BIMODAL LINEAR LOW-DENSITY POLYETHYLENE COPOLYMER, FILM AND METHOD FOR PRODUCING BIMODAL LINEAR LOW-DENSITY POLYETHYLENE COPOLYMER

Abstract

BIMODAL LINEAR LOW-DENSITY POLYETHYLENE COPOLYMER, FILM, AND METHOD FOR PRODUCING THE BIMODAL LINEAR LOW-DENSITY POLYETHYLENE COPOLYMER. Bimodal linear low-density polyethylene copolymers (B-LLDPE copolymers) are provided that have a combination of improved properties comprising at least one processability characteristic similar to that of an unmixed monomodal ZN-LLDPE and a dart impact property similar to or better than that of an unmixed monomodal MCN-LLDPE. For the various aspects, the B-LLDPE copolymer has a density of 0.8900 to 0.9300 g / cm3; a melt index (I2) of 0.1 g / 10 min to 5 g / 10 min; a Mz of 600,000 to 1,200,000 g / mol; and a hexane extractables content of up to 2.6% by weight, as measured in accordance with ASTM D-5227:95.The B-LLDPE copolymer can be further characterized by a first melt flow ratio (I21 / I2) of 25 to 65 and a first molecular weight ratio (Mz / Mw) of 3.5 to 5.5.

Description

1 / 50 BIMODAL LINEAR LOW-DENSITY POLYETHYLENE COPOLYMER, FILM AND METHOD FOR PRODUCING BIMODAL LINEAR LOW-DENSITY POLYETHYLENE COPOLYMER - DEVELOPMENT FIELD

[0001] The embodiments of the present disclosure are directed to polyethylene copolymers, more specifically, to bimodal linear low-density polyethylene copolymers. BACKGROUND

[0002] Linear low-density polyethylene (LLDPE) has a distinct composition from low-density polyethylene (LDPE) and possesses certain superior properties that have led to its replacement of LDPE in many commercial applications. These include films, sheets, and injection-molded articles. LLDPE films and sheets are used in packaging and non-packaging applications. Examples include agricultural films, food packaging, garment bags, grocery bags, heavy-duty bags, industrial sheets, shrink wrap and pallet films and bags. Injection-molded articles made of LLDPE include buckets, freezer containers, lids, and toys.

[0003] Polyethylenes are mentioned in documents CA 2427685 A1; US 7,576,166 B2; US 7,897,710 B2; US 8,008,403 B2; US 8,846,188 B2; US 8,957,158 B2; US 9,090,762 B2; US 9,284,389 B2; US 9,309,338 B2; WO 2006 / 045738 A1 and WO 2015 / 069637 A2.

[0004] US patent 7,576,166 B2 by J. Aarlla et al. refers to a process for the production of linear low-density polyethylene compositions using Ziegler-Natta catalysts, and includes a process for the production of bimodal linear low-density polyethylene polymer compositions, useful for the production of films.

[0005] US documents 8,846,188 B2 and US 8,957,158 B2, both by F. Fantinel et al., refer to impact-resistant LLDPE compositions and films made from them. The polyethylene is produced in a phase reactor. Petition 870240103360, dated 04 / 12 / 2024, page 12 / 122 2 / 50 gaseous.

[0006] AM Sukhadia's WO 2015 / 069637 A2 document refers to low-density polyolefin resins with low molecular weight and high molecular weight components, and films made from them. Ethylene-based polymers produced using double metallocene catalyst systems.

[0007] An improvement for each LLDPE provided above and generally in the art is to produce an LLDPE that is not only easy to process, as measured in terms of extruder cylinder pressure and rheology tests such as shear thinning (among others), but also has improved mechanical strength and toughness, as shown by improvements in melt strength, low tangent Delta values ​​and a wide average molecular weight z relative to the weight-average molecular weight (Mz / Mw), among other properties. SUMMARY

[0008] The present disclosure provides bimodal linear low-density polyethylene copolymers (B-LLDPE copolymers) that address many of the problems associated with the manufacture, use, and performance of previous metallocene catalyst-made LLDPEs (previous MCN-LLDPE). The B-LLDPE copolymer of the present disclosure further addresses the need in the manufacture, use, and performance of resin blends that include LLDPEs made with the Ziegler-Natta catalyst and the previous MCN-LLDPE. For example, regarding the processability of previous Ziegler-Natta catalyst-made LLDPEs (previous ZN-LLDPE), previous MCN-LLDPEs have inferior processability. For example, during the extrusion of previous MCN-LLDPE, the extruder cylinder pressure is higher than during the extrusion of previous ZNLLDPE. Furthermore, previous MCN-LLDPEs may have insufficient sealing capacity (e.g., hot seal / hot adhesion may be too weak) compared to previous ZN-LLDPE.Other disadvantages of the processability of previous MCN-LLDPEs may include tangent Delta values ​​that are too high, and a narrow range of average molecular weight z values. Petition 870240103360, dated 04 / 12 / 2024, page 13 / 122 3 / 50 in relation to the weight-average molecular weight (Mz / Mw), molecular weight distributions (MWD), for example, Mw / Mn, measured by gel permeation chromatography (GPC), which are very narrow and shear thinning index values ​​that are very low.

[0009] The B-LLDPE copolymers of the present disclosure provide a technical solution to many of the above problems, wherein the B-LLDPE copolymer has at least one processability characteristic similar to that of an unmixed monomodal ZN-LLDPE and at least one mechanical property / rigidity similar to that of an unmixed monomodal MCN-LLDPE. The B-LLDPE copolymer is made with a bimodal catalyst system, wherein products produced from the same, methods for producing and using the same, and articles containing the same are provided herein. The B-LLDPE copolymer has a combination of improved properties comprising at least one processability characteristic similar to that of an unmixed monomodal ZN-LLDPE and a dart impact property similar to that of an unmixed monomodal MCN-LLDPE.

[0010] In some respects, the B-LLDPE copolymer is characterized by a density of 0.8900 to 0.9300 grams per cubic centimeter (g / cm3), measured according to ASTM D792-13, method B; a melt index (I2) of 0.1 grams per 10 minutes (g / 10 min) to 5 g / 10 min, measured according to the melt index test method at 190 °C and 2.16 kilograms according to ASTM D1238-13; a Mz of 600,000 to 1,200,000 grams per mole (g / mol), measured according to the gel permeation chromatography (GPC) test method; and a hexane extractables content present in a value of up to 2.6%, by weight, as measured according to ASTM D-5227:95. The B-LLDPE copolymer is further characterized by having a first melt flow ratio (I21 / I2) of 25 to 65, measured according to the flow index test method and the melt index test method at 190 °C, and 21.6 and 2.16 kilograms, respectively, according to ASTM D1238-13. In another Petition 870240103360, dated 04 / 12 / 2024, page 14 / 122 4 / 50 aspect, the B-LLDPE copolymer is characterized by having a first melt flow ratio (I21 / I2) of 30 to 50, measured according to the flow index test method and the melt index test method at 190 °C and 21.6 and 2.16 kilograms, respectively, according to ASTM D1238-13. For the various aspects, the B-LLDPE copolymer has a first molecular weight ratio (Mz / Mw) of 3.5 to 5.5, measured according to the GPC test method, where Mz is the average molecular weight and Mw is the weight-average molecular weight.

[0011] In another aspect, the B-LLDPE copolymer is further characterized in that I2 is 0.30 g / 10 min to 0.9 g / 10 min, measured according to the melt index test method at 190 °C and 2.16 kilograms according to ASTM D1238-13; and the density is 0.91 g / cm³ to 0.92 g / cm³, measured according to ASTM D792-13, method B. The aspects of the B-LLDPE copolymer are further characterized as having a tangent Delta (tan δ) of 3 to 6, measured at 190 °C and a frequency of 0.1000 radians per second (rad / s) according to the tangent Delta (tan δ) test method.This additional aspect may further include a tan δ of 5.8 to 6.2, measured at 190 °C and a frequency of 0.1000 radians per second (rad / s) according to the tangent delta test method, a density of 0.916 to 0.919 g / cm3 measured according to the ASTM D792-13 standard, the Mz / Mw is 4.9 to 5.2, measured according to the GPC test method, and a melting index (I2) of 0.8 grams per 10 minutes (g / 10 min) to 0.9 g / 10 min, measured according to the melting index test method, at 190 °C and 2.16 kilograms according to the ASTM D1238-13 standard; and a melt flow ratio (I21 / I2) of 40 to 50, measured according to the flow index test method and the melt index test method at 190 °C, and 21.6 and 2.16 kilograms, respectively, according to ASTM D1238-13.Alternatively, this additional aspect may further include a tan δ of 2.8 to 3.2, measured at 190 °C and a frequency of 0.1000 radians per second (rad / s) according to the tangent delta test method, a density of 0.916 to 0.919 g / cm3 measured according to the ASTM D792-13 standard, method, and a Mz / Mw of 3.8 to 4.4, measured accordingly. Petition 870240103360, dated 04 / 12 / 2024, p. 15 / 122 5 / 50 with the GPC test method, with a melt index (I2) of 0.3 grams per 10 minutes (g / 10 min) to 0.4 g / 10 min, measured according to the melt index test method, at 190 °C and 2.16 kilograms according to ASTM D1238-13; and a melt flow ratio (I21 / I2) of 30 to 35, measured according to the flow index test method and the melt index test method at 190 °C and 21.6 and 2.16 kilograms, respectively, according to ASTM D1238-13. In another aspect, each of the B-LLDPE copolymers supplied here has a melt flow ratio (I21 / I5) of 5 to 20, measured according to the flow index test method and the flow rate test method at 190 °C and 21.6 and 5.0 kilograms, respectively, according to ASTM D1238-13.

[0012] In another aspect, each of the B-LLDPE copolymers provided here has a number of short-chain branches (SCBs) per 1000 carbon atoms, measured according to the GCP test method, which is higher in Mw than in Mn. In another aspect, the B-LLDPE copolymers provided here have an SCB per 1000 C that is 20 to 110 percent higher in Mw than in Mn.

[0013] The aspects of the B-LLDPE copolymers provided herein include a comonomer used in the formation of the B-LLDPE copolymer which is selected from 1-hexene, 1-butene or a combination thereof.

[0014] Aspects of the present disclosure include a manufactured article comprising a molded form of the B-LLDPE copolymers provided herein. Aspects of the present disclosure include a film formed from the B-LLDPE copolymers provided herein. For such aspects, a film produced solely from the B-LLDPE copolymer having a thickness of 25.4 micrometers (1 thousandth of an inch) has an average dart impact resistance of 900 grams (g) to 1300 g as measured in accordance with ASTM D1709 16a. For such aspects, the film also has a standardized Elmendorf tear in the transverse direction (DT) of 600 to 900 gf measured in accordance with ASTM D1922-09, Standard Test Methods for Tear Resistance Petition 870240103360, dated 04 / 12 / 2024, page 16 / 122 6 / 50 plastic film tear propagation and thin sheet formation by the pendulum method, constant radius type B. For such aspects, the film further has an Elmendorf tear ratio (DM / DT) of 0.3 to 0.4, wherein a normalized tear in a transverse direction (DT) and a machine direction (DM) is measured according to ASTM D1922-09, Standard Test Methods for Plastic Film Tear Propagation and Thin Sheet Formation Resistance by the Pendulum Method, Type B (Constant Radius). For the various aspects, the film provided herein is for food packaging. Aspects of the present disclosure also provide a process for producing the film provided herein by a melt molding or blow molding process.

[0015] Aspects of the present disclosure also include a method for producing the B-LLDPE copolymer, as provided herein, wherein the method comprises placing ethylene (C2) and a comonomer (Cx) selected from 1-butene (Cx=C4), 1-hexene (Cx=C6), or both (Cx=C4 and C6) at a molar ratio between comonomer and ethylene (Cx / C2) of 0.005 to 0.30 with a bimodal catalyst system comprising a complex of (1,3-dimethyl-tetrahydroindenyl)(methylcyclopentadienyl)zirconium and a complex of bis(2-pentamethylphenylamido)ethyl)amine zirconium in the presence of molecular hydrogen gas (H2) at a molar ratio between hydrogen and ethylene (H2 / C2) of 0.001 to less than 0.030, all in a single gas-phase polymerization reactor. containing a fluidized bed of resin at a temperature of 70 °C to 90 °C, thus producing the linear bimodal low-density polyethylene copolymer. For various aspects, the method can use a molar ratio between H2 / C2 of 0.006 to 0.015.The bimodal catalyst system may additionally comprise a metallocene catalyst in addition to a (1,3-dimethyl-tetrahydroindenyl)(methylcyclopentadienyl)zirconium complex. DESIGNS

[0016] Figure (Fig.) 1 contains drawings of (pro)catalyst formulas.

[0017] Figure (Fig.) 2 Molecular weight and branching distribution of Petition 870240103360, dated 04 / 12 / 2024, page 17 / 122 7 / 50 short chain for EI1. DETAILED DESCRIPTION

[0018] The Summary, Claims and Abstract are incorporated herein by reference.

