PROCESS FOR THE PRODUCTION OF BRANCHED POLYOLEFIN

Abstract

The present disclosure provides a process. In an embodiment, that process includes contacting, under polymerization conditions at a temperature from 160°C to 250°C, a single polymerization catalyst and a cocatalyst in a single reactor with (i) an ethylene monomer and an optional C3-C8 α-olefin in comonomer, (ii) an alkyl-aluminum chain transfer agent, and (iii) an alkyl-zinc chain transfer agent. The process includes forming an ethylene-based polymer having an I10 / I2 value greater than 8.0 and a vinyl content of greater than 50 / 1,000,000C.

Description

1 / 29 PROCESS FOR THE PRODUCTION OF BRANCHED POLYOLEFIN BACKGROUND

[001] A long-chain branching (LCB) olefin-based polymer is an olefin-based polymer containing one or more side-chain branches whose length is comparable to or greater than a critical cross-linking length. The incorporation of long-chain branching (LCB) is known to optimize processability and increase the strength of melted material in olefin-based polymers.

[002] Compared to a linear olefin-based polymer of the same molecular weight, an olefin-based polymer with LCB exhibits higher shear sensitivity, higher viscosity at zero shear, greater melt elasticity, greater impact resistance, and higher melt strength (“melt strength” being the tensile strength during elongation of the molten olefin-based polymer). High melt strength is a desirable mechanical property in thermoforming, extrusion coating, and blow molding processes involving olefin-based polymers.

[003] Furthermore, the LCB-based olefin polymer exhibits higher viscosity at low shear rate and lower viscosity at high shear rate when compared to the linear olefin-based polymer having the same molecular weight. The decrease in viscosity under shear is advantageous in polymer processing, such as under high shear conditions.

[004] For linear low-density polyethylene (LLDPE), a common mechanism for forming LCB during coordination polymerization (a form of addition polymerization mediated by transition metal-based catalysts) of olefin is made Petition 870250076401, dated 08 / 28 / 2025, page 12 / 51 2 / 29 through the insertion of vinyl-terminated polymer chains generated by thermal termination into transition metal catalytic sites. The level of LCB formed by this mechanism is typically low due to the low population of vinyl-terminated polymer chains. In contrast, low-density polyethylenes (LDPEs) produced by free-radical polymerization are known for their superior processability due to their unique branch-on-branch "tree" type structures. The addition of α,ω-dienes, such as decadiene, during olefin polymerization to cross-link two polymer chains is known. The α,ω-diene approach is disadvantageous because it increases the risk of gelation in the reactor system and generates logistical difficulties due to the limited availability and high cost of α,ω-diene quantities on an industrial scale.

[005] The technique recognizes the need for alternative processes to produce long-chain branching in olefin-based polymers. In particular, there is a need for a process to produce long-chain branching in olefin-based polymers (and ethylene-based polymers in particular) through olefin coordination polymerization. SUMMARY

[006] The present disclosure provides a process. In one embodiment, the process includes placing, under polymerization conditions at a temperature of 160 °C to 250 °C, a single polymerization catalyst and a cocatalyst in a single reactor in contact with (i) an ethylene monomer and an optional C3-C8 α-olefin comonomer, (ii) an alkyl-aluminum chain transfer agent and (iii) an alkyl-zinc chain transfer agent. The process includes the formation of an ethylene-based polymer having an I10 / I2 value greater than 8.0 and a vinyl content greater than 50 / 1,000,000C. BRIEF DESCRIPTION OF THE DRAWINGS Petition 870250076401, dated 08 / 28 / 2025, page 13 / 51 3 / 29

[007] Figure 1 is a graph showing the chemical structures for different types of carbon-carbon double bonds (unsaturation in the polymer chain) for vinylene, trisubstituted vinyl, and vinylidene.

[008] Figure 2 is a schematic representation of a polymerization process according to an embodiment of the present disclosure.

[009] Figure 3 is a graph showing the GPC curves and a Mark-Houwink plot for comparative sample 1 and the invention example 1.

[0010] Figure 4 is a graph showing the GPC curves and g' values ​​for comparative sample 1 and the invention example 1.

[0011] Figure 5 is a graph showing a viscosity overlay in DMS for comparative sample 6 and examples of the invention 6 to 13.

[0012] Figure 6 is a graph showing the tan delta overlap in DMS for comparative sample 6 and examples of the invention 6 to 13. DEFINITIONS

[0013] Any reference to the Periodic Table of Elements refers to that as published by CRC Press, Inc., 1990–1991. The reference to a group of elements in that table is by the new notation for numbered groups.

[0014] For purposes of United States patent practice, the contents of any patent, patent application or publication referenced are incorporated by reference in their entirety (or their U.S. equivalent version is thus incorporated by reference), especially with respect to the disclosure of definitions (to the extent not inconsistent with any definitions specifically provided in this disclosure) and general knowledge in the art.

[0015] The numerical ranges revealed here include all values ​​within, and including, the lower and upper values. For ranges that contain Petition 870250076401, dated 08 / 28 / 2025, p. 14 / 51 4 / 29 explicit values ​​(e.g., 1 or 2, or 3 to 5, or 6, or 7), any subrange between any two explicit values ​​is included (e.g., the range 1 to 7, above, includes subranges 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.).

[0016] Unless stated otherwise, or implied from the context, all parts and percentages are based on weight and all testing methods are current as of the filing date of this disclosure.

[0017] An “alkyl group”, as used herein, is a saturated hydrocarbonyl group.

[0018] The terms “blend” or “polymer blend,” as used in this document, refer to a blend of two or more polymers. This blend may or may not be miscible (not separated into phases at the molecular level). This blend may or may not be separated into phases. This blend may or may not contain one or more domain configurations, as determined from transmission electron spectroscopy, light scattering, X-ray scattering, and other methods known in the art.

[0019] The term “composition” refers to a mixture of materials that constitute the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0020] The terms “comprising”, “including”, “containing” and their derivatives are not intended to exclude the presence of any additional component, step or procedure, whether or not specifically disclosed. For the avoidance of doubt, all compositions claimed by the use of the term “comprising” or “comprising” may include any additive, adjuvant or additional compound, polymeric or not, unless stated otherwise. Conversely, the term “essentially consisting of” excludes from the scope of any subsequent citation any other component, step or procedure, except those that are not essential for operability. Petition 870250076401, dated 08 / 28 / 2025, p. 15 / 51 5 / 29 The term “consisting of” excludes any component, step, or procedure not specifically outlined or listed. The term “or,” unless otherwise indicated, refers to the listed members individually as well as in any combination. The use of the singular includes the use of the plural, and vice versa.

