Olefin polymerization activator

Abstract

Embodiments of the present disclosure include a process for polymerizing olefins, the process comprising the reaction of ethylene with (C3-C 40 ) an alpha-olefin comonomer, wherein the catalyst system comprises a Group IV metal-ligand complex and a metal activator ionic complex, the metal activator ionic complex comprising an anion and a countercation, the anion having a structure according to formula (I): [Formula 1] [Selection diagram] None

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority to U.S. Provisional Patent Application No. 62 / 650,453, filed March 30, 2018, which is incorporated herein by reference in its entirety.

[0002] Embodiments of this disclosure generally relate to olefin polymerization catalyst systems and processes, more specifically to olefin polymerization catalyst systems comprising a Group IV metal-ligand procatalyst complex and a metal activator, an ionic complex activator, or a co-catalyst. [Background technology]

[0003] As part of the catalyst composition in α-olefin polymerization reactions, activators may possess characteristics beneficial to the formation of α-olefin polymers and to the final polymer composition containing α-olefin polymers. Characteristics of activators that increase the formation of α-olefin polymers include, but are not limited to, rapid activation of the procatalyst, high catalytic efficiency, high-temperature capability, consistent polymer composition, and selective deactivation.

[0004] Olefin polymers, such as ethylene-based and propylene-based polymers, are produced through various catalytic systems. The selection of such catalytic systems can be an important factor contributing to the characteristics and properties of olefin polymers. Catalytic systems for producing polyethylene polymers include chromium-based catalytic systems, Ziegler-Natta catalytic systems, or molecular (either metallocene or non-metallocene) catalytic systems.

[0005] To generate catalytically active species for polymerization, the molecular polymerization procatalyst is activated as part of the catalytic system, and this activation can be achieved by any number of means. One such method is to use an activator or co-catalyst, which is a Brønsted acid. To activate molecular polymerization procatalysts, particularly those containing Group IV metal complexes, Brønsted salts containing weakly coordinating anions are commonly used. Fully ionized Brønsted salts are capable of transferring protons to form cationic derivatives of such Group IV metal complexes.

[0006] In activators such as Brønsted salts, the cationic component can be, for example, a proton-transferable cation such as ammonium, sulfonium, or phosphonium derivatives; an oxidizing cation such as ferrocenium, silver(I), or lead(II) cations; or a highly Lewis acidic cation such as carbonium or silirium.

[0007] However, when cations activate a procatalyst, the activator may remain in the polymer composition. As a result, cations and anions may affect the polymer composition. Different ions have different effects on the polymer composition because not all ions diffuse equally. Specifically, the size of the ion, the charge of the ion, the interaction between the ion and the surrounding medium, and the dissociation energy between the ion and available counterions will affect the ability of the ion to diffuse through the surrounding medium, such as a solvent, gel, or polymer material.

[0008] Conventional olefin polymerization activators include weakly coordinating or non-coordinating anions. It has been shown that weaker anion coordination leads to increased catalytic efficiency of cationic catalysts. However, the non-nucleophilic characteristics of non-coordinating anions also increase diffusion, so residual activator anions in the resulting polymer will decrease the polymer's electrical resistance, thereby increasing electrical losses and reducing the insulating ability of the resulting polymer. [Overview of the project]

[0009] Desirable characteristics of activators in polymer systems include the ability to increase the formation of olefin polymers, the ability to increase the rate of procatalytic activation, the ability to increase the overall efficiency of the catalyst, the ability to enable the catalyst system to operate at high temperatures, the ability to enable the catalyst system to provide a consistent polymer composition, and the ability to decompose the activator after olefin polymerization is complete. Non-coordinating anionic tetrakis(pentafluorophenyl) borate ( - The activator derived from B(C6F5)4) acquires many of these desirable characteristics. Nevertheless, under typical polymerization reaction conditions, - The B(C6F5)4 anion is not easily decomposed and may remain intact in the final polymer. The presence of the activator intact in the final polymer can be detrimental to the electrical properties of the final polymer.

[0010] Activators based on partially hydrolyzed metal trialkyls, such as methylarmoxane (MAO) or modified methylarmoxane (MMAO), are, for example, - Although it decomposes more easily than the B(C6F5)4 anion, it suffers from poor high-temperature catalytic efficiency and broader compositional drift in the final polymer.

[0011] There is a need for activators that efficiently activate metal-ligand procatalysts, are readily decomposed, and function well at high temperatures. The catalytic systems of this disclosure include combinations of Group IV metal-ligand complexes and activators or co-catalysts that address such needs. Specifically, to produce polyolefin resins, the activator readily reacts with the Group IV metal-ligand procomplex, and upon activation of the Group IV metal-ligand procomplex, the polyolefin resin exhibits useful polymer composition and electrical properties. The activators included in the catalytic systems of this disclosure exhibit the ability to increase the production of α-olefin polymers, the ability to increase the rate of procatalytic activation, the ability to increase the overall efficiency of the catalyst and enable the catalytic system to operate at high temperatures, the ability to enable the catalytic system to provide a consistent polymer composition, and the ability to decompose the activator.

[0012] According to one or more embodiments, the process of polymerizing olefins involves polymerizing ethylene and (C3-C3) in the presence of a catalyst system comprising a Group IV metal-ligand complex and a metal activator ionic complex. 40 This includes contacting with an α-olefin comonomer. The metal activator ionic complex comprises an anion and a countercation, the anion having a structure according to formula (I). [ka]

[0013] The countercation is any cation having a formal charge of +1. In equation (I), n is either 0 or 1. When n is 1, R is selected from the group consisting of radicals having equation (II) and radicals having equation (III). [ka]

[0014] In equations (II) and (III), each Y is independently carbon or silicon, and R 11 , R 12 , R 13 , R 21 , R22 , R 23 , R 24 , and R 25 each independently is selected from (C1-C 40 ) alkyl, (C6-C 40 ) aryl, -H, -OR C , -O-, or halogen, wherein R C is (C1-C 30 ) hydrocarbyl. When R is a radical according to formula (II), at least one of R 11-13 is halogen-substituted (C1-C 40 ) alkyl, halogen-substituted (C6-C 40 ) aryl, or -F, and when R is a radical according to formula (III), at least one of R 21-25 is halogen-substituted (C1-C 40 ) alkyl, halogen-substituted (C6-C 40 ) aryl, or -F. In some embodiments, the counter cation can be selected from a tertiary carbocation, an alkyl-substituted ammonium ion, anilinium, an alkyl-substituted alumocenium, or ferrocenium.

[0015] In formula (I), each X is a monodentate ligand independently selected from halogen, halogen-substituted (C1-C 20 ) alkyl, (C1-C 20 ) alkyl, halogen-substituted (C6-C 40 ) aryl, (C6-C 40 ) aryl, -OR C , or triflate (-OTf). Further, only one X is halogen, -OR C , triflate (-OTf), or (C1-C 20 ) alkyl. Optionally, two R groups of formula (I) are covalently bonded. Each R C is independently (C1-C 30) is hydrocarbyl, or -H. The metal activator complex contains a dielectric loss tangent percentage of 0.1 or less at a concentration of 200 micromoles of the metal activator complex and 20 mmol of water in a hydrocarbon solution, as measured by a hydrocarbon conductivity test. In some embodiments, the ratio of the total number of moles of one or more metal-ligand complexes of formula (XI) in the catalyst system to the total number of moles of one or more co-catalysts in the catalyst system is 1:10,000 to 100:1.

[0016] In one or more embodiments, specifically when two X groups of formula (I) are covalently bonded, the co-catalyst has a structure according to formula (IV). [ka]

[0017] In equation (IV), X and R are as defined in equation (I). The subscript z is 0 or 1, the subscript y is 0, 1, or 2, and the subscript x is 1 or 2, so 2x + y + z = 4. Each L representing the two covalently bonded X groups is independently a halogen substitution (C2-C 40 ) Alkylene, halogen substitution (C2-C 40 ) Heteroalkylene, or halogen-substituted (C6-C 40 ) Selected from arylene. When the subscript z is 1, the single-seat ligand X is halogen, halogenated -(C1-C 20 )alkyl, (C1-C 20 Selected from alkyl or -S(O)2CF3 (triflate). [Modes for carrying out the invention]

[0018] The following describes specific embodiments of the catalyst system. It should be understood that the catalyst system described herein may be implemented in different forms and should not be construed as being limited to the specific embodiments described herein.

[0019] Common abbreviations are listed below. Me: Methyl, Et: Ethyl, Ph: Phenyl, Bn: Benzyl, i-Pr: Isopropyl, t-Bu: Tert-butyl, t-Oct: Tert-octyl(2,4,4-trimethylpentan-2-yl), Tf: Trifluoromethanesulfonate, OTf: Triflate, ( t Bu F O)3Al:Al(OC(CF3)3)3, THF:Tetrahydrofuran, Et2O:Diethyl ether, CH2Cl2:Dichloromethane, C6D6:Deuterated benzene or benzene-d6, CDCl3:Deuterated chloroform, Na2SO4:Sodium sulfate, MgSO4:Mugnesium sulfate, HCl:Hydrogen chloride, n-BuLi:Butyllithium, t-BuLi:Tert-Butyllithium, K2CO3:Potassium carbonate, Cs2CO3:Cesium carbonate, HfCl4:Hafnium chloride (IV ), HfBn4: Hafnium(IV) tetrabenzyl, ZrCl4: Zirconium(IV) chloride, ZrBn4: Zirconium(IV) tetrabenzyl, TiBn4: Titanium(IV) tetrabenzyl, N2: Nitrogen gas, PhMe: Toluene, PPR: Parallel polymerization reactor, MAO: Methylaluminoxane, MMAO: Modified methylaluminoxane, NMR: Nuclear magnetic resonance, MS: Mass spectrometry, mmol: Millimole, mL: Milliliter, M: Mole, min or mins: Minute, h or hrs: Hour, d: Day.

[0020] The term "independently selected" is used in R 1 , R 2 , R 3 , R 4 , and R 5 The R groups, such as the R, may be the same or different (therefore, R 1 , R 2 , R 3 , R 4 , and R 5 All of them may be substituted alkyl groups, or R 1 and R 2 However, it may also be a substituted alkyl, R 3The term "R" is used herein to indicate, for example, that it may be an aryl group. Chemical names associated with the R group are intended to convey the chemical structure recognized in the art as corresponding to the chemical structure of the chemical name. Therefore, chemical names are intended to supplement and illustrate, and not to exclude, structural definitions known to those skilled in the art.

[0021] The term "procatalyst" refers to a compound that exhibits catalytic activity when combined with an activator. The term "activator" refers to a compound that chemically reacts with a procatalyst to convert it into a catalytically active catalyst. As used herein, the terms "co-catalyst" and "activator" are interchangeable.

[0022] When used to describe a specific carbon-carbon-containing chemical group, "(C x -C y The parenthetical expression in the form of ")" means that the unsubstituted form of the chemical group has x carbon atoms to y carbon atoms, including x and y. For example, (C1-C 50 ) Alkyl is an alkyl group having 1 to 50 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups are R S It may be replaced by one or more substituents such as (C x -C y R defined using ")" S Substituting chemical groups are any group R S It can contain more than y carbon atoms depending on its identity. For example, "R S The exact single group R is phenyl (-C6H5) S Replaced by (C1-C 50 )alkyl can contain 7 to 56 carbon atoms. Therefore, generally, the parenthetical "(C x -C y A chemical group defined using ) is a substituent containing one or more carbon atoms R S When substituted by, the minimum and maximum total number of carbon atoms in the chemical group is, for both x and y, all carbon-carbon-containing substituents RS It is determined by adding up the total number of carbon atoms from each origin.

[0023] The term "substitution" refers to the substitution of a substituent (e.g., R) in a corresponding unsubstituted compound, where at least one hydrogen atom (-H) bonded to a carbon or heteroatom or functional group is a substituent (e.g., R S This means that it can be replaced by ). The term "-H" means hydrogen or hydrogen radical that is covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless otherwise specified.

[0024] The term "halogen substitution" means that at least one hydrogen atom (-H) bonded to a carbon or heteroatom or functional group of the corresponding unsubstituted compound is replaced by a halogen. The terms "halogen substitution" and "halogenation" are interchangeable. The term "perhalogenation" means that all -H bonds to a carbon or heteroatom or functional group of the corresponding unsubstituted compound are replaced by halogens. The term "halogen substitution" means that at least one -H bonded to a carbon or heteroatom or functional group of the corresponding unsubstituted compound is replaced by a halogen atom.

