 to 0.100, alternatively from 0.011 to 0.094. Induced condensation agent (ICA). An inert liquid useful for cooling materials in the polymerization reactor(s) (e.g., a fluidized bed reactor); its use is optional. The ICA may be a (C5-C20) alkane, alternatively, a (C11-C20) alkane, alternatively, a (C5-C10) alkane, alternatively, a (C5) alkane, e.g., pentane or 2-methylbutane; a hexane; a heptane; an octane; a nonane; a decane; or a combination of any two or more of these. The ICA may be 2-methylbutane (i.e., isopentane). Aspects of the polymerization method that use the ICA may be referred to as an induced condensation mode operation (ICMO). ICMO is described in US 4,453,399; US 4,588,790; US 4,994,534; US 5,352,749; US 5,462,999; and US 6,489,408.Measure the concentration of ICA in the gas phase using gas chromatography by calibrating the peak area percentage with respect to the molar percentage (mol %) using a standard gas mixture of known concentrations of components in the ad rem gas phase. The ICA concentration can be from 1 to 10 mol %, or alternatively, from 3 to 8 mol %. Oxygen (O2) concentration relative to ethylene ([O2 / C2], parts by volume of O2 per million parts by volume of ethylene (ppmv)) in the GPP reactor. In some embodiments, the [O2 / C2] is from 0.0000 to 0.20 ppmv, alternatively from 0.0001 to 0.200 ppmv, alternatively from 0.0000 to 0.183 ppmv, alternatively from 0.0000 to 0.163 ppmv. The polymerization method uses a gas-phase polymerization (GPP) reactor, such as a stirred-bed gas-phase polymerization reactor (SB iviA / a / xuxu / u 1 χί ii reactor GPP) or a fluidized bed gas-phase polymerization reactor (FB-GPP reactor), for preparing the bimodal ethylene-co-l-hexene copolymer. Such reactors and methods are generally known in the art. For example, the FB-GPP reactor / method may be as described in US 3,709,853; US 4,003,712; US 4,011,382; US 4,302,566; US 4,543,399; US 4,882,400; US 5,352,749; US 5,541,270; EP-A-0 802 202; and Belgian patent no. 839,380. These SB-GPP and FB-GPP polymerization processes and reactors either mechanically agitate or fluidize by continuous flow of gaseous monomer and dilute the polymerization medium within the reactor, respectively. Other useful reagents / processes contemplated include serial or multi-stage polymerization processes, as described in US 5,627,242; US 5,665,818; US 5,677,375; EP-A-0 794 200; EP-B1-0 649 992; EPA-0 802 202; and EP-B-634421. The polymerization conditions may also include one or more additives such as a chain transfer agent or a promoter. Chain transfer agents are well known and may be alkylmetals such as diethylzinc. Promoters are known as in US 4,988,783 and may include chloroform, CFCl3, trichloroethane, and difluorotetrachloroethane. Before reactor startup, a removal agent may be used to react with moisture, and during reactor transitions, a removal agent may be used to react with excess activator. Removal agents may be trialkylaluminum. Gas-phase polymerizations may operate without removal agents (not deliberately added). The polymerization conditions for the gas-phase reactor / polymerization method may also include a quantity (e.g., 0.5 to 200 ppm (depending on all feeds to the reactor) of a static control agent and / or a continuity additive such as aluminum stearate or polyethyleneimine. Static control agents may be added to the FB-GPP reactor to inhibit the formation or accumulation of static charge within it. The start-up or restart of a GPP reactor can be illustrated using a fluidized bed GPP reactor. The start-up of a restarted FB-GPP reactor (cold start) or the restart of a transitioned FB-GPP reactor (hot start) includes a period of time prior to reaching the steady-state polymerization conditions of step (a). Start-up or restart may involve the use of a pre-charged or charged polymer seedbed, respectively, in the fluidized bed reactor. The polymer seedbed may consist of polyethylene powder, such as a polyethylene homopolymer or a pre-made batch of the bimodal ethylene-co-l-hexene copolymer. The start-up or restart of the FB-GPP reactor may also include gas atmosphere transitions comprising purging air or other unwanted gases from the reactor with a dry (anhydrous) inert purge gas, followed by purging the dry inert purge gas from the FB-GPP reactor with dry ethylene gas. The dry inert purge gas may consist essentially of molecular nitrogen (N2), argon, helium, or a mixture of any two or more of these. When not in operation, prior to start-up (cold start), the FB-GPP reactor contains an air atmosphere. The dry inert purge gas may be used to purge the air from a restarted FB-GPP reactor during the initial stages of start-up to provide an FB-GPP reactor with an atmosphere consisting of the dry inert purge gas.Before restarting (for example, after a seedling change), a transitioning FB-GPP reactor may contain an atmosphere of unwanted ICA or other unwanted gas or vapor. Dry inert purge gas can be used to purge the unwanted vapor or gas from the transitioning FB-GPP reactor during the initial restart stages, providing the reactor with an atmosphere consisting of dry inert purge gas. Any dry inert purge gas can then be purged from the FB-GPP reactor with dry ethylene gas. The dry ethylene gas may also contain molecular hydrogen gas, so the dry ethylene gas is fed to the fluidized bed reactor as a mixture of these. Alternatively, the dry molecular hydrogen gas can be introduced separately and after the fluidized bed reactor atmosphere has been converted to ethylene.Gas atmosphere transitions can be performed before, during, or after heating the FBGPP reactor to the reaction temperature of the polymerization conditions. The startup or restart of the FB-GPP reactor also includes introducing reactant and reagent feeds into it. Reactants include ethylene and alpha-olefins (e.g., 1-hexene). Reagents fed to the fluidized bed reactor include molecular hydrogen gas, induced condensation agent (ICA), bimodal catalyst system (e.g., PRODIGY™ BMC300 catalyst), and trimming catalyst. In one embodiment, the method uses a pilot-scale fluidized bed gas-phase polymerization reactor (Pilot Reactor) comprising a reactor vessel containing a fluidized bed of a bimodal ethylene-l-hexene copolymer powder, and a distributor plate disposed on a lower header, defining a lower gas inlet, and having an expanded section, or cyclone system, at the top of the reactor vessel to reduce the amount of resin fines that can escape from the fluidized bed. The expanded section defines a gas outlet. The pilot reactor further comprises a blower compressor of sufficient power to continuously cycle or loop the gas from the gas outlet in the expanded section at the top of the reactor vessel downwards to the lower gas inlet of the pilot reactor, and through the distributor plate and fluidized bed. The pilot reactor further comprises a cooling system to remove the heat of polymerization and maintain the fluidized bed at a target