[0021] “Ethylene-based polymer” and similar terms refer to a polymer containing, in polymerized form, a greater percentage by weight of ethylene-derived units, based on the total weight of the polymer. Non-limiting examples of ethylene-based polymers include low-density polyethylene (or “LDPE” which is an ethylene homopolymer, or ethylene / α-olefin copolymer comprising at least one C3-C10 α-olefin, preferably C3-C4 (and optional polar thermomer) having a density of 0.915 g / cm3 to 0.940 g / cm3 and containing long-chain branching with a wide molecular weight distribution (MWD), typically produced by high-pressure free-radical polymerization).Linear low-density polyethylene (or “LLDPE”) is a linear copolymer of ethylene / α-olefin containing a heterogeneous short-chain branching distribution comprising ethylene-derived units and units derived from at least one C3-C10 α-olefin comonomer or at least one C4-C8 α-olefin comonomer, or at least one C1-C8 α-olefin comonomer; LLDPE is characterized by having little or no long-chain branching, unlike conventional LDPE; LLDPE has a density of 0.880 g / cm3, or 0.890 g / cm3, or 0.900 g / cm3, or 0.910 g / cm3, or 0.915 g / cm3, or 0.920 g / cm3, or 0.925 g / cm3 to 0.930 g / cm3, or 0.935 g / cm3, or 0.940 g / cm3), very low-density polyethylene (VLDPE), ultra-low-density polyethylene (ULDPE), medium-density polyethylene (or “MDPE” homopolymer – ethylene homopolymer, or an ethylene / α-olefin copolymer comprising at least one C3-C10 α-olefin,which has a density of 0.926 g / cm3 to 0.940 g / cm3), Petition 870250076401, dated 08 / 28 / 2025, page 16 / 51 6 / 29 High-density polyethylene (or “HDPE”) is an ethylene homopolymer or an ethylene / α-olefin copolymer with at least one C4C10 α-olefin comonomer and a density greater than 0.94 g / cm3, or 0.945 g / cm3, or 0.95 g / cm3, or 0.955 g / cm3, or 0.96 g / cm3, or 0.97 g / cm3, or 0.98 g / cm3).

[0022] A “heteroatom” is an atom other than carbon or hydrogen. The heteroatom can be a non-carbon atom from Groups IV, V, VI, and VII of the Periodic Table. Non-limiting examples of heteroatoms include: F, N, O, P, B, Se, Si.

[0023] A “hydrocarbon” is a compound containing only hydrogen atoms and carbon atoms. A “hydrocarbonyl” (or hydrocarbonyl group) is a hydrocarbon that has one valence (typically univalent). A hydrocarbon can have a linear structure, a cyclic structure, or a branched structure.

[0024] An “interpolymer” is a polymer prepared by the polymerization of at least two different monomers. This generic term includes copolymers, generally used to refer to polymers prepared from two different monomers, and polymers prepared from more than two different monomers, for example, terpolymers, tetrapolymers, etc.

[0025] The term “long chain branch,” “LCB,” and similar terms refer to a branched chain that extends from the main polymer chain, with the branched chain comprising more than one carbon atom. If the polymer is a copolymer (such as ethylene / α-olefin copolymer, for example), then the LCB comprises a carbon atom more than two carbon atoms shorter than the total length of the longest comonomer copolymerized with ethylene. For example, in an ethylene / octene copolymer, the LCB is at least seven carbon atoms long. As a practical matter, the LCB is longer than the side chain resulting from the incorporation of the comonomer into the polymer chain. Petition 870250076401, dated 08 / 28 / 2025, page 17 / 51 7 / 29 main. The main polymer chain of an HDPE comprises coupled ethylene units.

[0026] An “olefin-based polymer” or “polyolefin” is a polymer that contains more than 50 percent by weight of polymerized olefin monomer (based on the total amount of polymerizable monomers) and may optionally contain at least one comonomer. Non-limiting examples of an olefin-based polymer include ethylene-based polymer or propylene-based polymer.

[0027] A “polymer” is a compound prepared by the polymerization of monomers, whether of the same type or of a different type, which, in the polymerized form, provides the multiple and / or repeating “units” or “mer units” that constitute a polymer. The generic term polymer thus encompasses the term homopolymer, generally used to refer to polymers prepared from only one type of monomer, and the term copolymer, generally used to refer to polymers prepared from at least two types of monomers. This also encompasses all forms of copolymer, for example, random, block, etc. The terms “ethylene / α-olefin polymer” and “propylene / α-olefin polymer” are indicative of copolymers, as described above, prepared from the polymerization of ethylene or propylene, respectively, and one or more additional polymerizable α-olefin monomers.It is noted that, although a polymer is often referred to as being “produced from” one or more specified monomers, “based on” a specified monomer or type of monomer, “containing” a specified monomer content, or similar, in this context, the term “monomer” is understood to refer to the polymerized remainder of the specified monomer and not to the unpolymerized species. In general, the polymers in this document are referred to as being based on “units” that are the polymerized form of a corresponding monomer. Petition 870250076401, dated 08 / 28 / 2025, page 18 / 51 8 / 29 Testing methods

[0028] 1H NMR. 1H nuclear magnetic resonance (11H NMR) detects the following types of carbon-carbon double bonds (“unsaturation”) in the polymer. “Vinylene” is a carbon-carbon double bond with the formula Ri - CH=CH - R2, where each Ri and R2 is a carbon atom, an alkyl group, or a heteroatom selected from N, O, P, B, S, and Si. “Trisubstituted” is a carbon-carbon double bond in which the doubly bonded carbons are bonded to a total of three carbon atoms and in which each Ri, R2, and R3 (in Figure 1) is a carbon atom. “Vinyl” is a carbon-carbon double bond with the formula R - CH=CH2, where R is a carbon atom or a heteroatom selected from N, O, P, B, S, and Si. “Vinylidene” is a carbon-carbon double bond with the formula C=CH2. "Total unsaturation" (or "total") is the sum of vinylene, trisubstituted vinyl, and vinylidene in a polymer.The chemical structures for vinylene, trisubstituted vinyl, and vinylidene are given in Figure 1.

