Low-density polyethylene, film and cast, blown or thermoformed film.

Abstract

LOW-DENSITY POLYETHYLENE HOMOPOLYMER, FILM, AND, BLOW-MOLDED OR THERMOFORMED MELTED FILM. The present invention relates to a low-density polyethylene with a melt strength measured at 190 °C that is greater than or equal to 5.5 cN, a density that is greater than or equal to 0.9210 g / cm3 and less than or equal to 0.9275 g / cm3, and a melt index I2 measured at 190 °C that is greater than or equal to 4.5 g / 10 min.

Description

1 / 53 Low-density polyethylene, film and cast, blown or thermoformed film. CROSS-REFERENCE TO RELATED ORDERS

[0001] This application claims priority over provisional patent application US No. 63 / 005,798, filed April 6, 2020, full disclosure of which is incorporated herein by reference. TECHNICAL FIELD

[0002] The embodiments of this disclosure generally refer to low-density polyethylene and, in particular, to low-density polyethylene with enhanced melt strength. BACKGROUND

[0003] The properties of resins used to produce films, such as melt strength, viscosity, molecular weight distribution, density, and the like, can affect the performance of films such as molded, blown, or thermoformed films. Blending different types of ethylene-based polymers, such as low-density polyethylene (LDPE) with linear low-density polyethylene (LLDPE), can improve some properties, but this blending can lead to inconsistencies between batches.

[0004] Ethylene-based polymers are presented in the following references: WO 2017 / 14698, WO 2010 / 042390, WO 2010 / 144784, WO 2011 / 019563, WO 2012 / 082393, WO 2006 / 049783, WO 2009 / 114661, US 2008 / 0125553, US 7,741,415, US 8,916,667, US 9,303,107 and EP 2239283Bl. However, these polymers do not provide improved melt strength or an optimized balance of film properties. Thus, the need remains for new ethylene-based polymers, such as LDPEs, that have an optimized balance of melt strength, processability, and density (stiffness). SUMMARY

[0005] In certain embodiments, a low-density polyethylene Petition 870250003166, dated 15 / 01 / 2025, page 10 / 121 2 / 53 comprises: a melt strength measured at 190 degrees Celsius (°C) that is greater than or equal to 5.5 centiNewtons (cN); a density that is greater than or equal to 0.9210 grams per cubic centicentimeter (g / cm3) and less than or equal to 0.9275 g / cm3; a melting index I2 measured at 190 °C that is less than or equal to 4.5 g / 10 min.

[0006] In certain embodiments, a low-density polyethylene comprises: a melt strength measured at 190 °C that is greater than 5.5 cN; and a density that is greater than or equal to 0.9210 g / cm3 and less than or equal to 0.9275 g / cm3.

[0007] Additional features and advantages will be presented in the detailed description below and, in part, will be readily apparent to those skilled in the art from this description or recognized by the practice of the embodiments described in this document, including the detailed description that follows, the claims, as well as the accompanying drawings.

[0008] It should be understood that both the preceding general description and the detailed description below describe various embodiments and are intended to provide an overview or context for understanding the nature and character of the subject matter claimed. The accompanying drawings are included to provide further understanding of the various embodiments and are incorporated into and form part of this descriptive report. The drawings illustrate the various embodiments described in this document and, together with the description, serve to explain the principles and operations of the subject matter claimed. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] Figure 1 schematically represents a process system according to the modalities disclosed and described in this document;

[0010] Figure 2 graphically represents a CDFIR chromatogram of low-density polyethylene according to embodiments disclosed and described in this document;

[0011] Figure 3 graphically represents a CDFDV chromatogram of Petition 870250003166, dated 15 / 01 / 2025, page 11 / 121 3 / 53 a low-density polyethylene according to embodiments disclosed and described in this document.

[0012] Figure 4 graphically represents a CDFls chromatogram of a low-density polyethylene according to embodiments disclosed and described in this document;

[0013] Figure 5 graphically represents an LSP chromatogram of a low-density polyethylene according to embodiments disclosed and described in this document; and

[0014] Figure 6 graphically represents a melt strength overlay at 190°C of a low-density polyethylene according to embodiments disclosed and described in this document. DETAILED DESCRIPTION

[0015] Specific modalities of this application will be described below. The disclosure may, however, be represented in different forms and should not be interpreted as limited to the modalities presented in this disclosure. Instead, these modalities are provided so that this disclosure is thorough and complete and will fully convey the scope of the subject to those skilled in the art.

[0016] According to certain embodiments, a low-density polyethylene comprises: a melt strength measured at 190°C that is greater than or equal to 5.5 cN; a density that is greater than or equal to 0.9210 g / cm3 and less than or equal to 0.9275 g / cm3; and a melt index I2 measured at 190°C that is greater than or equal to 4.5 g / 10 min. According to certain embodiments, a low-density polyethylene comprises: a melt strength measured at 190°C that is greater than 5.5 cN and a density that is greater than or equal to 0.9210 g / cm3 and less than or equal to 0.9275 g / cm3. Definitions

[0017] The term composition, as used in this document, includes a mixture of materials comprising the composition, as well as reaction products and decomposition products formed from the materials of the composition. Petition 870250003166, dated 15 / 01 / 2025, page 12 / 121 4 / 53

[0018] The terms blend or polymer blend, as used, refer to a mixture of two or more polymers. A blend may or may not be miscible (separated into phases at the molecular level). A blend may or may not be separated into phases. A blend may or may not contain one or more domain configurations, as determined by transmission electron spectroscopy, light scattering, X-ray scattering, and other methods known in the art. The blend may be made by physically mixing the two or more polymers at the macro level (e.g., melt blending or compounding resins) or at the micro level (e.g., simultaneous forming in the same reactor).

[0019] The terms comprising, including, having, and their derivatives, are not intended to exclude the presence of any additional component, step, or procedure, whether specifically disclosed or not. For the avoidance of doubt, all compositions claimed by the use of the term comprising or including may include any additive, adjuvant, or additional compound, polymeric or not, unless stated otherwise. Conversely, the term consisting essentially excludes from the scope of any subsequent recitation any other component, step, or procedure, except those not essential to operability. The term consisting excludes any component, step, or procedure not specifically outlined or cited.

[0020] The term low-density polyethylene, abbreviated as LDPE, as used in this document, may also be called high-pressure ethylene polymer or highly branched polyethylene. LDPE is known in the art, and in this document the term refers to an ethylene homopolymer prepared using a high-pressure free-radical polymerization (> 100 MPa (e.g., 100 to 400 MPa)). LDPE resins typically have a density in the range of 0.915 to 0.935 g / cm3. As referred to in this document, the terms low-density polyethylene, LDPE, or similar terms refer to the polyethylene polymer itself and do not include any additives that may be blended with the low-density polyethylene, unless Petition 870250003166, dated 15 / 01 / 2025, page 13 / 121 5 / 53 unless explicitly stated otherwise. Consequently, the properties of low-density polyethylene mentioned in this disclosure refer to the properties of the low-density polyethylene polymer itself without any additives, unless explicitly stated otherwise.

[0021] The term linear low-density polyethylene, abbreviated as LLDPE, as used herein, includes resin produced using Ziegler-Natta catalyst systems, as well as resin produced using single-site catalysts, including but not limited to bis-metallocene catalysts (sometimes referred to as m-LLDPE), phosphinimine, and restricted geometry catalysts; and resin made using post-metallocene molecular catalysts, including but not limited to bis(biphenylphenoxy) catalysts (also called polyvalent aryloxyether catalysts). LLDPE includes linear, substantially linear, or heterogeneous ethylene-based homopolymers or copolymers. LLDPEs include substantially linear ethylene polymers, which are further defined in U.S. Patent No. 5,272,236; U.S. Patent No. 5,278,272; in U.S. Patent No. 5,582,923; and in U.S. Patent No. 5,733.155; homogeneously branched ethylene polymers such as those of U.S. Patent No. 3,645,992; heterogeneously branched ethylene polymers such as those prepared according to the process disclosed in U.S. Patent No. 4,076,698; and blends thereof (such as those disclosed in U.S. Patent No. 3,914,342 or U.S. Patent No. 5,854,045). LLDPE resins may be made by gas-phase, solution-phase, or slurry polymerization, or any combination thereof, using any type of reactor or reactor configuration known in the art. Processes of the modalities

[0022] To produce low-density polyethylene, a combination autoclave tubular reactor polymerization process, initiated by free radicals under high pressure, was used. Two different types of high-pressure free-radical initiated polymerization processes are known. In the first type, a stirred autoclave vessel with one or more reaction zones is used. The reactor of Petition 870250003166, dated 15 / 01 / 2025, page 14 / 121 6 / 53 Autoclaves typically have multiple injection points for feeds of initiator or monomer, or both. In the second type, a jacketed tube is used as a reactor, which has one or more reaction zones. Suitable reactor lengths may be, but are not limited to, 100 to 3,000 meters (m), or 1,000 to 2,000 m. The start of a reactor reaction zone is typically defined by the lateral injection of any of the following: reaction initiator, ethylene, chain transfer agent (or telomere), comonomer (or comonomers), as well as any combination thereof. A high-pressure process may also be carried out in autoclaves or in tubular reactors with one or more reaction zones, or in a combination of autoclaves and tubular reactors, each comprising one or more reaction zones.

[0023] A chain transfer agent can be used to control molecular weight. In a preferred embodiment, one or more chain transfer agents (CTAs) can be added to a polymerization process. Typical CTAs include, but are not limited to, propylene, isobutane, n-butane, 1-butene, methyl ethyl ketone, acetone, and propionaldehyde. In one embodiment, the amount of CTA used in the process is from 0.03 to 10 percent by weight of the total reaction mixture.

[0024] The ethylene used for the production of low-density polyethylene can be purified ethylene, which is obtained by removing polar components from a loop recycling stream. It is not typical that purified ethylene is required to make low-density polyethylene. In such cases, ethylene from the recycling loop can be used.

[0025] Reference will now be made in detail to system and process modalities for the production of low-density polyethylene in accordance with the modalities disclosed and described in this document.

[0026] With reference now to Figure 1, which is a block diagram of a process reaction system used to produce low-density polyethylene according to certain embodiments, the process reaction system 100 shown in Figure 1 is a high-density polyethylene system. Petition 870250003166, dated 15 / 01 / 2025, page 15 / 121 7 / 53 pressure and low density partially closed cycle, double recycling. According to the embodiments shown in Figure 1, the process reaction system 100 may comprise a booster / primary compressor 110, a hypercompressor 120, an adiabatic autoclave reactor 130 coupled to the tube reactor 140, a high-pressure separator 150 and a low-pressure separator 160. The autoclave reactor 130 may, according to the embodiments, comprise three zones 130A, 130B, 130C. A first stream of peroxide initiator 124 can be injected into each zone one 130A of the autoclave reactor 130, and a third stream of peroxide initiator 125 can be injected into zone three 130C of the autoclave reactor 130. A second stream of peroxide initiator 123 can be mixed with a side stream 122 or injected into zone two of the reactor 130B. Similarly, a stream of peroxide initiator 132 can be injected into the inlet of the tube reactor 140.The 140 tube reactor may use cooling jackets (not shown) mounted around the outer casing of the 140 tube reactor. The cooling jackets of the 140 tube reactor may use high-pressure water to cool or regulate the temperature in the 140 tube reactor.