[0019] The linear bimodal low-density polyethylene copolymer (B-LLDPE copolymer) of the present disclosure has at least one improved property, such as, for example, at least one improved (increased) processability property and / or at least one improved (increased) stiffness property. The improved processability property may be at least one of decreased extruder cylinder pressure, increased sealing capacity (e.g., hot sealing / hot adhesion), decreased Delta tangent value, and increased shear thinning index value. The improved stiffness property may be at least an increase in Elmendorf tear (DT tear and / or DM tear), increased melt strength, increased secant modulus, and increased dart impact resistance.In some respects, the B-LLDPE copolymer is not characterized by an aggravation of any three, alternatively any two, alternatively any of the previous properties. The B-LLDPE copolymer can be used to make films, sheets and injection molded articles.

[0020] Certain embodiments of the invention are described below as enumerated aspects for ease of cross-referencing. Additional embodiments are described elsewhere in this document.

[0021] Aspect 1 - a B-LLDPE copolymer comprising a density of 0.8900 to 0.9300 grams per cubic centimeter (g / cm3), alternatively 0.8900 to 0.9295 g / cm3, alternatively 0.9000 to 0.9272 g / cm3, alternatively 0.9030 to 0.9266 g / cm3, alternatively 0.9100 to 0.9200 g / cm3, alternatively 0.9160 to 0.9190 g / cm3, measured in accordance with ASTM D792-13, method B; a melting index (I2) of 0.1 grams per 10 minutes (g / 10 min.) to 5 g / 10 min, alternatively from 0.1 to 3.5 g / 10 min, alternatively from 0.1 to 1.5 g / 10 min, alternatively from 0.3 to 0.9 Petition 870240103360, dated 04 / 12 / 2024, p. 18 / 122 8 / 50 g / 10 min, alternatively 0.8 to 0.9 g / 10 min, alternatively 0.3 to 0.4 g / 10 min, measured according to the melt index test method (melt index MI) at 190 °C and 2.16 kilograms according to ASTM D123813; a Mz of 600,000 to 1,200,000 grams per mole (g / mol), alternatively 600,000 to 1,000,000 g / mol, alternatively 600,000 to 900,000 g / mol, alternatively 600,000 to 800,000 g / mol, alternatively 600,000 to 700.000 g / mol, measured according to the gel permeation chromatography (GPC) test method described further below; and a hexane extractables content of up to 2.6% by weight, alternatively up to 2.5% by weight, alternatively up to 2.0% by weight, alternatively up to 1.8% by weight, alternatively up to 1.2% by weight, alternatively up to 1.0% by weight, alternatively up to 0.5% by weight as measured in accordance with ASTM D-5227:95. Aspect 2 - The B-LLDPE copolymer of aspect 1 is further described as having a first melt flow ratio (I21 / I2) of 25 to 65, alternatively 30 to 50, alternatively 32 to 85, alternatively 32 to 75, alternatively 35 to 75, measured according to the flow index test method and the melt index test method at 190 °C and 21.6 and 2.16 kilograms, respectively, according to ASTM D1238-13.Aspect 3 - the B-LLDPE copolymer of aspect 1 and / or aspect 2 further described by a first molecular weight ratio (Mz / Mw) of 3.5 to 5.5, alternatively 3.7 to 5.2, alternatively 3.9 to 5.1, alternatively 4.0 to 5.1, alternatively 4.1 to 5.1, measured according to the GPC test method, where Mz is the average molecular weight and Mw is the weight-average molecular weight. Aspect 1, aspect 2 and / or aspect 3 may additionally include a Mnde of 7,000 to 22,000 grams per mole (g / mol), alternatively 8,000 to 21,000 g / mol, alternatively 9,000 to 20,000 g / mol, alternatively 10,000 to 19,000 g / mol, alternatively 10,000 to 18,000 g / mol, measured according to the GPC test method described further below; a Mw of 100,000 to 190,000 g / mol, alternatively 110,000 to 180,000 g / mol, alternatively 120,000 to 170,000 g / mol. Petition 870240103360, dated 04 / 12 / 2024, p. 19 / 122 9 / 50 alternatively from 120,000 to 165,000 g / mol, measured according to the gel permeation chromatography (GPC) test method described further below; a tangent Delta (tan δ) of 3 to 6 measured at 190 °C and a frequency of 0.1000 radians per second (rad / s) according to the tangent Delta (tan δ) test method described further below.

[0022] Aspect 4 - the B-LLDPE copolymer of any one of aspect 1, aspect 2 and / or aspect 3 further described by I2 being from 0.30 g / 10 min to 0.9 g / 10 min, alternatively from 0.35 g / 10 min to 0.87 g / 10 min, measured according to the melt index test method at 190 °C and 2.16 kilograms according to ASTM D1238-13; and the density is from 0.91000 to 0.92000 g / cm3, measured according to ASTM D792-13, method B. The B-LLDPE copolymer of aspect 4 may additionally have a tangent Delta (tan δ) of 3 to 6, measured at 190 °C, and a frequency of 0.1000 radians per second (rad / s) according to the tangent Delta (tan δ) test method described further below.

[0023] Aspect 5 - the B-LLDPE copolymer of aspect 1 where tan δ is 5.8 to 6.2, measured at 190 °C, and a frequency of 0.1000 radians per second (rad / s) according to the Delta tangent test method; density is 0.9160 to 0.9190 g / cm3, measured according to ASTM D792-13, method B; Mz / Mw is 4.9 to 5.2, measured according to the GPC test method; melt index (I2) is 0.8 grams per 10 minutes (g / 10 min) to 0.9 g / 10 min, measured according to the melt index test method at 190 °C and 2.16 kilograms according to ASTM D1238-13; and a melt flow ratio (I21 / I2) of 40 to 50, measured according to the flow index test method and the melt index test method at 190 °C, and 21.6 and 2.16 kilograms, respectively, according to ASTM D1238-13.

[0024] Aspect 6 - the B-LLDPE copolymer of aspect 1 where tan δ is 2.8 to 3.2, measured at 190 °C, and a frequency of 0.1000 radians per second (rad / s) according to the Delta tangent test method; density is 0.9160 to 0.9190 g / cm3, measured according to ASTM D792-13, method B; Mz / Mw is 3.8 to 4.4, measured according to the GPC test method; the Petition 870240103360, dated 04 / 12 / 2024, p. 20 / 122 10 / 50 melt index (I2) of 0.3 grams per 10 minutes (g / 10 min) to 0.4 g / 10 min, measured according to the melt index test method at 190 °C and 2.16 kilograms according to ASTM D1238-13; and a melt flow ratio (I21 / I2) of 30 to 35, measured according to the flow index test method and the melt index test method at 190 °C and 21.6 and 2.16 kilograms, respectively, according to ASTM D1238-13.

[0025] Aspect 7 - the B-LLDPE copolymer of any combination of aspects 1 to 6 additionally having a flow index ratio (I21 / I2) of 5 to 20, alternatively 8 to 16, alternatively 10 to 15, measured according to the flow index test method and the flow rate test method at 190 °C and 21.6 and 5.0 kilograms, respectively, according to ASTM D1238-13. Aspect 8 - the B-LLDPE copolymer of any combination of aspects 1 to 7 has an I5 value as measured according to ASTM D1238-13 of 1 to 3.

[0026] Aspect 9 - the B-LLDPE copolymer of any combination of aspects 1 to 8 in which the number of short chain branches (SCBs) per 1000 carbon atoms (C), measured according to the GCP test method, is greater in Mw than in Mn. Aspect 10 - the B-LLDPE copolymer of any combination of aspects 1 to 9, in which the number of SCBs per 1000 C measured according to the GCP test method is 20 to 110 percent greater in Mw than in Mn, alternatively 100 to 110 percent greater in Mw than in Mn, alternatively 20 to 30 percent greater in Mw than in Mn. Aspect 11 - the B-LLDPE copolymer of any combination of aspects 1 to 9, wherein the number of SCB per 1000 C in Mw measured according to the GCP test method is 22 to 30, alternatively 24 to 28; and the SCB per 1000 C in Mn measured according to the GCP test method is 9 to 17, alternatively 11 to 15.Aspect 12 - the B-LLDPE copolymer of any combination of aspects 1 to 9, wherein the number of SCB per 1000 C in Mw measured according to the GCP test method is 16 to 24, alternatively 18 to 22; and the SCB per 1000 C in Mn measured accordingly. Petition 870240103360, dated 04 / 12 / 2024, p. 21 / 122 11 / 50 with the GCP test method is 12 to 20, alternatively 14 to 18. For aspects 11 and 12, the number of SCB per 1000 C measured according to the GCP test method is always greater in Mw than in Mn.

[0027] Aspect 13 - the B-LLDPE copolymer of any combination of aspects 1 to 12, wherein a comonomer used in the formation of the bimodal linear low-density polyethylene copolymer is selected from 1-hexene, 1-butene or a combination thereof.

[0028] Aspect 14 - a manufactured article comprising a molded form of B-LLDPE copolymers of any of aspects 1 to 13. Aspect 15 - the manufactured article of aspect 14 selected from: films, sheets, packaging film and non-packaging film and injection molded articles. Aspect 16 - the manufactured article of aspect 14 or 15 selected from agricultural film, food packaging, garment bags, garbage bags, trash bags, ice bags, grocery bags, heavy-duty bags, construction films, geomembrane, industrial sheets, heat-shrinkable and palletizing films, bags, buckets, freezer containers, lids and toys.

[0029] Aspect 17 - a film formed from the B-LLDPE copolymer of any one of Aspect 1 to Aspect 13. Aspect 18 - the film of Aspect 17, wherein the film produced only from the B-LLDPE copolymer having a thickness of 25.4 micrometers (1 thousandth of an inch) has an average dart impact resistance of 900 grams (g) to 1300 g as measured in accordance with ASTM D1709 16a. Aspect 19 - the film of any one of Aspect 17 and / or Aspect 18, wherein the film has a normalized Elmendorf tear in the transverse direction of 600 to 900 gf measured in accordance with ASTM D1922-09, Standard Test Methods for Plastic Film Tear Propagation Resistance and Thin Sheet Formation by the Pendulum Method, Constant Radius Type B.Aspect 20 - the film of any combination of aspect 17 to aspect 19, wherein the film having a thickness of 25 micrometers, has an Elmendorf tear ratio (DM / DT) of 0.3 to 0.4, wherein a normalized tear in a transverse direction (DT) is. Petition 870240103360, dated 04 / 12 / 2024, p. 22 / 122 12 / 50 a machine direction (DM) is measured in accordance with ASTM D192209, Standard Test Methods for Tear Propagation Resistance of Plastic Film and Thin Sheet Formation by Pendulum Method, Type B (Constant Radius). Aspect 21 - the film of any combination of Aspect 17 to Aspect 20, wherein the film is for food packaging. Aspect 22 - including a process for producing the film according to any combination of Aspect 17 to Aspect 21 which includes melt molding or blow extrusion.

[0030] Aspect 23 - a method for producing BLLDPE copolymers of any one of aspects 1 to 13, wherein the method comprises bringing ethylene (C2) and a comonomer (Cx, as provided herein) into contact with a bimodal catalyst system (as provided herein) in a single gas-phase polymerization reactor containing a fluidized bed of resin, thereby producing the BLLDPE copolymer of the present disclosure.

[0031] Aspect 24 - A method for producing the B-LLDPE copolymer according to any one aspect from aspect 1 to aspect 13, wherein the method comprises placing ethylene (C2) and a comonomer (Cx) selected from 1-butene (Cx=C4), 1-hexene (Cx=Ce), or both (Cx=C4 and C6) at a comonomer-to-ethylene molar ratio (Cx / C2) of 0.005 to 0.30, alternatively 0.008 to 0.20, alternatively 0.010 to 0.18 in contact with a bimodal catalyst system comprising a (1,3-dimethyl-tetrahydroindenyl)(methylcyclopentadienyl)zirconium complex and a bis(2-pentamethylphenylamido)ethyl)amine zirconium complex in the presence of molecular hydrogen gas (H2) at a ratio molar ratio between hydrogen and ethylene (H2 / C2) from 0.001 to less than 0.030, alternatively from 0.002 to less than 0.020, alternatively from less than 0.0030 to less than 0.0175, alternatively from 0.005 to less than 0.012,all in a single gas-phase polymerization reactor containing a fluidized bed of resin at a temperature of 70 degrees Celsius (°C) to 90 °C, alternatively 70 °C to 85 °C, alternatively 75 °C to 80 °C, thus producing the copolymer of, Petition 870240103360, dated 04 / 12 / 2024, p. 23 / 122 13 / 50 linear bimodal low-density polyethylene. Aspect 25 - the method of aspect 23 and / or aspect 24, where the molar ratio H2 / C2 is from 0.006 to 0.015.

