Bimodal linear low density polyethylene copolymer, article of manufacture and method for producing bimodal linear low density polyethylene copolymer

Abstract

BIMODAL LINEAR LOW-DENSITY POLYETHYLENE COPOLYMER, AND, MANUFACTURED ITEM. Bimodal linear low-density polyethylene copolymers (B-LLDPE copolymers) are supplied 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 1,900,000 g / mol; and a SHI of 5.35 to 75 Eta*(1.0) / Eta*(100). The B-LLDPE copolymer can be further characterized by a first melt flow ratio (I21 / I2) of 32 to 140 and a first molecular weight ratio (Mz / Mw) of 4.5 to 11.

Description

1 / 59 BIMODAL LINEAR LOW-DENSITY POLYETHYLENE COPOLYMER, ARTICLE MANUFACTURED AND METHOD FOR PRODUCING BIMODAL LINEAR LOW-DENSITY POLYETHYLENE COPOLYMER FIELD OF DISCOVERY

[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. LLDPE injection-molded articles include buckets, freezer containers, lids, and toys.

[0003] Polyethylenes are mentioned in 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 producing linear low-density polyethylene compositions using Ziegler-Natta catalysts and including a process for producing bimodal linear low-density polyethylene polymer compositions, useful for film production.

[0005] US 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 gas-phase reactor. Petition 870240092769, dated 10 / 30 / 2024, page 14 / 141 2 / 59

[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 copolymer) 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 MCNLLDPE, the extruder cylinder pressure is higher than during the extrusion of previous ZN-LLDPE. 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 ​​relative to molecular weight. Petition 870240092769, dated 10 / 30 / 2024, page 15 / 141 3 / 59 mean 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 the above problems, wherein the BLLDPE copolymer has at least one processability characteristic similar to that of an unmixed monomodal ZN-LLDPE and at least one stiffness / mechanical property 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 standards; 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 1,900,000 grams per mole (g / mol), measured according to the gel permeation chromatography (GPC) test method; and a shear viscosity reduction index (SHI) of 5.35 to 75 η*(1.0) / η*(100), measured according to the SHI Test Method. The B-LLDPE copolymer is further characterized by having a first melt flow ratio (I21 / I2) of 32 to 140, measured according to the melt index test method at 190 °C and 21.6 and 2.16 kilograms, respectively, according to ASTM D1238-13 standards; and having a first molecular weight ratio (Mz / Mw) Petition 870240092769, dated 10 / 30 / 2024, page 16 / 141 4 / 59 from 4.5 to 11, measured according to the GPC Test Method, where Mz is the average molecular weight and Mw is the weight-average molecular weight.

[0011] In a further aspect, the B-LLDPE copolymer is further characterized in that the I2 is from 0.80 g / 10 min to 1.2 g / 10 min, measured according to the Melting Index Test Method at 190 °C and 2.16 kilograms, according to ASTM D1238-13; and Mz is 630,000 to less than 1,700,000 g / mol, measured according to the GPC Test Method. For this further aspect, the density of the B-LLDPE copolymer is from 0.916 to 0.926 g / cm3, measured according to ASTM D792-13, Method B; and the B-LLDPE copolymer has a tan delta (tan δ) of 2 to 6, measured at 190 °C and a frequency of 0.1000 radians per second (rad / s), according to the Tan Delta (Tan δ) Test Method.This additional aspect may also include a Tan δ of 5.6 to 6, measured at 190 °C and a frequency of 0.1000 radians per second (rad / s) according to the Tan Delta Test Method, a density of 0.916 to 0.918 g / cm3, measured according to ASTM D792-13, Method B, and Mz / Mw of 5 to 5.6, measured according to the GPC Test Method.

[0012] In another aspect, the B-LLDPE copolymer has a density of 0.915 to 0.920 g / cm3, measured according to ASTM D792-13, Method B; an I2 of 3.2 g / 10 min. to 3.6 g / 10 min., measured according to the melt index test method at 190 °C and 2.16 kilograms, according to ASTM D1238-13 standards; an Mz of 800,000 to 1,200,000 g / mol, measured according to the GPC Test Method; and an SHI of 10 to 12η*(1.0) / η*(100), measured according to the SHI test method. For this given B-LLDPE copolymer, the Tan δ is 3 to 4, measured at 190 °C and a frequency of 0.1000 radians per second (rad / s) according to the Tan δ Test Method.

[0013] In a further aspect, the B-LLDPE copolymer has a density of 0.9160 to 0.9200 g / cm3, measured according to ASTM D792-13, Method B; an I2 of 0.1 g / 10 min to 0.8 g / 10 min, measured according to the Melting Index Test Method, at 190 °C and 2.16 kilograms, according to ASTM D1238-13; an Mz of 650,000 to 1,900,000 g / mol, measured according to the GPC Test Method; an SHI of 6 to 32 η*(1.0) / η*(100), Petition 870240092769, dated 10 / 30 / 2024, p. 17 / 141 5 / 59 measured according to the SHI Test Method. For this given B-LLDPE copolymer, the Tan δ is 1.6 to 3.1, measured at 190 °C and a frequency of 0.1000 radians per second (rad / s), according to the Tan δ Test Method. This additional aspect may also include an I2 value of 0.3 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.

[0014] In a further aspect, each of the B-LLDPE copolymers provided above has a number of short-chain branches per 1,000 carbon atoms, measured according to the GCP Test Method, which is greater in Mw than in Mn.

[0015] Aspects of the present disclosure include a manufactured article comprising a molded form of the B-LLDPE copolymers provided above.

[0016] Aspects of the present disclosure also include a method for making the B-LLDPE copolymer, as provided above, wherein the method comprises contacting ethylene (C2) and a comonomer (Cx) selected from 1-butene (Cx=C4), 1-hexene (Cx=C6) or both (Cx=C4) and C6 in a comonomer to ethylene molar ratio (Cx / C2) of 0.005 to 0.30 with a bimodal catalyst system comprising bis[(2-pentamethylphenylamido)ethyl]amine zirconium dibenzyl in the presence of molecular hydrogen gas (H2) in a hydrogen to ethylene molar ratio (H2 / C2) of 0.001 to less than 0.012, all in a single gas-phase polymerization reactor containing a fluidized bed of resin at a temperature of 70 °C to 90 °C, thus forming the copolymer of linear bimodal low-density polyethylene.For the various aspects, the method can use a molar ratio of H2 / C2 from 0.001 to 0.003. The bimodal catalyst system may further comprise a metallocene other than (tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconium-X2 (X=methyl chloride). DRAWINGS.

[0017] Figure (Figure) 1 contains drawings of (pro)catalyst formulas.

[0018] Figure (Fig.) 2 presents a graph of the molecular weight distribution and short-chain branching distribution of the polymer of Petition 870240092769, dated 10 / 30 / 2024, page 18 / 141 6 / 59 sample EI 1.

[0019] Figure (Figure) 3 presents a graph of the molecular weight distribution and short chain branching distribution of the polymer from sample EI 5. DETAILED DESCRIPTION

[0020] The Summary and Abstract are incorporated into this document by reference.

[0021] 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.

[0022] Certain embodiments of the invention are described below as enumerated aspects for ease of cross-referencing. Additional embodiments are described elsewhere in this document.

[0023] Aspect 1. A B-LLDPE copolymer comprising a density of 0.8900 to 0.9300 grams per cubic centimeter (g / cm3) measured in accordance with ASTM D792-13, 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, 0.9030 to 0.9255 g / cm3, alternatively, Petition 870240092769, dated 10 / 30 / 2024, p. 19 / 141 7 / 59 0,9110 a 0,9255 g / cm3, Método B; um índice de fusão (I2) de 0,1 grama por 10 minutos (g / 10 min) a 5 g / 10 min, alternamente de 0,1 a 3,5 g / 10 min, alternamente de 0,1 a 1,5 g / 10 min, alternamente de 0,1 a 0,8 g / 10 min, alternamente de 0,1 a 0,5 g / 10 min, alternamente de 0,1 a 0,4 g / 10 min, alternamente de 0,8 a 5,0 g / 10 min, alternamente de 3,0 a 5,0 g / 10 min, alternamente de 3,4 a 5,0 g / 10 min, medido de acordo com o Método de Melting Index (MI) test at 190 °C and 2.16 kilograms, according to ASTM D1238-13; a Mz of 600,000 to 1,900,000 grams per mole (g / mol), alternatively from 600,000 to 1,720,000 g / mol, alternatively from 600,000 to 1,700,000 g / mol, alternatively from 600,000 to 1,650,000 g / mol, alternatively from 600,000 to 1,600,000 g / mol, alternatively from 630,000 to 1,600,000 g / mol, alternatively from 680,000 to 1,600.000 g / mol, measured according to the Gel Permeation Chromatography (GPC) Test Method, described further below; and a shear viscosity decrease index (SHI) of 5.35 to 75 η*(1.0) / η*(100), alternatively from 5.35 to 70 η*(1.0) / η*(100), alternatively from 5.35 to 60 η*(1.0) / η*(100), alternatively from 5.35 to 50 η*(1.0) / η*(100), alternatively from 5.35 to 40 η*(1.0) / η*(100), alternatively from 5.35 to 38 η*(1.0) / η*(100), alternatively from 5.35 to 36 η*(1.0) / η*(100), alternatively from 5.35 to 34 η*(1.0) / η*(100), measured according to the SHI Test Method, described further below. Aspect 2. The B-LLDPE copolymer of aspect 1 is further described as having a first melt flow ratio (I21 / I2) of 32 to 140, alternatively 32 to 100, alternatively 32 to 85, alternatively 32 to 75, alternatively 35 to 75, measured according to the MI test method at 190 °C and 21.6 and 2.16 kilograms, respectively, according to ASTM D1238-13 standards.Aspect 3. The B-LLDPE copolymer of aspect 1 and / or aspect 2 is further described by a first molecular weight ratio (Mz / Mw) of 4 to 11, alternatively 4 to 10, alternatively 4 to 9.5, alternatively 4.1 to 9.5, alternatively 5.0 to 9.0, measured according to the GPC Test Method, where Mz is molecular weight and Mw is weight-average molecular weight. Aspect 1, aspect 2 and / or aspect 3 may further include a Mn of. Petition 870240092769, dated 10 / 30 / 2024, p. 20 / 141 8 / 59 7,000 to 32,500 grams per mol (g / mol), alternatively from 7,200 to 30,000 g / mol, alternatively from 7,500 to 27,000 g / mol, alternatively from 7,500 to 23,000 g / mol, alternatively from 7,500 to 20,000 g / mol, alternatively from 7,500 to 16,000 g / mol, alternatively from 7,500 to 15,500 g / mol, according to the GPC Test Method, described above; a Mw series from 116,000 to 200,000 g / mol, alternatively from 118,000 to 188,000 g / mol, alternatively from 120,000 to 180,000 g / mol, alternatively from 120,000 to 166,000 g / mol, alternatively from 120,000 to 160,000 g / mol, alternatively from 141,000 to 160,000 g / mol, alternatively from 146,000 to 160.000 g / mol, measured according to the Gel Permeation Chromatography (GPC) Test Method, described further below; a tan delta (tan δ) of 1.5 to 16.0, alternatively from 1.5 to 9.0, alternatively from 1.5 to 6.0, alternatively from 1.6 to 5.8, alternatively from 1.65 to 4.8, measured at 190 °C on the C side and a frequency of 0.1000 radians per second (rad / s) according to the Tan Delta (Tan δ) Test Method, described further below.