temperature. The compositions of gases such as ethylene, alpha-olefin (e.g., 1-hexene), hydrogen, and oxygen fed to the pilot reactor are controlled by an online gas chromatograph in the loop cycle to maintain specific concentrations that define and allow control of the polymer properties.In some configurations, the gases are cooled, causing their temperature to drop below their dew point, at which point the pilot reactor operates in condensation mode (CMO) or induced condensation mode (ICMO). In CMO, the liquids are present downstream from the cooler and in the lower header below the distributor plate. The bimodal catalyst system (e.g., PRODIGY™ BMC-300) can be fed as a slurry or dry powder into the pilot reactor from high-pressure devices, where the slurry is fed via a syringe pump and the dry powder via a metering disc. The bimodal catalyst system typically enters the fluidized bed in the lower third of its bed height.The pilot reactor further comprises a means of weighing the fluidized bed and isolation ports (Product Discharge System) to discharge the bimodal ethylene-co-l-hexene copolymer powder from the reactor vessel in response to an increase in the weight of the fluidized bed as the polymerization reaction progresses. In some forms, the FB-GPP reactor is a commercial-scale reactor, such as a UNIPOL™ reactor or UNIPOL™ II reactor, which are available through Univation Technologies, LLC, a subsidiary of The Dow Chemical Company, Midland, Michigan, USA. Catalysts, support materials, activators The bimodal catalyst system used in the synthesis method may essentially consist of a metallocene catalyst and a non-metallocene molecular catalyst, differing in functional ligand and / or catalytic metal M. The bimodal catalyst system may also essentially consist of a solid support material and / or at least one activator and / or at least one activator species, which is a byproduct of the reaction of the metallocene catalyst or non-metallocene molecular catalyst with the first activator. The metallocene catalyst of the bimodal catalyst system may be bis(butylcyclopentadienyl)zirconium dihalide, and the non-metallocene molecular catalyst of the bimodal catalyst system may be bis(2-(pentamethylphenylamido)ethyl)amine zirconium dibenzyl. The bimodal catalyst system may be PRODIGY BMC-300, available from Univation Technologies LLC, Houston, Texas, USA. Unconstrained by theory, it is believed that bis(2(pentamethylphenylamido)ethyl)-amine zirconium dibenzyl is effective for preparing the HMW component of the bimodal ethylene-co-l-hexene copolymer, and that each of bis(butylcyclopentadienyl) zirconium dihalide and bis(butylcyclopentadienyl) zirconium dialkyl is independently effective for preparing the LMW component of the bimodal ethylene-co-l-hexene copolymer. The molar ratio of the two catalysts in the bimodal catalyst system can be based on the molar ratio of their respective catalytic metal atom contents (M, e.g., Zr), which can be calculated from the weights of the ingredients or measured analytically. In an alternative embodiment of the method for preparing the bimodal ethylene-co-l-hexene copolymer, either or both of the bis(butylcyclopentadienyl)zirconium dihalide (i.e., (butylcyclopentadienyl)2MX2 where each X is a halide) and the bis(butylcyclopentadienyl)zirconium dialkyl (i.e., (butylcyclopentadienyl)2MX2 where each X is an alkyl) can be independently replaced with any one of the following metallocene catalysts: (pentamethylcyclopentadienyl)(propylcyclopentadienyl)MX2; (tetramethylcyclopentadienyl)(propylcyclopentadienyl)MX2; (tetramethylcyclopentadienyl)(butylcyclopentadienyl)MX2; (CH3)2Si(indenyl)MX2bridged; (CH3)2Si(4,5,6,7-tetrahydroindenyl)MX2bridged; (propylcyclopentadienyl)2MX2; (1-methyl3-butylcyclopentadienyl)2MX2; wherein each M is independently zirconium (Zr) or hafnium (Hf); and wherein each X is independently selected from F, Cl, Br, I, -CH3, CH2CH3, benzyl, -CH2Si(CH3)3, an alkyl (C1-C5) and an alkenyl (C2-Cs). The catalysts in the bimodal catalyst system can be spray-dried onto a solid support material before contact with an activator. The solid support material can be uncalcined or calcined before contact with the catalysts. The solid support material can be a hydrophobic fumed silica (e.g., fumed silica treated with dimethyldichlorosilane). The bimodal catalyst system (unsupported or supported) can be in the form of a free-flowing powdered solid. Support Material. The support material may be an inorganic oxide material. The terms support and support material are the same as used herein and refer to a porous inorganic or organic substance. In some embodiments, desirable support materials may be inorganic oxides, including oxides of Groups 2, 3, 4, 5, 13, or 14, or alternatively, atoms of Groups 13 or 14. Examples of inorganic oxide-type support materials are silica, alumina, titania, zirconia, thorium, and mixtures of any two or more of these inorganic oxides. Examples of such mixtures are silica-chromium, silica-alumina, and silica-titania. The inorganic oxide support material is porous and has a variable surface area, pore volume, and average particle size. In some embodiments, the surface area is 50 to 1000 square meters per gram (m² / g) and the average particle size is 20 to 300 micrometers (µm). Alternatively, the pore volume is 0.5 to 6.0 cubic centimeters per gram (cm³ / g) and the surface area is 200 to 600 m² / g. Alternatively, the pore volume is 1.1 to 1.8 cm³ / g and the surface area is 245 to 375 m² / g. Alternatively, the pore volume is 2.4 to 3.7 cm³ / g and the surface area is 410 to 620 m² / g. Alternatively, the pore volume is 0.9 to 1.4 cm3 / g and the surface area is 390 to 590 m2 / g. Each of the above properties is measured using conventional techniques known in the art. The support material may comprise silica, alternatively, amorphous silica (not quartz), alternatively, a high surface area amorphous silica (e.g., of 500 to 1000 m² / g). Silicas are commercially available from various sources, including the Davison Chemical Division of W.R. Grace and Company (e.g., Davison products 952 and Davison 955) and PQ Corporation (e.g., product ES70). Silica may be in the form of spherical particles, which are obtained by a spray-drying process. Alternatively, product MS3050 is a silica from PQ Corporation that is not spray-dried. As obtained, neither of these silicas is calcined (i.e., not dehydrated). Silica that is calcined prior to purchase can also be used as a support material. Before contact with a catalyst, the support material may be pretreated by heating it in air to obtain a calcined support material. The pretreatment comprises heating the support material to a maximum temperature of 350° to 850°C, or alternatively, 400° to 800°C, or alternatively, 400° to 700°C, or alternatively, 500° to 650°C, for a period of 2 to 24 hours, or alternatively, 4 to 16 hours, or alternatively, 8 to 12 hours, or alternatively, 1 to 4 hours, thereby