[0027] A fresh ethylene feed stream 101 can be mixed with a chain transfer agent (CTA) stream 102 and an ethylene-rich stream 162 to form a first mixed stream (i.e., a mixed stream of fresh ethylene, recycled high-pressure ethylene and CTA). This first mixed stream can be introduced into the booster / primary compressor 110, which is sequentially connected to the hypercompressor 120, which is downstream of the booster / primary compressor 110. In the booster / primary compressor 110, the mixed stream is compressed and exits the booster / primary compressor 110 as compressed stream 111. The compressed stream 111 can be mixed with a high-pressure recycle stream 154, which is a portion of an ethylene-rich stream 152 from the high-pressure separator 150, to form a second mixed stream (i.e., a mixed stream of fresh hypercompressed ethylene, ethylene). Petition 870250003166, dated 15 / 01 / 2025, page 16 / 121 8 / 53 recycled high-pressure and recycled CTA and high-pressure ethylene). This second mixed stream can be introduced into the hypercompressor 120 which is sequentially connected to the booster / primary compressor 110, which is upstream of the hypercompressor 120 and sequentially connected to the autoclave reactor 130, which is downstream of the hypercompressor 120. In the hypercompressor 120, the second mixed stream is further compressed to form a hypercompressed stream 121 which exits the hypercompressor 120.

[0028] The hypercompressed stream 121 is introduced into the autoclave reactor 130 which is sequentially connected to the hypercompressor 120, which is upstream of the autoclave reactor 130 and sequentially connected to the tube reactor 140, which is downstream of the autoclave reactor 130. A side stream 122 is separated from the hypercompressed stream 121, for example by a splitter (not shown), and introduced into the autoclave reactor 130 as a side stream 122. The side stream 122 and a portion of the hypercompressed stream 121 entering the autoclave reactor 130 may be in equal proportions. The hypercompressed stream portion 121 can be fed to the top of the autoclave reactor 130, as zone one 130A of the autoclave reactor 130. The side stream 122 can be fed to the side of the autoclave reactor 130, as zone two 130B.In autoclave reactor 130, the hypercompressed stream 121 and the side stream 122 can be partially polymerized and exit autoclave reactor 130 as stream 131. Stream 131 can then be fed to tube reactor 140, which is sequentially connected to autoclave reactor 130, which is upstream of tube reactor 140, and sequentially connected to high-pressure separator 150, which is downstream of tube reactor 140. In tube reactor 140, stream 131 can be further polymerized and exit tube reactor 140 as polymerized stream 141.

[0029] According to the modalities, polymerization can be initiated in the autoclave reactor 130 and in the tube reactor 140 with the aid of four mixtures, each containing one or more free radical initiation systems that can be injected into the entrance of each reaction zone. A first Petition 870250003166, dated 15 / 01 / 2025, page 17 / 121 9 / 53 stream of peroxide initiator 124 can be introduced into zone one 130A of the autoclave reactor 130. A second stream of peroxide initiator 123 can be introduced into zone two 130B of the autoclave reactor 130. A third stream of peroxide initiator 125 can be introduced into zone three 130C of the autoclave reactor 130. Finally, a fourth stream of peroxide initiator 132 can be introduced into the tube reactor 140.

[0030] The polymerized stream 141 is introduced into the high-pressure separator 150 which is sequentially connected to the tube reactor 140, which is upstream of the high-pressure separator 150 and sequentially connected to a low-pressure separator 160. In the high-pressure separator 150, the polymerized stream 141 is separated into an ethylene-rich stream 152 and a polymer-rich stream 151. A first portion of the ethylene-rich stream 153 is purged from the process reaction system 100 and a second portion of the ethylene-rich stream 154 is cooled and recycled back to the hypercompressor 120, where the ethylene-rich stream 152 is mixed with the compressed stream 111 which is introduced into the hypercompressor 120.

[0031] The polymer-rich stream 151 is introduced into the low-pressure separator 160, which is sequentially connected to the high-pressure separator 150, which is upstream of the low-pressure separator 160 and is sequentially connected to the booster / primary compressor 110, which is downstream of the low-pressure separator 160. In the low-pressure separator 160, the polymer-rich stream 151 is separated into a second polymer-rich stream 161 and a second ethylene-rich stream 162. The second polymer-rich stream 161 exits the process reaction system 100, where it can be introduced into an extruder (not shown). The second ethylene-rich stream 162 is mixed with the fresh ethylene feed stream 101 before being introduced into the booster / primary compressor 110, which is sequentially connected to the low-pressure separator 160.

[0032] According to the embodiments, the primers may be selected from the group consisting of t-butyl peroxypivalate (TBPIV), t-butyl peroxy-2-ethylhexanoate (TBPO), tert-butyl peroxyacetate (TBPA), di-tert-butyl Petition 870250003166, dated 15 / 01 / 2025, page 18 / 121 10 / 53 peroxide (DTBP), and mixtures thereof. Properties of low-density polyethylene types

[0033] A low-density polyethylene with improved melt strength and desirable melt index and density or modulus is provided in the embodiments disclosed and described herein. The properties of the low-density polyethylene according to the embodiments disclosed and described herein will now be provided. Although the properties shown below are recited in separate paragraphs, it should be understood that any property of any paragraph below can be combined with any other property of any paragraph below by modifying the various process conditions discussed above. Therefore, low-density polyethylenes with any combination of various properties shown below are provided for and can be produced according to the embodiments.

[0034] According to the modalities, low-density polyethylene may have a density greater than or equal to 0.9210 and less than or equal to 0.9275 grams per cubic centimeter (g / cm3). Density measurements were taken within one hour of sample pressing using ASTM D792-08, Method B. In the embodiments, low-density polyethylene has a density greater than or equal to 0.9215 g / cm3 and less than or equal to 0.9270 g / cm3, greater than or equal to 0.9220 g / cm3 and less than or equal to 0.9265 g / cm3, greater than or equal to 0.9225 g / cm3 and less than or equal to 0.9260 g / cm3, greater than or equal to 0.9230 g / cm3 and less than or equal to 0.9255 g / cm3, greater than or equal to 0.9235 g / cm3 and less than or equal to 0.9250 g / cm3, or greater than or equal to 0.9240 g / cm3 and less than or equal to 0.9245 g / cm3.

[0035] In embodiments, low-density polyethylene has a melt index (I2) - measured according to ASTM D 1238 at 190°C and a load of 2.16 kg - that is greater than or equal to 4.5 grams per 10 minutes (g / 10 min), for example greater than or equal to 4.6 g / 10 min, greater than or equal to 4.7 g / 10 min, greater than or equal to 4.8 g / 10 min, greater than or equal to 4.9 g / 10 min, greater than or equal to 5.0 g / 10 min, greater than or equal to 5.1 g / 10 min, greater than or equal to 5.2 g / 10 Petition 870250003166, dated 15 / 01 / 2025, p. 19 / 121 11 / 53 min, greater than or equal to 5.3 g / 10 min, greater than or equal to 5.4 g / 10 min, greater than or equal to 5.5 g / 10 min, greater than or equal to 5.6 g / 10 min, greater than or equal to 5.7 g / 10 min, greater than or equal to 5.8 g / 10 min, greater than or equal to 5.9 g / 10 min, or greater than or equal to 6.0 g / 10 min. In modalities, the melting index (I2) is less than or equal to 7.5 g / 10 min, for example less than or equal to 7.4 g / 10 min, less than or equal to 7.3 g / 10 min, less than or equal to 7.2 g / 10 min, less than or equal to 7.1 g / 10 min, less than or equal to 7.0 g / 10 min, less than or equal to 6.9 g / 10 min, less than or equal to 6.8 g / 10 min, less than or equal to 6.7 g / 10 min, less than or equal to 6.6 g / 10 min, less than or equal to 6.5 g / 10 min, less than or equal to 6.4 g / 10 min, less than or equal to 6.3 g / 10 min, less than or equal to 6.2 g / 10 min, or less than or equal to 6.1 g / 10 min. In modalities, the melting index (I2) is greater than or equal to 4.5 g / 10 min and less than or equal to 7.5 g / 10 min, for example greater than or equal to 4.6 g / 10 min and less than or equal to 7.5 g / 10 min, greater than or equal to 4,7 g / 10 min and less than or equal to 7.5 g / 10 min, greater than or equal to 4.8 g / 10 min and less than or equal to 7.5 g / 10 min, greater than or equal to 4.9 g / 10 min and less than or equal to 7.5 g / 10 min, greater than or equal to 5.0 g / 10 min and less than or equal to 7.5 g / 10 min, greater than or equal to 5.1 g / 10 min and less than or equal to 7.5 g / 10 min, greater than or equal to 5.2 g / 10 min and less than or equal to 7.5 g / 10 min, greater than or equal to 5.3 g / 10 min and less than or equal to 7.5 g / 10 min, greater than or equal to 5.4 g / 10 min and less than or equal to 7.5 g / 10 min, greater than or equal to 5.5 g / 10 min and less than or equal to 7.5 g / 10 min, greater than or equal to 5.6 g / 10 min and less than or equal to 7.5 g / 10 min, greater than or equal to 5.7 g / 10 min and less than or equal to 7.5 g / 10 min, greater than or equal to 5.8 g / 10 min and less than or equal to 7.5 g / 10 min, greater than or equal to 5.9 g / 10 min and less than or equal to 7.5 g / 10 min, or greater than or equal to 6.0 g / 10 min and less than or equal to 7.5 g / 10 min. In modalities, the melting index (I2) is greater than or equal to 190 °C at 4.5 g / 10 min and less than or equal to 7.0 g / 10 min.for example greater than or equal to 5.0 g / 10 min and less than or equal to 6.5 g / 10 min, or approximately 6.0 g / 10 min.