[0032] Aspect 26 - the method of aspect 23, aspect 24 and / or aspect 25, wherein the method includes an adjustment solution in the presence of molecular hydrogen gas (H2) and an inert condensing agent (ICA) under (co)polymerization conditions; wherein, before being mixed, the adjustment solution consists essentially of a (1,3-dimethyl-tetrahydroindenyl)zirconium complex (pro-catalyst, e.g., (1,3-dimethyltetrahydroindenyl)(methylcyclopentadienyl)zirconium dimethyl) and an inert liquid solvent (e.g., liquid alkane) and the bimodal catalyst system consists of an activating species (derived, for example, from a methylaluminoxane species), bis(2-pentamethylphenylamido)ethyl)amine zirconium dibenzyl and a (1,3-dimethyl-tetrahydroindenyl)zirconium complex, all arranged on a solid support (e.g., a hydrophobic pyrolyzed silica);and where the (co)polymerization conditions comprise a reaction temperature of 70 °C to 90 °C, alternatively 70 °C to 85 °C, alternatively 75 °C to 80 °C; a molar ratio between molecular hydrogen gas and ethylene (H2 / C2 molar ratio) of 0.001 to less than 0.030, alternatively 0.0002 to less than 0.020, alternatively 0.003 to 0.0175, alternatively 0.005 to 0.012, alternatively 0.006 to 0.012;and a molar ratio between comonomer (Cx) and ethylene (molar ratio of Cx / C2) of 0.005 to 0.030, alternatively 0.008 to 0.20, alternatively 0.010 to 0.18. The B-LLDPE copolymer can be that of any of aspects 1 to 13. In an alternative embodiment of aspect 23, aspect 24, aspect 25 and / or aspect 26, the bimodal catalyst system can be prepared and then introduced into the polymerization reactor(s) as a suspension (e.g., flow paste) in a mineral oil, and the adjustment solution can be prepared and introduced into the polymerization reactor(s) as a solution, for example, in a liquid alkane.

[0033] Aspect 27 - the method of aspect 23, aspect 24, aspect 25 Petition 870240103360, dated 04 / 12 / 2024, p. 24 / 122 14 / 50 and / or aspect 26, wherein the bimodal catalyst system comprises another metallocene catalyst in addition to the (1,3-dimethyl-tetrahydroindenyl)(methylcyclopentadienyl)zirconium complex.

[0034] Aspect 28 - the method of any combination of aspects 23 to 27, wherein more than one polymerization reactor can be used with the catalysts of the present disclosure in a fluidized gas phase and / or in a fluid paste phase reactor system, as are known, wherein the number of reactors can be one or two as are known (for example, two gas phase reactors, a single fluid paste phase reactor or two fluid paste phase reactors).

[0035] An activator (also known as a cocatalyst) for activating procatalysts to form catalysts can be used in the manner of the methods provided herein. The activator may include any metal-containing compound, material, or combination of compounds and / or substances, whether unsupported or supported on a support material, that can activate a procatalyst to provide a catalyst and an activator species. Activation may comprise, for example, extracting at least one leaving group from a metal of a procatalyst to provide the catalyst. The catalyst may be generically named by replacing the leaving group portion of the procatalyst name with complex. For example, a catalyst produced by the activation of bis(2-pentamethylphenylamido)ethyl)amine zirconium dibenzyl may be called bis(2-pentamethylphenylamido)ethyl)amine zirconium complex.

[0036] A catalyst produced by the activation of (1,3-dimethyltetrahydroindenyl)(methylcyclopentadienyl)zirconium dichloride or (1,3-dimethyltetrahydroindenyl)(methylcyclopentadienyl)zirconium dimethyl may be called a (1,3-dimethyltetrahydroindenyl)(methylcyclopentadienyl)zirconium complex. The catalyst produced by the activation of (1,3-dimethyltetrahydroindenyl)(methylcyclopentadienyl)zirconium dichloride may be the same as or different from the catalyst produced by the activation of (1,3-dimethyltetrahydroindenyl)(methylcyclopentadienyl)zirconium dimethyl. The activator metal is typically different. Petition 870240103360, dated 04 / 12 / 2024, page 25 / 122 15 / 50 of the metal content of the procatalyst. The molar ratio of the activator metal content to the procatalyst(s) metal content may be from 1.000:1 to 0.5:1, alternatively from 300:1 to 1:1, or alternatively from 150:1 to 1:1. The activator may be a Lewis acid, a non-coordinating ionic activator, or an ionizing activator or a Lewis base, an alkylaluminum, or an alkylaluminoxane. The alkylaluminum may be a trialkylaluminum, alkylaluminum halide, or alkylaluminum alkoxide (diethylaluminum ethoxide). The trialkylaluminum may be trimethylaluminum, triethylaluminum (TEAl), tripropylaluminum, triisobutylaluminum, and the like. The alkylaluminum halide may be diethylaluminum chloride. Alkylaluminoxane can be methyl aluminoxane (MAO), ethyl aluminoxane, or isobutyl aluminoxane. The activator can be an MAO that is a modified methyl aluminoxane (MMAO).The corresponding activating species may be a Lewis acid derivative, a non-coordinating ionic activator, an ionization activator, a Lewis base, an alkylaluminum, or an alkylaluminoxane, respectively. The activating species may have a different structure or composition from the activator from which it is derived and may be a byproduct of procatalyst activation or a derivative of the byproduct. An example of a byproduct derivative is a methylaluminoxane species that is formed by devolatilization during spray drying of a bimodal catalyst system made with methylaluminoxane. The activator may be commercially available. An activator may be fed into the polymerization reactor(s) (e.g., a fluidized bed gas phase reactor) in a feed separate from that feeding the reagents used to make the bimodal catalyst system (e.g., supported bimodal catalyst system) and / or adjustment solution therein.The activator can be fed into the polymerization reactor(s) in wet mode as a solution of the same in an inert liquid, such as mineral oil or toluene, in flowable paste mode as a suspension, or in dry mode as a powder.

[0037] Bimodal, having two different polymeric components (each produced from a separate and distinct catalyst and / or process condition) and / or having two peaks that can be determined from a Petition 870240103360, dated 04 / 12 / 2024, page 26 / 122 16 / 50 molecular weight distribution (MWD), such as MWD measured by gel permeation chromatography (GPC), for example, Mw / Mn measured by GPC.

[0038] Multimodal, having more than one different polymeric component (each produced from a separate and distinct catalyst and / or process condition) and / or having at least 2 peaks (e.g., 2 or 3 peaks) that can be determined from a DPM, such as DPM measured by GPC, e.g., Mw / Mn measured by GPC.

[0039] A bimodal catalyst system, as provided herein, is a combination of two or more independently useful catalyst compounds for increasing the polymerization rate of the same olefinic monomer and / or comonomer and producing a bimodal polyethylene composition. In some respects, the bimodal catalyst system has only two catalysts and is prepared from two, and only two, pro-catalyst compounds. One of the catalyst compounds may be a metallocene catalyst compound and the other a non-metallocene catalyst compound. One of the catalyst compounds produces, under (co)polymerization conditions, the lower molecular weight (LMW) polyethylene component and the other catalyst compound produces the higher molecular weight (HMW) polyethylene component.The polyethylene components of BPM and APM together constitute the bimodal polyethylene composition, which may be the B-LLDPE composition, produced with the bimodal catalyst system and having a multimodal molecular weight distribution (e.g., bimodal). Typically, the bimodal catalyst system of the present disclosure, the method employing the same, and the BLLDPE copolymer of the present disclosure are free of a Ziegler-Natta catalyst.

[0040] The bimodal catalyst system can be produced by placing at least two procatalysts in contact, having different structures from each other, with at least one activator. Each procatalyst can independently comprise a metal atom, at least one ligand attached to the metal atom, and at least one leaving group attached to and displaceable from the metal atom. Each metal can be an element from any of Groups 3 to 14, for example, a Group 4 metal. Each leaving group is H, Petition 870240103360, dated 04 / 12 / 2024, p. 27 / 122 17 / 50 an unsubstituted alkyl, an aryl group, an aralkyl group, a halide atom, an alkoxy group, or a primary or secondary amino group. In metallocenes, at least one ligand is a cyclopentadienyl or substituted cyclopentadienyl group. In non-metallocenes, no ligand is a cyclopentadienyl or substituted cyclopentadienyl group, and instead, at least one ligand has at least one O, N, and / or P atom that coordinates to the metal atom. Typically, the non-metallocene ligand(s) have at least two O, N, and / or P atoms that coordinate in a multidentate (e.g., bidentate or tridentate) linkage mode to the metal atom. Distinct structures mean that procatalysts and catalysts made from them have different ligands from each other, and the same metal atom or a different metal atom, and the same or different leaving groups.

[0041] One of the pro-catalysts, useful for making a bimodal catalyst system catalyst and / or making the adjustment solution, may be a metallocene compound of any of the formulas (I) to (IX) and another of the pro-catalysts may be a non-metallocene of any of the formulas (A) and (B), where the formulas are drawn in Figure 1.

[0042] In formula (I), Figure 1, each of the groups Ri to R10 is independently H, an alkyl group (C1-C20), an aryl group (C6-C20) or an aralkyl group (C7-C20); M is a Group 4 metal; and each X is independently H, a halide, an aryl group (C1-C20) or an aryl group (C7-C20). In some respects, each of R7 to R10 is H in formula (I).

[0043] In formula (I), Figure 1, each of the groups R1 to R6 is independently H, an alkyl group (C1-C20) or an aralkyl group (C7-C20); M is a Group 4 metal (e.g., Ti, Zr, or Hf); and each X is independently H, a halide, an alkyl group (C1-C20) or an aralkyl group (C7-C20). Two or more R1 to R5 together can form a ring having from 4 to 10 carbon atoms, and the ring can be carbocyclic or heterocyclic. Petition 870240103360, dated 04 / 12 / 2024, p. 28 / 122 18 / 50

[0044] In formula (I), Figure 1, each of the groups R1 to R12 is independently H, an alkyl group (C1-C20), an aryl group (C6-C20) or an aralkyl group (C?-C20), with at least one of R4 to R7 not being H; M is a Group 4 metal (e.g., Ti, Zr or Hf); and each X is independently H, a halide, an alkyl group (C1-C20) or an aralkyl group (C7-C20). In some respects, each of R9 to R12 is H in formula (III).

[0045] In some respects, each X in formulas (I) to (III) is independently a halide, alkyl (C1-C4) or benzyl; alternatively CI or benzyl. In some respects, each halide in formulas (I) to (III) is independently Cl, Br or I; alternatively CI or Br; alternatively CI. In some respects, each M in formulas (I) to (III) is independently Ti, Zr or Hf; alternatively Zr or Hf; alternatively Ti; alternatively Zr; alternatively Hf.

[0046] In formulas (IV) to (IX), Figure 1, Me is a methyl group (-CH3), Pr is a propyl group (i.e., -CH2CH2CH3), and each l substituent in a ring represents a methyl group.

[0047] In Formulas (A) and (B), Figure 1, M is a transition metal atom from Group 3 to 12 or a main group metal atom from Group 13 or 14, a metal atom from Group 4, 5, or 6. M can be a Group 4 metal atom, alternatively Ti, Zr, or Hf; alternatively Zr or Hf; alternatively Zr. Each X is independently a leaving group, as described above, such as an anionic leaving group. The subscript y is 0 or 1; when y is 0, the L' group is absent. The subscript n represents the formal oxidation state of the metal atom M and is +3, +4, or +5; alternatively n is +4. L is a Group 15 or 16 element, such as nitrogen or oxygen; L' is a Group 14-containing or Group 15 or 16 element, such as carbon, silicon, or germanium. Y is an element of Group 15, such as nitrogen or phosphorus; alternatively nitrogen. Z is an element of Group 15, such as nitrogen or phosphorus; alternatively nitrogen.The subscript m is 0, -1, -2, or -3; alternatively -2; and represents the total formal load of Y, Z, and L in formula (A). Petition 870240103360, dated 04 / 12 / 2024, p. 29 / 122 19 / 50 and the total formal loading of Y, Z and L' in formula (B). R1, R2, R3, R4, R5, R6, and R7 are independently H, a hydrocarbyl group (C1-C20), a heterohydrocarbyl group (C1-C20), or an organoheteryl group (C2-C20), wherein each of the heterohydrocarbyl (C1-C20) and organoheteryl (C1-C20) groups independently has at least one heteroatom selected from Si, Ge, Sn, Pb, or P. Alternatively, R1 and R2 are covalently linked to form a divalent group of formula -R1a-R2a- and / or R4 and R5 are covalently linked to form a divalent group of formula -R4a-R5a-, wherein -R1a-R2a- and -R4a-R5a- are independently a hydrocarbylene group (C2-C20), a group heterohydrocarbylene (C2-C20) or an organoheterylene group (C2-C20). R3 may be absent; alternatively, R3 is H, a halogen atom, a hydrocarbyl group (C1-C20), a heterohydrocarbyl group (C1-C20), or an organoheterylene group (C1-C20).R3 is absent if, for example, L is O, H, or an alkyl group. R4 and R5 may be an alkyl group (C1-C20), an aryl group (C1-C20), a substituted aryl group (C1-C20), a cycloalkyl group (C3-C20), a substituted cycloalkyl group (C3-C20), a bicyclic aralkyl group (C3-C20), or a substituted bicyclic aralkyl group (C3-C20). R6 and R7 may be H or be absent. R* may be absent or may be a hydrogen, a group containing an atom from Group 14, a halogen, or a group containing a heteroatom.