producing a calcined support material. In some respects, the support material is a calcined support material. The trimming catalyst can be any one of the aforementioned metallocene catalysts. For convenience, the cutting catalyst is fed to the reactor in solution in a hydrocarbon solvent (e.g., mineral oil or heptane). The hydrocarbon solvent may be an alkane, or a mixture of alkanes, wherein each alkane has independently from 5 to 20 carbon atoms, alternatively from 5 to 12 carbon atoms, or alternatively from 5 to 10 carbon atoms. Each alkane may be either acyclic or cyclic. Each acyclic alkane may be either linear or branched. The acyclic alkane may be pentane, 1-methylbutane (isopentane), hexane, 1-methylpentane (isohexane), heptane, 1-methylhexane (isoheptane), octane, nonane, decane, or a mixture of two or more of these. The cyclic alkane can be cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, methylcyclopentane, methylcyclohexane, dimethylcyclopentane, or a mixture of any two or more of these. For hydrocarbon solvent solubility, typically each of the X groups of the cutting catalyst is independently a hydrocarbyl (e.g., benzyl, a (C1-C5) alkyl, or a (C2-C5) alkenyl; e.g., methyl or ethyl) or -CH2Si(CH3)3. The X groups of the cutting catalyst may be different from the X groups of the metallocene catalyst of the bimodal catalyst system. However, upon contact activation of the cutting catalyst with an activator, the active catalyst species resulting from activation of the cutting catalyst is essentially the same as the active catalyst species resulting from activation of the metallocene catalyst of the bimodal catalyst system. For example, the metallocene catalyst of the bimodal catalyst system can be bis(n-butylcyclopentadienyl) zirconium dichloride (each X is Cl), and the cutting catalyst can be bis(n-butylcyclopentadienyl) zirconium dialkyl (e.g., dimethyl where X is CH3).After activation by treatment with a suitable activator or cocatalyst, both bis(n-butylcyclopentadienyl) zirconium dichloride and bis(n-butylcyclopentadienyl) zirconium dimethyl effectively produce the same activated catalyst species. Activator. Each catalyst in the bimodal catalyst system is activated by contact with the first activator. The clipping catalyst is activated by contact with the second activator. Additional activators may be used. Any activator may be the same as or different from any other and may independently be a Lewis acid, a non-coordinating ionic activator, an ionizing activator, a Lewis base, an alkylaluminum, or an alkylaluminoxane (alkylalumoxane). The alkylaluminum may be a trialkylaluminum, an alkylaluminum halide, or an alkylaluminum alkoxide (diethylaluminum ethoxide). The trialkylaluminum may be trimethylaluminum, triethylaluminum (TEA1), tripropylaluminum, or tris(2-methylpropyl)aluminum. The alkylaluminum halide may be diethylaluminum chloride. The alkylaluminum alkoxide may be diethylaluminum ethoxide.Alkylaluminoxane can be a methylaluminoxane (MAO), ethylaluminoxane, 2-methylpropylaluminoxane, or a modified methylaluminoxane (MMAO). Each alkyl group of the alkylaluminum or alkylaluminoxane can be independently a C1-C7 alkyl, alternatively a C1-C4 alkyl, or alternatively a C1-C4 alkyl. The molar ratio of the activator metal (Al) to the metal of a particular catalyst compound (catalytic metal, for example, Zr) can be from 1000:1 to 0.5:1, alternatively, 300:1 to 1:1, or alternatively, 150:1 to 1:1. Suitable activators are commercially available. Once the first activator and the (bis(2(pentamethylphenylamido)ethyl)-amine zirconium dibenzyl and bis(butylcyclopentadienyl) zirconium dihalide) of the bimodal catalyst system are brought into contact, the catalysts of the bimodal catalyst system are activated, and a first activator species can be synthesized in situ. Once the second activator and the trimming catalyst (a bis(butylcyclopentadienyl) zirconium dialkyl) are brought into contact, the trimming catalyst is activated, and a second activator species can be synthesized in situ. The activator species may have a different structure or composition than the activator from which it is derived and may be a byproduct of catalyst activation or a derivative of the byproduct. The corresponding activator species may be a Lewis acid derivative, a non-coordinating ionic activator, an ionizing activator, a Lewis base, an alkylaluminum, or an alkylaluminoxane, respectively.An example of the byproduct derivative is a type of methylaluminoxane that is formed by devolatilization during spray drying of a bimodal catalyst system made with methylaluminoxane. Each contact stage between the activator and the catalyst can be performed independently (a) in a separate vessel outside the GPP reactor (e.g., outside the FB-GPP reactor), (b) in a feed line to the GPP reactor, and / or (c) within the GPP reactor (in situ). In option (a), the bimodal catalyst system, once its catalysts are activated, can be fed to the GPP reactor as a dry powder, or alternatively as a suspension in a nonpolar aprotic (hydrocarbon) solvent. In option (c), the bimodal catalyst system can be fed to the reactor before activation via a first feed line, the first activator via a second feed line, the trimming catalyst via a third feed line, and the second activator via a fourth feed line.Any two of the first and fourth feed lines may be the same or different. The activator(s) may be fed to the reactor in wet mode as a solution in an inert liquid such as mineral oil or toluene, in suspension mode as a slurry, or in dry mode as a powder. Each contact stage may be performed in separate vessels, feed lines, or reactors simultaneously or at different times, or in the same vessel, feed line, or reactor at different times, to separately provide the bimodal catalyst system and the trimming catalyst. Alternatively, the contact stages may be performed in the same vessel, feed line, or reactor simultaneously to provide an in-situ mixture of the bimodal catalyst system and the trimming catalyst. Bimodal ethylene-co-l-hexene copolymexo Ethylene. A polymerizable monomer with the formula H2C=CH2. 