WO2024073260A1 - Ethylene copolymers for photovoltaic cells - Google Patents

Abstract

Ethylene copolymers capable of producing films with excellent optical properties at wavelengths of 280 to 1,100 nm, including moisture resistance, creep resistance, tensile strength, and tear strength. The ethylene copolymers are at least 50 wt% ethylene derived units and at least 20 wt% of at least one C3 to C20 comonomer and have branching indexes g'(Mz) and g'(Mz+1) coupled with tri substituted olefins and reactivity ratios (r1r2) that are significantly different than other ethylene copolymers of similar densities. The ethylene copolymers also have significantly improved processability properties and high volume resistivity (>10 15 Ohm*cm), making these copolymers particularly suitable for PV cell applications.

Description

2022EM127 ETHYLENE COPOLYMERS FOR PHOTOVOLTAIC CELLS INVENTORS: Huan Chen, Giriprasath Gururajan, Hamidreza Khakdaman, Alexandra K. Valdez, Zhifeng Bai, Narayanaswami Dharmarajan, Peijun Jiang, and Ru Xie CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application claims the benefit of U.S. Provisional Application 63/377,365, filed on September 28, 2022, the entire contents of which are incorporated herein by reference. FIELD [0002] Embodiments of the present invention generally relate to ethylene copolymers and electronic device modules embodying such copolymers. More particularly, embodiments provided herein relate to ethylene copolymers suitable for making photovoltaic cell applications. BACKGROUND [0003] Polyolefin plastomers, primarily copolymers of ethylene with butene or octene are finding increasing use as polymer encapsulant in photovoltaic (PV) cell applications. These polymers are replacing ethylene vinyl acetate (EVA) copolymers, where studies have shown that plastomer based encapsulant materials have increased power generation over a service life of 30 years compared to EVA. Plastomer films used as encapsulant materials have a high barrier to potential induced degradation (PID) and lower power degradation compared to EVA film, both of which contribute to lower power loss. Evolution of acetic acid in EVA resins from service use and discoloration due to yellowing leads to increased power loss for EVA film based encapsulant. [0004] Polymer film encapsulant for PV cell application needs to satisfy several functional attributes. Electrical properties denoted by high volume resistivity is useful for lower power loss. Good optical properties, often measured by high light transmission in the wavelength of 280 to 1100 nm, enhanced barrier to moisture represented by low water vapor transmission rates (WVTR), high cross-link density to provide creep resistance and good mechanical properties represented by tensile strength, flexural modulus and tear strength are considered important. The problem that needs to be addressed is how to obtain all these functional attributes in a single polyolefin polymer. [0005] There are several patents that disclose the use of plastomer resins as encapsulant material in PV Cell. For example, US 9,349,895B2 and its counterpart CN 103189996B 2022EM127 describe an ethylene alpha-olefin copolymer suitable as a PV cell encapsulant with a density in the range of 0.865 to 0.884 g/cc, MI (190°C) in the range of 2 to 10 and Shore A Hardness in the range of 60 to 85. US 8581094B2 and its counterpart CN101563786B describe a PV cell device with a polyolefin copolymer encapsulant having a density less than 0.9 g/cc, melting point less than 95°C, alpha-olefin content ranging from 15 to 50 wt%, a SCBDI of at least 50 and optionally a free radical initiator and a co-agent. KR 101191126B1 describes an encapsulant sheet for a solar cell, where the sheet comprises an ultra-low density ethylene alpha olefin copolymer (0.850 to 0.890 g/cc), a low density ethylene alpha olefin copolymer (0.890 to 0.920 g/cc) and a silane graft modified ultra-low density copolymer. KR 101723708 B1 describes a polyolefin resin ter-polymer used as encapsulant material, where the polyolefin has a first crystallization temperature in the range of 45°C to 60°C and a second crystallization temperature lower than the first crystallization temperature of the resin. [0006] US 8,329,848 B2 describes an ethylene butene copolymer with vinyl groups in the range of 0.06 to 1 per 1,000 C atoms, density in the range of 0.850 to 0.910 g/cc, MIR (I10/I2.16) < 7.7, MI in the range of 0.1 to 25 dg/min and ethylene content in the range of 80 to 95 mole %. US 10,774,205B2 describes polymers with multi-modal composition distribution each having a distinct crystallization peak in TREF in the range of 40°C to 110°C. [0007] However, there is still a need for new ethylene-based copolymers capable of producing a film that has excellent optical properties at wavelengths of 200 to 900 nm, good processability, moisture resistance, creep resistance, tensile strength, flexural modulus and tear strength. Such films would be particularly suitable for solving PV cell application needs. SUMMARY [0008] Ethylene copolymers, electronic device modules and methods for making both are provided herein. The ethylene copolymers include at least 50 wt% ethylene derived units and at least 20 wt% of at least one C3 to C20 comonomer. The ethylene copolymer has a melt index of 0.5 g/10 min to about 50 g/10 min, as measured according to ASTM D1238 (190°C/2.16 kg) and a density of about 0.860 g/cc to 0.880 g/cc, as measured according to ASTM D792. The copolymer has a first long chain branching index (g’(Mz)) of 0.80 to 0.93, a second long chain branching index (g’(Mz+1)) of 0.80 to 0.93, and less than 0.7 vinyl/total unsaturation. The unsaturation level of trisubstituted olefins is 50 to 500, and volume resistivity at 23°C is 4*10¹⁵ Ωcm or more. Such ethylene copolymers can be made using metallocene and post metallocene catalysts in solution polymerization processes, as further provided herein. 2022EM127 [0009] It has been surprisingly found that these ethylene based copolymers have significantly improved processability properties and high volume resistivity (>10 ¹⁵ Ohm*cm), and are capable of producing films having excellent optical properties at wavelengths of 200 to 900 nm, moisture resistance, creep resistance, tensile strength, flexural modulus and tear strength, making these copolymers particularly suitable for electronic device modules such as PV cell applications. BRIEF DESCRIPTION OF THE DRAWINGS [0010] So that the manner in which the above recited features of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments. [0011] Figure 1A shows the Volume resistivity plotted against the g’(Mz+1)/g’-avg values for Samples 1-6 and the other commercially available ethylene copolymers of similar densities. [0012] Figure 1B shows the Volume resistivity plotted against the g’(Mz+1)/g’-avg values for Samples 1-6 and the other commercially available ethylene copolymers of similar densities. [0013] Figure 1C shows the g’ (Mz+1)/g’ -avg plotted against the g’(Mz+1) values from GPC for Samples 1-6 and other commercially available ethylene copolymers of similar densities. [0014] Figure 2A shows the Trisubstituted Olefins determined from HNMR vs. g’(Mz+1) for Samples 1-6 and the other commercially available ethylene copolymers of similar densities. [0015] Figure 2B shows the Trisubstituted Olefins determined from HNMR vs. g’(Mz) from GPC for Samples 1-6 and the other commercially available ethylene copolymers of similar densities. [0016] Figure 3 shows the Vinyl/Total unsaturation determined from HNMR vs. g’(Mz) from GPC for Samples 1-6 and the other commercially available ethylene copolymers of similar densities. [0017] Figure 4A shows r1r2 values from NMR testing vs. g’(Mz+1) for Samples 1-6 and the other commercially available ethylene copolymers of similar densities. [0018] Figure 4B shows r1r2 values from NMR testing vs. g’Mz for Samples 1-6 and the other commercially available ethylene copolymers of similar densities. 