[0025] In this disclosure, the terms “halogen atom” or “halogen” mean a radical of a fluorine atom (F) or a chlorine atom (Cl). The term “halide” means the anionic form of a halogen atom, e.g., fluoride (F). - ) or chloride (Cl - ) means.

[0026] (C1-C 50 The term "(C1-C)" refers to a hydrocarbon radical having 1 to 50 carbon atoms. 50The term "hydrocarbylene" means a hydrocarbon diradical having from 1 to 50 carbon atoms, where each hydrocarbon radical and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, straight-chain or branched-chain, cyclic (having 3 or more carbons, including monocyclic and polycyclic, fused and non-fused polycyclic, and bicyclic) or acyclic, and is substituted or unsubstituted by one or more R S s.

[0027] In the present disclosure, (C1-C 50 )hydrocarbyl can be unsubstituted or substituted (C1-C 50 )alkyl, (C3-C 50 )cycloalkyl, (C3-C 20 )cycloalkyl-(C1-C 20 )alkylene, (C6-C 40 )aryl, or (C6-C 20 )aryl-(C1-C 20 )alkylene (such as benzyl (-CH2-C6H5)).

[0028] The terms "(C1-C 50 )alkyl" and "(C1-C 18 )alkyl" mean, respectively, a saturated straight-chain or branched hydrocarbon radical having from 1 to 50 carbon atoms and a saturated straight-chain or branched hydrocarbon radical having from 1 to 18 carbon atoms, which are unsubstituted or substituted by one or more R S s. Examples of unsubstituted (C1-C 50 )alkyl are unsubstituted (C1-C 20 )alkyl, unsubstituted (C1-C 10 )alkyl, unsubstituted (C1-C5)alkyl, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methylpropyl, 1,1-dimethylethyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-nonyl, and 1-decyl. Examples of substituted (C1-C 40 )alkyl are substituted (C1-C 20 )alkyl, substituted (C1-C 10 )alkyl, trifluoromethyl, and [C45 is alkyl. "C 45 alkyl" means that there are up to 45 carbon atoms in the radical including substituents. For example, each R which is (C1-C5) alkyl S substituted by (C 27 -C 40 ) alkyl. Each (C1-C5) alkyl may be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl. More broadly, the term "C z alkyl" means that there are up to z carbon atoms in the radical including substituents, where z is a positive integer.

[0029] The term "(C6-C 50 ) aryl" means an unsubstituted or (substituted by one or more R S ) monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radical having 6 to 40 carbon atoms, with at least 6 to 14 of the carbon atoms being aromatic ring carbon atoms. A monocyclic aromatic hydrocarbon radical contains one aromatic ring, a bicyclic aromatic hydrocarbon radical has two rings, and a tricyclic aromatic hydrocarbon radical has three rings. When a bicyclic or tricyclic aromatic hydrocarbon radical is present, at least one of the rings of the radical is aromatic. The other one or more rings of the aromatic radical can be independently fused or non-fused, aromatic or non-aromatic. Examples of unsubstituted (C6-C 50 ) aryl include unsubstituted (C6-C 20 ) aryl, unsubstituted (C6-C 18 ) aryl, 2-(C1-C5) alkyl-phenyl, phenyl, fluorenyl, tetrahydrofluorenyl, indacenyl, hexahydroindacenyl, indenyl, dihydroindenyl, naphthyl, tetrahydronaphthyl, and phenanthrene. Examples of substituted (C6-C 40 ) aryl include substituted (C1-C 20 ) aryl, substituted (C6-C 18 ) aryl, 2,4-bis([C 20Examples include alkyl)phenyl, polyfluorophenyl, pentafluorophenyl, fluoren-9-on-1-yl, and biphenyl.

[0030] (C3C 50 The term "cycloalkyl" refers to unsubstituted or one or more R S This refers to saturated cyclic hydrocarbon radicals having 3 to 50 carbon atoms that are substituted by other cycloalkyl groups (e.g., (C) x -C y A cycloalkyl group has x to y carbon atoms and is either unsubstituted or has one or more R atoms. S It is defined in a similar manner if it is either replaced by (C3-C). 50 Examples of cycloalkyl groups include unsubstituted (C3-C 20 )Cycloalkyl, unsubstituted (C3-C 10 These are cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Substitutions (C3-C 40 Examples of cycloalkyl groups include substitutions (C3-C 20 )Cycloalkyl, substituted (C3-C 10 These are cycloalkyl and 1-fluorocyclohexyl compounds.

[0031] (C1-C 50 Examples of hydrocarbylenes include unsubstituted or substituted (C6-C 50 ) Arrene, (C3-C 50 )Cycloalkylene, and (C1-C 50 )Alkylene (for example, (C1-C 20Examples include alkylenes. Diradicals may be located on the same carbon atom (e.g., -CH2-) or on adjacent carbon atoms (i.e., 1,2-diradicals), or separated by one, two, or three or more intervening carbon atoms (e.g., 1,3-diradicals, 1,4-diradicals, etc.). Some examples of diradicals include 1,2-, 1,3-, 1,4-, or α,ω-diradicals. The α,ω-diradical is a diradical with the largest carbon skeleton spacing between radical carbons. (C2-C 20 Some examples of alkylene α,ω-diradicals include ethane-1,2-diyl (i.e., -CH2CH2-), propane-1,3-diyl (i.e., -CH2CH2CH2-), and 2-methylpropane-1,3-diyl (i.e., -CH2CH(CH3)CH2-). (C6-C 50 Some examples of arylene α,ω-diradicals include phenyl-1,4-diyl, naphthalene-2,6-diyl, or naphthalene-3,7-diyl.

[0032] (C1-C 50 The term "alkylene" refers to an unsubstituted or one or more R S This refers to a saturated straight-chain or branched-chain diradical having 1 to 50 carbon atoms substituted by (i.e., the radical is not on a ring atom). Unsubstituted (C1-C 50 An example of alkylene is unsubstituted (C1-C 20 ) Alkylenes, including unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C*HCH3, and -(CH2)4C*(H)(CH3), where "C*" represents a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl radical. Substituted (C1-C 50 An example of alkylene is substitution (C1-C 20 ) Alkylene, -CF2-, -C(O)-, and -(CH2) 14It is C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted n-1,20-eicosylene). As mentioned above, there are two R S They come together, (C1-C 18 )It can form an alkylene, so substitution (C1-C 50 Examples of alkylenes include 1,2-bis(methylene)cyclopentane, 1,2-bis(methylene)cyclohexane, 2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane, and 2,3-bis(methylene)bicyclo[2.2.2]octane.

[0033] (C3C 50 The term "cycloalkylene" refers to a compound having 3 to 50 carbon atoms, either unsubstituted or with one or more R S This refers to a cyclic diradical (i.e., the radical is located on the ring atom) that is substituted by [a specific component].

[0034] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of groups containing one or more heteroatoms include O, S, S(O), and S(O)2Si(R). C )2P(R P ), Ge(R C )2, N(R N ), or -N=C(R C )2 is given, and in the formula, each R C and each R P However, non-substituted (C1-C 18 ) Hydrocarbyl or -H, each R N However, non-substituted (C1-C 18 ) is a hydrocarbyl. The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more carbon atoms of a hydrocarbon are replaced by heteroatoms. 50 The term "heterohydrocarbyl" refers to a heterohydrocarbon radical having 1 to 50 carbon atoms, or "(C1-C 50 The term "heterohydrocarbylene" refers to a heterohydrocarbon diradical having 1 to 50 carbon atoms. (C1-C 50) Heterohydrocarbyl or (C1-C 50 The heterohydrocarbon diradical of heterohydrocarbylene has one or more heteroatoms. The radical of heterohydrocarbylene can be located on a carbon atom or on a heteroatom. The two groups of heterohydrocarbylene can be located on a single carbon atom or on a single heteroatom. In addition, one of the two radicals of a diradical can be located on a carbon atom and the other radical can be located on a different carbon atom, one of the two radicals can be located on a carbon atom and the other can be located on a heteroatom, or one of the two radicals can be located on a heteroatom and the other radical can be located on a different heteroatom. Each (C1-C 50 )heterohydrocarbyl and (C1-C 50 ) Heterohydrocarbylenes are unsubstituted or (one or more R S They may be substituted, aromatic or non-aromatic, saturated or unsaturated, linear or branched, cyclic (including monocyclic and polycyclic, fused polycyclic and non-fused polycyclic) or acyclic.

[0035] (C1-C 50 ) Heterohydrocarbyl may be unsubstituted or substituted. (C1-C 50 )A non-limiting example of heterohydrocarbil is (C1-C 50 ) Heteroalkyl, (C1-C 50 ) Hydrocarbyl-O-, (C1-C 50 ) Hydrocarbyl-S-, (C1-C 50 )hydrocarbyl-S(O)-,(C1-C 50 )hydrocarbyl-S(O)2-,(C1-C 50 ) Hydrocarbyl-Si(R C )2-, (C l -C 50 ) Hydrocarbyl-N(R N )-, (C1-C 50 ) Hydrocarbil-P(R P )-, (C2-C 50 ) Heterocycloalkyl, (C2-C 19) Heterocycloalkyl-(C1-C 20 )Alkilen, (C3-C 20 )Cycloalkyl-(C1-C 19 )heteroalkylene, (C2-C 19 ) Heterocycloalkyl-(C1-C 20 ) Heteroalkylene, (C1-C 50 ) Heteroaryl, (C1-C 19 )heteroaryl-(C1-C 20 )Alkilen, (C6-C 20 )aryl-(C1-C 19 )heteroalkylene, or (C1-C 19 )heteroaryl-(C1-C 20 ) Heteroalkylenes are an example.

[0036] (C4C 50 The term "heteroaryl" refers to a compound with a total of 4 to 50 carbon atoms and 1 to 10 heteroatoms, which is unsubstituted or (one or more R) S This refers to monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon radicals (substituted by). A monocyclic heteroaromatic hydrocarbon radical contains one heteroaromatic ring, a bicyclic heteroaromatic hydrocarbon radical has two rings, and a tricyclic heteroaromatic hydrocarbon radical has three rings. If a bicyclic or tricyclic heteroaromatic hydrocarbon radical exists, at least one of the rings in the radical is heteroaromatic. One or more other rings in a heteroaromatic radical can independently be condensed or uncondensed and aromatic or nonaromatic. Other heteroaryl groups (e.g., generally (C)) x -C y )heteroaryl, (C4-C 12 (e.g., heteroaryl compounds) have x to y carbon atoms (e.g., 4 to 12 carbon atoms) and are unsubstituted or have one or more R atoms. S It is defined in a similar manner to those substituted by. Monocyclic heteroaromatic hydrocarbon radicals are five-membered or six-membered rings.

[0037] A five-membered ring monocyclic heteroaromatic hydrocarbon radical has 5 minus h carbon atoms, where h is the number of heteroatoms, which can be 1, 2, or 3, and each heteroatom can be O, S, N, or P. Examples of five-membered ring heteroaromatic hydrocarbon radicals include pyrrole-1-yl, pyrrole-2-yl, furan-3-yl, thiophen-2-yl, pyrazole-1-yl, isoxazole-2-yl, isothiazole-5-yl, imidazole-2-yl, oxazole-4-yl, thiazole-2-yl, 1,2,4-triazole-1-yl, 1,3,4-oxadiazole-2-yl, 1,3,4-thiadiazole-2-yl, tetrazole-1-yl, tetrazole-2-yl, and tetrazole-5-yl.

[0038] A six-membered monocyclic heteroaromatic hydrocarbon radical has 6 minus h carbon atoms, where h is the number of heteroatoms, which can be 1 or 2, and the heteroatoms can be N or P. Examples of six-membered monocyclic heteroaromatic hydrocarbon radicals include pyridine-2-yl, pyrimidine-2-yl, and pyrazine-2-yl.