[0029] Polymer samples for 1H NMR analysis were prepared by adding 130 mg of sample to 3.25 g of tetrachloroethaned2 / perchloroethylene 50 / 50 by weight with 0.001 M Cr(AcAc)3 in a 10 mm NMR tube. The samples were purged by bubbling N2 through the solvent via a pipette inserted into the tube for approximately 5 minutes to prevent oxidation, then capped and sealed with Teflon tape. The sample was heated and vortexed at 115°C to ensure homogeneity.

[0030] 1H NMR was performed on a Bruker AVANCE 400 / 600 MHz spectrometer equipped with a Bruker CryoProbe at high temperature and a sample temperature of 120°C. Two experiments were performed to obtain spectra, a control spectrum to quantify the total polymer protons and a double presaturation experiment, which suppresses the intense main structure peaks of the polymer and Petition 870250076401, dated 08 / 28 / 2025, page 19 / 51 9 / 29 allows for high-sensitivity spectra for quantification of end groups. The control was performed with ZG pulse, 4 scans, SWH 10,000 Hz, AQ 1.64s, D1 14s. The double pre-saturation experiment was performed with a modified pulse sequence, lc1prf2.zz1, TD 32768, 100 scans, DS 4, SWH 10,000 Hz, AQ 1.64s, D1 1s, D13 13s. The results are reported in the number of vinyl groups (and the number of vinylene, trisubstituted, vinylidene and total) per 1,000,000 carbon atoms or 1,000,000 C.

[0031] Density is measured according to ASTM D792, Method B. The result is recorded in grams per cubic centimeter (g / cm3).

[0032] Triple detector GPC (TD-GPC). The chromatographic system for triple detector gel permeation chromatography (TD-GPC) consisted of a PolymerChar GPC-IR high-temperature GPC chromatograph (Valencia, Spain) equipped with an internal IR5 (IR5) infrared detector. The autosampler oven compartment was set to 160 °C and the column compartment was set to 150 °C. Four 30 cm and 20 micron Agilent “Mixed A” linear mixed-bed columns and a 20 μm pre-column were used. 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.

[0033] The calibration of the GPC column array was performed with 21 polystyrene standards with restricted molecular weight distribution, with molecular weights ranging from 580 to 8400000, and were arranged in 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 at 0.025 grams in 50 milliliters of solvent for molecular weights equal to or greater than 1000000 and 0.05 grams in 50 milliliters of solvent for molecular weights Petition 870250076401, dated 08 / 28 / 2025, page 20 / 51 10 / 29 less than 1000000. 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)): ^ΡΰΕί>ίίΓ?πΰ—X (EQ1), where M is the molecular weight, A has a value of 0.4315, and B is equal to 1.0.

[0034] A fifth-order polynomial was used to fit the respective equivalent polyethylene calibration points. A small adjustment in A (from approximately 0.375 to 0.445) was made to correct for column resolution and band broadening effects so that the linear homopolymer polyethylene standard is obtained at Mw of 120000.

[0035] The total plate count of the GPC column array was performed with decane (prepared at 0.04 g in 50 milliliters of TCB and dissolved for 20 minutes with gentle stirring). Plate count (Equation 2) and symmetry (Equation 3) were measured in a 200 microliter injection according to the following equations: - Peak width a- height where RV is the retention volume in milliliters and peak width is in milliliters, peak maximum is the maximum position of the peak, one-tenth of the height is 1 / 10 of the height of the peak maximum, and where trailing peak refers to the tail of the peak in retention volumes after the peak maximum, and where leading peak refers to the front of the peak in retention volumes before the peak maximum. The plate count for the chromatographic system should be greater than 18,000 and the symmetry should be between 0.98 and 1.22.

[0036] The samples were prepared semi-automatically using the “Instrument Control” PolymerChar software, and the samples were Petition 870250076401, dated 08 / 28 / 2025, page 21 / 51 11 / 29 directed by weight to 2 mg / mL and the solvent (containing 200 ppm of BHT) was added to a septum-capped flask pre-sprayed with nitrogen via a high-temperature autosampler. PolymerChar. The samples were dissolved for 2 hours at 160° Celsius under stirring at “low speed”.

[0037] The calculations of Mu(gpc), Mw / gpc) and Mz(gpc) were based on the GPC results using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph, according to equations 4 to 6, using the PolymerChar GPCOne™ software, the IR chromatogram subtracted from the baseline at each equally spaced data collection point (i) and the equivalent molecular weight of polyethylene obtained from the standard calibration curve restricted to point (i) of equation 1. MM(GPC) = polyethylene, j (EQ 4) Mn(GPo = — polyethylene, / (EQ 5) r 2) polyethylene, / Mzifipc) = —7

[0038] \ i polyethylene,7(EQ6) 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 flow rate (RV) of the respective decane peak in the sample (RV(FM sample)) with that of the decane peak from the calibration with standards. Petition 870250076401, dated 08 / 28 / 2025, page 22 / 51 12 / 29 narrow (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 (effective flow rate) for the entire round. To facilitate the highest accuracy of a VR 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 as Equation 7. Processing of the flow marker peak was performed via PolymerChar GPCOne™ software. The 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(FM Sample)) (EQ7).

[0039] The melting indices (I2, I10) were measured according to ASTM Method D1238. I2 and I10 were measured at 190°C / 2.16 kg and 190°C / 10 kg, respectively. The results are reported in grams eluted per 10 minutes (g / 10 min).

[0040] Dynamic Mechanical Analysis (DMS) was performed using an ARES-G2 rheometer with two parallel plates, 25 mm in diameter. The test was performed at 190 °C, using a 1.8 mm gap with a frequency range of 0.1 to 100 rad / s, at a strain of 10%. By applying this strain and measuring the resulting torque with the transducer, parameters such as complex viscosity, storage modulus, and loss modulus at a given shear were determined. DETAILED DESCRIPTION

[0041] The present disclosure provides a process. In a Petition 870250076401, dated 08 / 28 / 2025, page 23 / 51 In embodiment 13 / 29, a process is provided which includes placing, under polymerization conditions at a temperature of 160 °C to 250 °C, a single polymerization catalyst and a cocatalyst in a single reactor in contact with (i) an ethylene monomer and an optional C3-Cs α-olefin comonomer, (ii) an alkyl-aluminum chain transfer agent and (iii) an alkyl-zinc chain transfer agent; and forming an ethylene copolymer having an I10 / I2 value greater than 8.0 and a vinyl content greater than 50 / 1,000,000C.