[0036] The resistance of the casting is measured using a Rheotens connected to a capillary rheometer as disclosed below. In embodiments, the resistance of the casting is greater than or equal to 5.5 centiNewtons (cN), for example greater than or equal to 5.6 cN, greater than or equal to 5.7 cN, greater than or equal to 5.5 centiNewtons (cN). Petition 870250003166, dated 15 / 01 / 2025, p. 20 / 121 12 / 53 equals 5.8 cN, greater than or equal to 5.9 cN, greater than or equal to 6.0 cN, greater than or equal to 6.1 cN, greater than or equal to 6.2 cN, greater than or equal to 6.3 cN, greater than or equal to 6.4 cN, greater than or equal to 6.5 cN, greater than or equal to 6.6 cN, greater than or equal to 6.7 cN, greater than or equal to 6.8 cN, greater than or equal to 7.1 cN, greater than or equal to 7.4 cN, greater than or equal to 7.7 cN, greater than or equal to 8.0 cN, greater than or equal to 6.9 cN, greater than or equal to 7.2 cN, greater than or equal to 7.5 cN, greater than or equal to 7.8 cN, greater than or equal to 8.1 cN, greater than or equal to 7.0 cN, greater than or equal to 7.3 cN, greater than or equal to 7.6 cN, greater than or equal to 7.9 cN, greater than or equal to 8.2 cN, greater than or equal to 8.3 cN, or greater than or equal to 8.4 cN. In some forms, the casting strength is greater than or equal to 5.5 cN and less than or equal to 8.5 cN, for example greater than or equal to 5.6 cN and less than or equal to 8.5 cN, greater than or equal to 5.7 cN and less than or equal to 8.5 cN, greater than or equal to 5.8 cN and less than or equal to 8.5 cN, greater than or equal to 5.9 cN and less than or equal to 8.5 cN.greater than or equal to 6.0 cN and less than or equal to 8.5 cN, greater than or equal to 6.1 cN and less than or equal to 8.5 cN, greater than or equal to 6.2 cN and less than or equal to 8.5 cN, greater than or equal to 6.3 cN and less than or equal to 8.5 cN, greater than or equal to 6.4 cN and less than or equal to 8.5 cN, greater than or equal to 6.5 cN and less than or equal to 8.5 cN, greater than or equal to 6.6 cN and less than or equal to 8.5 cN, greater than or equal to 6.7 cN and less than or equal to 8.5 cN, greater than or equal to 6.8 cN and less than or equal to 8.5 cN, greater than or equal to 6.9 cN and less than or equal to 8.5 cN, greater than or equal to 7.0 cN and less than or equal to 8.5 cN, greater than or equal to 7.1 cN and less than or equal to 8.5 cN, greater than or equal to 7.2 cN and less than or equal to 8.5 cN, greater than or equal to 7.3 cN and less than or equal to 8.5 cN, greater than or equal to 7.4 cN and less than or equal to 8.5 cN, greater than or equal to 7.5 cN and less than or equal to 8.5 cN, greater than or equal to 7.6 cN and less than or equal to 8.5 cN, greater than or equal to 7.7 cN and less than or equal to 8.5 cN, greater than or equal to 7.8 cN and less than or equal to 8.5 cN, greater than or equal to 7,9 cN and less than or equal to 8.5 cN, greater than or equal to 8.0 cN and less than or equal to 8.5 cN, greater than or equal to 8.1 cN and less than or equal to 8.5 cN, greater than or equal to 8.2 cN and less than or equal to 8.5 cN, greater than or equal to 8.3 cN and less than or equal to 8.5 cN, or greater than or equal to 8.4 cN and less than or equal to 8.5 cN. In embodiments, the casting strength is greater than or equal to 5.5 cN and less than or equal to 8.5 cN, for example greater than or equal to, Petition 870250003166, dated 15 / 01 / 2025, p. 21 / 121 13 / 53 to 5.5 cN and less than or equal to 8.3 cN, greater than or equal to 5.5 cN and less than or equal to 8.2 cN, greater than or equal to 5.5 cN and less than or equal to 8.1 cN, greater than or equal to 5.5 cN and less than or equal to 8.0 cN, greater than or equal to 5.5 cN and less than or equal to 7.9 cN, greater than or equal to 5.5 cN and less than or equal to 7.8 cN, greater than or equal to 5.5 cN and less than or equal to 7.7 cN, greater than or equal to 5.5 cN and less than or equal to 7.6 cN, greater than or equal to 5.5 cN and less than or equal to 7.5 cN, greater than or equal to 5.5 cN and less than or equal to 7.4 cN, greater than or equal to 5.5 cN and less than or equal to 7.3 cN, greater or equal to 5.5 cN and less than or equal to 7.2 cN, greater than or equal to 5.5 cN and less than or equal to 7.1 cN, greater than or equal to 5.5 cN and less than or equal to 7.0 cN, greater than or equal to 5.5 cN and less than or equal to 6.9 cN, greater than or equal to 5.5 cN and less than or equal to 6.8 cN, greater than or equal to 5.5 cN and less than or equal to 6.7 cN, greater than or equal to 5.5 cN and less than or equal to 6.6 cN, greater than or equal to 5.5 cN and less than or equal to 6.5 cN, greater than or equal to 5,5 cN and less than or equal to 6.4 cN, greater than or equal to 5.5 cN and less than or equal to 6.3 cN, greater than or equal to 5.5 cN and less than or equal to 6.2 cN, greater than or equal to 5.5 cN and less than or equal to 6.1 cN, greater than or equal to 5.5 cN and less than or equal to 6.0 cN, greater than or equal to 5.5 cN and less than or equal to 5.9 cN, greater than or equal to 5.5 cN and less than or equal to 5.8 cN, greater than or equal to 5.5 cN and less than or equal to 5.7 cN, or greater than or equal to 5.5 cN and less than or equal to 5.6 cN. According to the specifications, the casting strength is greater than or equal to 5.5 cN and less than or equal to 8.5 cN, for example greater than or equal to 6.0 cN and less than or equal to 8.0 cN, greater than or equal to 6.0 cN and less than or equal to 7.5 cN, greater than or equal to 6.4 cN and less than or equal to 7.0 cN, or greater than or equal to 6.4 cN and less than or equal to 6.8 cN.

[0037] According to the modalities, the relationship between the strength of the casting and the melting index can be such that the strength of the casting measured at 190°C in cN can be determined by the following expression: Melt strength (cN) > [-0.780 * (Melting index, / 2) + 9.9 cN] ± 5% Alternatively, the melt strength measured at 190°C can be determined by the following alternative expression: Melt strength (cN) > [-0.780 * (Melting index, / 2) + 10.3 cN] ± 5% Petition 870250003166, dated 15 / 01 / 2025, page 22 / 121 14 / 53

[0038] According to the embodiments, the amount of hexane extractables from low-density polyethylene is less than or equal to 2.60 percent by weight (% by weight), for example less than or equal to 2.50% by weight, less than or equal to 2.40% by weight, less than or equal to 2.30% by weight, less than or equal to 2.20% by weight, less than or equal to 2.10% by weight, less than or equal to 2.00% by weight, less than or equal to 1.90% by weight, less than or equal to 1.80% by weight, less than or equal to 1.70% by weight, less than or equal to 1.60% by weight, less than or equal to 1.50% by weight, or less than or equal to 1.40% by weight.In embodiments, the amount of extractables from low-density polyethylene using a hexane method is greater than or equal to 0.50% by weight and less than or equal to 2.60% by weight, for example greater than or equal to 0.60% by weight and less than or equal to 2.50% by weight, greater than or equal to 0.70% by weight and less than or equal to 2.40% by weight, greater than or equal to 0.80% by weight and less than or equal to 2.30% by weight, greater than or equal to 0.90% by weight and less than or equal to 2.30% by weight, greater than or equal to 1.00% by weight and less than or equal to 2.20% by weight, greater than or equal to 1.10% by weight and less than or equal to 2.10% by weight, greater than or equal to 1.20% by weight and less than or equal to 2.00% by weight, greater than or equal to 1.20% by weight and less or equal to 1.90% by weight, greater than or equal to 1.20% by weight and less than or equal to 1.80% by weight, greater than or equal to 1.20% by weight and less than or equal to 1.70% by weight, greater than or equal to 1.20% by weight and less than or equal to 1.60% by weight, greater than or equal to 1.20% by weight and less than or equal to 1.50% by weight, or approximately 1.40% by weight.

[0039] The number-average molecular weight (Mn(conv)) – measured by conventional GPC methods – of low-density polyethylene is, according to the embodiments, greater than or equal to 12,000 grams per mole (g / mol) and less than or equal to 18,500 g / mol, for example greater than or equal to 13,000 g / mol and less than or equal to 18,500 g / mol, greater than or equal to 14,000 g / mol and less than or equal to 17,000 g / mol, greater than or equal to 14,000 g / mol and less than or equal to 17,000 g / mol, or approximately 14,500 g / mol. Mn(conv) is measured according to the gel permeation chromatography (GPC) protocols (conventional) disclosed herein. Petition 870250003166, dated 15 / 01 / 2025, p. 23 / 121 15 / 53

[0040] The weight-average molecular weight (Mw(conv)) – measured by conventional GPC methods – of low-density polyethylene is, according to the embodiments, greater than or equal to 110,000 grams per mole (g / mol) and less than or equal to 140,000 g / mol, for example greater than or equal to 115,000 g / mol and less than or equal to 135,000 g / mol, greater than or equal to 117,500 g / mol and less than or equal to 130,000 g / mol, or approximately 125,000 g / mol. Mw(conv) is measured according to the conventional GPC protocols disclosed herein.

[0041] The average molecular weight z (Mz(conv)) - measured by conventional GPC methods - of low-density polyethylene is, according to the embodiments, greater than or equal to 500,000 grams per mole (g / mol), for example greater than or equal to 500,000 g / mol and less than or equal to 650,000 g / mol, for example greater than or equal to 510,000 g / mol and less than or equal to 640,000 g / mol, greater than or equal to 520,000 g / mol and less than or equal to 630,000 g / mol, greater than or equal to 530,000 g / mol and less than or equal to 620,000 g / mol, greater than or equal to 540,000 g / mol and less than or equal to 610,000 g / mol, greater than or equal to 550,000 g / mol and less than or equal 600,000 g / mol, greater than or equal to 560,000 g / mol and less than or equal to 590,000 g / mol, greater than or equal to 570,000 g / mol and less than or equal to 590,000 g / mol, or approximately 580,000 g / mol. Mz (conv) is measured according to the conventional GPC protocols disclosed herein.

[0042] In embodiments, the molecular weight distribution (Mw(conv) / Mn(conv)) - measured according to conventional GPC methods - of low-density polyethylene is greater than or equal to 7.2, for example greater than or equal to 7.3, greater than or equal to 7.4 or greater than or equal to 7.5. In embodiments, Mw (conv) / Mn (conv) is less than or equal to 9.5, for example less than or equal to 9.0, less than or equal to 8.8, less than or equal to 8.6, or less than or equal to 8.2.

[0043] The weight-average molecular weight Mw (abs) – measured according to the absolute methods provided below – of low-density polyethylene is, according to the embodiments, greater than or equal to 225,000 g / mol and less than or equal to 325,000 g / mol, greater than or equal to 235,000 g / mol and less than or equal to 315,000 g / mol, greater than or equal to 245,000 g / mol and less than or equal to Petition 870250003166, dated 15 / 01 / 2025, p. 24 / 121 16 / 53 305,000 g / mol, greater than or equal to 255,000 g / mol and less than or equal to 295,000 g / mol, greater than or equal to 265,000 g / mol and less than or equal to 285,000 g / mol, or approximately 275,000 g / mol. Mw (abs) is measured according to the absolute GPC protocols disclosed here.

[0044] The ratio between the weighted average molecular weight measured according to absolute methods and the weighted average molecular weight measured according to conventional GPC methods (Mw (abs) / Mw (conv)) disclosed in this document for low-density polyethylene is, according to the embodiments, greater than or equal to 2.1 and less than or equal to 2.7, for example greater than or equal to 2.1 and less than or equal to 2.4, or greater than or equal to 2.15 and less than or equal to 2.35.

[0045] According to the embodiments, the GPC branching ratio (gpcBR) of low-density polyethylene - measured with the absolute techniques disclosed in this document - is greater than or equal to 2.3 and less than or equal to 3.2, for example greater than or equal to 2.4 and less than or equal to 3.1, greater than or equal to 2.5 and less than or equal to 3.0, or greater than or equal to 2.6 and less than or equal to 2.9.

[0046] The light scattering property (LSP) of low-density polyethylene is, according to the embodiments, less than 3.8, for example less than or equal to 3.7, less than or equal to 3.6 or less than or equal to 3.5. In the embodiments, the LSP is greater than or equal to 2.5, greater than or equal to 2.6 or greater than or equal to 2.7. In the embodiments, the LSP is greater than or equal to 2.5 and less than or equal to 3.5, for example greater than or equal to 2.6 and less than or equal to 3.4, or greater than or equal to 2.7 and less than or equal to 3.3.

[0047] In various applications, low-density polyethylene has a viscosity measured at 0.1 radians / second (rad / s) and 190°C that is greater than or equal to 2,250 Pa^s and less than or equal to 4,250 Pa^s, for example greater than or equal to 2,400 Pa^s and less than or equal to 4,000 Pa^s, greater than or equal to 2,600 Pa^s and less than or equal to 3,800 Pa^s, greater than or equal to 2,800 Pa^s and less than or equal to 3,600 Pa^s, or greater than or equal to 2,900 Pa^s and less than or equal to 3,400 Pa^s, or approximately 3,200 Pa^s. Viscosity is measured according to the protocols Petition 870250003166, dated 15 / 01 / 2025, p. 25 / 121 17 / 53 published here.

[0048] In embodiments, low-density polyethylene has a viscosity measured at 100 radians / second (rad / s) and 190°C that is greater than or equal to 250 Pa^s and less than or equal to 400 Pa^s, for example greater than or equal to 270 Pa^s and less than or equal to 380 Pa^s, greater than or equal to 290 Pa^s and less than or equal to 360 Pa^s, or approximately 320 Pa^s. Viscosity is measured according to the protocols disclosed herein.

