Ethylene copolymer for photovoltaic cells

Abstract

Ethylene copolymers, electronic device modules, and methods of making the same. The ethylene copolymers are at least 50 wt% ethylene-derived units and at least 20 wt% of at least one C3 to C20 comonomer. The copolymers also have a melt index of 0.5 g / 10 min to about 50 g / 10 min as measured according to ASTM D1238 (190°C / 2.16 kg); a density of about 0.856 g / cc to 0.890 g / cc as measured according to ASTM D792; a 23°C volume resistivity of at least 5 x 10 15 Ωcm; and 0.01 to 4.0 wt ppm aluminum.

Description

Technical Field

[0001] This application claims the benefit of U.S. Provisional Patent Application 63 / 612,454, filed December 20, 2023, entitled "Ethylene copolymer for photovoltaic cells," the entire contents of which are incorporated herein by reference.

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

[0003] Polyolefin plastomers, primarily copolymers of ethylene with butene or octene, are increasingly being used as polymeric encapsulants in photovoltaic (PV) cell applications. These polymers are replacing ethylene vinyl acetate (EVA) copolymers, with studies showing that plastomer-based encapsulant materials offer increased power generation over a 30-year lifespan compared to EVA. Compared to EVA films, plastomer films used as encapsulant materials exhibit higher barriers to potential-induced degradation (PID) and lower power degradation, both contributing to lower power loss. The release of acetic acid from EVA resins used in services and discoloration due to yellowing lead to increased power loss in EVA-based encapsulants.

[0004] Polymer film encapsulants for PV battery applications need to meet several functional properties. Electrical properties, expressed as high volume resistivity, are useful for low power loss. Good optical properties (typically measured by high transmittance at wavelengths from 280 to 1100 nm), enhanced moisture barrier properties, expressed as low water vapor transmission rate (WVTR), high crosslink density providing creep resistance, and good mechanical properties, expressed as tensile strength, flexural modulus, and tear strength, are also important. The challenge is how to achieve all these functional properties in a single polyolefin polymer.

[0005] Several patents disclose the application of plastogenic resins as encapsulant materials in PV batteries. For example, US 9,349,895 B2 and its corresponding document CN 103189996B describe ethylene α-olefin copolymers suitable as PV battery encapsulants, having a density in the range of 0.865 to 0.884 g / cc, a 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 its corresponding document CN101563786B describe PV battery devices having a polyolefin copolymer encapsulant and optional free radical initiators and additives, wherein the polyolefin copolymer encapsulant has a density of less than 0.9 g / cc, a melting point of less than 95°C, an α-olefin content of 15 to 50% by weight, and a minimum SCBDI of 50%. KR 101191126B1 describes an encapsulant sheet for solar cells, wherein the sheet comprises an ultra-low density ethylene α-olefin copolymer (0.850 to 0.890 g / cc), a low density ethylene α-olefin copolymer (0.890 to 0.920 g / cc), and a silane-grafted 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 below the first crystallization temperature of the resin.

[0006] US 8,329,848 B2 describes ethylene-butene copolymers having 0.06 to 1 / 1,000 C atoms of vinyl groups, a density of 0.850 to 0.910 g / cc, a MIR (I10 / I2.16) of <7.7, an MI of 0.1 to 25 dg / min, and an ethylene content of 80 to 95 mol%. US 10,774,205 B2 describes polymers with a multi-peak compositional distribution, each exhibiting a distinct crystalline peak in the TREF range of 40°C to 110°C.

[0007] However, there remains a need for new ethylene-based copolymers capable of producing films with excellent optical properties, good processability, moisture resistance, creep resistance, tensile strength, flexural modulus, and tear strength at wavelengths from 200 to 900 nm. Such films would be particularly well-suited to address the needs of PV battery applications. Summary of the Invention Invention Overview

[0009] This document provides an ethylene copolymer, an electronic device module, and methods for preparing both. The ethylene copolymer comprises at least 50 wt% ethylene-derived units and at least 20 wt% at least one C3 to C20 comonomer. The ethylene copolymer has a melt index of approximately 0.5 g / 10 min to approximately 50 g / 10 min as measured according to ASTM D1238 (190°C / 2.16 kg) and a density of approximately 0.856 g / cc to approximately 0.890 g / cc as measured according to ASTM D792; and a density of at least 5 × 10⁻⁶ g / cc. 15 The copolymer exhibits a volume resistivity of Ωcm at 23°C and contains 0.01 to 4.0 ppm of aluminum by weight. In some 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 less than 0.7 vinyl groups per total unsaturated moiety. In some embodiments, the unsaturated moiety level of the trisubstituted olefin is 50 to 500. Such ethylene copolymers can be prepared using metallocene and post-metallocene catalysts in solution polymerization methods, as further described herein.

[0010] In at least one embodiment, the electronic device module has 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% by weight of ethylene-derived units; and at least 20% by weight of at least one C3 to C20 comonomer, wherein the copolymer has: a melt index of about 0.5 g / 10min to about 50 g / 10min as measured according to ASTM D1238 (190°C / 2.16 kg); a density of about 0.856 g / cc to about 0.890 g / cc as measured according to ASTM D792; and at least 5 × 10⁻⁶ g / cc. 15 Volume resistivity at 23 °C in Ωcm; and aluminum content from 0.01 to 4.0 ppm by weight.

[0011] In at least one embodiment, a method of manufacturing an electronic device module includes providing at least one electronic device and laminating an ethylene copolymer film onto at least one surface of the electronic device. The ethylene copolymer comprises at least 50% by weight of ethylene-derived units; and at least 20% by 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 as measured according to ASTM D1238 (190°C / 2.16 kg); a density of about 0.856 g / cc to 0.890 g / cc as measured according to ASTM D792; and at least 5 × 10⁻⁶ g / cc. 15 Volume resistivity at 23 °C in Ωcm; and aluminum content from 0.01 to 4.0 ppm by weight.

[0012] In at least one other embodiment, the method comprises polymerizing ethylene-derived units 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 wt% ethylene-derived units and at least 20 wt% at least one C3 to C20 comonomer, wherein said copolymer has: a melt index of about 0.5 g / 10 min to about 50 g / 10 min as measured according to ASTM D1238 (190°C / 2.16 kg); a density of about 0.857 g / cc to about 0.890 g / cc as measured according to ASTM D792; and a density of at least 5 × 10⁻⁶ g / cc. 15 Volume resistivity at 23 °C in Ωcm; and aluminum content from 0.01 to 4.0 ppm by weight.

[0013] Surprisingly, these ethylene-based copolymers have been found to have significantly improved processing properties, low aluminum residue, and high volume resistivity (>5×10⁻⁶). 15 Ohm These copolymers (cm) can produce films with excellent optical properties, moisture resistance, and creep resistance at wavelengths from 200 nm to 900 nm, making them particularly suitable for electronic device modules, such as PV battery applications. Surprisingly, these ethylene-based copolymers were found to have less than 4 ppm, or less than 2 ppm, or less than 0.1 ppm of aluminum residue, or no aluminum residue at all, further enhancing their suitability for PV batteries and / or modules. Attached Figure Description

[0014] To gain a more detailed understanding of the features listed above, a more specific description of the invention can be obtained by referring to some of the embodiments shown in the accompanying drawings. However, it should be noted that the drawings are merely illustrative of typical embodiments of the invention and are therefore not intended to limit the scope of the invention, as the invention can be practiced in other equally effective embodiments.

[0015] The accompanying drawings illustrate the volume resistivity of a molded plate plotted relative to aluminum residue (ppmw) in resins 1-4 according to one or more embodiments provided herein (1 mm thick film, 500 V, 5-minute charging time). Invention Details

[0017] This invention provides ethylene copolymers capable of producing films with excellent optical properties (including moisture resistance, creep resistance, tensile strength, and tear strength) at wavelengths from 280 to 1,100 nm. The ethylene copolymers possess branching indices g'(Mz) and g'(Mz+1) measured by GPC-4D, as well as trisubstituted olefins and reactivity ratios (r1r2) determined by NMR, which are significantly different from other ethylene copolymers of similar density. Surprisingly, these ethylene copolymers provided herein also exhibit significantly improved processability and high volume resistivity (>10⁻⁶). 15 Ohm It was also surprisingly found that these ethylene-based copolymers have less than 4 ppm, or less than 2 ppm, or less than 0.1 ppm of aluminum residue, or no aluminum residue, making them particularly suitable for electronic device modules such as PV battery applications.

[0018] Without being bound by theory, it has been surprisingly discovered that these ethylene-based copolymers with little or no aluminum residue can be prepared using highly branched activators soluble in one or more aliphatic solvents. Preferably, the desired 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 some embodiments, the formula weight of the activator can be in the range of about 1310, 1250, or 1400 lower limit to about 1600, 1700, or 1950 g / mol upper limit.

[0019] It should be understood that the disclosure provided herein offers several exemplary embodiments for implementing different features, structures, and / or functions of the present invention. The exemplary embodiments describing components, arrangements, and configurations are intended to simplify the disclosure; however, these exemplary embodiments are provided by way of example only and are not intended to limit the scope of the invention. Furthermore, reference numerals and / or letters may be repeated in various exemplary embodiments and in the accompanying drawings provided herein. 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. Moreover, the exemplary embodiments provided herein can be combined in any way; that is, any element from one exemplary embodiment may be used in any other exemplary embodiment without departing from the scope of the disclosure.

[0020] Additionally, certain terms are used in the following description and claims to refer to specific components. As those skilled in the art will understand, various entities may refer to the same component by different names, and therefore, unless specifically defined herein, the naming conventions of the elements described herein are not intended to limit the scope of the invention. Furthermore, the naming conventions used herein are not intended to distinguish between components with different names but different functions.

[0021] In the following discussion and claims, the terms "comprising" and "including" are open-ended and should therefore be interpreted as meaning "including but not limited to". The phrase "consisting substantially of" means that the described / claimed composition does not contain any other component exceeding 5% of said properties that would substantially alter them, and in any case, does not contain any other component at a level greater than 3% by mass.

[0022] The term "or" is intended to cover both exclusive and inclusive cases, meaning that "A or B" is intended to be synonymous with "at least one of A and B" unless otherwise expressly stated herein.

[0023] The indefinite articles “a” and “an” refer to the singular form (i.e., “one”) and the plural indicator (i.e., one or more) unless the context clearly indicates otherwise. For example, embodiments using “olefin” include embodiments in which one, two or more olefins are used, unless otherwise stated or the context clearly indicates that only one olefin is used.