[0039] Bicyclic heteroaromatic hydrocarbon radicals can be condensed 5,6- or 6,6-ring systems. Examples of condensed 5,6-ring bicyclic heteroaromatic hydrocarbon radicals include indole-1-yl and benzimidazole-1-yl. Examples of condensed 6,6-ring bicyclic heteroaromatic hydrocarbon radicals include quinoline-2-yl and isoquinoline-1-yl. Tricyclic heteroaromatic hydrocarbon radicals can be condensed 5,6,5-, 5,6,6-, 6,5,6-, or 6,6,6-ring systems. An example of a condensed 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indole-1-yl. An example of a condensed 5,6,6-ring system is 1H-benzo[f]indole-1-yl. An example of a condensed 6,5,6-ring system is 9H-carbazole-9-yl. An example of a condensed 6,6,6-ring system is acridine-9-yl.

[0040] (C1-C 50The term heteroalkyl refers to a saturated linear or branched radical containing 1 to 50 carbon atoms and one or more heteroatoms. 50 The term "heteroalkylene" refers to a saturated linear or branched diradical containing 1 to 50 carbon atoms and one or more heteroatoms. Examples of heteroatoms in heteroalkyl or heteroalkylene include Si(R) C )3, Ge(R C )3, Si(R C )2, Ge(R C )2, P(R P )2, P(R P ), N(R N )2, N(R N ), N, O, OR C S, SR C Examples include S(O) and S(O)2, where each of the heteroalkyl and heteroalkylene is unsubstituted or has one or more R S It is replaced by

[0041] Unsubstituted (C2-C 40 Examples of heterocycloalkyl groups include unsubstituted (C2-C 20 ) Heterocycloalkyl, unsubstituted (C2-C 10 Examples include heterocycloalkyls, aziridin-1-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidine-1-yl, tetrahydrothiophen-S,S-dioxide-2-yl, morpholine-4-yl, 1,4-dioxan-2-yl, hexahydroazepine-4-yl, 3-oxacyclooctyl, 5-thiocyclononyl, and 2-azacyclodecyl.

[0042] The term "saturated" means the absence of carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, and carbon-silicon double bonds. A saturated chemical group has one or more substituents R S If substituted by, one or more double and / or triple bonds may optionally be substituted with substituent R SIt may be present in the group. The term "unsaturated" refers to a group containing one or more carbon-carbon double bonds or carbon-carbon triple bonds, or one or more carbon-nitrogen double bonds, carbon-phosphorus double bonds, or carbon-silicon double bonds (in heteroatom-containing groups), with substituent R S This means that it does not contain any double bonds (if present), or double bonds that may be present in an aromatic ring or heteroaromatic ring (if present).

[0043] Embodiments of the present disclosure are processes for polymerizing olefins, wherein ethylene and (C3-C3) are polymerized in the presence of a catalyst system. 40 The process comprises contacting an alpha-olefin comonomer with a catalyst system comprising a group IV metal-ligand complex and a metal activator ionic complex, wherein the metal activator ionic complex comprises an anion and a countercation, and the anion has a structure according to formula (I). [ka]

[0044] In equation (I), each X is a halogen, halogen substitution (C1-C 20 )alkyl or halogen-substituted (C6-C 40 ) is a monodentate ligand selected independently of the aryl group. Furthermore, at most one X is a halogen.

[0045] In equation (I), the subscript n is either 0 or 1. Each R is independently selected from the group consisting of radicals having equation (II) and radicals having equation (III). [ka]

[0046] In equation (II), each Y is independently carbon or silicon, and each R 11 , R 12 , R 13 (C1-C 40 ) alkyl, (C6-C 40 )aryl, -H, -NRN 2, -OR C , -SR C , or selected from halogens. In some embodiments of formula (I), when each R is a radical according to formula (II) and Y is carbon, R 11-13 At least one of them is halogen substitution (C1-C 40 ) Alkyl, halogen-substituted (C6-C 40 ) Aryl, or -F.

[0047] In equation (III), each R 21 , R 22 , R 23 , R 24 , and R 25 (C1-C 40 ) alkyl, (C6-C 40 )aryl, -H, -NR N 2, -OR C , -SR C , or selected from halogens. When R is a radical according to formula (III), R 21 -R 25 At least one of them is halogen substitution (C1-C 40 ) Alkyl, halogen-substituted (C6-C 40 ) Aryl, or -F.

[0048] In one or more embodiments of the catalytic system, the subscript n of the anion in formula (I) is 0, and each X group is independently -C(H)(CF3)2, -C6F5, or -C(CF3)3. In some embodiments, one X is selected from -OH, triflate (-OTf), methyl, or halogen. In other embodiments, n is 0, three of the four X groups are -C(CF3)3, and one of the four X groups is -C6F5.

[0049] In the polymerization embodiment, the countercation is Me2PhN(H) + And when the anion is Al(C6F5)4, the procatalyst is not Ph2C(Cp)(Flu)ZrCl2 or Et(1-Ind)2ZrCl2. In some embodiments, the countercation is (Ph)3C+ Therefore, when the anion is Al(C6F5)4, the procatalyst is not Et(1-Ind)2ZrCl2.

[0050] In one or more embodiments of the catalytic system, the two X groups of the anion of formula (I) are covalently bonded, and the anion has a structure according to formula (IV). [ka]

[0051] In equation (IV), R and each X are as defined in equation (I), z is 0 or 1, y is 0, 1, or 2, x is 1 or 2, and 2x + y + z = 4. L represents two covalently bonded X groups, and L independently represents halogen substitution (C2-C 40 ) Alkylene, halogen substitution (C2-C 40 ) Heteroalkylene, or halogen-substituted (C6-C 40 ) Selected from Arirene.

[0052] In equation (IV), when z is 1, X is the halogenated -(C1-C 20 ) Selected from alkyl groups.

[0053] In one or more embodiments of a catalytic system containing the anion of formula (IV), L is a halogenated biphenyl diradical ion or a halogenated naphthalene-diyl. The halogenated biphenyl diradical ion may have a single radical on each phenyl ring. The diradical on the halogenated naphthalene-diyl may be separated by four or more carbon atoms of naphthalene.

[0054] In one or more embodiments, the metal activator ionic complex comprises an anion according to formula (I) or (IV) and a counter cation having a formal charge of +1 (+1). In some embodiments of the metal ionic complex, the counter cation is a protonated tri[(C1-C 40Selected from )hydrocarbylammonium cations. In some embodiments, the countercation is one or two (C) on the ammonium cation. 14 -C 20 ) is a protonated trialkylammonium cation containing an alkyl group. In one or more embodiments, the countercation is + N(H)R N 3, and in the formula, each R N However, (C1-C 20 ) alkyl, or (C6-C 20 ) Selected from aryls. In one or more embodiments, the countercation is + N(H)R N 3, and in the formula, at least two R N However, (C 10 -C 20 ) Selected from alkyl. In one or more embodiments, the countercation is + N(H)R N 3, and in the formula, R N However, (C 16 -C 18 ) is alkyl. In one or more embodiments, the countercation is, + N(CH3)HR N 2, and in the formula, R N However, (C 16 -C 18) is alkyl. In some embodiments, the countercation is selected from methyldi(octadecyl)ammonium cation, methyl(octadecyl)(hexadecyl)ammonium cation, methyldi(hexadecyl)ammonium cation, or methyldi(tetradecyl)ammonium cation. Methyldi(octadecyl)ammonium cation, methyl(octadecyl)(hexadecyl)ammonium cation, methyldi(hexadecyl)ammonium cation, or methyldi(tetradecyl)ammonium cation are collectively referred to herein as armeenium cation. Ionic compounds having armeenium cations are readily formed by protonating methyldi(octadecyl)amine, methyl(octadecyl)(hexadecyl)amine, methyldi(hexadecyl)amine, or methyldi(tetradecyl)amine (for example, with anhydrous HCl in ether), such as Armeen® M2HT, which is available from Akzo-Nobel under the trade name Armeen®. In other embodiments, the countercation is tritylphenylmethyl carbocation ( + It is C(C6H5)3) and is also called trityl. In one or more embodiments, the countercation is + C(C6H4R C )3 is a tris-substituted-triphenylmethylcarbocation, where each R is C (C1-C 30 ) Selected from alkyl groups. In other embodiments, the countercation is selected from anilinium, ferrocenium, or aluminocenium. The anilinium cation is [HN(R S )(R N )2] + These are protonated nitrogen cations, and in the formula, R N However, (C1-C 20 ) Alkyl, or H, R S However, (C6-C 20 ) Selected from aryls, and each alkyl or aryl is -OR C For example, C6H5NMe2H + It may be further substituted with. Aluminocenium is R S2Al(THF)2 + These are aluminum cations, and in the formula, R S However, (C1-C 30 ) Selected from alkyl groups.

[0055] In one or more embodiments, the metal activator ionic complex has a dielectric loss tangent of 0.1 or less at a concentration of 200 micromoles of the metal activator complex and 20 millimoles of water in a high-boiling point fully saturated hydrocarbon solution, as measured by a hydrocarbon conductivity test. In some embodiments, the metal activator ionic complex has a dielectric loss tangent of 0.05 or less, 0.03 or less, or 0.025 or less at a concentration of 200 micromoles of the metal activator ionic complex and 20 millimoles of water per liter of high-boiling point fully saturated hydrocarbon solution, as measured by a hydrocarbon conductivity test. The high-boiling point fully saturated hydrocarbon solution ("hydrocarbon solution") comprises a high-boiling point fully saturated hydrocarbon solvent, water, and the metal activator ionic complex. Examples of high-boiling point fully saturated hydrocarbon solvents include squalane, dodecane, eicosane, or triacontane. The term "high-boiling point" in relation to "high-boiling point fully saturated hydrocarbon solvent" refers to a solvent having a boiling point greater than 150°C or equal to 190°C.

[0056] To understand the comparative electrical properties of polyolefin elastomers produced by polymerization processes according to this disclosure, specifically elastomers produced by metal activator ionic complexes according to formula (I), hydrocarbon conductivity (HC) tests were performed. The HC test was performed using methyl di((C) 14 -C 20 This study simulates the difference in electrical properties between polyolefin elastomers produced by comparative activators such as alkyl)ammonium tetrakis(pentafluorophenyl)borate and polyolefin elastomers produced by the metal activator ionic complex of this disclosure. In the HC test, the activator is dissolved in a high-boiling point fully saturated hydrocarbon solvent at room temperature. (Room temperature is approximately 22.0 ± 2.5°C.)

[0057] In the HC test, the dielectric loss tangent (60 Hz) and conductivity of hydrocarbon samples are measured. Each hydrocarbon sample is measured using a standard method with a Novocontrol Technologies broadband dielectric spectrometer (Alpha-A). All sample preparation steps and measurements were performed at room temperature, except for gentle heating.

[0058] To prepare hydrocarbon samples, a fixed amount of activator is added to approximately 10 mL of hydrocarbon solvent to create a sample with an activator concentration of approximately 200 μM in solution. For aqueous hydrocarbon samples, deionized water is added to obtain a concentration of approximately 20 mM, and a fixed amount of activator is added to obtain a 200 μM activator hydrocarbon solution. All samples are heated below the boiling point of the hydrocarbon to remove water and any remaining low-boiling point solvent. Dielectric loss tangent and conductivity are measured as described in the previous paragraph.

[0059] The ratio of the total number of moles of one or more Group IV metal-ligand complexes in the catalytic system to the total number of moles of one or more metal activator ionic complexes in the catalytic system is between 1:10,000 and 100:1.

[0060] In exemplary embodiments, the catalyst system may include a metal activator ionic complex comprising an anion and a countercation, wherein the anion conforms to formula (I). Exemplary embodiments include an anionic structure that forms a complex with the countercation described herein and have the following structure: [ka]

[0061] Electrical properties of polymers The electrical insulation efficiency of a medium, such as polymer materials, can be evaluated by considering the electrical resistance and electrical losses of the medium. Electrical losses reduce the efficiency of the insulating medium in insulating electrical properties in the presence of an electric field. Since resistance is inversely correlated with power or electrical losses, the resistance of the insulating medium should be as high as possible in both alternating current (AC) and direct current (DC) systems.

[0062] In DC systems such as photovoltaic devices encapsulated in insulating media like polymer materials, electrical loss manifests as leakage current from the encapsulated device through the encapsulating material to the external environment. This current (I) correlates with the voltage (V) of the insulating medium, given by the equation I = V × R -1 Therefore, it is inversely correlated with the resistance (R) of the insulating medium. Consequently, the higher the resistance, the lower the current and leakage current.