[0048] In some respects, the bimodal catalyst system may comprise a combination of a metallocene catalyst compound and a non-metallocene catalyst compound. The metallocene catalyst compound may be a metallocene metal-ligand complex, such as a Group 4 metallocene metal-ligand complex, which may be produced by activation (with the activator) of a pre-catalyst compound selected from (pentamethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconium dichloride, bis(n-butylcyclopentadienyl)zirconium dichloride, (pentamethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconium dimethyl, bis(n-butylcyclopentadienyl)zirconium dimethyl, (1,3-dimethyl-tetrahydroindenyl)(methylcyclopentadienyl)zirconium dichloride and (1,3-dimethyl-tetra Petition 870240103360, dated 04 / 12 / 2024, page 30 / 122 20 / 50 hydroindenyl)(methylcyclopentadienyl)zirconium dimethyl. The non-metallocene catalyst compound may be a non-metallocene ligand-metal complex, such as a non-metallocene Group 4 ligand-metal complex, which may be produced by activation (with the activator) of a pro-catalyst compound selected from bis(2-(2,4,6-trimethylphenylamido)ethyl)amine zirconium dibenzyl and bis(2-(pentamethylphenylamido)ethyl)amine zirconium dibenzyl.

[0049] In some respects, the bimodal catalyst system can be produced by activating, according to the contact method with an activator, a combination of a metallocene procatalyst compound which is (1,3-dimethyl-tetrahydroindenyl)(methylcyclopentadienyl)zirconium dichloride and a non-metallocene procatalyst compound which is bis(2-pentamethylphenylamido)ethyl)amine zirconium dibenzyl. (Tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconium dichloride is a compound of formula (II) wherein M is Zr, each X is Cl, R6 is propyl (CH2CH2CH3) and each of R1 to R4 is methyl. Bis(2-pentamethylphenylamido)ethyl)amine zirconium dibenzyl is a pro-catalyst compound of formula (A), wherein M is Zr, each X is benzyl, R1 and R2 are each CH2CH2; R3 is H; L, Y and Z are all N; and R4 and R5 are each pentamethylphenyl; and R6 and R7 are absent.

[0050] Each of the catalytic compounds in the bimodal catalyst system can be independently unsupported, or alternatively supported on a support material, in which latter case the bimodal catalyst system is a supported catalyst system. When each catalyst compound is supported, the catalyst compounds can reside on the same support material (e.g., same particles), or on different support materials (e.g., different particles). The bimodal catalyst system includes mixtures of unsupported catalyst compounds in the form of a fluid paste and / or in the form of a solution. The support material can be silica (e.g., pyrolyzed silica), alumina, clay, or talc. Pyrolyzed silica can be hydrophilic (untreated), or alternatively hydrophobic (treated). In some respects, the support is hydrophobic pyrolyzed silica, which can be prepared by means of Petition 870240103360, dated 04 / 12 / 2024, page 31 / 122 21 / 50 treatment of an untreated pyrolyzed silica with a treatment agent such as dimethyldichlorosilane, a polydimethylsiloxane fluid or hexamethyldisilazane. In some respects, the treatment agent is dimethyldichlorosilane.

[0051] In some respects, the bimodal catalyst system is the bimodal catalyst system described in any of the following references: US 7,193,017 B2; US 7,312,279 B2; US 7,858,702 B2; US 7,868,092 B2; US 8,202,940 B2 and US 8,378,029 B2 (for example, column 4 / row 60 to column 5 / row 10 and column 10 / rows 6 to 38 and Example 1).

[0052] The bimodal catalyst system can be introduced into the polymerization reactor(s) in dry mode or wet mode, alternatively in dry mode, alternatively in wet mode. The dry mode is fed in the form of a dry powder or granules. The wet mode is fed in the form of a suspension of the bimodal catalyst system in an inert liquid such as mineral oil.

[0053] Alpha-olefins (C3-C20) are compounds, as seen in formula (I): H2C=C(H)-R, where R is a linear chain of the alkyl group (CrC18). The alkyl group (C1-C18) is an unsubstituted monovalent saturated hydrocarbon having from 1 to 18 carbon atoms. Examples of R are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl. In some embodiments, the alpha-olefin (C3-C20) is 1-propene, 1-butene, 1-hexene or 1-octene; alternatively 1-butene, 1-hexene or 1-octene; alternatively 1-butene or 1-hexene; alternatively 1-butene or 1-octene; alternatively 1-hexene or 1-octene; alternatively 1-butene; alternatively 1-hexene; alternatively 1-octene; alternatively a combination of any two of 1-butene, 1-hexene and 1-octene.The alpha-olefin (C3-C20) that is used as a comonomer from which the comonomeric units of the BPM polyethylene component are derived may be the same as, or alternatively different from, the alpha-olefin (C3-C20) from which the comonomeric units of the APM polyethylene component are derived. Petition 870240103360, dated 04 / 12 / 2024, p. 32 / 122 22 / 50 derivatives. Preferably, the alpha-olefin is 1-hexene, 1-butene, or a combination thereof.

[0054] Consist essentially of, consists (or consist) essentially of, and similar. Partially closed expressions that exclude anything that would affect the basic and innovative characteristics they describe, but otherwise allow for anything else. As applied to the description of an embodiment of the bimodal catalyst system consisting essentially of bis(2-pentamethylphenylamido)ethyl)amine zirconium dibenzyl and (1,3-dimethyl-tetrahydroindenyl)(methylcyclopentadienyl)zirconium dichloride, both arranged on a solid support and activated with an activating agent, the expression means that the embodiment does not contain a Ziegler-Natta catalyst or any other organic ligand besides the bis(2-pentamethylphenylamido)ethyl)amine, benzyl, 1,3-dimethyl-tetrahydroindenyl and methylcyclopentadienyl ligands. One or more of the benzyl and chloride leaving groups may be absent from Zr in the bimodal catalyst system.The expression consisting essentially of, as applied to the description of the adjustment solution, means that the adjustment solution is unsupported (i.e., not arranged in a particulate solid) and is free of a ZieglerNatta catalyst or any other organic ligand besides the 1,3-dimethyl-tetrahydroindenyl and methylcyclopentadienyl ligands. The expression consisting essentially of, as applied to a dry inert purge gas, means that the dry inert purge gas is free of, alternatively, has less than 5 parts per million based on the total parts by weight of water gas or any reactive compound that could oxidize a constituent of the present polymerization reaction. In some respects, either, alternatively, each comprising or comprising may be replaced by consisting essentially of or consisting essentially of, respectively; alternatively by consisting of or consisting of, respectively.

[0055] That consists of and consists of. Closed expressions that exclude anything not specifically described by the limitation they modify. In some respects, either one, alternatively, Petition 870240103360, dated 04 / 12 / 2024, page 33 / 122 23 / 50 each expression that consists essentially of or consists essentially of can be replaced by the expression that consists of or consists of, respectively.

[0056] (co)polymerization conditions. Any effective outcome variable or combination of such variables, such as catalyst composition; amount of reagent; molar ratio between two reagents; absence of interfering materials (e.g., H2O and O2); or a process parameter (e.g., feed rate or temperature), step or sequence that is effective and useful for the copolymerization method of the invention in the polymerization reactor(s) to provide the B-LLDPE copolymer.

[0057] Alternatively, at least one of the (co)polymerization conditions can be fixed (i.e., unchanged) during the production of the B-LLDPE copolymer. Such fixed (co)polymerization conditions can be referred to in the present invention as steady-state (co)polymerization conditions. Steady-state (co)polymerization conditions are useful for continuously producing embodiments of the B-LLDPE copolymer having the same polymeric properties.

[0058] Alternatively, at least one, alternatively two or more of the (co)polymerization conditions may be varied in their defined operating parameters during the production of the BLLDPE copolymer in order to transition from the production of a first embodiment of the B-LLDPE copolymer having a first set of polymeric properties to a second embodiment of the B-LLDPE copolymer having a second set of polymeric properties, wherein the first and second sets of polymeric properties are different and are within the limitations described herein for the B-LLDPE copolymer. For example, all other (co)polymerization conditions being equal, a higher molar ratio between the alpha-olefin (C3C20) / ethylene comonomer feeds in the copolymerization method of the invention produces a lower density of the resulting B-LLDPE copolymer product. At a given molar ratio between comonomer / ethylene, the molar ratio of the pro Petition 870240103360, dated 04 / 12 / 2024, p. 34 / 122 The 24 / 50 catalyst of the adjustment solution relative to the total moles of catalyst compounds in the bimodal catalyst system can be varied to adjust the density, melt index, melt flux, molecular weight, and / or melt flux ratio thereof. To illustrate one approach to making transitions, perform one of the copolymerization examples of the invention described later to achieve steady-state (co)polymerization conditions. Then, change one of the (co)polymerization conditions to begin producing a new embodiment of the B-LLDPE copolymer. Sample the new embodiment and measure a property thereof. If necessary, repeat the steps of changing the condition / sampling the product / measuring the property at intervals until the measurement shows that the desired value for the property is obtained.An example of such a variation of an operating parameter includes varying the operating temperature within the aforementioned range of 70 °C to 90 °C, such as by changing a first operating temperature of 80 °C to a second operating temperature of 81 °C, or by changing a third operating temperature of 82 °C to a third operating temperature of 85 °C. Similarly, another example of a variation of an operating parameter includes varying the molar ratio between molecular hydrogen and ethylene (H2 / C2) from 0.0070 to 0.0072, or from 0.0100 to 0.0095. Similarly, another example of a variation of an operating parameter includes varying the molar ratio between comonomer (Cx) and ethylene (molar ratio between Cx / C2) from 0.0130 to 0.0140 or from 0.0160 to 0.0158. Combinations of two or more of the preceding example variations are included here.The transition from one set to another set of (co)polymerization conditions is permitted in the direction of (co)polymerization conditions, since the operating parameters of both sets of (co)polymerization conditions are within the ranges defined in the present invention. A beneficial consequence of the aforementioned transition is that any property value described for the B-LLDPE copolymer, or its BPM or APM polyethylene component, can be... Petition 870240103360, dated 04 / 12 / 2024, page 35 / 122 25 / 50 achieved by someone skilled in the art, taking into account the teachings of the present invention.

[0059] The (co)polymerization conditions may additionally include a high-pressure liquid-phase or gas-phase polymerization reactor and the polymerization method to produce the B-LLDPE copolymer. A gas-phase polymerization process is preferred. Such reactors and methods are generally well known in the art. For example, the liquid-phase polymerization reactor / method may be solution-phase or flow-paste-phase, as described in US patent 3,324,095. The gas-phase polymerization reactor / method may employ an inert condensing agent and be conducted in condensation mode polymerization as described in US patents 4,453,399; 4,588,790; 4,994,534; 5,352,749; 5,462,999 and 6,489,408. The gas-phase polymerization reactor / method may be a fluidized bed reactor / method, as described in US patents 3,709,853; 4,003,712; 4,011,382; 4,302,566; 4,543,399; 4,882,400; and 5,352.749; US 5,541,270; EP-A-0 802 202 and Belgian patent no. 839,380. These patents disclose gas-phase polymerization processes in which the polymerization medium is mechanically agitated or fluidized by the continuous flow of gaseous monomer and diluent. Other gas-phase processes contemplated include serial or multi-stage polymerization processes, as described in US patents 5,627,242; US 5,665,818; US 5,677,375; EP-A-0 794 200; EP-B1-0 649 992; EP-A-0 802 202 and EP-B-634421.

[0060] The (co)polymerization conditions for liquid-phase or gas-phase reactors / methods may additionally include one or more additives, such as a chain transfer agent, a promoter, or a scavenging agent. Chain transfer agents are well known and may be alkylmetals, such as diethyl zinc. Promoters are well known, as in US patent 4,988,783, and may include chloroform, CFCl3, trichloroethane, and difluorotetrachloroethane. Scavenging agents may be a trialkylaluminum. Gas-phase or flow-paste polymerizations may be operated without scavenging agents (not deliberately added). Petition 870240103360, dated 04 / 12 / 2024, page 36 / 122 26 / 50 (co)polymerization conditions for gas phase reactors / polymerizations may additionally include an amount (e.g., from 0.5 to 200 ppm based on all feeds to the reactor) of static control agents and / or continuity additives, such as aluminum stearate or polyethyleneimine. Static control agents may be added to the gas phase reactor to inhibit the formation or accumulation of static charge within it.

[0061] The (co)polymerization conditions may additionally include the use of molecular hydrogen to control the final properties of the BPM and / or APM polyethylene components or the B-LLDPE copolymer. Such use of H2 is generally described in Polypropylene Handbook 76-78 (Hanser Publishers, 1996). All else being equal, the use of hydrogen can increase the melt flow rate (MFR) or melt index (MI), with MFR or MI being influenced by the hydrogen concentration. A molar ratio between hydrogen and total monomer (H2 / monomer), hydrogen and ethylene (H2 / C2) or hydrogen and comonomer (H2 / α-olefin) may be from 0.001 to less than 0.030, alternatively 0.002 to less than 0.020, alternatively from 0.003 to 0.0175, alternatively from 0.005 to 0.0120, alternatively from 0.006 to less than 0.015, alternatively 0.001 to 0.015, alternatively 0.001 to 0.013.