[0024] The terms "weight%" refer to weight percentage, "volume%" refer to volume percentage, "mol%" refer to molar percentage, "ppm" refer to parts per million, and "ppm wt" and "wppm" are used interchangeably and refer to parts per million by weight. Unless otherwise stated, all concentrations are expressed based on the total amount of the composition under discussion.

[0025] The term "polymer" refers to any two or more identical or different repeating units / monomer 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. The term "terpolymer" refers to a polymer having three different monomer units. The term "different" when referring to units means that the units differ from each other by at least one atom or are isomerically different. Similarly, the definition of polymer as used herein includes homopolymers, copolymers, and the like. For example, when a copolymer is said to have a "propylene" content of 10% to 30% by weight, it should be understood that the repeating units / monomer units, or simply units, in the copolymer are derived from propylene in the polymerization reaction, and the derived units are present in 10% to 30% by weight, based on the weight of the copolymer.

[0026] As used herein, "Mn" refers to the number-average molecular weight of the different polymers in the polymer material, "Mw" refers to the weight-average molecular weight of the different polymers in the polymer material, and "Mz" refers to the z-average molecular weight of the different polymers in the polymer material. The terms "molecular weight distribution" (MWD) and "polydispersity index" (PDI) are used interchangeably and refer to the ratio of Mw to Mn. Unless otherwise stated, all molecular weights (e.g., Mw, Mn, Mz) are reported in g / mol.

[0027] The nomenclature of the elements and their groups used in this article follows the periodic table used by the International Union of Pure and Applied Chemistry after 1988. An example of the periodic table is shown on the inside cover of the sixth edition of Advanced Inorganic Chemistry, edited by F. Albert Cotton et al. (John Wiley & Sons, Inc., 1999).

[0028] 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 lower ethylene content fraction can range from a lower limit of 55% by weight to an upper limit of 76% by weight. The ethylene content of the higher ethylene content fraction can range from a lower limit of 60% by weight to an upper limit of 90% by weight. The ethylene content of the total polymer can range from a lower limit of 60% by weight to an upper limit of 85% by weight.

[0029] Ethylene copolymers can have a melt index of approximately 0.5 g / 10 min to approximately 50 g / 10 min, as measured according to ASTM D1238 (190°C / 2.16 kg). The melt index can also range from a lower limit of approximately 0.5, 1.0, or 2.0 to an upper limit of approximately 30, 40, or 50 g / 10 min. Alternatively, the melt index can also range from a lower limit of approximately 0.5, 3.0, or 5.0 to an upper limit of approximately 20, 35, or 45 g / 10 min.

[0030] Ethylene copolymers can have densities ranging from 0.850 g / cc to 0.920 g / cc as measured according to ASTM D792, indicating that they can act as plastics with combined qualities of elastomers and polymers. Ethylene copolymers can also have densities ranging from about 0.860 g / cc to 0.880 g / cc. Densities can range from a lower limit of about 0.850, 0.855, 0.860, 0.865, or 0.870 to an upper limit of about 0.874, 0.876, 0.880, 0.900, or 0.920 g / cc.

[0031] Ethylene copolymers can have 5×10 15 Ωcm or greater volume resistivity at 23°C.

[0032] Ethylene copolymers can have a ratio of g'Mz+1 to g'-average value of 0.9 to 1.0. This ratio is also within the range of a lower limit of 0.91, 0.92 or 0.93 to an upper limit of 0.97, 0.98 or 0.99.

[0033] The ethylene copolymer may have less than 0.7 vinyl / total unsaturated fractions as estimated by H-NMR. The vinyl / total unsaturated fraction may range from a lower limit of about 0.01, 0.02, or 0.03 to an upper limit of about 0.5, 0.6, or 0.7. The vinyl / total unsaturated fraction may also range from a lower limit of about 0.1, 0.2, or 0.3 to an upper limit of about 0.5, 0.6, or 0.7.

[0034] Ethylene copolymers can have an unsaturated moiety of 50 to 500 of trisubstituted olefins as determined by H-NMR. The unsaturated moiety of the trisubstituted olefins can also be in the range of a lower limit of about 50, 80, or 100 to an upper limit of about 300, 400, or 500. The unsaturated moiety of the trisubstituted olefins can also be in the range of about 60 to 480; 80 to 420; or 100 to 300.

[0035] Ethylene copolymers can have a reaction reactivity ratio of 0.8 or lower. The reaction reactivity ratio can also be in the range of 0.2 to 0.8. The reaction reactivity ratio can also be in the range of the lower limit of 0.2, 0.3, or 0.35 to the upper limit of 0.5, 0.65, or 0.8. The reaction reactivity ratio can also be 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, or 0.8.

[0036] Aggregation methods

[0037] Ethylene copolymers can be prepared using solution polymerization. Preferably, solution polymerization is a bulk polymerization method, which refers to a polymerization method in which the monomers and / or comonomers undergoing polymerization are used as solvents or diluents, and little or no inert solvents are used as liquids or diluents. A small portion of the inert solvent may be used as a carrier for catalysts and scavengers.

[0038] The term "solution polymerization" refers to a polymerization method in which a polymer is dissolved in a liquid polymerization medium such as an inert solvent, monomer (one or more), or blend thereof. Solution polymerization is typically homogeneous, meaning that the polymer product is dissolved in the polymerization medium. Such a system is preferably not turbid, as described in J. Vladimir Oliveira, C. Dariva, and JCPinto, Ind. Eng, Chem. Res., 29, 2000, 4627. Homogeneous polymerization methods are generally methods in which at least 90% by weight of the product is soluble in the reaction medium.

[0039] Suitable solution polymerization methods for preparing the polymer blend compositions disclosed herein are generally described in more detail in U.S. Patent Nos. 9,359,535, 7,470,118, 7,226,553; and 7,033,152, which are incorporated herein by reference in their entirety. WO 2017 / 058385 A1 describes a solution polymerization method for the continuous polymerization of C2 to C40 olefins using a single or multiple spiral heat exchanger system, which may also be used and is also incorporated herein by reference in its entirety.

[0040] Ethylene copolymers can exhibit low levels of long-chain branching (LCB). Specifically, the ethylene copolymer can have a first long-chain branching index (g'(Mz)) of 0.30 to 1.00, preferably 0.70 to 0.97. The first long-chain branching index (g'(Mz)) can also be in the range of 0.80 to 0.93. The first long-chain branching index (g'(Mz)) can also be in the range of a lower limit of 0.80, 0.82, or 0.85 to an upper limit of 0.90, 0.92, or 0.93. The first long-chain branching index (g'(Mz)) can also be 0.80, 0.81, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88, 0.89, 0.90, 0.91, 0.92, or 0.93.

[0041] 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 also be in the range of 0.80 to 0.93. The second long-chain branching index (g'(Mz+1)) may also be in the range of a lower limit of 0.80, 0.82, or 0.85 to an upper limit of 0.90, 0.92, or 0.93. The second long-chain branching index (g'(Mz+1)) may also be 0.80, 0.81, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88, 0.89, 0.90, 0.91, 0.92, or 0.93.

[0042] The ethylene copolymers described herein can be used in a variety of end-use applications. They are particularly suitable for manufacturing solar 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. Solar cell modules typically have one or more cells made of silicon, gallium-arsenic, and copper-iridium-selenium, with a top transparent protective material and a bottom protective substrate material, wherein the solar cells and protective material are secured using an encapsulation material. The ethylene copolymers described herein can be used as the top protective material, the bottom protective material, or both. The ethylene copolymers can provide films with excellent flexibility, transparency, and heat resistance, making them particularly suitable for PV modules.

[0043] Such PV modules typically utilize electronics in combination with one or more substrates that provide protection and / or support for their manufacture, transport, and use. For example, these types of devices are often positioned behind one or more glass coverslips and / or between two substrates, one or both of which are made of glass, metal, plastic, rubber, or other materials. In these cases, ethylene copolymers can be used as encapsulants or sealants for devices within the module, or, depending on the module's design, directly as a cover or surface layer, such as the backskin layer in a solar cell module.

[0044] Ethylene copolymers can have any two or more unique combinations of the following properties:

[0045] a.>5×10 15 Volume resistivity at 23℃ in Ωcm;

[0046] b. For g'Mz+1(branched) < 0.93, the average value of g'Mz+1 / g'- is < 1;

[0047] c. For g'Mz(branching) < 0.93 and g'Mz+1(branching) < 0.93, significantly higher trisubstituted olefins;

[0048] d. For g'Mz < 0.94, < 0.2 vinyl groups / total unsaturated fraction;

[0049] e. For any g'Mz < 0.94, the reaction reactivity ratio 0.7; and / or

[0050] f. Lower r1r2 values ​​than the control copolymer (mostly >1 and at most ~1.5)

[0051] Another unique aspect of the ethylene copolymers presented in this article is the aluminum residue, attributable to the activators and scavengers used. It has been surprisingly found that ethylene copolymers with the aforementioned combination of properties can have aluminum residues of less than 4 ppm, or less than 2 ppm, or less than 1 ppm, or less than 0.5 ppm, or less than 0.2 ppm, or less than 0.1 ppm, or less than 0.01 ppm, or no aluminum residues at all, making these ethylene copolymers particularly suitable for PV cells and / or modules. These unique properties distinguish these ethylene copolymers from other comparative ethylene copolymers.

[0052] Comonomer

[0053] 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 strained or unstrained, monocyclic or polycyclic, and may optionally contain heteroatoms and / or one or more functional groups. The reactor C2 concentration may range from 0.1 to 40.0 wt%, while the reactor comonomer concentration may range from 0.1 to 40.0 wt%.

[0054] Specific examples of comonomers include butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, their substituted derivatives and isomers, preferably hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene and their respective homologues and derivatives, preferably norbornene, norbornadiene and dicyclopentadiene.

[0055] catalyst system

[0056] For the purposes of this disclosure, a "catalyst system" is a combination of at least one catalyst compound, an activator, and optionally a support material. A catalyst system may further include one or more additional catalyst compounds. For the purposes of this disclosure, when a catalyst system is described as comprising a neutral, stable form of a component, those skilled in the art will understand that the ionic form of said component is the form in which it reacts with the monomer to produce a polymer. In addition to the neutral form of the compound, the catalysts and activators of this disclosure are intended to cover ionic forms.

