Bimetallic activators for olefin polymerization

Abstract

A process for polymerizing olefins. The process involves the polymerization of ethylene and (C3-C6) olefins in the presence of a catalyst system comprising a procatalyst and a bimetallic activator complex. 40 ) an alpha-olefin comonomer and polymerizing the bimetallic activator complex. The bimetallic activator complex comprises an anion and a countercation. The anion has a structure according to formula (I): [Formula 1] JPEG2023528729000027.jpg22128

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to U.S. Provisional Patent Application No. 63 / 021,419, filed May 7, 2020, the entire disclosure of which is incorporated herein by reference.

[0002] FIELD OF THE INVENTION FIELD OF THE DISCLOSURE Embodiments of the present disclosure relate generally to olefin polymerization catalyst systems and processes, and more specifically to olefin polymerization catalyst systems comprising a Group IV metal-ligand complex and a bimetallic activator or cocatalyst. [Background technology]

[0003] As part of the catalyst composition in an α-olefin polymerization reaction, the activator can have beneficial characteristics for the production of α-olefin polymers and for the final polymer composition. Activator characteristics that increase the production of α-olefin polymers include, but are not limited to, rapid activation of the procatalyst, high catalyst efficiency, high temperature performance, consistent polymer composition, and selective deactivation.

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

[0005] As part of a catalyst system, a molecular polymerization procatalyst is activated to generate a catalytically active species for polymerization. Catalyst activation can be achieved by any number of means. One such method uses an activator or cocatalyst that is a Bronsted acid. To activate molecular polymerization procatalysts, particularly those containing Group IV metal complexes, Bronsted acid salts containing weakly coordinating anions are commonly utilized. A fully ionized Bronsted acid salt is capable of transferring a proton to form a cationic derivative of such a Group IV metal complex.

[0006] In the case of activators such as Bronsted acid salts, the cationic component can include cations capable of transferring hydrogen ions, such as, for example, ammonium, sulfonium, or phosphonium, or oxidizing cations, such as, for example, ferrocenium, silver, or lead, or highly Lewis acidic cations, such as, for example, carbonium or silylium.

[0007] However, when a cation activates a procatalyst, the activator may remain in the polymer composition. As a result, cations and anions may affect the polymer composition. Because not all ions diffuse equally, various ions affect the polymer composition differently. Specifically, the size and charge of the ion, the interaction of the ion with the surrounding medium, and the dissociation energy of the ion with available counterions will affect the ability of the ion to diffuse through the surrounding medium, such as a solvent, gel, or polymeric material.

[0008] Conventional olefin polymerization activators include weakly or non-coordinating anions. It has been shown that the weak coordination of the anions leads to an increase in the catalytic efficiency of cationic catalysts. However, since the non-nucleophilic character of non-coordinating anions also increases diffusion, the activator anions remaining in the produced polymer will reduce the electrical resistance of the polymer, thereby increasing electrical loss and thus reducing the applicability of the produced polymer. Summary of the Invention

[0009] In solution polymerization, the process catalyst components are generally delivered as either a slurry or a solution. A homogeneous solution, as opposed to a heterogeneous solution, does not require additional mixing elements to maintain uniformity of the contents. This reduces the complexity associated with delivering the catalyst components to the reactor. Solutions utilizing aliphatic hydrocarbon solvents, such as, but not limited to, hexane, methylcyclohexane, and Isopar E™, are preferred over the use of toluene and other aromatic solvents, because residues of these aromatic solvents can remain in the resulting polymer, potentially limiting the applications in which the polymer can be used.

[0010] A good activator for polymerization reactions increases the production of α-olefin polymers, enhances the activation rate of procatalyst activation, increases the overall efficiency of the catalyst, allows the catalyst system to operate at higher temperatures, enables the catalyst system to provide consistent polymer compositions, and is also anionic tetrakis(pentafluorophenyl)borate ( - The non-coordinating anion tetrakis(pentafluorophenyl)borate (B(C6F5)4) has the advantage of increasing the solubility of the activator compared to the non-coordinating anion tetrakis(pentafluorophenyl)borate ( - Activators derived from B(C(CF)) possess many of these aforementioned characteristics. Nevertheless, under typical polymerization reaction conditions, - The B(C6F5)4 anion may remain in the final polymer. The presence of the activator intact in the final polymer may be detrimental to the electrical properties of the final polymer.

[0011] Activators based on partially hydrolyzed metal trialkyls, such as methylalumoxane (MAO) or modified methylalumoxane (MMAO), can be used, for example, -It decomposes more easily than the B(C6F5)4 anion, but suffers from poor high temperature catalytic efficiency and wider composition and / or molecular weight drift in the final polymer.

[0012] There is a continuing need for activators that efficiently activate procatalysts, are soluble, function well at high temperatures, and do not remain in the final polymer. The catalyst system of the present disclosure includes a combination of a Group IV metal-ligand complex as a catalyst and an activator or cocatalyst that addresses this need. In particular, in the production of polyolefin resins, when the activator readily reacts with and activates the Group IV metal-ligand complex, the polyolefin resin exhibits useful polymer composition and electrical properties. The activators included in the catalyst system of the present disclosure exhibit characteristics such as the ability to increase the production of α-olefin polymers, the ability to increase the rate of procatalyst activation, the ability to increase the overall efficiency of the catalyst and enable the catalyst system to operate at high temperatures, the ability to enable the catalyst system to provide consistent polymer compositions, and the ability to selectively deactivate the activator.

[0013] According to one or more embodiments, the process for polymerizing olefins comprises the step of polymerizing ethylene and (C3-C6) in the presence of a catalyst system comprising a Group IV metal-ligand complex and a bimetallic activator ionic complex. 40 ) an α-olefin comonomer. The bimetallic activator ionic complex comprises an anion and a countercation, wherein the anion has a structure according to formula (I). [ka]

[0014] The countercation can be any cation that has a formal charge of +1. In formula (I), each M is independently aluminum or boron. 1 is C(H) and R 2 is C(R L ) or N, wherein each R L are independently -H, (C1 to C 30) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, or halogen-substituted (C1-C 30 ) hydrocarbyl. 3 is -H, (C1~C 30 ) Hydrocarbyl, halogen-substituted (C1-C 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, or (C-C 30 ) hydrocarbylene, and R 3 is optionally R 2 It is connected to form a ring. 3 When is -H, R 2 is N or C(R L ) where R L (C1~C 30 ) hydrocarbyl, and R 2 When is C(H), R 3 (C1~C 30 ) hydrocarbyl.

[0015] In formula (I), each R 4 are independently halogen-substituted (C1-C 30 ) alkyl and a radical having formula (II). [ka]

[0016] In formula (II), each R 21 , R 22 , R 23 , R 24 , and R 25 are independently halogen-substituted (C1-C 40 ) Alkyl, halogen-substituted (C6-C 40 ) Aryl, -H, -NR N 2, -OR C , -SR C or halogen. 4 is a radical according to formula (II), R 21~25 At least three of the groups are independently halogen-substituted (C1 to C 40) Alkyl, halogen-substituted (C6-C 40 ) aryl, or -F. Additionally, R 4 is halogen-substituted (C1-C 30 ) alkyl, halogen-substituted (C1-C 30 ) alkyl is substituted with at least three halogen atoms. N Or each R C are independently (C1~C 30 ) hydrocarbyl or -H. DETAILED DESCRIPTION OF THE INVENTION

[0017] Specific embodiments of the catalyst system will now be described. It should be understood that the catalyst system of the present disclosure may be embodied in different forms and should not be construed as limited to the specific embodiments set forth in this disclosure.

[0018] Common abbreviations are listed below.