2022EM127 [0019] Figure 5A shows Phase angle at 10,000 Pa complex modulus for Samples 1-6 and the other commercially available ethylene copolymer grades. [0020] Figure 5B shows Phase angle at 50,000 Pa complex modulus for Samples 1-6 and the other commercially available ethylene copolymer grades. [0021] Figure 6 shows the TREF-IR data, both differential and cumulative for Samples 1-4. [0022] Figure 7 compares the cooling cycle data for Samples 1 through 4. [0023] Figure 8 shows the water vapor transmission rate (WVTR) properties for Samples 1-4 [0024] Figure 9 shows Cure properties of single and dual reactor composition for Samples 1-4. [0025] Figure 10 shows melt pressure and screw torque for extrusion at 100°C melt temperature for 0.5 mm thickness film made from Samples 2 and 4 and two other commercially available comparative polymers of similar densities. DETAILED DESCRIPTION [0026] Ethylene copolymers capable of producing films with excellent optical properties at wavelengths of 280 to 1,100 nm, including moisture resistance, creep resistance, tensile strength, and tear strength are provided. The ethylene copolymers have branching indexes g’(Mz) and g’(Mz+1) measured from GPC-4D coupled with trisubstituted olefins and reactivity ratio (r1r2) determined using HNMR that are significantly different than other ethylene copolymers of similar densities. It has been surprisingly found that these ethylene copolymers provided herein also have significantly improved processability properties and high volume resistivity (>10 ¹⁵ Ohm*cm), making these copolymers particularly suitable for electronic device modules such as PV cell applications. [0027] It is to be understood that the disclosure provided herein provides several exemplary embodiments for implementing different features, structures, and/or functions of the invention. Exemplary embodiments of components, arrangements, and configurations are described to simplify the present disclosure; however, these exemplary embodiments are provided merely as examples and are not intended to limit the scope of the invention. Additionally, the present disclosure may repeat reference numerals and/or letters in the various exemplary embodiments and across the Figures provided herein. This repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various exemplary embodiments and/or configurations discussed in the Figures. Moreover, the exemplary embodiments presented herein can be combined in any combination of ways, i.e., any element from one 2022EM127 exemplary embodiment can be used in any other exemplary embodiment, without departing from the scope of the disclosure. [0028] Additionally, certain terms are used throughout the following description and claims to refer to particular components. As one skilled in the art will appreciate, various entities can refer to the same component by different names, and as such, the naming convention for the elements described herein is not intended to limit the scope of the invention, unless otherwise specifically defined herein. Further, the naming convention used herein is not intended to distinguish between components that differ in name but not function. [0029] In the following discussion and in the claims, the terms “including” and “comprising” are meant to be open-ended, and thus should be interpreted to mean “including, but not limited to.” The phrase “consisting essentially of” means that the described/claimed composition does not include any other components that will materially alter its properties by any more than 5% of that property, and in any case does not include any other component to a level greater than 3 mass%. [0030] The term “or” is intended to encompass both exclusive and inclusive cases, i.e., “A or B” is intended to be synonymous with “at least one of A and B,” unless otherwise expressly specified herein. [0031] The indefinite articles “a” and “an” refer to both singular forms (i.e., “one”) and plural referents (i.e., one or more) unless the context clearly dictates otherwise. For example, embodiments using “an olefin” include embodiments where one, two, or more olefins are used, unless specified to the contrary or the context clearly indicates that only one olefin is used. [0032] The term “wt%” means percentage by weight, “vol%” means percentage by volume, “mol%” means percentage by mole, “ppm” means parts per million, and “ppm wt” and “wppm” are used interchangeably and mean parts per million on a weight basis. All concentrations herein, unless otherwise stated, are expressed on the basis of the total amount of the composition in question. [0033] The term “polymer” refers to any two or more of the same or different repeating units/mer units or units. The term “homopolymer” refers to a polymer having units that are the same. The term “copolymer” refers to a polymer having two or more units that are different from each other, and includes terpolymers and the like. The term “terpolymer” refers to a polymer having three units that are different from each other. The term “different” as it refers to units indicates that the units differ from each other by at least one atom or are different isomerically. Likewise, the definition of polymer, as used herein, includes homopolymers, 2022EM127 copolymers, and the like. By way of example, when a copolymer is said to have a “propylene” content of 10 wt% to 30 wt%, it is understood that the repeating unit/mer unit or simply unit in the copolymer is derived from propylene in the polymerization reaction and the derived units are present at 10 wt% to 30 wt%, based on a weight of the copolymer. [0034] As used herein, "Mn" refers to the number average molecular weight of the different polymers in a polymeric material, "Mw" refers to the weight average molecular weight of the different polymers in a polymeric material, and "Mz" refers to the z average molecular weight of the different polymers in a polymeric material. The terms “molecular weight distribution” (MWD) and “polydispersity index” (PDI) are used interchangeably to refer to the ratio of Mw to Mn. Unless otherwise noted, all molecular weights (e.g., Mw, Mn, Mz) are reported in units of g/mol. [0035] Nomenclature of elements and groups thereof used herein are pursuant to the Periodic Table used by the International Union of Pure and Applied Chemistry after 1988. An example of the Periodic Table is shown in the inner page of the front cover of Advanced Inorganic Chemistry, 6th Edition, by F. Albert Cotton et al. (John Wiley & Sons, Inc., 1999). [0036] Considering the ethylene copolymers in more detail, the ethylene copolymers can be unimodal or bimodal compositions, and the ethylene copolymers can be produced with single or dual reactors. A single reactor ethylene copolymer can have a TREF elution temperature peak around 30°C. In the case of a dual-reactor copolymer, the first reactor can produce a lower crystalline component with a TREF peak typically at around 20°C, and the second reactor can produce copolymer with a TREF peak greater than 40°C. The dual reactor copolymers have a higher crystallization temperature (Tc) as determined by differential scanning calorimetry (DSC), lower WVTR and enhanced tear strength in comparison to the single reactor products. The crystalline component contributes to higher Tc that enhances pellet stability, provides barrier to water entry that is reflected in lower WVTR properties and enhances cross link density all of which are essential for application as a polymer encapsulant in PV cells. [0037] The ethylene copolymers contain ethylene and at least one other C3-C20 comonomer. Preferred ethylene copolymers are ethylene-butene and ethylene-octene plastomers. The ethylene content of the lower ethylene content fraction can range from a low of 55 wt% to a high of 76 wt%. The ethylene content of the higher ethylene content fraction can range from a low of 60 wt% to a high of 90 wt%. The ethylene content of the overall polymer can range from a low of 60 wt% to a high of 85 wt%. 