1-hexene. A polymerizable monomer of formula H2C=C (H) CH2CH2CH2CH3 . Bimodal copolymer of ethylene-co-l-hexene. A macromolecule, or collection of macromolecules, composed of repeating units wherein 50.0 to <100 mol percent (mol %), alternatively 70.0 to 99.99 mol %, alternatively 95.0 to 99.9 mol % of such repeating units are derived from ethylene monomer, and >0 to 50.0 mol %, alternatively 0.01 to 30.0 mol %, alternatively 0.1 to 5.0 mol % of the remaining repeating units are comonomeric units derived from 1-hexene; or a collection of such macromolecules. The macromolecule collection is characterized by two distinct peaks (no shoulders) on a plot of dW / dLog(MW) on the y-axis versus Log(MW) on the x-axis to provide a Gel Permeation Chromatography (GPC) chromatogram, wherein Log(MW) and dW / dLog(MW) are as defined below and measured by the Gel Permeation Chromatography (GPC) Test Method described herein. The bimodal ethylene-co-l-hexene copolymer is a high molecular weight high-density polyethylene (HMW HDPE). The bimodal ethylene-co-l-hexene copolymer may be further characterized by any one of the following limitations: a weighted average molecular weight (Mw) of 200,000.0 to 400,000.0 grams per mole (g / mol), alternatively from 250,000.0 to 320,000.0 g / mol; a number-average molecular weight (Mn) of 6,000.0 to 11,000.0 g / mol, alternatively from 7,000.0 to 9,000.0 g / mol; a z-average molecular weight (Mz) of 1,200,000.0 to 2,500,000.0 g / mol; a combination of any two of these; and a combination of all three of these. all measured according to the Gel Permeation Chromatography (GPC) Test Method. The cast elasticity of bimodal ethylene-co-l-hexene copolymer can be considered the behavior of a copolymer cast during a forming process such as extrusion or film forming. It is one of the determinants of viscoelastic cast behavior, where viscosity decreases as shear rate increases. Unsatisfactory cast elasticity can cause undesirable die swelling during extrusion or problems with bubble stability during film blowing.A measure of, or proxy of, the casting elasticity used herein is a ratio between the value of the casting storage modulus (G') and the casting loss modulus (G) that is measured using DMA (Dynamic Mechanical Analysis) on polymer melts at 190 °C by performing a small strain (10%) oscillatory shear stress at a variable frequency of 100 radians per second (rad / s) to approximately 0.1 rad / s using an ARES-G2 Advanced Rheometric Expansion System, from TA Instruments, with parallel plate geometry to obtain the G' / G ratio value at a dynamic frequency equal to 0.1 rad / s. The bimodal ethylene-co-l-hexene copolymer, the film, and the methods for manufacturing them are free of Ti and Cr metals. The polymerization conditions in the synthesis method are effective for producing the bimodal ethylene-l-hexene copolymer characterized by the melt space described above and, optionally, the resin properties and / or film properties. Movie The film. The film may be smooth or embossed. The film may be adapted for specific uses by adjusting the film thickness, combining it with other films or additives, or not. The film may be a single-layer film. The film may have a thickness of 0.0051 to 0.051 mm (0.200 mils to 2 mils), alternatively from 0.0077 mm to 0.051 mm (0.300 mils to 2 mils), alternatively from 0.0077 mm to 0.0254 mm (0.300 mils to 1.00 mils), alternatively from 0.0077 mm to 0.0203 mm (0.300 mils to 0.80 mils), alternatively from 0.0077 mm to 0.0152 mm (0.300 mils to 0.6 mils). The film can be manufactured using any extrusion or coextrusion method, including blown, stretched, and molded film methods. Blown film can be manufactured on a blown film line machine configured to manufacture polyethylene films. The machine can be configured with a feed hopper in fluid communication with an extruder in heating communication with a heating device capable of heating polyethylene in the extruder to a temperature of up to 500 °C (e.g., 430 °C), and wherein the extruder is IVIA / a / XUXU / Ul XI 11 in fluid communication with a die having an internal diameter of 12 centimeters (4.72 inches) and a fixed die clearance (e.g., a clearance of 1.2 millimeters (47 mils)), a blow ratio of 4.0:1, and a neck height (NH) of 96 centimeters (38 inches) from the die. Step (a) can be carried out in the feed hopper. The film can be misoriented, uniaxially oriented, or biaxially oriented. Uniaxial film can be oriented in the extrusion direction (machine direction or MD), or alternatively in the direction perpendicular to the extrusion direction (cross direction or TD). Biaxially oriented film can be oriented in either MD or TD by stretching or pulling MD, either simultaneously with or followed by stretching or pulling TD. The film may have one or more enhanced properties, such as improved (increased) bubble stability, improved (increased) MD and / or TD Elmendorf tear performance, improved (increased) MD and / or TD tensile strength, improved (increased) dart impact performance, or a combination of two or more of these. The film can constitute a layer of a film or multi-layer laminate. The blown film may optionally contain zero, one, or more film additives. A film additive is a compound or material other than a polyolefin polymer that imparts one or more properties and / or enhances one or more properties of the blown film. Examples of film additives include antimicrobial agents, antioxidants, catalyst neutralizers (of single-site catalysts), colorants, and light stabilizers. The film additive(s), when present, may be premixed with the bimodal ethylene-co-l-hexene copolymer before the melting stage in the blown film manufacturing method. Alternatively, the film additive(s) may be added to the melt of the bimodal ethylene-co-l-hexene copolymer during or after the melting stage and before the extrusion stage in the blown film manufacturing method.When two or more film additives are used, one or more film additives may be premixed with the bimodal ethylene-co-l-hexene copolymer before the melting stage in the blown film manufacturing method, and one or more film additives may be added to the melt of the bimodal ethylene-co-l-hexene copolymer during or after the melting stage and before the extrusion stage in the blown film manufacturing method. In some respects, the blown film essentially consists of the bimodal ethylene-co-l-hexene copolymer, at least one antioxidant, and at least one catalyst neutralizer. The film is useful for manufacturing containers and wrappers that have increased puncture resistance. Examples of such containers include bags like ice packs and grocery bags. Examples of such wrappers include stretch films, meat wraps, and food wrappers. The copolymer of the invention is also useful in a variety of non-film applications, including vehicle parts. Alternatively, it precedes a different modality. ASTM means the standards organization, ASTM International, West Conshohocken, Pennsylvania, USA. Any comparative examples are used for illustrative purposes and are not to be considered prior art. Free from or lacking means a complete absence; alternatively, it means not detectable. IUPAC is the International Union of Pure and Applied Chemistry (IUPAC Secretariat, Research Triangle Park, North Carolina, USA). May refer to a permitted option, not a requirement. Operational means functionally capable or effective. Optionally means absent (or excluded); alternatively, present (or included). Properties can be measured using standard test methods and conditions.The intervals include the boundary values, subintervals, and whole and / or fractional values ​​included within them, unless a whole number interval does not include fractional values. Temperature. IVIA / a / ZUZU / Ul ZI 11 ambient: 23 °C ± 1 °C. EXAMPLES Bimodality