[0042] The process involves placing, under polymerization conditions at a temperature of 160 °C to 250 °C, a single polymerization catalyst and a cocatalyst in contact with (i) an ethylene monomer and an optional C3-C8 α-olefin comonomer, (ii) an alkyl-aluminum chain transfer agent, and (iii) an alkyl-zinc chain transfer agent. The term “polymerization conditions,” as used herein, refers to process parameters under which ethylene (and the C3-C8 α-olefin comonomer) are copolymerized in the presence of a catalyst system. Polymerization conditions include, for example, polymerization reactor conditions (reactor type), reactor pressure, reactor temperature, reagent and polymer concentrations, solvent, carrier, residence time, and distribution, influencing the molecular weight distribution and polymer structure.The term polymerization conditions, as used herein, includes a single (one and only one) polymerization reaction and a temperature in the polymerization reactor of 160 °C to 250 °C, or 180 °C to 250 °C, or 182 °C to 240 °C, or 190 °C to 240 °C, or 192 °C to 230 °C, or 200 °C to 220 °C.

[0043] The single polymerization catalyst (one and only one) has the resilience for ethylene polymerization under high temperature, either at a temperature of 160 °C to 250 °C, or 180 °C to 250 °C. The single polymerization catalyst exhibits efficient chain transfer with Petition 870250076401, dated 08 / 28 / 2025, p. 24 / 51 14 / 29 alkyl-zinc and good ability to incorporate vinyl-terminated polymeryl chains. In one embodiment, the polymerization catalyst has Formula (1) in what M stands for titanium, zirconium, hafnium, or scandium; Each Y1 and Y2 is independently selected from the group consisting of hydrocarbyl (C1-C4o), trihydrocarbylsilyl hydrocarbyl (C1-C4o), halogen, alkoxide or amine, or two Y groups together are a divalent group of hydrocarbylene, hydrocarbadyl or trihydrocarbylsilyl; Each Ar1e Ar2, independently, is selected from the group consisting of aryl(C3-C40), substituted aryl(C3-C40), heteroaryl(C5-C40), and substituted heteroaryl(C3C40); T1, independently in each occurrence, is a divalent bridging group of 2 to 20 carbon atoms, optionally containing heteroatoms including Si, Ge, O, N, Se, P; and each R1, R2, R3, R4, R5, R6, R7, R8, R9, R1(o), R11, R12, R13, and R14 independently is selected from the group consisting of hydrogen, a halogen, hydrocarbyl(C1-C4o), substituted hydrocarbyl(C1-C4o), heterohydrocarbyl(C1-C4o), substituted heterohydrocarbyl(C1-C4o), aryl(C6-C4o), substituted aryl(C6-C4o), heteroaryl(C3-C4o), and substituted heteroaryl(C3-C4o), and nitro (NO2). [oo44] In one embodiment, the single polymerization catalyst has Formula (2) Formula (2) Petition 870250076401, dated 08 / 28 / 2025, p. 25 / 51 15 / 29

[0045] Polymerization conditions include the provision of a cocatalyst. Non-limiting examples of suitable cocatalysts include boron compounds that can be used as an activating cocatalyst in the preparation of the improved catalysts of this disclosure and include trisubstituted salts of tetrakis(pentafluorophenyl)borate, tetrakis(pentafluorophenyl)borate, tetrakis(pentafluorophenyl)borate, tetrakis(pentafluorophenyl)borate, trimethylammonium, tripropyltriethylammonium, tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium, tetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammonium, tetrakis(pentafluorophenyl)borate, butyltris(pentafluorophenyl)borate, benzyltris(pentafluorophenyl)borate. N,N-dimethylaniline, N,N-dimethylaniline, N,N-dimethylaniline, tetrakis(4-(t-butyldimethylsilyl)-2,3,5,6-tetrafluorophenyl)borate, N,N-dimethylaniline, tetrakis(4-(tri-isopropylsilyl)-2,3,5,6-tetrafluorophenyl)borate, N,N-dimethylaniline, pentafluorophenoxytri(pentafluorophenyl)borate, N,N-dimethylaniline, tetrakis(pentafluorophenyl)borate, N,N-diethylaniline, tetrakis(pentafluorophenyl)borate, tetrakis(pentafluorophenyl)borate, tetrakis(pentafluorophenyl)borate, tetrakis(pentafluorophenyl)borate, of of of N,N-dimethylaniline, N,N-dimethyl-2,4,6-trimethylaniline, dimethyl octadecyl ammonium, tetrakis(pentafluorophenyl) methyl dioctadecyl ammonium borate; various dialkyl ammonium salts, such as: tetrakis(pentafluorophenyl)borate di-(i-propyl)ammonium, tetrakis(pentafluorophenyl)borate methyl octadecyl ammonium, Petition 870250076401, dated 08 / 28 / 2025, page 26 / 51 16 / 29 tetrakis(pentafluorophenyl)borate methyl octadecyl ammonium and tetrakis(pentafluorophenyl)borate dioctadecyl ammonium; various trisubstituted phosphonium salts, such as: tetrakis(pentafluorophenyl)borate triphenyl phosphonium, tetrakis(pentafluorophenyl)borate methyl dioctadecyl phosphonium and tetrakis(pentafluorophenyl)borate tri(2,6-dimethylphenyl)phosphonium; disubstituted oxonium salts, such as: tetrakis(pentafluorophenyl)borate diphenyl oxonium, tetrakis(pentafluorophenyl)borate di(o-tolyl)oxonium and tetrakis(pentafluorophenyl)borate di(octadecyl)oxonium; and disubstituted sulfonium salts, such as: di(o-tolyl)sulfonium tetrakis(pentafluorophenyl)borate and methyl octadecyl sulfonium tetrakis(pentafluorophenyl)borate.

[0046] (i) an ethylene monomer and (ii) an optional C3-Cs α-olefin comonomer are polymerized under the polymerization conditions. Non-limiting examples of suitable optional C3-Cs α-olefin comonomers include α-olefins having from 3 carbon atoms to 5 carbon atoms, or from 4 carbon atoms to 5 carbon atoms. In one embodiment, the C3-Cs α-olefin comonomer is selected from ethylene, butene, hexene, and octene. In another embodiment, the C4-Cs α-olefin comonomer is present and the C4-Cs α-olefin monomer is selected from butene, hexene, and octene.