[0024] Aspect 4. The B-LLDPE copolymer of aspect 1, further described by I2, which is from 0.80 g / 10 min to 1.2 g / 10 min, alternatively from 0.9 g / 10 min to 1.1 g / 10 min, alternatively from 0.94 g / 10 min to 1.05 g / 10 min, measured according to Test Method MI at 190 °C and 2.16 kilograms, according to ASTM D1238-13; and Mz is from 630,000 g / mol to less than 1,700,000 g / mol, alternatively from 1,400,000 g / mol to 1,630,000 g / mol, measured according to Test Method GPC. Aspect 5. The B-LLDPE copolymer of aspect 4 is further described by a density of 0.916 to 0.926 g / cm3, or alternatively 0.916 to 0.919 g / cm3, measured in accordance with ASTM D792-13, Method B. Aspect 6. The B-LLDPE copolymer of aspect 4 and / or aspect 5 is further described by a Tan Delta (Tan δ) of 2 to 6, measured at 190 °C and a frequency of 0.1000 radians per second (rad / s) in accordance with the Tan Delta (Tan δ) Test Method described further below. Aspect 7.The B-LLDPE copolymer of aspect 6 is further described by a Tan δ of 5.6 to 6, measured at 190 °C and a frequency of 0.1000 rad / s according to the Tan Delta Test Method; a density of 0.916 to 0.918. Petition 870240092769, dated 10 / 30 / 2024, p. 21 / 141 9 / 59 g / cm3, measured in accordance with ASTM D792-13, Method; and an Mz / Mw value of 5 to 5.6, measured in accordance with the GPC Test Method, as provided herein. Aspect 8. The B-LLDPE copolymer of any combination of aspect 4, aspect 5, aspect 6 and / or aspect 7 further described by an I21 / I2 of 40 to 140, alternatively 45 to 120, alternatively 50 to 95, measured in accordance with the Melt Index Test Method at 190 °C and 21.6 and 2.16 kilograms, respectively, in accordance with ASTM D1238-13. Aspect 9. The B-LLDPE copolymer of any combination of aspect 4, aspect 5, aspect 6, aspect 7 and / or aspect 8 further described by a first molecular weight ratio (Mz / Mw) of 5 to 11, alternatively of 5.5 to 10.1, alternatively of 4.5 to 8, measured according to the GPC Test Method, wherein the molecular weight of Mz is the average molecular weight and Mw is the weight-average molecular weight. Aspect 10.The B-LLDPE copolymer of any combination of aspect 4, aspect 5, aspect 6, aspect 7, aspect 8 and / or aspect 9 further described by a low elution fraction of 1.7 percent to 10 percent, as measured by iCCD technique, described further below, from above 25 °C to below 35 °C. Aspect 11. The B-LLDPE copolymer of any combination of aspect 4, aspect 5, aspect 6, aspect 7, aspect 8, aspect 9 and / or aspect 10 further described by a high density fraction of 0.9 percent to 4.1 percent, alternatively from 0.9 percent to 3.4 percent, as measured by iCCD technique, described below, from above 95 °C to below 115 °C.The B-LLDPE copolymer of each of aspects 4 to 11 may have a molecular weight dispersion (Mw / Mn), which may be referred to as molecular weight distribution, of 5.0 to 16.5, alternatively, the Mw / Mn of the BLLDPE copolymer may be 5.0 to 10.0, all measured according to the GPC Test Method, described later. In addition, the B-LLDPE copolymer of each of aspects 4 to 11 may have a melt strength (measured at 190 °C) of 2.0 cN to 5.0 cN, alternatively, the melt strength is 2.4 cN to 5.0 cN, measured according to the Melt Strength Test Method, described later. Petition 870240092769, dated 10 / 30 / 2024, p. 22 / 141 10 / 59

[0025] Aspect 12. The B-LLDPE copolymer of aspect 1, wherein the density is 0.915 to 0.920 g / cm3, measured according to ASTM D792-13, Method B; the I2 is 3.2 g / 10 min to 3.6 g / 10 min, alternatively the handle I of side 2 is 3.4 g / 10 min to 3.6 g / 10 min measured according to Test Method MI at 190 °C and 2.16 kilograms, according to ASTM D1238-13; the Mz is 800,000 to 1,200,000 g / mol, measured according to the GPC Test Method; and the SHI is 10 to 12 η*(1.0) / η*(100) measured according to the SHI Test Method. Aspect 13. The B-LLDPE copolymer of aspect 12 is further described by a tan δ of 3 to 4, measured at 190 °C and a frequency of 0.1000 radians per second (rad / s) according to the Tan δ Test Method. Aspect 14. The B-LLDPE copolymer of aspect 12 and / or aspect 13 is further described by I21 / I2 of 90 to 100, measured according to the Melt Index Test Method, at 190 °C and 21.6 and 2.16 kilograms, respectively, according to ASTM D1238-13.Aspect 15 The B-LLDPE copolymer of any combination of aspect 12, aspect 13 and / or aspect 14 further described by a first MWR (Mz / Mw) of 8 to 9, measured in accordance with the GPC Test Method. The B-LLDPE copolymer of each of aspects 12 to 15 may have an Mw / Mn of 6.0 to 8.0, alternatively, the Mw / Mn of the B-LLDPE copolymer may be 6.5 to 7.5, all measured in accordance with the GPC Test Method described further. Furthermore, the B-LLDPE copolymer of each of aspects 12 to 15 may have a melt strength (measured at 190 °C) of 3.0 cN to 4.0 cN, or alternatively, the melt strength is 3.5 cN to 3.8 cN, measured according to the Melt Strength Test Method described later.

[0026] Aspect 16. The B-LLDPE copolymer of aspect 1 having a density of 0.9160 to 0.9200 g / cm3, alternatively, of 0.9170 to 0.9190 g / cm3, measured according to ASTM D792-13, Method B; the I2 of 0.1 g / 10 min to 0.8 g / 10 min, alternatively of 0.2 g / 10 min to 0.7 g / 10 min, alternatively of 0.3 g / 10 min to 0.7 g / 10 min, measured according to the Melt Index Test Method at 190 °C and 2.16 kilograms, according to ASTM D1238-13; the Mz of 650,000 to 1,900,000 g / mol, alternatively Petition 870240092769, dated 10 / 30 / 2024, p. 23 / 141 11 / 59 from 650,000 to 1,500,000 g / mol, alternatively from 850,000 to 1,500,000 g / mol, measured according to the GPC Test Method; and the SHI from 6 to 32 η*(1.0) / η*(100), alternatively from 12 to 32 η*(1.0) / η*(100), alternatively from 20 to 32 η*(1.0) / η*(100), measured according to the SHI Test Method. Aspect 17. The B-LLDPE copolymer of aspect 16 is further described by a Tan δ of 1.6 to 3.1, measured at 190 °C and a frequency of 0.1000 radians per second (rad / s) according to the Tan δ Test Method. Aspect 18. The B-LLDPE copolymer of aspect 16 and / or 17 further described by a low elution fraction of 3.8 percent to 4.6 percent, as measured by the iCCD technique, from above 25 °C to below 35 °C. Aspect 19.The B-LLDPE copolymer of any combination of aspect 16, aspect 17 and / or aspect 18 further described by a high-density fraction of 6 percent to 10 percent, as measured by the iCCD technique, above 95 °C to below 115 °C. Aspect 20. The B-LLDPE copolymer of any combination of aspect 16, aspect 17, aspect 18 and / or aspect 19, wherein I2 is 0.3 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. Aspect 21. The B-LLDPE copolymer of any combination of aspect 16, aspect 17, aspect 18, aspect 19 and / or aspect 20 further described by an I21 / I2 of 32 to 75, measured according to the Melt Index Test Method at 190 °C and 21.6 and 2.16 kilograms, respectively, according to ASTM D1238-13. Aspect 22.The B-LLDPE copolymer of any combination of aspect 16, aspect 17, aspect 18, aspect 19, aspect 20 and / or aspect 21 described further may have an Mw / Mn ratio of 4 to 10, measured according to the GPC Test Method. The B-LLDPE copolymer of each of aspects 16 to 22 may have an Mw / Mn ratio of 5.0 to 12.0, alternatively, the Mw / Mn of the B-LLDPE copolymer may be 5.5 to 6.5, all measured according to the GPC Test Method described further. In addition, the B-LLDPE copolymer of each of aspects 16 to 22 may have a melt strength (measured at 190 °C) of 7.0 cN to 10.0 cN. Petition 870240092769, dated 10 / 30 / 2024, p. 24 / 141 12 / 59 Alternatively, the fusion strength is 7.0 cN to 9.0 cN, measured according to the Fusion Strength Test Method described later.