test method: Determine the presence or absence of resolved bimodality by plotting dWf / dLogM (mass detector response) on the y-axis against LogM on the x-axis to obtain a GPC chromatogram curve containing local maximum values ​​of log(MW) for the peaks of the LMW and HMW polyethylene components, and observe the presence or absence of a local minimum between the peaks of the LMW and HMW polyethylene components. dWf is the change in weight fraction, dLogM is also known as dLog(MW) and is the change in the logarithm of molecular weight, and LogM is also known as Log(MW) and is the logarithm of molecular weight. Dart Impact Test Method: Measured in accordance with ASTM D1709-16a, Standard Test Methods for Impact Strength of Plastic Film by the Free-Fall Dart Test Method, Method A. Method A employs a dart with a hemispherical head 38.10 ± 0.13 mm (1.500 ± 0.005 in.) in diameter dropped from a height of 0.66 ± 0.01 m (26.0 ± 0.4 in.). This test method can be used for films whose impact strengths require masses of approximately 50 g to approximately 6 kg to fracture. Results are expressed in grams (g). Deconvolution Test Method: Segment the chromatogram obtained using the Bimodality Test Method into nine (9) Schulz-Flory molecular weight distributions. Such a deconvolution method is described in US 6,534,604. Assign the four lowest MW distributions to the LMW polyethylene component and the five highest MW distributions to the HMW polyethylene component. Determine the respective weight percents (wt%) of each of the LMW and HMW polyethylene components in the bimodal ethylene-co-l-hexene copolymer using summed values ​​of the weight fractions (Wf) of the LMW and HMW polyethylene components and the respective number-average (Mn) and weight-average (Mw) molecular weights by known mathematical treatment of aggregated Schulz-Flory MW distributions. Density is measured in accordance with ASTM D792-13, Standard Test Methods for Density and Specific Gravity (Relative Density) of Plastics by Displacement, Method B (for evaluating solid plastics in liquids other than water, e.g., in liquid 2-propanol). Report results in units of grams per cubic centimeter (g / cm³). Elmendorf tear test method: measured in accordance with ASTM D1922-09, Standard Test Methods for Propagation Tear Resistance of Plastic Films and Thin Sheets by the Pendulum Method, Type B (Constant Radius). (Technically equivalent to ISO 6383-2.) Report results as normalized tear in transverse direction (CD) or machine direction (MD) in gram-force (gf) · Film puncture test method: ASTM D5748-95(2012), Standard Test Method for Bulge Puncture Resistance of Stretch Film. Determine the puncture resistance of a film as the resistance to penetration of the film by a probe incising the film at a standard speed of 250 millimeters per minute (mm / min). The probe is coated with polytetrafluoroethylene and has an outside diameter of 1.905 cm (0.75 in). The film is clamped during the test. The probe eventually penetrates or breaks the clamped film. The maximum force at break, i.e., the maximum force, energy (work) required to break or penetrate the clamped film, and the distance the probe penetrated at break, are recorded using mechanical testing software.The probe imparts a biaxial tension to the clamped film that is representative of the type of tension films encounter in many end-use applications. This tension is a measure of a film's energy absorption capacity to resist puncture under these conditions. Gauge Variation Test Method: Determined in accordance with ASTM D8136-17, Standard Test Method for Determining Plastic Film Thickness and Thickness Variability Using a Non-Contact Capacitance Thickness Gauge. Prior to testing, samples are conditioned at 23° ± 2°C and 50% ± 10% relative humidity (RH) for at least 40 hours (per ASTM D618), and then tested under the same conditions. Gauge variation is calculated using the following equation: (Standard Deviation of Thickness / Average Thickness) x 100%. Gel permeation chromatography (GPC) test method: Weighted average molecular weight test method: Determine Mw, number average molecular weight (Mn), and Mw / Mn by chromatograms obtained on a High Temperature Gel Permeation Chromatography Instrument (HTGPC, Polymer Laboratories). The HTGPC is equipped with transfer lines, a differential refractive index (DRI) detector, and three Polymer Laboratories PLgel 10pm Mixed-B columns, all contained in an oven maintained at 160°C. The method uses a BHT-treated TCB composite solvent at a nominal flow rate of 1.0 milliliter per minute (ml / min) and a nominal injection volume of 300 microliters (pL). Prepare the solvent by dissolving 6 grams of butylated hydroxytoluene (BHT, antioxidant) in 4 liters (L) of reagent-grade 1,2,4-trichlorobenzene (TCB) and filtering the resulting solution through a 0.1 micrometer (pm) Teflon filter to obtain the solvent.Degas the solvent with an in-line degasser before it enters the HTGPC instrument. Calibrate the columns with a series of monodisperse polystyrene (PS) standards. Separately, prepare known concentrations of test polymer dissolved in solvent by heating known quantities of the polymer in known volumes of solvent to 160 °C with continuous stirring for 2 hours to obtain the solutions. (Measure all quantities gravimetrically.) Target solution concentrations, c, of the test polymer range from 0.5 to 2.0 milligrams of polymer per milliliter of solution (mg / ml), with lower concentrations, c, for higher molecular weight polymers. Before analyzing each sample, purge the DRI detector. Then, increase the flow rate in the instrument to 1.0 ml / min and allow the DRI detector to stabilize for 8 hours before injecting the first sample.Calculate Mwy using universal calibration relationships with column calibrations. Calculate MW in each elution volume with logM... =A—— logAf™ íj5- + i ar+1. A. The following equation: , where the subscript X represents the test sample, the subscript PS represents the PS, ps, psy, and ax standards obtained from published literature. For polyethylenes, ax / Kx = 0.695 / 0.000579. For polypropylenes, ax / Kx = 0.705 / 0.0002288. At each point of the resulting chromatogram, calculate the concentration, c, from a DRI signal subtracted from the initial value, Idri, using the following equation: c = KdriIdrt / (dn / dc), where Kdri is a constant determined by DRI calibration, / indicates division, and dn / dc is the refractive index increase of the polymer. For polyethylene, dn / dc = 0.109. Calculate the polymer mass recovery from the ratio of the integrated area of ​​the concentration chromatogram to the elution volume and the injection mass, which is equal to the predetermined concentration multiplied by the injection circuit volume. Report all molecular weights in grams per mole (g / mol) unless otherwise stated.Further details regarding the methods for determining Mw, Mn, and MWD are described in US 2006 / 0173123, pages 24-25, paragraphs