[0063] In AC systems that include insulating media such as cable insulators, electrical loss manifests as energy absorption by the insulating media in the presence of an electric field. This loss, measured in power (P), is given by the equation P=V 2 It is determined by ×ω × C × ε′ × tanδ, where ω is the angular frequency, ε' is the relative permittivity, C is the capacitance, and tanδ is the dielectric loss tangent, and tanδ = (C × R × ω) -1 Therefore, the equation P = V 2× ε′×R -1 This results in power loss. Since resistance is inversely correlated with power loss, the higher the resistance, the lower the power loss.

[0064] The electrical resistance of a medium generally decreases as a result of ion diffusion caused by an external electric field. In systems where ion diffusion prevails over electrical response, resistance is given by the equation R = 6 × π × ε′ × ε₀ × η × r × C -1 ×q -2 ×N -1 It correlates with ion diffusion according to the formula, where ε0 is the permittivity of vacuum (8.854 × 10⁻⁴). -12 F·m -1 ) where η is the kinematic viscosity of the medium, r is the hydrodynamic radius of the ion, q is the charge of the ion, and N is the ion concentration. Since increasing resistance reduces energy loss and decreasing ion concentration increases resistance, reducing the concentration of ions diffusing through the medium reduces energy loss.

[0065] The ability of ions to diffuse through a given medium is influenced by the ion's size, charge, interaction between the ion and the surrounding medium, and the ion's dissociation energy with available counterions. Since not all ions diffuse equally through a given medium, when the medium is a polymer, the ion diffusion rate generally affects the polymer's insulating ability. Not intended to be constrained by theory, but because the anions of the ionic metal activator complex of formula (I) have a low ability to diffuse through the resulting polymer, the resulting polymer of the catalytic system of this disclosure is thought to possess desirable electrical properties, such as reduced electrical loss.

[0066] Catalyst components Examples of catalytic systems include procatalysts. Procatalysts can be catalytically activated by contacting a complex with a metal activator having an anion and countercation of formula (I), or by combining a metal activator with a complex. Examples of procatalysts include titanium (Ti) metal-ligand complexes, zirconium (Zr) metal-ligand complexes, or hafnium (Hf) metal-ligand complexes, which consist of one or more Group IV metals (Group IVB according to CAS, or Group IV according to IUPAC nomenclature rules)-ligand complexes. Non-limiting examples of procatalysts include catalysts, procatalysts, or catalytically active compounds for polymerizing ethylene-based polymers, which are disclosed in one or more of US8372927, WO2010 / 022228, WO2011 / 102989, US6953764, US6900321, WO2017 / 173080, US7650930, US6777509, WO99 / 41294, US6869904, or WO2007 / 136496, all of which are incorporated herein by reference in their entirety.

[0067] In one or more embodiments, the group IV metal-ligand complex may be a bis-phenylphenoxy group IV metal-ligand complex or a group IV metal-ligand complex in a constrained form.

[0068] According to some embodiments, the bis-biphenylphenoxy group IV metal-ligand complex has a structure according to formula (XI). [ka]

[0069] In equation (XI), M is a metal selected from titanium, zirconium, or hafnium, and the metal is in a formal oxidation state of +2, +3, or +4. (X) n The subscript n is 0, 1, or 2. When the subscript n is 1, X is a monositu ligand or a bisitu ligand, and when the subscript n is 2, each X is a monositu ligand. L is (C1-C 40 ) Hydrocarbylene, (C1-C 40 ) Heterohydrocarbylene, -Si(R C )2-,-Si(R C )2OSi(R C )2-,-Si(R C )2C(R C )2-,-Si(R C )2Si(R C )2-,-Si(R C )2C(R C )2Si(R C )2-, -C(R C )2Si(R C )2C(R C )2-, -N(R N )C(R C )2-, -N(R N )N(R N )-,-C(R C )2N(R N )C(R C )2-,-Ge(R C )2-, -P(R P )-,-N(R N )-, -O-, -S-, -S(O)-, -S(O)2-, -N=C(R C )-, -C(O)O-, -OC(O)-, -C(O)N(R)-, and -N(R C It is a diradical selected from the group consisting of -C(O)-. Each Z is independently -O-, -S-, -N(R N)-, or -P(R P )- Selected from, R 2-4 , R 5-8 , R 9-12 , and R 13-15 These are independently -H, (C1-C 40 ) Hydrocarbyl, (C1-C 40 ) Heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C -NO2, -CN, -CF3, R C S(O)-, R C S(O)²⁻, -N=C(R) C )2, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C Selected from the group consisting of 2NC(O)- and halogens. 1 and R 16 This is selected from a radical having formula (XII), a radical having formula (XIII), and a radical having formula (XIV). [ka]

[0070] In equations (XII), (XIII), and (XIV), R 31 -R 35 , R 41 -R 48 , and R 51 -R 59 Each of these is independent of -H, (C1-C 40 ) Hydrocarbyl, (C1-C 40 ) Heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C -NO2, -CN, -CF3, R C S(O)-, RC S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C ) Selected from 2NC(O)-, or halogen.

[0071] In one or more embodiments, each X is independent of any other ligand X, and is halogen, unsubstituted (C1-C 20 ) Hydrocarbyl, unsubstituted (C1-C 20 ) Hydrocarbyl C(O)O-, or R K R L It can be a monodentate ligand of N-, in the formula R K and R L Each of them is independent of the non-substitution (C1-C 20 ) It is hydrocarbyl.

[0072] Examples of metal-ligand complexes following formula (XI) include, for example,

[0073] (2',2"-(propane-1,3-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-octyl-9H-carbazole-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0074] (2',2"-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-3'-chloro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0075] (2',2"-(propane-1,3-diylbis(oxy))bis(3'-chloro-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-5'-fluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0076] (2',2"-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0077] (2',2"-(propane-1,3-diylbis(oxy))bis(5'-cyano-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0078] (2',2"-(propane-1,3-diylbis(oxy))bis(5'-dimethylamino-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0079] (2',2"-(propane-1,3-diylbis(oxy))bis(3',5'-dimethyl-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0080] (2',2"-(propane-1,3-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-3'-ethyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0081] (2',2"-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-3'-methyl-5'-tert-butyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0082] (2',2"-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-5'-fluoro-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0083] (2',2"-(propane-1,3-diylbis(oxy))bis(3-(9H-carbazole-9-yl)-5'-chloro-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0084] (2',2"-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-3'-methyl-5'-trifluoromethyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0085] (2',2"-(2,2-dimethyl-2-silapropane-1,3-diylbis(oxy))bis(3',5'-dichloro-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0086] (2'2"-(2,2-dimethyl-2-silapropane-1-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9carbazole-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0087] (2',2"-(propane-1,3-diylbis(oxy))bis(3'-bromo-5'-chloro-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0088] (2',2”-(propane-1,3-diylbis(oxy))-(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-fluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)-(3",5”-dichloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0089] (2',2"-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-5'-fluoro-3'-trifluoromethyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0090] (2',2"-(butane-1,4-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0091] (2',2"-(ethane-1,2-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0092] (2',2"-(propane-1,3-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-zirconium;

[0093] (2',2"-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-3',5'-dichloro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-titanium; and

[0094] (2',2"-(propane-1,3-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazole-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-titanium is one example.

[0095] Other bis-biphenylphenoxy metal-ligand complexes that can be used in combination with the metal activator in the catalytic system of this disclosure will be apparent to those skilled in the art.

[0096] According to some embodiments, the group IV metal-ligand complex is a group IV metal-ligand complex according to formula (XV),

[0097] LP i MX m X' n X" p Alternatively, we can list the dimer of (XV).

[0098] In formula (XV), Lp is an anionic, delocalized π-bonding group bonded to M, containing up to 50 non-hydrogen atoms. In some embodiments of formula (XV), two Lp groups may bond together to form a bridging structure, and optionally, one Lp may be bonded to X.

[0099] In formula (XV), M is a Group 4 metal of the Periodic Table in a formal oxidation state of +2, +3, or +4. X is an optional divalent substituent of up to 50 non-hydrogen atoms that forms a metallacycle containing M together with Lp. X' is an optional neutral ligand having up to 20 non-hydrogen atoms, and each X" is independently a monovalent anionic moiety having up to 40 non-hydrogen atoms. Optionally, two X" groups may be covalently bonded together to form a divalent dianionic moiety in which both valences are bonded to M, or optionally, two X" groups may be covalently bonded together to form a neutral, conjugated or non-conjugated diene that is π-bonded to M where M is in the +2 oxidation state. In other embodiments, one or more X'' groups and one or more X' groups may be bonded together, thereby forming a moiety that is covalently bonded to M and coordinated to M by a Lewis base functional group.

[0100] Exemplary constrained geometry Group IV complexes that can be used in the practice of the present invention include

[0101] Cyclopentadienyltitanium trimethyl;

[0102] Cyclopentadienyltitanium triethyl;

[0103] Cyclopentadienyltitanium triisopropyl;

[0104] Cyclopentadienyltitanium triphenyl;

[0105] Cyclopentadienyltitanium tribenzyl;

[0106] Cyclopentadienyltitanium-2,4-dimethylpentadienyl;

[0107] Cyclopentadienyltitanium-2,4-dimethylpentadienyl·triethylphosphine;

[0108] Cyclopentadienyltitanium-2,4-dimethylpentadienyl·trimethylphosphine;

[0109] Cyclopentadienyl titanium dimethyl methoxide;

[0110] Cyclopentadienyl titanium dimethyl chloride;

[0111] Pentamethylcyclopentadienyltitanium trimethyl;

[0112] Indenyl titanium trimethyl;

[0113] Indenyl titanium triethyl;

[0114] Indenyl titanium tripropyl;

[0115] Indenyl titanium triphenyl;

[0116] Tetrahydroindenyl titanium tripenzyl;

[0117] Pentamethylcyclopentadienyltitanium triisopropyl;

[0118] Pentamethylcyclopentadienyltitaniumtribenzyl;

[0119] Pentamethylcyclopentadienyltitanium dimethyl methoxide;

[0120] Pentamethylcyclopentadienyl titanium dimethyl chloride;

[0121] Bis(η) 5 -2,4-dimethylpentadienyl)titanium;

[0122] Bis(η) 5 -2,4-dimethylpentadienyl)titanium trimethylphosphine;

[0123] Bis(η) 5 (-2,4-dimethylpentadienyl)titanium triethylphosphine;

[0124] Octahydrofluorenyltitanium trimethyl;

[0125] Tetrahydroindenyltitanium trimethyl;

[0126] Tetrahydrofluorenyltitanium trimethyl;

[0127] (tert-Butylamide)(1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalenyl)dimethylsilane titanium dimethyl;

[0128] (tert-Butylamide)(1,1,2,3-tetramethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalenyl)dimethylsilane titanium dimethyl;

[0129] (tert-Butylamide)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilane titanium dibenzyl;

[0130] (tert-Butylamide)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilane titanium dimethyl;<​​​​​​​​​​​​​​​​​​​​​​-Cyclopentadienyl)dimethylsilanthan(III) allyl;

[0135] (tert-butylamide)(tetramethyl-η) 5 -Cyclopentadienyl)dimethylsilanthan(III)2,4-dimethylpentadienyl;

[0136] (tert-butylamide)(tetramethyl-η) 5 -Cyclopentadienyl)dimethylsilanthan(II)1,4-diphenyl-1,3-butadiene;

[0137] (tert-butylamide)(tetramethyl-η) 5 -Cyclopentadienyl)dimethylsilanthan(II)1,3-pentadiene;

[0138] (tert-butylamide)(2-methylindenyl)dimethylsilanthan(II)1,4-diphenyl-1,3-butadiene;

[0139] (tert-butylamide)(2-methylindenyl)dimethylsilanthan(II)2,4-hexadiene;

[0140] (tert-butylamide)(2-methylindenyl)dimethylsilanthan(IV)2,3-dimethyl-1,3-butadiene;

[0141] (tert-butylamide)(2-methylindenyl)dimethylsilanthan(IV)isoprene;

[0142] (tert-butylamide)(2-methylindenyl)dimethylsilanthan(IV)1,3-butadiene;