[0027] Aspect 23. The B-LLDPE copolymer of any combination of aspect 1 to aspect 22, 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 24. The B-LLDPE copolymer of any combination of aspects 1 to 23, wherein the number of short-chain branches (SCB) per 1,000 carbon atoms (C) measured according to the GCP Test Method is greater in Mw than in Mn. Aspect 25. The BLLDPE copolymer of any combination of aspects 1 to 23, wherein the number of SCB per 1,000 C measured according to the GCP Test Method is 14 to 110 percent greater in Mw than in Mn. Aspect 26. The B-LLDPE copolymer of any combination of aspects 4 to 9 further described by an SCB per 1,000 C being 35 to 105 percent greater in Mw than in Mn. Aspect 27. The B-LLDPE copolymer of any combination of aspects 4 to 9 is still described by an SCB per 1,000 C being 35 to 45 percent higher in Mw than in Mn. Aspect 28. The B-LLDPE copolymer of any combination of aspects 12 to 15 is still described by an SCB per 1.000 C being 55 to 60 percent higher in Mw than in Mn. Aspect 29. The B-LLDPE copolymer of any combination of aspect 16 to aspect 22 further described by an SCB per 1,000 C being 20 to 55 percent higher in Mw than in Mn. Aspect 30. The B-LLDPE copolymer of any combination of aspects 1 to 23, wherein the number of SCB per 1,000 C in Mw measured according to the GCP Test Method is from 18 to 40. Aspect 31. The B-LLDPE copolymer of any combination of aspects 4 to 9 further described by an SCB per 1,000 C in Mw measured according to the GCP Test Method of 19 to 30. Aspect 32. The BLLDPE copolymer of any combination of aspects 4 to 9 further described by... Petition 870240092769, dated 10 / 30 / 2024, p. 25 / 141 13 / 59 one SCB per 1,000 C in Mw measured according to the GCP Test Method of 24.5 to 30 and one SCB per 1,000 C in Mn measured according to the GCP Test Method of 12 to 21.5. Aspect 33. The B-LLDPE copolymer of any combination of aspect 12 to aspect 15 further described by an SCB per 1,000 C in Mw measured according to GCP Test Method 27 to 30 and an SCB per 1,000 C in Mn measured according to GCP Test Method 17 to 19. Aspect 34. The B-LLDPE copolymer of any combination of aspect 16 to aspect 22 further described by an SCB per 1,000 C in Mw measured according to GCP Test Method 18.5 to 22 and an SCB per 1,000 C in Mn measured according to GCP Test Method 12.5 to 15.6. Aspect 35. The B-LLDPE copolymer of any combination of aspect 16 to aspect 22 further described by an SCB per 1,000 C in Mw measured according to GCP Test Method 19 to 22 and an SCB per 1.000 C in Mn measured according to the GCP Test Method of 12.5 to 15.6.

[0029] Aspect 36. The B-LLDPE copolymer of any combination of aspects 1 to 23 has an I5 value, as measured according to ASTM D1238-13, of 1 to 18 and an I21 / I5 value of 10 to 27. Aspect 37. The B-LLDPE copolymer of any combination of aspects 4 to 9 is further described by an I5 value, as measured according to ASTM D1238-13, of 2.5 to 5. Aspect 38. The B-LLDPE copolymer of any combination of aspects 4 to 9 is further described by an I5 value, as measured according to ASTM D1238-13, of 2.5 to 3.5. Aspect 39. The B-LLDPE copolymer of any combination of aspects 12 to 15 additionally described by an I5 value, as measured in accordance with ASTM D1238-13 17 to 18. Aspect 40. The BLLDPE copolymer of any combination of aspects 16 to 22 additionally described by an I5 value, as measured in accordance with ASTM D1238-13 1 to 3. Aspect 41.The B-LLDPE copolymer of any combination of aspect 16 to aspect 22 additionally described by a value of I5, as measured in accordance with ASTM D1238-13 from 1 to 2. Petition 870240092769, dated 10 / 30 / 2024, p. 26 / 141 14 / 59

[0030] Aspect 42. The B-LLDPE copolymer of any combination of aspects 1 to 23 has an I21 / I5 value of 10 to 27. Aspect 43. The B-LLDPE copolymer of any combination of aspects 4 to 9 is further described by an I21 / I5 value of 11 to 26. Aspect 44. The B-LLDPE copolymer of any combination of aspects 4 to 9 is further described by an I21 / I5 value of 14 to 18. Aspect 45. The B-LLDPE copolymer of any combination of aspects 12 to 15 is further described by an I21 / I5 value of 17 to 18. Aspect 46. The B-LLDPE copolymer of any combination of aspects 16 to 22 is further described by an I21 / I5 value of 10 to 22.

[0031] Aspect 47. A manufactured article comprising a molded form of B-LLDPE copolymers of any of aspects 1 to 46. Aspect 48. The manufactured article of aspect 47 selected from: films, sheets, packaging film and non-packaging film and injection molded articles. The manufactured article may be a film such as a molded film or a blown film. Aspect 49. The manufactured article of aspect 47 or 48 selected from agricultural film, food packaging, garment bags, waste bags, garbage bags, ice bags, supermarket bags, heavy-duty bags, construction film, geomembrane, industrial sheets, shrink films and pallet films, sacks, buckets, freezer containers, lids and toys.

[0032] Aspect 50. A method for making B-LLDPE copolymers of any one of aspect 1 to aspect 46, the method comprising contacting ethylene (C2) and a comonomer (Cx, as provided herein) with a bimodal catalyst system (as provided herein) in a single gas-phase polymerization reactor containing a fluidized resin bed, thereby producing the B-LLDPE copolymer of the present disclosure.

[0033] Aspect 51. A method for producing B-LLDPE copolymers of any one of aspect 1 to aspect 46, the method comprising contacting ethylene (C2) and a comonomer (Cx) selected from 1-butene (Cx = C4), 1-hexene (Cx = C6) or both (Cx = C4 and C6) in a molar ratio of Petition 870240092769, dated 10 / 30 / 2024, page 27 / 141 15 / 59 comonomer for ethylene (Cx / C2) from 0.005 to 0.30, alternatively 0.008 to 0.20, alternatively 0.010 to 0.18 with a bimodal catalyst system comprising bis[(2-pentamethylphenylamido)ethyl]amine zirconium dibenzyl in the presence of molecular hydrogen gas (H2) at a hydrogen to ethylene molar ratio (H2 / C2) of 0.001 to less than 0.012, alternatively 0.001 to less than 0.01, alternatively 0.001 to 0.008, alternatively 0.002 to 0.005, alternatively 0.001 to 0.003, alternatively 0.002 to less than 0.012, alternatively 0.002 to less than 0.01, alternatively 0.002 to 0.008, alternatively 0.002 to 0.005, alternatively 0.002 to 0.003 all in a simple gas-phase polymerization reactor containing a fluidized resin bed 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 bimodal linear low-density polyethylene copolymer. Aspect 52.The 50 and / or 51 aspect ratio method, where the H2 / C2 molar ratio is from 0.001 to 0.003.

[0034] Aspect 53. The method of aspect 50, aspect 51 and / or aspect 52, wherein the method includes an adjustment solution in the presence of molecular hydrogen gas (H2) and an inert condensation agent (ICA) under (co)polymerization conditions; wherein before being mixed with the adjustment solution it consists essentially of a (tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconium complex (pro-catalyst, e.g., (tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)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), the bis(2-pentamethylphenylamido)ethyl)amine zirconium dibenzyl complex and a (tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconium, all arranged on a solid support (e.g., a hydrophobic pyrolyzed silica);and wherein 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 (molar ratio; Petition 870240092769, dated 10 / 30 / 2024, page 28 / 141 16 / 59 of H2 / C2) from 0.001 to less than 0.012, alternatively 0.001 to less than 0.01, alternatively 0.001 to 0.008, alternatively 0.002 to 0.005, alternatively 0.001 to 0.003; alternatively and a molar ratio between comonomer (Cx) and ethylene (molar ratio of Cx / C2) from 0.005 to 0.30, alternatively 0.008 to 0.20, alternatively 0.010 to 0.18. The B-LLDPE copolymer can be of any of aspects 1 to 23. In an alternative embodiment of aspect 50, aspect 51, aspect 52 and / or 53, the bimodal catalyst system can be prepared and then introduced into the polymerization reactor(s) as a suspension (e.g., semi-fluid paste) in a mineral oil and the compensation solution can be prepared and introduced into the polymerization reactor(s) as a solution, for example, in a liquid alkane.

[0035] Aspect 54. The method of aspect 50, aspect 51, aspect 52 and / or aspect 53, wherein the bimodal catalyst system comprises a metallocene other than (tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconium-X2 (X = chloride, methyl).

[0036] Aspect 55. The method of aspect 50, aspect 51, aspect 52, aspect 53 and / or 54, wherein the bimodal catalyst system comprises (1,3-dimethyl-tetrahydroindenyl)(methylcyclopentadienyl)-zirconium dimethyl.

[0037] Aspect 56. The method of aspect 50, aspect 51, aspect 52, aspect 53, aspect 54 and / or aspect 55, 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 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 fluidized paste phase reactor or two fluidized paste phase reactors).

[0038] An activator (also known as a cocatalyst) to activate procatalysts to form catalysts can be used with the aspect 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. A Petition 870240092769, dated 10 / 30 / 2024, page 29 / 141 17 / 59 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's 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.

[0039] A catalyst produced by activation of (tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconium dichloride or (tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconium dimethyl chloride may be called a (tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconium complex. The catalyst produced by activation of (tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconium dichloride may be the same as or different from the catalyst produced by activation of (tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconium dimethyl chloride. The activator metal is typically different from the procatalyst metal. The molar ratio of the activator metal content to the pro-catalyst(s) metal content can 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 can be a Lewis acid, a non-coordinating ionic activator, or an ionizing activator or a Lewis base, an alkylaluminum, or an alkylaluminoxane.Alkylaluminum may be a trialkylaluminum, alkylaluminum halide, or alkylaluminum alkoxide (diethylaluminum ethoxide). Trialkylaluminum may be trimethylaluminum, triethylaluminum (TEAl), tripropylaluminum, triisobutylaluminum, and the like. Alkylaluminum halide may be diethylaluminum chloride. Alkylaluminoxane may be a methylaluminoxane (MAO), ethylaluminoxane, or isobutylaluminoxane. The activator may be an MAO that is a modified methylaluminoxane (MMAO). The corresponding activating species may be a Lewis acid derivative, non-coordinating ionic activator, ionization activator, Lewis base, alkylaluminum, or 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. Petition 870240092769, dated 10 / 30 / 2024, p. 30 / 141 18 / 59 derived from the byproduct is a type of methylaluminoxane 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 may be fed into the polymerization reactor(s) in wet mode as a solution thereof in an inert liquid such as mineral oil or toluene, in semi-fluid paste mode as a suspension, or in dry mode as a powder.

[0040] Bimodal, having two different polymer components (each produced from a separate and distinct catalyst and / or process condition) and / or having two peaks that can be determined from a molecular weight distribution (MWD), such as MWD measured by gel permeation chromatography (GPC), for example, Mw / Mn measured by GPC.

[0041] Multimodal, which has more than one different polymeric component (each produced from a separate and distinct catalyst condition and / or process) and / or which has at least 2 peaks (e.g., 2 or 3 peaks) that can be determined from an MWD, such as MWD measured by GPC, e.g., Mw / Mn measured by GPC.

[0042] 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 yields a bimodal polyethylene composition. In some respects, the bimodal catalyst system has only two catalysts and is prepared from two, and only two, procatalyst 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 the conditions of Petition 870240092769, dated 10 / 30 / 2024, page 31 / 141 19 / 59 (co)polymerization, the lower molecular weight (LMW) polyethylene component and the other catalyst compound produce the higher molecular weight (HMW) polyethylene component. The LMW and HMW polyethylene components 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 B-LLDPE copolymer of the present disclosure are free of a Ziegler-Natta catalyst.

[0043] 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 of the activators. 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, 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) bonding 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.