[0047] In one embodiment, the process involves placing, under polymerization conditions at a temperature of 160 °C to 250 °C, the single polymerization catalyst and the cocatalyst in contact with only (i) ethylene monomer and (ii) one or more C4-Cs olefin comonomers, excluding diene and / or excluding a branching agent. [004s] The process involves placing, under polymerization conditions at a temperature of 160 °C to 250 °C, a single polymerization catalyst and a cocatalyst in contact with (i) an ethylene monomer and an optional C3-Cs α-olefin comonomer, (ii) an alkyl-aluminum chain transfer agent and (iii) a chain transfer agent of Petition 870250076401, dated 08 / 28 / 2025, page 27 / 51 17 / 29 alkyl-zinc. A “chain transfer agent”, as used herein, refers to a compound that is capable of exchanging an alkyl group or a polymeryl group in the chain transfer agent for a growing polymer chain in the catalyst, the exchange resulting in the termination of polymer chain growth under polymerization conditions. An “alkyl-aluminum chain transfer agent”, as used herein, is a chain transfer agent that is a compound having the formula R1AlR2R3, wherein R1, R2 and R3 are each independently a C1-C20, or C2-C10, or C2-C4 alkyl group. An “alkyl-zinc chain transfer agent”, as used herein, is a chain transfer agent that is a compound having the formula R4ZnR5, wherein R4 and R5 are each independently a C1-C20, or C2-C10, or C2-C4 alkyl group.Non-limiting examples of alkyl aluminum chain transfer agents include trialkyl aluminum, such as trimethyl aluminum, triethyl aluminum, tripropyl aluminum, tributyl aluminum, triisobutyl aluminum, trihexyl aluminum, triisohexyl aluminum, trioctyl aluminum, and triisooctyl aluminum. Non-limiting examples of alkyl zinc chain transfer agents include dialkyl zinc, such as dimethyl zinc, diethyl zinc, dipropyl zinc, dibutyl zinc, diisobutyl zinc, dihexyl zinc, diisohexyl zinc, dioctyl zinc, and diisooctyl zinc.

[0049] Figure 2 is a schematic representation of the present process for producing branched polymers. Under polymerization conditions in a single polymerization reactor at a temperature of 160 °C to 250 °C, the contact of the single polymerization catalyst, the cocatalyst, the ethylene monomer (and optional C3-Csα-olefin comonomer), the alkyl-aluminum chain transfer agent and the alkyl-zinc chain transfer agent forms, or otherwise polymerizes, the ethylene monomer (and the optional C3-Csα-olefin comonomer) into one or more (or a plurality of) polymer chains in Petition 870250076401, dated 08 / 28 / 2025, page 28 / 51 18 / 29 growth 12. The growing polymer chains 12 on the transition metal (M) of the single polymerization catalyst (M being Hf, Zr, Ti or Sc) are subjected to chain transfer reaction with the alkyl-zinc chain transfer agent and form one or more zinc-terminated polymer chains 14. The process includes the conversion of one or more zinc-terminated polymer chains 14 into aluminum-terminated polymer chains 16. The process includes the conversion of the plurality of aluminum-terminated polymer chains 16 by beta-hydride elimination into one or more (or a plurality of) vinyl-terminated polymer chains 18. The vinyl-terminated polymer chains 18 incorporate into the growing polymer chains 12, forming branched growing polymer chains 12a.The growing branched polymer chains 12a repeat the three steps above to transfer to zinc-terminated polymer chains and then again to aluminum to form aluminum-terminated branched polymer chains 16a, followed by beta-hydride elimination to form vinyl-terminated branched polymer chains 18a, which incorporate into growing polymer chains 12a or 12 to form branch-on-branch polymer chains 12b or 12c. In other words, growing polymer chains 12 first transfer from M to alkyl-zinc to form zinc-terminated polymer chains 14 and then transfer again from zinc-terminated polymer chains to aluminum to form aluminum-terminated polymer chains 16.Without adhering to any specific theory, it is believed that catalyst transfer with zinc increases the overall transfer rate to aluminum, with the transfer from zinc to aluminum occurring rapidly. Thus, the presence of the alkyl-zinc chain transfer agent increases (i.e., shortens) the transfer rate and reinforces the chain transfer step compared to the rate of... Petition 870250076401, dated 08 / 28 / 2025, page 29 / 51 19 / 29 transfer with alkyl-aluminum in isolation.

[0050] The polymerization of the growing branched chains and the repeated transfer / elimination / incorporation steps continue and the process forms a highly branched ethylene-based polymer having an I10 / I2 value greater than 8.0 and a vinyl content greater than 50 / 1,000,000C.

[0051] In one embodiment, the process includes placing, under polymerization conditions at a temperature of 160 °C to 250 °C, or 180 °C to 240 °C, with a single polymerization catalyst and a cocatalyst in a single polymerization reactor in contact with (i) an ethylene monomer, (ii) an alkyl-aluminum chain transfer agent, or TEA, (iii) an alkyl-zinc chain transfer agent, or DEZ; and forming an ethylene homopolymer having an I10 / I2 value greater than 8.0 and a vinyl content greater than 50 / 1,000,000C.

[0052] In one embodiment, the process includes placing, under polymerization conditions at a temperature of 160 °C to 250 °C, or 180 °C to 240 °C, a single polymerization catalyst and a cocatalyst in a single polymerization reactor in contact with (i) an ethylene monomer and a propylene comonomer, (ii) an alkyl-aluminum chain transfer agent, or TEA, (iii) an alkyl-zinc chain transfer agent, or DEZ; and forming an ethylene / propylene copolymer having a vinyl content greater than 50 / 1,000,000C, or from 200 / 1,000,000C to 3000 / 1,000,000C, or from 250 / 1,000,000C to 2500 / 1,000,000C, or from 275 / 1,000,000C to 2100 / 1,000,000C. Petition 870250076401, dated 08 / 28 / 2025, page 30 / 51 20 / 29

[0053] In one embodiment, the process includes placing, under polymerization conditions at a temperature of 160 °C to 250 °C, or 180 °C to 240 °C, a single polymerization catalyst and a cocatalyst in a single polymerization reactor in contact with (i) an ethylene monomer and an octene comonomer, (ii) an alkyl-aluminum chain transfer agent, or TEA, (iii) an alkyl-zinc chain transfer agent, or DEZ; and forming an ethylene / octene copolymer having an I10 / I2 value greater than 8.0, or from 9.0 to 25, or from 10 to 20, or from 12 to 19 and a vinyl content greater than 50 / 1,000,000C, or from 60 / 1,000,000C to 300 / 1,000,000C, or from 70 / 1,000,000C to 250 / 1,000,000C, or from 80 / 1,000,000C to 200 / 1,000,000C.