[0019] Me: methyl, Et: ethyl, Ph: phenyl, Bn: benzyl, i-Pr: iso-propyl, t-Bu: tert-butyl, t-Oct: tert-octyl (2,4,4-trimethylpentan-2-yl), Tf: trifluoromethane sulfonate, OTf: triflate, ( t Bu FO)3Al: Al(OC(CF3)3)3, THF: tetrahydrofuran, Et2O: diethyl ether, CH2Cl2: dichloromethane, CV: column volume (used in column chromatography), EtOAc: ethyl acetate, C6D6: deuterated benzene or benzene-d6, CDCl3: deuterated chloroform, Na2SO4: sodium sulfate, MgSO4: magnesium sulfate, HCl: hydrogen chloride, n-BuLi: butyllithium, t-BuLi: tert-butyllithium, N2: nitrogen gas, PhMe: toluene, PPR: parallel polymerization reactor, MAO: methylaluminoxane, MMAO: modified methylaluminoxane, GC: gas chromatography, LC: liquid chromatography, NMR: nuclear magnetic resonance, MS: mass spectrometry, mmol: millimole, mL: milliliter, M: mole, min or mins: minute, h or hrs: hour, d: day, R f : retention factor, TLC: thin layer chromatography, rpm: revolutions per minute.

[0020] The term "independently selected" refers to 1 , R 2 , R 3 , R 4 , and R 5 and the R groups may be the same or different (e.g., R 1 , R 2 , R 3 , R 4 , and R 5 may all be substituted alkyl, or R 1 and R 2 may be substituted alkyl, R 3 The R group is used herein to indicate that the R group may be an aryl group, etc. Chemical names associated with R groups are intended to convey chemical structures recognized in the art as corresponding to the chemical structure of the chemical name. Thus, the chemical names are intended to supplement and illustrate, not preclude, structural definitions known to those of skill in the art.

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

[0022] When used to describe certain chemical groups containing one or more carbon atoms, the form "(C x ~C y A parenthetical expression having "x to y carbon atoms" means that the unsubstituted form of the chemical group has x to y carbon atoms, inclusive. For example, (C1 to C 50 ) Alkyl, in its unsubstituted form, is an alkyl group having 1 to 50 carbon atoms. In some embodiments and general structures, certain chemical groups are R S The parenthesized "(C x ~C y )" S The substituted chemical group can be any group R S For example, "R S exactly one group R is phenyl (-C6H5) S (C1~C 50 A "(C ) alkyl" can contain from 7 to 56 carbon atoms. Thus, the parenthesized "(C ) alkyl" is generally used. x ~C y )" is a group defined using one or more carbon atom-containing substituents R S When substituted by, the minimum and maximum total number of carbon atoms in the chemical group is the sum of all carbon atom-containing substituents R S It is determined by adding the total number of carbon atoms from

[0023] The term "substituted" means that at least one hydrogen atom (-H) bonded to a carbon or heteroatom of the corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R SThe term "hypersubstituted" means that all hydrogen atoms (H) bonded to carbon atoms or heteroatoms of the corresponding unsubstituted compound or functional group are substituted with a substituent (e.g., R S ) The term "polysubstituted" means that at least two, but fewer than all, hydrogen atoms bonded to carbon atoms or heteroatoms of the corresponding unsubstituted compound or functional group are replaced by substituents. The term "-H" means a hydrogen or hydrogen group covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless otherwise specified.

[0024] The term "halogen substituted" means that at least one hydrogen atom (-H) bonded to a carbon atom or heteroatom or functional group of a corresponding unsubstituted compound has been replaced with a halogen. The terms "halogen substituted" and "halogenated" are interchangeable. The term "perhalogenated" means that all hydrogen atoms (-H) bonded to a carbon atom or heteroatom or functional group of a corresponding unsubstituted compound have been replaced with a halogen. The term "halogen substituted" means that at least one hydrogen atom (-H) bonded to a carbon atom or heteroatom or functional group of a corresponding unsubstituted compound has been replaced with a halogen.

[0025] In this disclosure, the term "halogen atom" or "halogen" refers to the radical of a fluorine atom (F) or a chlorine atom (Cl). The term "halide" refers to the anionic form of a halogen atom, i.e., fluoride (F - ) or chloride (Cl - ) means

[0026] "(C1~C 50 The term "(C1-C)hydrocarbyl" means a hydrocarbon group of 1 to 50 carbon atoms. 50The term "hydrocarbylene" means a hydrocarbon diradical of 1 to 50 carbon atoms, each hydrocarbon group and each hydrocarbon diradical being aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (having 3 or more carbons, including monocyclic and polycyclic, fused and non-fused polycyclic, and bicyclic) or acyclic, and containing one or more R S is or is not replaced by

[0027] In this disclosure, (C1 to C 50 ) hydrocarbyl is 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 (e.g., benzyl (CH2-C6H5)).

[0028] "(C1~C 50 ) alkyl" and "(C1-C 18 The term "alkyl" refers to an unsubstituted or alkyl group containing one or more R S and saturated straight-chain or branched-chain hydrocarbon groups of 1 to 50 carbon atoms and 1 to 18 carbon atoms, respectively. 50 Examples of 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. 40 Examples of substituted (C1-C 20 ) Alkyl, substituted (C1-C 10 ) alkyl, trifluoromethyl, and [C 45 ] alkyl.45 The term "alkyl" refers to a group having up to 45 carbon atoms in the radical, including the substituents, e.g., one R that is (C1-C5) alkyl. S replaced by (C 27 ~C 40 Each (C1-C5) alkyl can be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl, or 1,1-dimethylethyl.

[0029] "(C6~C 50 The term "aryl" refers to an unsubstituted or (one or more R S "Aromatic hydrocarbon radical" refers to a monocyclic, bicyclic, or tricyclic aromatic hydrocarbon radical substituted (by C6-C), wherein at least 6 to 14 of the carbon atoms are 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 ring or rings of the aromatic radical may independently be fused or non-fused, and aromatic or non-aromatic. Unsubstituted (C6-C 50 Examples of 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. 40 Examples of aryl include substituted (C1-C 20 ) Aryl, substituted (C6-C 18 )aryl, 2,4-bis([C 20 ]alkyl)-phenyl, polyfluorophenyl, pentafluorophenyl, fluoren-9-on-1-yl, and biphenyl.

[0030] "(C3~C 50The term "cycloalkyl" refers to an unsubstituted or substituted group having one or more R S means a saturated cyclic hydrocarbon group of 3 to 50 carbon atoms substituted with other cycloalkyl groups (e.g., (C x ~C y )cycloalkyl) has x to y carbon atoms and is unsubstituted or has one or more R S Unsubstituted (C3 to C 40 Examples of cycloalkyl are unsubstituted (C-C 20 ) Cycloalkyl, unsubstituted (C3-C 10 ) cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. 40 Examples of cycloalkyl are substituted (C3-C 20 ) Cycloalkyl, substituted (C3-C 10 ) cycloalkyl, and 1-fluorocyclohexyl.