[0049] In embodiments, low-density polyethylene has a ratio between the viscosity measured at 0.1 radians / second and 190°C and the viscosity measured at 100 radians / second and 190°C (V at 0.1 / V at 100 and 190°C) that is greater than or equal to 8.0, for example greater than or equal to 8.5, greater than or equal to 9.0 or greater than or equal to 9.5. In modalities, a ratio between the viscosity measured at 0.1 radians / second and 190°C and the viscosity measured at 100 radians / second and 190°C is greater than or equal to 8.0 and less than or equal to 12.0, for example greater than or equal to 8.5 and less than or equal to 11.0, greater than or equal to 9.0 and less than or equal to 10.5, or greater than or equal to 9.2 and less than or equal to 10.8.

[0050] In embodiments, the cumulative distribution fraction (CDF) for infrared spectrum analysis (CDFIR) at a molecular weight less than 5.000 g / mol is less than or equal to 0.081, for example less than or equal to 0.079, less than or equal to 0.077, less than or equal to 0.075, less than or equal to 0.073, or less than or equal to 0.071. In embodiments, the CDFIR at a molecular weight less than 5.000 g / mol is greater than or equal to 0.040 and less than or equal to 0.081, for example greater than or equal to 0.040 for example greater than or equal to 0.055 and less than or equal to 0.079, greater than or equal to 0.055 and less than or equal to 0.077, greater than or equal to 0.055 and less than or equal to 0.075, greater than or equal to 0.055 and less than or equal to 0.075.

[0051] In embodiments, the CDFIR at a molecular weight greater than 200,000 g / mol is greater than or equal to 0.135, for example greater than or equal to 0.145, greater than or equal to 0.150, greater than or equal to 0.155, or greater than or equal to 0.160. In embodiments, the CDFIR at a molecular weight greater than 200,000 g / mol is greater than or equal to 0.135 and less than or equal to 0.180, for example greater than or equal to 0.145 and less than or equal to Petition 870250003166, dated 15 / 01 / 2025, p. 26 / 121 18 / 53 0.175, greater than or equal to 0.150 and less than or equal to 0.170, or greater than or equal to 0.155 and less than or equal to 0.163.

[0052] In embodiments, the CDF for viscometer analysis (CDFdv) at a molecular weight less than 25,000 g / mol is less than or equal to 0.130, for example less than or equal to 0.127, less than or equal to 0.126, less than or equal to 0.125, less than or equal to 0.123, less than or equal to 0.121, or less than or equal to 0.119. In embodiments, the CDFdv at a molecular weight less than 25,000 g / mol is greater than or equal to 0.050 and less than or equal to 0.130, for example greater than or equal to 0.100 and less than or equal to 0.128, greater than or equal to 0.110 and less than or equal to 0.125, or greater than or equal to 0.115 and less than or equal to 0.126.

[0053] In embodiments, the CDFdv at a molecular weight greater than 1,000,000 g / mol is greater than or equal to 0.042, for example greater than or equal to 0.048, greater than or equal to 0.053, greater than or equal to 0.058, or greater than or equal to 0.061. In embodiments, the CDFdvem at a molecular weight greater than 1,000,000 g / mol is greater than or equal to 0.042 and less than or equal to 0.070, for example greater than or equal to 0.048 and less than or equal to 0.065, or greater than or equal to 0.053 and less than or equal to 0.064.

[0054] In embodiments, the cumulative distribution fractions (CDF) for light scattering analysis (CDFls) at a molecular weight less than 100,000 g / mol is less than or equal to 0.140, for example less than or equal to 0.130, less than or equal to 0.120, or less than or equal to 0.110. In embodiments, CDFLs at a molecular weight less than 100,000 g / mol is greater than or equal to 0.075 and less than or equal to 0.140, for example greater than or equal to 0.085 and less than or equal to 0.130 or greater than or equal to 0.095 and less than or equal to 0.115.

[0055] In embodiments, the CDFLS at a molecular weight greater than 1,500,000 g / mol is greater than or equal to 0.110, for example greater than or equal to 0.120, greater than or equal to 0.130, greater than or equal to 0.135, greater than or equal to 0.140, or greater than or equal to 0.145. In embodiments, the CDFLS at a molecular weight greater than 1,500,000 g / mol is greater than or equal to 0.110 and less than or equal to 0.160, for example greater than or equal to 0.120 and less than or equal to 0.155, or greater than or equal to 0.130 and less than or equal to 0.155. Petition 870250003166, dated 15 / 01 / 2025, p. 27 / 121 19 / 53

[0056] In embodiments, low-density polyethylene has greater than or equal to 1.5 amyl (C5) groups per 1,000 total carbon atoms and less than or equal to 3.0 amyl (C5) groups per 1,000 total carbon atoms, as determined by 13C NMR.

[0057] In embodiments, the polymer has no C1 branches (methyl branches) per 1,000 total carbon atoms.

[0058] In embodiments, low-density polyethylene has 1.5 or more 1,3-diethyl branches per 1,000 total carbon atoms and 5.0 or fewer 1,3-diethyl branches per 1,000 total carbon atoms.

[0059] In embodiments, low-density polyethylene has 3.0 or more and 4.0 or fewer C6+ branches per 1,000 total carbon atoms.

[0060] In embodiments, low-density polyethylene has 0.018 or more vinyls per 1,000 total carbon atoms and 0.043 or fewer vinyls per 1,000 total carbon atoms.

[0061] In embodiments, low-density polyethylene has 0.01 or more cis and trans (vinylene) groups per 1,000 total carbon atoms and 0.03 or fewer cis and trans (vinylene) groups per 1,000 total carbon atoms.

[0062] In embodiments, low-density polyethylene has 0.05 or more vinylidenes per 1,000 total carbon atoms and 0.25 or less vinylidenes per 1,000 total carbon atoms. Additives

[0063] The embodiments of the compositions may comprise one or more additives. Additives include stabilizers, plasticizers, antistatic agents, pigments, dyes, nucleating agents, fillers, slip agents (such as erucamide, oleamide and stearamide), flame retardants, processing aids, smoke inhibitors, viscosity control agents, antiblocking agents (including talc and silicon dioxide) and oils, for example mineral oils. The polymer composition may, for example, comprise less than 10 percent (by combined weight) of one or more additives, based on the weight of the low-density polyethylene of the embodiments. In embodiments, the low-density polyethylene may be Petition 870250003166, dated 15 / 01 / 2025, page 28 / 121 20 / 53 treated with one or more stabilizers, for example antioxidants, for example IRGANOX 1010, IRGANOX 1076 and IRGAFOS 168 (BASF). It should be understood that in the embodiments, no stabilizer is used.

[0064] Blends and mixtures of low-density polyethylene of the modalities can be made with other polymers. Polymers suitable for blending with low-density polyethylene of the modalities include natural and synthetic polymers. Exemplary polymers for blending include propylene-based polymers (both atactic polypropylene, isotactic polypropylene, and impact-modified polypropylene polymers, as well as random ethylene / propylene copolymers), various types of ethylene-based polymers, including high-pressure free-radical LDPE, LLDPE prepared with Ziegler-Natta catalysts, PE prepared with single-site catalysts, including multi-reactor PE (reactor blends of Ziegler-Natta PE and single-site catalyzed PE, for example, products disclosed in USP documents 6,545,088 (Kolthammer et al.); 6,538,070 (Cardwell et al.); 6,566,446 (Parikh et al.); 5,844,045 (Kolthammer et al.); 5,869,575 (Kolthammer et al.); and 6,448.341 (Kolthammer et al.)), EVA, ethylene / vinyl alcohol copolymers, polystyrene, impact-modified polystyrene, ABS, styrene / butadiene block copolymers and hydrogenated derivatives thereof (SBS and SEBS), and thermoplastic polyurethanes. Homogeneous polymers, for example olefin plastomers and elastomers, ethylene-propylene-based copolymers (e.g., polymers available under the trade names VERSIFY™ Plastomers & Elastomers (The Dow Chemical Company) and VISTAMAXX (ExxonMobil Chemical Co.)) can also be useful as components in blends comprising low-density polyethylene of the embodiments. LLDPEs such as INNATE™, DOWLEX™ and DOWLEX™ GM (The Dow Chemical Company) and Exceed and Exceed XP (Exxon Chemical Company) can also be used.

[0065] Additives such as slip additives, antioxidants, or antiblocking agents can affect the properties of the resin. Additionally, oils, such as mineral oil, which can be used as additive carriers, can also affect the properties of the resin. A low-density polyethylene Petition 870250003166, dated 15 / 01 / 2025, page 29 / 121 21 / 53 can be analyzed to determine the presence of additives using various methods, including a slip additive method, a primary and secondary antioxidant method, an antiblocking method, and a mineral oil method, described in more detail below.

[0066] The presence of additives can affect molecular weight, hexane extractables, and density. For example, low molecular weight properties of additives can decrease the molecular weight of the ethylene-based polymer. Therefore, as detailed in this document, in the low molecular weight region of the GPC elution curve, when a peak is known to be caused by the presence of antioxidants or other additives, the presence of such a peak may cause an underestimation of the number-average molecular weight (Mn) of the polymer sample, resulting in an overestimation of the sample polydispersity defined as Mw / Mn, where Mw is the weight-average molecular weight. Similarly, when additives are present, a measurement of hexane extractables includes all hexane-soluble additives, but the measurement of hexane extractables does not include additives that are not hexane-soluble, for example, antiblocking agents.Therefore, the percentage of hexane extractables in a resin with additives would be equal to the sum of the percentage of hexane extractables in the ethylene-based polymer without additives and the percentage of hexane-soluble additives (such as slip agents and antioxidants) and / or any hexane-soluble oils (such as those that can be used as a vehicle for additives). Finally, additives, for example antiblocking agents, can increase the density of the ethylene-based polymer. The density (in g / cm3) of an ethylene-based polymer free of any additives (when the additive is an antiblocking agent such as talc or silicon dioxide) can be expressed by the following expression: Density of the additive-free polymer (mm / cm3) = Density of the polymer with antiblocking agent (mm / cm3) P pp, flppm. of additive - [°'0006'J-m'^1M0) Applications Petition 870250003166, dated 15 / 01 / 2025, page 30 / 121 22 / 53

[0067] Low-density polyethylene of the embodiments can be employed in a variety of conventional thermoplastic manufacturing processes to produce useful articles, including monolayer and multilayer films; molded articles, for example blow-molded, injection-molded, mold-molded, or rotomolded articles; coatings; fibers; and woven or non-woven fabrics.Low-density polyethylene of this type can be used in a variety of films, including but not limited to extrusion coating, food packaging, industrial, agricultural or consumer applications or films, lamination films, films for fresh fruits and vegetables, melt-blown films, blown films, thermoformed films, meat films, cheese films, candy films, transparent shrink films, shrink films for ready meals, stretch films, silage films, greenhouse films, fumigation films, coating films, stretch covers, heavy-duty transport bags, pet food, sandwich bags, seals and diaper bottom layers.

[0068] Low-density polyethylene of the various forms is also useful in other direct end-use applications. Low-density polyethylene of the various forms can be used for wire and cable sheathing operations, in sheet extrusion for vacuum forming operations and forming of molded articles, including the use of injection molding, blow molding or rotomolding processes. Other suitable applications for low-density polyethylene of the various forms include elastic fibers and films; soft-touch products, for example utensil handles; trims and profiles; parts and profiles for vehicle interiors; foam products (open-cell and closed-cell); impact modifiers for other thermoplastic polymers, for example high-density polyethylene or other olefin polymers; lid liners; and flooring.