[0054] The present process enables rapid chain transfer to aluminum (relative to alkyl-zinc), followed by beta-hydride elimination from aluminum-terminated polymer chains to form vinyl-terminated polymeryl chains. Without adhering to any specific theory, it is believed that the polymerization conditions, including the polymerization catalyst and the polymerization temperature of 160 °C to 250 °C, promote better chain transfer capability and efficient beta-hydride elimination, enabling significantly high amounts of vinyl-terminated polymeryl chains to be inserted into growing polymer chains for the formation of long-chain branches and also for the generation of branch-on-branch structures.

[0055] By way of example, and without limitation, some embodiments of the present disclosure are described in detail in the following examples. Examples Petition 870250076401, dated 08 / 28 / 2025, p. 31 / 51 21 / 29

[0056] Table 1 below shows catalysts, cocatalysts and chain transfer agents used to prepare Comparative Samples (CS) A to C and Examples of the Invention (EI) 1 to 5. Table 1 - Materials Formula (2) (polymerization catalyst) qcP Qcc Me Me X=y / O\ θBθ Hafnium, [[rel-2',2”'-[(lR,2R)-l,2-cyclohexanediylbis(methylene-oxy,kappa.O)]bis[3-(9H-carbazol-9-yl)-5-methylf 1, Γ-biphenyl]-2-olato-.kappa.O]](2)]dimethyl-, Formula (3) (polymerization catalyst) Q-0 CTfO1 Me Me -%— O - \= / cT / 0)50 Zirconium, [[2',2'”-[l,2-cyclohexanediylbis(methylene-oxy-,kappa.O)]bis[3-(9H-carbazol-9-yl)-5-methyl[l,r-biphenyl]-2- 0 lato -. kappa. O] ] (2 -) ] dimethyl - Formula (4) (polymerization catalyst) Me Me AzH 01,3ΰΌ / H / / — / °^\ / \ —\ \7 \7 . FF Zirconium, dimethylf [2 ' ,2 ' ” - [ 1,3 - propanediylbis(oxy-.kappa.O)]bis[3-[3,6bis( 1,1 -dimethylethyl)-9H-carbazol-9-yl] -5 ' fluoro -5 -(1,1,3,3 -tetramethylbutyl) [ 1, Γ biphenyl]-2-olato-.kappa.O]](2-)]-, Formula (5) (polymerization catalyst) Me Me \ / —x / —\ / 7—' / °^\ / \ / FF Hafnium, dimethylf [2 ' ,2 ' ” - [ 1,3 - butanediylbis(oxy-.kappa.O)]bis[3-[3,6bis(1,1-dimethylethyl)-9H-carbazol-9-yl]-5' fluoro-5-(1,1,3,3-tetramethylbutyl) [1,1'biphenyl]-2-olato-.kappa.O]](2-)]-,. Petition 870250076401, dated 08 / 28 / 2025, p. 32 / 51 22 / 29 Cocatalyst (borate activator) R2MeNH+' (R = hydrogenated tallow alkyl) Γ F ~Ί ” F 2. F f 'fU__ F __ Amines, bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate( 1 -) Cocatalyst (MMAC Γ Me] 1 X Al L() / 2r >-3A) jBu Al AU — —n Modified methylaluminoxane (MMAO) Type 3 A (no further purification performed) (Akzo Nobel) Alkyl-aluminum chain transfer agent —A|Z Triethyl aluminum (TEA); Alkyl-zinc chain transfer agent -z^ZrTX'' Diethyl zinc (DEZ) Example of invention 1 (Ell) - Polymerization of ethylene in a batch reactor

[0057] A single one-gallon stirred autoclave reactor was loaded with mixed alkane solvent Isopar™ E (~1.3 kg). The reactor was heated to 180 °C and loaded with triethyl aluminum (1 mmol), diethyl zinc (0.25 mmol), and ethylene (20 g). The catalyst composition is prepared in a dry box under an inert atmosphere by mixing the catalyst of Formula (2) and the cocatalyst (mixture of 1.2 equiv of borate activator and 10 equiv of modified methyl aluminoxane (MMA0-3A)) with 0.5 mL of toluene and injected into the autoclave reactor to initiate polymerization. The reactor pressure and temperature were kept constant by feeding ethylene during polymerization and cooling the reactor as needed. After 10 minutes, the ethylene feed was turned off and the solution was transferred to a resin vat purged with nitrogen. Petition 870250076401, dated 08 / 28 / 2025, page 33 / 51 23 / 29 An additive solution containing a phosphorus stabilizer and phenolic antioxidant (Irgafos® 168 and Irganox*1010 at a ratio of 2:1, by weight, in toluene) is added to generate a total additive content of approximately 0.1% in the polymer. The polymer is completely dried in a vacuum oven. Comparative sample (AC1)

[0058] The same procedure as described in Example of the invention 1 (EI1) was followed, except that hydrogen (20 mmol) was charged to replace triethyl aluminum and diethyl zinc.

[0059] The results of Example of invention 1 and Comparative Sample 1 are compared in Table 2. Table 2 - Polymerization of ethylene Catalyst DEZ TEA H2 Yield Mn Mw Mw / Mn g· Vinyl mmol mmol mmol g per million of carbon AC1 Formula (2) 0 0 20 17 80.425 253.063 3.15 1.001 35 EI1 Formula (2) 0.25 1 0 21 25.144 52.370 2.08 0.892 390