[0044] One of the pro-catalysts, useful for making a bimodal catalyst system and / or making the adjustment solution, can be a Petition 870240092769, dated 10 / 30 / 2024, p. 32 / 141 20 / 59 composed of a metallocene 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.

[0045] In formula (I), Figure 1, each of the groups R1 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).

[0046] 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.

[0047] 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 (C7-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).

[0048] In some respects, each X in formulas (I) to (III) is independently a halide, alkyl (01-04) 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.

[0049] In formulas (IV) to (IX), Figure 1, Me is methyl (CH3), Pr represents Petition 870240092769, dated 10 / 30 / 2024, p. 33 / 141 21 / 59 a propyl group (i.e., CH2CH2CH3) and each l substituent in a ring represents a methyl group.

[0050] 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 containing group 14 or a 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 charge of Y, Z, and L in formula (A) and the total formal charge 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 organo-heterohydrolene (C2-C20) group.R3 may be absent; alternatively, R3 is H, a halogen atom, a hydrocarbyl group (C1-C20), a heterohydrocarbyl group (C1-C20), or an organoheteroyl 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 (C6Petition 870240092769, dated 10 / 30 / 2024, page 34 / 141. 22 / 59 C20), a substituted aryl (C6-C20) group, a cycloalkyl (C3-C20) group, a substituted cycloalkyl (C3-C20) group, a bicyclic aralkyl (C8-C20) group, or a substituted bicyclic aralkyl (C8-C20) group. R6 and R7 may be H or 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.

[0051] 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 made by activation (with the activator) of a pro-catalyst compound selected from (pentamethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconium dichloride, bis(n-butylcyclopentadienyl)zirconium dichloride, (pentamethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconium dimethyl and bis(n-butylcyclopentadienyl)zirconium dimethyl.The non-metallocene catalyst compound can be a non-metallocene ligand-metal complex, such as a non-metallocene group 4 ligand-metal complex, which can be produced by activation (with the activator) of a pro-catalyst compound selected from bis(2-(2,4,6-trimethylphenylamido)ethyl)aminozirconium dibenzyl and bis(2(pentamethylphenylamido)ethyl)aminozirconium dibenzyl.

[0052] In some respects, the bimodal catalyst system can be made by activating, according to the contact method with an activator, a combination of a metallocene catalyst compound which is (tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconium dichloride and a non-metallocene pro-catalyst 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, Petition 870240092769, dated 10 / 30 / 2024, page 35 / 141 23 / 59 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.

[0053] Each of the catalyst 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., fumed silica), alumina, a clay, or talc. Fumed silica can be hydrophilic (untreated), or alternatively hydrophobic (treated).In some respects, the carrier is hydrophobic fumed silica, which can be prepared by treating untreated fumed silica with a treatment agent such as dimethyldichlorosilane, a polydimethylsiloxane fluid, or hexamethyldisilazane. In some respects, the treatment agent is dimethyldichlorosilane.

[0054] 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).

[0055] The bimodal catalyst system can be introduced to 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. In some aspects of the present development, the bimodal catalyst system is commercially available under the brand name PRODIGY™ Bimodal Catalysts, for example, BMC-200, from Univation Technologies, LLC. Petition 870240092769, dated 10 / 30 / 2024, p. 36 / 141 24 / 59

[0056] Alpha-oleins (C3-C20) are compounds, as seen in formula (I): H2C=C(H)-R, where R is a linear chain of the alkyl group (C1-C18). The alkyl group (C1-C18) is a monovalent unsubstituted 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 i, the other embodiment, the alpha-olefin (C3-C20) is selected from 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) 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 (C3C20) from which the comonomeric units of the APM polyethylene component are derived. Preferably, the alpha-olefin is 1-hexene, 1-butene, or a combination thereof.

[0057] Consisting 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 anything else. As applied to the description of an embodiment of the bimodal catalytic system consisting essentially of bis(2-pentamethylphenylamido)ethyl)amine zirconium dibenzyl and (tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)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 other than the ligands bis(2-pentamethylphenylamido)ethyl)amine, benzyl, tetramethylcyclopentadienyl and n-propylcyclopentadienyl. One or more of the benzyl and chloride leaving groups may be absent from the Zr in the bimodal catalyst system. The expression consisting essentially of being applied to Petition 870240092769, dated 10 / 30 / 2024, p. 37 / 141 25 / 59 description of the fitting solution means that the fitting solution is unsupported (i.e., not arranged in a particulate solid) and is free of a Ziegler-Natta catalyst or any other organic ligand other than tetramethylcyclopentadienyl and n-propylcyclopentadienyl ligands. The expression essentially consists 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 essentially consists of or essentially consists of, respectively; alternatively by consists of or consists of, respectively.

[0058] Consists of and that consists of. Closed expressions that exclude anything not specifically described by the limitation they modify. In some respects, either, alternatively, each expression that essentially consists of or essentially consists of can be replaced by the expression that consists of or consists of, respectively.

[0059] (co)polymerization conditions. Any effective outcome variable or combination of such variables, such as catalyst composition; amount of reagent; molar ratio of 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.

[0060] Alternatively, at least one of the (co)polymerization conditions may be fixed (i.e., unchanged) during the production of the B-LLDPE copolymer. Such fixed (co)polymerization conditions may be referred to herein as steady-state (co)polymerization conditions. Steady-state (co)polymerization conditions Petition 870240092769, dated 10 / 30 / 2024, page 38 / 141 26 / 59 permanent are useful for continuously producing B-LLDPE copolymer modalities having the same polymeric properties.

[0061] Alternatively, at least one, alternatively two or more of the (co)polymerization conditions may be varied within their defined operating parameters during the production of the BLLDPE copolymer in order to transition from the production of a first embodiment of B-LLDPE conditions having a first set of polymer properties to a second embodiment of B-LLDPE copolymer having a second set of polymer properties, wherein the first and second sets of polymer 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 of alpha-olefin (C3-C20) / ethylene comonomer feeds in the inventive copolymerization method produces a lower density of the resulting B-LLDPE copolymer product.At a given comonomer / ethylene molar ratio, the molar ratio of the procatalyst in 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 changing from a first operating temperature of 80 °C to a second operating temperature of 81 °C, or changing from a third. Petition 870240092769, dated 10 / 30 / 2024, page 39 / 141 27 / 59 operating temperature of 82 °C to a third operating temperature of 85 °C. Similarly, another example of variation of an operating parameter includes variation of the molar ratio between molecular hydrogen and ethylene (H2 / C2) from 0.0017 to 0.0018 or from 0.0020 to 0.0019. Likewise, another example of variation of an operating parameter includes variation of the molar ratio between the comonomer (Cx) and ethylene (molar ratio of Cx / C2) from 0.006 to 0.010 or from 0.008 to 0.009. Combinations of two or more of the preceding example variations are included herein. Transition from one set to another set of (co)polymerization conditions is permitted in the direction of (co)polymerization conditions, provided that the operating parameters of both sets of (co)polymerization conditions are within the ranges defined in this document.A beneficial consequence of the previous transition is that any property value described for the B-LLDPE copolymer, or its BPM or APM polyethylene component, can be achieved by one skilled in the art by considering the teachings of the present invention.

[0062] The (co)polymerization conditions may also include a high-pressure liquid-phase or gas-phase polymerization reactor and 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 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 4,453,399; US 4,588,790; US 4,994,534; US 5,352,749; US 5,462,999; and US 6,489,408. The gas-phase polymerization reactor / method may be a fluidized bed reactor / method, as described in US 3,709,853; US 4,003,712; US 4,011,382; US 4,302,566; US 4,543,399; US 4,882,400; US 5,352,749; US 5,541,270; EP-A-0 802 202 and Belgian patent no. 839,380.These patents reveal gas-phase polymerization processes in which the medium of... Petition 870240092769, dated 10 / 30 / 2024, page 40 / 141 28 / 59 Polymerization 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 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.

[0063] The (co)polymerization conditions for liquid 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 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). The (co)polymerization conditions for gas phase reactors / polymerizations may additionally include an amount (e.g., 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 can be added to the gas-phase reactor to inhibit the formation or accumulation of static charge within it.

[0064] The (co)polymerization conditions may also 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 of hydrogen to total monomer (H2 / monomer), hydrogen to ethylene (H2 / C2) or hydrogen to comonomer (H2 / α-olefin) can be from 0.0001 to less than 0.012, alternatively 0.001 to less than 0.01, Petition 870240092769, dated 10 / 30 / 2024, page 41 / 141 29 / 59 alternatively 0.0005 to 0.009, alternatively 0.0009 to 0.008, alternatively 0.001 to less than 0.01, alternatively 0.001 to 0.005, alternatively 0.001 to 0.003.

[0065] The (co)polymerization conditions may include a partial pressure of ethylene in the polymerization reactor(s) independently of 690 to 3,450 kilopascals (kPa, 100 to 500 pounds per square inch absolute (psia)), alternatively 1,030 to 2,070 kPa (150 to 300 psia), alternatively 1,380 to 1,720 kPa (200 to 250 psia), alternatively 1,450 to 1,590 kPa (210 to 230 psia), for example, 1,520 kPa (220 psia). 1,000 psia = 6.8948 kPa.

[0066] 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.

[0067] Ethylene. A compound with the formula H2C=CH2. A polymerizable monomer.

[0068] Feeds. Quantities of reagents and / or reactants 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 reagents and reactants in the reactor at any given time.

[0069] 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 can Petition 870240092769, dated 10 / 30 / 2024, pp. 42 / 141 30 / 59 overlaps the upper portion of the Mw range for the BPM polyethylene component, provided that in any embodiment of the BLLDPE 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 the catalyst prepared by activation of a non-metallocene group 4 metal-ligand complex.

[0070] 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.

[0071] Inert condensing agent (ICA). An inert liquid useful for cooling materials in polymerization reactor(s) (e.g., a fluidized bed reactor). In some respects, the ICA is an alkane (C5-C20), alternatively an alkane (C5-C15), alternatively an alkane (C5-C10). In some respects, the 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 two or more thereof. In some respects, the ICA is isopentane (i.e., 2-methylbutane). The polymerization method of the invention, which uses the ICA, may be referred to herein as an inert condensation mode operation (ICMO).Gas phase concentration 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 mol percent, alternatively, from 3 to 12 mol percent, alternatively, from 5 to 10 mol percent. Other values ​​are also possible (e.g., up to 26 mol percent; when used in quantities of about 20 mol percent to 26 mol percent, the process can be termed as operating in supercondensation mode). Petition 870240092769, dated 10 / 30 / 2024, pp. 43 / 141 31 / 59

[0072] 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.