[0069] In the embodiments disclosed and described in this document, low-density polyethylene is low-density polyethylene without additives, unless explicitly indicated otherwise, and the Petition 870250003166, dated 15 / 01 / 2025, p. 31 / 121 23 / 53 properties disclosed in this document refer to low-density polyethylene without additives, unless otherwise disclosed. Testing methods Testing methods include the following: Density

[0070] Samples for density measurements were prepared according to ASTM D 4703-10. Samples were pressed at 190 °C (374 °F) for five minutes at 68 MPa (10,000 psi). The temperature was maintained at 190 °C (374 °F) for the five minutes mentioned above, and then the pressure was increased to 207 MPa (30,000 psi) and maintained for three minutes. This was followed by a one-minute hold at 21 °C (70 °F) and 207 MPa (30,000 psi). Measurements were taken within one hour of sample pressing using ASTM D792-08, Method B. Merger index

[0071] The melt flow index or melt index or I2, was measured according to ASTM D 1238-10, under conditions of 190 °C / 2.16 kg, Method B, and was reported in grams eluted over 10 minutes. Nuclear magnetic resonance (13C NMR)

[0072] Samples were prepared by adding approximately 3 g of 1,1,2,2-tetrachloroethane (TCE) containing 12% by weight of TCE-d2 and 0.025 M Cr(AcAc)3 to a 0.25–0.40 g polymer sample in a 10 mm NMR tube. Oxygen was removed from the sample by purging the headspace of the tube with nitrogen. The samples were then dissolved and homogenized by heating the tube and its contents to 120–140 °C using a heating block and heat gun. Each dissolved sample was visually inspected to ensure homogeneity. The samples were thoroughly mixed immediately before analysis and were not allowed to cool before insertion into the heated NMR sample holders.

[0073] All data were collected using a 600 MHz Bruker spectrometer equipped with a 10 extended temperature cryogenic probe. Petition 870250003166, dated 15 / 01 / 2025, page 32 / 121 24 / 53 mm. Data were acquired using a pulse repetition delay of 7.8 seconds, a nutation angle of 90 degrees, and inverse discontinuous decoupling, with a sample temperature of 120 °C. All measurements were made on non-rotating samples in locked mode. Samples were allowed to thermally equilibrate for seven minutes before data acquisition. 13C NMR chemical shifts were internally referenced to the EEE triad at 30.0 ppm. The C6+ value is a direct measure of C6+ branching in low-density polyethylene, where long branches are indistinguishable from chain ends. The 32.2 ppm peak, representing the third carbon from the end of all chains or branches of six or more carbons, is used to determine the C6+ value. Table 1: Branching type and integral bands of 13C NMR used for quantification Type of branching Integrated peak(s) Identity of integrated carbon peak(s) 1,3-diethyl approximately 10.5 to 11.5 ppm 1,3-diethyl branching C2 on quaternary carbon approximately 7.5 to 8.5 ppm 2 ethyl branches on a quaternary carbon, C1 methyls approximately 19.75 to 20.50 ppm C1, C4 methyl branches approximately 23.3 to 23.5 ppm Second CH2 in a 4-carbon branch, counting the methyl as the first C C5 approximately 32.60 to 32.80 ppm Third CH2 in a 5-carbon branch, counting the methyl as the first C or Cg+ approximately 32.1 to 32.3 ppm The third CH2 (counting the methyl as the first C) in any 6-carbon branch or more carbons in length Nuclear magnetic resonance (1H NMR)

[0074] Samples were prepared by adding approximately 120 mg of sample to 3.25 g of 50 / 50, by weight, tetrachloroethane-d2 / perchloroethylene with 0.001 M Cr(AcAc)3 in a 10 mm NMR tube. The sample was purged by bubbling N2 through the Petition 870250003166, dated 15 / 01 / 2025, p. 33 / 121 25 / 53 solvent, using a pipette inserted into the tube, for about five minutes to prevent oxidation. Each tube was capped and sealed with Teflon tape. The sample was heated and vortexed at 110 to 115 °C to ensure homogeneity.

[0075] 1H NMR was performed on a 600 MHz Bruker spectrometer equipped with a 10 mm extended temperature cryogenic probe. Data were acquired with ZG pulse, 64 scans, pulse repetition delay of 15.8 seconds and sample temperature of 120 °C.

[0076] The whole polymer signal, about 3 to -0.5 ppm, was set to an arbitrary value, typically 20000. The corresponding integrals for unsaturation (vinylene at about 5.40 to 5.60 ppm, trisubstituted at about 5.16 to 5.35 ppm, vinyl at about 4.95 to 5.15 ppm and vinylidene at about 4.70 to 4.90 ppm) were obtained.

[0077] The integral of the entire polymer from the control experiment was divided by two, to obtain a value that represents X thousand carbons (that is, if the polymer integral = 20,000, this represents 10,000 carbons and X = 10).

[0078] The integrals of unsaturated groups, divided by the corresponding number of protons that contribute to that integral, represent the moles of each type of unsaturation per X thousand carbons. Dividing the moles of each type of unsaturation by X, the number of moles of unsaturated groups per 1,000 moles of carbons is then given. Casting strength

[0079] The casting strength measurements were performed on a Gottfert Rheotens 71.97 (Gottfert Inc.; Rock Hill, SC, USA), coupled to a Gottfert Rheotester 2000 capillary rheometer. The molten sample (approximately 25 to 30 grams) was fed into a Gottfert Rheotester 2000 capillary rheometer, equipped with a flat entry angle (180 degrees) of 30 mm length, 2.0 mm diameter, and an aspect ratio (length / diameter) of 15. After the samples were equilibrated at 190 °C for 10 minutes, the piston was operated at a constant speed of 0.265 mm / second. The standard test temperature was Petition 870250003166, dated 15 / 01 / 2025, page 34 / 121 26 / 53 190 °C. The sample was extended uniaxially in a set of acceleration jaws, 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 jaw rollers. The casting strength was reported as the average plateau force (cN) before weld rupture. The following conditions were used in the casting strength measurements: piston speed = 0.265 mm / second; wheel acceleration = 2.4 mm / s²; capillary diameter = 2.0 mm; capillary length = 30 mm; and tube diameter = 12 mm. Dynamic mechanical spectroscopy (DMS)

[0080] The resins were compression molded into circular plates 3 mm thick x 1 inch in diameter at 177 °C for five minutes under 25000 psi pressure in air. The sample was then removed from the press and placed on a bench to cool.

[0081] A constant-temperature frequency sweep was performed using a TA Instruments Advanced Rheometric Expansion System (ARES) equipped with 25 mm (diameter) parallel plates under a nitrogen purge. The sample was placed on the plate and allowed to melt for five minutes at 190 °C. The plates were then closed to a 2 mm gap, the sample was trimmed (excess sample extending beyond the circumference of the 25 mm diameter plate was removed), and the test was initiated. The method had a predefined additional delay of five minutes to allow for temperature equilibration. The experiments were performed at 190 °C in a frequency range of 0.1 to 100 rad / s. The strain amplitude was constant at 10%. The complex viscosity η*, tan (δ) or tan delta, the viscosity at 0.1 rad / s (V0.1), the viscosity at 100 rad / s (V100), and the viscosity ratio (V0.1 / V100) were calculated from these data. GPC Triple-detection gel permeation chromatography (TDGPC)

[0082] The chromatographic system consisted of a PolymerChar GPC-IR high-temperature GPC chromatograph (Valencia, Spain) equipped with an internal IR5 infrared detector (IR5) and a 4-capillary viscometer (DV) Petition 870250003166, dated 15 / 01 / 2025, p. 35 / 121 A 27 / 53 instrument coupled to a 2-angle laser light scattering (LS) detector, Model 2040, from Precision Detectors (currently Agilent Technologies). For all light scattering measurements, a 15-degree angle was used for measurement purposes. The autosampling oven compartment was set to 160° Celsius and the column compartment to 150° Celsius. The columns used were four 30 cm long, 20 micron Agilent Mixed A linear mixed-bed columns and one 20 µm pre-column. The chromatographic solvent used was 1,2,4-trichlorobenzene containing 200 ppm butylated hydroxytoluene (BHT). The solvent source was sprayed with nitrogen. The injection volume used was 200 microliters and the flow rate was 1.0 milliliter / minute.

[0083] The calibration and calculation of conventional molecular weight moments and distribution (using 20 pm Mixed A columns) were performed according to the method described in the conventional GPC procedure.

[0084] The systematic approach to determining multidetector deviations is consistent with that published by Balke, Mourey, et al. (Mourey and Balke, Chromatography Polym. Chapter 12, (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym. Chapter 13, (1992)), optimizing the log (MW and IR) results of the triple detector from a broad homopolymer polyethylene standard (Mw / Mn > 3) to the narrow standard column calibration results of the narrow standard calibration curve using PolymerChar GPCOne™ software. As used in this document, MW refers to molecular weight.

[0085] Absolute molecular weight data were obtained in a manner consistent with that published by Zimm (Zimm, BH, J. Chem. Phys., 16, 1099 (1948)) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987)) using PolymerChar GPCOne™ software. The total injected concentration, used in the molecular weight determination, was obtained from the mass detector area and the mass detector constant, derived from a suitable linear polyethylene homopolymer, or from one of the medium molecular weight polyethylene standards. Petition 870250003166, dated 15 / 01 / 2025, page 36 / 121 28 / 53 known weight. The calculated molecular weights (using GPCOne™) were obtained using a light scattering constant derived from one or more of the polyethylene standards mentioned below, and a refractive index concentration coefficient, dn / dc, of 0.104. In general, the mass detector response (IR5) and the light scattering constant (determined using GPCOne™) should be determined from a linear standard with a molecular weight above approximately 50,000 g / mol. The viscometer calibration (determined using GPCOne™) can be performed using the methods described by the manufacturer or, alternatively, using published values ​​of suitable linear standards, for example Standard Reference Materials (SRM) 1475a (available from the National Institute of Standards and Technology (NIST)).A viscometer constant (obtained using GPCOne™) is calculated that relates the specific viscosity area (DV) and the injected mass of the calibration standard to its intrinsic viscosity (IV). Chromatographic concentrations are assumed to be low enough to eliminate the effects of the 2nd viral coefficient (concentration effects on molecular weight).

[0086] The absolute weight-average molecular weight (Mw(Abs)) is obtained (using GPCOne™) from the integrated light scattering (LS) chromatogram area (factored by the light scattering constant) divided by the recovered mass from the mass constant and the mass detector area (IR5). The molecular weight and intrinsic viscosity responses are extrapolated at the chromatographic ends where the signal-to-noise ratio becomes low (using GPCOne™). Other respective momenta, Mn(Abs) and Mz(Abs), are calculated according to equations 1 and 2 as follows: (MnçAbs) = GO, (EQ 1) Petition 870250003166, dated 15 / 01 / 2025, p. 37 / 121 29 / 53 Y(lR, *MAbsoluto^ MZ(Abs) = —--------------Σ( / Ã'·*MQ>2)'oí) (EQ 2) Conventional GPC

[0087] The chromatographic system consisted of a PolymerChar GPC-IR high-temperature GPC chromatograph (Valencia, Spain), equipped with an internal IR5 infrared detector (IR5) coupled to a Precision Detectors (currently Agilent Technologies) Model 2040 2-angle laser light scattering (LS) detector. For all light scattering measurements, a 15-degree angle was used for measurement purposes. The autosampling oven compartment was set at 160° Celsius and the column compartment was set at 150° Celsius. The columns used were 4 Agilent Mixed A linear mixed-bed columns, 30 cm, 20 microns. The chromatographic solvent used was 1,2,4-trichlorobenzene and contained 200 ppm butylated hydroxytoluene (BHT). The solvent source was sprayed with nitrogen. The injection volume used was 200 microliters and the flow rate was 1.0 milliliter / minute.