2022EM127 [0038] The ethylene copolymers can have a melt index of 0.5 g/10 min to about 50 g/10 min, as measured according to ASTM D1238 (190°C/2.16 kg). The melt index can also range from a low of about 0.5, 1.0 or 2.0 to a high of about 30, 40, or 50 g/10 min. The melt index can also range from a low of about 0.5, 3.0 or 5.0 to a high of about 20, 35, or 45 g/10 min. [0039] The ethylene copolymers can also have a broad melt index ratio (MIR) or (MI_21.6/MI_2.16) ranging from 20.0 to about 100.0, as measured according to ASTM D1238 (190°C/2.16 kg). The MIR can also range from a low of about 25, 30, or 40 to a high of about 60, 80, or 95. [0040] The ethylene copolymers can have a density of from 0.850 g/cc to 0.920 g/cc, as measured according to ASTM D792, which indicates that they can serve as plastomers having the combined qualities of elastomers and polymers. The ethylene copolymers can also have a density of about 0.860 g/cc to 0.880 g/cc. The density can range from a low of about 0.850, 0.855, 0.860, 0.865, or 0.870 to a high of about 0.874, 0.876, 0.880, 0.900, or 0.920 g/cc. [0041] The ethylene copolymers can have a volume resistivity at 23°C of 8*10¹⁵ Ωcm or more. The volume resistivity at 23°C can be at least 8.5*10¹⁵ Ωcm; 9.5*10¹⁵ Ωcm, 1*10¹⁶ Ωcm, or 1.5*10¹⁶ Ωcm. [0042] The ethylene copolymer can have a g’Mz+1 to g’-avg ratio of 0.9 to 1.0. This ratio can also range from a low of 0.91, 0.92 or 0.93 to a high of 0.97, 0.98, or 0.99. [0043] The ethylene copolymers can have less than 0.7 vinyl/total unsaturation as estimated by H-NMR. The vinyl/total unsaturation can range from a low of about 0.01, 0.02, or 0.03 to a high of about 0.5, 0.6, or 0.7. The vinyl/total unsaturation can also range from a low of about 0.1, 0.2, or 0.3 to a high of about 0.5, 0.6, or 0.7. [0044] The ethylene copolymer can have an unsaturation level of trisubstituted olefins of 50 to 500, as determined by H-NMR. The unsaturation level of trisubstituted olefins can also range from about 50, 80 or 100 to a high of about 300, 400, or 500. The unsaturation level of trisubstituted olefins can also range from about 60 to 480; 80 to 420; or 100 to 300. [0045] The ethylene copolymers can have a reactivity ratio of 0.8 or less. The reactivity ratio can also range from 0.2 to 0.8. The reactivity ratio can also range from a low of 0.2, 0.3, or 0.35 to a high of 0.5, 0.65, or 0.8. The reactivity ratio can also be 0.2, 0.3, 0.4, 0.5, 0.6, 0.7 or 0.8. Polymerization Process [0046] The ethylene copolymers can be made using a solution polymerization process. Preferably, the solution polymerization process is a bulk polymerization process, which refers 2022EM127 to a polymerization process in which the monomers and/or comonomers being polymerized are used as a solvent or diluent using little or no inert solvent as a liquid or diluent. A small fraction of inert solvent might be used as a carrier for a catalyst and a scavenger. [0047] The term "solution polymerization" refers to a polymerization process in which the polymer is dissolved in a liquid polymerization medium, such as an inert solvent, monomer(s), or blends thereof. A solution polymerization is typically homogeneous, which refers to a polymerization process where the polymer product is dissolved in the polymerization medium. Such systems are preferably not turbid as described in J. Vladimir Oliveira, C. Dariva, and J. C. Pinto, Ind. Eng. Chem. Res., 29, 2000, 4627. A homogeneous polymerization process is typically a process where at least 90 wt% of the product is soluble in the reaction media. [0048] A suitable solution polymerization process for preparing the polymer blend compositions disclosed herein is generally described in more detail in U.S. Patent Nos. 9,359,535, 7,470,118, 7,226,553; and 7,033,152, which are incorporated by reference herein in their entirety. WO 2017/058385A1 describes a solution polymerization process using single or multiple spiral heat exchanger systems for continuous polymerization of C2 to C40 olefins, which can also be used and is also incorporated by reference herein in its entirety. [0049] The ethylene copolymers can exhibit low levels of long chain branching (LCB). In particular, the ethylene copolymers can have a first long chain branching index (g’(Mz)) ranging from 0.30 to 1.00, preferably from 0.70 to 0.97. The first long chain branching index (g’(Mz)) can also range from 0.80 to 0.93. The first long chain branching index (g’(Mz)) can also range from a low of 0.80, 0.82, or 0.85 to high of 0.90, 0.92, or 0.93. The first long chain branching index (g’(Mz)) can also be 0.80, 0.81, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88, 0.89, 0.90, 0.91, 0.92, or 0.93. [0050] The ethylene copolymers can have a second long chain branching index (g’(Mz+1)) of from 0.30 to 1.00, preferably from 0.70 to 0.97. The second long chain branching index (g’(Mz+1)) can also range from 0.80 to 0.93. The second long chain branching index (g’(Mz+1)) can also range from a low of 0.80, 0.82, or 0.85 to high of 0.90, 0.92, or 0.93. The second long chain branching index (g’(Mz+1)) can also be 0.80, 0.81, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88, 0.89, 0.90, 0.91, 0.92, or 0.93. Comonomer [0051] The at least one other comonomer can include any one or more C4 to C20 olefins. The C4 to C20 comonomers can be linear, branched, or cyclic. Suitable C4 to C20 cyclic olefins can be strained or unstrained, monocyclic or polycyclic, and can optionally include 2022EM127 heteroatoms and/or one or more functional groups. The reactor C2 concentration can range from 0.1 to 40.0 wt% while the reactor comonomer concentration can range from 0.1 to 40.0 wt%. [0052] Specific examples of comonomers include butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7- oxanorbornadiene, substituted derivatives thereof, and isomers thereof, preferably hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5 -cyclooctadiene, l-hydroxy-4- cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene, and their respective homologs and derivatives, preferably norbornene, norbornadiene, and dicyclopentadiene. [0053] In a preferred embodiment, one or more dienes (diolefin comonomer) are added to the polymerization process. The diene can be present in the polymer produced herein at up to 10 wt%, preferably at 0.00001 to 8.0 wt%, preferably 0.002 to 8.0 wt%, even more preferably 0.003 to 8.0 wt%, based upon the total weight of the composition. In some embodiments, 500 ppm or less of diene is added to the polymerization, preferably 400 ppm or less, preferably 300 ppm or less. In other embodiments, at least 50 ppm of diene is added to the polymerization, or 100 ppm or more, or 150 ppm or more. [0054] Suitable diolefin comonomers include any hydrocarbon structure, preferably C4 to C30, having at least two unsaturated bonds, where at least one of the unsaturated bonds are readily incorporated into a polymer chain during chain growth. It is further preferred that the diolefin comonomers be selected from alpha, omega-diene monomers (i.e., di-vinyl monomers). More preferably, the diolefin comonomers are linear di-vinyl monomers, most preferably those containing from 4 to 30 carbon atoms. Specific examples of preferred dienes include butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, particularly preferred dienes