[0334] to

[0341] . A plot of dW / dLog(MW) on the y-axis compared to Log(MW) on the x-axis is used to obtain a GPC chromatogram, where Log(MW) and dW / dLog(MW) are as defined above. High Loading Melt Flow Index (HLMI) Test Method I21: Use ASTM D1238-13, Standard Test Method for Melt Flow Indices of Thermoplastics by Extrusion Platometer, using conditions of 190 °C / 21.6 kilograms (kg). Report results in units of grams eluted over 10 minutes (g / 10 min). iviA / a / zuzu / u 1 z 1 ii Melt Flow Index (I2) Test Method: For ethylene-based (co)polymer, it is measured in accordance with ASTM D1238-13, using conditions of 190 °C / 2.16 kilograms (kg), formerly known as Condition E. Melt Index I5 (Is) Test Method: Use ASTM D1238-13, using conditions of 190 °C / 5.0 kg. Report results in units of grams eluted over 10 minutes (g / 10 min). MFR5 Flow Ratio Test Method: (I21 / I5) : calculated by dividing the HLMI Test Method I21 value by the Flow Index Test Method I5 value. Casting elasticity test method: On polymers molten at 190 °C, perform a small strain (10%) oscillatory shear at a variable frequency of 100 radians per second (rad / s) to approximately 0.1 rad / s using a TA Instruments ARES-G2 Advanced Rheometric Expansion System with parallel plate geometry to obtain the G' / G ratio value at a dynamic frequency equal to 0.1 rad / s. Antioxidants: 1. Pentaerythritol tetrakis(3-(3,5-di(l',l'-dimethylethyl)-4-hydroxyphenyl)propionate); obtained as IRGANOX 1010 from BASF. 2. Tris(2,4-di(1',1'-dimethylethyl)phenyl)phosphite. Obtained as IRGAFOS 168 from BASF. IVIA / a / XUXU / Ul XI ii Catalyst neutralizers: 1. Calcium stearate. 2. Zinc stearate. Bimodal catalyst system: the PRODIGY™ BMC-300 catalyst system. Obtained from Univation Technologies, LLC, Houston, Texas, USA. Cutting catalyst: bis(butylcyclopentadienyl)zirconium dimethyl obtained as UT-TR-300 cutting catalyst from Univation Technologies LLC, Houston, Texas, USA. Comonomer = 1-hexene. See below for the gas molar ratio Cg / C2. Ethylene (C2): see below for the partial pressure of C2. Molecular hydrogen gas (H2): see below for the molar ratio of H2 gas / C2. Molecular oxygen gas (O2): see below for the O2 / C2 gas volume ratio. Inventive Examples 1 to 7 (IE1 to IE7): Polymerization process: Implementations began with the bimodal catalyst PRODIGY™ BMC-300 and the comonomer 1-hexene according to the Pilot Reactor and method described above to provide in different parts, as described below, different modalities of the bimodal ethylene-co-l-hexene copolymer as granular resins and having target properties of a high loading melt flow index (I21) of 8.0 to 10.0 g / 10 mins, a melt flow ratio I21 / I5 of 26.6 to 30.6, a melt flow index I5 of 0.25 to 0.35 g / 10 mins, a cast elasticity of 0.50 to 0.70, and a density of 0.948 to 0.950 g / cm3. The polymerization operating conditions are indicated below in Table 1 (IE1 to IE4) or Table 2 (IE5 to IE7). Table 1: Operating conditions from IE1 to IE4. IE1 IE2 IE3 IE4 PART No. 13 11 11 11 Reactor type S, CM, PP, FB GPP* S, CM, PP, FB GPP S, CM, PP, FB GPP S, CM, PP, FB GPP Reactor purge gas N2 anhydrous N2 anhydrous N2 anhydrous N2 anhydrous Bed temperature (°C) 90.0 90.0 90.0 90.0 Rx pressure (kPa)Λ 2400 2400 2400 2400 Partial pressure of C2 (kPa) 1520 1520 1520 1520 H2 / C2 molar ratio 0.0041 0.0042 0.0042 0.0042 Molar ratio C6 / C2 0.0054 0.0054 0.0054 0.0054 Induced condensation. Agent (% mol) 1-methylbutane (11.4) 1-methylbutane (11.4) 1-methylbutane (11.4) 1-methylbutane (11.4) Surface gas velocity (m / s) 0.646 0.616 0.616 0.616 PRODIGY™ BMC-300 Bimodal Catalyst System PRODIGY™ BMC-300 PRODIGY™ BMC-300 PRODIGY™ BMC-300 UT-TR-300 UT-TR-300 UT-TR-300 Zr catalyst conc. (% by weight) 0.49 0.49 0.49 0.49 Al catalyst conc. (% by weight) 18.29 18.29 18.29 18.29 Initial seedbed = granular HDPE resin Pre-charged Pre-charged Pre-charged Pre-charged Fluidized bed weight (kg) 45.8 46.3 46.3 46.3 Copolymer production rate (kg / hour) 17.5 17.9 17.9 17.9 Copolymer residence time (hour) 2.63 2.59 2.59 2.59 Apparent density of copolymer fluid (kg / m3) 275 280 280 280 O2 adaptation level (%) 0 4 7 10 Residual Zr (ppmw) 1.48 1.51 1.51 1.51 *S, CM, PP, FB, GPP: gas-phase fluidized bed polymerization, pilot plant, single-mode, continuous. PressureARx (kPa): total reactor pressure in kilopascals. Table 2: Operating conditions from IE5 to IE7. IE5 IE6 IE7 PART No. 12 12 12 Reactor Type S, CM, PP, FB GPP S, CM, PP, FB GPP S, CM, PP, FB GPP Reactor Purge Gas Anhydrous N2 Anhydrous N2 Anhydrous N2 Bed Temperature (°C) 90.0 90.0 90.0 ARx Pressure (kPa) 2400 2400 2400 C2 Partial Pressure (kPa) 1520 1520 1520 H2 / C2 Molar Ratio 0.0040 0.0040 0.0040 Ce / C2 Molar Ratio 0.0055 0.0055 0.0055 Induced Condensing Agent 1-Methylbutane (11.4) 1-Methylbutane (11.4) 1-Methylbutane (11.4) Surface gas velocity (m / s) 0.671 0.671 0.671 PRODIGY™ BMC-300 Bimodal Catalyst System PRODIGY™ BMC-300 PRODIGY™ BMC-300 Trimming Catalyst UT-TR-300 UT-TR-300 UT-TR-300 Zr Catalyst Concentration (wt. %) 0.49 0.49 0.49 Al Catalyst Concentration (wt. %) 18.29 18.29 18.29 Initial Seedbed = Granular HDPE Resin Pre-filled Pre-filled Pre-filled Fluidized bed weight (kg) 45.4 45.4 45.4 Copolymer production rate (kg / hour) 17.6 17.6 17.6 Copolymer residence time (hour) 2.57 2.57 2.57 Copolymer fluid apparent density (kg / m3) 271 271 271 O2 adaptation level (%) 4 7 10 Residual Zr (ppmw) 1.52 1.52 1.52 *S, CM, PP, FB, GPP: gas-phase polymerization of IVIA / a / ZUZU / Ul ZI 11 fluidized bed, pilot plant, single mode, continuous. PressureARx (kPa): total reactor pressure in kilopascals. As shown in Tables 1 and 2, the operating conditions used to prepare the bimodal ethylene-co-l-hexene copolymers IE1 to IE7 comprise a bed temperature of 90.0 °C; an ethylene (C2) partial pressure of 1520 kPa; an H2 / C2 molar ratio of 0.0040 to 0.0042; a Ce / C2 molar ratio of 0.0054 to 0.0055; and a surface gas velocity of 0.616 to 0.671 m / s (meters per second). In certain embodiments, the synthesis method for the bimodal ethylene-co-l-hexene copolymer employs the operating conditions mentioned