Ethylene copolymer for photovoltaics

Abstract

Ethylene copolymer, electronic device module, and method for manufacturing the same. The ethylene copolymer is at least 50 weight% of ethylene-derived units and at least 20 weight% of at least one C3 to C20 comonomer. The copolymer also has a melt index of 0.5 g / 10 min to about 50 g / 10 min when measured according to ASTM D1238 (190°C / 2.16 kg); a density of about 0.856 g / cc to 0.890 g / cc when measured according to ASTM D792; a volume resistivity at 23°C of at least 5 x 10¹⁵ Ωcm; and 0.01 to 4.0 weight ppm of aluminum.

Description

Technology Field

[0001] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 612,454, filed on December 20, 2023, with the title of invention “ETHYLENE COPOLYMERS FOR PHOTOVOLTAIC CELLS,” the entirety of which is incorporated herein by reference.

[0002] Embodiments of the present invention generally relate to ethylene copolymers and electronic device modules implementing such copolymers. More specifically, embodiments provided herein relate to ethylene copolymers suitable for manufacturing photovoltaic applications. Background Technology

[0003] Polyolefin plastomers, which are copolymers of ethylene and butene or octene, are increasingly being used as polymer encapsulants in photovoltaic (PV) applications. These polymers are replacing ethylene vinyl acetate (EVA) copolymers, and studies have shown that plastomer-based encapsulants increase power generation over a 30-year service life compared to EVA. Plastomer films used as encapsulants have a higher barrier to potential-induced degradation (PID) and lower power degradation compared to EVA films, both of which contribute to lowering power loss. The formation of acetic acid in EVA resins due to service use and discoloration caused by yellowing lead to increased power loss in EVA film-based encapsulants.

[0004] Polymer film encapsulants for PV cell applications must satisfy various functional properties. Electrical properties, expressed as high volume resistivity, are useful for reducing power loss. Excellent optical properties, often measured by high light transmittance at wavelengths of 280 to 1100 nm; enhanced moisture barrier properties, expressed as low water vapor transmission rate (WVTR); high crosslinking density, which provides creep resistance; and excellent mechanical properties, expressed as tensile strength, flexural modulus, and tear strength, are considered important. The problem to be solved is how to obtain all these functional properties from a single polyolefin polymer.

[0005] There are several patents disclosing the use of plastomous resins as encapsulants in PV cells. For example, US 9,349,895B2 and the corresponding CN 103189996B describe an ethylene alpha-olefin copolymer suitable as a PV cell encapsulant having a density in the range of 0.865 to 0.884 g / cc, an MI (190°C) in the range of 2 to 10, and a Shore A hardness in the range of 60 to 85. US 8581094B2 and the corresponding CN101563786B describe a PV cell device using a polyolefin copolymer encapsulant having a density of less than 0.9 g / cc, a melting point of less than 95°C, an alpha-olefin content in the range of 15 to 50 weight%, an SCBDI of at least 50, and optionally a free radical initiator and a co-agent. KR 101191126B1 describes an encapsulant sheet for a photovoltaic cell, wherein 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 terpolymer used as an encapsulant material, wherein 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 having vinyl groups in the range of 0.06 to 1 per 1,000 C atoms, a density in the range of 0.850 to 0.910 g / cc, an MIR (I10 / I2.16) < 7.7, an MI in the range of 0.1 to 25 dg / min, and an ethylene content in the range of 80 to 95 mol%. US 10,774,205 B2 describes a polymer having a multimode compositional distribution having distinct crystallization peaks in TREF in the range of 40°C to 110°C.

[0007] However, there is still a need for novel ethylene-based copolymers capable of producing films having 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 may be particularly suitable for addressing the requirements of PV cell applications.

[0008] An ethylene copolymer, an electronic device module, and a method for manufacturing the same are provided herein. The ethylene copolymer comprises at least 50 weight percent of ethylene-derived units and at least 20 weight percent 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 when measured according to ASTM D1238 (190°C / 2.16 kg), and a density of about 0.856 g / cc to 0.890 g / cc when measured according to ASTM D792; at least 5 x 10 15 It has a volume resistivity of Ωcm at 23°C; and aluminum of 0.01 to 4.0 weight ppm. In certain embodiments, 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 vinyl / total unsaturation of less than 0.7. In certain embodiments, the unsaturation level of the trisubstituted olefin is 50 to 500. Such ethylene copolymers can be prepared using metallocene and post-metallocene catalysts in a solution polymerization process as further provided herein.

[0009] In at least one embodiment, the electronic device module comprises 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 comprises at least 50 weight percent of ethylene-derived units; and at least 20 weight percent 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 when measured according to ASTM D1238 (190°C / 2.16 kg); a density of about 0.856 g / cc to 0.890 g / cc when measured according to ASTM D792; and at least 5 x 10 15 It has a volume resistivity of Ωcm at 23°C; and aluminum of 0.01 to 4.0 weight ppm.

[0010] In at least one embodiment, a method for manufacturing an electronic device module comprises the steps of providing at least one electronic device and laminating an ethylene copolymer film on at least one surface of the electronic device. The ethylene copolymer comprises at least 50 weight% of ethylene-derived units; and at least 20 weight% 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 when measured according to ASTM D1238 (190°C / 2.16 kg); a density of about 0.856 g / cc to 0.890 g / cc when measured according to ASTM D792; and at least 5 x 10 15 It has a volume resistivity of Ωcm at 23°C; and aluminum of 0.01 to 4.0 weight ppm.

[0011] In at least one other embodiment, the method comprises the steps of polymerizing an ethylene-derived unit and at least one C3 to C20 comonomer in the presence of a catalyst system, and obtaining an ethylene-based copolymer polyolefin comprising at least 50 weight% of an ethylene-derived unit; and at least 20 weight% 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 when measured according to ASTM D1238 (190°C / 2.16 kg); a density of about 0.857 g / cc to 0.890 g / cc when measured according to ASTM D792; and at least 5 x 10 15 It has a volume resistivity of Ωcm at 23°C; and aluminum of 0.01 to 4.0 weight ppm.

[0012] Surprisingly, these ethylene-based copolymers have significantly improved processability, low aluminum residue, and high volume resistivity (>5x10 15 It was found that films with excellent optical properties, moisture resistance, and creep resistance at wavelengths of 200 to 900 nm (Ohm*cm) can be manufactured, making these copolymers particularly suitable for electronic device modules, such as PV cell applications. Furthermore, surprisingly, these ethylene-based copolymers were found to have aluminum residues of less than 4 ppm, less than 2 ppm, or less than 0.1 ppm, or were absent, making these ethylene-based copolymers particularly suitable for use in PV cells and / or modules. Brief explanation of the drawing

[0013] In order to enable a detailed understanding of the foregoing features of the present invention, a more specific description of the present invention, as briefly summarized above, may be made by referring to embodiments, some of which are illustrated in the accompanying drawings. However, it should be noted that the accompanying drawings illustrate only typical embodiments of the present invention and should not be construed as limiting the scope, and that the present invention may allow for other equally effective embodiments. The drawing shows the volume resistivity of a molded plaque (1 mm thick film, 500 V, 5 min charging time) plotted against aluminum residue (ppmw) of resins 1 to 4 according to one or more embodiments provided herein. Specific details for implementing the invention

[0014] An ethylene copolymer is provided that can be used to produce films having excellent optical properties at wavelengths of 280 to 1,100 nm, including moisture resistance, creep resistance, tensile strength, and tear strength. The ethylene copolymer has branching indices g'(Mz) and g'(Mz+1) measured from GPC-4D coupled with trisubstituted olefins, and a reactivity ratio (r1r2) determined using NMR, which are significantly different from other ethylene copolymers of similar density. Surprisingly, the ethylene copolymer provided herein has significantly improved processability and a volume resistivity (>10 15 It was found that the (Ohm*cm) value was high. Furthermore, surprisingly, these ethylene-based copolymers were found to have less than 4 ppm, less than 2 ppm, or less than 0.1 ppm, or no aluminum residue, making these ethylene-based copolymers particularly suitable for electronic device modules, such as PV cell applications.

[0015] Although not bound by theory, it has been found that these ethylene-based copolymers, surprisingly free of little to no aluminum residue, can be prepared using a large, highly branched activator that is soluble in aliphatic solvent(s). Preferably, the preferred activator has a formula weight greater than 1310 g / mol, greater than 1350 g / mol, greater than 1380 g / mol, greater than 1400 g / mol, greater than 1450 g / mol, greater than 1500 g / mol, greater than 1550 g / mol, greater than 1600 g / mol, or greater than 1650 g / mol. In certain embodiments, the formula weight of the activator may range from a lower limit of about 1310, 1250, or 1400 g / mol to an upper limit of about 1600, 1700, or 1950 g / mol.

[0016] It should be understood that the disclosures provided herein provide various exemplary embodiments for implementing various features, structures, and / or functions of the present invention. Exemplary embodiments of components, arrangements, and configurations are described to simplify the disclosures, but such exemplary embodiments are provided merely as examples and are not intended to limit the scope of the invention. Additionally, the disclosures may repeat reference numbers and / or letters in the various exemplary embodiments provided herein and throughout the drawings. Such repetition is for simplicity and clarity and does not, in itself, indicate a relationship between the various exemplary embodiments and / or configurations discussed in the drawings. Furthermore, the exemplary embodiments presented herein may be combined in any combination of ways; that is, any element of one exemplary embodiment may be used in any other exemplary embodiment without departing from the scope of the disclosures.

[0017] Additionally, specific terms are used throughout the following description and claims to refer to specific components. As recognized by those skilled in the art, various entities may refer to the same component by various names; as such, the naming conventions for the elements described herein are not intended to limit the scope of the invention unless specifically defined herein. Furthermore, the naming conventions used herein are not intended to distinguish components that differ in name but do not differ in function.

[0018] In the following discussion and claims, the terms “including” and “comprising” are open in nature and should therefore be interpreted as meaning “including without limitation.” The phrase “essentially made” means that the described / claimed composition does not include any other component that could substantially alter the characteristic by more than 5% and in no case includes any other component at a level of more than 3% by mass.

[0019] The term "or" is intended to include both exclusive and inclusive cases; that is, "A or B" is intended to be synonymous with "at least one of A and B" unless explicitly stated otherwise herein.

[0020] The singular form refers to both the singular (i.e., "one") and the plural referent (i.e., one or more) unless the context clearly specifies otherwise. For example, an embodiment using "olefin" includes an embodiment using one, two, or more olefins, unless otherwise stated or the context clearly indicates that only one olefin is used.

[0021] The term "weight%" means a percentage based on weight, "volume%" means a percentage based on volume, "molar%" means a percentage based on moles, "ppm" means parts per million, and "ppm wt" and "wppm" are used interchangeably to mean parts per million based on weight. Unless otherwise specified, all concentrations in this invention are expressed based on the total amount of the composition discussed.