[0062] The (co)polymerization conditions may include a partial pressure of ethylene in the polymerization reactor(s) independently of 690 to 3450 kilopascals (kPa, 100 to 500 pounds per square inch absolute (psia)), alternatively 1030 to 2070 kPa (150 to 300 psia), alternatively 1380 to 1720 kPa (200 to 250 psia), alternatively 1450 to 1590 kPa (210 to 230 psia), for example, 1520 kPa (220 psia). 1,000 psia = 6.8948 kPa.

[0063] Dry. Generally, a moisture content of 0 to less than 5 parts per million based on total parts by weight. The materials fed into the polymerization reactor(s) during a polymerization reaction under (co)polymerization conditions are typically dry. Petition 870240103360, dated 04 / 12 / 2024, page 37 / 122 27 / 50

[0064] Ethylene. A compound with the formula H2C=CH2. A polymerizable monomer.

[0065] Feeds. Quantities of initial substances and / or reagents that are added or fed into a reactor. In continuous polymerization operation, each feed, independently, can be continuous or intermittent. The quantities or feeds can be measured, for example, by dosing, to control quantities and relative amounts of the various initial substances and reagents in the reactor at any given time.

[0066] Higher molecular weight (HMW). Relative to LMW, it has a higher average molecular weight (Mw). The APM polyethylene component of the B-LLDPE copolymer can have an Mw of 10,000 to 1,000,000 g / mol. The lower endpoint of Mw for the APM polyethylene component can be 20,000, alternatively 40,000, alternatively 60,000, alternatively 80,000, alternatively 100,000 g / mol. The upper endpoint of Mw can be 1,000,000, alternatively 800,000, alternatively 700,000, alternatively 600,000, alternatively 580,000 g / mol. When describing the B-LLDPE copolymer, the lower portion of the Mw range for the APM polyethylene component may overlap with the upper portion of the Mw range for the BPM polyethylene component, provided that in any embodiment of the B-LLDPE copolymer, the specific Mw for the APM polyethylene component is greater than the specific Mw for the BPM polyethylene component.The BPM polyethylene component can be made with a catalyst prepared by activating a non-metallocene Group 4 metal-ligand complex.

[0067] Inert. Generally, not (perceptibly) reactive or not interfering (perceptibly) with the polymerization reaction of the invention. The term inert applied to purge gas or ethylene feed means a molecular oxygen (O2) content of 0 to less than 5 parts per million based on the total parts, by weight, of the purge gas or ethylene feed.

[0068] Inert condensing agent (ICA). An inert liquid useful for Petition 870240103360, dated 04 / 12 / 2024, page 38 / 122 28 / 50 Cooling of materials in the polymerization reactor(s) (e.g., a fluidized bed reactor). In some respects, ICA is an alkane (C5-C20), alternatively an alkane (C5-C15), alternatively an alkane (C5-C10). In some respects, ICA is an alkane (C5-C20). In some respects, the alkane (C5C20) is a pentane, for example, normal pentane or isopentane; a hexane; a heptane; an octane; a nonane; a decane; or a combination of any two or more of the same. In some respects, ICA is isopentane (i.e., 2-methylbutane). The polymerization method of the invention, which uses ICA, may be referred to in the present invention as an inert condensation mode operation (IMC). Concentration in the gas phase measured using gas chromatography by calibrating the percentage peak area in mol percent (% mol) with a standard gas mixture of known concentrations of ad rem gas phase components.The concentration can be from 1 to 15%, by mole, alternatively, from 3 to 12%, by mole, alternatively, from 5 to 10%, by mole. Other values ​​are also possible (for example, up to 26%, by mole, when used in quantities of about 20%, by mole, to 26%, by mole, the process can be described as operating in supercondensation mode).

[0069] Lower molecular weight (LMW). Relative to LW, having lower weight-average molecular weight (Mw). The LW polyethylene component of the B-LLDPE copolymer can have an Mw of 3,000 to 100,000 g / mol. The lower endpoint of Mw for the LW polyethylene component can be 5,000, alternatively 8,000, alternatively 10,000, alternatively 12,000, alternatively 15,000, alternatively 20,000 g / mol. The upper endpoint of Mw can be 100,000, alternatively 80,000, alternatively 60,000, alternatively 58,000 g / mol. The LW polyethylene component can be produced with a catalyst prepared by activating a metallocene Group 4 ligand-metal complex.

[0070] Polyethylene. A macromolecule, or collection of macromolecules, composed of repeating units, wherein 50 to 100 mol percent (mol percent), alternatively 70 to 100 mol percent, alternatively 80 to 100 mol percent, Petition 870240103360, dated 04 / 12 / 2024, page 39 / 122 29 / 50 alternatively 90 to 100%, by mol, alternatively 95 to 100%, by mol, alternatively any of the preceding ranges where the upper endpoint is < 100%, by mol, of such repeating units are derived from the ethylene monomer and, in aspects where there are less than 100%, by mol, of ethylene repeating units, the remaining repeating units are comonomeric units derived from at least one alpha-olefin (C3-C20); or collection of such macromolecules. Linear low-density polyethylene (LDPE). The macromolecule with a substantially linear structure.

[0071] Pro-catalyst. Also referred to as a catalyst compound or pre-catalyst (as opposed to the active catalyst compound), generally a material, compound or combination of compounds that exhibits no or extremely little polymerization activity (e.g., catalyst efficiency may be 0 or <1.000) in the absence of an activator, but after activation with an activator produces a catalyst that shows efficiency at least 10 times greater than the catalyst efficiency of, if any, the pro-catalyst.

[0072] Initialization or restart of the polymerization reactor(s) illustrated with a fluidized bed reactor. Initialization of an annealed fluidized bed reactor (cold initialization) or restart of a transition fluidized bed reactor (hot initialization / transition) includes a period of time preceding the (co)polymerization conditions. Initialization or restart may include the use of a pre-loaded or loaded seed, respectively, in the fluidized bed reactor. The seed may be composed of polyethylene powder. The polyethylene bed may be an LDPE, alternatively an LLDPE, alternatively a bimodal LLDPE, alternatively a previously produced embodiment of the B-LLDPE copolymer.

[0073] The start-up or restart of the fluidized bed reactor may also include gaseous atmosphere transitions comprising purge air or other unwanted gas (or gases) from the reactor with a dry (anhydrous) inert purge gas, followed by purging the dry inert purge gas from the reactor with dry ethylene gas. The purge gas Petition 870240103360, dated 04 / 12 / 2024, p. 40 / 122 30 / 50 dry inert can consist essentially of molecular nitrogen (N2), argon, helium, or a mixture of two or more of these. When not in operation, prior to start-up (cold start), the fluidized bed reactor contains an air atmosphere. Dry inert purge gas can be used to sweep the air from a reconditioned fluidized bed reactor during the early stages of start-up to give the fluidized bed reactor an atmosphere consisting of dry inert purge gas. Before restarting (e.g., after a change in seeding or before a change in the alpha-olefin comonomer), a transition fluidized bed reactor may contain an atmosphere of unwanted alpha-olefin, unwanted ICA, or other unwanted gas or vapor.Dry inert purge gas can be used to sweep away unwanted vapor or gas from the transition fluidized bed reactor during the initial restart stages to give the fluidized bed reactor an atmosphere consisting of dry inert purge gas. Any dry inert purge gas can itself be swept from the fluidized bed reactor along with dry ethylene gas. The dry ethylene gas may also contain molecular hydrogen gas so that the dry ethylene gas is fed into the fluidized bed reactor as a mixture thereof. Alternatively, dry molecular hydrogen gas can be introduced separately and after the fluidized bed reactor atmosphere has transitioned to ethylene. Gas atmosphere transitions can be made before, during, or after heating the fluidized bed reactor to the reaction temperature under (co)polymerization conditions.

[0074] The start-up or restart of the fluidized bed reactor also includes the introduction of reagent feeds and reagents. The reagents include ethylene and alpha-olefin. The reagents introduced into the fluidized bed reactor include molecular hydrogen and the inert condensing agent (ICA) and the mixture of the bimodal catalyst system and the adjustment solution.

[0075] Substance or article requiring coating. A naturally occurring or man-made material or a manufactured article that would benefit from having a layer of B-LLDPE copolymer on or around it. Substances requiring coating include those that are Petition 870240103360, dated 04 / 12 / 2024, page 41 / 122 31 / 50 vulnerable to their external environments and those requiring segregation from them. External environments may contain oxygen, moisture, and / or light, which can degrade these substances, except for the B-LLDPE copolymer layer. Such substances include clothing, drugs, food, electronic components, hygroscopic compounds, plants, and any other light, oxygen, and / or moisture-sensitive material or manufactured article. Articles requiring covering include orderly arrangements of materials (e.g., stacks of manufactured articles on a pallet requiring packaging), boxes requiring shrink wrapping, loose manufactured articles needing to be shipped, and toxic or corrosive materials.

[0076] Adjustment solution. Any of the metallocene procatalytic compounds or non-metallocene procatalytic compounds described above dissolve in the inert liquid solvent (e.g., liquid alkane). The adjustment (trim) solution is mixed with the bimodal catalyst system to produce the mixture, and the mixture is used in the polymerization reaction of the invention to modify at least one property of the B-LLPDE copolymer thus made. Examples of such at least one property are density, melt index I2, melt flow ratio, and molecular weight dispersion (Mw / Mn), which may be referred to as molecular weight distribution. The mixture of the bimodal catalyst system and the adjustment solution can be fed into the polymerization reactor(s) in wet mode, or alternatively, it can be devolatilized and fed in dry mode. The dry mode is fed in the form of a dry powder or granules.When the mixture contains a solid support, the wet mode is fed in the form of a semi-fluid suspension or paste. In some respects, the inert liquid is a liquid alkane, such as isopentane, heptane, or ISOPAR™ C, available from ExxonMobil Chemical.

[0077] Ziegler-Natta catalysts, as used herein, are heterogeneous materials that increase the polymerization reaction rates of olefins and are typically products that are prepared by contacting inorganic titanium compounds, such as titanium halides supported on a Petition 870240103360, dated 04 / 12 / 2024, page 42 / 122 32 / 50 magnesium chloride support, with an activator. The activator may be an alkylaluminum activator, such as triethylaluminum (TEA), triisobutylaluminum (TIBA), diethylaluminum chloride (DEAC), diethylaluminum ethoxide (DEAE), or ethylaluminum dichloride (EADC).

[0078] Advantageously, the B-LLDPE copolymer has physical properties that are surprising and useful. For example, the copolymer has at least one improved property such as at least one improved (increased) processability property and / or at least one improved (increased) stiffness property. The improved processability property may be at least one of decreased extruder drum pressure, increased sealing capacity (e.g., hot sealing / hot adhesion), decreased tan delta value, and increased thinning index value. The improved stiffness property may be at least an increase in Elmendorf rupture (CD Tear), increased melt strength, and increased desiccant modulus. In some respects, the B-LLDPE copolymer is not characterized by an aggravation of any three, alternatively, any two, alternatively, any of the above properties.

[0079] Test samples of unfilled and filled composition modalities can be produced separately in compression molded plates. The mechanical properties of these compositions can be characterized using test samples cut from the compression molded plates.

[0080] A compound includes all of its naturally occurring isotopes and isotopically enriched forms. The enriched forms may have medical or anti-counterfeiting uses.

[0081] In some respects, any compound, composition, formulation, mixture or reaction product in the present invention may be free of any of the chemical elements selected from the group consisting of: H, Li, Be, B, C, N, O, F, Na, Mg, Al, Si, P, S, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Br, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Petition 870240103360, dated 04 / 12 / 2024, page 43 / 122 33 / 50 Cd, In, Sn, Sb, Te, I, Cs, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, TI, Pb, Bi, lanthanides and actinides; provided that the chemical elements necessary for the compound, composition, formulation, mixture or reaction product (e.g., C and H, necessary for a polyolefin or C, H and O necessary for an alcohol) are not excluded.

[0082] The following applies unless otherwise indicated. Alternatively, a distinct embodiment precedes. ASTM is the technical standards body, ASTM International, West Conshohocken, Pennsylvania, USA. ISO is the technical standards body, International Organization for Standardization, Geneva, Switzerland. Any comparative examples are used for illustrative purposes only and are not of the prior art. Exempt from or devoid means a complete absence of; alternatively, undetectable. IUPAC means International Union of Pure and Applied Chemistry (IUPAC Secretariat, Research Triangle Park, North Carolina, USA). May confers a permitted choice, not an imperative. Operational means functionally capable or effective. Optionally means to be absent (or excluded), alternatively, to be present (or included).Properties are measured using a standard test method and measurement conditions (e.g., viscosity: 23 °C and 101.3 kPa). Ranges include endpoints, subranges, and integer and / or fractional values ​​included therein, except that a range of integers does not include fractional values. Room temperature: 23 °C ± 1 °C. Substituted, when referring to a compound, means having, in place of hydrogen, one or more substituents, up to and including by substitution.