include 1,6-heptadiene, 1,7- octadiene, 1,8-nonadiene, 1 ,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12- tridecadiene, 1,13 -tetradecadiene, and low molecular weight polybutadienes (Mw less than 1000 g/mol). Preferred cyclic dienes include cyclopentadiene, 5-vinyl-2-norbornene, 2022EM127 norbornadiene, 5-ethylidene-2-norbornene, divinylbenzene, and dicyclopentadiene or higher ring containing diolefins with or without substituents at various ring positions. Catalyst System [0055] A suitable catalyst system for making the ethylene copolymers provided herein can include one or more bridged metallocene compounds having a single substituted carbon or silicon atom bridging two ancillary monanionic ligands, such as substituted or unsubstituted cyclopentadienyl-containing (Cp) ligands and/or substituted and unsubstituted Group 13-16 heteroatom ligands, of the metallocene metal centers. The bridge substituents can be substituted aryl groups, the substituents including at least one solubilizing hydrocarbylsilyl substituent located on at least one of the aryl group bridge substituents. Substituents present on the cyclopentadienyl and/or heteroatom ligands can include Cι-C₃₀ hydrocarbyl, hydrocarbylsilyl, or hydrofluorocarbyl groups as replacements for one or more of the hydrogen groups on those ligands, or those on fused aromatic rings on the cyclopentadienyl rings. Aromatic rings can be substituents on the cyclopentadienyl ligands and are inclusive of the indenyl and fluorenyl derivatives of cyclopentadienyl groups and their hydrogenated counterparts. Such aromatic rings typically include one or more aromatic ring substituents selected from linear, branched, cyclic, aliphatic, aromatic or combined structure groups, including fused-ring or pendant configurations. Examples include methyl, isopropyl, n-propyl, n-butyl, isobutyl, tertiary butyl, neopentyl, phenyl, n-hexyl, cyclohexyl, benzyl, and adamantyl. As used herein, the term "hydrocarbon" or "hydrocarbyl" is meant to include those compounds or groups that have essentially hydrocarbon characteristics but optionally contain not more than about 10 mol% non-carbon heteroatoms, such as boron, silicon, oxygen, nitrogen, sulfur, and phosphorous. Additionally, the term is meant to include hydrofluorocarbyl substituted groups. "Hydrocarbylsilyl" is exemplifyed by, but not limited to, dihydrocarbyl- and trihydrocarbylsilyls, where the preferred hydrocarbyl groups are Cι-C₃o substituent hydrocarbyl, hydrocarbylsilyl or hydrofluorocarbyl substitutents for the bridging group phenyls. For heteroatom containing catalysts, see International Publication No. WO 92/00333. Also, the use of hetero-atom containing rings or fused rings, where a non-carbon Group 13, 14, 15 or 16 atom replaces one of the ring carbons is considered herein to be within the terms "cyclopentadienyl", "indenyl", and "fluorenyl". See, for example, the background and teachings of International Publication Nos. WO 98/37106 and WO 98/41530, which are incorporated herein by reference. 2022EM127 [0056] Particularly suitable cyclopentadienyl-based complexes are the compounds, isomers, or mixtures, of (para-trimethylsilylphenyl)(para-n-butylphenyl)methylene (fluorenyl) (cyclopentadienyl) hafnium dimethyl, di(para-trimethylsilylphenyl)methylene (2,7-di-tertbutyl fluorenyl) (cyclopentadienyl) hafnium dimethyl, di(para-triethylsilylphenyl)methylene (2,7-di- tertbutyl-fluorenyl) (cyclopentadienyl) hafnium dimethyl, (para-triethylsilylphenyl) (para-t- butylphenyl) methylene (2,7-di tertbutyl fluorenyl) (cyclopentadienyl) hafnium dimethyl or dibenzyl, and di(para-triethylsilyl-phenyl)methylene (2,7- dimethylfluorenyl)(cyclopentadienyl) hafnium dimethyl or dibenzyl. Other suitable cyclopentadienyl-based complexes are described in WO/2000/024793, which is also incorporated by reference herein. Activator [0057] The bridged metallocene compounds can be activated for polymerization catalysis in any manner sufficient to allow coordination or cationic polymerization. This can be achieved for coordination polymerization when one ligand can be abstracted and another will either allow insertion of the unsaturated monomers or will be similarly abstractable for replacement with a ligand that allows insertion of the unsaturated monomer (labile ligands), e.g., alkyl, silyl, or hydride. The traditional activators of coordination polymerization art are suitable, for example, Lewis acids such as alumoxane compounds, and ionizing, anion precursor compounds that abstract one so as to ionize the bridged metallocene metal center into a cation and provide a counter-balancing noncoordinating anion. [0058] For example, suitable activators can include a cationic component. In any embodiment, the cationic component can have the formula [R¹R²R³AH]⁺, where A is nitrogen, R¹ and R² are together a -(CH₂)_a- group, where a is 3, 4, 5, or 6 and form, together with the nitrogen atom, a 4-, 5-, 6-, or 7-membered non-aromatic ring to which, via adjacent ring carbon atoms, optionally one or more aromatic or heteroaromatic rings can be fused, and R³ is C1, C2, C3, C4, or C5 alkyl, or N-methylpyrrolidinium or N-methylpiperidinium. Alternatively, in any embodiment, the cationic component can have the formula [R_nAH4__n]⁺, where A is nitrogen, n is 2 or 3, and all R are identical and are C1 to C3 alkyl groups, such as trimethylammonium, trimethylanilinium, triethylammonium, dimethylanilinium, and dimethylammonium. [0059] Suitable activators can also be or include an anionic component, [Y]. The anionic component can be a non-coordinating anion (NCA), having the formula [B(R⁴)4]- , where R⁴ is an aryl group or a substituted aryl group, of which the one or more substituents are identical or different and are selected from the group consisting of alkyl, aryl, a halogen atom, halogenated 2022EM127 aryl, and haloalkylaryl groups. The substituents can be perhalogenated aryl groups, or perfluorinated aryl groups, including, perfluorophenyl, perfluoronaphthyl and perfluorobiphenyl. [0060] Together, the cationic and anionic components of the catalyst system disclosed herein can form an activator compound. In any embodiment, the activator can be N,N- dimethylanilinium-tetra(perfluorophenyl)borate, N,N-dimethylanilinium- tetra(perfluoronaphthyl)borate, N,N-dimethylanilinium-tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium-tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium- tetra(perfluorophenyl)borate, triphenylcarbenium-tetra(perfluoronaphthyl)borate, triphenylcarbenium-tetrakis(perfluorobiphenyl)borate, and/or triphenylcarbenium- tetrakis(3,5-bis(trifluoromethyl)phenyl)borate. [0061] A particularly advantageous activator is dimethylaniliniumtetrakis (heptafluoro naphthyl) borate. See also International Publication Nos. WO/2021/162748; WO/2013/134038; WO/2000/024793, for detailed descriptions of suitable catalyst systems and activators. each of which is incorporated by reference herein. [0062] As noted, suitable polymerization processes employ a polymerization catalyst system, and in particular a polymerization catalyst system comprising at least one activator, at least one support and at least one catalyst composition. A “catalyst composition” or “catalyst system” is the combination of at least two catalyst compounds, a support material, an optional activator, and an optional co-activator. It is believed the high volume resistivity of the ethylene-based copolymer provided herein can be achieved or enhanced due to the particular catalyst system used to polymerize the copolymer. In a photovoltaic cell, a feasible way to mitigate potential induced degradation (PID) is to hinder the ionic current flow through the encapsulant. Volume resistivity is an intrinsic property of encapsulant polymeric material and is characterized by how strongly a given material opposes the flow of electrical current. [0063] For a given catalyst system, once the cations of the activator activate the catalyst, the activators may remain in the polymer composition. As a result, the cations and anions may affect the polymer electric conductivity. Since not all ions diffuse equally, different ions affect the polymer composition differently. In particular, the size of the ion, the charge of the ion, the interaction of the ion with the surrounding medium, and the dissociation energy of the ion with available counter-ions will all affect the ion's ability to diffuse through a surrounding medium such as a polymer material. 