[0031] (C1~C 50 Examples of hydrocarbylene include unsubstituted or substituted (C-C 50 ) arylene, (C3-C 50 ) cycloalkylene, and (C1-C 50 ) alkylene (e.g., (C1-C 20 ) alkylene). Divalent groups can be on the same carbon atom (e.g., —CH—) 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 divalent groups include 1,2-, 1,3-, 1,4-, or α,ω-diradicals, while others include 1,2-diradicals. α,ω-diradicals are diradicals with the greatest carbon backbone spacing between the radical carbons. (C2-C 20Some examples of alkylene α,ω-diradicals include ethane-1,2-diyl (i.e., -CHCH-), propane-1,3-diyl (i.e., -CHCHCH-), and 2-methylpropane-1,3-diyl (i.e., -CHCH(CH)CH-). (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 substituted group having one or more R S means a saturated straight or branched chain divalent group of 1 to 50 carbon atoms (i.e., the group is not on a ring atom) substituted by 50 Examples of alkylene are unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C * HCH3 and -(CH2)4C * Unsubstituted (C1-C, including (H)(CH3) 20 ) alkylene, wherein "C * " denotes a carbon atom from which a hydrogen atom has been removed to form a secondary or tertiary alkyl group. 50 Examples of alkylene are substituted (C1-C 20 ) alkylene, -CF2-, -C(O)-, and -(CH2) 14 C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted normal-1,20-eicosylene). As mentioned above, the two R S are combined together (C1~C 18 ) alkylene, so that the substituted (C1-C 50 Examples of )alkylene also 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] "(C3~C 50 The term "cycloalkylene" refers to a group that is unsubstituted or has one or more R S means a cyclic diradical of 3 to 50 carbon atoms substituted by: Both radicals in the cyclic diradical are on ring atoms of the cyclic diradical.

[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), S(O), Si(R C )2, P(R P ), N(R N ), -N=C(R C )2, -Ge(R C )2-, or -Si(R C )-, wherein each R C and each R P is unsubstituted (C1 to C 18 ) hydrocarbyl or —H, wherein each R N is unsubstituted (C1 to C 18 The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more carbon atoms of a hydrocarbon are replaced with a heteroatom. 50 The term "(C1-C)heterohydrocarbyl" means a heterohydrocarbon group having 1 to 50 carbon atoms. 50 The term "heterohydrocarbylene" means a heterohydrocarbon divalent radical having 1 to 50 carbon atoms. 50 ) heterohydrocarbyl or (C1-C 50The heterohydrocarbon of the heterohydrocarbylene has one or more heteroatoms. The heterohydrocarbyl group can be on a carbon atom or a heteroatom. The two groups of the heterohydrocarbylene can be on a single carbon atom or a single heteroatom. In addition, one of the two groups of the divalent group can be on a carbon atom and the other group can be on a different carbon atom, one of the two groups can be on a carbon atom and the other group can be on a heteroatom, or one of the two groups can be on a heteroatom and the other group can be on a different heteroatom. Each (C1-C 50 ) heterohydrocarbyl and (C1-C 50 ) heterohydrocarbylene is unsubstituted or (one or more R S and may be aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

[0035] (C1~C 50 ) Heterohydrocarbyl can be unsubstituted or substituted. (C1-C 50 Non-limiting examples of heterohydrocarbyls include (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 )-, (C l ~C 50 ) hydrocarbyl-P(R P )-, (C2~C 50 ) heterocycloalkyl, (C2-C 19 )Heterocycloalkyl-(C1-C 20 ) alkylene, (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 ) Alkylene, (C6-C 20 )Aryl-(C1-C 19 ) heteroalkylene, or (C1-C 19 )Heteroaryl-(C1-C 20 ) heteroalkylene.

[0036] "(C4~C 50 The term "heteroaryl" refers to an unsubstituted or substituted heteroaryl group of 4 to 50 total carbon atoms and 1 to 10 heteroatoms. S " refers to a monocyclic, bicyclic, or tricyclic heteroaromatic hydrocarbon group substituted with (e.g., (C4-C6)). Monocyclic heteroaromatic hydrocarbon groups include one heteroaromatic ring, bicyclic heteroaromatic hydrocarbon groups have two rings, and tricyclic heteroaromatic hydrocarbon groups have three rings. When a bicyclic or tricyclic heteroaromatic hydrocarbon radical is present, at least one of the rings in the radical is heteroaromatic. The other ring(s) of the heteroaromatic group may independently be fused or non-fused, and aromatic or non-aromatic. Other heteroaryl groups (e.g., (C4-C6) 12 ) heteroaryl, etc. x ~C y ) heteroaryl (general) has x to y carbon atoms (e.g., 4 to 12 carbon atoms) and is unsubstituted or contains one or more R S The monocyclic heteroaromatic hydrocarbon group is defined in the same manner as being substituted with: The monocyclic heteroaromatic hydrocarbon group is a 5-membered or 6-membered ring.

[0037] A 5-membered monocyclic heteroaromatic hydrocarbon radical has 5 minus h carbon atoms, where h is the number of heteroatoms and can be 1, 2, or 3, and each heteroatom can be O, S, N, or P. Examples of 5-membered heteroaromatic hydrocarbon radicals include pyrrol-1-yl, pyrrol-2-yl, furan-3-yl, thiophen-2-yl, pyrazol-1-yl, isoxazol-2-yl, isothiazol-5-yl, imidazol-2-yl, oxazol-4-yl, thiazol-2-yl, 1,2,4-triazol-1-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, tetrazol-1-yl, tetrazol-2-yl, and tetrazol-5-yl.

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

[0039] The bicyclic heteroaromatic hydrocarbon group may be a fused 5,6- or 6,6-ring system. Examples of fused 5,6-ring bicyclic heteroaromatic hydrocarbon radicals are indol-1-yl and benzimidazol-1-yl. Examples of fused 6,6-ring bicyclic heteroaromatic hydrocarbon radicals are quinolin-2-yl and isoquinolin-1-yl. The tricyclic heteroaromatic hydrocarbon group may be a fused 5,6,5-, 5,6,6-, 6,5,6-, or 6,6,6-ring system. An example of a fused 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indol-1-yl. An example of a fused 5,6,6-ring system is 1H-benzo[f]indol-1-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl.An example of a fused 6,6,6-ring system is acridine-9-yl.

[0040] "(C1~C 50The term "(C1-C)heteroalkyl" means a saturated straight or branched chain radical containing 1 to 50 carbon atoms and one or more heteroatoms. 50 The term "heteroalkylene" refers to a saturated straight or branched chain diradical containing 1 to 50 carbon atoms and one or more heteroatoms. The heteroatoms of a 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, S.R. C , S(O), and S(O)2, wherein each of the heteroalkyl and heteroalkylene groups is unsubstituted or contains one or more R S has been replaced by

[0041] Unsubstituted (C2~C 40 Examples of heterocycloalkyl include unsubstituted (C-C 20 ) Heterocycloalkyl, unsubstituted (C2-C 10 ) heterocycloalkyl, aziridin-1-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-1-yl, tetrahydrothiophene-S,S-dioxid-2-yl, morpholin-4-yl, 1,4-dioxan-2-yl, hexahydroazepin-4-yl, 3-oxa-cyclooctyl, 5-thio-cyclononyl, and 2-aza-cyclodecyl.

[0042] The term "saturated" means lacking 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 is one or more substituents R S When substituted by, one or more double and / or triple bonds may optionally be replaced by a substituent R SThe term "unsaturated" refers to a group containing one or more carbon-carbon double bonds or carbon-carbon triple bonds, or (in heteroatom-containing groups) one or more carbon-nitrogen double bonds, carbon-phosphorus double bonds, or carbon-silicon double bonds, and the substituent R S This means that the aromatic ring or heteroaromatic ring does not contain any double bonds that may be present in the ring (if present), or in the aromatic or heteroaromatic ring (if present).

[0043] According to one or more embodiments, the process for polymerizing olefins comprises the step of polymerizing ethylene and (C3-C6) in the presence of a catalyst system comprising a Group IV metal-ligand complex and a bimetallic activator ionic complex. 40 ) an α-olefin comonomer. The bimetallic activator ionic complex comprises an anion and a countercation, wherein the anion has a structure according to formula (I). [ka]

[0044] The countercation can be any cation that has a formal charge of +1. In formula (I), each M is independently aluminum or boron. 1 is C(H) and R 2 is C(R L ) or N, wherein each R L are independently -H, (C1 to C 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, or halogen-substituted (C1-C 30 ) hydrocarbyl. 3 is -H, (C1~C 30 ) Hydrocarbyl, halogen-substituted (C1-C 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, or (C-C 30 ) hydrocarbylene, and R 3 is optionally R 2 It is connected to form a ring. 3 When is -H, R 2 is N or C(RX ) where R X (C1~C 30 ) hydrocarbyl, and R 2 When is C(H), R 3 (C1~C 30 ) hydrocarbyl.