[0143] (tert-butylamide)(2,3-dimethylindenyl)dimethylsilanthan(IV)2,3-dimethyl-1,3-butadiene;

[0144] (tert-butylamide)(2,3-dimethylindenyl)dimethylsilanthan(IV) isoprene;

[0145] (tert-butylamide)(2,3-dimethylindenyl)dimethylsilanthan(IV)dimethyl;

[0146] (tert-butylamide)(2,3-dimethylindenyl)dimethylsilanthan(IV) dibenzyl;

[0147] (tert-butylamide)(2,3-dimethylindenyl)dimethylsilanthan(IV)1,3-butadiene;

[0148] (tert-butylamide)(2,3-dimethylindenyl)dimethylsilanthan(II)1,3-pentadiene;

[0149] (tert-butylamide)(2,3-dimethylindenyl)dimethylsilanthan(II)1,4-diphenyl-1,3-butadiene;

[0150] (tert-butylamide)(2-methylindenyl)dimethylsilanthan(II)1,3-pentadiene;

[0151] (tert-butylamide)(2-methylindenyl)dimethylsilanthan(IV)dimethyl;

[0152] (tert-butylamide)(2-methylindenyl)dimethylsilanthan(IV)dibenzyl;

[0153] (tert-butylamide)(2-methyl-4-phenylindenyl)dimethylsilanthan(II)1,4-diphenyl-1,3-butadiene;

[0154] (tert-butylamide)(2-methyl-4-phenylindenyl)dimethylsilanthan(II)1,3-pentadiene;

[0155] (tert-butylamide)(2-methyl-4-phenylindenyl)dimethylsilanthan(II)2,4-hexadiene;

[0156] (tert-butylamide)(tetramethyl-η) 5 -Cyclopentadienyl)dimethyl-silantitane(IV)1,3-butadiene;

[0157] (tert-butylamide)(tetramethyl-η) 5 -Cyclopentadienyl)dimethylsilanthan(IV)2,3-dimethyl-1,3-butadiene;

[0158] (tert-butylamide)(tetramethyl-η) 5 -Cyclopentadienyl)dimethylsilanthan(IV)isoprene;

[0159] (tert-butylamide)(tetramethyl-η) 5 -Cyclopentadienyl)dimethyl-silantitane(II)1,4-dibenzyl-1,3-butadiene;

[0160] (tert-butylamide)(tetramethyl-η) 5 -Cyclopentadienyl)dimethylsilanthan(II)2,4-hexadiene;

[0161] (tert-butylamide)(tetramethyl-η) 5 -Cyclopentadienyl)dimethyl-silantitane(II)3-methyl-1,3-pentadiene;

[0162] (tert-butylamide)(2,4-dimethylpentadien-3-yl)dimethylsilantitanedimethyl;

[0163] (tert-butylamide)(6,6-dimethylcyclohexadienyl)dimethylsilanthandimethyl;

[0164] (tert-butylamide)(1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalene-4-yl)dimethylsilantitanedimethyl;

[0165] (tert-butylamide)(1,1,2,3-tetramethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalene-4-yl)dimethylsilantitanedimethyl;

[0166] (tert-butylamide)(tetramethyl-η) 5 -Cyclopentadienylmethylphenylsilanthan(IV)dimethyl;

[0167] (tert-butylamide)(tetramethyl-η) 5 -Cyclopentadienylmethylphenylsilanthan(II)1,4-diphenyl-1,3-butadiene;

[0168] 1-(tert-butylamide)-2-(tetramethyl-η) 5 -Cyclopentadienyl)ethanediyltitanium(IV)dimethyl;

[0169] 1-(tert-butylamide)-2-(tetramethyl-η) 5 Examples include cyclopentadienyl)ethanediyl-titanium(II)1,4-diphenyl-1,3-butadiene.

[0170] Other catalysts, specifically catalysts containing other Group IV metal-ligand complexes, will be obvious to those skilled in the art.

[0171] The catalyst systems of this disclosure may include, in addition to the metal activator ionic complex having the anion and countercation of formula (I), co-catalysts or activators. Examples of such additional co-catalysts include tri(hydrocarbyl)aluminum compounds having 1 to 10 carbon atoms in each hydrocarbyl group, oligomeric or polymeric alumoxane compounds, di(hydrocarbyl)(hydrocarbyloxy)aluminum compounds having 1 to 20 carbon atoms in each hydrocarbyl or hydrocarbyloxy group, or mixtures of the aforementioned compounds. These aluminum compounds are typically useful due to their beneficial ability to capture impurities such as oxygen, water, and aldehydes from polymerization mixtures.

[0172] The di(hydrocarbyl)(hydrocarbyloxy)aluminum compounds that can be used in combination with the activators described herein are those of formula T 1 2AlOT 2 Or T1Al(OT 2 ) corresponds to 2, and in the formula, T 1 However, it is a secondary or tertiary (C3-C6) alkyl such as isopropyl, isobutyl, or tert-butyl, and T 2 However, alkyl substitutions such as 2,6-di(tert-butyl)-4-methylphenyl, 2,6-di(tert-butyl)-4-methylphenyl, 2,6-di(tert-butyl)-4-methyltolyl, or 4-(3',5'-di-tert-butyltolyl)-2,6-di-tert-butylphenyl (C6-C 30 ) Aryl radical, or aryl substitution (C1-C 30 It is an alkyl radical.

[0173] Additional examples of aluminum compounds include [C6]trialkylaluminum compounds, specifically those in which the alkyl group is ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, neopentyl, or isopentyl; dialkyl(aryloxy)aluminum compounds containing 1 to 6 carbon atoms in the alkyl group and 6 to 18 carbon atoms in the aryl group (specifically, (3,5-di(t-butyl)-4-methylphenoxy)diisobutylaluminum); methylaluminoxanes; modified methylaluminoxanes; and diisobutylaluminoxanes.

[0174] In catalyst systems according to embodiments of this disclosure, the molar ratio of the metal activator ionic complex to the group IV metal-ligand complex may be 1:10,000 to 1000:1, such as 1:5000 to 100:1, 1:100 to 100:1, 1:10 to 10:1, 1:5 to 1:1, or 1.25 to 1:1. The catalyst system may include a combination of one or more metal activator ionic complexes described in this disclosure.

[0175] The catalyst systems of this disclosure may include, in addition to the metal activator ionic complex having the anion and countercation of formula (I), co-catalysts or activators. Examples of such additional co-catalysts include tri(hydrocarbyl)aluminum compounds having 1 to 10 carbon atoms in each hydrocarbyl group, oligomeric or polymeric alumoxane compounds, di(hydrocarbyl)(hydrocarbyloxy)aluminum compounds having 1 to 20 carbon atoms in each hydrocarbyl or hydrocarbyloxy group, or mixtures of the aforementioned compounds. These aluminum compounds are typically useful due to their beneficial ability to capture impurities such as oxygen, water, and aldehydes from polymerization mixtures.

[0176] The di(hydrocarbyl)(hydrocarbyloxy)aluminum compounds that can be used in combination with the activators described herein are those of formula T 1 2AlOT 2 Or T1Al(OT 2 ) corresponds to 2, and in the formula, T 1However, it is a secondary or tertiary (C3-C6) alkyl such as isopropyl, isobutyl, or tert-butyl, and T 2 However, alkyl substitutions such as 2,6-di(tert-butyl)-4-methylphenyl, 2,6-di(tert-butyl)-4-methylphenyl, 2,6-di(tert-butyl)-4-methyltolyl, or 4-(3',5'-di-tert-butyltolyl)-2,6-di-tert-butylphenyl (C6-C 30 ) Aryl radical, or aryl substitution (C1-C 30 It is an alkyl radical.

[0177] Additional examples of aluminum compounds include [C6]trialkylaluminum compounds, specifically those in which the alkyl group is ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, neopentyl, or isopentyl; dialkyl(aryloxy)aluminum compounds containing 1 to 6 carbon atoms in the alkyl group and 6 to 18 carbon atoms in the aryl group (specifically, (3,5-di(t-butyl)-4-methylphenoxy)diisobutylaluminum); methylaluminoxanes; modified methylaluminoxanes; and diisobutylaluminoxanes.

[0178] In catalyst systems according to embodiments of this disclosure, the molar ratio of the metal activator ionic complex to the group IV metal-ligand complex may be 1:10,000 to 1000:1, such as 1:5000 to 100:1, 1:100 to 100:1, 1:10 to 10:1, 1:5 to 1:1, or 1.25 to 1:1. The catalyst system may include a combination of one or more metal activator ionic complexes described in this disclosure.

[0179] Polyolefins The catalyst systems described in the previous paragraph are used for the polymerization of olefins, mainly ethylene and propylene. In some embodiments, only a single type of olefin or α-olefin is present in the polymerization scheme to produce homopolymers. However, additional α-olefins may be incorporated into the polymerization procedure. Additional α-olefin comonomers typically have 20 or fewer carbon atoms. For example, an α-olefin comonomer may have 3 to 10 carbon atoms or 3 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene, 5-ethyldiene-2-norbornene, and 5-vinyl-2-norbornene. For example, one or more α-olefin comonomers may be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene, or alternatively from the group consisting of 1-hexene and 1-octene.

[0180] Ethylene-based polymers, such as homopolymers of ethylene and / or interpolymers (including copolymers) of ethylene with one or more comonomers, such as α-olefins, may contain at least 50 mole percent (mol%) of monomer units derived from ethylene. All individual values ​​and subranges encompassed by "at least mol%" are disclosed herein as separate embodiments, for example, ethylene-based polymers, homopolymers of ethylene and / or interpolymers (including copolymers) of ethylene with one or more comonomers, such as α-olefins, may contain at least 60 mole percent of monomer units derived from ethylene, at least 70 mole percent of monomer units derived from ethylene, at least 80 mole percent of monomer units derived from ethylene, or 50 to 100 mole percent of monomer units derived from ethylene, or 80 to 100 mole percent of units derived from ethylene.

[0181] In some embodiments, the polymerization process of the present disclosure produces an ethylene-based polymer that may contain at least 90 mole percent of ethylene-derived units. All individual values ​​and partial ranges from at least 90 mole percent are included herein and disclosed herein as separate embodiments. For example, the ethylene-based polymer may contain at least 93 mole percent of ethylene-derived units, at least 96 mole percent of units, at least 97 mole percent of ethylene-derived units, or alternatively, 90 to 100 mole percent of ethylene-derived units, 90 to 99.5 mole percent of ethylene-derived units, or 97 to 99.5 mole percent of ethylene-derived units.

[0182] In some embodiments of ethylene polymers, the ethylene polymer contains a certain amount of (C3-C 40 ) May contain α-olefins. (C3-C 40 The amount of α-olefin is less than 50 mol percent. In some embodiments, the ethylene polymer is at least 0.5 mol percent to 25 mol percent (C3-C 40 ) may contain α-olefins, and in further embodiments, the ethylene polymer may contain at least 5 mol% to 10 mol% (C3-C 40 ) may contain α-olefins. In some embodiments, (C3-C 40 )α-olefin is 1-octene.

[0183] Ethylene-based polymers can be produced using any conventional polymerization process combined with a catalyst system according to embodiments of the present disclosure. Such conventional polymerization processes include, but are not limited to, solution polymerization processes, gas-phase polymerization processes, slurry-phase polymerization processes, and any combination thereof, using one or more conventional reactors, such as loop reactors, isothermal reactors, fluidized bed gas-phase reactors, stirred tank reactors, batch reactors, etc., in parallel, in series, or in any combination thereof.

[0184] In one embodiment, the ethylene polymer may be produced by solution polymerization in a double reactor system, for example, a double-loop reactor system, where ethylene and optionally one or more α-olefins are polymerized in the presence of the catalyst system described herein and optionally one or more co-catalysts. In another embodiment, the ethylene polymer may be produced by solution polymerization in a double reactor system, for example, a double-loop reactor system, where ethylene and optionally one or more α-olefins are polymerized in the presence of the catalyst system described herein and optionally one or more other catalysts. The catalyst system described herein may be used in combination with optionally one or more other catalysts in a first reactor or a second reactor. In one embodiment, the ethylene polymer may be produced by solution polymerization in a double reactor system, for example, a double-loop reactor system, where ethylene and optionally one or more α-olefins are polymerized in both reactors in the presence of the catalyst system described herein.