[0088] The GPC column assembly calibration was performed using 21 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 g / mol to 8,400,000 g / mol, which were arranged into 6 cocktail mixtures with at least a decade of separation between the individual molecular weights. The standards were purchased from Agilent Technologies. The polystyrene standards were prepared with 0.025 grams in 50 milliliters of solvent for molecular weights equal to or greater than 1,000,000 g / mol, and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000 g / mol. The polystyrene standards were dissolved at 80 degrees Celsius with gentle stirring for 30 minutes. The standard peak molecular weights of polystyrene were converted to polyethylene molecular weights using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)): Petition 870250003166, dated 15 / 01 / 2025, page 38 / 121 30 / 53 MWpolyethylene A ^ Ç^^polystyrene') (EQ 3) where MW is the molecular weight, A has a value of 0.4315 and B is equal to 1.0.

[0089] A fifth-order polynomial was used to fit the respective equivalent polyethylene calibration points. A small adjustment of A (from approximately 0.3950 to 0.440) was made to correct for column resolution and band broadening effects such that the linear homopolymer polyethylene standard is obtained at 120,000 Mw.

[0090] The total plate count of the GPC column array was performed with decane (prepared with 0.04 g in 50 milliliters of TCB). The plate count (Equation 4) and symmetry (Equation 5) were measured in a 200 microliter injection according to the following equations: Plate count = 5.54 * Peak maximum voltage (RVmáx.), . 1 .. Peak Width a - Height (EQ 4) where RV is the retention volume in milliliters, peak width is expressed in milliliters, peak maximum is the maximum height of the peak, and ½ height is ½ of the height of the peak maximum. Symmetry = Rear Peak RV One tenth of the height Peak RV I^^Max. of peak peakFrontalRVOne tenth of the height) (EQ 5) where RV is the retention volume in milliliters and the peak width is expressed in milliliters, the maximum peak is the maximum position of the peak, one tenth of the height is 1 / 10 of the peak maximum height, and rear peak refers to the peak tail in retention volumes after the peak maximum, and front peak refers to the peak front in retention volumes before the peak maximum. The chromatographic system plate count must be greater than 20,000 and the symmetry must be between 0.98 and 1.22.

[0091] Samples were prepared semi-automatically using PolymerChar Instrument Control software, with a target sample weight of 2 mg / ml, and the solvent (containing 200 ppm BHT) was added to a septum-capped ampoule pre-sprayed with nitrogen using the PolymerChar high-temperature autosampler. Samples Petition 870250003166, dated 15 / 01 / 2025, page 39 / 121 31 / 53 were dissolved for 2 hours at 160° Celsius under low-speed stirring.

[0092] The calculations of Mn (conv), Mw (conv) and Mz (conv) were based on the GPC results using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph according to Equations 6 to 8, using the PolymerChar GPCOne™ software, the IR chromatogram was subtracted from the baseline at each of the equally spaced data collection points (i) and the equivalent molecular weight of polyethylene was obtained from the narrow standard calibration curve for point (i) of Equation 1. Σιΐϋι Mn(conv) =tí(irí / ) y / ^poíietiíeno^ / (EQ 6) Mw(conv) =Σ'(,ί,|'ιΣ'°“«“«'·°ί) (eq 7) ..z ΆZÍ(íRí*Mpolyethylene,·2)ox Mz(conv) = '-- (EQ 8) XI(7Ri*Mp0(iefi(en0^J

[0093] In the low molecular weight region of the GPC elution curve, when a peak is known to be caused by the presence of antioxidants or other additives, the presence of such a peak will cause an underestimation of the number-average molecular weight (Mn) of the polymer sample, resulting in an overestimation of the sample's polydispersity defined as Mw / Mn, where Mw is the weight-average molecular weight. The true molecular weight distribution of the polymer sample must therefore be calculated from the GPC elution, excluding this extra peak. This process is commonly described as the peak scrubbing feature in data processing procedures in liquid chromatography analyses. In this process, this additive peak is scrubbed from the GPC elution curve before the sample molecular weight calculation is performed from the curve. Petition 870250003166, dated 15 / 01 / 2025, page 40 / 121 32 / 53 of GPC elution. The chromatographic system plate count must be greater than 24,000 and the symmetry must be between 0.98 and 1.22.

[0094] In order to monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate (Flow rate(nominal)) of each sample by aligning the RV of the respective decane peak of the sample (RV(FM Sample)) with that of the decane peak of the narrow standard calibration (RV(FM Calibrated)). Any changes in the decane marker peak over time were then assumed to be related to a linear shift in the flow rate (Flow rate(effective)) for the entire round. To facilitate obtaining the highest possible accuracy of a flow rate measurement of the flow marker peak, a least squares fitting routine is used to fit the peak of the flow marker concentration chromatogram to a quadratic equation.The first derivative of the quadratic equation is then used to solve for the true peak position. After calibrating the system based on a flow marker peak, the effective flow rate (relative to the narrow standard calibration) is calculated according to Equation 9. Flow marker peak processing was performed using PolymerChar GPCOne™ software. An acceptable flow rate correction is such that the effective flow rate should be within + / - 1% of the nominal flow rate. Effective flow rate = Nominal flow rate * (RV(calibrated FM) / RV(sample FM)) (EQ 9)

[0095] The systematic approach to determining multi-detector deviations is consistent with that published by Balke, Mourey, et al. (Mourey and Balke, Chromatography Polym. Chapter 12, (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym. Chapter 13, (1992)), optimizing the log (MW and IR) results of the triple detector from a broad homopolymer polyethylene standard (Mw / Mn > 3) to the narrow calibration results of the standard column curve. Petition 870250003166, dated 15 / 01 / 2025, page 41 / 121 33 / 53 Calibration of narrow standards using PolymerChar GPCOne™ software.

[0096] Absolute molecular weight data were obtained in a manner consistent with that published by Zimm (Zimm, BH, J. Chem. Phys., 16, 1099 (1948)) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987)) using PolymerChar GPCOne™ software. The total injected concentration, used in the molecular weight determination, was obtained from the mass detector area and the mass detector constant, derived from a suitable linear polyethylene homopolymer, or from one of the polyethylene standards of known weight-average molecular weight. The calculated molecular weights (using GPCOne™) were obtained using a light scattering constant derived from one or more of the polyethylene standards mentioned below, and a refractive index concentration coefficient, dn / dc, of 0.104.In general, the mass detector response (IR5) and the light scattering constant (determined using GPCOne™) should be determined from a linear standard with a molecular weight above approximately 50,000 g / mol. CDF Calculation Method

[0097] The calculation of the cumulative detector fractions (CDF) of the IR5 measurement detector (CDFIR), the cumulative viscosity detector fractions (CDFDV) and the small-angle laser light scattering detector (CDFLS) are performed by the following steps (visually represented as Figure 2, Figure 3 and Figure 4 for CDFIR, CDFDV and CDFLS): 1) Linearly correct the chromatogram flow based on the ratio of the relative air peak retention volume between the sample and that of a cocktail mixture of narrow, consistent standards. 2) Correct the displacement of the light scattering detector relative to the refractometer, as described in the Gel Permeation Chromatography (GPC) section. 3) Calculate the molecular weights in each slice of retention volume (RV) data based on the polystyrene calibration curve, modified by the polystyrene conversion factor. Petition 870250003166, dated 15 / 01 / 2025, page 42 / 121 34 / 53 polyethylene of approximately (0.3950 to 0.44), as described in the Gel Permeation Chromatography (GPC) section. 4) Subtract baselines from the refractometer and light scattering chromatograms and set up integration windows using standard GPC practices, integrating the entire low molecular weight retention volume range in the light scattering chromatogram that is observable from the refractometer chromatogram (thus setting the maximum RV limit to the same index in each chromatogram). Do not include in the integration any material corresponding to less than 150 g / mol in either chromatogram. 5) Calculate the cumulative detector fraction (CDF) of the IR5 measurement sensor (CDFIR), viscosity chromatogram (CDFDV), and small-angle laser light scattering chromatogram (LALLS) (CDFLS) based on its peak height subtracted from the baseline (H), from high molecular weight to low molecular weight (low to high retention volume) in each data slice (j) according to Equations 10A, 10B, 10C, 10D, 10E, and 10F and as shown in Figure 2, Figure 3, and Figure 4 for Example 1: yj=RV in the maximum integrated volume. CDF _ ^j= RV in MW of 3,000__________^1 / Pn 1 ΠΔA rR<5,000MW ~J=RV in the maximum integrated volume __ . (Eq. 10A) ^j = RV in the minimum integrated volume n1 yj = RV in MW of 200,000 „. CDF _ ^j = RV in the minimum integrated volume ^1 / p 1AR) IR > 200,000 MW yj = RV in the maximum integrated volume __ . (Eq. 10B) ^j = RV in the minimum integrated volume n1 jj = RV in the maximum integrated volume . CDF _ Lj = RV in MW of 25,000__________HJ / pj DV < 25,000 MW yj = RV in the maximum integrated volume „ (Eq. 10C) Σί = RV in the minimum integrated volume n1 Σ j = RV in MW of 1,000,000 „. CDF, _ ^j = RV in the minimum integrated volume ^1 / q 1fih\ 9V>1,000,000MW ~J=RV in the maximum integrated volume __ . (Eq· 10D) ^j= RV in the minimum integrated volume n1 yj=RV in the maximum integrated volume . CDF _ Fj= RV in MW of 100,000_________™J / p LS<100,000MW ~J=RV in the minimum integrated volume „. (Eq' 10E)Σ]= RV in the minimum integrated volume n1 yj=RV in MW of 1,500,000 „. CDF _ ^j=RV in the minimum integrated volume ^1 / q ΗΛO LS>1,500.000MW yj=RV in the maximum integrated volume __ . (Eq· 10F) ^'j= RV in the minimum integrated volume n1. Petition 870250003166, dated 15 / 01 / 2025, page 43 / 121 35 / 53 Branching index of gpcBR by triple detector GPC (3D-GPC)

[0098] The branching index of gpcBR is determined by first calibrating the light scattering, viscometer, and concentration detectors, as described previously. Baselines are then subtracted from the light scattering, viscometer, and concentration chromatograms. Integration windows are then configured to ensure integration of the entire low molecular weight retention volume range in the light scattering and viscometer chromatograms that indicate the presence of detectable polymer from the infrared chromatogram (IR5). Linear polyethylene standards are then used to establish Mark-Houwink constants for polyethylene and polystyrene. After obtaining the constants, the two values ​​are used to construct two conventional linear reference calibrations for the molecular weight of polyethylene and the intrinsic viscosity of polyethylene as a function of elution volume, as shown in Equations (11) and (12): MWPE= (KPS / KPE)1 / apE +1· MWPS“ps+1 / “pe+1(EQ 11) [η]ΡΕ= Kps · MWps“+1 / MWpe (EQ 12).

[0099] The gpcBR branching index is a robust method for characterizing long-chain branching, as described in Yau, Wallace W., Examples of Using 3D-GPC—TREF for Polyolefin Characterization, Macromol. Symp., 2007, 257, 29-45. The index avoids the slice-by-slice 3D-GPC calculations traditionally used in determining g' values ​​and branching frequency calculations, in favor of whole polymer detector areas. From the 3D-GPC data, the absolute weight-average molecular weight of the sample (Mw (abs)) can be obtained by the light scattering (LS) detector, using the peak area method. The method avoids the slice-by-slice ratio between the light scattering detector signal and the concentration detector signal, as required in a traditional g' determination.