[0022] The term "polymer" refers to any two or more identical or different repeating units / mer units or units. The term "homopolymer" refers to a polymer having identical units. The term "copolymer" refers to a polymer having two or more different units, including terpolymers, etc. "Terpolymer" refers to a polymer having three different units. When referring to units, the term "different" indicates that the units are different from each other or isomerically different by at least one atom. Likewise, the definition of polymer used herein includes homopolymers, copolymers, etc. For example, when a copolymer is described as having a "propylene" content of 10% to 30% by weight, it is understood that the repeating units / mer units or simply units of the copolymer are derived from propylene in the polymerization reaction, and that the derived units are present in an amount of 10% to 30% by weight based on the weight of the copolymer.

[0023] As used herein, "Mn" refers to the number-average molecular weight of various polymers within a polymer material, "Mw" refers to the weight-average molecular weight of various polymers within a polymer material, and "Mz" refers to the z-average molecular weight of various polymers within a polymer material. The terms "Molecular Weight Distribution (MWD)" and "Polydispersion 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 expressed in units of g / mol.

[0024] The nomenclature of the elements and their groups used in this document follows the periodic table used by the International Union of Pure and Applied Chemistry since 1988. An example of the periodic table is shown on the inside front cover of the literature [Advanced Inorganic Chemistry, 6th Edition, by F. Albert Cotton et al. (John Wiley & Sons, Inc., 1999)].

[0025] The ethylene copolymer contains ethylene and at least one other C3-C20 comonomer. Preferred ethylene copolymers are ethylene-butene and ethylene-octene plastomers. The ethylene content of the low ethylene content fraction may range from a minimum of 55 weight% to a maximum of 76 weight%. The ethylene content of the high ethylene content fraction may range from a minimum of 60 weight% to a maximum of 90 weight%. The ethylene content of the total polymer may range from a minimum of 60 weight% to a maximum of 85 weight%.

[0026] The ethylene copolymer may have a melt index of 0.5 g / 10 min to about 50 g / 10 min when measured according to ASTM D1238 (190°C / 2.16 kg). The melt index may also range from a minimum of about 0.5, 1.0, or 2.0 to a maximum of about 30, 40, or 50 g / 10 min. The melt index may also range from a minimum of about 0.5, 3.0, or 5.0 to a maximum of about 20, 35, or 45 g / 10 min.

[0027] Ethylene copolymers may have a density of 0.850 g / cc to 0.920 g / cc when measured according to ASTM D792, which indicates that they can act as a plastomer with combined elastomer and polymer characteristics. Ethylene copolymers may also have a density of about 0.860 g / cc to 0.880 g / cc. The density may range from a minimum of about 0.850, 0.855, 0.860, 0.865, or 0.870 to a maximum of about 0.874, 0.876, 0.880, 0.900, or 0.920 g / cc.

[0028] Ethylene copolymer is 5*10 15 It can have a volume resistivity of Ωcm or higher at 23℃.

[0029] The ethylene copolymer may have a ratio of g'Mz+1 to g'-avg of 0.9 to 1.0. This ratio may range from a minimum of 0.91, 0.92, or 0.93 to a maximum of 0.97, 0.98, or 0.99.

[0030] Ethylene copolymers may have vinyl / total unsaturation of less than 0.7 when estimated by H-NMR. Vinyl / total unsaturation may range from a minimum of about 0.01, 0.02, or 0.03 to a maximum of about 0.5, 0.6, or 0.7. Vinyl / total unsaturation may also range from a minimum of about 0.1, 0.2, or 0.3 to a maximum of about 0.5, 0.6, or 0.7.

[0031] The ethylene copolymer may have an unsaturated level of trisubstituted olefins of 50 to 500 when determined by H-NMR. The unsaturated level of trisubstituted olefins may range from about 50, 80, or 100 to a maximum of about 300, 400, or 500. The unsaturated level of trisubstituted olefins may range from about 60 to 480; 80 to 420; or 100 to 300.

[0032] The ethylene copolymer may have a reactivity ratio of 0.8 or less. The reactivity ratio may be in the range of 0.2 to 0.8. The reactivity ratio may be in the range of at least 0.2, 0.3, or 0.35 to at most 0.5, 0.65, or 0.8. The reactivity ratio may be 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, or 0.8.

[0033] Polymerization process

[0034] Ethylene copolymers can be manufactured using a solution polymerization process. Preferably, the solution polymerization process is a bulk polymerization process, which refers to a polymerization process in which monomers and / or comonomers to be polymerized are used as a solvent or diluent without using little or no inert solvent as a liquid or diluent. A small amount of inert solvent may be used as a scavenger and a support for the catalyst.

[0035] The term "solution polymerization" refers to a polymerization process in which a polymer is dissolved in a liquid polymerization medium, such as an inert solvent, monomer(s), or a blend thereof. Solution polymerization is typically homogeneous, which refers to a polymerization process in which the polymer product is dissolved in the polymerization medium. Such a system is preferably not turbid, as described in the literature [J. Vladimir Oliveira, C. Dariva, and JC Pinto, Ind. Eng. Chem. Res., 29, 2000, 4627]. A homogeneous polymerization process is typically a process in which at least 90 weight percent of the product is soluble in the reaction medium.

[0036] Suitable solution polymerization processes for preparing the polymer blend compositions disclosed herein are generally described in more detail in U.S. Patents No. 9,359,535, 7,470,118, 7,226,553; and 7,033,152, the entirety of which is incorporated herein by reference. WO 2017 / 058385A1 also describes a solution polymerization process using a single or multiple helical heat exchanger system for the continuous polymerization of C2 to C40 olefins that may be used, the entirety of which is incorporated herein by reference.

[0037] The ethylene copolymer may exhibit a low level of long chain branching (LCB). In particular, the ethylene copolymer may have a first long chain branching index (g'(Mz)) in the range of 0.30 to 1.00, preferably 0.70 to 0.97. The first long chain branching index (g'(Mz)) may be in the range of 0.80 to 0.93. The first long chain branching index (g'(Mz)) may be in the range of at least 0.80, 0.82, or 0.85 to at most 0.90, 0.92, or 0.93. The first long chain branch index (g'(Mz)) may 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.

[0038] The ethylene copolymer may have a second long-chain branching index (g'(Mz+1)) of 0.30 to 1.00, preferably 0.70 to 0.97. The second long-chain branching index (g'(Mz+1)) may be in the range of 0.80 to 0.93. The second long-chain branching index (g'(Mz+1)) may be in the range of at least 0.80, 0.82, or 0.85 to at most 0.90, 0.92, or 0.93. The second long chain branch index (g'(Mz+1)) may 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.

[0039] The ethylene copolymer provided herein can be used in various end-use applications. The ethylene copolymer provided herein is particularly suitable for use in the manufacture of photovoltaic cells (also known as photovoltaic cells), photovoltaic (PV) modules, and other low-current electronic devices or modules, such as liquid crystal panels, electroluminescent devices, and plasma display units. A photovoltaic cell module typically has one or more cells made of silicon, gallium-arsenide, and copper-iridium-selenium, a transparent protective material on top, and a protective substrate material on the bottom, and the photovoltaic cell and the protective material are secured using an encapsulation material. The ethylene copolymer provided herein can be used as an upper protective material, a lower protective material, or both. The ethylene copolymer can provide a film with excellent flexibility, transparency, and heat resistance, making the film particularly suitable for use in PV modules.

[0040] These PV modules generally utilize electronic devices combined with one or more substrates that provide protection and / or support for manufacturing, transportation, and use. For example, this type of device is often placed behind one or more glass cover sheets and / or between two substrates, where one or both of the substrates are made of glass, metal, plastic, rubber, or other materials. In such cases, ethylene copolymer may be used as an encapsulant or sealant for the devices inside the module, or, depending on the design of the module, directly as a cover or surface layer of the module, for example, as the back of the photovoltaic module.

[0041] Ethylene copolymers may have a unique combination of any two or more of the following characteristics:

[0042] a. Volume resistivity at 23℃ > 5*10 15 Ωcm;

[0043] b. If g'Mz+1(branch) < 0.93, g'Mz+1 / g'-avg < 1;

[0044] c. When g'Mz(branch) < 0.93 and g'Mz+1(branch) < 0.93, a significantly high trisubstituted olefin content;

[0045] d. For g'Mz < 0.94, vinyl / total unsaturation < 0.2;

[0046] e. In all cases where g'Mz < 0.94, reactivity ratio ≤ 0.7; and / or

[0047] f. r1r2 values ​​lower than comparison copolymers (most > 1 and maximum about 1.5)

[0048] Another unique aspect of the ethylene copolymer provided herein is aluminum residues attributable to the activators and scavengers used. Surprisingly, ethylene copolymers with the aforementioned combination of characteristics may have aluminum residues of less than 4 ppm, less than 2 ppm, less than 1 ppm, less than 0.5 ppm, less than 0.2 ppm, less than 0.1 ppm, less than 0.01 ppm, or may have no aluminum residues at all, which has been found to make these ethylene copolymers particularly suitable for use in PV cells and / or modules. These unique characteristics distinguish the ethylene copolymer from other comparative ethylene copolymers.

[0049] comonomer

[0050] At least one other comonomer may comprise any one or more C4 to C20 olefins. The C4 to C20 comonomer may be linear, branched, or cyclic. Suitable C4 to C20 cyclic olefins may be modified or unmodified, monocyclic or polycyclic, and may optionally comprise heteroatoms and / or one or more functional groups. The reactor C2 concentration may be in the range of 0.1 to 40.0 weight%, while the reactor comonomer concentration may be in the range of 0.1 to 40.0 weight%.

[0051] Specific examples of comonomers are butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornene, substituted derivatives thereof and isomers thereof, preferably hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornene, and each of the homologs and derivatives thereof, preferably norbornene. It includes norbornadiene and dicyclopentadiene.

[0052] Catalytic system

[0053] For the purposes of this disclosure, a “catalytic system” is a combination of at least one catalytic compound, an activator, and an optional support material. The catalytic system may further comprise one or more additional catalytic compounds. For the purposes of this disclosure, where a catalytic system is described as comprising a component in a neutral, stable form, those skilled in the art understand that the ionic form of the component is a form that reacts with a monomer to produce a polymer. The catalysts and activators of this disclosure are intended to include an ionic form in addition to the neutral form of the compound.

[0054] A catalyst system suitable for producing an ethylene copolymer provided herein may comprise one or more cross-linked metallocene compounds represented by the following formula: CpA(T)CpBM'X'n, wherein each CpA and CpB are independently selected from cyclopentadienyl ligands (e.g., Cp, Ind, or Flu) and ligands that are isoloval to cyclopentadienyl, wherein one or both of CpA and CpB may contain heteroatoms, and one or both of CpA and CpB may be substituted by one or more R'' groups; M' is selected from atoms of groups 3 to 12 and lanthanides, preferably group 4; X' is an anionic leaving group; and n is 0 or an integer from 1 to 4; (T) is divalent alkyl, substituted divalent alkyl, divalent heteroalkyl, divalent alkenyl, substituted divalent alkenyl, divalent heteroalkenyl, divalent alkynyl, substituted divalent alkynyl, divalent heteroalkynyl, divalent alkoxy, divalent aryloxy, divalent alkylthio, divalent arylthio, divalent aryl, substituted divalent aryl, divalent heteroaryl, divalent aralkyl, divalent aralkylene, divalent alkaryl, divalent alkaryllene, divalent haloalkyl, divalent haloalkenyl, divalent haloalkynyl, divalent heteroalkyl, divalent heterocycle, divalent heteroaryl, divalent heteroatom-containing group, divalent hydrocarbyl, substituted divalent hydrocarbyl, It is a crosslinking group selected from divalent heterohydrocarbyl, divalent silyl, divalent boryl, divalent phosphino, divalent phosphine, divalent amino, divalent amine, divalent ether, and divalent thioether.R'' is selected from alkyl, substituted alkyl, heteroalkyl, alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, aryloxy, alkylthio, arylthio, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene, alkalyl, alkalylene, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocycle, heteroaryl, heteroatom-containing group, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, silyl, boryl, phosphino, phosphine, amino, amine, germanium, ether, and thioether.