[0045] In formula (I), each R 4 are independently radicals having formula (II): [ka]

[0046] In formula (II), each R 21 , R 22 , R 23 , R 24 , and R 25 are independently halogen-substituted (C1-C 40 ) Alkyl, halogen-substituted (C6-C 40 ) Aryl, -H, -NR N 2, -OR C , -SR C or halogen. 4 is a radical according to formula (II), R 21~25 At least three of the groups are independently halogen-substituted (C1 to C 40 ) Alkyl, halogen-substituted (C6-C 40 ) aryl, or -F. Additionally, R 4 is halogen-substituted (C1-C 30 ) alkyl, halogen-substituted (C1-C 30 ) alkyl is substituted with at least three halogen atoms. N and each R C are independently (C1~C 30 ) hydrocarbyl or —H. In some embodiments, R 4 is halogen-substituted (C1-C 30 ) alkyl, halogen-substituted (C1-C 30) The alkyl is substituted with at least four halogen atoms, at least five halogen atoms, or at least six halogen atoms.

[0047] In formula (I), C(R 3 ) carbon atoms and R 2 The dotted line between may be a double bond, or the dotted line may indicate resonance.

[0048] In embodiments of the catalyst system, in the anion of formula (I), each R 4 is a radical having formula (II) and R 21 , R 22 , R 23 , R 24 , and R 25 is fluorine.

[0049] In some embodiments, R 1 is C(H) and R 2 is C(H) and R 3 is (C1~C 30 ) hydrocarbyl or (C1-C 30 ) heterohydrocarbyl. In embodiments, R 1 is C(H) and R 2 is C(H) and R 3 is (C1~C 30 ) alkyl. In various embodiments, R 1 is C(H) and R 2 is (C1~C 10 ) alkyl and R3 is -H.

[0050] In various embodiments, R 2 is C(H) and R 3 is (C1~C 10 ) alkyl.

[0051] In one or more embodiments, R 1 is C(H) and R 2 is C(H) and R 3is methyl, ethyl, propyl, 2-propyl, n-butyl, tert-butyl, 2-methylpropyl, pentyl, hexyl, heptyl, n-octyl, or tert-octyl. 1 is C(H) and R 2 is C(H) and R 3 is n-octyl or tert-octyl.

[0052] In one or more embodiments, R 3 is R 2 are connected to form a ring, and the anion of the bimetallic activator complex has a structure according to formula (Ia). [ka]

[0053] In formula (Ia), R 31 , R 32 , R 33 , and R 34 are independently (C1~C 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, or —H, and R 1 , R, and M are as defined in formula (I).

[0054] In some embodiments, in the bimetallic activator complex according to Formula (Ia), each R 4 is -C6F5.

[0055] In embodiments, R 32 and R 33 At least one of the groups is -CH2Si(R C ) 3, wherein each R C are independently (C1~C 10 ) alkyl. In one or more embodiments, R 32 and R 33 At least one of the groups is -CH2Si(CH3)2(R C ) where R C are independently (C1~C 10) alkyl. In some embodiments, R 32 and R 33 At least one of the groups is -CH2Si(CH3)2(C8H 17 )

[0056] In some embodiments, each M is boron.

[0057] In an exemplary embodiment, the catalyst system can include a bimetallic activator ionic complex comprising an anion and a countercation, wherein the anion conforms to formula (I). An exemplary embodiment includes an anion structure complexed with a countercation according to the present disclosure, having the following structure: [ka] Polymer Electrical Properties

[0058] The electrical insulating efficiency of a medium, such as a polymeric material, can be evaluated by considering the medium's electrical resistance and the medium's electrical losses. Electrical losses reduce the effectiveness of an insulating medium in electrically insulating in the presence of an electric field. Because resistance is inversely related to power or electrical losses, the resistance of an insulating medium should be as high as possible in both alternating current (AC) and direct current (DC) systems.

[0059] In DC systems, such as photovoltaic devices encapsulated in an insulating medium such as a polymeric material, electrical losses manifest themselves as leakage current from the encapsulated device through the encapsulant to the external environment. This current (I) is directly proportional to the voltage (V) across the insulating medium, according to the equation I = V × R. -1 is inversely proportional to the resistance (R) of the insulating medium, according to: Therefore, for a given operating voltage, the higher the resistance, the lower the leakage current.

[0060] In AC systems that contain insulating media, such as cable insulation, electrical losses manifest themselves as the absorption of energy by the insulating medium in the presence of an electric field. This loss, measured in power (P), is expressed by the equation P=V 2×ω×C×ε'×tanδ, where ω is the angular frequency (e.g., 50 or 60 Hz), ε' is the relative permittivity, C is the capacitance, and tanδ is the dielectric loss tangent, where tanδ=(C×R×ω). -1 and the equation P=V 2 ×ε'×R -1 Resistance is inversely related to power loss, so the higher the resistance, the lower the power loss.

[0061] The electrical resistance of a medium generally decreases as a result of ionic diffusion induced by an external electric field. In systems where ionic diffusion dominates the electrical response, the resistance is calculated by the equation R = ε' × ε0 × C -1 ×q -1 ×N -1 ×μ -1 is related to the diffusing ions according to 0 is the dielectric constant of a vacuum (8.854×10 -12 F m -1 ), where q is the charge of the ion, N is the concentration of the ion, and μ is the electrical mobility of the ion. Since an increase in resistance reduces energy loss and a decrease in ion concentration increases resistance, reducing the concentration of ions diffusing through the medium or reducing their electrical mobility (e.g., decreasing solubility) reduces energy loss.

[0062] The ability of an ion to diffuse through a given medium is affected by the size of the ion, the charge of the ion, the interaction of the ion with the surrounding medium, and the dissociation energy of the ion with available counterions. Because not all ions diffuse equally through a given medium, when the medium is a polymer, the diffusivity of the ion generally affects the insulating ability of the polymer. Without intending to be bound by theory, it is believed that the anion of the ionic bimetallic activator complex of formula (I) has a low ability to diffuse through the produced polymer and / or is low in concentration in the final product due to intentional decomposition, resulting in the produced polymer of the catalyst system of the present disclosure having desirable electrical properties, such as reduced electrical losses. Catalyst System Components

[0063] The catalyst system includes a procatalyst. The procatalyst can be selected from a Group IV metal-ligand complex, such as a titanium (Ti) metal-ligand complex, a zirconium (Zr) metal-ligand complex, or a hafnium (Hf) metal-ligand complex. In one or more embodiments, the Group IV metal-ligand complex includes a bis-biphenylphenoxy Group IV metal-ligand complex, a procatalyst that can become catalytically active upon contact with an activator of the present disclosure.

[0064] According to some embodiments, the bis-biphenylphenoxy Group IV metal-ligand complex has a structure according to formula (X): [ka]

[0065] In formula (X), M is a metal selected from titanium, zirconium, or hafnium, the metal being in a formal oxidation state of +2, +3, or +4. (X) n The subscript n in is 0, 1, or 2. When the subscript n is 1, X is a monodentate or bidentate ligand, and when the subscript n is 2, each X is a monodentate ligand. Each Z is independently -O-, -S-, -N(R N )-, or -P(R P )-, and R 2~4 , R 5~8 , R 9~12 , and R 13~15 are independently -H, (C1 to 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 CC(O)N(R)-, (R C )NC(O)-, and halogen. 1 and R 16 is selected from a radical having formula (XI), a radical having formula (XII), and a radical having formula (XIII). [ka]

[0066] In formulas (XI), (XII), and (XIII), R 31~35 , R 41~48 , and R 51~59 Each of the groups independently represents -H, (C1 to 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-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C )2NC(O)-, or halogen.