[0073] Polyethylene. A macromolecule, or collection of macromolecules, composed of repeating units, wherein 50 to 100 mol percent (mol %), alternatively 70 to 100 mol percent, alternatively 80 to 100 mol percent, alternatively 90 to 100 mol percent, alternatively 95 to 100 mol percent, alternatively any of the preceding ranges wherein the upper endpoint is < 100 mol percent, of such repeating units are derived from the ethylene monomer and, in aspects wherein there are less than 100 mol percent of ethylene repeating units, the remaining repeating units are comomeric units derived from at least one alpha-olefin (C3-C20); or a collection of such macromolecules. Linear low-density polyethylene (LDPE). A macromolecule with a substantially linear structure.

[0074] 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.

[0075] Initialization or restart of the polymerization reactor(s) illustrated with a fluidized bed reactor. The initialization of a reactor Petition 870240092769, dated 10 / 30 / 2024, page 44 / 141 32 / 59 Annealed fluidized bed (cold start) or the restart of a transition fluidized bed reactor (hot start / transition) includes a period of time preceding (co)polymerization conditions. The start or restart may include the use of a pre-loaded or loaded seeding, respectively, in the fluidized bed reactor. The seeding may consist of polyethylene powder. The bed polyethylene may be an LDPE, alternatively an LLDPE, alternatively a bimodal LLDPE, or alternatively a previously produced embodiment of the B-LLDPE copolymer.

[0076] Fluidized bed reactor startup or restart may also include gas atmosphere transitions comprising purge air or other unwanted reactor gas(es) with a dry (anhydrous) inert purge gas, followed by purging the dry inert purge gas from the reactor with dry ethylene gas. The dry inert purge gas may consist essentially of molecular nitrogen (N2), argon, helium, or a mixture of two or more thereof. When not in operation, prior to startup (cold start), the fluidized bed reactor contains an air atmosphere. The dry inert purge gas may be used to sweep the air from a reconditioned fluidized bed reactor during the early startup stages to give the fluidized bed reactor an atmosphere consisting of the dry inert purge gas.Before restarting (for example, 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 the 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 with dry ethylene gas. The dry ethylene gas may additionally 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. Petition 870240092769, dated 10 / 30 / 2024, page 45 / 141 33 / 59 can be introduced separately and after the fluidized bed reactor atmosphere has been transferred to the ethylene. Gas atmosphere transitions can be made before, during, or after heating the fluidized bed reactor to the reaction temperature under (co)polymerization conditions.

[0077] 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.

[0078] Substance or article requiring covering. A naturally occurring or man-made material or manufactured article that would benefit from having a layer of B-LLDPE copolymer over, around, or on top of it. Substances requiring covering include those that are vulnerable to their external environments and those that require 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.Items requiring covering include orderly arrangements of materials (e.g., stacks of manufactured goods on a pallet that need packaging), boxes requiring shrink wrapping, loose manufactured goods that need to be shipped, and toxic or corrosive materials.

[0079] Adjustment solution. Any of the metallocene procatalyst compounds or non-metallocene procatalyst compounds described above are dissolved in the inert liquid solvent (e.g., liquid alkane). The adjustment 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 BLLPDE copolymer thus made. Examples of such at least one property are density, melt index I2, melt flow ratio, and mass dispersion. Petition 870240092769, dated 10 / 30 / 2024, pp. 46 / 141 34 / 59 molecular weight (Mw / Mn), which can be called the molecular weight distribution. The mixture of the bimodal catalyst system and the compensation solution can be fed into the polymerization reactor(s) in wet mode, or alternatively, it can be devolatilized and fed in dry mode. Dry mode is fed in the form of a dry powder or granules. When the mixture contains a solid support, 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.

[0080] 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 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 ethylaluminum dichloride).

[0081] Advantageously, the B-LLDPE copolymer has physical properties that are both 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.

[0082] Test samples of unfilled formulation modalities and Petition 870240092769, dated 10 / 30 / 2024, page 47 / 141 35 / 59 filled components can be produced separately in compression-molded plates. The mechanical properties of these formulations can be characterized using test samples cut from the compression-molded plates.

[0083] A compound includes all of its naturally occurring isotopes and isotopically enriched forms. The enriched forms may have medical or anti-counterfeiting uses.

[0084] In some respects, any compound, composition, formulation, mixture or reaction product in this document 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, 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 required for the compound, composition, formulation, mixture or reaction product (e.g., C and H, required by a polyolefin, or C, H and O required by an alcohol) are not excluded.

[0085] The following applies unless otherwise indicated. Alternatively, precedes a distinct embodiment. 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 lacking 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. Petition 870240092769, dated 10 / 30 / 2024, pp. 48 / 141 36 / 59 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.

[0086] Melt strength test method. Melt strength (MS) measurements were conducted on a Gottfert Rheotens 71.97 (Gottfert Inc. Rock Hill, SC, USA) connected to a Gottfert Rheotester 2000 capillary rheometer. A molten polymer (approximately 20–30 grams, pellets) was extruded through a capillary die with a flat entry angle (180 degrees), a capillary diameter of 2.0 mm, and an 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 to an acceleration clamping 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 velocity transmitted to the jawing rollers. The fusion strength was reported as the plateau force (cN) before wire rupture.The following conditions were used in the fusion resistance measurements: piston speed = 0.265 mm / second; wheel acceleration = 2.4 mm / s²; capillary diameter = 2.0 mm; capillary length = 30 mm; and barrel diameter = 12 mm.

[0087] Dart impact test method: measured in accordance with ASTM D1709-16a, Method A, Standard Test Methods for Impact Resistance of Plastic Film 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).

[0088] Density test method: measured in accordance with standards Petition 870240092769, dated 10 / 30 / 2024, pp. 49 / 141 37 / 59 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).

[0089] Elmendorf tear test method: measured in accordance with ASTM D1922-09, Standard Test Methods for Tear Propagation Resistance of Plastic Film and Thin Sheet Formation by Pendulum Method, Type B (Constant Radius). (Technically equivalent to ISO 6383-2.) Report results as normalized tear in the cross direction (DC) or machine direction (DM) in gram-force (gf).

[0090] Melt Index Test Method (190 °C, 2.16 kg, l2): Use ASTM D1238-13, Standard Test Method for Melt Rates 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).

[0091] Flow Index Test Method (190 °C, 21.6 kg, I21): Use ASTM D1238-13, Standard Test Method for Flow Rates of Thermoplastics by Extrusion Platform, using conditions of 190 °C / 21.6 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).

[0092] Flow rate test method (190 °C, 5.0 kg, I5): Test method: Use ASTM D1238-13, 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).

[0093] Flow Rate Ratio Test Method (190 °C, I21 / I2): calculated by dividing the Flow Index I21 Temperature Test Method value by the Melting Index I2 Melting Test Method value.

[0094] Flow Index Ratio Test Method (190 °C, I21 / I5): Petition 870240092769, dated 10 / 30 / 2024, page 50 / 141 38 / 59 calculated by dividing the Flow Index Temperature Test Method value I21 by the Flow Rate Control Test Method value I5.

[0095] Gel permeation chromatography (GPC) test method: number of short chain branches (SCB) per 1,000 carbon atoms; weight-average molecular weight test method: determine the z-average molecular weight (Mz), number-average molecular weight (Mn), and 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 three Polymer Laboratories PLgel 10 pm Mixed-B columns, all contained in an oven maintained at 160 °C. The method uses a BHT-treated TCB solvent 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 solvent-dissolved test polymer 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 range 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.Increase the flow rate in the apparatus 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: Petition 870240092769, dated 10 / 30 / 2024, page 51 / 141 39 / 59 logMx=& Ά--— logMpsaγ+1 αχ+1 where the subscript X represents the test sample, the subscript PS represents the PS standards, aPs = 0.67, KPs = 0.000175 and ax / 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 Kdri is a constant determined by calibrating the DRI, / indicates division and 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 circuit 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.

[0096] 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 to 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, Petition 870240092769, dated 10 / 30 / 2024, page 52 / 141 40 / 59 Rongjuan Cong and A. Willem deGroot. DeGroot. Analytical Chemistry 2014 86 (17), 8,649 to 8,656.

[0097] Secant modulus test method 1% or 2%: measured according to ASTM D882-12, Standard Test Methods for Tensile Properties of Thin Plastic Sheets. 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.

[0098] Shear Thinning Index (SHI) Test Method: Perform small strain (10%) oscillatory shear measurements on molten polymer at 190 °C using an advanced ARES-G2 rheometric expansion system 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. SHI (1 / 100) is defined as the ratio between the two viscosities and the two viscosities η*(1.0 kPa) en*(100 kPa), that is, η*(1.0) / η*(100).

[0099] Delta tangent test (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 advanced ARES-G2 rheometric expansion system 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 of the loss modulus (G) to the storage modulus (G') obtained at that frequency (ω), i.e., tan δ = G / G'. The value of the tangent δδ at the frequency Petition 870240092769, dated 10 / 30 / 2024, page 53 / 141 41 / 59 (ω) 0.1 radian / second is used later in Table 2.

[0100] 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.

[0101] Film Puncture Test Methods: ASTM D5748-95(2012), Standard Test Method for Stretch Film Lump 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 rate, such as 250 millimeters per minute (mm / min). The probe is coated with a 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 ability to absorb energy and resist puncture under these conditions. Results are expressed in strength in pounds per cubic inch (ft*lbf / in³).

[0102] Optical gloss test method: ASTM D2457-13, 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.

[0103] Optical opacity test method: ASTM D1003-13, Standard test method for opacity and luminous transmittance of transparent plastics. Measure opacity using an opacity meter. Express opacity as a percentage of luminous transmittance that passes through Petition 870240092769, dated 10 / 30 / 2024, page 54 / 141 42 / 59 of the film deflects from an incident beam by direct scattering. Results expressed as a percentage (%).

[0104] Method for determining zero shear viscosity: Perform small deformation (10%) oscillatory shear measurements on polymer melts at 190 °C using an advanced ARES-G2 rheometric expansion system from TA Instruments with parallel plate geometry to obtain complex viscosity data |η*| versus frequency data (ω). Determine the values ​​for the three parameters—zero shear viscosity, η0, characteristic viscous relaxation time, τη, and the width parameter, a—by curve fitting the obtained data using the following CY Model: L· . / α li + (τηω) 5 where |h*(w)| is the magnitude of the complex viscosity, h0 is zero shear viscosity, th is the viscous relaxation time, a is the width parameter, n is the power law index, and w is the angular frequency of the oscillatory shear.

[0105] Improved comonomer content distribution (iCCDI) 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 20-27 micron glass-packed guard column (MoSCi Corporation, USA) in 0.635 cm (ID) (or 1 / 4 (ID)) 10 cm (length) stainless steel 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 0.2-0.5 mm, EMD Chemicals catalog number 10181-3) can be used to pre-dry the ODCB solvent. The CEF instrument is equipped with an autosampler capable of... Petition 870240092769, dated 10 / 30 / 2024, page 55 / 141 43 / 59 N2 purge. 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. The flow rate during elution is 0.50 ml / min. Data is collected at one data point / second.