[0055] In at least one embodiment, CpA and CpB are each independently selected from cyclopentadienyl, indenyl, fluorenyl, cyclopentaphenantrenyl, benzindenyl, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, phenanthrindenyl, 3,4-benzofluorenyl, 9-phenylfluorenyl, 8-H-cyclopent[a]acenaphthylenyl, 7-H-dibenzofluorenyl, indeno[1,2-9]antrene, thiopenoindenyl, thiopenofluorenyl, hydrogenated and substituted versions thereof, preferably cyclopentadienyl, n-propylcyclopentadienyl, indenyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, and n-butylcyclopentadienyl. Each CpA and CpB may independently be indacenyl or tetrahydrodenyl. Particularly suitable cyclopentadienyl-based complexes are described in WO2000 / 024793, which is incorporated herein by reference.

[0056] Activator

[0057] Cross-linked metallocene compounds can be activated for polymerization catalytic activity in any manner sufficient to allow coordination or cationic polymerization. This can be achieved by coordination polymerization where one ligand can be extracted to replace an unstable ligand, e.g., an alkyl, silyl, or hydride, which allows the insertion of unsaturated monomers, and another ligand can be extracted to allow the insertion of unsaturated monomers or similarly. An activator suitable for use herein comprises an ammonium or phosphonium group having a long-chain aliphatic hydrocarbyl group to improve the solubility of the activator in aliphatic solvents compared to conventional activator compounds. An activator suitable for use herein may further provide a polyolefin having a weight-average molecular weight (Mw) of about 100,000 g / mol or more and a melting temperature (Tm) of about 110°C or more. In addition, an activator having a cation having at least one methyl group and optionally at least one C10 to C50 linear alkyl group can provide enhanced activity for polymer manufacturing.

[0058] The present disclosure provides an activator such as an ammonium or phosphonium metallate or metalloid activator compound comprising an ammonium or phosphonium group having a long-chain aliphatic hydrocarbyl group bonded to a metallate or metalloid anion such as a borate or aluminate. When the activator of the present disclosure is used in conjunction with a catalytic compound (e.g., a group 4 metallocene compound) in olefin polymerization, a polymer having a higher molecular weight and melting temperature than a polymer formed using a comparative activator can be formed. Similarly, when the activator of the present disclosure, where R1 is methyl, is used in conjunction with a group 4 metallocene catalyst in olefin polymerization, the catalytic system activity is substantially better than that of a comparative activator, and a polymer having a higher molecular weight and / or melting temperature compared to a polymer formed using a comparative activator can be formed.

[0059] The present invention relates to an active agent compound represented by the following formula (AI):

[0060]

[0061] In the above formula, E is nitrogen or phosphorus, preferably nitrogen;

[0062] d is 1, 2, or 3; k is 1, 2, or 3 (preferably 3); n is 1, 2, 3, 4, 5, or 6 (preferably 4, 5, or 6); n - k = d (preferably d is 1, 2, or 3; k is 3; n is 4, 5, or 6, and preferably, when M is B, n is 4);

[0063] R 1 is an optionally substituted C1-C 20 (or C1 to C 10 , or C1-C6, or C1-C4, or C1-C2, or C1) linear alkyl groups;

[0064] R 2 and R 3 Each is an independently and selectively substituted C1-C 40 Linear alkyl groups (e.g., C6 to C 40 Linear alkyl group, or C 10 to C 30 A linear alkyl group) or a meta- and / or para-substituted phenyl group, wherein the meta and para substituents are independently and optionally substituted C1 to C 40 Hydrocarbyl groups (e.g., C6 to C 40 Aryl group or linear alkyl group, C 12 to C 30 aryl group or linear alkyl group, or C 10 to C 20 aryl group or linear alkyl group), optionally substituted alkoxy group, optionally substituted silyl group, halogen (Br, Cl, I, F, etc.), or halogen-containing group (e.g., bromoalkyl or bromoaryl), and

[0065] Here, R1 , R 2 , and R 3 It comprises 15 or more carbon atoms together (e.g., 18 or more carbon atoms, e.g., 20 or more carbon atoms, e.g., 22 or more carbon atoms, e.g., 25 or more carbon atoms, e.g., 30 or more carbon atoms, e.g., 35 or more carbon atoms, e.g., 38 or more carbon atoms, e.g., 40 or more carbon atoms, e.g., 15 to 100 carbon atoms, e.g., 25 to 75 carbon atoms);

[0066] M is selected from Group 13 of the periodic table, preferably boron or aluminum;

[0067] Each Q is independently a hydride, cross-linked or non-cross-linked dialkylamido, halide, alkoxide, aryl oxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halosubstituted-hydrocarbyl radical, provided that if Q is a fluorophenyl group, R 2 is C1-C 40 It is not a linear alkyl group, preferably R 2 is an optionally substituted C1-C 40 It is not a linear alkyl group (alternatively, if Q is a substituted phenyl group, R 2 is C1-C 40 It is not a linear alkyl group, preferably R 2 is an optionally substituted C1-C 40 Not a linear alkyl group). Preferably, when Q is a fluorophenyl group (alternatively when Q is a substituted phenyl group), R 2 is a meta- and / or para-substituted phenyl group, where the meta and para substituents are independently and optionally substituted C1 to C 40 Hydrocarbyl groups (e.g., C6 to C 40 Aryl group or linear alkyl group, C 12 to C 30 aryl group or linear alkyl group, or C 10to C 20 It is an aryl group or a linear alkyl group), an optionally substituted alkoxy group, or an optionally substituted silyl group. Preferably, each Q is a fluorinated hydrocarbyl group having 1 to 30 carbon atoms, more preferably, each Q is an aryl fluoride (e.g., phenyl or naphthyl) group, and most preferably, each Q is an aryl perfluoride (e.g., phenyl or naphthyl) group. Suitable [M k+ Q n ] d- Examples also include the diborone compound disclosed in U.S. Patent No. 5,447,895, which is incorporated herein by reference in its entirety. Preferably, at least one Q is not a substituted phenyl, and preferably, not all Qs are substituted phenyls. Preferably, at least one Q is not a perfluorophenyl, and preferably, not all Qs are perfluorophenyls.

[0068] In some embodiments of the present invention, R1 is not methyl, R2 is not a C18 alkyl, R3 is not a C18 alkyl, alternatively R1 is not methyl, R2 is not a C18 alkyl, R3 is not a C18 alkyl, and at least one Q is not a substituted phenyl, preferably all Qs are not substituted phenyls.

[0069] In the embodiments, the meta and para substituents are independently optionally substituted linear alkyl groups (e.g., n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tritecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, n-henicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, or n-tricontyl), optionally substituted silyl groups, such as trialkylsilyl groups (wherein each alkyl is independently optionally substituted C1 to C 20alkyl (e.g., trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triheptylsilyl, trioctysilyl, trinonylsilyl, tridecylsilyl, triundecylsilyl, tridodecylsilyl, tri-tridecylsilyl, tri-tetradecylsilyl, tri-pentadecylsilyl, tri-hexadecylsilyl, tri-heptadecylsilyl, tri-octadecylsilyl, tri-nonadecylsilyl, tri-icosylsilyl), or optionally substituted alkoxy groups (e.g., -OR*, where R* is an optionally substituted C1 to C 20 It is an alkyl or aryl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, phenyl, phenyl alkyl (e.g., methylphenyl, propylphenyl, etc.), naphthyl, or anthracenyl), a halogen (e.g., Br or Cl) or a halogen-containing group (e.g., bromomethyl, bromophenyl, etc.).

[0070] In certain embodiments, the meta-substituted phenyl is methylphenyl, ethylphenyl, n-propylphenyl, n-butylphenyl, n-pentylphenyl, n-hexylphenyl, n-heptylphenyl, n-octylphenyl, n-nonylphenyl, n-decylphenyl, n-undecylphenyl, n-dodecylphenyl, n-tridecylphenyl, n-tetradecylphenyl, n-pentadecylphenyl, n-hexadecylphenyl, n-heptadecylphenyl, n-octadecylphenyl, n-nonadecylphenyl, n-icosylphenyl, n-henicosylphenyl, n-docosylphenyl, n-tricosylphenyl, n-tetracosylphenyl, n-pentacosylphenyl, n-hexacosylphenyl, n-heptacosylphenyl, n-octacosylphenyl, n-nonacosylphenyl, n-tricontylphenyl, dimethylphenyl, diethylphenyl, di-n-propylphenyl, di-n-butylphenyl, These are di-n-pentylphenyl, di-n-hexylphenyl, di-n-heptylphenyl, di-n-octylphenyl, di-n-nonylphenyl, di-n-decylphenyl, di-n-undecylphenyl, di-n-dodecylphenyl, di-n-tridecylphenyl, di-n-tetradecylphenyl, di-n-pentadecylphenyl, di-n-hexadecylphenyl, di-n-heptadecylphenyl, di-n-octadecylphenyl, di-n-nonadecylphenyl, di-n-icosylphenyl, di-n-henicosylphenyl, di-n-docosylphenyl, di-n-tricosylphenyl, di-n-tetracosylphenyl, di-n-pentacosylphenyl, di-n-hexacosylphenyl, di-n-heptacosylphenyl, di-n-octacosylphenyl, di-n-nonacosylphenyl, and di-n-tricontylphenyl. The two meta substituents may be the same or different.

[0071] In the embodiments, the para-substituted phenyl is methylphenyl, ethylphenyl, n-propylphenyl, n-butylphenyl, n-pentylphenyl, n-hexylphenyl, n-heptylphenyl, n-octylphenyl, n-nonylphenyl, n-decylphenyl, n-undecylphenyl, n-dodecylphenyl, n-tridecylphenyl, n-tetradecylphenyl, n-pentadecylphenyl, n-hexadecylphenyl, n-heptadecylphenyl, n-octadecylphenyl, n-nonadecylphenyl, n-icosylphenyl, n-henicosylphenyl, n-docosylphenyl, n-tricosylphenyl, n-tetracosylphenyl, n-pentacosylphenyl, n-hexacosylphenyl, n-heptacosylphenyl, n-octacosylphenyl, n-nonacosylphenyl, or n-tricontylphenyl.