[0185] In another embodiment, ethylene-based polymers can be produced via solution polymerization in a single reactor system, such as a single-loop reactor system, in which ethylene and optionally one or more α-olefins are polymerized in the presence of the catalyst system described herein.

[0186] The polymer process may further involve incorporating one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. The ethylene polymer may contain any amount of additives. Based on the weight of the ethylene polymer and one or more additives, the ethylene polymer may contain about 0 to about 10 percent by weight of such additives. The ethylene polymer may further contain fillers, which may include, but are not limited to, organic or inorganic fillers. Based on the total weight of the ethylene polymer and all additives or fillers, the ethylene polymer may contain about 0 to about 20 percent by weight of fillers, such as calcium carbonate, talc, or Mg(OH)2. The ethylene polymer can be further compounded with one or more polymers to form blends.

[0187] In some embodiments, a polymerization process for producing an ethylene-based polymer may involve polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst system, the catalyst system incorporating at least one metal-ligand complex and a metal-activating ionic complex. The polymer obtained from such a catalyst system incorporating the metal-ligand complex and the metal-activating ionic complex is, for example, 0.850 g / cm³ according to ASTM D792 (which is incorporated herein by reference in its entirety). 3 ~0.950g / cm 3 , 0.870 g / cm³ 3 ~0.920g / cm 3 , 0.870 g / cm³ 3 ~0.910 g / cm³ 3 , or 0.870 g / cm³ 3 ~0.900g / cm 3 It may have a density of .

[0188] In another embodiment, the polymer obtained from a catalyst system comprising a metal-ligand complex and a metal activator ionic complex has a melt flow ratio of 5 to 15 (I 10The melt index I2 is measured at 190°C and a load of 2.16 kg according to ASTM D1238 (which is incorporated herein by reference in its entirety), and the melt index I 10 However, it is measured at 190°C and a load of 10 kg according to ASTM D1238. In other embodiments, the melt flow ratio (I 10 The I2 ratio is 5-10, while the melt flow ratio is 5-9.

[0189] In some embodiments, the polymer obtained from a catalytic system comprising a metal-ligand complex and a metal activator ionic complex has a molecular weight distribution (MWD) of 1 to 25, where the MWD is M w / M n Defined as, M w However, it is the weight-average molecular weight, M n However, this is the number-average molecular weight. In other embodiments, the polymer produced from the catalyst system has 1 to 6 MWDs. Another embodiment includes 1 to 3 MWDs, and yet another embodiment includes 1.5 to 2.5 MWDs.

[0190] The embodiments of the catalyst systems described herein result in unique polymer properties such as a narrow composition and a narrow molecular weight.

[0191] Batch reactor procedure A 2 L Parr reactor is used for all reaction experiments. The reactor is heated by an electrically heated mantle and cooled by an internal serpentine cooling coil containing water. Both the reactor and the heating / cooling system are controlled and monitored by a Camile TG process computer. All chemicals used for polymerization or catalyst composition are passed through purification columns. 1-Octene, toluene, and Isopar-E (a mixed alkane solvent available from ExxonMobil, Inc.) are passed through two columns: a first column containing A2 alumina and a second column containing the Q5 reactant (available from Engelhard Chemicals Inc.). Ethylene gas is passed through two columns: a first column containing A204 alumina and activated 4A molecular sieves, and a second column containing the Q5 reactant. Hydrogen gas is passed through the Q5 reactant and A2 alumina. Nitrogen gas is passed through a single column containing A204 alumina, activated 4A° molecular sieves, and the Q5 reactant. The catalyst and metal activator ionic complex solutions are handled in a glove box filled with nitrogen.

[0192] Using an Ashcroft differential pressure cell, pack the packed column with Isopar-E and 1-octene to the packing setpoint and transfer the materials to the reactor. Immediately upon completion, begin heating the reactor toward the reaction setpoint. Immediately after adding the solvent / comonomer, fill the reactor with hydrogen gas (as specified) via a shot tank with an internal volume of approximately 75 mL. When the temperature reaches 25°C before the setpoint, add triethylaluminum (AlEt3) (10 μmol) solution to the reactor via the shot tank. At 10°C before the setpoint, add ethylene to the specified pressure while monitoring via a micromotion flow meter. Next, mix the (as specified) diluted toluene solution of the catalyst and metal activator complex, transfer it to the shot tank, and add it to the reactor to initiate the polymerization reaction. Maintain the polymerization conditions for 10 minutes, adding replenishment ethylene as needed to maintain the specified pressure. Exothermic reactions are continuously removed from the reaction vessel via an internal cooling coil. The resulting solution is removed from the reactor and stabilized by adding 5 mL of toluene solution containing approximately 33.5 mg of hindered phenol antioxidant (Irganox 1010 from Ciba Geigy Corp.) and 66.5 mg of phosphorus stabilizer (Irgafos 168 from Ciba Geigy Corp.). The resulting polymer is recovered by removing moisture overnight in a hood and then drying in a temperature gradient vacuum oven at a final set point of 140°C for approximately 12 hours. During the polymerization, at least one washing cycle is performed, during which Isopar-E (850 g) is added and the reactor is heated to a set point of 160°C to 190°C. The heated solvent is then removed from the reactor immediately before starting a new polymerization run. [Examples]

[0193] Examples 1-2 are synthesis procedures for intermediates of activator 1, and Example 3 is the synthesis procedure for activator 1. Examples 4-6 are synthesis procedures for intermediates of activator 2, and Example 7 is the synthesis procedure for activator 2. Example 8 is the synthesis procedure for intermediates of activator 3, and Example 9 is the synthesis procedure for activator 3. In Example 10, polymer resins were synthesized using various activators. The characteristics of the polymer resins were measured and recorded in Tables 1-7. One or more features of this disclosure are illustrated in terms of the following examples.

[0194] Example 1: Synthesis of Activator 1 Precursor - Synthesis of Lithium Tetrakis(Pentafluorophenyl)aluminate [ka]

[0195] In a glove box filled with nitrogen, bromopentafluorobenzene (1.0 mL, 8.02 mmol, 4 equivalents) and diethyl ether (17 mL) were placed in a 100 mL round-bottom flask. The container was sealed with a diaphragm, removed from the box, and mounted in a Schlenk tube filled with nitrogen. The reaction mixture was cooled in a dry ice / isopropanol bath for 2 hours. 1.65 M n-BuLi solution in hexane (4.86 mL, 8.02 mmol, 4.0 equivalents) was added dropwise. The reaction mixture was stirred at -78°C for 20 minutes. AlCl3 solution in diethyl ether (5.5 mL) (267.4 mg, 2.00 mmol, 1 equivalent) was added via syringe. The AlCl3 solution vial was rinsed with additional diethyl ether (5.5 mL) and added to the solution. The solution was slowly heated to room temperature and stirred for a total of 18 hours to form a solid precipitate in the solution. The suspension was returned to the glove box. The suspension was passed through a 0.2 μm syringe filter and a row of 0.45 μm syringe filters. The filters were washed twice with 4 mL of diethyl ether. The combined filtrate was concentrated under vacuum to obtain a concentrated oil containing some white precipitate. The white precipitate was pulverized with hexane (10 mL), and all volatile substances were removed under vacuum to obtain an off-white solid. The residue was dissolved in toluene (10 mL). The solution was passed through a 0.2 μm syringe filter and a row of 0.45 μm syringe filters. The filters were washed twice with 5 mL of toluene, and the combined filtrate was concentrated under vacuum to obtain a clear oil. The substance was pulverized with hexane (10 mL) and dried under vacuum (this process was repeated a total of two times) to obtain 1.63 g of product as a white solid, with a yield of 96%. The yield was calculated based on two equivalents of diethyl ether coordinated to the lithium cation.

[0196] 1 H NMR(400MHz,THF-d8)δ3.38(q,J=7.0Hz,1H),1.11(t,J=7.0Hz,1H). 19F NMR(376MHz,THF-d8)δ-119.03(8F,d,J=26.8Hz),-156.28(4F,t,J=19.1Hz),-162.09(8F,ddd,J=30.4,19.1,12.3Hz). 13 C NMR(126MHz,THF-d8)δ149.23-148.19(m),147.45-146.27(m),139.76-138.75 (m),137.67-136.72(m),135.51-134.77(m),133.80-132.64(m),63.43,12.79. 27 Al NMR(104MHz,THF-d8)δ116.34.C 24 AlF 20 [M - The calculated value for ] is HRMS(ESI) 694.9502, and the measured value is 694.9465.

[0197] Example 2: Synthesis of countercations of activator 1: Synthesis of Armeenium M 2HT chloride [ka]

[0198] In a nitrogen-filled glove box, Armeen M2HT (5.36 g, 10.0 mmol, 1 equivalent), a dihydroalkylmethylamine dihydrogenate available from Akzo-Nobel, was dissolved in hexane (150 mL). A 2 M HCl solution in diethyl ether (5.0 mL, 10.0 mmol, 1 equivalent) was slowly added dropwise to the stirred amine solution, immediately forming a white solid precipitate. The suspension was stirred at room temperature for 15 minutes. The precipitate was abundant and fine, forming a thick, gel-like suspension. Attempts were made to filter the suspension, but it did not pass through the filter. The suspension was returned to a glass bottle and dried under vacuum to obtain 4.76 g of white solid, with a yield of 83%.

[0199] 1H NMR (400MHz, toluene-d8) δ13.02-12.71(m,1H),2.90(dtd,J=43.2,12.4,6.8Hz,4H),2.67(d,J=4 .7Hz,3H),1.72(ddt,J=50.3,13.3,6.7Hz,4H),1.32(d,J=22.5Hz,60H),0.91(t,J=6.6Hz,6H). 13 ¹³C NMR (101MHz, Toluene-d8): δ 54.75, 39.08, 32.03, 30.00, 29.98, 29.95, 29.92, 29.86, 29.53, 29.48, 27.04, 23.62, 22.77, 13.96.

[0200] Example 3: Synthesis of Activator 1 [ka]

[0201] In a glove box filled with nitrogen, lithium tetrakis(pentafluorophenyl) aluminate (1.40 g, 1.65 mmol, 1 equivalent), Armeenium M2HT chloride (0.943 g, 1.65 mmol, 1 equivalent), and toluene (35 mL) were stirred at room temperature for 1 hour to produce a slightly turbid solution. The solution was filtered through a 0.2 μm syringe filter and a series of 0.45 μm syringe filters. The combined filtrate was concentrated under vacuum to obtain turbid oil. The substance was pulverized with hexane (5 mL) and dried under vacuum (this process was repeated a total of two times) to obtain 1.72 g of product as turbid oil, with a yield of 85%.

[0202] 1 ¹H NMR (400 MHz, toluene-d8): δ 4.22 (br s, 1H), 2.06-1.95 (m, 4H), 1.68 (s, 3H), 1.40-1.18 (m, 60H), 1.17-1.06 (m, 4H), 0.97-0.88 (m, 6H). 19F NMR(376MHz,Toluene-d8)δ-121.84(8F,dd,J=29.6,11.3Hz),-156.99(4F,t,J=19.6Hz),-163.42 8F,(ddd,J=30.5,19.2,11.8Hz). 13 ¹³C NMR (101MHz, Toluene-d8) δ: 151.65-150.79(m), 149.45-148.52(m), 141.99-141.30(m), 139.48-138.79(m), 138.07-137.35(m), 135.70-134.90(m), 56.54, 39.71, 32.00, 31.60, 29.86, 29.85, 29.80, 29.79, 29.73, 29.54, 29.49, 29.34, 28.89, 25.95, 23.88, 22.73, 13.87. 27 Al NMR (104 MHz, Toluene-d8) δ 115.71.C 37 H 78 N [M + The calculated value for ] is HRMS(ESI) 536.6129, and the measured value is 536.6145. C 24 AlF 20 [M - The calculated value for ] is 694.9502, and the measured value is 694.9520.