[0060] The polymer of Example 1 contained a significantly higher amount of terminal vinyl groups compared to Comparative Sample 1, demonstrating effective polymer chain transfer to aluminum and subsequent beta-hydride elimination. The vinyl unsaturation formed in the batch reactor shows the amount of vinyl-terminated polymer available for insertion and is therefore a good indicator of the ability to form long-chain branches. The formation of some long-chain branches is evident in the Mark-Houwink plot of GPC (Figure 3) and the g' value (Figure 4). The Mark-Houwink plot is produced by plotting molecular weight (MW) against intrinsic viscosity (IV) on a log-log graph. The presence of long-chain branching results in lower intrinsic viscosity (VI) and causes the graph to deviate from that of a structure Petition 870250076401, dated 08 / 28 / 2025, page 34 / 51 24 / 29 linear with the same composition. As shown in Figure 3, the Mark-Houwink plot of Eli deviates from AC1, indicating the presence of a higher quantity of long-chain branching in Eli. The g' value is also used to characterize the quantity of long-chain branching, being the ratio between the intrinsic viscosity determined of the polymer using the calibrated viscometer and concentration detector, and the intrinsic viscosity calculated of an ethylene homopolymer with the same weight-average molecular weight. The intrinsic viscosity of the ethylene homopolymer is calculated using the MarkHouwink equation, VI = k* Pma, with a k value of 4.06 x 10-4 and an α value of 0.725 (Th.G. Scholte, NIJ Meijerink, HM Schoffeleers, and AMG Brands, J. Appl. Polym. Sci., 29, 3763 - 3782 (1984)).As shown in Table 2 and Figure 4, EI1 has a lower g' value, which is consistent with the presence of a higher amount of long-chain branching. Examples of the invention 2 to 5 - Ethylene-propylene copolymerization

[0061] A single one-gallon stirred autoclave reactor was charged with mixed alkane solvent Isopar™ E (~1.3 kg) and heated to 180 °C. Triethyl aluminum (1 mmol), diethyl zinc (0.25 mmol), propylene (30 g) (“P” in Table 3) and ethylene (30 g) were added sequentially. The various catalyst compositions are prepared in a dry box under an inert atmosphere by mixing the catalyst of Formula (2), Formula (3), Formula (4) and Formula (5) and the cocatalyst (mixture of 1.2 equiv of borate activator and 10 equiv of modified methyl aluminoxane (MMAO3A)) with 0.5 mL of toluene, and injected into the reactor to initiate the polymerization. For each polymerization, only a single catalyst was used. The reactor pressure and temperature were kept constant by feeding ethylene during polymerization and cooling the reactor as needed.After 10 minutes, the ethylene feed was turned off and the solution was transferred to a resin vat purged with nitrogen. Petition 870250076401, dated 08 / 28 / 2025, page 35 / 51 25 / 29 An additive solution containing a phosphorus stabilizer and phenolic antioxidant (Irgafos® 168 and Irganox*1010 at a 2:1 ratio, by weight, in toluene) is added to generate a total additive content of approximately 0.1% in the polymer. The polymer is completely dried in a vacuum oven. Comparative samples 2 to 5

[0062] The same polymerization procedure was followed, as described in Examples of the invention 2 to 5, except that hydrogen (20 mmol) was charged to replace triethyl aluminum and diethyl zinc.

[0063] The results of Examples of the invention 2 to 5 and the corresponding comparative samples 2 to 5 are given in Table 3 below. Petition 870250076401, dated 08 / 28 / 2025, pp. 36 / 51 26 / 29 Vinyl / vinylidene 3.7 12.0 8T 4.4 2.5 3.7 2.8 3.6 Unsaturation unit / million carbons total 449 2312 607 1548 226 384 210 567 vinylidene 103 175 213 281 30 80 50 118 vinyl 383 2084 385 1236 154 294 140 430 trisubstituted n· 03 n· 00 30 ' / L vinylene o> 30 00 ' / L %, in mol, of P 0'lI 0'lI 12.4 10.5 15.3 14.5 15.0 16.0 Mw / Mn 2.91 2.23 1.96 88'I 2.56 2.00 2.56 1.95 Mw 106.189 48.836 O oo 49.454 169.013 81.940 204.006 57.172 Mn 36.553 21.993 23.920 26.342 65.912 40.885 79.799 29.343 Yield Oh 20 28 40 82 29 G9 03 25 h2 mmol 20 20 20 20 Table 3 Copolymerization of ei TEA mmol DEZ mmol 0.25 0.25 0.25 0.25 Catalyst O e 0.3 0.88 0.25 0.85 0.25 0.75 0.8 6'I Name Formula (3) Formula (3) Formula (4) Formula (4) Formula (5) Formula (5) Formula (2) Formula (2) Example AC2 EI 2 AC3 EI 3 AC4 EI 4 AC5 EI 5 P - Propylene Petition 870250076401, dated 08 / 28 / 2025, pp. 37 / 51 27 / 29

[0064] In comparative samples 2 to 5, the terminal unsaturations in the polymer were formed by means of beta-hydride elimination or chain transfer to monomers in the transition metal center, whereas in Examples of the invention 2 to 5, the unsaturation values ​​included contributions from thermal termination reactions in the catalyst and beta-hydride elimination in the aluminum metals. Two observations were made: (1) for all catalysts, a significantly higher amount of vinyl-terminated chains was generated in Examples of the invention 2 to 5, compared with the respective comparative samples 2 to 5, which reflected the effectiveness of chain transfer to aluminum metals and subsequent beta-hydride elimination; (2) Examples of the invention 2 to 5 showed a higher vinyl / vinylidene ratio, implying that catalyst-to-aluminum chain transfer occurred when ethylene was the last unit.This demonstrates the formation of branching, since only vinyl groups can insert themselves into growing polymer chains. Examples of the invention 6 to 14 and Comparative sample 6 - Ethylene / octene copolymer in a continuous reactor. Polymerization was conducted in a single continuous mixed reactor using Formula (2) as the sole catalyst and the activator borate (shown as “cocat 1” in Table 4) and MMAO shown in Table 1 as the cocatalysts. The process conditions and results are shown in Tables 4 and 5 below. Petition 870250076401, dated 08 / 28 / 2025, pages 38 / 51 28 / 29 Table 4 Polymerization in a continuous solution reactor Execution Solvent feed flow, kg / h Ethylene feed flow, kg / h Octene feed flow, kg / h Hydrogen feed flow, SCCM Molar ratio between Catalyst: Cocat 1 H2 flow, SCCM Al-CTA / MMAO Al-CTA / MMAO flow, g / h Al-CTA / MMAO solution concentration, mmol / kg Name ZnCTA AL: Zn Molar ratio Temperature, °C Ethylene conversion, % AC6 22.12 5.30 0.67 430 1.19 430 MMAO3A 24.91 3.0 None 0.00 190 94.93 EI6 22.23 5.30 0.60 549 1.20 549 TeAl 135.07 120.0 DEC 2.99 190 94.91 EI7 22.05 5.30 0.80 519 1.20 519 TeAl 134.81 120.0 DEC 3.00 192 94.59 EI8 22.09 5.30 0.80 519 1.20 519 TeAl 135.13 120.0 DEC 3.03 190 94.79 EI9 22.23 5.31 0.70 499 1.20 499 TeAl 189.95 120.0 DEC 3.00 190 94.76 EI10 22.14 5.31 0.72 499 1.20 499 TeAl 232.64 120.0 DEC 2.90 190 94.88 EI11 22.43 5.30 0.70 374 1.20 374 TeAl 374.20 120.0 DEC 2.96 190 94.84 EI12 21.61 1.62 0.27 117 1.03 117 TeAl 151.38 120.0 DEC 2.84 182 -58.39 EI13 19.67 3.77 0.50 295 1.22 295 TeAl 196.04 120.0 DEC 2.94 190 80.62 EI14 19.48 3.85 0.50 286 1.20 286 TeAl 197.04 120.0 DEC 2.95 190 95.86 Table 5 Polymer properties Performance Melting index dg / min I10 / I2 Density g / cc Mn Mw Mw / Mn Unit of unsaturation 1,000,000 carbon vinylene trisubstituted vinyl vinylidene total AC6 1.1 7.7 0.9205 38.822 88.552 2.28 4 1 12 1 19 EI6 0.54 15.1 0.9127 29.774 75.514 2.54 8 1 89 5 109 EI7 1.13 12.3 0.9208 27.375 69.036 2.52 7 1 93 13 115 EI9 1.06 12.8 0.9203 26.899 68.271 2.54 6 2 104 8 119 EI11 0.46 16.5 0.9196 28.871 79.486 2.75 9 3 180 14 206 EI12 0.3 18.3 0.92 27.087 75.302 2.78 9 2 179 14 204 EI13 0.33 17.6 0.9213 27.216 75.232 2.76 11 1 138 12 162 EI14 0.3 18.1 0.922 27.335 75.720 2.77 10 1 139 14 165