[0072] In an embodiment, the meta- and / or para-substituted phenyl group is represented by the following formula:

[0073]

[0074] In the above equation, R 17 and R 21 is hydrogen, and R 18 , R 19 , and R 20 Each independently hydrogen, C1-C 40 Hydrocarbyl or C1-C 40 Substituted hydrocarbyl, halogen, or halogen-containing group (only R 18 , R 19 , and R 20 At least one of them is not H, or alternatively R 18 , R 19 , and R 20 At least two of them are not H, or alternatively R 18 , R 19 , and R 20 All three are not H), or are selected from a combination of these.

[0075] Preferably, R 17 and R 21 is hydrogen, and R 18 , R 19 , and R 20 Each is hydrogen, C1 to C 40 Linear alkyl or C1-C 40 Selected from the group consisting of substituted linear alkyls (where R 18 , R 19 , and R 20 At least one of them is not H, or alternatively R 18 , R 19 , and R 20 At least two of them are not H, or alternatively R 18 , R 19 , and R 20 All three are not H).

[0076] Preferably, R 17 and R 21is H, and R 18 , R 19 , and R 20 One, two, or three of them are H, linear alkyl groups (e.g., n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, n-henicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, or n-tricontyl), each alkyl is independently C1 to C 20 Optionally substituted alkyl, optionally substituted trialkylsilyl group (e.g., trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triheptylsilyl, trioctysilyl, trinonylsilyl, tridecylsilyl, triundecylsilyl, tridodecylsilyl, tri-tridecylsilyl, tri-tetradecylsilyl, tri-pentadecylsilyl, tri-hexadecylsilyl, tri-heptadecylsilyl, tri-octadecylsilyl, tri-nonadecylsilyl, tri-icosylsilyl), halogen (e.g., Br, Cl, or F), or optionally substituted alkoxy group (e.g., -OR*, where R* is C1 to C 20 Selected from the group consisting of optionally substituted alkyl or aryl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, phenyl, phenylalkyl (e.g., methylphenyl, propylphenyl, etc.), naphthyl, or anthracene), provided that R 18 , R 19 , and R 20 At least one of them is not H, or alternatively R 18 , R 19 , and R 20 At least two of them are not H, or alternatively R 18 , R 19 , and R 20 All three are not H.

[0077] In an embodiment, R 1 is methyl, and R 2 is C1 to C 40 Linear alkyl groups (e.g., C6 to C 40 Linear alkyl, or C 10 to C 30 It is a linear alkyl) and R 3 is a para-substituted phenyl group, where the para substituent is an independently and selectively substituted C1 to C 40 Hydrocarbyl groups (e.g., C6 to C 40 Aryl group or linear alkyl group, C 12 to C 30 aryl group or linear alkyl group, or C 10 to C 20 It is an aryl group or a linear alkyl group), an optionally substituted alkoxy group, an optionally substituted silyl group, a halogen, or a halogen-containing group.

[0078] In an embodiment, R 1 is methyl, and R 2 is n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, or n-icosyl, and R 3 is methylphenyl, ethylphenyl, n-propylphenyl, n-butylphenyl, n-pentylphenyl, n-hexylphenyl, n-heptylphenyl, n-octylphenyl, n-nonylphenyl, n-decylphenyl, n-undecylphenyl, n-dodecylphenyl, n-tridecylphenyl, n-tetradecylphenyl, n-pentadecylphenyl, n-hexadecylphenyl, n-heptadecylphenyl, n-octadecylphenyl, n-nonadecylphenyl, or n-icosylphenyl.

[0079] In an embodiment of any active agent formula of the present invention, each R 2 and / or R 3 is independently a halide, C1-C 50 Alkyl, C5-C 50 Aryl, C6-C 35 Arylalkyl, or C6-C35 It can be optionally substituted with at least one of alkylaryls, except that the substituted R 2 and R 3 The group is not a branched alkyl group (defined above).

[0080] In at least one embodiment of the present invention, the activator is an ionic ammonium or phosphonium borate represented by the following formula (I):

[0081]

[0082] In the above formula,

[0083] E is nitrogen or phosphorus;

[0084] R 1 C1-C 40 It is a linear alkyl, and

[0085] R 2 and R 3 Each is independently C1-C 40 Linear alkyl, C5-C 22 -aryl, C5 to C 50 arylalkyl (wherein the alkyl group has 1 to 30 (or 1 to 10) carbon atoms and the aryl group has 6 to 20 carbon atoms), or a 5-, 6-, or 7-membered heterocyclile comprising at least one atom selected from N, P, O, and S, wherein R 1 R 2 , and R 3 Each is selectively substituted by a halogen, and R 2 is optionally R 5 Combines with to independently form a 5-, 6-, or 7-membered ring, preferably where R 1 , R 2 , and R 3It comprises together 15 or more carbon atoms, e.g., 18 or more carbon atoms, e.g., 20 or more carbon atoms, e.g., 22 or more carbon atoms, e.g., 25 or more carbon atoms, e.g., 30 or more carbon atoms, e.g., 35 or more carbon atoms, e.g., 40 or more carbon atoms, and R 4 , R 5 , R 6 , and R 7 Each is independently a fluorinated hydrocarbyl group having 1 to 30 carbon atoms, and more preferably R 4 , R 5 , R 6 , and R 7 Each is independently an aryl fluoride (e.g., phenyl or naphthyl) group, most preferably R 4 , R 5 , R 6 , and R 7 Each is independently an aryl perfluorinated (e.g., phenyl or naphthyl) group, and R 4 , R 5 , R 6 , and R 7 At least one of them is substituted with 1 to 7 fluorine atoms, preferably R 4 , R 5 , R 6 , and R 7 At least one of them is not a substituted phenyl, and preferably R 4 , R 5 , R 6 , and R 7 Not all of them are substituted phenyls.

[0086] In a preferred embodiment, R 1 is not methyl, and R 2 is not C18, R 3 is not C18. In a preferred embodiment, R 1 is not methyl, and R 2 is not C18, R 3 is not C18, and R 4, R 5 , R 6 , and R 7 At least one of them is not a substituted phenyl, and preferably R 4 , R 5 , R 6 , and R 7 Not all of them are substituted phenyls.

[0087] The present invention also relates to an active agent compound represented by the following formula (I):

[0088]

[0089] In the above formula, E is nitrogen or phosphorus;

[0090] R 1 , R 2 , and R 3 Each is independently C1-C 40 Linear alkyl, C5-C 50 -Aril, and here R 1 , R 2 , and R 3 Each independently is unsubstituted or a halide, C1-C 50 Alkyl, C5-C 50 Aryl, C6-C 35 Arylalkyl, or C6-C 35 Substituted with at least one of alkylaryls, where R 1 , R 2 , and R 3 It comprises together 15 or more carbon atoms, e.g., 18 or more carbon atoms, e.g., 20 or more carbon atoms, e.g., 22 or more carbon atoms, e.g., 25 or more carbon atoms, e.g., 30 or more carbon atoms, e.g., 35 or more carbon atoms, e.g., 40 or more carbon atoms, and R 4 , R 5 , R 6 , and R 7 Each is naphthyl, where R 4 , R 5 , R 6 , and R 7At least one of them is replaced with 1 to 7 fluorine atoms.

[0091] In a preferred embodiment, the activator is an ionic ammonium borate represented by formula (I):

[0092]

[0093] In the above formula,

[0094] E is nitrogen or phosphorus;

[0095] R 1 is a methyl group;

[0096] R 2 is C6-C 50 It is an aryl, and is a halide, C1-C 35 Alkyl, C5-C 15 Aryl, C6-C 35 Arylalkyl, and C6-C 35 Optionally substituted with at least one of alkylaryls;

[0097] R 3 C1-C 40 Linear alkyl or C5-C 42 - It is an aryl, and this is a halide, C1-C 35 Alkyl, C5-C 15 Aryl, C6-C 35 Arylalkyl, and C6-C 35 It is optionally substituted with at least one of alkylaryls, wherein R 2 is optionally R 3 Combines with to independently form a 5-, 6-, or 7-membered ring, and R 2 and R 3 It includes together 20 or more carbon atoms, e.g., 21 or more carbon atoms, e.g., 22 or more carbon atoms, e.g., 25 or more carbon atoms, e.g., 30 or more carbon atoms, e.g., 35 or more carbon atoms, e.g., 40 or more carbon atoms, and

[0098] R 4 , R 5 , R 6 , and R 7Each is independently naphthyl or substituted naphthyl, where R 4 , R 5 , R 6 , and R 7 At least one of them is naphthyl substituted with 1 to 7 fluorine atoms.

[0099] In any embodiment of formula (I) or (AI), R 2 is an unsubstituted phenyl or a substituted phenyl. In at least one embodiment, R 2 is phenyl, methylphenyl, n-butylphenyl, n-octadecylphenyl, or an isomer thereof, preferably R 2 is a meta- or para-substituted phenyl, e.g., a meta- or para-substituted alkyl-substituted phenyl. In at least one embodiment, R 3 is independently C1 to C 30 Linear alkyls are selected, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-icosyl.

[0100] In any embodiment of formula (I) or (AI), R 4 , R 5 , R 6 , and R 7 Each is independently naphthyl, where R 4 , R 5 , R 6 , and R 7 At least one of them is naphthyl substituted with 1, 2, 3, 4, 5, 6 or 7 fluorine atoms.

[0101] In any embodiment of formula (I) or (AI), preferably R 4 , R 5 , R 6 , and R 7 At least one of them is not a substituted phenyl, and preferably R4 , R 5 , R 6 , and R 7 Not all are substituted phenyls. In a preferred embodiment, R 1 is not methyl, and R 2 is not C18, R 3 It is not C18.

[0102] In any embodiment of formula (I) or (AI), preferably all Q or R 4 , R 5 , R 6 , and R 7 Not all of them are perfluoroaryls, such as perfluorophenyls.

[0103] In any embodiment of formula (I) or (AI), R 4 , R 5 , R 6 , and R 7 They are all naphthyl, and R 4 , R 5 , R 6 , and R 7 At least 1, 2, 3, or 4 of them are substituted with 1, 2, 3, 4, 5, 6, or 7 fluorine atoms.

[0104] In any of the embodiments described herein, preferably R 4 , R 5 , R 6 , and R 7 Each is a naphthyl containing independently 1 fluorine atom, 2 fluorine atoms, 3 fluorine atoms, 4 fluorine atoms, 5 fluorine atoms, 6 fluorine atoms, or 7 fluorine atoms, preferably 7 fluorine atoms.

[0105] In at least one embodiment, R 4 It is a naphthyl containing independently 1 fluorine atom, 2 fluorine atoms, 3 fluorine atoms, 4 fluorine atoms, 5 fluorine atoms, 6 fluorine atoms, or 7 fluorine atoms.

[0106] In any embodiment described herein, R 4 , R 5 , R 6 , and R 7 Each is independently a fluorinated hydrocarbyl group having 1 to 30 carbon atoms, and more preferably R 4 , R 5 , R 6 , and R 7 Each is independently an aryl fluoride group (e.g., phenyl, biphenyl, [(C6H3(C6H5)2)4B], or naphthyl), most preferably R 4 , R 5 , R 6 , and R 7 Each is independently a perfluorinated aryl group (e.g., biphenyl, [(C6H3(C6H5)2)4B], or naphthyl), preferably at least one R 4 , R 5 , R 6 , and R 7 It is not perfluorophenyl.