2022EM127 [0064] Conventional olefin polymerization activators include weakly-coordinating or non- coordinating anions. It has been shown that weak coordination of the anion leads to increased catalytic efficiency of the cationic catalyst. However, since the non-nucleophilic character of the non-coordinating anion also increases diffusion, the residual activator anion in the produced polymer will lower the electrical resistance of the polymer, thereby increasing electrical loss, and decreasing the insulation ability of the produced polymer [0065] It has been surprisingly discovered that the volume resistivity of an ethylene-based copolymer can be enhanced (increased) by reducing the level of residual ion and achieving a low ion diffusion rate. A transition metal bis(phenolate) complex according to the formula (I) that is shown and described in US Patent No. 11,225,539 has the capability of producing ethylene copolymer with high catalyst activity (about 3 times higher than in conventional bridged metallocene compounds such as those mentioned in Paragraph [0055]). High catalyst activity leads to low residual ion in the polymer. Particularly suitable catalysts include: Dimethylzirconium[2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'- biphenyl]-2-olate)] (Cat-Zr) or Dimethylhafnium[2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1- yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-olate)] (Cat-Hf). [0066] It has also been surprisingly discovered that bulky activators, such as those compatible with the aforementioned Cat-Zr and Cat-Hf catalysts, slow down the ion diffusion rate in polymerization process. Such activators may include: N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate (DMAH-BF20) or dimethylanilinium tetrakis(heptafluoronaphthyl) borate (DMAH-BF28). [0067] The ethylene copolymers can have a unique combination of the following attributes: a. a volume resistivity at 23°C >8*10¹⁵ Ωcm; b. g’Mz+1/g’-avg<1 for g’Mz+1(branching)<0.931; c. significantly higher trisubstituted olefins for g’Mz (branching) <0.93 and g’Mz+1(branching) <0.93; d. <0.2 vinyl/total unsaturation for g’Mz < 0.94; e. reactivity ratios ≤ 0.7 for any g’Mz<0.94; and/or f. lower r1r2 values than comparative copolymers (most >1 and up to ~1.5), as seen in Fig 4, which indicates less chain blockiness levels. [0068] These unique attributes distinguish the ethylene copolymers provided herein from other comparative ethylene copolymers. 2022EM127 Examples: [0069] The foregoing discussion can be further described with reference to the following non- limiting examples. Six (6) different ethylene copolymers were prepared. Samples 1-4 were ethylene-butene copolymers and Samples 5-6 were ethylene-octene copolymers. All 6 copolymers were produced in a pilot sized solution reactor using di(para- triethylsilylphenyl)methylene (2,7-di-tertbutyl-fluorenyl) (cyclopentadienyl) hafnium dimethyl, as the catalyst and dimethylaniliniumtetrakis (heptafluoro naphthyl) borate as the co- catalyst, both available from ExxonMobil Product Solutions Company. [0070] Tables 1 and 2 provide more information about each reactor component and the overall copolymer of Samples 1-6. Table 3 and 4 provide similar information for comparative commercially available copolymers. Table 5 reports tensile strength and flex modulus of compression molded samples from Samples 1-4. [0071] Table 1: Properties of Samples 1-6

[0072] Table 2: Additional properties of Samples 1-6

2022EM127 [0073] Table 3: Comparative commercially available copolymers properties.

[0074] Table 4: Comparative commercially available copolymer properties.

[0075] Table 5: Tensile and Flex properties of compression molded Samples 1-4

[0076] Figure 1A shows the Volume resistivity plotted against the g’ Mz+1 values and Figure 1B shows the Volume resistivity plotted against the g’ (Mz+1)/g’ -avg values for Samples 1-6 and other commercially available ethylene copolymers of similar densities. Figure 2022EM127 1C shows the g’ (Mz+1)/g’ -avg plotted against the g’(Mz+1) values from GPC for the same copolymers. As shown in Figures 1A-1C, volume resistivity at 23°C is >4*1015 Ωcm & g’Mz+1/g’-avg<1 for g’Mz+1(branching)<0.93 for both the inventive copolymers and the comparative commercially available copolymers. [0077] Figure 2A shows the Trisubstituted Olefins determined from HNMR vs. g’ (Mz+1) for Samples 1-6 and the other commercially available ethylene copolymers of similar densities and Figure 2B shows the Trisubstituted Olefins determined from HNMR vs. g’ (Mz). As shown in Figures 2A and 2B, Samples 1-6 exhibited significantly higher trisubstituted olefins for g’Mz (branching) <0.93 and g’Mz+1(branching) <0.93. [0078] Figure 3 shows the Vinyl/Total unsaturation determined from HNMR vs. g’ (Mz) from GPC for Samples 1-6 and the other commercially available ethylene copolymers of similar densities. Figure 3 shows the inventive resins have <0.2 vinyl/total unsaturation for g’Mz < 0.94. [0079] Figure 4A shows r1r2 values from NMR testing vs. g’ (Mz+1) for Samples 1-6 and the other commercially available ethylene copolymers of similar densities, and Figure 4B shows r1r2 values from NMR testing vs. g’Mz. The reactivity ratios of the inventive copolymers are ≤ 0.7 for any g’Mz<0.94 and have much lower r1r2 value than the comparative copolymers (most >1 and up to ~1.5), which refers to less chain blockiness levels. [0080] Figure 5A shows Phase angle at 10,000 Pa complex modulus for Samples 1-6 and the other commercially available ethylene copolymer grades, and Figure 5B shows Phase angle at 50,000 Pa complex modulus. As shown, the phase angle @10,000 & 50,000 Pa Complex modulus measured for ~5 MI and ~14 MI are significantly lower than the comparative examples at similar MIs. [0081] Figure 6 shows the TREF-IR data, both differential and cumulative for Samples 1- 4. The TREF data contains a soluble fraction that is below 0°C and insoluble fractions that have distinct elution temperatures. For Samples 1 and 3, there was one distinct peak elution temperature around 30°C. For Samples 3 and 4 there were two peak elution temperatures corresponding to the density of the components in each reactor. The elution peak of the lower density component occurred around 20°C, while that of the higher density fraction was between 45 and 50°C. [0082] Figure 7 compares the cooling cycle data for Samples 1 through 4, respectively. The peak crystallization temperature and the corresponding heat of crystallization is plotted for each sample. Comparing Sample 3 to Sample 1, a higher Tc (56°C vs 45°C) is observed, which is 2022EM127 also the case while comparing Sample 4 to Sample 2 (61°C, vs 49°C). The heat of crystallization was lower for Sample 3 compared to Sample 1 (32 J/g vs 34 J/g) and higher when comparing Sample 4 vs Sample 2 (36 J/g vs 33 J/g). The increase in Tc, which was due to the higher crystallinity in the second reactor component was particularly significant for maintaining stable pellets at lower polymer density. Figure 7 also shows that the dual reactor Sample 4 sample has