[0106] 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") stainless steel tubing (ID). 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.

[0107] Column temperature calibration was performed using a mixture of linear homopolymer polyethylene from 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 through 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 measured soluble fraction. Petition 870240092769, dated 10 / 30 / 2024, page 56 / 141 44 / 59 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).

[0108] For all resin, the integration windows are adjusted to integrate all chromatograms at elution temperatures (temperature calibration is specified above) ranging from 25.0 °C to 115 °C. The weight percentage of the high-density resin fraction (HDF) is defined by the following equation: HDF integrated area of ​​the elution window 95 to 115 °C integrated area of ​​the entire elution window 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 25–35 °C integrated area of ​​the entire elution window 25–115 °C x 100% Examples

[0109] 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 fumed silica produced by surface treatment with hydrophilic fumed silica (untreated) supported by dimethyldichlorosilane and methylaluminoxane (MAO) and used to feed a gas-phase polymerization reactor as a 20.0% by weight flowable paste in mineral oil. The molar ratio of MAO moles to (moles of bis(2-pentamethylphenylamido)ethyl)amine zirconium dibenzyl + moles of (tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconium dichloride) was 120:1.

[0110] 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 on CAB-O-SIL TS610, a hydrophobic pyrogenic silica produced Petition 870240092769, dated 10 / 30 / 2024, page 57 / 141 45 / 59 by surface treatment of hydrophilic (untreated) pyrogenic silica with dimethyldichlorosilane and methylaluminoxane (MAO) support, and used to feed a gas-phase polymerization reactor as a 20.9% by weight semi-fluid paste in mineral oil. The molar ratio of moles of MAO to (moles of bis(2-pentamethylphenylamido)ethyl)amine zirconium dibenzyl chloride + moles of (tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconium dichloride) was 148:1.

[0111] 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.

[0112] 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 the gas phase. Reported later in Table 1a / 1b.

[0113] Molecular hydrogen gas (H2): used in the molar ratio of H2 / C2 in Table 1a / 1b.

[0114] Compensation solution 1 (Compensation1): 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 procatalyst.

[0115] Compensation solution 2 (Compensation2): 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 procatalyst.

[0116] Inventive Examples (IE) 1 to 15: synthesis of embodiments of B-LLDPE copolymers. Embodiments of the BLLDPE copolymer of EI1 and EI15 were produced in separate polymerization reaction tests in a single continuous gas-phase fluidized bed reactor. The reactor of Petition 870240092769, dated 10 / 30 / 2024, page 58 / 141 A 46 / 59 fluidized bed reactor was configured with multiple gas feed inlets, catalyst feed inlets, and a product discharge outlet. The polymerization reaction utilized a bimodal catalyst system, a compensation solution, ethylene (C2), a comonomer, iCA1, and H2 gas. The compensation solution was used to adjust the melt flow index properties of the B-LLDPE copolymer. In one experimental run, the reactor was preloaded prior to startup with the granular resin comprising the seedbed. First, the gaseous atmosphere in the reactor containing the preloaded seedbed was dried using high-purity anhydrous molecular nitrogen to a moisture content below 5 ppm.Next, ethylene (C2), comonomer, molecular hydrogen gas (H2), and ICA1 (isopentane) feed gases were introduced to produce gas-phase conditions in the reactor for the desired operational gas-phase conditions, while the reactor was heated to the desired operating temperature. Gas-phase conditions were created and operational gas-phase conditions were maintained in the reactor at a partial pressure of ethylene in the reactor of 1,500 kPa (220 psia) and by measuring the gas feeds to the reactor at a molar ratio of comonomer / C2, a molar ratio of H2 / C2, and a molar percentage (mol%) of isopentane, as listed later in Tables 1a / 1b for each example and in Table 2 for specific Comparative Examples.Next, a feed from the adjustment solution was mixed with a feed from the Bimodal Catalyst System to generate a mixture of these, which is then fed to the reactor, where the mixture can be made with different molar ratios to refine the melt index and density properties of the bimodal LLDPE polymer being produced in the reactor to the desired target values ​​to give the modalities of the B-LLDPE copolymers (product) from EI1 to EI15. The 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 from... Petition 870240092769, dated 10 / 30 / 2024, page 59 / 141 47 / 59 copolymers from the Comparative Examples are summarized further in Tables 2a / 2b. To produce another embodiment of BLLDPE copolymer, wherein the density is 0.8900 to 0.9300 g / cm3, replicate the procedure, except adjust the comonomer / C2 molar ratio as necessary to achieve the desired density. Petition 870240092769, dated 10 / 30 / 2024, pp. 60 / 141 48 / 59 Table 1a. (Co)polymerization conditions for EI 1 to EI 8 EI 1 EI 2 EI 3 EI 4 EI 5 EI 6 EI 7 EI 8 Catalyst BMC1 BMC1 BMC1 BMC1 BMC1 BMC1 BMC1 BMC2 Compensation Type Compensation Compensation Compensation Compensation Compensation Compensation Compensation Compensation 11111112 Catalyst feed rate, ml / h 2.3 1.8 1.1 2.0 1.3 1.8 1.5 4.5 Compensation feed rate, ml / h 11.2 3.6 19.9 13.3 6.3 55.9 12.8 183 Production rate, kg / h 17.87 17.55 20.00 16.69 19.96 22.50 18.96 21.59 Residence time, h 2.21 2.20 1.92 2.30 2.00 1.82 2.10 1.90 Temp.Reactor bed temperature, °C 85.00 80.00 80.00 85.00 80.00 80.00 85.00 78.00 Bed weight, kg 39.51 38.37 38.37 39.33 39.87 39.55 39.33 40.10 FBD, lb / ft³ 13.90 13.40 13.40 14.00 13.50 14.50 12.90 15.60 Comonomer hexene butene butene hexene hexene hexene hexene hexene Molar ratio Cx / C² 0.047 0.140 0.139 0.039 0.046 0.043 0.040 0.0377 Flow ratio Cx / C2, kg / kg 0.106 0.241 0.222 0.084 0.100 0.083 0.079 0.086 Molar ratio H2 / C2 0.010 0.010 0.001 0.010 0.003 0.001 0.003 0.0110 Flow ratio H2 / C2, g / kg 0.707 0.722 0.062 0.719 0.187 0.063 0.195 0.713 APS, cm 0.272 0.130 0.147 0.203 0.206 0.201 0.152 0.133 Fine solids, % by weight 0.0 0.3 0.4 0.1 0.1 0.1 0.2 0.40. 48 / 59 Petition 870240092769, dated 10 / 30 / 2024, pp. 61 / 141 49 / 59 Table 1b: (co)polymerization conditions for EI 9 to EI 15 EI 9 EI 10 EI 11 EI 12 EI 13 EI 14 EI 15 Catalyst BMC1 BMC1 BMC1 BMC1 BMC2 BMC1 BMC1 Compensation Type Compensation Compensation Compensation Compensation Compensation Compensation Compensation 1 1 1 1 2 1 1 Catalyst Feed Rate, ml / h 1.5 1.6 2.7 2.0 4.5 1.2 1.7 Compensation Feed Rate, ml / h 9.7 0 27.2 38.4 10.5 1.6 0 Production Rate, kg / h 19.64 17.06 17.96 18.64 19.10 19.50 18.28 Residence Time, h 2.01 2.30 2.20 2.11 2.10 2.00 2.15 Temp.Reactor bed temperature, °C 80.00 80.00 80.00 80.00 78.00 70.00 80.00 Bed weight, kg 39.51 38.15 39.51 39.19 39.55 38.87 39.28 FBD, lb / ft³ 15.10 12.00 14.70 14.60 14.60 13.60 13.77 Comonomer hexene hexene hexene hexene Hexene hexene hexene Molar ratio Cx / C2 0.0460 0.0385 0.040 0.042 0.0310 0.0486 0.0435 Flow ratio Cx / C2, kg / kg 0.101 0.087 0.080 0.082 0.071 0.129 0.103 Molar ratio H2 / C2 0.0030 0.0055 0.001 0.001 0.0110 0.0030 0.0094 Flow rate H2 / C2, g / kg 0.343 0.473 0.061 0.064 0.715 0.322 0.656 APS, cm 0.180 0.198 0.180 0.183 0.170 0.234 0.201 Fine solids, % by weight 0.18 0.06 0.1 0.1 0.09 0.03 0.04. 49 / 59 Petition 870240092769, dated 10 / 30 / 2024, page 62 / 141 50 / 59

[0117] Comparative Examples EC A to EC E, EC H to EC Q are commercially available: EC A - EXCEED™ 1018 HA (ExxonMobil); EC BELITE™ 5400 G (DOW, Inc.); EC C - Alkamax® ML1810 PN (QENOS); EC DAlkamax® ML2610 PN (QENOS); EC E-INNATE™ ST50 (DOW, Inc.); EC H EXCEED™ 3518 (ExxonMobil); EC I - Alkamax® ML1735 SCX (QENOS); EC J-ELITE™ 5230G (DOW, Inc.); EC K - DOWLEX™ GM 8480G (DOW, Inc.); EC L - EXCEED™ XP 8656 (ExxonMobil); EC M - DOWLEX™ 2020G; EC N AFFINITY™ PL 1880G; EC P-INNATE™ TH60 (DOW, Inc.); EC Q-ELITE™ AT 6101 (DOW, Inc.).

[0118] Comparative Examples EC F, EC G, EC R and EC S are produced according to the following examples from the cited documents. EC F - 2016-VHH Part 6 found in WO 2018 / 089193 A1; EC G - 2016-VHH Part 7 found in WO 2018 / 089193 A1; EC R - Comparative PE 2 found in WO 2019 / 070329 and EC S - Comparative PE 1 found in WO 2019 / 070329.