[0107] In any embodiment of the present invention, when Q is a fluorophenyl group, R 2 is an optionally substituted C1-C 20 It is not a linear alkyl group.

[0108] In at least one embodiment, the activator is an ionic ammonium borate represented by the following formula (I):

[0109]

[0110] In the above formula,

[0111] E is nitrogen or phosphorus;

[0112] R 1 , R 2 , and R 3 Each is independently C1-C 40 Linear alkyl, C5-C 22- It is a 5-, 6-, or 7-membered heterocyclile comprising an aryl, arylalkyl (wherein the alkyl group has 1 to 10 carbon atoms and the aryl group has 6 to 20 carbon atoms), or at least one atom selected from N, P, O, and S, wherein R 1 R 2 , and R 3 Each is optionally substituted by a halogen, -NR'2, -OR' or -SiR'3 (where R' is independently hydrogen or C1-C 20 hydrocarbyl), where R 2 is optionally R 5 It combines with to independently form a 5-, 6-, or 7-membered ring. R 1 , R 2 , and R 3 It comprises together 15 or more carbon atoms, e.g., 18 or more carbon atoms, e.g., 20 or more carbon atoms, e.g., 22 or more carbon atoms, e.g., 25 or more carbon atoms, e.g., 30 or more carbon atoms, e.g., 35 or more carbon atoms, e.g., 40 or more carbon atoms. In at least one embodiment, R 1 and R 2 C1-C independently 22 -alkyl, substituted C1-C 22 -alkyl, unsubstituted phenyl, or substituted phenyl. In at least one embodiment, R 1 , R 2 and R 3 Each is independently selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-butadecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-icosyl.

[0113] In at least one embodiment, R 4 , R 5 , R 6 , and R 7Each is independently aryl- or naphthyl, where R 4 , R 5 , R 6 , and R 7 At least one of them is naphthyl substituted with 1 to 7 fluorine atoms. In at least one embodiment, R 4 , R 5 , R 6 , and R 7 Each is naphthyl, and R 4 , R 5 , R 6 , and R 7 At least one of them is replaced with 1 to 7 fluorine atoms.

[0114] In at least one embodiment, R 4 , R 5 , R 6 , and R 7 Each is a naphthyl containing independently 1 fluorine atom, 2 fluorine atoms, 3 fluorine atoms, 4 fluorine atoms, 5 fluorine atoms, 6 fluorine atoms, or 7 fluorine atoms.

[0115] In at least one embodiment, R 4 is a naphthyl containing independently 1, 2, 3, 4, 5, 6, or 7 fluorine atoms, and R 5 , R 6 , and R 7 Each is independently a phenyl containing 1, 2, 3, 4, or 5 fluorine atoms, or a naphthyl containing 1, 2, 3, 4, 5, or 7 fluorine atoms.

[0116] In at least one embodiment of the present invention, the activator is represented by the formula (I) or (AI):

[0117]

[0118] In the above formula,

[0119] M is a group 13 atom, preferably B or Al;

[0120] d is 1, 2, or 3; k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6 (preferably 1, 2, 3, or 4); n - k = d (preferably d is 1, 2, or 3; k is 3; n is 4, 5, or 6, and preferably, when M is B, n is 4);

[0121] E is nitrogen or phosphorus, preferably nitrogen;

[0122] R 1 , R 2 , and R 3 Each is independently C1-C 40 Linear alkyl, C5-C 22 -Aryl, C7 to C 30 It is an arylalkyl (wherein the alkyl group has 1 to 10 carbon atoms and the aryl group has 6 to 20 carbon atoms), or a 5-, 6-, or 7-membered heterocyclile comprising at least one atom selected from N, P, O, and S, and R 1 R 2 , and R 3 Each is selectively substituted by a halogen, where R 2 is optionally R 5 Combines with to independently form a 5-, 6-, or 7-membered ring, preferably where R 1 , R 2 , and R 3It comprises together 15 or more carbon atoms, e.g., 18 or more carbon atoms, e.g., 20 or more carbon atoms, e.g., 22 or more carbon atoms, e.g., 25 or more carbon atoms, e.g., 30 or more carbon atoms, e.g., 35 or more carbon atoms, e.g., 38 or more carbon atoms, e.g., 40 or more carbon atoms. In at least one embodiment, R 1 and R 2 C1-C independently 22 -alkyl, substituted C1-C 22 -alkyl, unsubstituted phenyl, or substituted phenyl (in at least one embodiment, R 1 , R 2 and R 3 Each is independently selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-icosyl;

[0123] R 4 , R 5 , R 6 , and R 7 Each is independently naphthyl, where R 4 , R 5 , R 6 , and R 7 At least one of them is naphthyl substituted with 1 to 7 fluorine atoms, and preferably at least one R 4 , R 5 , R 6 , and R 7 is not a substituted phenyl, and preferably R 4 , R 5 , R 6 , and R 7 Not all are substituted phenyls;

[0124] Each Q is independently a hydride, cross-linked or non-cross-linked dialkylamido, halide, alkoxide, aryl oxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halosubstituted-hydrocarbyl radical. Preferably, each Q is a fluorinated hydrocarbyl group having 1 to 30 carbon atoms, more preferably, each Q is a fluorinated aryl (e.g., phenyl or naphthyl) group, and most preferably, each Q is a perfluorinated aryl (e.g., phenyl or naphthyl) group. In a preferred embodiment of the present invention, at least one Q is not a substituted phenyl, e.g., perfluorophenyl, and preferably, all Qs are not substituted phenyl, e.g., perfluorophenyl.

[0125] The terms “co-catalyst” and “activator” are used interchangeably herein and are defined as any compound capable of activating any one of the catalytic compounds of this disclosure by converting a neutral catalytic compound into a catalytic compound cation having catalytic activity.

[0126] The catalyst system of the present disclosure may be formed by combining a catalyst and an activator in any suitable manner, including supporting it for use in slurry or gas phase polymerization. The catalyst system may also be added to or formed in solution polymerization or bulk polymerization (in monomers, i.e., in the absence or with little solvent).

[0127] Both the cation portion of formulas (A1) and (I) and the anion portion, which is NCA, will be described in more detail below. Any combination of cations and NCA disclosed herein is suitable for use in the processes of the present disclosure and is therefore incorporated herein.

[0128] cationic components

[0129] The cationic component of the activator described herein (e.g., formulas (AI) and (I)) is a protonated Lewis base capable of protonating a moiety, such as an alkyl or aryl, from a transition metal compound. Thus, when a neutral leaving group (e.g., an alkane formed from the combination of a proton provided from the cationic component of the activator and an alkyl substituent of the transition metal compound) is released, a transition metal cation is produced, which is a catalytically active species.

[0130] In at least one embodiment of formula (I) or (AI), the cation is [R 1 R 2 R 3 EH] + and, E is nitrogen or phosphorus, and R 1 , R 2 , and R 3 Each is independently C1-C 40 Linear alkyl, C5-C 22 - It is a 5-, 6-, or 7-membered heterocyclile comprising an aryl, arylalkyl (wherein the alkyl group has 1 to 10 carbon atoms and the aryl group has 6 to 20 carbon atoms) or at least one atom selected from N, P, O, and S, wherein R 1 R 2 , and R 3 Each is optionally substituted by a halogen, -NR'2, -OR' or -SiR'3 (where each R' is independently hydrogen or C1-C 20 hydrocarbyl), where R 2 is optionally R 5 It combines with to independently form a 5-, 6-, or 7-membered ring. R 1 , R 2 , and R 3It comprises together 15 or more carbon atoms, e.g., 18 or more carbon atoms, e.g., 20 or more carbon atoms, e.g., 22 or more carbon atoms, e.g., 25 or more carbon atoms, e.g., 30 or more carbon atoms, e.g., 35 or more carbon atoms, e.g., 37 or more carbon atoms, e.g., 40 or more carbon atoms, e.g., 45 or more carbon atoms. In at least one embodiment, R 1 , R 2 , and R 3 C1-C are independently substituted or non-substituted 22 It is a linear alkyl, or a substituted or unsubstituted phenyl. In at least one embodiment, R 1 , R 2 and R 3 Each is independently selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-icosyl. In at least one embodiment, R 2 and R 3 Each is independently selected from methylphenyl, ethylphenyl, n-propylphenyl, n-butylphenyl, n-pentylphenyl, n-hexylphenyl, n-heptylphenyl, n-octylphenyl, n-nonylphenyl, n-decylphenyl, n-undecylphenyl, n-dodecylphenyl, n-tridecylphenyl, n-tetradecylphenyl, n-pentadecylphenyl, n-hexadecylphenyl, n-heptadecylphenyl, n-octadecylphenyl, n-nonadecylphenyl, and n-icosylphenyl.

[0131] In a preferred embodiment, R 1 is methyl, and R 2 is a substituted phenyl, and R 3 C 10 to C 30 It is a linear alkyl. Preferably R 2 is not a meta-substituted phenyl.

[0132] In a preferred embodiment, R1 is methyl, and R 2 is C1 to C 35 It is an alkyl-substituted phenyl (preferably ortho- or meta-substituted), and R 3 C 10 to C 30 It is a linear alkyl.

[0133] In a preferred embodiment, R 1 is methyl, and R 2 is C1 to C 35 It is an alkyl-substituted phenyl (preferably para-substituted), and R 3 C 10 to C 30 It is a linear alkyl.

[0134] In a preferred embodiment, R 1 is methyl; R 2 is C1 to C 35 Alkyl-substituted phenyls, e.g., methylphenyl, ethylphenyl, n-propylphenyl, n-butylphenyl, n-pentylphenyl, n-hexylphenyl, n-heptylphenyl, n-octylphenyl, n-nonylphenyl, n-decylphenyl, n-undecylphenyl, n-dodecylphenyl, n-tridecylphenyl, n-tetradecylphenyl, n-pentadecylphenyl, n-hexadecylphenyl, n-heptadecylphenyl, n-octadecylphenyl, n-nonadecylphenyl, and n-icosylphenyl, n-henicosylphenyl, n-docosylphenyl, n-tricosylphenyl, n-tetracosylphenyl, n-pentacosylphenyl, n-hexacosylphenyl, n-heptacosylphenyl, n-octacosylphenyl, n-nonacosylphenyl, n-triacontylphenyl; and R 3 C 10 to C 30 Linear alkyls, such as n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, n-henicosyl, n-docosyl, n-tricosyl; n-tetracosyl, n-pentacosyl; n-hexacosyl; n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl.

[0135] In a preferred embodiment, R 2 is C1 to C35 Alkyl-substituted phenyls, e.g., methylphenyl, ethylphenyl, n-propylphenyl, n-butylphenyl, n-pentylphenyl, n-hexylphenyl, n-heptylphenyl, n-octylphenyl, n-nonylphenyl, n-decylphenyl, n-undecylphenyl, n-dodecylphenyl, n-tridecylphenyl, n-tetradecylphenyl, n-pentadecylphenyl, n-hexadecylphenyl, n-heptadecylphenyl, n-octadecylphenyl, n-nonadecylphenyl, and n-icosylphenyl, n-henicosylphenyl, n-docosylphenyl, n-tricosylphenyl, n-tetracosylphenyl, n-pentacosylphenyl, n-hexacosylphenyl, n-heptacosylphenyl, n-octacosylphenyl, n-nonacosylphenyl, n-triacontylphenyl; and R 3 C 10 to C 30 Linear alkyls, such as n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, n-henicosyl, n-docosyl, n-tricosyl; n-tetracosyl, n-pentacosyl; n-hexacosyl; n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl.