higher modulus. [0083] Figure 8 shows the water vapor transmission rate (WVTR) properties of Samples 1 through 4. The transmission rate expressed in g/m2*day is normally considered. A lower value indicates enhanced barrier to water penetration. Both Sample 3 and Sample 4 have lower WVTR values compared to the single reactor analogs of Sample 1 and Sample 3 respectively. The lower WVTR values of the dual reactor grades can be attributed to the higher crystalline fraction in the second reactor component. [0084] Samples 1-4 were compounded with peroxide (Luperox 101) at 2.5 phr. The peroxide was added to the polymer in a Brabender Plasticorder using a batch size of 270 gm. The melt temperature in the Brabender was maintained at 70°C to mitigate premature crosslinking. The sample was added to the Brabender with the rotor running at 50 rpm, until the polymer fluxed and homogenized in the cavity. The peroxide was added to the polymer and the mixture was compounded for an additional 3 minutes before being discharged from the chamber. [0085] The cure properties of the samples were tested using an Oscillating Disc Rheometer (ODR) at 180°C, 3 degree arc and 30 min test time. Cure state determined by MH-ML, the difference between the highest torque value (MH) and the lowest torque value (ML), and the maximum cure rate was determined as [(MH-ML)*0.9-2]/(Tc₉₀-Ts₂), where Tc90 is the time to achieve 90% of the maximum HF, and Ts₂ is the cure time to 2 torque units increase. [0086] Figure 9 shows the ODR parameters (cure rate and cure state) comparing the single reactor samples (Sample 1 and Sample 2) with the corresponding dual reactor analogs of Sample 3 and Sample 4 respectively. Both max cure rate and the cure state is higher in the dual reactor polymers compared to the single reactor candidates. [0087] Samples 2 and 4 (14 MI) were extruded to form 0.5 mm thickness film in a sheet extrusion machine with melt temperature at 100°C. Figure 10 shows melt pressure and screw torque for extrusion at 100°C melt temperature for 0.5 mm thickness film made from Samples 2 and 4 and two other commercially available comparative polymers of similar densities. These copolymer samples showed lower torque than the commercially available reference 2022EM127 copolymers, which indicates better processability at this specific application. It was further discovered that the tailoring of the individual molecular weights provided advantages in processability, especially during film extrusion versus the single reactor polymer that was produced at a fixed MI. Test Procedures [0088] In the foregoing Examples, the following test methods and procedures were used: [0089] Densities were measured according to ASTM D792, and the MI values and MIR values (MI_21.6/MI_2.16) were measured according to ASTM D1238 (190°C/2.16 kg). [0090] The distribution and the moments of molecular weight (Mw, Mn, Mz, Mw/Mn, Mz/Mn, etc.), the comonomer content (C8), and the long chain branching indices (g’) were determined using a high temperature Gel Permeation Chromatography (Polymer Char GPC- IR) equipped with a multiple-channel band-filter based Infrared detector IR5, an 18-angle light scattering detector and a viscometer. Three Agilent Plgel 10µm Mixed-B LS columns are used to provide polymer separation. Detailed analytical principles and methods for molecular weight determinations are described in paragraphs [0044] – [0051] of International Publication No. WO/2019/246069A1, which is herein incorporated herein by reference (noting that the equation for c referenced in Paragraph [0044] therein for concentration I at each point in the chromatogram, is c = βI, where β is mass constant and I is the baseline-subtracted IR5 broadband signal intensity (I)). Unless specifically mentioned, all the molecular weight moments used or mentioned in the present disclosure are determined according to the conventional molecular weight (IR molecular weight) determination methods (e.g., as referenced in Paragraphs [0044] – [0045] of the just-noted publication), noting that for the equation in such Paragraph [0044], a = 0.695 and K = 0.000579(1-0.75Wt) are used, where Wt is the weight fraction for hexane comonomer, and further noting that comonomer composition is determined by the ratio of the IR5 detector intensity corresponding to CH₂ and CH₃ channel calibrated with a series of PE and PP homo/copolymer standards whose nominal values are predetermined by NMR or FTIR (providing methyls per 1000 total carbons (CH₃/1000 TC)) as noted in Paragraph [0045] of the just-noted International Publication). [0091] The TREF technique was performed as described in Wild, et al., J. Poly. Sci., Poly. Phys. Ed., Vol. 20, pg. 441 (1982) and U.S. Pat. No. 5,008,204. which is incorporated by reference herein. 2022EM127 [0092] SDBI measures the breadth of a solubility distribution curve for a given polymer. The procedure used herein for calculating SDBI is described in International Publication No. WO 93/03093 (pages 16 to 18), which is incorporated by reference herein. [0093] The long chain branching indices (g’) was measured using GPC-4D. A typical GPC- 4D profile has Log M vs. g’ and is used to estimate a g’average, based on the average across the molecular weight. The branching index g’ avg values range from 1 to 0 with 1 being linear (no branching) and 0 being fully branched. The g’avg does not clearly differentiate branching changes at low levels (0.85 to 1), so g’(Mz) and g’(Mz+1) were estimated at higher molecular weight moments (Mz, Mz+1). The branching index g’(Mz) is the g’ from GPC-4D profiles estimated at the z-average (third moment) molecular weight average. This calculation is performed by curve fitting the g’ vs molecular weight data to a nth order polynomial using the MATLAB program. The value of n is typically between 3 and 4. The Mz value obtained from GPC-IR measurements are inserted into the curve fit to calculate the g’ associated with that molecular weight. ¹³C NMR for C2% and r1r2 [0094] Samples were dissolved in deuterated 1,1,2,2-tetrachloroethane-d2 (tce-d2) at a concentration of 67mg/mL at 140°C. Spectra were recorded at 120°C using a Bruker NMR spectrometer of at least 600MHz with a 10mm cryoprobe. A 90° pulse, 10s delay, 512 transients, and gated decoupling were used for measuring the 13C NMR. Polymer resonance peaks are referenced to Polyethylene main peak at 29.98 ppm. [0095] Chemical shift assignments for the ethylene-octene copolymers are described by Randall in “A Review Of High Resolution Liquid Carbon Nuclear Magnetic Resonance Characterization of Ethylene-Based Polymers”, Polymer Reviews, 29:2,201-5317 (1989). The copolymer content, mole and weight %, triad sequencing, and diad calculations are also calculated and described in the method established by Randall in this paper. Calculations for reactivity ratio (r1r2) were based on the equation r1r2=4*[EE]*[OO]/[EO]²; where [EE], [EO], [OO] are the diad molar concentrations; E is ethylene, O is octene. [0096] The reactivity ratio of product r1r2 is described more fully in Textbook of Polymer Chemistry, F. W. Billmeyer, Jr., Interscience Publishers, New York, p.221 et seq. (1957). The reactivity ratio product r₁r₂, where r_l is the reactivity of ethylene and r₂ is the reactivity of propylene, can be calculated from the measured diad distribution (OO, EE, EO and OE in this nomenclature) by the application of the following formulae: r ₁ r ₂=4(EE)(OO)/(EO)² 2022EM127 r ₁ =K ₁₁ /K ₁₂=[2(EE)/EO]X r ₂ =K ₂₂ /K ₂₁=[2(PP)/(EO)]X O=(OO)+(EO/2) E=(EE)+(EO/2) where Mol % E=[(E)/(E+O)]*100 and X=E/O in reactor; K₁₁ and K₁₂ are kinetic insertion constants for ethylene; and K₂₁ and K₂₂ are kinetic insertion constants for propylene. [0097] As is known to those skilled in the art, a reactivity ratio