[0065] Comparative sample 6 was conducted under conventional conditions using hydrogen as a molecular weight regulator, producing a linear ethylene / octene copolymer with an I10 / I2 of 7.7. Examples of the invention 6 to 14 were performed with the addition of triethyl aluminum and diethyl zinc. Significantly higher I10 / I2 values ​​of 12.3 to 18.1 were observed, indicating the formation of long-chain branching, compared to an I10 / I2 of 7.7 for AC6.

[0066] DMS analysis is shown in Figures 5 and 6. Examples of the invention 6 to 14 show significantly different rheological behavior, for example higher shear thinning and values Petition 870250076401, dated 08 / 28 / 2025, pp. 39 / 51 29 / 29 lower tan-delta values, compared to the ethylene / octene copolymer produced from Comparative Sample 6.

[0067] It is specifically intended that the present disclosure is not limited to the embodiments and illustrations contained in this document, but includes modified forms of those embodiments, including portions of the embodiments and combinations of elements from different embodiments, as occurs within the scope of the following claims. Petition 870250076401, dated 08 / 28 / 2025, pp. 40 / 51

Claims

1 / 4 CLAIMS 1. A process, characterized in that it comprises: placing, under polymerization conditions at a temperature of 160 °C to 250 °C, a single polymerization catalyst and a cocatalyst in a single polymerization reactor in contact with: (i) an ethylene monomer and a C3-C8 olefin comonomer, (ii) an alkyl-aluminum chain transfer agent, and (iii) an alkyl-zinc chain transfer agent; and forming an ethylene-based polymer having an I10 / I2 value greater than 8.0 and a vinyl content greater than 50 / 1,000,000C.

2. Process according to claim 1, characterized in that the polymerization catalyst has Formula (1) Formula (1) wherein M is titanium, zirconium, hafnium or scandium; each Y1 and Y2 is independently selected from the group consisting of hydrocarbyl(C1-C4o), trihydrocarbylsilyl hydrocarbyl(C1-C4o), halogen, alkoxide or amine, or two Y groups together are a divalent group of hydrocarbylene, hydrocarbadiyl or trihydrocarbylsilyl; each Ar1 and Ar2 independently is selected from the group consisting of aryl(C6-C4o), substituted aryl(C6-C4o), heteroaryl(C3-C4o) and Petition 870250076401, dated 08 / 28 / 2025, page.41 / 51 2 / 4 substituted heteroaryl(C3-C4o); T1, independently in each occurrence, is a divalent bridging group of 2 to 20 carbon atoms, optionally containing heteroatoms including Si, Ge, O, N, S and P; and each R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, and R14 is independently selected from the group consisting of hydrogen, a halogen, hydrocarbyl(C1-C40), substituted hydrocarbyl(C1-C40), heterohydrocarbyl(C1-C40), substituted heterohydrocarbyl(C1-C40), aryl(C6-C40), substituted aryl(C6-C40), heteroaryl(C3-C40), and substituted heteroaryl(C3-C40), and nitro (NO2).

3. Process according to any of claims 1 and 2, characterized in that the polymerization catalyst has Formula (2) 4. Process according to any of claims 1 to 3, characterized in that it comprises: placing, under polymerization conditions at a temperature of 180 °C to 250 °C, the polymerization catalyst of Formula (2) Formula (2) Petition 870250076401, dated 28 / 08 / 2025, page 42 / 51 3 / 4 and a cocatalyst in contact with: (i) an ethylene monomer and a C3-C8 α-olefin comonomer, (ii) an alkyl-aluminum chain transfer agent, and (iii) an alkyl-zinc chain transfer agent; forming an ethylene copolymer having an I10 / I2 value greater than 8.0 and a vinyl content greater than 50 / 1,000,000C.

5. Process according to any one of claims 1 to 4, characterized in that it comprises: placing, under polymerization conditions at a temperature of 180 °C to 250 °C, the polymerization catalyst of Formula (2) and a cocatalyst in contact with: (i) an ethylene monomer and an olefin comonomer selected from the group consisting of propylene, 1-butene, 1-hexene, 1-octene and combinations thereof; (ii) a triethyl aluminum chain transfer agent; and Petition 870250076401, dated 28 / 08 / 2025, page 43 / 51 4 / 4 (iii) a diethyl zinc chain transfer agent; and form an ethylene / C3-Cg α-olefin copolymer having an I10 / I2 value greater than 8.0 and a vinyl content greater than 50 / 1,000,000C. Petition 870250076401, dated 08 / 28 / 2025, pp. 44 / 51

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