[0067] In one or more embodiments, each X, independently of any other ligand X, is selected from halogen, unsubstituted (C1-C 20 ) hydrocarbyl, unsubstituted [(C1-C 20 )hydrocarbyl]C(O)O—, or R K R L N-, wherein R K and R L Each of is independently unsubstituted (C1 to C 20 ) hydrocarbyl.

[0068] Exemplary metal-ligand complexes according to formula (X) include, for example:

[0069] (2',2"-(propane-1,3-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-octyl-9H-carbazol-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium,

[0070] (2',2"-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-chloro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium,

[0071] (2',2"-(propane-1,3-diylbis(oxy))bis(3'-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5'-fluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium,

[0072] (2',2"-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium,

[0073] (2',2"-(propane-1,3-diylbis(oxy))bis(5'-cyano-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-methyl5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium,

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

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

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

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

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

[0079] (2',2"-(propane-1,3-diylbis(oxy))bis(3-(9H-carbazol-9-yl)-5'-chloro-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium,

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

[0081] (2',2"-(2,2-dimethyl-2-silapropane-1,3-diylbis(oxy))bis(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,

[0082] (2'2''-(2,2-dimethyl-2-silapropane-1-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9-carbazol-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium,

[0083] (2',2"-(propane-1,3-diylbis(oxy))bis(3'-bromo-5'-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium,

[0084] (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,

[0085] (2',2''-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5'-fluoro-3'-trifluoromethyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium,

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

[0087] (2',2''-(ethane-1,2-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium,

[0088] (2',2"-(propane-1,3-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-methyl5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-zirconium,

[0089] (2',2"-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3',5'-dichloro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-titanium, and

[0090] (2',2"-(propane-1,3-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-methyl5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-titanium.

[0091] Other bis-biphenylphenoxy Group IV metal-ligand complexes that can be used in combination with bimetallic activators in the catalyst systems of the present disclosure will be apparent to those skilled in the art.

[0092] In one or more embodiments, the Group IV metal-ligand complex comprises a constrained geometry Group IV complex. Exemplary constrained geometry Group IV complexes that may be used in embodiments include:

[0093] cyclopentadienyltitanium trimethyl,

[0094] cyclopentadienyltitanium triethyl,

[0095] cyclopentadienyltitanium triisopropyl,

[0096] cyclopentadienyltitanium triphenyl,

[0097] cyclopentadienyltitanium tribenzyl,

[0098] cyclopentadienyltitanium-2,4-dimethylpentadienyl,

[0099] Cyclopentadienyltitanium-2,4-dimethylpentadienyl·triethylphosphine,

[0100] Cyclopentadienyltitanium-2,4-dimethylpentadienyl-trimethylphosphine,

[0101] cyclopentadienyl titanium dimethyl methoxide,

[0102] cyclopentadienyltitanium dimethyl chloride,

[0103] pentamethylcyclopentadienyltitanium trimethyl,

[0104] Indenyltitanium trimethyl,

[0105] Indenyltitanium triethyl,

[0106] Indenyl titanium tripropyl,

[0107] Indenyl titanium triphenyl,

[0108] tetrahydroindenyltitanium tribenzyl,

[0109] pentamethylcyclopentadienyltitanium triisopropyl,

[0110] pentamethylcyclopentadienyl titanium tribenzyl,

[0111] pentamethylcyclopentadienyl titanium dimethyl methoxide,

[0112] pentamethylcyclopentadienyl titanium dimethyl chloride,

[0113] Bis(η 5 -2,4-dimethylpentadienyl)titanium,

[0114] Bis(η 5 (2,4-dimethylpentadienyl)titanium trimethylphosphine

[0115] Bis(η 5 (2,4-dimethylpentadienyl)titanium·triethylphosphine

[0116] Octahydrofluorenyltitanium trimethyl,

[0117] tetrahydroindenyltitanium trimethyl,

[0118] tetrahydrofluorenyltitanium trimethyl,

[0119] (tert-butylamido)(1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalenyl)dimethylsilanetitanium dimethyl,

[0120] (tert-butylamido)(1,1,2,3-tetramethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalenyl)dimethylsilanetitanium dimethyl,

[0121] (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium dibenzyl,

[0122] (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium dimethyl,

[0123] (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)-1,2-ethanediyltitanium dimethyl,

[0124] (tert-butylamido)(tetramethyl-η 5 -indenyl)dimethylsilanetitanium dimethyl,

[0125] (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(III) 2-(dimethylamino)benzyl,

[0126] (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(III) allyl,

[0127] (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(III) 2,4-dimethylpentadienyl,

[0128] (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(II) 1,4-diphenyl-1,3-butadiene,

[0129] (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(II) 1,3-pentadiene,

[0130] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(II) 1,4-diphenyl-1,3-butadiene,

[0131] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(II) 2,4-hexadiene,

[0132] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(IV) 2,3-dimethyl-1,3-butadiene,

[0133] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(IV) isoprene,

[0134] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(IV) 1,3-butadiene,

[0135] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(IV) 2,3-dimethyl-1,3-butadiene,

[0136] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(IV) isoprene,

[0137] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(IV) dimethyl,

[0138] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(IV) dibenzyl,

[0139] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(IV) 1,3-butadiene,

[0140] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(II) 1,3-pentadiene,

[0141] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(II) 1,4-diphenyl-1,3-butadiene,

[0142] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(II) 1,3-pentadiene,

[0143] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(IV) dimethyl,

[0144] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(IV) dibenzyl,

[0145] (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium(II) 1,4-diphenyl-1,3-butadiene,

[0146] (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium(II) 1,3-pentadiene,

[0147] (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium(II) 2,4-hexadiene,

[0148] (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethyl-silanetitanium(IV) 1,3-butadiene,

[0149] (tert-butylamido)(tetramethyl-η 5-cyclopentadienyl)dimethylsilanetitanium(IV) 2,3-dimethyl-1,3-butadiene,

[0150] (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(IV) isoprene,

[0151] (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethyl-silanetitanium(II) 1,4-dibenzyl-1,3-butadiene,

[0152] (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(II) 2,4-hexadiene,

[0153] (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethyl-silanetitanium(II) 3-methyl-1,3-pentadiene,

[0154] (tert-butylamido)(2,4-dimethylpentadien-3-yl)dimethylsilanetitanium dimethyl,

[0155] (tert-butylamido)(6,6-dimethylcyclohexadienyl)dimethylsilanetitanium dimethyl,

[0156] (tert-butylamido)(1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanetitanium dimethyl,

[0157] (tert-butylamido)(1,1,2,3-tetramethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanetitanium dimethyl,

[0158] (tert-butylamido)(tetramethyl-η 5-cyclopentadienylmethylphenylsilanetitanium(IV) dimethyl,

[0159] (tert-butylamido)(tetramethyl-η 5 -cyclopentadienylmethylphenylsilanetitanium(II) 1,4-diphenyl-1,3-butadiene,

[0160] 1-(tert-butylamido)-2-(tetramethyl-η 5 -cyclopentadienyl)ethanediyltitanium(IV) dimethyl,

[0161] 1-(tert-butylamido)-2-(tetramethyl-η 5 -cyclopentadienyl)ethanediyl-titanium(II) 1,4-diphenyl-1,3-butadiene.

[0162] Other catalysts, particularly catalysts containing one or more other Group IV metal complexes not specifically listed above, will be apparent to those skilled in the art.