[0057] Suitable catalyst systems for manufacturing the ethylene copolymers provided herein may comprise one or more bridged metallocene compounds represented by the formula: CpA(T)CpBM'X'n, wherein each CpA and CpB is independently selected from a cyclopentadienyl ligand (e.g., Cp, Ind, or Flu) and a ligand isomorphic to the cyclopentadienyl group, wherein one or both of CpA and CpB may contain heteroatoms, and one or both of CpA and CpB may be substituted with one or more R' groups; M' is selected from Groups 3 to 12 and lanthanides, preferably Group 4; X ' is an anion leaving group; n is 0 or an integer from 1 to 4; (T) is a bridging group selected from the following: divalent alkyl, divalent substituted alkyl, divalent heteroalkyl, divalent alkenyl, divalent substituted alkenyl, divalent heteroalkenyl, divalent alkynyl, divalent aryloxy, divalent alkyl sulfide, divalent aryl sulfide, divalent aryl, divalent substituted aryl, divalent heteroaryl, divalent arylalkyl, divalent arylenealkyl, divalent alkylaryl, divalent arylenealkyl, divalent haloalkyl, divalent haloalkenyl, divalent haloalkynyl, divalent heteroalkyl, divalent heterocyclic, divalent heteroaryl, mono- or divalent heteroatom-containing group, divalent hydrocarbon group. Divalent substituted hydrocarbon groups, divalent heteroalkyl groups, divalent silyl groups, divalent boron groups, divalent phosphin groups, divalent phosphine groups, divalent amino groups, divalent amine groups, divalent ether groups, and divalent thioether groups. R" is selected from alkyl groups, substituted alkyl groups, heteroalkyl groups, alkenyl groups, substituted alkenyl groups, heteroalkenyl groups, alkynyl groups, aryloxy groups, alkyl thioses, aryl thioses, aryl groups, substituted aryl groups, heteroaryl groups, aralkyl groups, arylene alkyl groups, alkylaryl groups, alkylene aryl groups, alkylene aryl groups, haloalkyl groups, haloalkenyl groups, haloalkynyl groups, heteroalkyl groups, heterocyclic groups, heteroaryl groups, heteroatom-containing groups, hydrocarbon groups, substituted hydrocarbon groups, heteroalkyl groups, silyl groups, boron groups, phosphin groups, phosphine groups, amino groups, amine groups, germanium groups, ethers, and thioethers.

[0058] In at least one embodiment, each of CpA and CpB is independently selected from: cyclopentadienyl, indene, fluorenyl, cyclopentadienylphenanthrene, benzo[a]indene, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentocyclododecene, phenanthreneindene, 3,4-benzo[a]fluorenyl, 9-phenylfluorenyl, 8-H-cyclopenta[a]acenaphthel, 7-H-dibenzo[a]fluorenyl, indene[1,2-9]anthracene, thieno[a]indene, thieno[a]fluorenyl, their hydrogenated and substituted forms, preferably cyclopentadienyl, n-propylcyclopentadienyl, indene, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, and n-butylcyclopentadienyl. Each CpA and CpB may independently be indene or tetrahydroindene. Particularly suitable cyclopentadienyl-based complexes are described in WO2000 / 024793, which is incorporated herein by reference.

[0059] Activator

[0060] Bridged metallocene compounds can be activated for polymerization catalysis in any manner sufficient to allow coordination or cationic polymerization. This can be achieved for coordination polymerization when one ligand can be extracted and another will allow insertion into an unsaturated monomer, or similarly extractable to be replaced by a ligand that allows insertion into an unsaturated monomer (an unstable ligand) (e.g., alkyl, silyl, or hydride). Suitable activators used herein, compared to conventional activator compounds, include ammonium or... The activator is formulated with groups to improve its solubility in aliphatic solvents. Suitable activators used herein can further provide polyolefins having a weight-average molecular weight (Mw) of about 100,000 g / mol or greater and a melt temperature (Tm) of about 110 °C or greater. Furthermore, activators having cations containing at least one methyl group and optionally at least one C10 to C50 linear alkyl group can provide enhanced activity for polymer production.

[0061] This disclosure provides activators, such as ammonium or Metallide or quasi-metal activator compounds comprising an ammonium or... Group. When the activator of this disclosure is used together with a catalyst compound (such as a Group 4 metallocene compound) for olefin polymerization, polymers with higher molecular weights and melting temperatures than polymers formed using a comparative activator can be formed. Similarly, when the activator of this disclosure (where R1 is methyl) is used together with a Group 4 metallocene catalyst for olefin polymerization, the catalyst system activity is significantly superior to that of the comparative activator, and polymers with higher molecular weights and / or melting temperatures (relative to polymers formed using the comparative activator) can be formed.

[0062] The present invention further relates to activator compounds represented by formula (AI):

[0063] [R 1 R 2 R 3 EH] d + [Mk+Qn]d- (AI)

[0064] Wherein: E is nitrogen or phosphorus, preferably nitrogen;

[0065] 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); nk = d (preferably d is 1, 2 or 3; k is 3; n is 4, 5 or 6, preferably n is 4 when M is B);

[0066] R 1 It is an optional substitution of C1-C 20 (or C1 to C)10 (or C1-C6, or C1-C4, or C1-C2, or C1) linear alkyl groups;

[0067] R 2 and R 3 Each of them is independently an optional substituted C1-C 40 Linear alkyl groups (e.g., C6 to C6) 40 Linear alkyl 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 optionally substituted C1 to C1. 40 Hydrocarbon groups (e.g., C6 to C5) 40 Aryl or linear alkyl, C 12 To C 30 aryl or linear alkyl or C 10 To C 20 Aryl or linear alkyl), optionally substituted alkoxy, optionally substituted silyl, halogen (Br, Cl, I, F, etc.) or halogen-containing groups (e.g., bromoalkyl or bromoaryl),

[0068] Where R 1 R 2 and R 3 Together they contain 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, e.g., 15 to 100 carbon atoms, e.g., 25 to 75 carbon atoms);

[0069] M is an element selected from Group 13 of the periodic table, preferably boron or aluminum; and

[0070] Each Q is independently a hydrogen group, a bridged or unbridged dialkylamido, a halide, an alkoxide, an aryloxide, a hydrocarbon group, a substituted hydrocarbon group, a halocarbyl group, a substituted halocarbyl group, or a halosubstituted-hydrocarbyl radical, provided that R is a fluorophenyl group. 2 Not C1-C 40 Linear alkyl groups, preferably R 2 C1-C is not an optional substitute 40 Linear alkyl (or R when Q is a substituted phenyl) 2 Not C1-C 40 Linear alkyl groups, preferably R2 C1-C is not an optional substitute 40 Linear alkyl). Preferably, when Q is a fluorophenyl (or when Q is a substituted phenyl), then R 2 A phenyl group that is meta- and / or para-substituted, wherein the meta- and para-substituents are independently optional C1 to C1 substituents. 40 Hydrocarbon groups (e.g., C6 to C5) 40 Aryl or linear alkyl, C 12 To C 30 aryl or linear alkyl or C 10 To C 20 Aryl or linear alkyl), optionally substituted alkoxy or optionally substituted silyl. Preferably, each Q is a fluorinated hydrocarbon group containing 1 to 30 carbon atoms, more preferably, each Q is a fluorinated aryl (e.g., phenyl or naphthyl), and most preferably, each Q is a perfluorinated aryl (e.g., phenyl or naphthyl). Suitable [M k+ Q n ] d- Examples also include diboron compounds such as those 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 group, and more preferably, all Q are not substituted phenyl groups. Preferably, at least one Q is not a perfluorophenyl group, and more preferably, all Q are not perfluorophenyl groups.

[0071] In some embodiments of the present invention, R 1 Not methyl, R 2 Not C 18 Alkyl and R 3 Not C 18 Alkyl, or R 1 Not methyl, R 2 Not C 18 Alkyl and R 3 Not C 18 Alkyl group and at least one Q is not a substituted phenyl group, preferably all Q are not substituted phenyl groups.

[0072] In the embodiments, the meta and para substituents are independently optional linear alkyl groups (e.g., n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, n-heptadecyl, n-octadecyl, n-nonadecanyl, n-eicosyl, n-undecanyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecanyl, or n-triadecyl), or optional silyl groups, such as trialkylsilyl, wherein each alkyl group is independently optional C1 to C2. 20Alkyl groups (e.g., trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triheptylsilyl, trioctylsilyl, trinonylsilyl, tridecylsilyl, tri(undecyl)silyl, tri(dodecyl)silyl, tri(tridecyl)silyl, tri(tetradecyl)silyl, tri(pentadecanyl)silyl, tri(hexadecyl)silyl, tri(heptadecyl)silyl, tri(octadecyl)silyl, tri(nonadecanyl)silyl, tri(eicosyl)silyl) or optionally substituted alkoxy groups (e.g., -OR) , where R C1 to C are optional replacements 20 Alkyl or aryl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, phenyl, phenylalkyl (e.g., methylphenyl, propylphenyl, etc.), naphthyl or anthracene), halogen (e.g., Br or Cl) or halogen-containing groups (e.g., bromomethyl, bromophenyl, etc.).

[0073] In some embodiments, the meta-substituted phenyl group 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-pentadecaylphenyl, n-hexadecylphenyl, n-heptadecylphenyl, n-octadecylphenyl, n-nonadecaylphenyl, n-eicosylphenyl, n-timosylphenyl, n-timosylphenyl, n-timosylphenyl, n-timosylphenyl, n-timosylphenyl, n-timosylphenyl, n-timosylphenyl, n-timosylphenyl, n-timosylphenyl, n-timosylphenyl, n-timosylphenyl, n-timosylphenyl, dimethylphenyl, diethylphenyl, di-n-propylphenyl, di- -n-Butylphenyl, di-n-pentylphenyl, di-n-hexylphenyl, di-n-heptylphenyl, di-n-octylphenyl, di-n-nonylphenyl, di-n-decylphenyl, di-undecylphenyl, di-n-dodecylphenyl, di-n-tetratephenyl, di-n-tetradecylphenyl, di-n-pentadedecylphenyl, di-n-hexadecylphenyl, di-n-heptadecylphenyl, di-n-octadecylphenyl, di-n-nonadedecylphenyl, di-eicosylphenyl, di-eicosylphenyl, di-eicosylphenyl, di-eicosylphenyl, di-eicosylphenyl, di-eicosylphenyl, di-eicosylphenyl, di-eicosylphenyl, di-eicosylphenyl, di-eicosylphenyl, and di-eicosylphenyl. The two meta-substituents can be the same or different.