[0203] Example 4: Synthesis of activator 2 precursor 1-tris(pentafluorophenyl)alanetoluene adduct [ka]

[0204] In a glove box filled with nitrogen, a solution of tris(pentafluorophenyl)borane (0.250 g, 0.488 mmol, 1 equivalent) was dissolved in toluene (1 mL). A solution of trimethylaluminum in hexane (4 mL) (47 μL, 0.488 mmol, 1 equivalent) was added to the toluene solution. The reaction mixture was stirred at room temperature for 3 hours. After approximately 5 minutes, a white precipitate formed. The vial was placed in a freezer at -30°C for 2 days. The solid was filtered, washed with cold (-30°C) hexane, and dried under vacuum to obtain 0.203 g of product as a white solid, with a yield of 72%.

[0205] 1 ¹H NMR (400 MHz, toluene-d8): δ 7.14-7.07 (m, 2H), 7.05-7.01 (m, 1H), 7.00-6.95 (m, 2H), 2.12 (s, 3H). 19 F NMR (376 MHz, toluene-d8): δ -122.86 (6F, ddd, J=23.0, 8.0, 4.4 Hz), -151.08 (3F, tt, J=20.1, 2.9 Hz), -160.58--161.05 (6F, m).

[0206] Example 5: Synthesis of activator precursor 2-lithium pentafluorophenolate [ka]

[0207] In a glove box filled with nitrogen, a 10.7 mL (17.1 mmol, 1.05 equivalent) solution of n-BuLi in hexane was added dropwise to a stirred solution of pentafluorophenol (3.00 g, 16.3 mmol, 1 equivalent) in hexane (50 mL). Immediately, a white solid precipitated from the solution. The reaction mixture was stirred at room temperature for 1 hour. The solid was filtered, washed with hexane, and dried under vacuum to obtain 2.85 g of product as a white solid, with a yield of 92%.

[0208] 19 F NMR(376MHz,THF-d8)δ-168.96(dd,J=18.8,12.6Hz,2F),-169.97--170.24(m,2F),-185.62--186.98(m,1F). 13 C NMR(101MHz,THF-d8)δ145.94-145.06(m),143.77(tt,J=8.5,3.3Hz),141.98-141.08(m),139.77-138.51(m),130.32(dtt,J=232.0,14.4,4.7Hz).

[0209] Example 6: Synthesis of activator 2 precursor 3-lithium(perfluorophenoxy)tris(perfluorophenyl)aluminate [ka]

[0210] In a glove box filled with nitrogen, a suspension of tris(pentafluorophenyl)alane toluene adduct (121.4 mg, 0.211 mmol, 1 equivalent) in toluene (1 mL) was added to a vial containing lithium pentafluorophenolate (40.2 mg, 0.211 mmol, 1 equivalent). The tris(pentafluorophenyl)alane vial was washed four times with 0.5 mL of toluene, and the toluene from the washing solution was added to the reaction mixture. After a few minutes, a clear solution was obtained. The reaction mixture was stirred at room temperature for 18 hours to obtain a slightly yellowish, clear solution. The solution was passed through a 0.2 μm syringe filter and a row of 0.45 μm syringe filters. The filters were washed twice with 1 mL of toluene, and the combined filtrate was concentrated under vacuum to obtain a slightly cloudy, concentrated oil. The oil was pulverized with hexane (5 mL) and concentrated under vacuum (this process was repeated a total of two times) to obtain 0.1673 g of product as a slightly cloudy, concentrated oil, with a yield of 98%. The yield was calculated as mono-toluene adduct.

[0211] 19 1F NMR (376MHz, Toluene-d8): δ -126.98–-127.43 (m, 6F), -151.95 (t, J=19.4Hz, 3F), -158.78 (d, J=21.6Hz, 2F), -159.89–-160.72 (m, 6F), -163.53 (td, J=21.0, 3.4Hz, 2F), -164.46 (tt, J=22.2, 4.2Hz, 1F). 13 ¹³C NMR (101 MHz, toluene-d8): δ 151.61–150.20 (m), 149.26–147.93 (m), 143.23–142.35 (m), 142.27–141.74 (m), 138.80–137.65 (m), 136.00–135.01 (m). 27Al NMR (104 MHz, Toluene-d8) δ 120.11 (br).C 24 AlF 20 O[M - The calculated value for ] is HRMS(ESI) 710.9451, and the measured value is 710.9426.

[0212] Example 7: Synthesis of Activator 2 [ka]

[0213] In a glove box filled with nitrogen, Armeenium M2HT chloride (118.2 mg, 0.207 mmol, 1 equivalent), lithium (perfluorophenoxy)tris(perfluorophenyl)aluminate (167.3 mg, calculated as 0.207 mmol including 1 equivalent of toluene, 1 equivalent), and toluene (5 mL) were stirred at room temperature for 1 hour. A slightly turbid solution was obtained. The solution was passed through a 0.2 μm syringe filter and a row of 0.45 μm syringe filters. The filters were washed twice with 1 mL of toluene, and the combined filtrate was concentrated under vacuum to obtain a turbid, thick white oil. The turbid, thick white oil was dissolved in hexane (5 mL) to obtain a turbid solution. The solution was passed through a 0.2 μm syringe filter and a row of 0.45 μm syringe filters, but the solution remained turbid. All volatile substances were removed under vacuum to obtain 0.2065 g of cloudy white concentrated oil with an 80% yield.

[0214] 1 H NMR (400MHz, toluene-d8) δ6.32(s,1H),2.14(dd,J=10.2,6.2Hz,4H),1.86(s,3H),1.40- 1.20(m,52H),1.13(h,J=8.4,7.6Hz,8H),0.99(t,J=7.6Hz,4H),0.91(t,J=6.7Hz,6H). 19F NMR (376MHz, toluene-d8)δ-122.34--122.82(m,6F),-156.12(t,J=19.6Hz,3F),-161.69--162.06(m,2F) ,-163.08(dq,J=19.6,11.9Hz,6F),-167.22(dd,J=22.6,19.0Hz,2F),-174.36(tt,J=22.8,7.6Hz,1F). 13 ¹³C NMR (101MHz, Toluene-d8) δ: 152.65-150.61(m), 149.88-148.24(m), 143.02-141.27(m), 139.90-138.71(m), 138.61-137.42(m), 135.72-134.53(m), 56.45, 39.57, 32.01, 29.89, 29.87, 29.84, 29.82, 29.77, 29.61, 29.51, 29.42, 29.01, 26.17, 23.93, 22.76, 13.91. 27 Al NMR (104 MHz, Toluene-d8) δ113.16.C 37 H 78 N [M + The calculated value for ] is HRMS(ESI) 536.6129, and the measured value is 536.6123. C 24 AlF 20 O[M - Calculated value for ]: 710.9451, measured value: 710.9426.

[0215] Example 8: Synthesis of activator 3 precursor 1-lithium 1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propane-2-olate [ka]

[0216] In a glove box filled with nitrogen, a 100 mL round-bottom flask was placed with a 1.6 M solution of n-BuLi in hexane (8.9 mL, 14.3 mmol, 1.05 equivalents) and pentane (100 mL). The container was sealed with a diaphragm, the glove box was removed and attached to a Schlenk tube filled with nitrogen, and cooled to -78°C in a dry ice isopropanol bath. Perfluoro-tert-butanol (1.9 mL, 13.6 mmol, 1 equivalent) was added dropwise, and a white solid precipitate was formed. The cooling bath was removed, and the reaction mixture was warmed to room temperature. The diaphragm was firmly secured, and the reaction mixture was transferred to the glove box. The solution was cooled in a freezer at -30°C for 3 days. The solid was filtered, washed with cold (-30°C) pentane, and dried under vacuum to obtain the product as a white solid (2.92 g, yield 88%).

[0217] 19 F NMR (376 MHz, THF-d8) δ-75.51. 13 C NMR(101MHz,THF-d8)δ131.97-120.43(m),87.49-84.80(m).

[0218] Example 9: Synthesis of Activator 3 [ka]

[0219] In a glove box filled with nitrogen, tris(pentafluorophenyl)alane toluene adduct (see Example 4) (200 mg, 0.348 mmol, 1 equivalent) and toluene (2 mL) were added to a reaction vial. The suspension was added to a solution of lithium perfluoro-tert-butoxide (75.8 mg, 0.314 mmol, 0.9 equivalents) and diethyl ether (4 mL). The tris(pentafluorophenyl)alane vial was washed three times with 1 mL of toluene, and the solvent from the washing solution was added to the reaction product. After adding alan and stirring, a slightly cloudy colorless solution was obtained. The reaction product was stirred at room temperature for 22 hours to obtain a slightly cloudy colorless solution. The solution was passed through a 0.2 μm syringe filter and a row of 0.45 μm syringe filters to obtain a cloudy colorless solution. The syringe filters were washed twice with 1 mL of diethyl ether. When additional diethyl ether was added to the filtrate, a clear, homogeneous solution was obtained. All volatile substances were removed under vacuum. The residue was ground with hexane (5 mL), and all volatile substances were removed under vacuum (this process was repeated a total of two times) to obtain a thick, clear oil.

[0220] Armeenium M2HT chloride (179.5 mg, 0.314 mmol, 0.9 equivalents) and toluene (5 mL) were added to the thick, clear oil product. The reaction mixture was stirred at room temperature for 18 hours to obtain a cloudy, pale yellow solution. The solution was passed through a 0.2 μm syringe filter and a series of 0.45 μm syringe filters to obtain a clear, pale yellow solution. The syringe filters were washed twice with 1 mL of toluene, and the combined filtrate was concentrated under vacuum to obtain a clear, pale yellow oil. The residue was pulverized with hexane (5 mL), and all volatile substances were removed under vacuum (this process was repeated a total of two times) to obtain 0.4342 g of product as clear oil, in quantitative yield.

[0221] 1H NMR (400MHz, toluene-d8) δ3.65(s,1H),2.20-2.09(m,4H),1.95(dq,J=11.9,6. 2,5.4Hz,4H),1.73(d,J=5.1Hz,3H),1.42-1.08(m,56H),0.96-0.79(m,10H). 19 F NMR (376 MHz, toluene-d8): δ -74.40 (s, 9F), -121.74–-122.59 (m, 6F), -156.91 (t, J=19.6 Hz, 3F), -163.77 (ddd, J=30.9, 19.6, 12.1 Hz, 6F). 13 ¹³C NMR (101MHz, Toluene-d8) δ152.03-150.92(m),149.63-148.63(m),142.05-141.15(m),139.44-138.95(m),138.14-137.40(m),135.69-134.86(m),81.06-78.93(m),80.25,79.95,79.65,79.34,56.75,39.88,32.01,29.87,29.86,29.85,29.80,29.72,29.52,29.50,29.29,28.83,25.79,23.82,22.74,13.90. 27 Al NMR (104 MHz, Toluene-d8) δ101.74.C 37 H 78 N[M + The calculated value for ] is HRMS(ESI) 536.6129, and the measured value is 536.6129. C 22 AlF 24 O[M - Calculated value for ]: 762.9387, measured value: 762.9367.

[0222] Example 10 - Polymerization Results Polymerization was carried out in a batch reactor according to the procedure described above. Specifically, in the case of the results summarized in Tables 1-5, a 2 L batch reactor was heated to 170°C. Polymerization conditions included the use of 860 g Isopar® E, 70 g octene, and 210 psig ethylene. The activator-to-pro-catalyst ratio was approximately 1.2, and 10 μmol AlEt3 was used as an impurity scavenger. The co-catalyst efficiency and characteristics of the resulting polymers were evaluated with activators 1, 2, and 3 having an anionic structure according to formula (I) and bis-biphenylphenoxy group IV metal-ligand catalysts. In the case of the results summarized in Tables 6-7, a 2 L batch reactor was heated to 140°C. Polymerization conditions included the use of 605 g Isopar® E, 300 g octene, and 300 psig ethylene. The activator-to-procatalyst ratio was approximately 1.2, and 50 equivalents (compared to the procatalyst) of AlEt3 were used as an impurity scavenger. The co-catalyst efficiency and characteristics of the resulting polymers were evaluated for activators 1-3, each having an anionic structure and a group IV metal-ligand complex according to formula (I), specifically the constrained shape shown in Table 6 for the procatalyst, or the bis-indenyl shown in Table 7.