[0083] Melt strength test method. Melt strength (MS) measurements were conducted on a Gottfert Rheotens 71.97 (Gottfert Inc.; Rock Hill, SC, USA) attached to a Gottfert Rheotester 2000 capillary rheometer. A molten polymer (approximately 20 to 30 grams, pellets) was extruded through a capillary die with a flat entry angle (180 degrees), a capillary diameter of 2.0 mm, and a Petition 870240103360, dated 04 / 12 / 2024, page 44 / 122 34 / 50 aspect ratio (capillary length / capillary diameter) of 15. After equilibrizing the samples at 190 °C for 10 minutes, the piston was operated at a constant piston speed of 0.265 mm / second. The standard test temperature was 190 °C. The sample was uniaxially stretched into an acceleration jaw assembly, located 100 mm below the die, with an acceleration of 2.4 mm / s². The tensile force was recorded as a function of the retraction speed of the jaw rollers. The melt strength was reported as the plateau force (cN) before wire rupture. The following conditions were used in the melt strength measurements: piston speed = 0.265 mm / second; wheel acceleration = 2.4 mm / s²; capillary diameter = 2.0 mm; capillary length = 30 mm; and cylinder diameter = 12 mm.

[0084] Dart Impact Test Method: Measured in accordance with ASTM D1709-16a, Method A, Standard Test Methods for Plastic Film Impact Resistance by the Free-Fall Dart Test Method. Method A employs a dart with a hemispherical head with a diameter of 38.10 ± 0.13 mm (1.500 ± 0.005 in) 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 resistances require masses of about 50 g or less to about 6 kg to fracture them. Results expressed in grams (g).

[0085] Density test method: measured in accordance with ASTM D792-13, Standard Test Methods for Density and Specific Gravity (Relative Density) of Plastics by Displacement, Method B (for testing solid plastics in liquids other than water, for example, in liquid 2-propanol). Report results in units of grams per cubic centimeter (g / cm3).

[0086] Elmendorf tear test method: measured in accordance with ASTM D1922-09, Standard test methods for tear propagation resistance of plastic film and thin film formation by the pendulum method, type B (constant radius). (Technically equivalent to ISO 6383-2.) Petition 870240103360, dated 04 / 12 / 2024, p. 45 / 122 35 / 50 Report the results as normalized tear in the cross direction (CD) or in the machine direction (MD) in gram-force (gf).

[0087] Melt Index Test Method (190 °C, 2.16 kg, l2): Use ASTM D1238-13, Standard Test Method for Melt Index of Thermoplastics by Extrusion Plateau, using conditions of 190 °C / 2.16 kilograms (kg). Report results in units of grams eluted per 10 minutes (g / 10 min) or the equivalent in decigrams per 1.0 minute (dg / 1 min).

[0088] Flow index test method (190 °C, 21.6 kg, l21): Use the ASTM D 1238-13 standard, Standard test method for melt flow indices of thermoplastics by extrusion plateau, using conditions of 190 °C / 21.6 kilograms (kg). Report the results in units of grams eluted per 10 minutes (g / 10 min) or the equivalent in decigrams per 1.0 minute (dg / 1 min).

[0089] Flow test method (190 °C, 5.0 kg, I5): Test method: Use ASTM D1238-13 standard, using conditions of 190 °C / 5.0 kg. Report results in units of grams eluted per 10 minutes (g / 10 min) or the equivalent in decigrams per 1.0 minute (dg / 1 min).

[0090] Flow index test method (190 °C, I21 / I2): calculated by dividing the value of the flow index test method (I21) by the value of the melting index test method (I2).

[0091] Flow index ratio test method (190 °C, I21 / I5): calculated by dividing the value of the flow index test method (I21) by the value of the flow rate test method (I5).

[0092] Gel permeation chromatography (GPC) test method: number of short-chain branches (SCB) per 1000 carbon atoms; weight-average molecular weight test method: determine the z-average molecular weight (Mz), the number-average molecular weight (Mn), and the Mw / Mn using 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 Petition 870240103360, dated 04 / 12 / 2024, page 46 / 122 36 / 50 three Polymer Laboratories PLgel 10 μm Mixed-B columns, all contained in an oven maintained at 160 °C. The method uses a solvent composed of TCB treated with BHT at a nominal flow rate of 1.0 milliliter per minute (mL / min) and a nominal injection volume of 300 microliters (µL). Prepare the solvent by dissolving 6 g 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 (µm) Teflon filter to generate 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 at 160 °C with continuous stirring for 2 hours to produce the solutions.(Measure all quantities gravimetrically). Target solution concentrations, c, of test polymer from 0.5 to 2.0 milligrams of polymer per milliliter of solution (mg / mL), where lower concentrations, c, are used for higher molecular weight polymers. Before running each sample, purge the DRI detector. Then increase the flow rate in the instrument to 1.0 mL / minute and allow the DRI detector to stabilize for 8 hours before injecting the first sample. Calculate Mw and Mn using universal calibration relationships with the column calibrations. Calculate MW at each elution volume using the following equation: . log(ÁV / Â' ) a„ç+lt__ logÀfA. =A, + logA / ps. ÍZy + 1 ßχ + 1 where the subscript X represents the test sample, the subscript PS represents the PS standards, aps = 0.67, Kps = 0.000175 and ax and Kx are obtained from published literature. For polyethylenes, aX / Kx = 0.695 / 0.000579. For polypropylenes, ax / Kx = 0.705 / 0.0002288. At each point in the resulting chromatogram, calculate the concentration, c, from a DRI signal subtracted from the reference base, Idri, using the following equation: c = KDRi / (dn / dc), where KDR is a constant determined by calibrating the DRI, / indicates division and Petition 870240103360, dated 04 / 12 / 2024, p. 47 / 122 37 / 50 dn / dc is the refractive index increment for the polymer. For polyethylene, dn / dc = 0.109. Calculate the polymer mass recovery from the ratio of the integrated area of ​​the concentration chromatography chromatogram to the elution volume and the injection mass, which is equal to the predetermined concentration multiplied by the injection loop volume. Report all molecular weights in grams per mole (g / mol) unless otherwise indicated. Additional details regarding methods for determining Mw, Mn, MWD are described in US patent 2006 / 01731 23, pages 24 and 25, paragraphs

[0334] to

[0341] . Plot dW / dlog(MW) on the geometric y-axis versus Log(MW) on the geometric x-axis to generate a GPC chromatogram, where Log(MW) and dW / dlog(MW) are as defined above.

[0093] Short Chain Branching is determined using gel permeation chromatography (GPC), where the comonomer content incorporated into the polymers (% by weight) is determined by fast FT-IR spectroscopy on the polymer dissolved in a GPC measurement. For example, the comonomer content is determined relative to the molecular weight of the polymer by using an infrared detector such as an IR5 detector in a gel permeation chromatography measurement, as described in Analytical Chemistry 2014, 86(17), 8649-8656. Toward Absolute Chemical Composition Distribution Measurement of Polyolefins by High-Temperature Liquid Chromatography Hyphenated with Infrared Absorbance and Light Scattering Detectors by Dean Lee, Colin Li Pi Shan, David M. Meunier, John W. Lyons, Rongjuan Cong, and A. Willem deGroot. DeGroot. Analytical Chemistry 2014 86 (17), 8,649 to 8,656.

[0094] Secant modulus test method 1% or 2%: measured according to ASTM D882-12, Standard Test Methods for Tensile Properties of Thin Plastic Sheets. The secant modulus 1% or 2% was used in the transverse direction (DT) or in the machine direction (DM). Report results in megapascals (MPa). 1,000 pounds per square inch (psi) = 6.8948 MPa.

[0095] Shear Thinning Index (SHI) test method: Perform oscillatory shear measurements of Petition 870240103360, dated 04 / 12 / 2024, page 48 / 122 38 / 50 small deformation (10%) in molten polymer at 190 °C using an advanced rheometric expansion system ARES-G2, available from TA Instruments, with parallel plate geometry to obtain the storage modulus (G'), loss modulus (G”), complex modulus (G*) and complex viscosity (η*) values ​​as a function of frequency (ω). Obtain an SHI value by calculating the complex viscosities at given complex modulus values ​​and calculating the ratio between the two viscosities. For example, using complex modulus values ​​of 1 kilopascal (kPa) and 100 kPa, obtain η*(1.0 kPa) and η*(100 kPa) at a constant complex modulus value of 1.0 kPa and 100 kPa, respectively. kPa) en*(100 kPa), i.e., η*(1.0) / η*(100).

[0096] Delta Tangent Test Method (Tan δ): A dynamic mechanical analysis (DMA) method measured at 190°C and 0.1000 radians per second (rad / s) using the following procedure: Perform small deformation (10%) oscillatory shear measurements on molten polymer at 190°C using an ARES-G2 advanced rheometric expansion system, available from TA Instruments, with parallel plate geometry to obtain the values ​​of storage modulus (G'), loss modulus (G"), complex modulus (G*), and complex viscosity (η*) as a function of frequency (ω). A Delta tangent (δ) at a specific frequency (ω) is defined as the ratio between the loss modulus (G") and the storage modulus (G') obtained at that frequency (ω), i.e., tangent δδ = G" / G'. The value of tangent δδ at frequency (ω) 0.1 radian / second is used later in Table 2.

[0097] Tensile modulus test method: measured in accordance with ASTM D882-12, Standard Test Methods for Tensile Properties of Thin Plastic Sheet Forming. Report results in the cross direction (DC) as mean yield stress in percent (%) or mean yield stress in megapascals (MPa) or in the machine direction (DM) as mean yield stress in percent (%). 1,000 pounds per square inch (psi) = 6.8948 MPa.

[0098] Film puncture test method: ASTM Standard D5748 Petition 870240103360, dated 04 / 12 / 2024, page 49 / 122 39 / 50 95(2012), Standard Test Method for Stretch Film Protrusion Puncture Resistance. Determines the puncture resistance of a film, as the resistance to penetration of the film by a probe impinging on the film at a standard speed, such as 250 millimeters per minute (mm / min). The probe is coated with polytetrafluoroethylene and has an outer diameter of 1.905 cm (0.75 inch). The film is clamped during the test. The probe eventually penetrates or ruptures the clamped film. The peak force at rupture, i.e., the maximum force, energy (work) until rupturing or penetrating the clamped film and the distance the probe penetrated at rupture, are recorded using mechanical testing software. The probe transmits a biaxial stress to the clamped film that is representative of the type of stress encountered by films in many end-use product applications. This resistance is a measure of a film's energy absorption capacity to resist puncture under these conditions.Results expressed in force in pounds per cubic inch (ft*lbf / in3).

[0099] Optical gloss test method: ASTM D2457-13 Standard, Standard test method for specular gloss of plastic films and solid plastics. Measure specular gloss using a gloss meter at incident angles of 20°, 45°, 60°, or 75°. Specular gloss has no unit.

[0100] Optical opacity test method: ASTM D1003-13 Standard, Opacity and Light Transmittance Test Method for Transparent Plastics. Measure opacity using an opacity meter. Express opacity as the percentage of light transmission that, upon passing through the film, deviates from an incident beam by direct scattering. Results expressed as a percentage (%).

[0101] Method for determining zero shear viscosity: Perform oscillatory shear measurements of small deformation (10%) on polymer melts at 190 °C using an advanced ARES-G2 rheometric expansion system, available from TA Instruments, with parallel plate geometry to obtain complex viscosity |η*| as a function of frequency data (ω). Determine the values ​​for the three parameters - zero shear viscosity, ηο, characteristic viscous relaxation time, τη and the Petition 870240103360, dated 04 / 12 / 2024, page 50 / 122 40 / 50 width parameter, a, by curve fitting of the data obtained using the following CY model: ln'Cw)l =-------η II 4- (τηω) I 5 where |η*(ω)| is the magnitude of the complex viscosity, η0 is zero shear viscosity, τη is the viscous relaxation time, a is the width parameter, n is the power law index, and ω is the angular frequency of the oscillatory shear.

[0102] Improved comonomer content distribution (iCCD) analysis was performed using Crystallization Elution Fractionation (CEF) instrumentation (PolymerChar, Spain) equipped with an IR-5 detector (PolymerChar, Spain) and two Model 2040 angle scattering detectors (precision detectors currently available from Agilent Technologies). A 0.635 cm (ID) (or 1 / 4 (ID)) 10 cm (length) packed guard column with 20-27 micron glass (MoSCi Corporation, USA) was installed immediately before the IR-5 detector in the detector oven. Ortho-Dichlorobenzene (ODCB, 99% anhydrous or technical grade) is used, and silica gel 40 (particle size 0.2 to 0.5 mm, catalog number 10181-3 available from EMD Chemicals) can be used to pre-dry the ODCB solvent.The CEF instrument is equipped with an autosampler with N2 purge capability. The ODCB is sprayed with dry nitrogen (N2) for one hour before use. Sample preparation is done with an autosampler at 4 mg / mL (unless otherwise indicated) under agitation at 160 °C for 1 hour. The injection volume is 300 μL. The iCCD temperature profile is: crystallization at 3 °C / min from 105 °C to 30 °C, thermal equilibrium at 30 °C for 2 minutes (including the elution time of the soluble fraction being defined as 2 minutes), and elution at 3 °C / min from 30 °C to 140 °C. The flow rate during crystallization is 0.0 mL / min. A. Petition 870240103360, dated 04 / 12 / 2024, page 51 / 122 41 / 50 flow rate during elution is 0.50 mL / min. Data is collected at one data point / second.