above. Formulation and pelletizing procedure: each of the different granular resins from IE1 to IE7 was blended separately with 800 parts per million by weight / weight (ppm) of Antioxidant 1, 200 ppm of Antioxidant 2, 1000 ppm of Catalyst Neutralizer 1, and 500 ppm of Catalyst Neutralizer 2 were mixed in a ribbon blender and then blended into strand-cut pellets using an LCM100 twin-screw extruder according to the methods described in US 5,728,335; US 6,456,976; and US 6,989,423. The resulting pellets of each resin were tested for HLMI(I21), MFR5(I21 / I5) / cast elasticity, and density according to their respective test methods mentioned above. The results are reported below. In certain embodiments, the bimodal ethylene-co-l-hexene copolymer further comprises at least one antioxidant selected from Antioxidants 1 and 2; at least one catalyst neutralizer selected from Catalyst Neutralizers 1 and 2; or a combination of these. The results are reported below in Table 3, which also includes the oxygen (O2) adaptation level again for convenience. iviA / a / ¿u¿u / u 1 ¿i 11 Table 3: Casting properties from IE1 to IE7. Test IE1 IE2 IE3 IE4 IE5 IE6 IE7 O2 adaptation level 0 4 7 10 4 7 10 I21 (190 °C, 21.6 kg) (g / 10 min) 8.4 9.4 9.5 7.4 9.2 9.2 8.2 MFR5 (I2i / I5) 26.6 28.4 29.6 27.6 30.4 30.6 29. 2 Casting elasticity (G' / G at 0.1 rad / s) 0.53 0.58 0.65 0.68 0.57 0.62 0.6 6 I2 (190 °C, 2.16 kg) (g / 10 min) 0.08 0.08 0.07 0.06 0.08 0.07 0.0 6 I5 (190 °C, 5.0 kg) (g / 10 min) 0.32 0.33 0.32 0.27 0.30 0.30 0.2 8 As shown in Table 3, the melt properties of the ethylene-co-l-hexene bimodal copolymers from IE1 to IE7 comprise a high loading melt index I21 (190 °C, 21.6 kg) of 7.4 to 9.5 g / 10 min; a melt flow ratio MFR5 (I2i / I5) of 26.6 to 30.6; a melt elasticity (G' / G at 0.1 rad / s) of 0.53 to 0.68 Pa; a melt index I2 (190 °C, 2.16 kg) of 0.06 to 0.08 g / 10 min; and a melt index I5 (190 °C, 5.0 kg) of 0.27 to 0.33 g / 10 min). In certain embodiments, the bimodal ethylene-col-hexene copolymer is characterized by any one, alternatively all but one, or alternatively each of the aforementioned melting properties. The casting property data in Table 3 for the bimodal ethylene-co-l-hexene copolymer were analyzed to determine which reactor / process operating conditions influence the casting properties. The following operating conditions were found to influence the casting properties of the resulting bimodal ethylene-co-l-hexene copolymer: increasing the H2 / C2 molar ratio in the process resulted in an inventive bimodal ethylene-co-l-hexene copolymer with a beneficially improved casting property range for use in blown film processes and for producing blown films. The granular resins from IE1 to IE7 were characterized by their density; component molecular weight dispersion (Mw-hw / Mw-lmw ratio); component fraction splitting; molecular weights; and molecular mass dispersion (Mw / Mn), Dm. The results are reported below in Table 4. iviA / a / ¿u¿u / u 1 ¿i 11 Table 4: Resin properties from IE1 to IE7. Test IE1 IE2 IE3 IE4 IE5 IE6 IE7 Density (g / cm3) 0.949 0.949 0.949 0.949 0.949 0.949 0.949 HMW component division (% by weight) 58.6 59.0 58.1 59.4 57.9 57.6 58.4 LMW component division (% by weight) 41.4 41.0 41.9 40.6 42.1 42.4 41.6 Mw-hmw / Mw-LMW ratio 42.1 41.6 42.4 41.0 41.7 41.5 41.7 Mn (kg / mol) 7.61 7.68 7.47 7.74 7.82 7.61 7.92 Mw (kg / mol) 293.7 281.6 278.9 268.8 295.3 288.1 286.2 Mw / Mn (Dm) 38.6 36.7 37.3 34.8 37.8 37.8 36.2 Mz (kg / mol) 2,110 1,952 1,835 1,594 2,088 2,023 1,844 As shown in Table 4, the resin properties of the bimodal ethylene-co-l-hexene copolymers from IE1 to IE7 comprise a density of 0.949 g / cm3; a high molecular weight (HMW) component split from 57.6 to 59.4 wt%; a low molecular weight (LMW) component split from 42.4 to 40.6 wt%; a numerical average molecular weight of 7,470 to 7,920 g / mol; a weighted average molecular weight of 268,800 to 295,300 g / mol; a molecular mass dispersion Mw / Mn(Dm) of 34.8 to 38.6; and an average molecular weight z of 1,835,000 to 2,110,000 g / mol. In certain embodiments, the bimodal ethylene-co-l-hexene copolymer is characterized by any one, alternatively all but one, or alternatively each of the aforementioned resin properties. Film Formation Procedure: The granular resin pellets of the bimodal ethylene-co-1-hexene copolymer from IE1 to IE7 were melted separately at the melting temperature described herein and blown separately into films using a 50 mm (mm) Alpine single-screw barrier extruder with a length-to-diameter (L / D) ratio of 25:1, a 120 mm internal diameter die, a 1.2 mm die gap, and no internal bubble cooling (IBC). Gauge variation, dart impact, and Elmendorf tear properties were measured on films that were 0.0127 mm (mm) thick (12.7 micrometers) according to the test methods described above. See Table 5 below. Table 5: Film properties from IE1 to IE7. Test IE1 IE2 IE3 IE4 IE5 IE6 IE7 Extrusion speed (rpm) 97 97 97 97 97 97 97 Motor load 73.6 71.9 73.2 75.4 73.8 74.4 75.0 Melting temperature (°C) 206.0 205.2 205.9 207.0 206.3 204.9 205.6 Die pressure (MPa) N / a N / a N / a N / a N / a N / a N / a Gauge variation (%) 14.7 16.2 11.2 14.3 15.2 12.9 14. 5 Average Tear CD (gf) 181 143 103 61 136 85 83 Average Tear MD (gf) 18 20 26 30 21 28 32 Dart Impact (g) 315 291 294 276 312 375 360 N / A means not available. As shown in Table 5, the film properties of blown films of bimodal ethylene-co-l-hexene copolymers IE1 to IE7 comprise a gauge variation of 11.2% to 16.2%, an average transverse (CD) Elmendorf tear of 61 to 181 gf, an average machine (MD) Elmendorf tear of 18 to 32 gf, and a dart impact of 276 to 375 g. In certain embodiments, the bimodal ethylene-co-l-hexene copolymer, and blown films thereof, are independently characterized by any one, alternatively all but one, or alternatively each of the aforementioned film properties. It is hereby stated that, as of this date, the best method known to the applicant for putting the aforementioned invention into practice is the one that is clear from the present description of the invention.