[0074] In the implementation scheme, the para-substituted phenyl group 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-pentadecaylphenyl, n-hexadecylphenyl, n-heptadecylphenyl, n-octadecylphenyl, n-nonadecaylphenyl, n-eicosylphenyl, n-timosylphenyl, n-timosylphenyl, n-timosylphenyl, n-tridecylphenyl, n-tetradecylphenyl, n-pentadecaylphenyl, n-timosylphenyl, n-heptadecylphenyl, n-octadecylphenyl, n-nonadecaylphenyl, or n-triadecylphenyl.

[0075] In the embodiments, meta- and / or para-substituted phenyl groups are represented by the following formula:

[0076] ,

[0077] Where R 17 and R 21 It is hydrogen, and R 18 R 19 and R 20 Each of them is independently selected from hydrogen, C1-C 40 Hydrocarbon group or C1-C 40 Substituted hydrocarbon group, halogen or halogen-containing group (provided R is present) 18 R 19 and R 20 At least one of them is not H, or R 18 R 19 and R 20 At least two of them are not H, or R. 18 R 19 and R 20 All three of them are not H), or combinations thereof.

[0078] Preferably, R 17 and R 21 It is hydrogen, and R 18 R 19 and R 20 Each of them is selected from hydrogen, C1 to C2. 40 Linear alkyl or C1-C 40 Substituted linear alkyl (condition is R) 18 R 19 and R 20 At least one of them is not H, or R 18 R 19 and R 20 At least two of them are not H, or R. 18 R 19 and R20 All three of them are not H).

[0079] Preferably, R 17 and R 21 It is H, and R 18 R 19 and R 20 One, two, or three of the following are selected from 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-pentadecanyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecanyl, n-eicosyl, n-titanyl, n-pentadecanyl, n-hexadecyl, n-octadecyl, n-nonadecanyl, or n-triadecyl), or optionally substituted trialkylsilyl groups, wherein each alkyl group is independently C1 to C2. 20 Optionally substituted alkyl groups (e.g., trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triheptylsilyl, trioctylsilyl, trinonylsilyl, tridecylsilyl, triundecylsilyl, tridodecylsilyl, tridecylsilyl, tritetradecylsilyl, tridecylsilyl, tridecylsilyl, tridecylsilyl, tridecylsilyl, tridecylsilyl, tridecylsilyl, trihexadecylsilyl, triheptylsilyl, trioctadecylsilyl, tridecylsilyl, trieicosylsilyl), halogens (e.g., Br, Cl, or F), or optionally substituted alkoxy groups (e.g., -OR) , where R C1 to C 20 Optional substituted alkyl or aryl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, 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 R 18 R 19 and R 20 At least two of them are not H, or R. 18 R 19 and R 20 All three of them are not H).

[0080] In the implementation plan, R 1 For methyl, R 2 C1 to C 40 Linear alkyl groups (e.g., C6 to C6)40 Linear alkyl, or C 10 To C 30 Linear alkyl), and R 3 It is a para-substituted phenyl group, wherein the para-substituent is independently an optional C1 to C2 substituent. 40 Hydrocarbon groups (e.g., C6 to C5) 40 Aryl or linear alkyl, C 12 To C 30 aryl or linear alkyl or C 10 To C 20 (aryl or linear alkyl), optionally substituted alkoxy, optionally substituted silyl, halogen or halogen-containing groups.

[0081] In the implementation plan, R 1 It is methyl, R 2 It is n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecanyl, or n-eicosyl, and R 3 It 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-pentadecanylphenyl, n-hexadecylphenyl, n-heptadecylphenyl, n-octadecylphenyl, n-nonadecanylphenyl, or n-eicosylphenyl.

[0082] In any implementation of the activator formulation described herein, each R 2 and / or R 3 Can be independently and optionally subjected to halogens, C1-C 50 Alkyl, C5-C 50 Aryl, C6-C 35 Arylalkyl or C6-C 35 At least one of the alkyl aryl groups is substituted, provided that the substituted R is... 2 and R 3 The group is not a branched alkyl group (as defined above).

[0083] In at least one embodiment of the present invention, the activator is an ionic ammonium borate or boric acid represented by formula (I). :

[0084] [R 1 R 2 R 3 EH] + [BR 4 R 5 R 6 R 7 ]- (I)

[0085] in:

[0086] E is nitrogen or phosphorus;

[0087] R 1 It is C1-C 40 Linear alkyl,

[0088] R 2 and R 3 Each of them is independently C1-C 40 Linear alkyl, C5-C 22 Aryl, C5 to C 50 arylalkyl groups, 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 is a 5, 6, or 7-membered heterocyclic group containing at least one atom selected from N, P, O, and S, wherein R 1 R 2 and R 3 Each of them is optionally replaced by a halogen, wherein R 2 Optional with R 5 Bonding to independently form 5, 6, or 7-membered rings, preferably R 1 R 2 and R 3 Together they contain 15 or more carbon atoms, such as 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 40 or more carbon atoms, and R 4 R 5 R 6 and R 7 Each of these is independently a fluorinated hydrocarbon group having 1 to 30 carbon atoms, more preferably R. 4 R 5 R 6 and R 7 Each of them is independently a fluorinated aryl (e.g., phenyl or naphthyl) group, and most preferably R 4 R 5 R 6 and R 7 Each of these is independently a perfluorinated aryl (e.g., phenyl or naphthyl) group, wherein R 4 R 5 R 6 and R 7 At least one of them is substituted by one to seven fluorine atoms, preferably R 4 R 5 R 6 and R7 At least one of them is not a substituted phenyl group, preferably R 4 R 5 R 6 and R 7 None of them are substituted phenyl groups.

[0089] In the preferred embodiment, R 1 Not methyl, R 2 Not C 18 And R 3 Not C 18 In a preferred embodiment, R 1 Not methyl, R 2 Not C 18 And R 3 Not C 18 And R 4 R 5 R 6 and R 7 At least one of them is not a substituted phenyl group, preferably R 4 R 5 R 6 and R 7 None of the phenyl groups are substituted.

[0090] The present invention also relates to activator compounds represented by the following formula (I):

[0091] [R 1 R 2 R 3 EH] + [BR 4 R 5 R 6 R 7 ] - (I)

[0092] Where: E is nitrogen or phosphorus;

[0093] R 1 R 2 and R 3 Each of them is independently C1-C 40 Linear alkyl, C5-C 50 Aryl, wherein R 1 R 2 and R 3 Each of them is independently unsubstituted or unused by halogens, C1-C 50 Alkyl, C5-C 50 Aryl, C6-C 35 Arylalkyl or C6-C 35 At least one substitution of alkyl aryl groups, wherein R 1 R2 and R 3 Together they contain 15 or more carbon atoms, such as 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 40 or more carbon atoms, and R 4 R 5 R 6 and R 7 Each of them is a naphthyl group, where R 4 R 5 R 6 and R 7 At least one of them is replaced by 1 to 7 fluorine atoms.

[0094] In a preferred aspect, the activator is ammonium borate ion represented by the following formula (I):

[0095] [R 1 R 2 R 3 EH] + [BR 4 R 5 R 6 R 7 ] - (I)

[0096] in:

[0097] E is nitrogen or phosphorus;

[0098] R 1 It is methyl;

[0099] R 2 It is optionally covered by halogens, C1-C 35 Alkyl, C5-C 15 Aryl, C6-C 35 Arylalkyl and C6-C 35 At least one substituted C6-C of the alkyl aryl group 50 Aryl;

[0100] R 3 It is C1-C 40 Linear alkyl or C5-C 42 -aryl, which is optionally halogenated, C1-C 35 Alkyl, C5-C 15 Aryl, C6-C 35 Arylalkyl and C6-C 35 At least one substitution of alkyl aryl groups, wherein R 2 Optional with R 3 Bonding can independently form pentagonal, hexagramal, or heptagonal rings, and R2 and R 3 Together they contain 20 or more carbon atoms, such as 21 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 40 or more carbon atoms.

[0101] R 4 R 5 R 6 and R 7 Each of them is independently a naphthyl or a substituted naphthyl group, where R 4 R 5 R 6 and R 7 At least one of them is a naphthyl group substituted with 1 to 7 fluorine atoms.

[0102] In any implementation of formula (I) or (AI), R 2 It is an unsubstituted phenyl or a substituted phenyl. In at least one embodiment, R 2 It is phenyl, methylphenyl, n-butylphenyl, n-octadecylphenyl or its isomers, preferably R. 2 It is a meta- or para-substituted phenyl group, such as a meta- or para-substituted alkyl-substituted phenyl group. In at least one embodiment, R 3 Independently selected from C1 to C 30 Linear alkyl groups, 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-pentadecanyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecanyl, and n-eicosyl.

[0103] In either embodiment of formula (I) or (AI), R 4 R 5 R 6 and R 7 Each of them is independently a naphthyl group, where R 4 R 5 R 6 and R 7 At least one of them is a naphthyl group substituted with one, two, three, four, five, six or seven fluorine atoms.

[0104] In any embodiment of formula (I) or (AI), at least one R is preferred. 4 R 5 R 6 and R 7 Not a substituted phenyl group, R is preferred. 4 R 5 R6 and R 7 All are non-substituted phenyl groups. In a preferred embodiment, R 1 Not methyl, R 2 Not C 18 And R 3 Not C 18 .

[0105] In any implementation of formula (I) or (AI), it is preferred that all Q or all R 4 R 5 R 6 and R 7 Not perfluoroaryl, such as perfluorophenyl.

[0106] In either embodiment of formula (I) or (AI), R 4 R 5 R 6 and R 7 All of them are naphthyl groups, of which R 4 R 5 R 6 and R 7 At least one, two, three, or four of them are replaced by one, two, three, four, five, six, or seven fluorine atoms.

[0107] In any of the embodiments described herein, R is preferred. 4 R 5 R 6 and R 7 Each of the groups is independently a naphthyl group containing one, two, three, four, five, six, or seven fluorine atoms, preferably seven fluorine atoms.

[0108] In at least one implementation, R 4 It is independently a naphthyl group containing one, two, three, four, five, six, or seven fluorine atoms.