product r1r2 of zero (0) can define an “alternating” copolymer, and a reactivity ratio product of one (1) is said to define a “statistically random” copolymer. In other words, a copolymer having a reactivity ratio product r1r2 of between 0.6 and 1.5 is generally said to be random (in strict theoretical terms, generally only a copolymer having a reactivity ratio product r1r2 greater than 1.5 contains relatively long homopolymer sequences and is said to be “blocky”). [0098] ¹H NMR data was collected at 120°C using a 10 mm CryoProbe with a Bruker Spectrometer at a ¹H frequency of at least 600 MHz. Data were recorded using a maximum pulse width of 45°, 5 seconds between pulses and signal averaging 512 transients. Samples were prepared by dissolving 80-100 mg of sample in 3 mL of solvent heated at 140°C. For purposes of this invention and the claims thereto, unsaturations in a polymer are determined by ¹H NMR with reference to Macromolecules, 2014, 47, 3782 and Macromolecules, 2005, 38, 6988, but in event of conflict Macromolecules, 2014, 47, 3782, shall control. Peak assignments are determined referencing the solvent of 1,1,2,2-tetrachloroethane-d2 at 5.98 ppm. US 2018162973A1 provides additional details, which are incorporated by reference herein. [0099] Volume resistivity (VR) was tested according to an ExxonMobil method, which is based on ASTM D257. The measurement is done with a Keithley 6517B electrometer and keithley 8009 test fixture. The leakage current is directly tested with the instrument and volume resistivity is calculated with following equation, ^_{^^^ =} ^{^^^^ ^^^^} ^^^^ ^^^^ where ρ is volume resistivity (Ω.cm), V is the applied voltage (volts), A is electrode contact area (cm2), I is the leakage current (amps) and t is the average thickness of the samples. The volume resistivity test was conducted at 500 Volts at room temperature, three compression molded films are tested to get the average. [00100] Differential scanning calorimetry (DSC) was conducted using a Perkin Elmer instrument using 5 mg to 10 mg samples with two melting cycles and one cooling cycle 2022EM127 between -80 C to 200 C at the rate of 10 C/min. The melt temperature (Tm ) and crystallization temperature (Tc) are reported in °C. [00101] Small angle Oscillatory Shear (SAOS) measurements were conducted at 190°C between 0.01 s-1 to 500 s-1 shear rates. The van Gurp-Palmen plot was constructed by plotting phase angle (δ) as a function of constant modulus (G*). The phase angles at a complex modulus of 10000 Pa and 50000 Pa are reported. [00102] For estimation of water vapor transmission rate (WVTR, g/m²-day) on compression molded films, an internal method was used. PermatranW-700 manufactured by MOCON was utilized for the measurements. The test was conducted at 37.8°C, 760 mm Hg barometric pressure and 100% relative humidity. The WVTR values reported in gm/m²-day are converted into permeance in metric perms (gm.mil/m²-day). [00103] The ethylene copolymers provided herein are particularly suitable for use in making solar cells (also known as photovoltaic cells), photovoltaic (PV) modules and other low-current electronic devices or modules such as liquid crystal panels, electro-luminescent devices and plasma display units. A solar cell module typically has one or more cells made from silicon, gallium-arsenic and copper-iridium-selenium with a top transparent protective material and a bottom protective substrate material, with the solar cell and the protective materials fixed by use of an encapsulating material. The ethylene copolymers provided herein can be used as the top protective material, the bottom protective material or both. The ethylene copolymers can provide a film having excellent flexibility, transparency and heat resistance, making the film particularly suitable for use in PV modules. [00104] The ethylene copolymers can also be used for packaging. Such modules noted above often utilize an electronic device in combination with one or more substrates that provide protection and or support for their manufacture, transportation, and use. For example, these types of devices are frequently positioned behind one or more glass cover sheets and/or between two substrates in which one or both of the substrates are made of glass, metal, plastic, rubber or other material. In these cases, the ethylene copolymer can be used as an encapsulant or sealant for the device within the module or, depending upon the design of the module, directly as a covering or skin layer of the module, e.g., a backskin in a solar cell module. Listing of Embodiments [00105] This disclosure may further include any one or more of the following non-limiting embodiments: 2022EM127 [00106] Embodiment 1. An ethylene copolymer, comprising at least 50 wt% ethylene derived units; and at least 20 wt% of at least one C3 to C20 comonomer, wherein the copolymer has a melt index of 0.5 g/10 min to about 50 g/10 min, as measured according to ASTM D1238 (190°C/2.16 kg); a density of about 0.860 g/cc to 0.880 g/cc, as measured according to ASTM D792; a first long chain branching index (g’(Mz)) of 0.80 to 0.93; a second long chain branching index (g’(Mz+1)) of 0.80 to 0.93; less than 0.7 vinyl/total unsaturation; an unsaturation level of trisubstituted olefins of 50 to 500; and a volume resistivity at 23°C of 4*1015 Ωcm or more. [00107] Embodiment 2. The ethylene copolymer of embodiment 1, further comprising a g’Mz+1/g’-avg ratio of 0.9 to 1.0. [00108] Embodiment 3. The ethylene copolymer of embodiments 1 or 2, wherein the copolymer has less than 0.6 vinyl/total unsaturation. [00109] Embodiment 4. The ethylene copolymer of any embodiment 1 to 3, wherein the unsaturation level of trisubstituted olefins is 60 to 450. [00110] Embodiment 5. The ethylene copolymer of any embodiment 1 to 4, further comprising two or more TREF elution temperature peaks. [00111] Embodiment 6. The ethylene copolymer of any embodiment 1 to 5, further comprising a first peak elution temperature of less than 30°C and a second peak elution temperature of greater than 40°C. [00112] Embodiment 7. The ethylene copolymer of any embodiment 1 to 6, further comprising a r1r2 reactivity ratio less than or equal to 0.8. [00113] Embodiment 8. The ethylene copolymer of any embodiment 1 to 7, further comprising a r1r2 reactivity ratio of 0.2 to 0.8. [00114] Embodiment 9. The ethylene copolymer of any embodiment 1 to 8, further comprising less than 10 wt% of diene derived units. [00115] Embodiment 10. The ethylene copolymer of any embodiment 1 to 9, wherein the at least one C3 to C20 comonomer is butene or octene or a combination thereof. [00116] Embodiment 11. An electronic device module comprising at least one electronic device, and an ethylene copolymer film in direct contact with at least one surface of the electronic device, the ethylene copolymer comprising at least 50 wt% ethylene derived units; and at least 20 wt% of at least one C3 to C20 comonomer, wherein the copolymer has a melt index of 0.5 g/10 min to about 50 g/10 min, as measured according to ASTM D1238 (190°C/2.16 kg); a density of about 0.860 g/cc to 0.880 g/cc, as measured according to ASTM 2022EM127 D792; a first long chain branching index (g’(Mz)) of 0.80 to 0.93; a second long chain branching index (g’(Mz+1)) of 0.80 to 0.93; less than 0.7 vinyl/total unsaturation; an unsaturation level of trisubstituted olefins of 50 to 500; and a volume resistivity at 23°C of 4*1015 Ωcm or more. [00117] Embodiment 12. The electronic device module of embodiment 11, wherein the copolymer further comprises a g’Mz+1/g’-avg ratio of 0.9 to 1.0. [00118] Embodiment 13. The electronic device module of embodiment 11 or 12, wherein the copolymer further comprises a first peak elution temperature of less than 30oC and a second