Claims

CLAIMS Having described the invention as above, the following claims are claimed as property:

1. A bimodal ethylene-co-l-hexene copolymer, characterized in that it essentially consists of a higher molecular weight (HMW) component and a lower molecular weight (LMW) component and, when in the molten form at 190 °C, is characterized by a cast property space defined by a combination of high loading melt index (HLMI or I21), melt flow ratio I21 / I5 (MFR5), and cast elasticity (G' / G at 0.1 rad / s) properties, wherein the HLMI is 7.0 to 11.0 grams per 10 minutes (g / 10 min) and is measured in accordance with ASTM D1238-13 (190 °C, 21.6 kg); The MFR5 is from 22.0 to 35.0, where the I21 and I5 values ​​used to calculate the MFR5 are each in g / 10 min and are measured according to ASTM D1238-13 (190 °C, 21.6 kg, I21; and 190 °C, 5.0 kg, I5, respectively), and the casting elasticity is from 0.5 to 0.8 pascals (Pa), wherein the casting elasticity = G' / G determined at 0.1 radians per second (rad / s) according to the Casting Elasticity Test Method, and wherein the bimodal ethylene-co-1hexene copolymer has a density of 0.9410 to 0.9550 cubic centimeters (g / cm3), measured according to ASTM D792-13, Method B.

2. The bimodal ethylene-co-l-hexene copolymer according to claim 1, characterized in that the melt property space of the bimodal ethylene-co-l-hexene copolymer is further defined by any one of the limitations (i) to (iii): (i) a melt flow index I2 of 0.05 to 0.10 measured in accordance with ASTM D1238-13 (190 °C, 2.16 kg, I2); (ii) a melt flow index I5 of 0.20 to 0.40 g / 10 min, measured in accordance with ASTM D1238-13 (190 °C, 5.0 kg, I5); and (iii) a fluidity flow ratio I2i / I2 (MFR2) of 80.0 to 150.0, wherein the I22 and I2 values ​​used to calculate MFR2 are each in g / 10 min and are measured according to ASTM D1238-13 (190 °C, 21.6 kg, I2i; and 190 °C, 2.16 kg, I2, respectively).

3. The bimodal ethylene-co-l-hexene copolymer according to claim 1 or 2, characterized in that any of the resin property limitations (i) to (iv): (i) a density of 0.9450 to 0.9530 g / cm3, alternatively 0.9480 to 0.9500 g / cm3, measured in accordance with ASTM D792-13, Method B; (ii) a split component fraction characterized by a weight fraction of the HMW component of 50.0 to 63 wt.%, alternatively 55 to 60.0 wt.%, alternatively 57.0 to 59.4 wt.%; and a weight fraction of the LWM component fraction of 50.0 to 37 wt.%, alternatively 45 to 40.0 wt.%, alternatively 43.0 to 40.0 wt.%, alternatively 43.0 to 40.0 wt.%, or 40 ...6% by weight, respectively, of the combined weight of the HMW and LMW components, measured according to the Gel Permeation Chromatography (GPC) Test Method; (iii) a component molecular weight dispersion characterized by a ratio of the weighted average molecular weight of the HMW component (Mw-hmw) to the weighted average molecular weight of the LMW component (Mw-lmw) (i.e., Mw-hmw / Mw-lmw ratio) of 30.0 to 50.0, alternatively 40.0 to 45, alternatively 40.9 to 42.5, measured according to the GPC Test Method; and (iv) a molecular mass dispersion (Mw / Mn), Dm, of 30.0 to 40.0, alternatively from 34 to 39, alternatively from 34.8 to 38.6, wherein Mw and Mn are measured according to the GPC Test Method.

4. The bimodal ethylene-co-l-hexene copolymer according to any one of claims 1 to 3, characterized in that when characterized in the form of a blown film and having a thickness of 0.0127 millimeters, it is characterized by any one of the limitations (i) to (iv): (i) a dart impact of 250 to 400 grams (g), measured according to the Dart Impact Test Method; (ii) an Elmendorf tear in the transverse direction (CD) of 60.0 to 190.0 grams-force (gf), measured according to the Elmendorf Tear Test Method; (iii) an Elmendorf tear in the machine direction (MD) of 15 to 35 gf, measured according to the Elmendorf Tear Test Method; and (iv) a gauge variation of 10.5% to 17%, measured in accordance with the Gauge Variation Test Method.

5. A method for synthesizing the bimodal ethylene-co-l-hexene copolymer according to any one of claims 1 to 4, characterized in that it essentially consists of copolymerizing ethylene and 1-hexene with a combination of a bimodal catalyst system and a trimming catalyst in the presence of molecular hydrogen gas (H2) and, optionally, an induced condensation agent (ICA) in a polymerization reactor under polymerization conditions effective to provide an initial bimodal ethylene-co-l-hexene copolymer, and optionally oxygen-adapted ethylene-co-l-hexene copolymer to provide an oxygen-adapted bimodal ethylene-co-l-hexene copolymer; wherein the bimodal catalyst system is prepared by contacting a first activator with bis(2(pentamethylphenylamido)ethyl)-zincyl dibenzylamine and a bis(butylcyclopentadienyl)zirconium dihalide;wherein the cutting catalyst is prepared by contacting a second activator with bis(butylcyclopentadienyl)zirconium dialkyl; wherein the first and second activators are the same or different; and wherein the effective polymerization conditions comprise a reaction temperature of 80 degrees (°) to 110° Celsius (°C); a molar ratio of molecular hydrogen gas to ethylene (H2 / C2 molar ratio) of 0.001 to 0.020; and a molar ratio of 1-hexene (C6) to ethylene (C6 / C2 molar ratio) of 0.005 to 0.

050.

6. The method according to claim 5, characterized in that it further consists essentially of removing the bimodal ethylene-co-l-hexene copolymer from the reactor to provide a removed bimodal ethylene-co-l-hexene copolymer.

7. A manufactured article characterized in that it comprises the bimodal ethylene-co-l-hexene copolymer in accordance with any of claims 1 to 4.

8. A film characterized in that it essentially consists of the bimodal ethylene-co-l-hexene copolymer according to any of claims 1 to 4.

9. A method for making a blown film, characterized in that it comprises melting the bimodal ethylene-co-l-hexene copolymer according to any one of claims 1 to 5 to provide a melt thereof, extruding the melt through a die configured to form a bubble to make a bubble of the bimodal ethylene-co-l-hexene copolymer, and blowing the bubble with a film blowing machine, thereby making the blown film.

10. A blown film manufactured by the method according to claim 9, characterized in that IVIA / a / ZUZU / Ul ZI 11 consists essentially of the bimodal ethylene-l-hexene copolymer according to any one of claims 1 to 4.