[0136] In a preferred embodiment of formula (I), R 1 is methyl, and R 2 is a substituted phenyl, and R 3 C 10 to C 30 It is a linear alkyl, and R 4 , R 5 , R 6 , R 7 It is perfluoronaphthyl.

[0137] In a preferred embodiment of formula (AI), R 1 is methyl, and R 2 is a substituted phenyl, and R 3 C 10 to C 30 It is a linear alkyl, E is nitrogen, and each Q is perfluoronaphthyl.

[0138] In a preferred embodiment, R 1 is methyl; R2 is C1 to C 35 Alkyl-substituted phenyls, e.g., methylphenyl, ethylphenyl, n-propylphenyl, n-butylphenyl, n-pentylphenyl, n-hexylphenyl, n-heptylphenyl, n-octylphenyl, n-nonylphenyl, n-decylphenyl, n-undecylphenyl, n-dodecylphenyl, n-tridecylphenyl, n-tetradecylphenyl, n-pentadecylphenyl, n-hexadecylphenyl, n-heptadecylphenyl, n-octadecylphenyl, n-nonadecylphenyl, and n-icosylphenyl, n-henicosylphenyl, n-docosylphenyl, n-tricosylphenyl, n-tetracosylphenyl, n-pentacosylphenyl, n-hexacosylphenyl, n-heptacosylphenyl, n-octacosylphenyl, n-nonacosylphenyl, n-triacontylphenyl; and R 3 C 10 to C 30 Linear alkyls, e.g., n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, n-henicosyl, n-docosyl, n-tricosyl; n-tetracosyl, n-pentacosyl; n-hexacosyl; n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl; and each Q or R 4 , R 5 , R 6 , R 7 Each is perfluoronaphthyl.

[0139] In a preferred embodiment of the present invention, R 1 is o-MePh, and R 2 and R 3 It is n-octadecyl.

[0140] In a preferred embodiment of the present invention, R 1 is m-MePh, and R 2 and R 3 It is n-octadecyl.

[0141] In a preferred embodiment of the present invention, R 1 It is not para-alkylphenyl, e.g., p-MePh.

[0142] In a preferred embodiment of the present invention, R1 is Me, and R 2 is n-octadecylaryl, and R 3 It is n-octadecyl.

[0143] In a preferred embodiment of the present invention, R 1 is Me, and R 2 is n-octadecylphenyl, and R 3 It is n-octadecyl.

[0144] In a preferred embodiment of the present invention, R 1 is Me, and R 2 is n-butylaryl, and R 3 It is n-octadecyl.

[0145] In a preferred embodiment of the present invention, R 1 is Me, and R 2 is n-butylphenyl, and R 3 It is n-octadecyl.

[0146] In a preferred embodiment of the present invention, R 1 is n-decyl, and R 2 is n-butylaryl, and R 3 is n-decyl.

[0147] In a preferred embodiment of the present invention, R 1 is n-decyl, and R 2 is n-butylphenyl, and R 3 is n-decyl.

[0148] In a preferred embodiment of the present invention, R 1 is an n-profile, and R 2 is p-methylphenyl, and R 3 It is n-octadecyl.

[0149] In a preferred embodiment of the present invention, R 1 , R 2 and R 3It includes together 20 or more carbon atoms, e.g., 21 or more carbon atoms, e.g., 22 or more carbon atoms, e.g., 25 or more carbon atoms, e.g., 30 or more carbon atoms, e.g., 35 or more carbon atoms, e.g., 37 or more carbon atoms, e.g., 40 or more carbon atoms, e.g., 45 or more carbon atoms, e.g., 15 to 100 carbon atoms, e.g., 25 to 75 carbon atoms, e.g., 38 to 70 carbon atoms.

[0150] In at least one embodiment, the cation is selected from the group consisting of the following:

[0151]

[0152]

[0153] In at least one embodiment of formulas (AI) and (I), E is nitrogen or phosphorus, and R 1 is a methyl group; R 2 is C6-C 40 It is an aryl (e.g., substituted phenyl), and R 3 C1-C independently 35 Linear alkyl, C5-C 40 -Aril, and here R 2 and R 3 Each is independently unsubstituted or C1-C 35 Alkyl, C5-C 30 Aryl, C6-C 305 Arylalkyl, C6-C 30 Substituted with at least one of an alkylaryl or a halogen, where R 2 is optionally R 3 Combines with to independently form a 5-, 6-, or 7-membered ring, where R 2 , and R 3 It contains 20 or more carbon atoms together; optionally R 1 , R 2 , and R 3It comprises together 21 or more carbon atoms, e.g., 22 or more carbon atoms, e.g., 25 or more carbon atoms, e.g., 30 or more carbon atoms, e.g., 35 or more carbon atoms, e.g., 40 or more carbon atoms. In at least one embodiment, R 2 is an independently substituted C1-C 22 -alkyl, unsubstituted phenyl, or substituted phenyl. In at least one embodiment, R 3 is independently selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-icosyl.

[0154] Preferably, the cation is selected from the group consisting of the following:

[0155]

[0156] Preferably, the compounds represented by formulas (AI) and (I) comprise cations selected from the group consisting of the following:

[0157]

[0158] Anion component

[0159] The anionic component of the active agent described herein is formula [M k+ Q n ] -It includes being represented as, where k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6 (preferably 1, 2, 3, or 4), (preferably k is 3; n is 4, 5, or 6, and preferably n is 4 when M is B); M is an element selected from Group 13 of the periodic table, preferably boron or aluminum, and Q is independently a hydride, cross-linked or non-cross-linked dialkylamido, halide, alkoxide, aryl oxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halosubstituted-hydrocarbyl radical, said Q has up to 20 carbon atoms, provided that Q being a halide does not occur more than once. Preferably, each Q is a fluorinated hydrocarbyl group having 1 to 20 carbon atoms, more preferably, each Q is a fluorinated aryl group, and most preferably, each Q is a perfluorinated aryl group. Preferably, at least one Q is not a substituted phenyl, e.g., perfluorophenyl, and preferably, all Qs are not substituted phenyl, e.g., perfluorophenyl.

[0160] In a preferred embodiment among any embodiment of formula (AI), R 1 This is methyl, and R 2 ga is C18, and R 3 In the case of this C18, each Q is not a perfluorophenyl.

[0161] In at least one embodiment, the borate moiety of the activator represented by formula (I) ([BR 4 R 5 R 6 R 7 ] - In ), R 4 , R 5 , R 6 , and R 7 Each is independently an aryl (e.g., naphthyl), where R 4 , R 5 , R 6, and R 7 At least one of them is substituted with 1 to 7 fluorine atoms. In at least one embodiment, R 4 , R 5 , R 6 , and R 7 Each is naphthyl, and R 4 , R 5 , R 6 , and R 7 At least one of them is replaced with 1 to 7 fluorine atoms.

[0162] In at least one embodiment, R 4 , R 5 , R 6 , and R 7 Each is a naphthyl containing independently 1 fluorine atom, 2 fluorine atoms, 3 fluorine atoms, 4 fluorine atoms, 5 fluorine atoms, 6 fluorine atoms, or 7 fluorine atoms.

[0163] In a preferred embodiment among any embodiment of Formula (I), R 1 This is methyl, and R 2 ga is C18, and R 3 In the case of this C18, R 4 , R 5 , R 6 , and R 7 Each one is not a perfluorophenyl.

[0164] In at least one embodiment, R 4 is a naphthyl containing independently 1, 2, 3, 4, 5, 6, or 7 fluorine atoms, and R 5 , R 6 , and R 7Each is independently a phenyl containing 1, 2, 3, 4, or 5 fluorine atoms, or a naphthyl containing 1, 2, 3, 4, 5, or 7 fluorine atoms.

[0165] In one embodiment, the borate activator comprises tetrakis(heptafluoronaft-2-yl)borate.

[0166] In at least one preferred embodiment, the activator is represented by formula (B):

[0167]

[0168] In the above formula, M is an element selected from Group 13 of the periodic table; each Q is independently a hydride, cross-linked or non-cross-linked dialkylamido, halide, alkoxide, aryl oxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halosubstituted-hydrocarbyl radical; [cation] + is selected from the group consisting of the following:

[0169]

[0170] In at least one preferred embodiment, [MQ4] - is a perfluoroaryl. In at least one other preferred embodiment, [cation] + is as follows:

[0171]

[0172] The activator can be added to the polymerization in the form of an ion pair, for example, using [M2HTH]+ [NCA]-, where the di(hydrogenated tallow)methylamine ("M2HTH") cation reacts with the basic leaving group of the transition metal complex to form [NCA]- with the transition metal complex cation. Alternatively, the transition metal complex is B(C 10It can react with neutral NCA precursors such as F7)3, which extract anionic groups from the complex to form an activated species. A useful activator is di(hydrogenated tallow)methylamine(perfluoronaphthyl)borate (i.e., [M2HTH]B(C 10 F7)4) and di(octadecyl)tolylamine (perfluoronaphthyl)borate (i.e., [DOdTH]B(C 10 Includes C7)4).

[0173] In at least one embodiment, the activator obtained in the form of a salt used in a borate activator compound is as follows: lithium tetrakis(heptafluoronaphthalene-2-yl)borate etherate (Li-BF28), N,N-dimethylanilinium tetrakis(heptafluoronaphthalene-2-yl)borate (DMAH-BF28), sodium tetrakis(heptafluoronaphthalene-2-yl)borate (Na-BF28), and N,N-dimethylanilinium tetrakis(heptafluoronaphthalene-2-yl)borate (DMAH-BF28).

[0174] In at least one embodiment, the activator of the present disclosure, when combined with a group 4 metallocene catalyst compound to form an active olefin polymerization catalyst, produces a polymer with a higher molecular weight (e.g., Mw) than a comparative activator using other borate anions.

[0175] In at least one embodiment, R 1 The activator of the present disclosure, which is this methyl, produces a polymer with a higher molecular weight (e.g., Mw) than a comparative activator using other borate anions when combined with a group 4 metallocene to form an active olefin polymerization catalyst.

[0176] A typical activator-to-catalyst ratio, for example, for all NCA activators-to-catalysts, is a molar ratio of about 1:1. Alternative preferred ranges include 0.1:1 to 100:1, alternatively 0.5:1 to 200:1, alternatively 1:1 to 500:1, and alternatively 1:1 to 1000:1. A particularly useful range is 0.5:1 to 10:1, preferably 1:1 to 5:1. The molar ratio of activator to catalyst can also vary from 0.5 to 2.0.

[0177] In addition, the combination of a catalyst compound with a combination of alumonic acid and the activator described herein is also included within the scope of the present disclosure.