[0100] With 3D-GPC, the intrinsic viscosities of the sample also Petition 870250003166, dated 15 / 01 / 2025, page 44 / 121 36 / 53 are obtained independently using Equation (13). This area calculation offers more precision because, as a general sample area, it is much less sensitive to variations caused by detector noise and 3D-GPC settings in the baseline and integration limits. And most importantly, the peak area calculation is not affected by detector volume deviations. Similarly, the intrinsic viscosity (IV) of the high-precision sample is obtained by the area method shown in Equation (13): jy Z / Ci / Vi Viscometer AreaWΣί Ct Σι Ci Cone Area.1where qspi represents the specific viscosity obtained from the viscometer detector.

[0101] To determine the branching index of gpcBR, the light scattering elution area of ​​the sample polymer is used to determine the molecular weight of the sample. The viscosity detector elution area for the sample polymer is used to determine the intrinsic viscosity (IV or [η]) of the sample.

[0102] Initially, the molecular weight and intrinsic viscosity of a standard linear polyethylene sample, for example SRM1475a or equivalent, are determined using conventional calibrations (cc) for molecular weight and intrinsic viscosity as a function of elution volume, according to Equations (14) and (15): ZiCiIVtcc Σ,ί^Κ ÇMicc)a Σ / Σ / ci (EQ14) Equation (15) is used to determine the branching index of gpcBR: gpcBR = (EQ 15) where [η] is the measured intrinsic viscosity, [q]c is the intrinsic viscosity Petition 870250003166, dated 15 / 01 / 2025, page 45 / 121 37 / 53 obtained from conventional calibration, Mw is the measured weight-average molecular weight and Mw,cc is the weight-average molecular weight from conventional calibration. The light scattering (LS) weight-average molecular weight is commonly referred to as the absolute weight-average molecular weight or Mw(abs). The Mw,cc from Equation (7) using the conventional GPC molecular weight calibration curve (conventional calibration) is often referred to as the main polymer chain molecular weight, conventional weight-average molecular weight and Mw (conv).

[0103] All statistical values ​​with the subscript cc are determined using their respective elution volumes, the corresponding conventional calibration as previously described, and the concentration (Ci). Values ​​without subscripts are measured values ​​based on the areas of the mass detector, LALLS, and viscometer. The Kpe value is iteratively adjusted until the linear reference sample has a measured gpcBR value equal to zero. For example, the final values ​​of α and Log K for the determination of gpcBR in this particular case are 0.725 and -3.391, respectively, for polyethylene, and 0.722 and -3.993, respectively, for polystyrene. After the K and α values ​​are determined using the procedure discussed previously, the procedure is repeated for the branched samples. The branched samples are analyzed using the final Mark-Houwink constants obtained from the linear reference as the best cc calibration values.For linear polymers, the gpcBR calculated by Equation (15) will be close to zero, since the values ​​measured by LS and viscometry will be close to the conventional calibration standard. For branched polymers, the gpcBR will be greater than zero, especially with high levels of long-chain branching, due to the fact that the measured polymer molecular weight will be greater than the calculated Mw,cc, and the calculated IVcc will be greater than the measured polymer IV. In fact, the gpcBR value represents the fractional change in IV due to the molecular size contraction effect as a result of polymer branching. A gpcBR value of 0.5 or 2.0 signifies a molecular size concentration effect of the IV at the 50% level. Petition 870250003166, dated 15 / 01 / 2025, page 46 / 121 38 / 53 200%, respectively, versus that of a linear polymer molecule of equivalent weight. For these particular examples, the advantage of using gpcBR, compared to a traditional g' index and branching frequency calculations, is the greater precision of gpcBR. All parameters used in the determination of the gpcBR index are obtained with good precision and are not affected by the low response of the 3D-GPC detector at high molecular weight detector concentrations. Detector volume alignment errors also do not affect the precision of the gpcBR index determination. LSP Parameter

[0104] Representative values ​​for the GPC light scattering parameters (LSP) can be found in Tables 1 and 2 and Figure 5 for Example 1. The analysis of the materials was performed similarly to that of US patent No. 8,916,667B2 (Karjala et al.). The x-axis of the graph is the logarithmic molecular weight value by conventional GPC calculation, or cc-GPC molecular weight. The y-axis is the LS detector response. The specific characteristics of the LS elution profile are captured as defined by two logarithmic molecular weight limits. The lower limit corresponds to an MW1 value of 100,000 g / mol and the upper limit corresponds to an MW2 value of 900,000 g / mol. The vertical lines of these two molecular weight limits intersect the LS elution curve at two points. A line segment is drawn connecting these two intercept points. The height of the LS signal at the first intercept (log MW1) gives the LS1 quantity.The height of the LS signal at the second intercept (log MW2) gives the LS2 quantity. The area under the LS elution curve within the two molecular weight limits gives the Area B quantity. Comparing the LS curve with the line segment connecting the two intercepts, there may be part of the segregated area that is above the line segment (see A2 in Figure 5, defined as a negative value) or below the line segment (as A1 in Figure 5, defined as a positive value). The sum of A1 and A2 gives the Area A quantity, the Total Area A. This Total Area A can be calculated as the difference between Area B and the area below the line segment. Petition 870250003166, dated 15 / 01 / 2025, page 47 / 121 39 / 53

[0105] The steps for calculating the LS quantity are illustrated with Example 1 shown in Table 2 and Table 3.

[0106] Step 1 Calculate F_slope] in Table 1, using equations 1 and 17 below: FLS2-LS11 Valorda.t. = =ί LS2 J(EQ 16)dainclinaçao dLogMW ' ' ^inclinação = função da inclinação = abs (valordainclinação— 0,42^ + 0,001 (EQ 17)

[0107] Step 2, calculate 'F_area' and LSF in Table 2, using equations 18 and 19 below: F_area = area function = Abs (Abs (A / B) + 0.033) — 0.005) (EQ 18) where A / B = (Area A) / (Area B) LSP = Log (Area * Slope) + 4 (EQ 19) Table 2: Calculation of F slope MW1 100.0 g / mol 00 MW2 = 1900,000 g / mol Log (MW2) Log (MW1) Abs (slope 0.42) + 0.001 Sample Ls1 Log MW1 LS2 Log MW2 dLog MW Slope value F_slope Ex. 1 0.84 5.00 3.65 5.95 0.95 0.8072 0.3882 Table 3: Calculation of F area and LSP Sample Area B of the LS Curve Area A (A1+A2) A / B Abs (Abs (A / B)+0.033)0.005= Area F Log (F_area * F_slope) + 4 = LSP Ex. 1 304.125 63.5520 0.20897 0.2370 2.96 Extractables with hexane

[0108] Polymer pellets (from a polymerization pelletizing process, without further modification; approximately 2.2 grams per 1-inch x 1-inch square film) were pressed in a Carver Press to a thickness of 3.0 to 4.0 mils. The pellets were pressed at 190°C for 3 minutes at 8000 psi followed by cooling for 3 minutes followed by another pressing at 190°C for 3 minutes at 40000 psi followed by cooling (12 minutes total). Residue-free gloves (PIP* CleanTeam* CottonLisle inspection gloves, part number: 97-501) were used to prevent contamination of the film with residual oils from the operator's hands. Each film was Petition 870250003166, dated 15 / 01 / 2025, page 48 / 121 40 / 53 trimmed until a 1 inch x 1 inch square weighing (2.5 ± 0.05 g) was obtained. The films were extracted for 2 hours in a hexane container containing approximately 1000 ml of hexane at 49.5 ± 0.5 °C in a heated water bath. The hexane was an isomeric mixture of hexanes (e.g., Hexanes (Optima), Fisher Chemical, high-purity mobile phase for HPLC and / or extraction solvent for GC applications). After two hours, the films were removed, rinsed in clean hexane, and dried in a vacuum oven at (80 ± 5 °C) under total vacuum (ISOTEMP vacuum oven, model 281A, at approximately 30 inches of Hg) for two hours. The films were then placed in a desiccator and allowed to cool to room temperature for at least one hour. The films were then weighed again and the amount of mass loss due to hexane extraction was calculated. This method is based on procedure 21 CRF 177.1520 (d)(3)(ii), with a single deviation from the FDA protocol which is the use of hexanes instead of n-hexane; reported average of 3 measurements. Slip additives

[0109] Approximately 5 grams of sample were weighed (and recorded with a resolution of 0.0001 g) into a 16-ounce glass vial. A polytetrafluoroethylene (PTFE) coated stir bar was added to the vial along with 120 ml of 0.04% triethyl phosphite in o-xylene using a solvent dispenser. The vial was loosely stoppered and placed on a heated shaker for 30 minutes at 130°C with stirring. After 30 minutes, the vial was removed to cool the solution to room temperature with stirring for at least 2 hours. The polymer was then precipitated by adding 250 ml of methanol to the vial using a solvent dispenser. The solution was stirred during this addition. The solution was stirred for a further 2 hours. After 2 hours of stirring, the vial was removed and the solids were allowed to settle. An aliquot of the solution was removed with a glass pipette and transferred to a 2 ml glass autosampler bottle.The vial was capped and placed in the gas chromatograph for analysis. The samples and standard solutions were analyzed by gas chromatography. Petition 870250003166, dated 15 / 01 / 2025, page 49 / 121 41 / 53 with pulsed injection without splitting and a flame ionization detector. The concentrations of the extracts were determined using an external standard calibration procedure. Data relating to erucamide, oleamide or stearamide in the resin are reported in parts per million (ppm; pg / g). Antioxidants

[0110] Approximately 5 grams of sample were weighed (and recorded with a resolution of 0.0001 g) into a 4-ounce glass vial. A PTFE-coated stir bar was added to the vial along with 25 ml of 0.04% triethyl phosphite in o-xylene using a solvent dispenser. The vial was loosely stoppered and placed on a heated shaker for 30 minutes at 130°C with stirring. After 30 minutes, the vial was removed to cool the solution to room temperature with stirring for at least 2 hours. The polymer was then precipitated by adding 50 ml of methanol to the vial using a solvent dispenser. The solution was stirred during this addition. The solution was stirred for a further 2 hours. After 2 hours of stirring, the vial was removed and the solids were allowed to settle.An aliquot of the solution was removed with a glass pipette and filtered with a 0.2 µm (25 mm) PTFE syringe filter and a polypropylene syringe into a 2 ml glass autosampler bottle. The bottle was stoppered and placed in the liquid chromatograph for analysis. Samples and standard solutions were analyzed using a reversed-phase liquid chromatography method with a UV / Vis absorbance detector. Extract concentrations were determined using an external standard calibration procedure. Antioxidant data in resin are reported in parts per million (ppm; pg / g). More details can be found in Green, S.; Bai, S.; Cheatham, M.; Cong, R.; Yau, W., Determination of Antioxidants in Polyolefins Using Total Dissolution Methodology Followed by RPLC, Journal of Separation Science, 33 (22), 3455 - 3462 (2010). Antiblocking.