[0109] In any of the implementations described herein, R 4 R 5 R 6 and R 7 Each of these is independently a fluorinated hydrocarbon group having 1 to 30 carbon atoms, more preferably R. 4 R 5 R 6 and R 7 Each of the groups is independently a fluorinated aryl group (e.g., phenyl, biphenyl, [(C6H3(C6H5)2)4B] or naphthyl) group, most preferably R. 4 R 5R 6 and R 7 Each of these groups is independently a perfluorinated aryl group (e.g., biphenyl, [(C6H3(C6H5)2)4B] or naphthyl) group, preferably R. 4 R 5 R 6 and R 7 At least one of them is not a perfluorophenyl.

[0110] In any embodiment of the invention, when Q is a fluorophenyl, then R 2 C1-C is not an optional substitute 20 Linear alkyl group.

[0111] In at least one embodiment, the activator is ammonium borate ion represented by the following formula (I):

[0112] [R 1 R 2 R 3 EH] + [BR 4 R 5 R 6 R 7 ] - (I)

[0113] in:

[0114] E is nitrogen or phosphorus;

[0115] R 1 R 2 and R 3 Each of them is independently C1-C 40 Linear alkyl, C5-C 22 Aryl, 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 heterocyclic group comprising at least one atom selected from N, P, O and S, wherein R 1 R 2 and R 3 Each of these can optionally be halogenated, -NR'2, -OR', or -SiR'3 (where R' is independently hydrogen or C1-C). 20 Hydrocarbon group) substitution, wherein R 2 Optional with R 5 Bonding can independently form 5, 6, or 7-membered rings. R 1 R 2 and R 3Together, they contain 15 or more carbon atoms, such as 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 40 or more carbon atoms. In at least one embodiment, R 1 and R 2 Independently for C1-C 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 of them 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-pentadecanyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecanyl, and n-eicosyl.

[0116] In at least one implementation, R 4 R 5 R 6 and R 7 Each of them is independently aryl or naphthyl, wherein R 4 R 5 R 6 and R 7 At least one of them is a naphthyl group substituted with 1 to 7 fluorine atoms. In at least one embodiment, R 4 R 5 R 6 and R 7 Each of them is a naphthyl group, where R 4 R 5 R 6 and R 7 At least one of them is replaced by 1 to 7 fluorine atoms.

[0117] In at least one implementation, R 4 R 5 R 6 and R 7 Each of them is independently a naphthyl group containing one, two, three, four, five, six, or seven fluorine atoms.

[0118] In at least one implementation, R 4 Independently, it is a naphthyl group containing one, two, three, four, five, six, or seven fluorine atoms, and R 5 R6 and R 7 Each of them is independently a phenyl group containing one, two, three, four, or five fluorine atoms, or a naphthyl group containing one, two, three, four, five, six, or seven fluorine atoms.

[0119] In at least one embodiment of the present invention, the activator is represented by the following formula (I) or (AI):

[0120] [R 1 R 2 R 3 EH] + [BR 4 R 5 R 6 R 7 ] - (I)

[0121] [R 1 R 2 R 3 EH] d + [Mk+Qn]d- (AI)

[0122] in:

[0123] M is a group 13 atom, preferably B or Al;

[0124] 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), nk=d (preferably d is 1, 2 or 3; k is 3; n is 4, 5 or 6, preferably n is 4 when M is B);

[0125] E is either nitrogen or phosphorus, with nitrogen being preferred;

[0126] R 1 R 2 and R 3 Each of them is independently C1-C 40 Linear alkyl, C5-C 22 Aryl, C7 to C 30 An arylalkyl group (wherein the alkyl group has 1 to 10 carbon atoms and the aryl group has 6 to 20 carbon atoms) or a five-, six-, or seven-membered heterocyclic group comprising at least one atom selected from N, P, O, and S, wherein R 1 R 2 and R 3 Each of them is optionally replaced by a halogen, wherein R 2 Optional with R 5 Bonding to independently form pentagonal, hexagramal, or heptagonal rings, preferably R. 1R 2 and R 3 Together, they contain 15 or more carbon atoms, such as 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 38 or more carbon atoms, such as 40 or more carbon atoms. In at least one embodiment, R 1 and R 2 Independently for C1-C 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 of the following 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-pentadecanyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecanyl, and n-eicosyl);

[0127] R 4 R 5 R 6 and R 7 Each of them is independently a naphthyl group, where R 4 R 5 R 6 and R 7 At least one of them is a naphthyl group 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 group, preferably R 4 R 5 R 6 and R 7 All non-substituted phenyl groups; and

[0128] Each Q is independently a hydrogen group, a bridged or unbridged dialkylamide, a halogen group, an alkoxy group, an aryloxy group, a substituted alkyl group, a halocarbon group, a substituted halocarbon group, or a halosubstituted alkyl group. Preferably, each Q is a fluorinated alkyl group containing 1 to 30 carbon atoms; more preferably, each Q is a fluorinated aryl group (e.g., phenyl or naphthyl); and most preferably, each Q is a perfluorinated aryl group (e.g., phenyl or naphthyl). In a preferred embodiment of the invention, at least one Q is not a substituted phenyl group, such as a perfluorophenyl group, and preferably all Q are not substituted phenyl groups, such as perfluorophenyl groups.

[0129] The terms “co-catalyst” and “activator” are used interchangeably herein and are defined as any compound capable of activating any of the catalyst compounds disclosed herein by converting a neutral catalyst compound into a catalytically active catalyst compound cation.

[0130] The catalyst systems disclosed herein can be formed by combining catalysts with activators in any suitable manner, including by loading them for use in slurry or gas-phase polymerization. The catalyst systems can also be added to or generated in solution polymerization or bulk polymerization (in monomers, i.e., with little to no solvent).

[0131] The cation portion and its anion portion (which is NCA) of formulas (A1) and (I) will be further described below. Any combination of the cation and NCA disclosed herein is applicable to the methods of this disclosure and is therefore incorporated herein.

[0132] cationic components

[0133] The cationic components of the activators described herein (e.g., those of formulas (AI) and (I) above) are protonated Lewis bases capable of protonating structural moieties (e.g., alkyl or aryl) derived from transition metal compounds. Thus, upon release of a neutral leaving group (e.g., an alkane resulting from a combination of a proton provided by the cationic component of the activator and an alkyl substituent of the transition metal compound), a transition metal cation, which is catalytically active, is generated.

[0134] In at least one embodiment of formula (I) or (AI), when the cation is [R 1 R 2 R 3 EH] + When E is nitrogen or phosphorus, R 1 R 2 and R 3 Each of them is independently C1-C 40 Linear alkyl, C5-C 22 - aryl, arylalkyl (wherein the alkyl group has 1 to 10 carbon atoms and the aryl group has 6 to 20 carbon atoms) or a five-, six-, or seven-membered heterocyclic group containing at least one atom selected from N, P, O, and S, wherein R 1 R 2 and R 3 Each of these can optionally be halogenated, -NR'2, -OR', or -SiR'3 (where each R' is independently hydrogen or C1-C). 20 Hydrocarbon group) substitution, wherein R 2 Optional with R 5 Bonding can independently form pentagonal, hexagramal, or heptagonal rings. R 1 R 2 and R 3Together, they contain 15 or more carbon atoms, such as 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 37 or more carbon atoms, such as 40 or more carbon atoms, such as 45 or more carbon atoms. In at least one embodiment, R 1 R 2 and R 3 Independently substituted or unsubstituted C1-C 22 Linear alkyl or substituted or unsubstituted phenyl. In at least one embodiment, R 1 R 2 and R 3 Each of the following 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-pentadecanyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecanyl, and n-eicosyl. In at least one embodiment, R 2 and R 3 Each of them 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-pentadecanylphenyl, n-hexadecylphenyl, n-heptadecylphenyl, n-octadecylphenyl, n-nonadecanylphenyl and n-eicosylphenyl.

[0135] In the preferred embodiment, R 1 It is methyl, R 2 It is a substituted phenyl group, R 3 It is C 10 To C 30 Linear alkyl group. Preferably, R 2 It is not a meta-substituted phenyl group.

[0136] In the preferred embodiment, R 1 It is methyl, R 2 It is C1 to C 35 Alkyl-substituted phenyl groups (preferably ortho- or meta-substituted), R 3 It is C 10 To C 30 Linear alkyl group.

[0137] In the preferred embodiment, R 1 It is methyl, R 2 It is C1 to C 35 Alkyl-substituted phenyl (preferably para-substituted), R3 It is C 10 To C 30 Linear alkyl group.

[0138] In the preferred embodiment, R 1 It is methyl; R 2 It is C1 to C 35 Alkyl-substituted phenyl groups, such as methylphenyl, ethylphenyl, n-propylphenyl, n-butylphenyl, n-pentylphenyl, n-hexylphenyl, n-heptylphenyl, n-octylphenyl, n-nonylphenyl, n-decylphenyl, n-undecylphenyl, phenyl, n-dodecylphenyl, n-tridecylphenyl, n-tetradecylphenyl, n-pentadecadecylphenyl, n-hexadecylphenyl, n-heptadecylphenyl, n-octadecylphenyl, n-nonadecadecylphenyl, and n-eicosylphenyl, n-timodecylphenyl, n-timodecylphenyl, n-timodecylphenyl, n-timodecylphenyl, n-tridecylphenyl, n-tetradecylphenyl, n-timodecylphenyl, n-timodecylphenyl, n-timodecylphenyl, n-timodecylphenyl; and R 3 It is C 10 To C 30 Linear alkyl groups, such as n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecanyl, n-eicosyl, n-unidecyl, n-timodecyl, n-timodecyl, n-tridecyl; n-tetradecyl, n-pentadecanyl; n-hexadecyl; n-heptadecyl, n-octadecyl, n-nonadecanyl, n-triadecyl.