[0119] EXCEED™ 1018 HA (ExxonMobil) is an ethylene / 1-hexene LLDPE produced with the metallocene catalyst XCAT™ HP. Alkamax® ML1810 PN (QENOS) is an ethylene / 1-hexene LLDPE produced with the metallocene catalyst XCAT™ VP from Univation Technologies, LLC. Petition 870240092769, dated 10 / 30 / 2024, pp. 63 / 141 51 / 59 Table 2a - Copolymer properties for examples of the invention and comparative examples Sample Density (ASTM D792-13, Method B) Melting Index (I2, ASTM D1238-13) I21 (ASTM D1238-13) I5 (ASTM D1238-13) I21 / I5 I21 / I2 Comonomer H2 / C2 Process Number of reactors EI 1 0.9168 0.97 58.2 3.24 18.0 60.0 hexene 0.01 gas 1 EI 2 0.9178 1.05 55.4 3.40 16.3 52.7 butene 0.01 gas 1 EI 3 0.9169 1.00 47.4 4.10 11.6 47.4 butene 0.001 gas 1 EI 4 0.9242 1.10 85.5 3.85 22.2 77.7 hexene 0.01 gas 1 EI 5 0.9185 1.00 119.3 4.95 24.1 119.3 hexene 0.003 gas 1 EI 6 0.9182 0.94 47.1 3.84 12.3 50.1 hexene 0.001 gas 1 EI 7 0.9252 0.91 126.2 4.85 26.0 138.8 hexene 0.003 gas 1 EI 8 0.9176 0.85 37.6 2.69 14.0 44.2 hexene 0.011 gas 1 EC A 0.918 1.02 16.0 --- --- 15.6 --- --- gas 1 EC B 0.916 1.00 --- --- --- --- --- --- sol. 2 EC C 0.918 0.98 30.7 --- --- 31.5 --- --- gas 1 EC D 0.926 1.06 19.6 --- --- 18.5 --- --- gas 1 EC E 0.918 0.85 --- --- --- --- --- --- sol.2 EC F 0.9183 1.17 37.9 3.48 10.9 32.4 hexene 0.017 gas 1 EC G 0.9266 1.02 33.3 3.04 10.9 32.6 hexene 0.018 gas EI 1.97 0.97 3.43 332.5 17.64 18.8 96.9 hexene 0.003 gas 1 EC H 0.918 3.53 56.0 --- --- 15.9 --- --- gas 1 EC I 0.917 3.22 66.4 --- --- 20.6 --- 16.9 EC J 4.00 --- --- --- --- --- --- sol. 2 EC K 0.917 3.00 --- --- --- --- --- --- sol. 1 EI 10 0.9183 0.34 25.5 1.19 21.4 74.9 hexene 0.0055 gas 1 EI 11 0.9182 0.34 25.1 1.55 16.2 73.9 hexene 0.001 1.18 EI 184 0.63 38.3 2.76 13.9 60.5 hexene 0.001 gas 1 EI 13 0.9175 0.37 12.0 1.10 10.9 32.4 hexene 0.0110 gas 1 EC L 0.916 13.69 3.69 28.0 hexene --- gas 1 EC M 0.918 0.50 --- --- --- --- --- --- sol. 1 EI 14 0.9032 1.10 101.5 4.75 21.4 92.2 hexene 0.0030 gas 1 EI 15 0.9124 0.87 49.3 2.87 17.2 56.7 hexene 0.094 NEC gas 10.90 --- --- --- --- --- --- sol. 1 EC O 0.912 0.85 --- --- --- --- --- --- sol. 2 EC P 0.905 0.8 --- --- --- --- --- --- sol.2 EC Q 0.9296 0.99 87.6 --- --- 88.5 hexene 0.00124 gas 1 EC R 0.9273 0.61 46.94 --- --- 77.0 hexene 0.00124 gas 1. 51 / 59 Petition 870240092769, dated 10 / 30 / 2024, p. 64 / 141 52 / 59 Table 2b - Copolymer properties for examples of the invention and examples Comparative values ​​Mz Mw / Mn Mz / Mw SCB per 1,000°C at Mn SCB per 1,000°C at Mw Sample Mn Mw EI 1 9.165 125.208 695.344 13.66 5.55 17.28 24.61 EI 2 7.519 119.216 697.422 15.86 5.85 21.42 29.60 EI 3 29.479 153.792 1.500.371 5.22 9.76 19.73 23.68 EI 4 7.352 118.313 760.459 16.09 6.43 14.12 20.47 EI 5 15,444 136,184 1,368,958 8.82 10.05 16.66 26.76 EI 6 26,872 156,873 1,615,450 5.84 10.30 13.85 19.13 EI 7 14,343 141,325 1,493,394 9.85 10.57 12.75 19.40 EI 8 10,598 126,490 637,760 11.93 5.04 12.82 26.00 EC A 42,598 112,934 218,088 2.65 1.93 12.70 13.10 EC B 27,478 106,905 345,513 3.89 3.23 13.20 17.73 EC C 30,894 114,423 304,424 3.70 2.66 9.85 17.04 EC D 39,341 115,144 271,212 2.93 2.36 6.14 7.90 EC E 28,169 112,563 298,979 4.00 2.66 11.14 18.78 EC F 7,121 113,371 420,057 15.92 3.71 9.68 12.44 EC G 5,953 119,929 479,156 20.15 4.00 7.23 8.32 EI 9 14,739 102,594 909,585 6.96 8.87 17.78 28.17 EC H 29,269 79,142 147,071 2.70 1.86 14.61 15.18 EC I 26,300 82,363 186,220 3.13 2.26 12.41 16.24 EC J 23.382 74,231 176,932 3.17 2.38 17.00 16.50 EC K 24,023 84,637 259,384 3.52 3.06 18.27 15.35 EI 10 13,831 164,788 879,591 11.91 5.34 14.87 21.40 EI 11 29,002 187,732 1,876,141 6.47 9.99 12.97 19.52 EI 12 28,843 162,200 1,449,907 5.62 8.94 13.40 18.79 EI 13 17,134 158,423 655,534 9.25 4.14 15.65 19.27 EC L 35,285 138,399 365,701 3.92 2.64 11.24 21.32 EC M 32,607 145,182 559,955 4.45 3.86 15.38 12.67 EI 14 17,999 130,596 1,032,375 7.26 7.91 23.34 37.15 EI 15 10,367 131,719 636,382 12.71 4.83 17.8 25.70 EC N 37,621 88,555 168,403 2.35 1.90 24.52 23.80 EC 27,153 109,554 276,655 4.03 2.53 14.7 23.13 EC P 36,110 105,350 242,403 2.92 2.30 22.54 20.00. Petition 870240092769, dated 10 / 30 / 2024, page 65 / 141 53 / 59 Table 2c - Copolymer properties for examples of the invention and comparative examples %HDF strength Show SHI (1 / 100) and δ at 0.1 rad / s fusion (cN at 50 mm / s) %LEF (iCCD 25-35) (iCCD 95B 115) EI 1 6.75 5.88 2.85 7,63 EI 2.72 9.31 0.98 EI 3 19 2.03 4.33 1.74 1.24 EI 4 7.79 5.67 2.03 5.33 3.39 EI 2.75 EI 7 37 2.85 2.48 2.07 4.04 EI 8 5.35 5.96 3.22 9.74 3.75 EC A 1.61 25.65 2.11 0.29 EC 9 C 2.84 24.52 1.73 0.31 5.89 EC D 2.06 26.95 1.29 0.15 20.52 EC E 4.54 BBB BBB 0.65 17.18 EC F 3.86 9.43 ^B 1.89 9.37 2.05 ^B ^B ^B BBB EI 9 11.5 3.62 1.39 5.04 2.11 EC H 1.58 151.18 0.47 0.84 2.91 EC I 34.39 BBB 1.97 4.58 EC K 2.85 16.72 BBB 3.85 7.73 EI 10 11.67 2.95 7.17 3.99 6.06 EI 11 31.5 1.67 BBB 7.02 BBB BBB EI 13 6 3.01 8.92 4.51 9.36 EC L 3.19 13.47 4.88 0.88 4.42 EC M ^B ^B ^B 6.18 BBB 2.24 12.436 EI 14.89 2.02 EI 15 7.06 5.34 N / A 8.69 3.67 EC N BBB BBB N / A 0.81 0.20 EC O BBB BBB BBB 1.23 6,82 EC P 4 5.97 N / A 0.89 0.25

[0120] The B-LLDPE copolymers of the invention examples demonstrate the potential for improved processability, as evidenced by the shear thinning index values ​​seen above, along with the wider tangent δ and Mz / Mw and MWD values, for example, Mw / Mn, measured by GPC, in the value ranges observed above. By way of further example, Figure 2 and Figure 3 provide graphs of the molecular weight distribution and short-chain branching distribution of the polymer of samples EI 1 and EI 5, respectively. As illustrated, the short-chain branching per 1,000 C Petition 870240092769, dated 10 / 30 / 2024, page 66 / 141 54 / 59 in Mw is observed to be greater than the SCB per 1,000 C in Mn for EI 1 and EI 5. Blown films

[0121] Preparation of a 25 micron thick monolayer film of B-LLDPE copolymers and copolymers from the Comparative Examples, as described in Tables 3a to 3d below. Additional comparative examples seen below include: EC T - TUFLIN™ HS-7028 NT 7 (DOW, Inc.), EC U - TUFLIN™ HS-7066 NT 7 (DOW, Inc.); EC V - DOWLEX™ 2020G; EC W-VPR-0516MA (Univation).

[0122] TUFLIN™ HS-7028 NT 7 is an ethylene / 1-hexene LLDPE produced with a Ziegler-Natta UCAT™ J catalyst. TUFLIN™ HS-7066 NT 7 (DOW, Inc.) is an ethylene / 1-hexene LLDPE produced with a Ziegler-Natta UCAT™ J catalyst. DOWLEX™ 2020G is an ethylene / HAO LLDPE produced with a Ziegler-Natta catalyst. VPR 0516 MA (Univation) is a gas-phase metallocene LLDPE from Univation.