[0163] The catalyst system of the present disclosure may include a cocatalyst or activator in addition to the bimetallic activator ionic complex having an anion and countercation of Formula (I). Such additional cocatalysts may include, for example, tri(hydrocarbyl)aluminum compounds having 1 to 10 carbons in each hydrocarbyl group, oligomeric or polymeric alumoxane compounds, di(hydrocarbyl)(hydrocarbyloxy)aluminum compounds having 1 to 20 carbons in each hydrocarbyl or hydrocarbyloxy group, or mixtures of the foregoing compounds. These aluminum compounds are typically useful for their beneficial ability to scavenge impurities such as oxygen, water, and aldehydes from the polymerization mixture.

[0164] Di(hydrocarbyl)(hydrocarbyloxy)aluminum compounds that may be used in conjunction with the activators described in this disclosure are represented by the formula T 1 2AlOT 2 or T1Al(OT 2 )2, where T1 is a secondary or tertiary (C3-C6) alkyl, for example, isopropyl, isobutyl, or tert-butyl, and T 2 is alkyl-substituted (C6-C 30 ) aryl radical or aryl-substituted (C1-C 30 ) alkyl radicals, 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.

[0165] 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 carbons in the alkyl group and 6 to 18 carbons in the aryl group (specifically, (3,5-di(t-butyl)-4-methylphenoxy)diisobutylaluminum); methylalumoxane, modified methylalumoxane, and diisobutylalumoxane.

[0166] In catalyst systems according to embodiments of the present disclosure, the molar ratio of bimetallic activator ionic complex to Group IV metal-ligand complex can be from 1:10,000 to 1000:1, e.g., from 1:5000 to 100:1, from 1:100 to 100:1, from 1:10 to 10:1, from 1:5 to 1:1, or from 1:1.5 to 1:1. The catalyst system can include a combination of one or more bimetallic activator ionic complexes described herein.

[0167] Polyolefin The catalyst system described in the previous paragraph is utilized in the polymerization of olefins, primarily ethylene and propylene. In some embodiments, only a single type of olefin, or α-olefin, is present in the polymerization scheme, producing a homopolymer. However, additional α-olefins may be incorporated into the polymerization procedure. The additional α-olefin comonomer typically has 20 or fewer carbon atoms. For example, the 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, the 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.

[0168] An ethylene-based polymer, e.g., a homopolymer and / or interpolymer (including copolymer) of ethylene and, optionally, one or more comonomers such as α-olefins, can comprise at least 50 mole percent (mol%) of monomer units derived from ethylene. All individual values ​​and subranges encompassed by "from at least 50 mol%" are disclosed herein as separate embodiments; for example, an ethylene-based polymer, a homopolymer and / or interpolymer (including copolymer) of ethylene, and, optionally, one or more comonomers such as α-olefins, can comprise at least 60 mol% of monomer units derived from ethylene, at least 70 mol% of monomer units derived from ethylene, at least 80 mol% of monomer units derived from ethylene, or 50 to 100 mol% of monomer units derived from ethylene, or 80 to 100 mol% of units derived from ethylene.

[0169] In some embodiments of the ethylene-based polymer, the ethylene-based polymer may comprise an amount of (C3-C 40) α-olefins (C3 to C 40 In some embodiments, the ethylene-based polymer comprises at least 0.5 mol % to 25 mol % (C to C) α-olefins. 40 In further embodiments, the ethylene-based polymer may comprise at least 5 mol % to 10 mol % of a (C3 to C) α-olefin. 40 ) The α-olefin is 1-octene.

[0170] Any conventional polymerization process in combination with the catalyst system according to embodiments of the present disclosure can be used to produce ethylene-based polymers, including, but not limited to, solution polymerization processes, gas phase polymerization processes, slurry phase polymerization processes, and combinations thereof, using one or more conventional reactors, such as loop reactors, isothermal reactors, fluidized bed gas phase reactors, stirred tank reactors, batch reactors, and the like, in parallel, series, or any combination thereof.

[0171] In one embodiment, an ethylene-based polymer can be produced by solution polymerization in a dual reactor system, e.g., a dual loop reactor system, where ethylene and, optionally, one or more α-olefins are polymerized in the presence of a catalyst system described herein and, optionally, one or more cocatalysts. In another embodiment, an ethylene-based polymer can be produced by solution polymerization in a dual reactor system, e.g., a dual loop reactor system, where ethylene and, optionally, one or more α-olefins are polymerized in the presence of a catalyst system described herein and herein and, optionally, one or more other catalysts. The catalyst system described herein, optionally in combination with one or more other catalysts, can be used in the first reactor or the second reactor. In one embodiment, an ethylene-based polymer can be produced by solution polymerization in a dual reactor system, e.g., a dual loop reactor system, where ethylene and, optionally, one or more α-olefins are polymerized in both reactors in the presence of a catalyst system described herein.

[0172] In another embodiment, the ethylene-based polymer can be produced via solution polymerization in a single reactor system, for example, a single loop reactor system, in which ethylene and optionally one or more α-olefins are polymerized in the presence of a catalyst system described within this disclosure.

[0173] The polymer process may further include 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-based polymer may include any amount of additives. The ethylene-based polymer may contain from about 0 to about 10 percent total weight of such additives, based on the weight of the ethylene-based polymer and the one or more additives. The ethylene-based polymer may further include a filler, which may include, but is not limited to, organic or inorganic fillers. The ethylene-based polymer may contain from about 0 to about 20 percent by weight of a filler, such as calcium carbonate, talc, or Mg(OH)2, based on the total weight of the ethylene-based polymer and all additives or fillers. The ethylene-based polymer may be further compounded with one or more polymers to form a blend.

[0174] In some embodiments, a polymerization process for producing an ethylene-based polymer can include polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst system incorporating at least one metal-ligand complex and a bimetallic activator ionic complex. Polymers obtained from such catalyst systems incorporating a metal-ligand complex and a bimetallic activator ionic complex can have a densitometric value of, for example, 0.850 g / cm according to ASTM D792, which is incorporated herein by reference in its entirety. 3 ~0.950g / cm 3 , 0.870g / cm 3 ~0.920g / cm 3 , 0.870g / cm 3 ~0.910g / cm 3 , or 0.870 g / cm3 ~0.900g / cm 3 The density may be

[0175] In another embodiment, the polymers obtained from the catalyst system comprising the metal-ligand complex and the bimetallic activator ionic complex have a melt flow ratio (I) of 5 to 15. 10 / I2), where the melt index I2 is measured at 190°C and a load of 2.16 kg in accordance with ASTM D1238 (which is incorporated herein by reference in its entirety), and the melt index I 10 is measured according to ASTM D1238 at 190°C and a load of 10 kg. In other embodiments, the melt flow ratio (I 10 / I2) is 5-10, and in another embodiment the melt flow ratio is 5-9.

[0176] In some embodiments, the polymers obtained from the catalyst system comprising the metal-ligand complex and the bimetallic activator ionic complex have a molecular-weight distribution (MWD) of 1 to 25, w / M n is defined as M w is the weight average molecular weight, and M n is the number average molecular weight. In another embodiment, the polymer resulting from the catalyst system has an MWD of 1 to 6. Another embodiment includes an MWD of 1 to 3, and another embodiment includes an MWD of 1.5 to 2.5. Continuous polymerization

[0177] The feedstocks (ethylene, 1-octene) and process solvent (a high-purity narrow-boiling isoparaffin solvent commercially available from ExxonMobil Corporation under the trademark ISOPAR E) were purified with molecular sieves. Hydrogen was supplied as a high-purity grade in a pressurized cylinder without further purification. The reactor monomer feed (ethylene) stream was pressurized via a mechanical compressor to a pressure above the reaction pressure of 525 psig. The solvent and comonomer (1-octene) feed were pressurized via a mechanical positive displacement pump to a pressure above the reaction pressure of 525 psig. MMAO-3A, ​​commercially available from Nouryon, was used as an impurity scavenger. The individual catalyst components (procatalyst / activator / scavenger) were manually batch diluted with purified solvent (Isopar E) to the specified component concentrations and pressurized to a pressure above the reaction pressure of 525 psig. The activator was used at a 1.2 molar ratio relative to the procatalyst. The scavenger was used at a constant flow rate so that its contribution to the reactor Al concentration was 0.6 ppm. All reaction feed streams are measured using mass flow meters and independently controlled by computer-automated valve control systems.