[0139] In a preferred embodiment, R 2 It is C1 to C 35 Alkyl-substituted phenyl groups, such as methylphenyl, ethylphenyl, n-propylphenyl, n-butylphenyl, n-pentylphenyl, n-hexylphenyl, n-heptylphenyl, n-octylphenyl, n-nonylphenyl, n-decylphenyl, n-undecylphenyl, phenyl, n-dodecylphenyl, n-tridecylphenyl, n-tetradecylphenyl, n-pentadecadecylphenyl, n-hexadecylphenyl, n-heptadecylphenyl, n-octadecylphenyl, n-nonadecadecylphenyl, and n-eicosylphenyl, n-timodecylphenyl, n-timodecylphenyl, n-timodecylphenyl, n-timodecylphenyl, n-tridecylphenyl, n-tetradecylphenyl, n-timodecylphenyl, n-timodecylphenyl, n-timodecylphenyl, n-timodecylphenyl; and R 3 It is C 10 To C 30Linear alkyl groups, such as n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecanyl, n-eicosyl, n-unidecyl, n-timodecyl, n-timodecyl, n-tridecyl; n-tetradecyl, n-pentadecanyl; n-hexadecyl; n-heptadecyl, n-octadecyl, n-nonadecanyl, n-triadecyl.

[0140] In the preferred embodiment of formula (I), R 1 It is methyl, R 2 It is a substituted phenyl group, R 3 It is C 10 To C 30 Linear alkyl, and R 4 R 5 R 6 R 7 It is perfluoronaphthyl.

[0141] In a preferred embodiment of formula (AI), R 1 It is methyl, R 2 It is a substituted phenyl group, R 3 It is C 10 To C 30 Linear alkyl, E is nitrogen, and each Q is a perfluoronaphthyl group.

[0142] In the preferred embodiment, R 1 It is methyl; R 2 It is C1 to C 35 Alkyl-substituted phenyl groups, such as methylphenyl, ethylphenyl, n-propylphenyl, n-butylphenyl, n-pentylphenyl, n-hexylphenyl, n-heptylphenyl, n-octylphenyl, n-nonylphenyl, n-decylphenyl, n-undecylphenyl, phenyl, n-dodecylphenyl, n-tridecylphenyl, n-tetradecylphenyl, n-pentadecadecylphenyl, n-hexadecylphenyl, n-heptadecylphenyl, n-octadecylphenyl, n-nonadecadecylphenyl, and n-eicosylphenyl, n-timodecylphenyl, n-timodecylphenyl, n-timodecylphenyl, n-timodecylphenyl, n-timodecylphenyl, n-timodecylphenyl, n-timodecylphenyl, n-timodecylphenyl; R 3 It is C 10 To C 30 Linear alkyl groups, such as n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadedecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadedecyl, n-eicosyl, n-unidecyl, n-timodecyl, n-timodecyl, n-tridecyl; n-tetradecyl, n-pentadedecyl; n-hexadecyl, n-octadecyl, n-nonadedecyl, n-trianedecyl; and each Q or R4 R 5 R 6 R 7 Each of them is a perfluoronaphthyl group.

[0143] In a preferred embodiment of the present invention, R 1 It is o-MePh, R 2 and R 3 It is an octadecyl group.

[0144] In a preferred embodiment of the present invention, R 1 It is m-MePh, R 2 and R 3 It is an octadecyl group.

[0145] In a preferred embodiment of the present invention, R 1 Not alkylphenyl, such as p-MePh.

[0146] In a preferred embodiment of the present invention, R 1 It's Me, R 2 It is n-octadecylaryl, R 3 It is an octadecyl group.

[0147] In a preferred embodiment of the present invention, R 1 It's Me, R 2 It is n-octadecylphenyl, R 3 It is an octadecyl group.

[0148] In a preferred embodiment of the present invention, R 1 It's Me, R 2 It is n-butylaryl, R 3 It is an octadecyl group.

[0149] In a preferred embodiment of the present invention, R 1 It's Me, R 2 It is n-butylphenyl, R 3 It is an octadecyl group.

[0150] In a preferred embodiment of the present invention, R 1 It is a positive gui base, R 2 It is n-butylaryl, R 3 It is n-decyl.

[0151] In a preferred embodiment of the present invention, R 1 It is a positive gui base, R 2 It is n-butylphenyl, R 3 It is n-decyl.

[0152] In a preferred embodiment of the present invention, R1 It is n-propyl, R 2 p-Methylphenyl, R 3 It is an octadecyl group.

[0153] In a preferred embodiment of the present invention, R 1 R 2 and R 3 Together they contain 20 or more carbon atoms, such as 21 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 37 or more carbon atoms, such as 40 or more carbon atoms, such as 45 or more carbon atoms, such as 15 to 100 carbon atoms, such as 25 to 75 carbon atoms, such as 38 to 70 carbon atoms.

[0154] In at least one embodiment, the cation is selected from:

[0155]

[0156]

[0157] In at least one embodiment of formulas (AI) and (I), E is nitrogen or phosphorus, and R... 1 It is methyl; R 2 It is C6-C 40 Aryl (e.g., substituted phenyl) and R 3 Independently, it is C1-C 35 Linear alkyl, C5-C 40 Aryl, wherein R 2 and R 3 Each of them is independently unsubstituted or C1-C 35 Alkyl, C5-C 30 Aryl, C6-C 30 Arylalkyl, C6-C 30 At least one substitution of alkylaryl and halogen, wherein R 2 Optional with R 3 Bonding can independently form pentagonal, hexagramal, or heptagonal rings, where R 2 and R 3 Together they contain 20 or more carbon atoms; and optionally R 1 R 2 and R 3 Together, they contain 21 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 40 or more carbon atoms. In at least one embodiment, R 2 Independently replaceable C1-C22 Alkyl, unsubstituted phenyl, or substituted phenyl. In at least one embodiment, R 3 It 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-pentadecanyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecanyl, and n-eicosyl.

[0158] Preferably, the cation is selected from:

[0159]

[0160] Preferably, the compounds represented by formulas (AI) and (I) contain cations selected from:

[0161]

[0162] and

[0163] .

[0164] Anionic components

[0165] The anionic components of the activator described in this article include those derived from the formula [Mk + Qn]. - The elements represented are: 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, preferably n is 4 when M is B); M is an element selected from Group 13 of the periodic table, preferably boron or aluminum; Q is independently a hydrogen group, a bridged or unbridged dialkylamide, a halogen group, an alkoxy group, an aryloxy group, a substituted alkyl group, a halocarbon group, a substituted halocarbon group, and a halosubstituted alkyl group, wherein Q contains at most 20 carbon atoms, provided that a halogen group appears at most once in Q. Preferably, each Q is a fluorinated alkyl group optionally having 1 to 20 carbon atoms; more preferably, each Q is a fluorinated aryl group; most preferably, each Q is a perfluorinated aryl group. Preferably, at least one Q is not a substituted phenyl group, such as a perfluorophenyl group; preferably, all Q are not substituted phenyl groups, such as perfluorophenyl groups.

[0166] In a preferred embodiment of any implementation of formula (AI), when R 1 It is methyl, R 2 It is C18 and R 3 It is C 18 When Q is not a perfluorophenyl, then each Q is not a perfluorophenyl.

[0167] In at least one embodiment, for the borate structural portion of the activator represented by formula (I) ([BR) 4 R 5 R 6 R7 ] - ), R 4 R 5 R 6 and R 7 Each of them is independently 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 of them is a naphthyl group, where R 4 R 5 R 6 and R 7 At least one of them is replaced by 1 to 7 fluorine atoms.

[0168] In at least one implementation, R 4 R 5 R 6 and R 7 Each of them is independently a naphthyl group containing one, two, three, four, five, six, or seven fluorine atoms.

[0169] In a preferred embodiment of any implementation of formula (I), when R 1 It is methyl, R 2 It is C 18 And R 3 It is C 18 When, then R 4 R 5 R 6 and R 7 Each of them is not a perfluorophenyl.

[0170] In at least one implementation, R 4 Independently, it is a naphthyl group containing one, two, three, four, five, six, or seven fluorine atoms, and R 5 R 6 and R 7 Each of them is independently a phenyl group containing one, two, three, four, or five fluorine atoms, or a naphthyl group containing one, two, three, four, five, six, or seven fluorine atoms.

[0171] In one embodiment, the borate activator comprises tetra(heptafluoronaphth-2-yl)borate.

[0172] In at least one preferred embodiment, the activator is represented by the following formula (B):

[0173] [cation] + [MQ4] - (B)

[0174] Where M is an element selected from Group 13 of the periodic table; each Q is independently a hydrogen group, a bridged or unbridged dialkylamide, a halogroup, an alkoxy group, an aryloxy group, a substituted hydrocarbon group, a halocarbon group, a substituted halocarbon group, or a halosubstituted hydrocarbon group; and [cation]. + Selected from:

[0175]

[0176] In at least one preferred embodiment, [MQ4] - It is a perfluoroaryl group. In at least one other preferred embodiment, [cationic] + yes

[0177] .

[0178] Activators such as [M2HTH] can be used. + [NCA] - It is added to the polymerization in the form of ion pairs, wherein the di(hydrogenated tallow)methylamine (“M2HTH”) cation reacts with the basic leaving group on the transition metal complex to form the transition metal complex cation and [NCA]. - Alternatively, transition metal complexes can react with neutral NCA precursors such as B(C) 10 The F7)3 reaction extracts anionic groups from the complex to form an activating substance. Useful activators include 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 C7)4).

[0179] In at least one embodiment, the activator used for the borate activator compound, obtained in its salt form, is: lithium tetra(heptafluoronaphthyl-2-yl)borate ether compound (Li-BF28), N,N-dimethylphenylammonium tetra(heptafluoronaphthyl-2-yl)borate (DMAH-BF28), sodium tetra(heptafluoronaphthyl-2-yl)borate (Na-BF28), and N,N-dimethylphenylammonium tetra(heptafluoronaphthyl-2-yl)borate (DMAH-BF28).

[0180] In at least one embodiment, when combined with a Group 4 metallocene catalyst compound to form an active olefin polymerization catalyst, the activator of this disclosure produces a polymer (e.g., Mw) with a higher molecular weight than that of a comparative activator using other borate anions.

[0181] In at least one embodiment, when combined with Group 4 metallocenes to form an active olefin polymerization catalyst, wherein R 1 The activator of this disclosure, which is methyl, produces polymers with higher molecular weights (e.g., Mw) than those using other borate anions as comparative activators.

[0182] A typical activator-to-catalyst ratio, for example, in all NCAs, is a molar ratio of approximately 1:1. Alternative preferred ranges include 0.1:1–100:1, or 0.5:1–200:1, or 1:1–500:1, or 1:1–1000:1. Particularly useful ranges are 0.5:1–10:1, preferably 1:1–5:1. The molar ratio of activator to catalyst can also vary between 0.5 and 2.0.

[0183] Catalyst compounds can be combined with combinations of the aluminoxanes and activators described herein, which are also within the scope of this disclosure.