[0111] The ASTM D6247 standard was used to determine metal contents by X-ray fluorescence. Talc or silicon dioxide can be determined from elemental silicon (Si) or magnesium (Mg) by Petition 870250003166, dated 15 / 01 / 2025, page 50 / 121 42 / 53 X-ray fluorescence. In a laboratory where many different types of materials are analyzed, both Si and Mg can be measured. The talc result can be reported as calculated from Si or Mg, as appropriate. For example, the talc content can be calculated by measuring Mg and Si. It can also be calculated by measuring the percentage of residual ash. If only Mg and Si are present (without other additives), the three measurements (by X-ray fluorescence and percentage of residual ash) should be equal. Talc (Mg) = Talc<sí> Talc (ashes). Talc can be determined using either Mg or Si. If the two values ​​are different, further analysis may be needed to determine the talc content. For example, SiO2 would indicate a higher value for talc when calculated using the X-ray fluorescence value for Si. Talc (Mg) < Talc (Si). The difference could be used to calculate the amount of SiO2. After the SiO2 content is determined, the talc correction value can be calculated from the measurement of the residual ash percentage. Talc (corrected ash) = Talc (ash) - Talc (SiO2). Furthermore, if only SiO2 is present and no Mg, the elemental determination of talc from Mg may result in zero talc. Residual ash can be determined using ASTM D5630: Standard test method for ash content in plastics. Mineral oil

[0112] Approximately 5 grams of sample were weighed (and recorded with a resolution of 0.0001 g) into a 4-ounce glass vial, and then 20 mL of methylene chloride were added. The vial was sealed with a PTFE-coated cap. Samples were extracted for 24 h at room temperature using a hand shaker. An aliquot of the extract was removed with a glass pipette and transferred to a 2 mL glass autosampler vial. The vial was capped and placed in the gas chromatograph for analysis. Samples and standard solutions were Petition 870250003166, dated 15 / 01 / 2025, page 51 / 121 43 / 53 analyzed by gas chromatography with flame ionization detection. The standard solution was prepared in methylene chloride using the same mineral oil reference material found in the resin. The mineral oil peak of the chromatogram was integrated. Oligomers and peak areas of additives in the same retention time window as the mineral oil are subtracted from the mineral oil peak area. Extract concentrations were determined using an external standard calibration procedure. Mineral oil data in resin are presented in parts per million (ppm; pg / g). Examples Example 1 and Comparative Example 1 Preparation of low-density polyethylenes

[0113] According to the previous description in Figure 1, a mixture containing t-butyl peroxy-2-ethylhexanoate (TBPO) and an isoparaffinic hydrocarbon solvent with a boiling range greater than 179 °C was used as the initiating mixture for the first and second injection points. A mixture containing TBPO, t-butyl peroxyacetate (TBPA), and an isoparaffinic hydrocarbon solvent was used as the initiating mixture for the third injection point. A mixture containing di-t-butyl peroxide (DTBP), TBPA, TBPO, and the isoparaffinic hydrocarbon solvent was used for the fourth injection point. Table 4 shows the weight % composition of the peroxide initiator and solvent solution used for each of the injection points. Petition 870250003166, dated 15 / 01 / 2025, page 52 / 121 44 / 53 Table 4 Example 1 Comparative Example 1 Injection Point Material % by weight % by weight No. 1 TBPO 20 20 No. 1 Solvent 80 80 No. 2 TBPO 20 20 No. 2 Solvent 80 80 No. 3 TBPO 10 10 No. 3 TBPA 10 10 No. 3 Solvent 80 80 No. 4 TBPO 6.3 6.3 No. 4 TBPA 3.5 3.5 No. 4 DTBP 4.2 4.2 No. 4 Solvent 86 86

[0114] Isobutane was used as a chain transfer agent. Isobutane was injected into the ethylene stream on the suction side of the booster / primary compressor. The composition of the CTA feed to the process can be adjusted to maintain a desirable melting index in the product.

[0115] The process conditions used to manufacture the additive-free example and the comparative example are given in Table 5. The reaction temperatures of each autoclave zone and the tube are controlled by adjusting the peroxide flow rates for each of the reaction zones. The reactor pressure and reactor control temperatures are used to ultimately control the molecular weight distribution of the product. Table 5 Process Variable Example 1 Comparative Example 1 Reactor pressure (psig) 24,501 25,490 Upper feed temperature (°C) 41 63 Lower feed temperature (°C) 40 40 Zone 1 temperature (°C) 218 ​​218 Zone 2 temperature (°C) 235 235 Zone 3 temperature (°C) 255 255 Restart temperature (°C) 233 229 Peak tube temperature (°C) 281 282 Petition 870250003166, dated 15 / 01 / 2025, page 53 / 121 45 / 53 Fresh ethylene flow (lb / h) (kg / s) (19,167) 8,694.01 (19,020) 8,627.33 Ethylene rate to reactor (lb / h) (kg / s) (67,149) 30,458.28 (67,103) 30,437.41 Ethylene conversion (%) 23 23 Isobutane flow (lb / h) (kg / s) (75) 34.02 (105) 45.36 Ethylene purge flow (lb / h) (kg / s) (999) 453.14 (995) 451.32 Boiling water drum temperature to tube (°C) 126 126 Boiling water return temperature from tube (°C) 139 140

[0116] The examples and comparative examples were tested according to the test procedures disclosed in this document to measure density, melt index (I2), melt strength, and hexane extractables. The density, melt index (I2), melt strength, and hexane extractables results for Example 1 and Comparative Example 1 are shown in Table 6 below. With reference to Figure 6, the melt strength curves for Example 1 and Comparative Example 1, along with the melt strength plateau region as drawn by the horizontal line approaching the average high-speed melt strength before the end of the data (cord break), are graphically represented. Table 6 Description Density (g / cm3) I2 (g / 10 min) Melt strength (cN) Hexane extractables (% by weight) Example 1 0.923 5.05 6.6 1.39 Comparative Example 1 0.923 5.56 5.3 1.31

[0117] The molecular weight data of the various examples were measured according to the test procedures disclosed in this document and the results are shown in Table 7 below using both conventional (conv) and light scattering or absolute (abs) GPC methods. Petition 870250003166, dated 15 / 01 / 2025, page 54 / 121 46 / 53 Table 7 Description Mn (g / mol) (conv) Mw (g / mol) (conv) Mz (g / mol) (conv) Mw / Mn (conv) Mw (g / mol) (abs) Mz (abs) Mw(abs) / Mw(conv) gpcBR Example 1 14,700 125,000 580,200 8.53 279,200 2,674,900 2.23 2.64 Comparative Example 1 15,000 108,100 479,500 7.22 223,400 2,247,800 2.07 2.23 46 / 53 Petition 870250003166, dated 15 / 01 / 2025, page 55 / 121 47 / 53

[0118] The CDF and LSP data from the various examples were measured according to the test procedures disclosed in this document and the results are shown in Table 8 below. Petition 870250003166, dated 15 / 01 / 2025, p. 56 / 121 48 / 53 Table 8 Description CDF IR < 5,000 g / mol CDF IR > 200,000 g / mol CDF DV < 25,000 g / mol CDF DV > 1,000,000 g / mol CDF LS < 100,000 g / mol CDF LS > 1,500,000 g / mol LSP Example 1 0.0746 0.1559 0.1194 0.0608 0.1034 0.1428 2.96 Comparative Example 1 0.0743 0.1348 0.1275 0.417 0.1352 0.1107 2.46 48 / 53 Petition 870250003166, dated 15 / 01 / 2025, p. 57 / 121 49 / 53

[0119] The CDF and LSP data from the various examples were measured according to the test procedures disclosed in this document and the results are shown in Table 9 below. Petition 870250003166, dated 15 / 01 / 2025, p. 58 / 121 50 / 53 Table 9 Description Viscosity at 0.1 radians / second and 190 °C (Pa-s) Viscosity at 1.0 radians / second and 190 °C (Pa-s) Viscosity at 10 radians / second and 190 °C (Pa-s) Viscosity at 100 radians / second and 190 °C (Pa-s) Viscosity ratio (V at 0.1 / V at 100) and 190 °C Tan delta at 0.1 and 190 °C Example 1 3.250 2.094 930 318 10.2 5.2 Comparative Example 1 2.855 1.937 891 310 9.2 6.1 50 / 53 Petition 870250003166, dated 15 / 01 / 2025, p. 59 / 121 51 / 53

[0120] The branching data per 1000 C by 13C NMR of the various examples were measured according to the test procedures disclosed in this document and the results are shown in Table 10 below. Petition 870250003166, dated 15 / 01 / 2025, pp. 60 / 121 52 / 53 Table 10 Description Branching C1,3 diethyl (per 1,000 total carbons) C2 (per 1,000 total carbons) C4 (per 1,000 total carbons) C5 (per 1,000 total carbons) C6+ (per 1,000 total carbons) Example 1 Not detected 3.5 1.2 7.2 2.3 3.4 Comparative Example 1 Not detected 3.7 1.2 6.9 2.2 3.4 52 / 53 Petition 870250003166, dated 15 / 01 / 2025, page 61 / 121 53 / 53

[0121] The 1H NMR unsaturation data of the various samples and comparative examples were measured according to the test procedures disclosed in this document and the results are shown in Table 11 below. Table 11 Description Vinyl (per 1,000 total carbons) Cis and trans vinylenes (per 1,000 total carbons) Trisubstituted (per 1,000 total carbons) Vinylidene (per 1,000 total carbons) Total unsaturation (per 1,000 total carbons) Example 1 0.033 0.022 0.056 0.163 0.274 Comparative Example 1 0.023 0.020 0.048 0.147 0.238 Petition 870250003166, dated 15 / 01 / 2025, page 62 / 121

Claims

1 / 2 CLAIMS 1. Low-density polyethylene, characterized in that it comprises: - a melt strength measured at 190 °C that is greater than or equal to 5.5 cN; - a density that is greater than or equal to 0.9210 g / cm3 and less than or equal to 0.9275 g / cm3; and - a melt index I2 measured at 190 °C that is greater than or equal to 4.5 g / 10 min; wherein the low-density polyethylene is a homopolymer of ethylene prepared using a free radical, high-pressure polymerization.

2. Low-density polyethylene, according to claim 1, characterized in that the melting index I2 measured at 190 °C is greater than or equal to 4.5 g / 10 min and less than or equal to 7.5 g / 10 min.

3. Low-density polyethylene, according to either claim 1 or 2, characterized in that the melting index I2 measured at 190 °C is greater than or equal to 4.5 g / 10 min and less than or equal to 6.5 g / 10 min.

4. Low-density polyethylene, according to any one of claims 1 to 3, characterized in that the melt strength measured at 190 °C is greater than or equal to 6.0 cN and less than or equal to 8.5 cN.

5. Low-density polyethylene, according to any one of claims 1 to 4, characterized in that the melt strength measured at 190 °C is greater than or equal to 6.4 cN and less than or equal to 7.0 cN.

6. Low-density polyethylene, according to any one of claims 1 to 5, characterized in that the melt strength measured at 190 °C in cN is greater than or equal to -0.780*(melting index, I2)+9.9 cN ± 5%.

7. Low-density polyethylene, according to any one of claims 1 to 6, the low-density polyethylene being characterized in that it comprises a molecular weight distribution (Mw(conv) / Mn(conv)) that is greater than or equal to 7.

2.

8. Low-density polyethylene, according to any of the claims 1 to 7, characterized in that the density is greater than or equal to 0.9220 g / cm3 and less than or equal to 0.9265 g / cm3.

9. Low-density polyethylene, according to any one of claims 1 to 8, characterized in that the hexane extractables content is less than or equal to 2.60%.

10. Low-density polyethylene, according to any one of claims 1 to 9, the low-density polyethylene being characterized in that it comprises an average molecular weight z Mz (conv) greater than 500,000 g / mol.

11. Low-density polyethylene, according to any one of claims 1 to 10, the low-density polyethylene being characterized in that it comprises an average molecular weight z Mz (conv) that is greater than or equal to 530,000 g / mol and less than or equal to 620,000 g / mol.

12. Low-density polyethylene, according to any one of claims 1 to 11, the low-density polyethylene being characterized in that it comprises a light scattering parameter (LSP) GPC that is greater than 2.

5.

13. Film, characterized in that it comprises low-density polyethylene as defined in any one of claims 1 to 12.

14. Film, characterized in that it comprises a mixture of linear low-density polyethylene (LLDPE) and low-density polyethylene as defined in any one of claims 1 to 12.

15. Cast, blown or thermoformed film, characterized in that it comprises low-density polyethylene as defined in any one of claims 1 to 12. Petition 870250003166, dated 15 / 01 / 2025, pp. 64 / 121

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