[0178] Continuous solution polymerization is carried out in a 1-gallon continuously stirred-tank reactor (CSTR). The reactor feed, which combines solvent, monomer, comonomer, and hydrogen, is temperature-controlled between 5°C and 30°C, typically at 15°C. All of these materials are fed to the polymerization reactor along with the solvent feed. The catalyst is fed to the reactor to achieve a specific ethylene conversion. The activator is fed separately to the catalyst components based on a specific calculated molar ratio (1.2 molar equivalents). The TEA scavenger shares the same line as the activator, and the flow is based either on the Al concentration in the reactor or on a specific molar ratio to the catalyst components. The effluent from the polymerization reactor (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) exits the reactor and is contacted with water to terminate the polymerization. Additionally, various additives, such as antioxidants, can be added at this point. The flow then passes through a static mixer to uniformly distribute the catalyst stopper and additives.

[0179] Following additive addition, the effluent (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) passes through a heat exchanger to raise the stream's temperature in preparation for separation of the polymer from other low-boiling reaction components. The stream then passes through a reactor pressure control valve, where the pressure is significantly reduced throughout. From there, the effluent enters a two-stage separation system consisting of a devolatizer and a vacuum extruder, where the solvent, as well as unreacted hydrogen, monomer, comonomer, and water, are removed from the polymer. At the extruder exit, the formed strands of molten polymer pass through a cold water bath, where they solidify. The strands are then fed through a strand chopper, where, after air drying, the polymer is chopped into pellets. Plaque preparation for electrical testing

[0180] For all samples, the resin is placed in a 420 mL Brabender mixer bowl, the cam blade set to 80°C, and fluxed for 1 minute once melted. If the sample contains a partitioning agent, add it to the resin and flux until the powder is visibly incorporated. The antioxidant is added slowly, and once melted, the blend is fluxed for 3 minutes. Perkadox BC-FF is melted in a sealed vial using a water bath set to 60°C, and the liquid peroxide is added and mixed at 40 rpm for 3 minutes. The polymer melt temperature should not exceed 125°C. The mixture is removed from the mixing bowl and cold-pressed into a "pancake."

[0181] For plaque preparation, the sample is first pressed at 120°C under low pressure (500 psi) for 3 minutes. After 3 minutes, the compression is switched to high pressure (2500 psi) for an additional 3 minutes at the same temperature. The sample is cut into uniform specimens and reloaded into the press. The sample is then pressed at 120°C under low pressure for 3 minutes. The temperature is then increased to 182°C and the pressure is increased to the high pressure condition. Once the press reaches the desired temperature, the sample is cured at high pressure for an additional 12 minutes. Following the cure period, the sample is cooled to approximately 30°C under high pressure.

[0182] Using the plaque preparation and curing method described above, 50 mil and 20 mil plaques are produced from the cold press. The plaques are then placed in a vacuum oven and degassed at 65°C under house vacuum for 3 days. Sample disks are then punched out and tested for DC / DF (dielectric constant / dissipation factor) and VR (volume resistivity). Duplicate samples are punched out from the same plaque.

[0183] The dielectric constant and dissipation factor were measured using the ASTM D150-18 method, and the volume resistivity (VR = R × sample area × sample thickness) -1 ) is measured using ASTM D257-14 method. The present specification includes the following aspects. Section 1. A process for polymerizing olefins, comprising the steps of: polymerizing ethylene and (C3-C6) in the presence of a catalyst system comprising a procatalyst and a bimetallic activator complex; 40 ) contacting an alpha-olefin comonomer with the bimetallic activator complex, wherein the bimetallic activator complex comprises an anion and a countercation, the anion having a structure according to formula (I): [ka] During the ceremony, each M is independently aluminum or boron; R 1 is C(H), R 2 However, C(R L ) or N, wherein each R L are independently -H, (C1 to C 30 ) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, or halogen-substituted (C1-C 30 ) hydrocarbyl, R 3 But -H, (C1~C 30 ) Hydrocarbyl, halogen-substituted (C1-C 30 ) hydrocarbyl, (C1-C 30) heterohydrocarbyl, or (C-C 30 ) hydrocarbylene; R 3 but optionally R 2 is connected to form a ring, R 3 When is -H, R 2 is N or C(R L ) where R L (C1~C 30 ) hydrocarbyl, R 2 When is C(H), R 3 (C1~C 30 ) hydrocarbyl, Each R 4 are independently substituted with at least three fluorine atoms (C1-C 30 ) alkyl and radicals having formula (II), [ka] In the formula, R 21 , R 22 , R 23 , R 24 , and R 25 are independently halogen-substituted (C1-C 40 ) Alkyl, halogen-substituted (C6-C 40 ) Aryl, -H, -NR N 2, -OR C , -SR C or halogen, provided that R 21~25 At least three of the halogen-substituted (C1-C 40 ) Alkyl, halogen-substituted (C6-C 40 ) selected from the group consisting of aryl, and -F; Each R N and each R C However, independently, (C1~C 30 ) hydrocarbyl or -H. Section 2. Each R 4 Item 1. The catalyst system according to item 1, wherein is —C6F5. Section 3. 3. The catalyst system of claim 1 or 2, wherein each M is boron. Section 4. R 1 is C(H) and R 2 is C(H) and R 3 However, (C1~C 30 ) hydrocarbyl or (C1-C 30 Item 4. The catalyst system according to any one of Items 1 to 3, wherein the heterohydrocarbyl is a heterohydrocarbyl. Section 5. R 2 is C(H) and R 3 However, (C1~C 20 ) alkyl or (C1-C 10 Item 4. The catalyst system according to any one of Items 1 to 3, wherein R is 1 or 2. Section 6. R 2 is C(H) and R 3 However, (C1~C 10 Item 4. The catalyst system according to any one of Items 1 to 3, wherein R is 1 or 2. Section 7. R 2 is C(H) and R 3 4. The catalyst system according to any one of items 1 to 3, wherein is methyl, ethyl, propyl, 2-propyl, n-butyl, tert-butyl, 2-methylpropyl, pentyl, hexyl, heptyl, n-octyl, or tert-octyl. Section 8. R 2 is C(H) and R 3 Item 4. The catalyst system according to any one of Items 1 to 3, wherein is n-octyl or tert-octyl. Section 9. R 3 But R 2 is connected to form a ring, and the anion of the bimetallic activator complex has a structure according to formula (Ia); [ka] In the formula, R 31 , R 32 , R 33 , and R 34 However, independently, (C1~C 30) hydrocarbyl, (C1-C 30 ) heterohydrocarbyl, or —H, and R 1 , R 4 and M is as defined in formula (I). Section 10. Each R 4 Item 10. The catalyst system according to item 9, wherein is —C6F5. Section 11. R 32 and R 33 At least one of the groups is -CH2Si(R C ) 3, wherein each R C are independently (C1~C 10 Item 10. The catalyst system according to item 9, wherein the alkyl is . Section 12. R 32 and R 33 At least one of the groups is -CH2Si(CH3)2(R C ) where each R C are independently (C1~C 10 Item 10. The catalyst system according to item 9, wherein the alkyl is . Section 13. R 32 and R 33 At least one of the following is -CH2Si(CH3)2(C8H 17 Item 10. The catalyst system according to item 9, wherein [Example]

[0184] Examples 1-3 are synthetic procedures for intermediates of Activators 1-3. In Example 4, polymer resins were synthesized using various activators. The characteristics of the polymer resins were measured and recorded in Tables 1-3. One or more features of the present disclosure will be illustrated in view of the following examples.