[0184] synthesis

[0185] In at least one embodiment, the general synthesis of the activator can be carried out using a two-step method. In the first step, an amine or phosphine is dissolved in a solvent (e.g., hexane, cyclohexane, methylcyclohexane, ether, dichloromethane, toluene) and an excess (e.g., 1.2 molar equivalents) of hydrogen chloride is added to form a chloride salt. This salt is typically separated from the reaction medium by filtration and dried under reduced pressure. The separated chloride is then heated under reflux in a solvent (e.g., cyclohexane, dichloromethane, methylcyclohexane) with about 1 molar equivalent of an alkali metal compound or metalloid (e.g., borate or aluminate) to form the desired borate or aluminate and the byproduct alkali metal chloride, which is typically removed by filtration.

[0186] The activator disclosed herein is soluble in aliphatic solvents. Aromatic solvents, such as toluene, are absent (e.g., present at zero mol% or less than 1 mol%). Preferably, the catalyst system, polymerization reaction, and / or the resulting polymer are free of "detectable aromatic hydrocarbon solvents," such as toluene. For the purposes of this disclosure, "detectable aromatic hydrocarbon solvents" refers to those measured by gas chromatography at concentrations of 0.1 mg / m³. 2 Or more. For the purposes of this disclosure, "detectable toluene" means 0.1 mg / m³ as determined by gas chromatography. 2More. The polyolefins produced herein preferably contain 0 ppm (or less than 1 ppm) of aromatic hydrocarbons. Preferably, the polyolefins produced herein contain 0 ppm (or less than 1 ppm) of toluene. The catalyst system used herein preferably contains 0 ppm (or less than 1 ppm) of aromatic hydrocarbons. Preferably, the catalyst system used herein contains 0 ppm (or less than 1 ppm) of toluene.

[0187] In at least one embodiment, the general synthesis of the activator can be carried out using a two-step method. In the first step, the amine is dissolved in a solvent. In one or more embodiments, a 20% by weight mixture of the compound in n-hexane, isohexane, cyclohexane, methylcyclohexane, or combinations thereof forms a clear, homogeneous solution at 25°C; preferably, a 30% by weight mixture of the compound in n-hexane, isohexane, cyclohexane, methylcyclohexane, or combinations thereof forms a clear, homogeneous solution at 25°C.

[0188] The activator has a solubility greater than 10 mM (or greater than 20 mM, or greater than 50 mM) in methylcyclohexane at 25 °C (stirring for 2 hours). The activator has a solubility greater than 1 mM (or greater than 10 mM, or greater than 20 mM) in isohexane at 25 °C (stirring for 2 hours). The activator has a solubility greater than 10 mM (or greater than 20 mM, or greater than 50 mM) in methylcyclohexane at 25 °C (stirring for 2 hours) and a solubility greater than 1 mM (or greater than 10 mM, or greater than 20 mM) in isohexane at 25 °C (stirring for 2 hours).

[0189] After the activator is added to the solvent, an excess (e.g., 1.2 molar equivalents) of hydrogen chloride is added to form an ammonium chloride salt. This salt is typically separated from the reaction medium by filtration and dried under reduced pressure. The separated ammonium chloride is then heated to reflux with about 1 molar equivalent of an alkali metal borate in a solvent (e.g., cyclohexane, dichloromethane, methylcyclohexane) to form ammonium borate and the byproduct alkali metal chloride, which can typically be removed by filtration.

[0190] In at least one embodiment, the activator of this disclosure is soluble in an aliphatic solvent at a concentration of about 10 mM or higher, such as about 20 mM or higher, such as about 30 mM or higher, such as about 50 mM or higher, such as about 75 mM or higher, such as about 100 mM or higher, such as about 200 mM or higher, such as about 300 mM or higher. In at least one embodiment, the activator of this disclosure is dissolved in isohexane or methylcyclohexane at 25°C to form a homogeneous solution with a concentration of at least 10 mM.

[0191] In at least one embodiment, the solubility of the borate or aluminate activator of this disclosure in aliphatic hydrocarbon solvents varies with the cationic group (i.e., ammonium or...). The number of aliphatic carbons in the ammonium carbonate is increased. In at least one embodiment, ammonium carbonate with about 21 or more aliphatic carbon atoms, such as about 25 or more aliphatic carbon atoms, such as about 35 or more carbon atoms, is used. The activator of the group achieves a solubility of at least 10 mM.

[0192] In at least one embodiment, the solubility of the ammonium borate activator of this disclosure in aliphatic hydrocarbon solvents increases with the number of aliphatic carbons in the ammonium group. In at least one embodiment, an activator having an ammonium group having about 21 or more aliphatic carbon atoms, such as about 25 or more aliphatic carbon atoms, such as about 35 or more carbon atoms, achieves a solubility of at least 10 mM.

[0193] Useful aliphatic hydrocarbon solvents can be isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. In at least one embodiment, the aromatic compound is present in the solvent in less than 1% by weight, for example less than 0.5% by weight, for example less than 0% by weight, based on the weight of the solvent. The activator of this disclosure can be dissolved in one or more additional solvents. Additional solvents include ether solvents, halogenated solvents, and N,N-dimethylformamide solvents. The aliphatic solvent is preferably isohexane and / or methylcyclohexane.

[0194] Optional cleaning agent or co-activator

[0195] In addition to these activators, scavengers or co-activators can also be used. Alkyl aluminum or organoaluminum compounds that can be used as scavengers or co-activators include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum (TNOA), and diethylzinc.

[0196] In at least one embodiment, little or no scavenger is used (i.e., zero molar percentage) in the method for producing ethylene polymers. In at least one embodiment, one or more scavengers are added to the method at a scavenger metal to transition metal molar ratio of less than 100:1, for example less than 50:1, for example less than 15:1, for example less than 10:1.

[0197] Further details on the preparation of suitable catalyst systems using bridged metallocenes (one or more), activators (one or more), and support materials (one or more) can be found in USP 11,011,031 and 11,414,436. Detailed Implementation

[0198] Example:

[0199] The above discussion can be further described with reference to the following non-limiting examples. Five examples (C2 / C4) of ethylene-butene copolymers (resins 1-5) were prepared in a pilot-scale solution reactor. The catalyst was dimethyl di(p-triethylsilylphenyl)methylene(2,7-di-tert-butylfluorenyl)(cyclopentadienyl)hafnium, and the activator was tetra(heptafluoronaphthyl)boronic acid N-methyl-4-nonadecanyl-N-octadecylphenylammonium dimethylphenylammonium, both of which were available from ExxonMobil Chemical Company.

[0200] Two comparative examples of ethylene-butene copolymers (C2 / C4) were also prepared. The comparative resin samples (CE1 and CE2) were produced in a pilot-scale solution reactor using the same catalyst as resins 1-5 (i.e., dimethyl di(p-triethylsilylphenyl)methylene(2,7-di-tert-butylfluorenyl)(cyclopentadienyl)hafnium), but activated with different activators, as shown in Table 1 below.

[0201] Table 1 shows the activators used to prepare the resins 1-5 of the present invention and the comparative resin samples CE1 and CE2.

[0202]

[0203] Before feeding into the pilot-scale solution polymerization reactor, the activator was diluted with aliphatic hydrocarbons to prepare an activator solution. The activator solution and catalyst solution were fed separately into the reactor and mixed within the reactor to prepare an activated catalyst for polymerization. The scavenger tri-n-octyl aluminum (TNOA) was fed as a diluted solution of 3 wt% pure TNOA and 97 wt% process solvent. This solution was metered by a mass flow meter and continuously fed into the reactor after being mixed with the remaining monomers. Table 2 summarizes the copolymer properties, aluminum residue, and volume resistivity, and Table 3 summarizes the key process conditions.

[0204] Table 2: Properties of copolymers of resins 1-5 and comparative examples CE1 and CE2

[0205]

[0206] Table 3: Key Process Conditions

[0207]

[0208] Table 4 provides similarity information for comparing commercially available copolymers.

[0209]

[0210] The copolymer was molded into a slab and the volume resistivity (1 mm thick film, 500 V, 5-minute charging time) and aluminum residue were tested. The attached figure shows the volume resistivity of the molded slab plotted relative to aluminum residue (ppmw). Resins 1-5 all have >10 15 Ohm The volume resistivity is cm, with aluminum residue less than 2.0 ppmw, and several others are 0.1 ppm or less, even though all copolymers have similar density, MI and branching index.

[0211] Test program

[0212] In the foregoing embodiments, the following testing methods and procedures were used:

[0213] Density was measured according to ASTM D792, and MI value was measured according to ASTM D1238 (190℃ / 2.16kg).

[0214] The distribution and fractions of molecular weights (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 bandpass-filter-based infrared detector IR5, an 18-angle light scattering detector, and a viscometer. Three Agilent PLgel 10 μm mixed-B LS columns were used to provide polymer separation. The detailed analytical principles and methods used for molecular weight determination are described in paragraphs

[0044] -

[0051] of International Publication No. WO2019 / 246069A1, which are incorporated herein by reference (it should be noted that the formula for c for the concentration I at each point in the chromatogram mentioned in paragraph

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

[0044] -

[0045] of the disclosure just mentioned). It should be noted that for the formula in this paragraph

[0044] , a = 0.695 and K = 0.000579 (1 - 0.75Wt) are used, where Wt is the weight fraction of the hexane comonomer. It should also be noted that the comonomer composition is determined by the ratio of the intensity of the IR5 detector corresponding to the CH2 and CH3 channels, which are calibrated with a series of PE and PP homopolymer / copolymer standards whose nominal values ​​are predetermined by NMR or FTIR (providing methyl groups per 1000 total carbons (CH3 / 1000TC)), as noted in paragraph

[0045] of the PCT disclosure just mentioned.

[0215] The branching index (g') of long chains is measured using GPC-4D. A typical GPC-4D curve has log M vs. g' and is used to estimate the average g' based on the average across molecular weights. The average branching index g' ranges from 1 to 0, where 1 is linear (unbranched) and 0 is fully branched. The average g' does not clearly distinguish branching variations at low levels (0.85 to 1), so g'(Mz) and g'(Mz+1) are estimated at higher molecular weight components (Mz, Mz+1). The branching index g'(Mz) is g' estimated from the GPC-4D curve at the z-mean (third-order component) molecular weight average. This calculation is performed by fitting the g' vs. molecular weight data curve to an nth-order polynomial using a MATLAB program. The value of n is typically between 3 and 4. The Mz value obtained from GPC-IR measurements is interpolated into the curve fit to calculate g' associated with the stated molecular weight.