peak elution temperature of greater than 40oC. [00119] Embodiment 14. The electronic device module of any embodiment 11 to 13, wherein the copolymer further comprises a r1r2 reactivity ratio of 0.2 to 0.8. [00120] Embodiment 15. The electronic device module of any embodiments 11 to 14, wherein the copolymer further comprises less than 10 wt% of diene derived units and the at least one C3 to C20 comonomer is butene or octene or a combination thereof. [00121] Embodiment 16. A method for making an electronic device module comprising providing at least one electronic device, and laminating an ethylene copolymer film onto at least one surface of the electronic device, the ethylene copolymer comprising at least 50 wt% ethylene derived units; and at least 20 wt% of at least one C3 to C20 comonomer, wherein the copolymer has a melt index of 0.5 g/10 min to about 50 g/10 min, as measured according to ASTM D1238 (190°C/2.16 kg); a density of about 0.860 g/cc to 0.880 g/cc, as measured according to ASTM D792; a first long chain branching index (g’(Mz)) of 0.80 to 0.93; a second long chain branching index (g’(Mz+1)) of 0.80 to 0.93; less than 0.7 vinyl/total unsaturation; an unsaturation level of trisubstituted olefins of 50 to 500; and a volume resistivity at 23°C of 4*1015 Ωcm or more. [00122] Embodiment 17. The method of embodiment 16, wherein the copolymer further comprises a g’Mz+1/g’-avg ratio of 0.9 to 1.0. [00123] Embodiment 18. The method of embodiment 16 or 17, wherein the copolymer further comprises a first peak elution temperature of less than 30oC and a second peak elution temperature of greater than 40oC. [00124] Embodiment 19. The method of any embodiment 16 to 18, wherein the copolymer further comprises a r1r2 reactivity ratio of 0.2 to 0.8. 2022EM127 [00125] Embodiment 20. The method of any embodiment 16 to 19, wherein the copolymer further comprises less than 10 wt% of diene derived units and the at least one C3 to C20 comonomer is butene or octene or a combination thereof. [00126] Certain embodiments and features have been described using a set of numerical upper limits and a set of numerical lower limits. It should be appreciated that ranges including the combination of any two values, e.g., the combination of any lower value with any upper value, the combination of any two lower values, and/or the combination of any two upper values are contemplated unless otherwise indicated. Certain lower limits, upper limits and ranges appear in one or more claims below. All numerical values are "about" or "approximately" the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary skill in the art. [00127] Various terms have been defined above. To the extent a term used in a claim is not defined above, it should be given the broadest definition persons in the pertinent art have given that term as reflected in at least one printed publication or issued patent. Furthermore, all patents, test procedures, and other documents cited in this application are fully incorporated by reference to the extent such disclosure is not inconsistent with this application and for all jurisdictions in which such incorporation is permitted. [00128] While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

Claims

2022EM127 CLAIMS What is claimed is: 1. An ethylene copolymer, comprising: at least 50 wt% ethylene derived units; and at least 20 wt% of at least one C3 to C20 comonomer, wherein the copolymer has: a melt index of 0.5 g/10 min to about 50 g/10 min, as measured according to ASTM D1238 (190°C/2.16 kg); a density of about 0.860 g/cc to 0.880 g/cc, as measured according to ASTM D792; a first long chain branching index (g’(Mz)) of 0.80 to 0.93; a second long chain branching index (g’(Mz+1)) of 0.80 to 0.93; less than 0.7 vinyl/total unsaturation; an unsaturation level of trisubstituted olefins of 50 to 500; and a volume resistivity at 23°C of 4*10¹⁵ Ωcm or more. 2. The ethylene copolymer of claim 1, further comprising a g’Mz+1/g’-avg ratio of 0.9 to 1.0. 3. The ethylene copolymer of claim 1, wherein the copolymer has less than 0.6 vinyl/total unsaturation. 4. The ethylene copolymer of claim 1, wherein the unsaturation level of trisubstituted olefins is 60 to 450. 5. The ethylene copolymer of claim 1, further comprising two or more TREF elution temperature peaks. 6. The ethylene copolymer of claim 1, further comprising a first peak elution temperature of less than 30^oC and a second peak elution temperature of greater than 40^oC. 7. The ethylene copolymer of claim 1, further comprising a r1r2 reactivity ratio ≤ 0.8. 2022EM127 8. The ethylene copolymer of claim 1, further comprising a r1r2 reactivity ratio of 0.2 to 0.8. 9. The ethylene copolymer of claim 1, further comprising less than 10 wt% of diene derived units. 10. The ethylene copolymer of claim 1, wherein the at least one C3 to C20 comonomer is butene or octene or a combination thereof. 11. An electronic device module comprising: at least one electronic device, and an ethylene copolymer film in direct contact with at least one surface of the electronic device, the ethylene copolymer comprising: at least 50 wt% ethylene derived units; and at least 20 wt% of at least one C3 to C20 comonomer, wherein the copolymer has: a melt index of 0.5 g/10 min to about 50 g/10 min, as measured according to ASTM D1238 (190°C/2.16 kg); a density of about 0.860 g/cc to 0.880 g/cc, as measured according to ASTM D792; a first long chain branching index (g’(Mz)) of 0.80 to 0.93; a second long chain branching index (g’(Mz+1)) of 0.80 to 0.93; less than 0.7 vinyl/total unsaturation; an unsaturation level of trisubstituted olefins of 50 to 500; and a volume resistivity at 23°C of 4*10¹⁵ Ωcm or more. 12. The electronic device module of claim 11, wherein the copolymer further comprises a g’Mz+1/g’-avg ratio of 0.9 to 1.0. 13. The electronic device module of claim 12, wherein the copolymer further comprises a first peak elution temperature of less than 30^oC and a second peak elution temperature of greater than 40^oC. 2022EM127 14. The electronic device module of claim 13, wherein the copolymer further comprises a r1r2 reactivity ratio of 0.2 to 0.8. 15. The electronic device module of claim 14, wherein the copolymer further comprises less than 10 wt% of diene derived units and the at least one C3 to C20 comonomer is butene or octene or a combination thereof. 16. A method for making an electronic device module comprising: providing at least one electronic device, and laminating an ethylene copolymer film onto at least one surface of the electronic device, the ethylene copolymer comprising: at least 50 wt% ethylene derived units; and at least 20 wt% of at least one C3 to C20 comonomer, wherein the copolymer has: a melt index of 0.5 g/10 min to about 50 g/10 min, as measured according to ASTM D1238 (190°C/2.16 kg); a density of about 0.860 g/cc to 0.880 g/cc, as measured according to ASTM D792; a first long chain branching index (g’(Mz)) of 0.80 to 0.93; a second long chain branching index (g’(Mz+1)) of 0.80 to 0.93; less than 0.7 vinyl/total unsaturation; an unsaturation level of trisubstituted olefins of 50 to 500; and a volume resistivity at 23°C of 4*10¹⁵ Ωcm or more. 17. The method of claim 16, wherein the copolymer further comprises a g’Mz+1/g’-avg ratio of 0.9 to 1.0. 18. The method of claim 17, wherein the copolymer further comprises a first peak elution temperature of less than 30^oC and a second peak elution temperature of greater than 40^oC. 19. The method of claim 18, wherein the copolymer further comprises a r1r2 reactivity ratio of 0.2 to 0.8. 2022EM127 20. The method of claim 19, wherein the copolymer further comprises less than 10 wt% of diene derived units and the at least one C3 to C20 comonomer is butene or octene or a combination thereof.