[0123] For the data seen in Tables 3a to 3d, 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 having a fixed die span of 1,778 millimeters (70.00 mils), a blow ratio of 2.5:1. The cooling line height (FLH) is 81 ± 5.1 centimeters (32 ± 2 inches) from the die. The machine used a feed rate of 89.6 kg (197.6 lb) per hour at a melt temperature of 202 ° ± 1 °C and an extrusion speed of 28.5 revolutions per minute (rpm). The film properties of the Inventive Examples (B-LLDPE copolymer) and the Comparative Examples are described below in Tables 3a to 3d. Petition 870240092769, dated 10 / 30 / 2024, p. 67 / 141 55 / 59 Table 3a - Properties of the 25-micron monolayer film Polymer EC F EC T EI 1 EI 2 EI 3 EI 5 EI 6 EI 8 EC A EC C EC B Average dart (g) 904 142 1000 121 72 146 229 965 1100 1072 1072 Average brightness 45 degrees 25 46 28 39 33 15 33 30 30 21 57 Average opacity (%) 34 17 27 20 23 48 23 25 26 31 10 Average perforation (ft*lb / inA3) 128 160 217 190 135 149 217 229 314 258 272 Average secant modulus at DT 2% (Psi) 36910 34665 32325 322 86 29210 29336 3026 4 41686 27659 33423 2865 3 Average secant modulus in DM 2% (Psi) 32263 31433 28676 287 63 25013 25173 2706 8 33520 26576 30920 2558 3 Average tear DT (gf) 605 579 712 553 466 699 585 653 351 414 535 Average tear dm (gf) 316 370 259 137 29 258 217 243 270 246 256 Blown film line head pressure (psi) 3000 3471 3308 330 8 3501 2576 3594 3844 5145 4434 3898 Petition 870240092769, dated 10 / 30 / 2024, pp. 68 / 141 56 / 59 Table 3b - Properties of the 25-micron monolayer film Polymer EC U EC D EC G EI 4 EI 7 Average dart (g) 127 155 183 227 118 Average brightness 45 degrees 41 24 14 25 10 Average opacity (%) 20 33 46 30 62 Average perforation (ft*lb / inA3) 165 161 109 112 107 Average secant modulus at DT 2% (psi) 47686 49700 50500 53820 46907 Average secant modulus at DM 2% (psi) 42796 45347 46887 44577 39943 Average tear DT (gf) 654 368 656 655 786 Average tear DM (gf) 240 201 260 142 65 Blown film line head pressure (psi) 4080 5680 3161 3048 2444 Table 3c - Properties of the 25-micron monolayer film Polymer EI 10 EI 11 EI 12 EI 13 EC V EC W Average Dart (g) 1096 907 264 1276 808 1276 Average Gloss at 45 degrees 18 15 24 41 62 41 Average Opacity (%) 39 48 31 15 12 20 Average Perforation (ft*lb / inA3) 152 173 151 175 234 211 Average Secant Modulus at DT 2% (psi) 41166 39552 37336 41862 30056 30334 Average Secant Modulus at DM 2% (psi) 34447 34738 31601 35805 27807 26993 Medium tear DT (gf) 1021 680 617 799 620 371 Medium tear dm (gf) 232 121 182 269 461 243 Blown film line head pressure (psi) 3898 3939 3288 5051 4600 4730 Petition 870240092769, dated 10 / 30 / 2024, page 69 / 141 57 / 59 Table 3D - Properties of a 25-micron monolayer film Polymer Blend EI 10 + AGILITY™ 1200 (80 / 20% w / % w) EI 11 + AGILITY™ 1200 (80 / 20% w / % w) EI 12 + AGILITY™ 1200 (80 / 20% w / % w) EI 13 + AGILITY™ 1200 (80 / 20% w / % w) EC V + AGILITY™ 1200 (80 / 20% w / % w) EC W + AGILITY™ 1200 (80 / 20% w / % w) EI 16 EI 17 EI 18 EI 19 EC X EC Y Medium dart (g) 193 154 127 193 355 637 Medium brightness 45 degrees 45 32 37 42 52 51 Average Opacity (%) 15 21 19 15 11 12 Average Perforation (ft*lb / inA3) 159 163 153 165 191 225 Average secant modulus at DT 2% (psi) 511 168 439 158 434 51 477 85 372 48 423 47 Average secant modulus at DM 2% (psi) 412 02 352 75 346 17 410 22 310 53 334 34 Average tear DT (gf) 911 616 560 741 739 539 Average tear dm (gf) 48 43 48 72 95 63 Blown film line head pressure (psi) 3940 4005 3376 5053 4738 4775

[0124] 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), increased melt strength, increased dart impact intensity, and increased secant modulus. In some aspects, the B-LLDPE copolymer of the present disclosure is not characterized by an aggravation of any Petition 870240092769, dated 10 / 30 / 2024, pp. 70 / 141 58 / 59 three, alternatively, any two, alternatively, any of the previous properties. Molded films

[0125] Preparation of a 20 micron thick molded film from B-LLDPE copolymers and the copolymers from the Comparative Examples, as described in Table 4 below. For the data shown in Table 4, a molded 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 293 °C. The extruder is in fluid communication with a die that has a fixed die opening of 0.508 millimeters (20.00 mils) and an air opening of 8.9 cm. The machine was set to a line speed of 122 meters / min with a feed rate of 89.6 kg (197.6 lb) per hour at a melt temperature of 202 °C ± 1 °C and an extruder rate of 28.5 revolutions per minute (rpm). The temperature of the cooling cylinder was 70 °C.The film properties of the Inventive Examples (B-LLDPE copolymer) and the Comparative Examples are described below in Table 4. Table 4 - Properties of 20 micron molded films. Polymer EI 9 EC H EC I EC J EC K Average dart (g) 77 84 90 101 97 Average brightness - 45 degrees 5 3 3 1 0.7 Average opacity (%) 156 236 198 237 246 Average perforation (ft*lb / inA3) 20065 17602 20468 17274 18980 Average secant modulus at 2% CD (psi) 19483 17436 20856 17471 18562 Average secant modulus at 2% MD (psi) 422 369 390 489 415 Average rupture-CD (gf) 292 297 329 335 284 Average rupture-MD (gf) 5 10 9 8 9 Motor load (Amps) 77 84 90 101 97

[0126] As seen above in Table 4, the B-LLDPE copolymer of the present disclosure can be made into a molded film using a motor load that is significantly lower than that of the molded films of Petition 870240092769, dated 10 / 30 / 2024, pp. 71 / 141 59 / 59 Comparative Examples. Petition 870240092769, dated 10 / 30 / 2024, pp. 72 / 141

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 1,900,000 grams per mole (g / mol), measured according to the gel permeation chromatography (GPC) test method; and - a shear viscosity decrease index (SHI) of 5.35 to 75η*(1.0) / η*(100), measured according to the SHI Test Method.

2. Bimodal linear low-density polyethylene copolymer, according to claim 1, characterized in that it has a first melt flow ratio (I21 / I2) of 32 to 140, measured according to the melt index test method at 190 °C, and 21.6 and 2.16 kilograms, respectively, according to ASTM D1238-13 standards.

3. Bimodal linear low-density polyethylene copolymer, according to any one of claims 1 or 2, characterized in that it has a first molecular weight ratio (MZ / MW) of 4 to 11, measured according to the GPC test method, wherein MZ is the average molecular weight and MW is the weight-average molecular weight.

4. Bimodal linear low-density polyethylene copolymer, according to claim 1, characterized in that the I2 is from 0.80 g / 10 min. to 1.2 g / 10 min., measured according to the melt index test method at 190°C and 2.16 kilograms, according to ASTM D792-13 standards, and the Mz is from 630,000 to less than 1,700,000 g / mol, measured according to the GPC Test Method.

5. Bimodal linear low-density polyethylene copolymer, according to claim 4, characterized in that the density is from 0.915 to 0.920 g / cm3, measured according to ASTM D792-13, Method B; or having a tan delta (tan δ) of 2 to 6, measured at 190 °C and a frequency of 0.1000 radians per second (rad / s) according to the Tan Delta Test Method.

6. A bimodal linear low-density polyethylene copolymer according to claim 5, characterized in that the tan δ is 5.6 to 6, measured at 190 °C and a frequency of 0.1000 radians per second (rad / s), according to the Tan Delta Test Method; the density is 0.916 to 0.918 g / cm3 measured according to ASTM D792-13, Method B; and the Mz / Mw is 5 to 5.6, measured according to the GPC Test Method.

7. Bimodal linear low-density polyethylene copolymer, according to any one of claims 4 to 6, characterized in that it has a low elution fraction of 1.7% to 10%, as measured by the iCCD technique, above 25°C to below 35°C; or having a high-density fraction of 0.9% to 4.1%, as measured by the iCCD technique, from above 95°C to below 115°C.

8. Bimodal linear low-density polyethylene copolymer according to claim 1, characterized in that the density is from 0.915 to 0.920 g / cm3, measured according to ASTM D792-13, Method B; the I2 is from 3.2 g / 10 min. to 3.6 g / 10 min., measured according to the melt index test method at 190 °C and 2.16 kilograms, according to ASTM D1238-13 standards; the Mz is from 800,000 to 1,200,000 g / mol, measured according to the GPC Test Method; and the SHI is from 10 to 12 η*(1.0) / η*(100), measured according to the SHI Test Method.

9. A linear bimodal low-density polyethylene copolymer according to claim 8, characterized in that it has a tan delta (tan δ) of 3 to 4, measured at 190 °C, and a frequency of 0.1000 radians per second (rad / s) according to the Tan Delta Test Method.

10. Bimodal linear low-density polyethylene copolymer, according to claim 1, characterized in that the density is from 0.9160 to 0.9200 g / cm3, measured according to ASTM D792-13, Method B; the I2 is from 0.1 g / 10 min to 0.8 g / 10 min, measured according to the Melt Index Test Method at 190 °C and 2.16 kilograms, according to ASTM D1238-13; the Mz is from 650,000 to 1,900,000 g / mol, measured according to the GPC Test Method; and the SHI is between 6 and 32 η*(1,0) / η*(100), measured according to the SHI Test Method.

11. A bimodal linear low-density polyethylene copolymer according to claim 10, characterized in that it has a tan delta (Tan δ) of 1.6 to 3.1, measured at 190 °C and a frequency of 0.1000 radians per second (rad / s) according to the Tan Delta Test Method, or has a low elution fraction of 3.8 percent to 4.6 percent, as measured by iCCD technique, from above 25 °C to below 35 °C; or has a high-density fraction of 6% to 10%, as measured by iCCD technique, from above 95 °C to below 115 °C; or has an I2 of 0.3 g / 10 min. at 0.4 g / 10 min., measured according to the melt index test method at 190 °C and 2.16 kilograms, in accordance with ASTM D1238-13 standards.

12. A linear bimodal low-density polyethylene copolymer according to any one of claims 1 to 11, characterized in that a comonomer used in the formation of the linear bimodal low-density polyethylene copolymer is selected from 1-hexene, 1-butene, or a combination thereof; or in that the number of short-chain branches per 1,000 carbon atoms, measured according to the GCP test method, is greater in Mw than in Mn.

13. Manufactured article, characterized in that it comprises a molded form of bimodal linear low-density polyethylene copolymer, according to any one of claims 1 to 12.

14. Method for producing bimodal linear low-density polyethylene copolymer according to any one of claims 1 to 12, Petition 870240092769, dated 10 / 30 / 2024, p. 75 / 141 4 / 4 characterized by comprising the contact between 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 bis[(2-pentamethylphenylamido)ethyl]amine zirconium dibenzyl in the presence of molecular hydrogen gas (H2) at a molar ratio between hydrogen and ethylene (H2 / C2) of 0.001 to less than 0.012, all in a single gas-phase polymerization reactor containing a fluidized resin bed at a temperature of 70 °C to 90 °C, thereby forming the bimodal linear low-density polyethylene copolymer.

15. Method according to claim 14, characterized in that the molar ratio of H2 / C2 is from 0.001 to 0.003; or wherein the bimodal catalyst system comprises a metallocene other than (tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconium-X2 (X=methyl chloride). Petition 870240092769, dated 10 / 30 / 2024, p. 76 / 141

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