[0103] The iCCD column is packed with gold-coated nickel particles (Bright 7GNM8-NiS, Nippon Chemical Industrial Co.) in a 15 cm (length) by 0.635 cm (1 / 4”) (ID) stainless steel tubing. The packing and conditioning of the column were performed using a fluid paste method according to the reference (Cong, R.; Parrott, A.; Hollis, C.; Cheatham, M. WO2017 / 040127A1). The final pressure with the TCB fluid paste packing was 150 bar.

[0104] Column temperature calibration was performed using a mixture of linear homopolymer polyethylene as the reference material (with zero comonomer content, melt index (I2) of 1.0, Mw / Mn polydispersity of approximately 2.6 by conventional gel permeation chromatography, 1.0 mg / mL) and eicosane (2 mg / mL) in ODCB. iCCD temperature calibration consisted of four steps: (1) Calculation of the delay volume defined as the temperature shift between the measured peak elution temperature of eicosane minus 30.00 °C; (2) Subtraction of the temperature shift from the elution temperature to the raw iCCD temperature data. It is noted that this temperature shift is a function of experimental conditions such as elution temperature, elution flow rate, etc.(3) Creation of a linear calibration line transforming the elution temperature into a range of 30.00 °C and 140.00 °C, so that the linear homopolymer polyethylene reference has a peak temperature at 101.0 °C, and eicosane has a peak temperature of 30.0 °C; (4) For the soluble fraction measured isothermally at 30 °C, the elution temperature below 30.0 °C is linearly extrapolated by using the elution heating rate of 3 °C / min according to the reference (Cerk and Cong et al., US patent 9,688,795).

[0105] For all resin, the integration windows are adjusted to integrate all chromatograms at the elution temperature (the calibration of Petition 870240103360, dated 04 / 12 / 2024, page 52 / 122 42 / 50 temperature (as specified above) ranges from 25.0 °C to 115 °C. The percentage by weight of the high-density resin fraction (HDF) is defined by the following equation: HDF (integrated area of ​​the elution window from 95 to 115 °C) (integrated area of ​​the entire elution window from 25 to 115 °C) x 100% The percentage by weight of the low-density fraction of the resin (LDF) is defined by the following equation: LDF (integrated area of ​​the elution window from 25 to 35 °C) (integrated area of ​​the entire elution window from 25 to 115 °C) x 100% Examples

[0106] Bimodal catalyst system 1 (BMC1): consisting essentially of or produced from bis(2-pentamethylphenylamido)ethyl)amine zirconium dibenzyl and spray-dried (tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconium dichloride in a molar ratio of 3:1 in CAB-O-SIL TS610, a hydrophobic pyrolyzed silica produced by surface treatment with hydrophilic (untreated) pyrolyzed silica supported by dimethyl-dichlorosilane and methylaluminoxane (MAO) and used to feed a gas-phase polymerization reactor as a 20.0% by weight mineral oil flowable paste. The molar ratio between moles of MAO and (moles of bis(2-pentamethylphenylamido)ethyl)amine zirconium dibenzyl + moles of (tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconium dichloride) was 120:1.

[0107] Bimodal catalyst system 2 (BMC2): consisting essentially of or produced from bis(2-pentamethylphenylamido)ethyl)amine zirconium dibenzyl and spray-dried (1,3-dimethyl-tetrahydroindenyl)(methylcyclopentadienyl)zirconium dichloride in a 3:1 molar ratio in CAB-O-SIL TS610, a hydrophobic pyrolyzed silica produced by surface treatment of hydrophilic (untreated) pyrolyzed silica with dimethyl-dichlorosilane and methylaluminoxane (MAO) support, and used to feed a gas-phase polymerization reactor Petition 870240103360, dated 04 / 12 / 2024, page 53 / 122 43 / 50 as a fluid paste of 20.9% by weight in mineral oil. The molar ratio between MAO and (moles of bis(2-pentamethylphenylamido)ethyl)amine zirconium dibenzyl + moles of (1,3-dimethyl-tetrahydroindenyl)(methylcyclopentadienyl)zirconium dimethyl chloride) was 148:1.

[0108] Comonomer 1: 1-hexene, used at a molar ratio of 1-hexene / C2 in Tables 1a / 1b. Comonomer 2: 1-butene, used at a molar ratio of 1-butene / C2 in Tables 1a / 1b. Ethylene (C2): the partial pressure of C2 was maintained as described later in Table 1a / 1b.

[0109] Inert condensing agent 1 (ICA1): isopentane, used at a percent molar concentration (% mol) in the gas phase of a gas phase reactor relative to the total molar content of matter in the gas phase. Reported later in Table 1a / 1b.

[0110] Molecular hydrogen gas (H2): used in the molar ratio between H2 / C2 in Table 1a / 1b.

[0111] Adjustment Solution 1 (Trim1): consisted essentially of or was made of tetramethylcyclopentadienyl(n-propylcyclopentadienyl)zirconium dimethyl (pro-catalyst) dissolved in isopentane to produce a solution having 0.04 percent by weight of pro-catalyst.

[0112] Adjustment Solution 2 (Trim2): consisted essentially of or was made of (1,3-dimethyl-tetrahydroindenyl)(methylcyclopentadienyl)zirconium dimethyl (pro-catalyst) dissolved in isopentane to produce a solution having 0.04 percent by weight of pro-catalyst.

[0113] Examples of the invention (EI) 1 and 2: synthesis of BLLDPE copolymer embodiments. The BLLDPE copolymer embodiments of EI 1 and EI 2 were produced in separate polymerization reaction tests in a single continuous gas-phase fluidized bed reactor. The fluidized bed reactor was configured with a plurality of gas feed inlets and catalyst feed inlets and a product discharge outlet. The polymerization reaction used a bimodal catalyst system, an adjustment solution, ethylene (C2), a comonomer, ICA1, and H2 gas. The adjustment solution was used to adjust the melt flow index properties of the BLLDPE copolymer. [Reference to patent application 870240103360, dated 04 / 12 / 2024, page 54 / 122] 44 / 50 LLDPE. In an experimental run, the reactor was pre-loaded prior to startup with the granular resin comprising the seedbed. First, the gaseous atmosphere in the reactor containing the pre-loaded seedbed was dried using high-purity anhydrous molecular nitrogen to a moisture content below 5 ppm. Then, the feed gases ethylene (C2), comonomer, molecular hydrogen gas (H2), and ICA1 (isopentane) were introduced to produce gaseous phase conditions in the reactor for the desired gaseous phase operating conditions, while the reactor was heated to the desired operating temperature.Gas phase conditions were established and operating gas phase conditions were maintained in the reactor at a partial pressure of ethylene in the reactor of 1500 kPa (220 psia) and by measuring the gas feed to the reactor at a molar ratio between comonomer / C2, a molar ratio between H2 / C2 and a molar percentage (mol%) of isopentane, as listed further in Tables 1a / 1b for each Example and in Tables 2a / 2b / 2c for specific comparative Examples. Next, a feed of adjustment solution 1 was mixed with a feed of the bimodal catalyst system to produce a mixture of the same, which is then fed to the reactor. The mixture can be made with different molar ratios to adjust the melt index and density properties of the bimodal LLDPE polymer being produced in the reactor to the desired target values ​​and produce the EI 1 and EI 2 B-LLDPE copolymer modalities (product).B-LLDPE copolymers were collected from the product discharge outlet and characterized. The constituents and operating parameters are summarized below in Tables 1a, 1b. The properties of the B-LLDPE copolymers from the Examples and the copolymers from the comparative Examples are summarized below in Tables 2a / 2b / 2c. To produce another embodiment of B-LLDPE copolymer, where the density is from 0.8900 to 0.9300 g / cm3, replicate the procedure, except for adjusting the molar ratio between comonomer / C2, as necessary to achieve the desired density. Petition 870240103360, dated 04 / 12 / 2024, page 55 / 122 Table 1a: (Co)polymerization conditions for EC A to EC E and EI 1 EC A EC B EC C EC D EC E EI 1 Catalyst BMC1 BMC1 BMC1 BMC1 BMC1 BMC2 Adjustment Type Trim1 Trim1 Trim1 Trim1 Trim1 Trim2 Catalyst Feed Rate, mL / h 2.3 1.8 1.1 1.3 1.8 4.5 Adjustment Feed Rate, mL / h 11.2 3.6 19.9 6.3 55.9 183 Production Rate, kg / h 17.87 17.55 20.00 19.96 22.50 21.59 Residence Time, h 2.21 2.20 1.92 2.00 1.82 1.90 Temp. Reactor bed temperature, °C 85.00 80.00 80.00 80.00 80.00 78.00 Bed weight, kg 39.51 38.37 38.37 39.87 39.55 40.10 FBD, lb / ft³ 13.90 13.40 13.40 13.50 14.50 15.60 Comonomer hexene butene butene hexene hexene hexene Molar ratio Cx / C2 0.047 0.140 0.139 0.046 0.043 0.0377 Flow rate Cx / C2, kg / kg 0.106 0.241 0.222 0.100 0.083 0.086 Molar ratio H2 / C2 0.010 0.010 0.001 0.003 0.001 0.0110 Flow rate H2 / C2, g / kg 0.707 0.722 0.062 0.187 0.063 0.713 APS, cm 0.272 0.130 0.147 0.206 0.201 0.133 Fine solids, % by weight 0.0 0.3 0.4 0.1 0.1 0.40 Petition 870240103360, dated 04 / 12 / 2024, page 56 / 122 46 / 50 Table 1b: (co)polymerization conditions for EC G to EC I and EI 2 EC G EC H EC I EI 2 Catalyst BMC1 BMC1 BMC1 BMC2 Adjustment type Trim1 Trim1 Trim1 Trim2 Catalyst feed rate, mL / h 1.6 2.7 2.0 4.5 Adjustment feed rate, mL / h 0 27.2 38.4 10.5 Production rate, kg / h 17.06 17.96 18.64 19.1 Residence time, h 2.30 2.20 2.11 2.10 Temp. Reactor bed temperature, °C 80.00 80.00 80.00 78.00 Bed weight, kg 38.15 39.51 39.19 39.55 FBD, lb / ft³ 12.00 14.70 14.60 14.60 Comonomer hexene hexene hexene hexene Molar ratio Cx / C2 0.0385 0.040 0.042 0.031 Flow rate Cx / C2, kg / kg 0.087 0.080 0.082 0.071 Molar ratio H2 / C2 0.0055 0.001 0.001 0.011 Flow rate H2 / C2, g / kg 0.473 0.061 0.064 0.715 APS, cm 0.198 0.180 0.183 0.170 Fine solids, % by weight 0.06 0.1 0.1 0.09

[0114] Comparative Examples EC F and EC J are produced according to the following examples from the cited documents. EC F - 2016-VHH Part 6 found in document WO 2018 / 089193 A1; EC J - EXCEED™ XP 8656 (ExxonMobil). Petition 870240103360, dated 04 / 12 / 2024, p. 57 / 122 47 / 50 Table 2a - Copolymeric properties of the Examples of the invention and the Comparative Examples Sample Density (ASTM D792-13, Method B) Melting Index (I2, ASTM D1238-13 standard) I21 (ASTM D1238-13 standard) I5 (ASTM D1238-13 standard) I21 / I5 I21 / I2 Comonomer H2 / C2 Process Number of reactors EC A 0.9168 0.97 58.2 3.24 18.0 60.0 hexene 0.01 gas 1 EC B 0.9178 1.05 55.4 3.40 16.3 52.7 butene 0.01 gas 1 EC C 0.9169 1.00 47.4 4.10 11.6 47.4 butene 0.001 gas 1 EC D 0.9185 1.00 119.3 4.95 24.1 119.3 hexene 0.003 gas 1 EC E 0.9182 0.94 47.1 3.84 12.3 50.1 hexene 0.001 gas 1 EC F 0.9183 1.17 37.9 3.48 10.9 32.4 hexene 0.017 gas 1 EI 1 0.9176 0.85 37.6 2.69 14.0 44.2 hexene 0.011 gas 1 EC G 0.9183 0.34 25.5 1.19 21.4 74.9 hexene 0.0055 gas 1 EC H 0.9182 0.34 25.1 1.55 16.2 73.9 hexene 0.001 gas 1 EC I 0.9184 0.63 38.3 2.76 13.9 60.5 hexene 0.001 gas 1 CE J 0.916 0.49 13.6 1.38 9.9 28.0 hexene N / D gas 1 EI 2 0.9175 0.37 12.0 1.10 10.9 32.4 hexene 0.0110 gas 1 47 / 50 Petition 870240103360, dated 04 / 12 / 2024, p. 58 / 122 48 / 50 Table 2b - Copolymeric properties of the Examples of the invention and of Comparative examples Sample Mn Mw Mz Mw / Mn Mz / Mw SCB per 1000 C in Mn SCB per 1000 C in Mw EC A 9,165 125,208 695,344 13.66 5.55 17.28 24.61 EC B 7,519 119,216 697,422 15.86 5.85 21.42 29.60 EC C 29,479 153,792 1,500,371 5.22 9.76 19.73 23.68 EC D 15,444 136,184 1,368,958 8.82 10.05 16.66 26.76 CE E 26,872 156,873 1,615,450 5.84 10.30 13.85 19.13 EC F 7,121 113,371 420,057 15.92 3.71 9.68 12.44 EI 1 10,598 126,490 637,760 11.93 5.04 12.82 26.00 EC G 13,831 164,788 879,591 11.91 5.34 14.87 21.40 EC H 29,002 187,732 1,876,141 6.47 9.99 12.97 19.52 CE I 28,843 162,200 1,449,907 5.62 8.94 13.40 18.79 CE J 35,285 138,399 365,701 3.92 2.64 11.24 21.32 EI 2 17,134 158,423 655,534 9.25 4.14 15.65 19.27 Table 2c - Copolymeric properties of the Examples of the invention and of Comparative examples Sample SHI (1 / 100) tangent δ at 0.1 rad / s Melting strength (cN at 50 mm / s) %LEF (iCCD 25 to 35) %HDF (iCCD 95 to 115) EC A 6.75 5.88 2.85 7.63 2.72 EC B 5.63 5.63 2.8 9.31 0.98 EC C 19 2.03 4.33 1.74 1.24 EC D 75 2.94 2.52 4.33 2.60 EC E 18.92 2.07 4.85 2.35 2.75 EC F 3.86 9.43 1.95 EI 1 5.35 5.96 3.22 9.74 3.75 EC G 11.67 2.95 7.17 3.99 6.06 EC H 31.5 1.67 9.83 EC I 21.43 1.86 7.02 EC J 3.19 13.47 4.88 0.88 4.42 EI 2 6 3.01 8.92 4.51 9.36