[0178] synthesis

[0179] In at least one embodiment, the general synthesis of the activator may be carried out using a two-step process. In the first step, an amine or phosphine is dissolved in a solvent (e.g., hexane, cyclohexane, methylcyclohexane, ether, dichloromethane, toluene) and an excess amount (e.g., 1.2 molar equivalents) of hydrogen chloride is added to form a chloride salt. This salt is typically isolated from the reaction medium by filtration and dried under reduced pressure. The isolated chloride is then heated and refluxed in a solvent (e.g., cyclohexane, dichloromethane, methylcyclohexane) with about 1 molar equivalent of an alkali metal metallate or metalloid (e.g., borate or aluminate) to form the desired borate or aluminate together with the alkali metal chloride as a byproduct, the latter of which can typically be removed by filtration.

[0180] The activator of the present disclosure is soluble in aliphatic solvents. Aromatic solvents such as toluene are absent (e.g., present at 0 mol% or alternatively at less than 1 mol%, preferably the catalytic system, polymerization reaction and / or resulting polymer is free of "detectable aromatic hydrocarbon solvents" such as toluene). For the purposes of the present disclosure, "detectable aromatic hydrocarbon solvents" are 0.1 mg / m³ when determined by vapor phase chromatography. 2 The above means. For the purposes of this disclosure, "detectable toluene" is 0.1 mg / m³ when determined by vapor phase chromatography. 2 The above means. The polyolefin produced herein preferably contains 0 ppm (alternatively less than 1 ppm) of aromatic hydrocarbons. Preferably, the polyolefin produced herein contains 0 ppm (alternatively less than 1 ppm) of toluene. The catalyst system used herein preferably contains 0 ppm (alternatively less than 1 ppm) of aromatic hydrocarbons. Preferably, the catalyst system used herein contains 0 ppm (alternatively less than 1 ppm) of toluene.

[0181] In at least one embodiment, the general synthesis of the activator may be carried out using a two-step process. In the first step, an amine is dissolved in a solvent. In one or more embodiments, a mixture of 20 weight percent of a compound selected from n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combination thereof forms a clear, homogeneous solution at 25°C, and preferably, a mixture of 30 weight percent of a compound selected from n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combination thereof forms a clear, homogeneous solution at 25°C.

[0182] The activator may have a solubility of more than 10 mM (or more than 20 mM, or more than 50 mM) in methylcyclohexane at 25°C (stirred for 2 hours). The activator may have a solubility of more than 1 mM (or more than 10 mM, or more than 20 mM) in isohexane at 25°C (stirred for 2 hours). The activator may have a solubility of more than 10 mM (or more than 20 mM, or more than 50 mM) in methylcyclohexane at 25°C (stirred for 2 hours) and a solubility of more than 1 mM (or more than 10 mM, or more than 20 mM) in isohexane at 25°C (stirred for 2 hours).

[0183] After adding an activator to the solvent, an excess amount (e.g., 1.2 molar equivalents) of hydrogen chloride is added to form an ammonium chloride salt. This salt is typically isolated from the reaction medium by filtration and dried under reduced pressure. The isolated ammonium chloride is then heated and refluxed in a solvent (e.g., cyclohexane, dichloromethane, methylcyclohexane) with about 1 molar equivalent of alkali metal borate to form ammonium borate together with alkali metal chloride as a byproduct, the latter of which can typically be removed by filtration.

[0184] In at least one embodiment, the activator of the present disclosure can be dissolved in an aliphatic solvent at a concentration of about 10 mM or more, e.g., about 20 mM or more, e.g., about 30 mM or more, e.g., about 50 mM or more, e.g., about 75 mM or more, e.g., about 100 mM or more, e.g., about 200 mM or more, e.g., about 300 mM or more. In at least one embodiment, the activator of the present disclosure is dissolved in isohexane or methylcyclohexane at 25°C to form a homogeneous solution with a concentration of at least 10 mM.

[0185] In at least one embodiment, the solubility of the borate or aluminate activator of the present disclosure in an aliphatic hydrocarbon solvent increases as the number of aliphatic carbons of the cation group (i.e., ammonium or phosphonium) increases. In at least one embodiment, for an activator having an ammonium or phosphonium group having about 21 or more aliphatic carbon atoms, e.g., about 25 or more aliphatic carbon atoms, e.g., about 35 or more aliphatic carbon atoms, a solubility of at least 10 mM is achieved.

[0186] In at least one embodiment, the solubility of the ammonium borate activator of the present disclosure in an aliphatic hydrocarbon solvent increases as the number of aliphatic carbons of the ammonium group increases. In at least one embodiment, for an activator having an ammonium group having about 21 or more aliphatic carbon atoms, e.g., about 25 or more aliphatic carbon atoms, e.g., about 35 or more aliphatic carbon atoms, a solubility of at least 10 mM is achieved.

[0187] Useful aliphatic hydrocarbon solvents may be isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, e.g., cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. In at least one embodiment, the aromatic is present in the solvent at less than 1 weight percent, e.g., less than 0.5 weight percent, e.g., 0 weight percent, based on the weight of the solvent. The active agent of the present disclosure may be dissolved in one or more additional solvents. The additional solvents are ether-based solvents, halogenated solvents, and N,N - It includes a dimethylformamide solvent. The aliphatic solvent is preferably isohexane and / or methylcyclohexane.

[0188] Selective scavenger or coactivator

[0189] In addition to these activators, scavengers or coactivators may be used. Aluminum alkyl or organoaluminum compounds that can be utilized as scavengers or coactivators include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum (TNOA), and diethyl zinc.

[0190] In at least one embodiment, little or no scavenger (i.e., 0 mol%) is used in the process for manufacturing an ethylene polymer. In at least one embodiment, one or more scavengers are added to the process, wherein the molar ratio of the scavenger metal to the transition metal is less than 100:1, e.g., less than 50:1, e.g., less than 15:1, e.g., less than 10:1.

[0191] Further details regarding the preparation of a suitable catalyst system using cross-linked metallocene(s), activator(s), and support material(s) can be found in U.S. Patents No. 11,011,031 and No. 11,414,436.

[0192] Example:

[0193] The foregoing discussion may be further explained with reference to the following non-limiting examples. Five types of ethylene-butene copolymer examples (resins 1 to 5) (C2 / C4) were prepared in a pilot-scale solution reactor. The catalyst was di(para-triethylsilylphenyl)methylene(2,7-di-tert-butyl-fluorenyl)(cyclopentadienyl)hafnium dimethyl, and the activator was N-methyl-4-nonadecyl-N-octadecylanilinium dimethylanilinium tetrakis(heptafluoronaphthyl)borate as an activator / co-catalyst, both of which were available from ExxonMobil Chemical Company.

[0194] Comparative examples of two types of ethylene-butene copolymers (C2 / C4) were also prepared. Comparative resin samples (CE1 and CE2) were prepared in a pilot-scale solution reactor using the same catalyst as resins 1 to 5 (i.e., di(para-triethylsilylphenyl)methylene(2,7-di-tert-butyl-fluorenyl)(cyclopentadienyl)hafnium dimethyl), but activated with different activators as shown in Table 1 below.

[0195] Table 1 shows the active agents used to prepare resins 1 to 5 of the present invention and comparative resin samples CE1 and CE2.

[0196]

[0197] The activator solution was prepared by diluting the activator with an aliphatic hydrocarbon before being fed into the pilot-scale solution polymerization reactor. The activator solution and the catalyst solution were fed into the reactor separately and mixed within the reactor to produce the activated catalyst for polymerization. Tri-n-octylaluminum (TNOA), acting as a scavenger, was fed as a diluted solution of 3 wt% pure TNOA and 97 wt% processing solvent. This solution was metered using a mass flow meter, mixed with the remaining monomers, and fed continuously into the reactor. Table 2 summarizes the copolymer properties, aluminum residue, and volume resistivity, and Table 3 summarizes the key process conditions.

[0198]

[0199]

[0200] Table 4 provides similar information regarding commercial copolymers for comparison.

[0201]

[0202] The copolymers were molded into molding plaques and tested for volume resistivity (1 mm thick film, 500 V, 5 min charging time) and aluminum residue. The figure shows the volume resistivity of the molding plaques plotted against aluminum residue (ppmw). All resins 1 to 5, despite all copolymers having similar densities, MI, and branching indices, had a volume resistivity >10 15 It was Ohm*cm, and at this time, the aluminum residue was less than 2.0 ppmw, and some were less than 0.1 ppm.

[0203] Test Procedure

[0204] In the aforementioned embodiments, the following test methods and procedures were used:

[0205] Density was measured according to ASTM D792, and MI value was measured according to ASTM D1238 (190℃ / 2.16 kg).

[0206] The molecular weight distribution and moments (Mw, Mn, Mz, Mw / Mn, Mz / Mn, etc.) and the long chain branching index (g') were determined using high-temperature gel permeation chromatography (Polymer Char GPC-IR) equipped with a multi-channel band filter-based infrared detector IR5, an 18-angle light scattering detector, and a viscometer. Polymer separation was provided using three Agilent Plgel 10 μm Mixed-B LS columns. Detailed analytical principles and methods for molecular weight determination are described in paragraphs

[0044] to

[0051] of International Publication No. WO / 2019 / 246069A1, which is incorporated herein by reference (note that the equation for c with respect to concentration I at each point of the chromatogram referenced in paragraph

[0044] is c = βI, where β is a mass constant and I is the IR5 broadband signal intensity (I) minus the baseline). Unless specifically stated otherwise, all molecular weight moments used or mentioned in this disclosure are determined according to conventional molecular weight (IR molecular weight) determination methods (e.g., as referenced in paragraphs

[0044] to

[0045] of the immediately preceding disclosure), and it is further noted that in the formula of paragraph

[0044] , a = 0.695 and K = 0.000579 (1-0.75 Wt) are used, where Wt is the weight fraction of the hexane comonomer, and as mentioned in paragraph

[0045] of the immediately preceding international disclosure, the comonomer composition is determined by the ratio of IR5 detector intensities corresponding to the CH2 and CH3 channels calibrated with a series of PE and PP homopolymer / copolymer standards in which nominal values ​​are predetermined by NMR or FTIR (providing methyl (CH3 / 1000 TC) per 1000 total carbons).

[0207] The long chain branching index (g') was measured using GPC-4D. A typical GPC-4D profile has Log M vs g' and is used to estimate the average g' based on the average of the entire molecular weight. The branching index g'avg values ​​range from 1 to 0, where 1 is linear (unbranched) and 0 is fully branched. Since g'avg does not clearly distinguish branching variations at low levels (0.85 to 1), g'(Mz) and g'(Mz+1) were estimated at higher molecular weight moments (Mz, Mz+1). The branching index g'(Mz) is the g' of the GPC-4D profile estimated from the z-average (third moment) molecular weight average. This calculation is performed by curve fitting the g' versus molecular weight data to an n-th degree polynomial using a MATLAB program. The value of n is typically 3 to 4. The Mz value obtained from GPC-IR measurements is inserted into the curve fitting to calculate g' related to the corresponding molecular weight.