[0216] 13C NMR of r1r2

[0217] The sample was dissolved in deuterated 1,1,2,2-tetrachloroethane-d2 (tce-d2) at a concentration of 67 mg / mL at 140 °C. The spectrum was recorded at 120 °C using a Bruker NMR spectrometer with a cryoprobe of at least 600 MHz and a 10 mm cryoprobe. A 90 o Measurement using pulses, 10s delay, 512 transients, and gated decoupling. 13 C NMR. The polymer resonance peak is the main peak of polyethylene at 29.98 ppm.

[0218] Randall described the chemical shift distribution of ethylene-octene copolymers in "A Review of High Resolution Liquid Carbon Nuclear Magnetic Resonance Characterization of Ethylene-Based Polymers", Polymer Reviews, 29:2,201-5317 (1989). The copolymer content, molar percentage and weight percentage, ternary sequence, and binary calculations were also calculated and described using the method established by Randall in the aforementioned paper. The reactive reactivity ratio (r1r2) was calculated based on the formula r1r2 = 4 × [EE] × [OO] / [EO]²; where [EE], [EO], and [OO] are the binary molar concentrations; E is ethylene, and O is octene.

[0219] The reactivity ratios of the product r1r2 are described more fully in the Textbook of Polymer Chemistry, FW Billmeyer, Jr., Interscience Publishers, New York, pp. 221 and onwards (1957). The reactivity ratio product r1r2 (where r1 is the reactivity of ethylene and r2 is the reactivity of propylene) can be calculated by applying the following formula from the measured binary group distributions (OO, EE, EO, and OE in this nomenclature):

[0220]

[0221] Where mol%E = [(E) / (E+O)] × 100, X = E / O in the reactor;

[0222] K 11 and K 12 It is the kinetic interpolation constant of ethylene; and

[0223] K 21 and K 22 It is the kinetic interpolation constant of propylene.

[0224] As is known to those skilled in the art, the reaction reactivity product r1r2 of zero (0) can define an "alternating" copolymer, and the reaction reactivity product of one (1) is called the definition of a "statistically random" copolymer. In other words, copolymers with a reaction reactivity product r1r2 of 0.6 to 1.5 are generally considered to be random copolymers (according to strict theory, generally only copolymers with a reaction reactivity product r1r2 greater than 1.5 contain a longer homopolymer sequence and are considered to be "block copolymers").

[0225] Aluminum residues in the polymer were tested by ICP-OES using a combustion ashing sample preparation method. ±20 g of sample was accurately weighed on an analytical balance in a clean platinum crucible. The crucible was placed in a muffle furnace and a temperature program from room temperature to 550 °C was initiated for 5 hours. An empty, clean crucible was placed in an oven, with each batch of sample serving as a blank reference. The muffle furnace was allowed to cool to near room temperature, and the crucible was transferred to an acid hood. 1 ml of nitric acid was added, and the crucible was carefully swirled to wet all ash. 0.5 ml of hydrofluoric acid was added, and the crucible was again carefully swirled. The reaction was allowed to proceed for at least 30 minutes. If necessary, another 0.5 ml of hydrofluoric acid was added to dissolve all ash in the solution. ±5 ml of Milli-Q water and 1 ml of hydrochloric acid were added, and the crucible was carefully vortexed. Using a clean, disposable plastic pipette, the mixture was quantitatively transferred to a clean 50 ml PFA flask. The crucible was rinsed with Milli-Q water at least three times, with quantitative transfer to the flask each time. Add Milli-Q water until labeled. Establish a calibration line using multi-element standards before measuring the sample, then test the elements using ICP-OES. Report aluminum residues as ppm by weight.

[0226] Volume resistivity (VR) was tested according to the ExxonMobil method based on ASTM D257. Measurements were performed using a Keithley 6517B electrometer and a Keithley 8009 test fixture. Leakage current was directly measured using the instrument, and volume resistivity was calculated using the following formula.

[0227]

[0228] Where ρ is the volume resistivity (Ω·cm), V is the applied voltage (volts), and A is the electrode contact area (cm²). 2 I is the leakage current (amperes), and t is the average thickness of the sample. Volume resistivity was measured at room temperature at 500 volts and a charging time of 300 s, with three 1 mm thick molded plates tested to obtain the average value for each sample.

[0229] Certain embodiments and features have been described using a set of upper and lower limits for numerical values. It is self-evident that ranges including combinations of any two values, such as any lower limit value combined with any upper limit value, any two lower limit values, and / or any two upper limit values, are considered, unless otherwise stated. Certain lower limits, upper limits, and ranges appear in one or more of the following claims. All numerical values ​​are "approximately" or "roughly" indicating values, and experimental errors and deviations that a person skilled in the art would expect are taken into account.

[0230] The various terms have been defined above. If a term used in the claims is not defined above, it should be given the broadest definition possible, as those skilled in the art will know that the term is reflected in at least one printed publication or issued patent. Furthermore, all patents, experimental procedures, and other documents cited in this application are consistent with this invention and are fully incorporated herein by reference to the extent permitted by all rights.

[0231] While the foregoing relates to 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, and the scope of the present invention is determined by the following claims.

Claims

1. An ethylene copolymer, comprising: At least 50% by weight of ethylene-derived units; and At least 20% by weight of at least one C3 to C20 comonomer, wherein said copolymer has: Melt index from 0.5 g / 10 min to approximately 50 g / 10 min as measured by ASTM D1238 (190°C / 2.16 kg); Density of approximately 0.856 g / cc to 0.890 g / cc as measured according to ASTM D792; At least 5×10 15 The volume resistivity at 23℃ is Ωcm; and Aluminum from 0.01 to 4.0 ppm by weight.

2. The ethylene copolymer of claim 1 further comprises a first long-chain branching index (g'(Mz)) of 0.80 to 0.

93.

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

93.

4. The ethylene copolymer of claim 1 further comprises an average ratio of 0.9 to 1.0 g'Mz+1 to g'(Mz).

5. The ethylene copolymer of claim 1 further comprises less than 0.7 vinyls / total unsaturated portion and 50 to 500 trisubstituted olefins at the unsaturated portion level.

6. The ethylene copolymer of claim 1, further comprising a reactive polymerization ratio of r1r2 of 0.2 to 0.

8.

7. The ethylene copolymer of claim 1, wherein the at least one C3 to C20 comonomer is butene or octene or a combination thereof.

8. Electronic device module, including: At least one electronic device, and An ethylene copolymer film in direct contact with at least one surface of the electronic device, the ethylene copolymer comprising: At least 50% by weight of ethylene-derived units; and At least 20% by weight of at least one C3 to C20 comonomer, wherein said copolymer has: Melt index from 0.5 g / 10 min to approximately 50 g / 10 min as measured by ASTM D1238 (190°C / 2.16 kg); Density of approximately 0.856 g / cc to 0.890 g / cc, as measured according to ASTM D792; At least 5×10 15 The volume resistivity at 23℃ is Ωcm; and Aluminum from 0.01 to 4.0 ppm by weight.

9. The electronic device module of claim 8, wherein the copolymer further comprises a first long-chain branching index (g'(Mz)) of 0.80 to 0.

93.

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

93.

11. The electronic device module of claim 8, wherein the copolymer further comprises an average ratio of 0.9 to 1.0 of g'Mz+1 to g'(Mz).

12. The electronic device module of claim 8, wherein the copolymer further comprises less than 0.7 vinyl / total unsaturated portion and 50 to 500 levels of trisubstituted olefin unsaturated portion.

13. The electronic device module of claim 8, wherein the copolymer further comprises a reactive polymerization ratio of r1r2 of 0.2 to 0.

8.

14. The electronic device module of claim 8, wherein the at least one C3 to C20 comonomer is butene or octene or a combination thereof.

15. A method for manufacturing an electronic device module, including: Provide at least one electronic device, and An ethylene copolymer film is laminated onto at least one surface of the electronic device, the ethylene copolymer comprising: At least 50% by weight of ethylene-derived units; and At least 20% by weight of at least one C3 to C20 comonomer, wherein said copolymer has: Melt index from 0.5 g / 10 min to approximately 50 g / 10 min as measured by ASTM D1238 (190°C / 2.16 kg); Density of approximately 0.856 g / cc to 0.890 g / cc as measured according to ASTM D792; At least 5×10 15 The volume resistivity at 23℃ is Ωcm; and Aluminum from 0.01 to 4.0 ppm by weight.

16. The electronic device module of claim 15, wherein the copolymer further comprises a first long-chain branching index (g'(Mz)) of 0.80 to 0.

93.

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

93.

18. The electronic device module of claim 15, wherein the copolymer further comprises an average ratio of 0.9 to 1.0 of g'Mz+1 to g'(Mz).

19. The electronic device module of claim 15, wherein the copolymer further comprises less than 0.7 vinyl / total unsaturated moiety and 50 to 500 levels of trisubstituted olefin unsaturated moiety.

20. The electronic device module of claim 15, wherein the copolymer further comprises a reactive polymerization ratio of r1r2 of 0.2 to 0.

8.

21. The electronic device module of claim 15, wherein the C3 to C20 comonomer is butene or octene or a combination thereof.

22. A method for manufacturing an ethylene-based copolymer, comprising polymerizing ethylene-derived units 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 wt% ethylene-derived units and at least 20 wt% of at least one C3 to C20 comonomer, wherein the copolymer has: Melt index from 0.5 g / 10 min to approximately 50 g / 10 min as measured by ASTM D1238 (190°C / 2.16 kg); Density of approximately 0.857 g / cc to 0.890 g / cc as measured according to ASTM D792; At least 5×10 15 The volume resistivity at 23℃ is Ωcm; and Aluminum from 0.01 to 4.0 ppm by weight.

23. The method of claim 22, wherein the catalyst system comprises at least one bridged metallocene and at least one ammonium borate or boric acid ion represented by the following formula. Activator [cation] + [MQ4] - Among them, [MQ4] - It is tetra(heptafluoronaphthyl)borate, and [cation]. + Selected from: 。 24. The method of claim 22, wherein [cation] + yes 。 25. The method of claim 22, wherein the at least one C3 to C20 comonomer is butene or octene or a combination thereof.

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