[0115] The B-LLDPE copolymers of the Examples of the invention demonstrate the potential for improved processability, as evidenced by the shear thinning index values ​​seen above, together with the wider tangent δ and Mz / Mw and DPM values, for example, Mw / Mn, measured by GPC, in the value ranges observed above.

[0116] As a further example, Figure 2 provides a graph of the molecular weight distribution and the short-chain branching distribution. Petition 870240103360, dated 04 / 12 / 2024, page 59 / 122 49 / 50 of the EI 1 polymer. As illustrated, the short-chain branching per 1000 C in Mw is observed to be greater than the SCB per 1000 C in Mn for EI 1. Blown films

[0117] Preparation of a single-layer film 25.4 microns thick of B-LLDPE copolymers and the copolymers of the Comparative Example as set out in Tables 3a and 3b below.

[0118] For the data seen in Tables 3a and 3b, a blown film line machine configured to produce polyethylene films with a feed hopper in fluid communication with an extruder in heating communication with a heating device heated to a temperature of 221 °C. The extruder is in fluid communication with a die that has a fixed die span of 1,778 millimeters (70.00 mils), a blow ratio of 2.5:1. The frost line height (FLH') is 81 ± 5.1 centimeters (32 ± 2 inches) from the die. The machine utilized a feed rate of 89.6 kg (197.6 lb) per hour at a melt temperature of 202 °C ± 1 °C and an extrusion speed of 28.5 revolutions per minute (rpm). The film properties of the Examples of the Invention (EI) (B-LLDPE copolymer) and Comparative Examples (CE) are shown below in Tables 3a and 3b. Table 3a - Properties of the 25.4 micron single-layer film Polymer EI 1 EI 2 EC A EC B EC C EC D Average dart (g) 965 1279 1000 121 72 146 Average brightness 45 degrees 30 41 28 39 33 15 Average opacity (%) 25 15 27 20 23 48 Average perforation (ft*lb / inA3) 229 175 217 190 135 149 Average secant modulus at DT 2% (psi) 41686 41862 32325 32286 29210 29336 Average secant modulus at DM 2% (psi) 33520 35805 28676 28763 25013 25173 Average tear DT (gf) 653 799 712 553 466 699 Average tear DM (gf) 243 269 259 137 29 258 Blown film line head pressure (psi) 3844 5051 3308 3308 3501 2576 Hexane extractables (% by weight) 1.79 1.15 3.08 4.54 0.49 1.09 Petition 870240103360, dated 04 / 12 / 2024, pp. 60 / 122 50 / 50 Table 3b - Properties of the 25.4 micron single-layer film Polymer EC E EC F EC G EC H EC I EC J Average Dart (g) 229 904 1096 907 264 1276 Average Gloss at 45 degrees 33 25 18 15 24 41 Average Opacity (%) 23 34 39 48 31 20 Average Perforation (ft*lb / inA3) 217 ​​128 152 173 151 211 Average Secant Modulus at DT 2% (psi) 30264 36910 41166 39552 37336 30334 Average Secant Modulus at DM 2% (psi) 27068 32263 34447 34738 31601 26993 Average Tear DT (gf) 585 605 1021 680 617 371 Average tear DM (gf) 217 ​​316 232 121 182 243 Blown film line head pressure (psi) 3594 3000 3898 3939 3288 4730 Hexane extractables (% by weight) 0.42 3.01 1.66 0.43 0.41 0.24

[0119] The B-LLDPE copolymer of the present disclosure can produce a film having at least one improved property such as, for example, at least one improved (increased) processability property and / or at least one improved (increased) stiffness property. The improved processability property can be at least one of decreased extruder cylinder pressure, decreased tangent Delta value, and increased shear thinning index value. The improved stiffness property can be at least an increase in Elmendorf tear (DT tear), an increase in melt strength, an increase in dart impact intensity, and an increase in secant modulus. In some respects, the B-LLDPE copolymer of the present disclosure is not characterized by an aggravation of any three, alternatively, any two, alternatively, any of the aforementioned properties. Petition 870240103360, dated 04 / 12 / 2024, pages 61 / 122

Claims

1 / 4 CLAIMS 1. Bimodal linear low-density polyethylene copolymer, characterized by comprising: - a density of 0.8900 to 0.9300 grams per cubic centimeter (g / cm3) measured according to ASTM D792-13, method B; - a melt index (I2) of 0.1 grams per 10 minutes (g / 10 min) to 5 g / 10 min, measured according to the Melt Index Test Method at 190 °C and 2.16 kilograms, according to ASTM D1238-13; - a Mz of 600,000 to 1,200,000 grams per mole (g / mol), measured according to the gel permeation chromatography (GPC) test method; and - a hexane extractables content of up to 2.6% by weight, as measured in accordance with ASTM D-5227:95, wherein the linear bimodal low-density polyethylene copolymer has a delta tan (Tan δ) of 3 to 6, measured at 190°C and a frequency of 0.1000 radians per second (rad / s) according to the Delta Tan Test Method.

2. A bimodal linear low-density polyethylene copolymer according to claim 1, characterized in that it has a melt flow ratio (I21 / I2) of 25 to 65, measured according to the flow index test method and the melt index test method at 190 °C and 21.6 and 2.16 kilograms, respectively, according to ASTM D1238-13; and additionally has a melt flow ratio (I21 / I2) of 30 to 50, measured according to the flow index test method and the melt index test method at 190 °C and 21.6 and 2.16 kilograms, respectively, according to ASTM D1238-13; or have a first molecular weight ratio (Mz / Mw) of 3.5 to 5.5, measured according to the GPC Test Method, where Mz is the average molecular weight and Mw is the weight-average molecular weight.

3. A bimodal linear low-density polyethylene copolymer according to either claim 1 or 2, characterized in that the I2 value is from 0.3 g / 10 min to 0.9 g / 10 min, measured according to the Melt Index Test Method at 190 °C and 2.16 kilograms, according to Petition 870240103360, dated 04 / 12 / 2024, p. 62 / 122 2 / 4 ASTM D1238-13; and the density being from 0.900 to 0.9200 g / cm3, measured according to ASTM D792-13, Method B.

4. Bimodal low-density polyethylene copolymer according to claim 1, characterized in that it has: - a tan δ of 5.8 to 6, measured at 190 °C and a frequency of 0.1000 radians per second (rad / s) according to the Delta Tangent Test Method; - a density of 0.9160 to 0.9190 g / cm3, measured according to ASTM D792-13, method B; - a Mz / Mw ratio of 4.9 to 5.2, measured according to the GPC test method; - a melt index (I2) of 0.8 grams per 10 minutes (g / 10 min) to 0.9 g / 10 min, measured according to the melt index test method at 190 °C and 2.16 kilograms, according to ASTM D1238-13; and - a melt flow ratio (I21 / I2) of 40 to 50, measured according to the flow index test method and the melt index test method at 190 °C and 21.6 and 2.16 kilograms, respectively, according to ASTM D1238-13.

5. Bimodal low-density polyethylene copolymer, according to claim 1, characterized in that the linear bimodal low-density polyethylene copolymer has: a tan δ of 3 to 3.2, measured at 190 °C and a frequency of 0.1000 radians per second (rad / s) according to the Delta Tangent Test Method; - a density of 0.9160 to 0.9190 g / cm3, measured according to ASTM D792-13, method B; - a Mz / Mw ratio of 3.8 to 4.4, measured according to the GPC test method; - a melt index (I2) of 0.3 grams per 10 minutes (g / 10 min) to 0.4 g / 10 min, measured according to the melt index test method at 190 °C and 2.16 kilograms, according to ASTM D1238-13; and - a melt flow ratio (I21 / I2) of 30 to 35, measured according to the flow index test method and the melt index test method at 190 °C and 21.6 and 2.16 kilograms, respectively, according to ASTM D1238-13.

6. Bimodal linear low-density polyethylene copolymer, according to any one of claims 1 to 5, characterized in that it has a flow index ratio (I21 / I5) of 5 to 20, measured according to the flow index test method and the melt index test method at 190 °C and 21.6 and 5.0 kilograms, respectively, according to ASTM D1238-13.

7. A linear bimodal low-density polyethylene copolymer according to any one of claims 1 to 5, characterized in that it has a number of short-chain branches per 1,000 carbon atoms measured according to the GCP Test Method that is greater in Mw than in Mn; and optionally in that the number of short-chain branches (SCB) per 1,000 C is 20 to 110 percent greater in Mw than in Mn.

8. A linear bimodal low-density polyethylene copolymer according to any one of claims 1 to 7, characterized in that the comonomer used to form the linear bimodal low-density polyethylene copolymer is selected from 1-hexene, 1-butene, or a combination thereof.

9. Film, characterized in that it is formed from a bimodal linear low-density polyethylene copolymer as defined in any one of claims 1 to 8.

10. Film, according to claim 9, the film being characterized in that it is produced exclusively from linear bimodal low-density polyethylene copolymer having a thickness of 25.4 micrometers (1 thousandth of an inch) characterized in having an average dart impact resistance of 900 grams (g) to 1,300 g measured in accordance with ASTM D170916a; and / or the film having a standardized Elmendorf tear in the transverse direction of 600 to 900 gf measured in accordance with ASTM D1922-09, standard test methods for tear propagation resistance in plastic films and thin sheet formation by the pendulum method, constant radius type B; and / or Petition 870240103360, dated 04 / 12 / 2024, p.64 / 122 4 / 4 wherein the film which has a thickness of 25 micrometers has an Elmendorf tear ratio (DM / DT) of 0.3 to 0.4, wherein a normalized tear in a transverse direction (DT) and in a machine direction (DM) is measured according to ASTM D1922-09, Standard Test Methods for Propagation Tear Resistance of Plastic Film and Thin Sheeting by Pendulum Method, type B (constant radius).

11. Film, according to either of claims 9 and 10, the film being characterized by the fact that it is intended for packaging food products.

12. Method for producing the linear bimodal low-density polyethylene copolymer, as defined in any one of claims 1 to 5, the method being characterized in that it comprises placing ethylene (C2) and a comonomer (Cx) selected from 1-butene (Cx=C4), 1-hexene (Cx=C6) or both (Cx=C4 and C6) at a comonomer to ethylene molar ratio (Cx / C2) of 0.005 to 0.30 in contact with a bimodal catalyst system comprising a (1,3-dimethyl-tetrahydroindenyl)(methylcyclopentadienyl)zirconium complex and a bis(2-pentamethylphenylamido)ethyl)aminezirconium complex in the presence of molecular hydrogen gas (H2) at a hydrogen to ethylene molar ratio (H2 / C2) of 0.001 to less than 0.030, all in a single reactor of Gas-phase polymerization containing a fluidized bed of resin at a temperature of 70 °C to 90 °C, thus producing the linear bimodal low-density polyethylene copolymer.

13. Method according to claim 12, characterized in that the molar ratio of H2 / C2 is from 0.006 to 0.

015.

14. Method, according to any one of claims 12 or 13, characterized in that the bimodal catalyst system further comprises a metallocene catalyst that is not a (1,3-dimethyl-tetrahydroindenyl)(methylcyclopentadienyl)zirconium complex. Petition 870240103360, dated 04 / 12 / 2024, p. 65 / 122

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