[0208] 13C NMR for r1r2

[0209] The sample was dissolved in deuterated 1,1,2,2-tetrachloroethane-d2 (tce-d2) at a concentration of 67 mg / mL at 140°C. Spectra were recorded at 120°C using a Bruker NMR spectrometer of at least 600 MHz equipped with a 10 mm cryoprobe. To measure 13C NMR, a 90° pulse, 10 second delay, 512 transients, and gate decoupling were used. The polymer resonance peak is referenced to the polyethylene main peak at 29.98 ppm.

[0210] The chemical shift configuration of the ethylene-octene copolymer was described in the literature [Randall, "A Review Of High Resolution Liquid Carbon Nuclear Magnetic Resonance Characterization of Ethylene-Based Polymers", Polymer Reviews, 29:2,201-5 317 (1989)]. Copolymer content, mol% and weight%, triad sequencing, and diad calculations are also calculated and described using the method established by Randall in the aforementioned paper. The calculation of the reactivity ratio (r1r2) is based on the equation r1r2 = 4 * [EE] * [OO] / [EO]2; where [EE], [EO], and [OO] are diad molar concentrations; E is ethylene, and O is octene.

[0211] The product of reactivity ratios r1r2 is described in more detail in the literature [Textbook of Polymer Chemistry, FW Billmeyer, Jr., Interscience Publishers, New York, p.221 et seq. (1957)]. The product of reactivity ratios r1r2 (where r1 is the reactivity of ethylene and r2 is the reactivity of propylene) can be calculated from the measured Dyad distributions (OO, EE, EO, and OE in this nomenclature) by applying the following formula:

[0212]

[0213] Here, Mol % E =[( E ) / ( EO )]*100 and X=E / O in the reactor;

[0214] K 11 and K 12 is the kinetic insertion constant for ethylene;

[0215] K 21 and K 22 is the kinetic insertion constant for propylene.

[0216] As is known to those skilled in the art, if the product of the reactivity ratios r1r2 is zero (0), an “alternating” copolymer can be defined, and if the product of the reactivity ratios is one (1), a “statistically random” copolymer is defined. In other words, copolymers with a product of the reactivity ratios r1r2 of 0.6 to 1.5 are generally random (in strict theoretical terms, generally only copolymers with a reactivity product ratio r1r2 greater than 1.5 contain relatively long homopolymer sequences and are called “block type”).

[0217] Aluminum residues in the polymer were tested by ICP-OES using the incineration-ash sample pretreatment method. Accurately weigh ± 20 g of the sample into a clean platinum crucible using an analytical balance. Place the crucible in a muffle oven and start the temperature program from room temperature to 550°C for 5 hours. Place an empty clean crucible in the oven along with each sample batch as a blank reference. Cool the muffle oven to near room temperature and transfer the crucible to an acid hood. Add 1 ml of nitric acid and carefully rotate the crucible so that the nitric acid wets all the ash. Add 0.5 ml of hydrofluoric acid and carefully rotate the crucible again. React for at least 30 minutes. If necessary, add an additional 0.5 ml of hydrofluoric acid to dissolve all the ash. Add ± 5 ml of milli-Q water and 1 ml of hydrochloric acid and carefully rotate the crucible. Using a clean disposable plastic pipette, quantitatively transfer the mixture to a clean 50 ml volumetric PFA flask. Rinse the crucible with milli-Q water at least three times and quantitatively transfer it to the flask each time. Add milli-Q water up to the mark. Before measuring the sample, prepare a calibration curve using multi-element standards, and then test for elements using ICP-OES. Aluminum residue was reported in weight ppm.

[0218] Volume resistivity (VR) was tested according to the ExxonMobil method based on ASTM D257. Measurements were performed using a Keithley 6517B potentiometer and a Keithley 8009 test fixture. Leakage current was tested directly with the instrument, and volume resistivity was calculated using the following formula:

[0219]

[0220] Here, ρ is the volume resistivity (Ω·cm), V is the applied voltage (volts), A is the electrode contact area (cm2), I is the leakage current (amperes), and t is the average thickness of the sample. The volume resistivity test was performed at room temperature with 500 volts and a charging time of 300 seconds, and three 1 mm thick molded plaques were tested to calculate the average of each sample.

[0221] Specific embodiments and features have been described using a set of numerical upper limits and a set of numerical lower limits. Unless otherwise indicated, it should be recognized that a range is considered that includes any combination of two values, e.g., a combination of any lower limit and any upper limit, a combination of any two lower limits, and / or a combination of any two upper limits. Specific lower limits, upper limits, and ranges appear in one or more of the following claims. All numerical values ​​are expressed as “approximately” or “roughly,” taking into account experimental errors and differences that can be expected by a person skilled in the art.

[0222] Various terms have been defined prior to this. Where a term used in a claim is not previously defined, it shall be interpreted according to the broadest definition given to such term by those skilled in the art, as reflected in at least one printed publication or published patent. Furthermore, all patents, test procedures, and other documents cited in this application are incorporated herein in their entirety to the extent that such disclosures do not conflict with this application and in all jurisdictions where such inclusion is permitted.

[0223] Although the foregoing describes embodiments of the present invention, other and additional embodiments of the present invention may be devised without departing from the basic scope of the present invention, the scope thereof is determined by the following claims.

Claims

Claim 1 As an ethylene copolymer, At least 50 weight percent of ethylene-derived units; and It comprises at least 20 weight% of at least one C3 to C20 comonomer, and A melt index of 0.5 g / 10 min to about 50 g / 10 min when measured according to ASTM D1238 (190℃ / 2.16 kg); Density of approximately 0.856 g / cc to 0.890 g / cc when measured according to ASTM D792; At least 5x10 15 Volume resistivity at 23°C of Ωcm; and Ethylene copolymer having 0.01 to 4.0 weight ppm of aluminum. Claim 2 The ethylene copolymer according to claim 1, further comprising a first long-chain branching index (g'(Mz)) of 0.80 to 0.

93. Claim 3 The ethylene copolymer according to claim 1, further comprising a second long-chain branching index (g'(Mz+1)) of 0.80 to 0.

93. Claim 4 An ethylene copolymer according to claim 1, further comprising an average ratio of g'Mz+1 to g'(Mz) of 0.9 to 1.

0. Claim 5 The ethylene copolymer of claim 1, further comprising vinyl / total unsaturation of less than 0.7 and unsaturation levels of trisubstituted olefins of 50 to 500. Claim 6 The ethylene copolymer according to claim 1, further comprising an r1r2 reactivity ratio of 0.2 to 0.

8. Claim 7 In claim 1, at least one C3 to C20 comonomer is an ethylene copolymer that is butene or octene or a combination thereof. Claim 8 As an electronic device module, At least one electronic device; and The ethylene copolymer film in direct contact with at least one surface of an electronic device comprises, wherein the ethylene copolymer At least 50 weight percent of ethylene-derived units; and The copolymer comprises at least 20 weight percent of at least one C3 to C20 comonomer, and the copolymer A melt index of 0.5 g / 10 min to about 50 g / 10 min when measured according to ASTM D1238 (190℃ / 2.16 kg); Density of approximately 0.856 g / cc to 0.890 g / cc when measured according to ASTM D792; At least 5x10 15 Volume resistivity at 23°C of Ωcm; and An electronic device module having 0.01 to 4.0 weight ppm of aluminum. Claim 9 An electronic device module according to claim 8, wherein the copolymer further comprises a first long-chain branching index (g'(Mz)) of 0.80 to 0.

93. Claim 10 An electronic device module according to claim 8, wherein the copolymer further comprises a second long-chain branching index (g'(Mz+1)) of 0.80 to 0.

93. Claim 11 An electronic device module according to claim 8, wherein the copolymer further comprises an average ratio of g'Mz+1 to g'(Mz) of 0.9 to 1.

0. Claim 12 An electronic device module according to claim 8, wherein the copolymer further comprises vinyl / total unsaturation of less than 0.7 and unsaturation levels of trisubstituted olefins of 50 to 500. Claim 13 An electronic device module according to claim 8, wherein the copolymer further comprises an r1r2 reactivity ratio of 0.2 to 0.

8. Claim 14 An electronic device module according to claim 8, wherein at least one C3 to C20 comonomer is butene or octene or a combination thereof. Claim 15 As a method for manufacturing an electronic device module, The step of providing at least one electronic device, and The method includes the step of laminating an ethylene copolymer film on at least one surface of an electronic device, wherein the ethylene copolymer is At least 50 weight percent of ethylene-derived units; and The copolymer comprises at least 20 weight percent of at least one C3 to C20 comonomer, and the copolymer A melt index of 0.5 g / 10 min to about 50 g / 10 min when measured according to ASTM D1238 (190℃ / 2.16 kg); Density of approximately 0.856 g / cc to 0.890 g / cc when measured according to ASTM D792; At least 5x10 15 Volume resistivity at 23°C of Ωcm; and A method for manufacturing an electronic device module having 0.01 to 4.0 weight ppm of aluminum. Claim 16 An electronic device module according to claim 15, wherein the copolymer further comprises a first long-chain branching index (g'(Mz)) of 0.80 to 0.

93. Claim 17 An electronic device module according to claim 15, wherein the copolymer further comprises a second long-chain branching index (g'(Mz+1)) of 0.80 to 0.

93. Claim 18 An electronic device module according to claim 15, wherein the copolymer further comprises an average ratio of g'Mz+1 to g'(Mz) of 0.9 to 1.

0. Claim 19 An electronic device module according to claim 15, wherein the copolymer further comprises vinyl / total unsaturation of less than 0.7 and unsaturation levels of trisubstituted olefins of 50 to 500. Claim 20 An electronic device module according to claim 15, wherein the copolymer further comprises an r1r2 reactivity ratio of 0.2 to 0.

8. Claim 21 An electronic device module in paragraph 15, wherein the C3 to C20 comonomer is butene or octene or a combination thereof. Claim 22 A method for manufacturing an ethylene-based copolymer comprises the steps of polymerizing an ethylene-derived unit and at least one C3 to C20 comonomer in the presence of a catalyst system, and obtaining an ethylene-based copolymer polyolefin comprising at least 50 weight% of an ethylene-derived unit and at least 20 weight% of at least one C3 to C20 comonomer, wherein the copolymer A melt index of 0.5 g / 10 min to about 50 g / 10 min when measured according to ASTM D1238 (190℃ / 2.16 kg); Density of approximately 0.857 g / cc to 0.890 g / cc when measured according to ASTM D792; At least 5x10 15 Volume resistivity at 23°C of Ωcm; and A method for producing an ethylene-based copolymer having 0.01 to 4.0 weight ppm of aluminum. Claim 23 In paragraph 22, the catalyst system comprises at least one cross-linked metallocene and at least one ionic ammonium borate or phosphonium borate activator represented by the following formula: [cation] + [MQ4] - Here [MQ4] - is tetrakis(heptafluoronaphthyl) borate, and [cation] + A manufacturing method selected from the group consisting of the following: Claim 24 In Paragraph 22, [cation] + Is Phosphorus, manufacturing method. Claim 25 A method of manufacturing in paragraph 22, wherein at least one C3 to C20 comonomer is butene or octene or a combination thereof.

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