[0223] Metal activators 1, 2, and 3, and comparative activator C1 (hereinafter referred to as "comparative C1") were mixed with pro-catalysts A to D to form a catalytic system. Comparative C1 was used as a countercation. + HN(Me)(C 18 H 37 ) had 2. [ka]

[0224] The efficiencies of activators 1, 2, and 3 of the present invention, as well as comparative activator C1 (hereinafter referred to as "comparative C1"), and the polymer characteristics of polymers obtained from activators 1, 2, and 3 of the present invention, as well as comparative C1, were determined. The results are summarized in Tables 1 to 7. Comparative C1 has a proven track record of use in industrial applications. [Table 1] [Table 2] [Table 3] [Table 4] [Table 5] [Table 6] [Table 7] [Table 8]

[0225] The hydrocarbon conductivity test described herein simulates the post-polymerization process, where the generated polymer resin is washed with water to remove catalyst and co-catalyst residues. The results summarized in Table 8 show that when activator 1 is present in comparison C1, - This demonstrates that it has a better dielectric loss tangent than the B(C6F5)4 anion.

[0226] Based on the results summarized in Table 8, it is thought that water interacts with the activator of the present invention in some way, reducing the activator's contribution to the electrical properties. Although we do not wish to be bound by such an idea, it is thought that water chemically reacts with the activator, giving priority to the decomposition of the product, and the decomposed product does not significantly contribute to charge transport, and therefore the polymer produced by the activator of the present invention exhibits low conductivity. However, it is thought that comparative C1 does not react with water under the conditions of the HC test. Since comparative C1 consists of anions and cations, which are ionic species, it contributes to ionic charge transport both before and after the addition of water.

[0227] As mentioned above, the hydrocarbon solution in the HC test is heated to remove water. While we do not wish to be bound by such an idea, it is thought that water, antioxidants, and / or the heat of the process decompose the activator of the present invention, giving priority to the decomposition of the product and not significantly contributing to charge transport. Comparative C1 does not significantly decompose under polymerization conditions and is expected to contribute to ionic charge transport in the elastomer as an ionic species. [Table 9]

[0228] Table 9 contains the results obtained from the thermogravimetric analysis curves. Activator 1 decomposes at a high temperature of 179°C. Therefore, activator 1 is stable and can produce polymers at temperatures above 140°C, as demonstrated in Tables 1-4 and 6-7.

[0229] equipment standards All solvents and reagents were obtained from commercial sources and used as received unless otherwise noted. Anhydrous toluene, hexane, tetrahydrofuran, and diethyl ether were purified by passing them through activated alumina and, in some cases, the Q-5 reactant. Solvents used in experiments performed in a nitrogen-filled glove box were further dried by storing them on activated 4A molecular sieves. Glassware for humidity-sensitive reactions was dried in an oven overnight before use. NMR spectra were recorded using a Bruker Avance III HD 400 MHz NMR, Varian 400-MR, or VNMRS-500 spectrometer. LC-MS analysis was performed using a Waters e2695 separation module combined with a Waters 2424 ELS detector, Waters 2998 PDA detector, and Waters 3100 ESI mass detector. LC-MS separation is performed using an XBridge C18 3.5 μm 2.1 × 50 mm column with a 5:95 to 100:0 acetonitrile and water gradient (containing 0.1% formic acid as an ionizing agent). HRMS analysis is performed using an Agilent 1290 Infinity LC with a Zorbax Eclipse Plus C18 1.8 μm 2.1 × 50 mm column in combination with an Agilent 6230 TOF mass spectrometer with electrospray ionization. 1 ¹H NMR data are reported as follows: chemical shift (multiplicity (br=broadline, s=montablic, d=doubleline, t=triplet, q=quadtablic, p=quintablic, sex=hexablic, sept=hentablic, and m=multiplicate), integral value, and assignment). Using residual protons in a deuterated solvent as the reference material, 1 We report the chemical shift of 1H NMR data from within tetramethylsilane at low magnetic field levels in ppm (TMS, δ scale). 13 The 1C NMR data is 1 The chemical shift is determined using H decoupling, and the shift is reported as a low magnetic field (ppm) from tetramethylsilane (TMS, δ scale), using residual carbon in the deuterated solvent as the reference. The present invention includes the following embodiments. Section 1. A process for polymerizing olefins, wherein ethylene and (C3-C) are polymerized in the presence of a catalyst system. 40 ) comprising contacting with an alpha-olefin comonomer, wherein the catalyst system comprises a procatalyst and a metal activator ionic complex, the metal activator comprises an anion and a countercation, and the anion has a structure according to formula (I), [ka] During the ceremony, n is 0 or 1, Each R is independently selected from the group consisting of radicals having formula (II) and radicals having formula (III), [ka] Each Y is independently either carbon or silicon. Each R 11 , R 12 , R 13 , R 21 , R 22 , R 23 , R 24 , and R 25 ((C1-C 40 )alkyl, halogen-substituted (C1-C 40 ) alkyl, (C6-C 40 ) Aryl, halogen substitution (C6-C 40 ) Aryl, -OR C , -SR C Selected from -H, -F, or Cl, in the formula, R 11-13 At least one of the following, and R 21-25 One of them is halogen substitution (C1-C 40 ) Alkyl, halogen-substituted (C6-C 40 )aryl, or -F, Each X is halogen-substituted (C1-C 20 )alkyl or halogen-substituted (C6-C 40 ) A monodentate ligand selected independently of aryl, The two X groups in formula (I) are covalently bonded, Each R C Independently, halogen substitution (C1-C 30 ) Hydrocarbil, however, The aforementioned cation pair is Me2PhN(H) + And when the anion is Al(C6F5)4, the procatalyst is not Ph2C(Cp)(Flu)ZrCl2 or Et(1-Ind)2ZrCl2, The aforementioned countercation is (Ph)3C + The process is such that when the anion is Al(C6F5)4, the procatalyst is not Et(1-Ind)2ZrCl2. Section 2. A process for polymerizing an olefin according to item 1, wherein the pro-catalyst is a bis-biphenylphenoxy group IV metal-ligand complex. Section 3. A process for polymerizing the olefins described in item 1 or 2, wherein n is 0 and each X is independently -C(H)(CF3)2, -C6F5, or -C(CF3)3. Section 4. A process for polymerizing an olefin as described in item 1 or item 2, wherein n is 1, R is -C(CF3)3, and each X is -C6F5. Section 5. A process for polymerizing the olefin described in item 1 or item 2, wherein n is 0 and three of the four X groups are -C6F5. Section 6. A process for polymerizing the olefin described in item 1 or item 2, wherein n is 0 and all four X groups are -C6F5. Section 7. A process for polymerizing an olefin according to any one of claims 1 to 6, wherein the countercation is selected from substituted ammonium, substituted and unsubstituted triarylcarbonium, or substituted and unsubstituted ferrocenium. Section 8. The aforementioned cation pair + N(H)R N 3, and in the formula, each R N (C1-C30 ) alkyl, or (C6-C 20 A process for polymerizing an olefin as described in any one of items 1 to 6, selected from aryls. Section 9. The aforementioned cation pair + N(H)R N 3, and in the formula, at least two R N (C 10 -C 30 A process for polymerizing the olefin described in item 6, selected from alkyl groups. Section 10. The aforementioned cation pair + A process for polymerizing an olefin described in any one of items 1 to 6, which is C(C6H5)3. Section 11. The aforementioned cation pair + C(C6H4R S )3, and in the formula, R S However, (C1-C 20 A process for polymerizing an olefin described in any one of items 1 to 6, wherein the olefin is alkyl. Section 12. A process for polymerizing an olefin as described in any one of items 1 to 11, wherein n is 0. Section 13. Two X groups are covalently bonded, and the anion has a structure according to formula (IV). [ka] During the ceremony, R and each X are as defined in equation (I), z is 0 or 1, y is 0, 1, or 2, x is 1 or 2, and 2x + y + z = 4. L represents the two X groups that are covalently bonded, L independently replaces halogen (C2-C 40 ) Alkylene, halogen substitution (C2-C 40 ) Heteroalkylene, or halogen-substituted (C6-C 40 ) Selected from Alliren, When z is 1, X is a halogen, halogen substitution (C1-C 20 ) Alkyl, halogen-substituted (C6-C 40 A process for polymerizing the olefin described in item 1, selected from aryls. Section 14. A process for polymerizing an olefin according to item 13, wherein L is a halogenated diradical biphenyl or a halogenated diradical naphthalene-diyl. Section 15. A polymerization process according to any one of claims 1 to 14, wherein the high-boiling point fully saturated hydrocarbon solution has a concentration of 200 micromoles of the metal activator ionic complex and 20 millimoles of water per liter, and the metal activator ionic complex in the high-boiling point fully saturated hydrocarbon solution has a dielectric loss tangent percentage of 0.1 or less as measured by a hydrocarbon conductivity test.

Claims

1. A process for polymerizing olefins, wherein ethylene and (C) are polymerized in the presence of a catalyst system. ３ -C ４０ ) comprising contacting with an alpha-olefin comonomer, wherein the catalyst system comprises a procatalyst and a metal activator ionic complex, and the metal activator comprises anions and countercations, The anion has a structure according to formula (I), 【Chemistry 1】 During the ceremony, n is 0 or 1, Each R is independently selected from the group consisting of radicals having formula (II) and radicals having formula (III), 【Chemistry 2】 Each Y is independently either carbon or silicon. Each R １１ 、R １２ 、R １３ 、R ２１ 、R ２２ 、R ２３ 、R ２４ 、and R ２５ are independently selected from halogen-substituted (C １ -C ４０ ) alkyl, halogen-substituted (C ６ -C ４０ ) aryl, -F, or -Cl, wherein at least one of R １１－１３ and one of R ２１－２５ is halogen-substituted (C １ -C ４０ ) alkyl, halogen-substituted (C ６ -C ４０ ) aryl, or -F, Each X is halogen-substituted (C ６ -C ４０ ) A monodentate ligand selected independently of aryl, A process in which the countercation is +N(H)RN3, where each RN is independently selected from (C1-C30)alkyl or (C6-C20)aryl, and at least two RNs are independently selected from (C10-C30)alkyl.

2. The process for polymerizing an olefin according to claim 1, wherein the pro-catalyst is a bis(phenylphenoxy) group IV metal-ligand complex.

3. n is 1 and R is -C(CF ３ ) ３ And X is -C ６ F ５ A process for polymerizing an olefin according to claim 1 or claim 2.

4. n is 0, and 3 of the 4 X groups are -C ６ F ５ A process for polymerizing an olefin according to claim 1 or claim 2.

5. n is 0, and all four X groups are -C ６ F ５ A process for polymerizing an olefin according to claim 1 or claim 2.

6. A process for polymerizing an olefin according to claim 1 or claim 2, wherein n is 0.

7. A process for polymerizing an olefin, comprising contacting ethylene with a (C3-C40) alpha-olefin comonomer in the presence of a catalyst system, wherein the catalyst system comprises a procatalyst and a metal activator ionic complex, and the metal activator comprises anions and countercations. The anion has a structure according to formula (IV), 【Transformation 3】 During the ceremony, z is 0 or 1, y is 0, 1, or 2, x is 1 or 2, and 2x + y + z = 4. Each R is independently selected from the group consisting of radicals having formula (II) and radicals having formula (III), 【Chemistry 2】 Each Y is independently either carbon or silicon. Each of R11, R12, R13, R21, R22, R23, R24, and R25 is independently selected from halogen-substituted (C1-C40) alkyl, halogen-substituted (C6-C40) aryl, -F, or -Cl, where at least one of R11-13 and one of R21-25 is halogen-substituted (C1-C40) alkyl, halogen-substituted (C6-C40) aryl, or -F. Each X is a monodentate ligand independently selected from halogen-substituted (C6-C40) aryl groups. L independently forms halogen-substituted (C2-C40) alkylene, halogen-substituted (C2-C40) heteroalkylene, or halogen-substituted (C ６ -C ４０ A process for polymerizing olefins, selected from arylene.

8. A process for polymerizing an olefin according to claim 7, wherein L is a halogenated diradical biphenyl or a halogenated diradical naphthalene-diyl.

9. A process for polymerizing an olefin according to any one of claims 1 to 8, wherein the high-boiling point fully saturated hydrocarbon solution has a concentration of 200 micromoles of the metal activator ionic complex and 20 millimoles of water per liter, and the metal activator ionic complex in the high-boiling point fully saturated hydrocarbon solution has a dielectric loss tangent percentage of 0.1 or less as measured by a hydrocarbon conductivity test.

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