[0185] Example 1: Synthesis of Activator 1 [ka]

[0186] In a drybox, Armeen M2HT (3.35 g, 6.24 mmol), 4-ethylimidazole (0.600 g, 6.24 mmol), and tris(pentafluorophenyl)borane (6.39 g, 12.5 mmol) were transferred to a round-bottom flask and toluene (70 mL) was added. The reaction mixture was heated to 100° C. for 25 hours and then cooled to 25° C. The solvent was removed under vacuum. Pentane (50 mL) was added and the mixture was stirred vigorously for 30 minutes. The pentane was decanted, and the remaining oil was further dried under vacuum to give the product (9.63 g, 93%) as a light brown oil. 1 H NMR(400MHz,benzene-d6)δ 7.97(d,J=4.7Hz,1H),6.90(s,1H),1.98(d,J=7.8Hz,4H),1.73(s,3H),1.46~1.24(m,57H),0.91(q,J=5.8,4.8Hz,16H),0.79(t,J=7.4Hz,3H). 19 F NMR (376MHz, benzene-d6)δ:-128.35,-128.51~-128.90,-130.74~-131.38(m), -132.14(d,J=22.5Hz),-133.56(d,J=85.7Hz),-135.62(d,J=24.5Hz),-138 .96,-156.96(t,J=20.8Hz),-157.97,-158.47(t,J=20.7Hzz),-158.98,-16 1.46(td,J=23.2,22.7,7.3Hz),-164.19~-164.97(m),-165.16~-166.34(m).

[0187] Synthesis of 2-bromodecanal: [ka]

[0188] A round-bottom flask was charged with 1-decanal (5.00 g, 32 mmol) and dissolved in 200 mL of chloroform. Bromine (3.99 g, 25 mmol, 0.78 equiv.) was dissolved in chloroform (200 mL) and charged to an addition funnel. Using the addition funnel, the bromine solution was added dropwise to the decanal solution. After the addition was complete, the reaction was monitored by GC / MS to confirm complete conversion to the desired product. The solution was slowly poured onto 100 mL of saturated sodium bicarbonate solution. The organic layer was separated, washed with water (3 × 80 mL), dried over sodium sulfate, filtered, and the solvent was removed by rotary evaporation. The reagent was used directly in subsequent reactions (yield: 7.52 g, 86%). 1 H NMR (400 MHz, chloroform-d) δ 9.42 (d, J = 3.1 Hz, 1H), 4.21 (ddd, J = 8.2, 6.2, 3.1 Hz, 1H), 2.03 (ddt, J = 14.5, 9.9, 5.9 Hz, 1H), 1.90 (dddd, J = 14.6, 9.9, 8.1, 5.1 Hz, 1H), 1.35–1.18 (m, 10H), 0.93–0.80 (m, 3H). 13 C NMR (101 MHz, chloroform-d) δ 192.74, 55.41, 31.72, 31.61, 29.18, 29.06, 28.85, 26.86, 22.57, 14.02.

[0189] Synthesis of 4-octyl-1H-imidazole: [ka]

[0190] A round-bottom flask was charged with 2-bromooctanal (4.3 g, 18.3 mmol), formamide (5.8 g, 146.3 mmol), and a stir bar. The solution was heated to 185 °C with a reflux condenser and stirred overnight. The solution was cooled, an aliquot was taken, quenched with water, and analyzed by GC / MS to assess conversion. The solution was returned to 185 °C and refluxed overnight. After cooling to room temperature, the reaction solution separated into a dark, viscous, oily upper layer and a pale, watery lower layer. Both were sampled, and the lower layer showed more product. The entire solution was quenched with ice water and then transferred to a separatory funnel. The aqueous solution was washed three times with CHCl. ​​The organic phase was dried over sodium sulfate overnight. An aliquot of the solution was taken, and the solvent was removed under vacuum. The brown oil was then purified by silica gel column chromatography (yield: 410 mg, 12%). 1 H NMR (400 MHz, chloroform-d) δ 12.49 (s, 1H), 7.52 (s, 1H), 6.73 (s, 1H), 2.57 (t, J = 7.7 Hz, 1H), 1.60 (p, J = 7.5 Hz, 1H), 1.48–0.99 (m, 12H), 0.83 (q, J = 4.0, 2.9 Hz, 3H). 13 C NMR (101 MHz, chloroform-d) δ 136.67, 134.31, 117.95, 31.91, 29.51, 29.46, 29.40, 29.31, 26.62, 22.69, 14.11.

[0191] Example 2: Synthesis of activator 2 [ka]

[0192] In a dry box, solid Armeen M2HT (907 mg, 1.69 mmol), 4-octyl-imidazole (305 mg, 1.69 mmol), tris(pentafluorophenyl)borate (FAB, 1.73 g, 3.38 mmol), and toluene (5 mL) were each placed in a flask. The reaction was heated to 100 °C, during which time the reaction became homogeneous. After 2 h, the reaction was 19F NMR analysis confirmed incomplete conversion, but no FAB was present in the F19(C6D6) spectrum. Most of the toluene was removed in vacuo, then 40 mL of pentane was added, and the mixture was stirred vigorously for at least 30 minutes. Stirring was stopped, and the mixture was cooled to 0 °C, allowing the solution to phase separate. Most of the pentane solution was decanted, and the remaining oil and traces of solvent were then dried under vacuum, yielding 1.95 g of a viscous reddish-brown oil. The decanted pentane was returned to the refrigerator to see if additional material would produce an oil. After several days at 0 °C, no apparent separation occurred. The solvent was removed in vacuo (yield: approximately 1 g, 34%). 1 H NMR(400MHz,benzene-d6)δ 7.97(d,J=4.8Hz,1H),6.92(s,1H),3.04(s,1H),2.65(s,1H),1.89(s,3H),1.70(s,3H),1.46~1.23 (m,47H),1.23~1.08(m,3H),1.04(q,J=7.1Hz,7H),0.90(dt,J=14.7,7.0Hz,9H),0.85~0.68(m,9H). 19 F NMR (376 MHz, benzene-d6, 23 °C) δ -128.02(1F),-128.88(1F),-130.82(1F,d,J=23.5Hz),-132.14(6F,d,J=2 2.5Hz),-133.54(1F),-134.23(1F),-138.37(1F),-156.88(1F,t,J=21.0H z),-157.93(1F),-158.33(6F,t,J=20.8Hz),-158.92(1F),-160.83~-161. 59(1F,m),-164.15,-164.42(6F,t,J=20.6Hz),-165.48(1F),-165.98(1F). 19 F NMR (376 MHz, toluene-d8, 80 °C) δ −128.02, −131.00, −131.83 (d, J = 21.5 Hz), −133.48, −158.02, −159.21 (t, J = 20.0 Hz), −164.63 to −165.12 (m), −165.63.

[0193] Synthesis of 5-((dimethyl(octyl)silyl)methyl)benzo[c][1,2,5]thiadiazole: [ka]

[0194] In a nitrogen-filled glovebox, a reaction vial was charged with a 0.88 M solution of ((dimethyl(octyl)silyl)methyl)magnesium chloride (1.36 mL, 1.20 mmol, 1.2 equiv.) in diethyl ether. A solution of zinc chloride (245 mg, 1.8 equiv.) in THF (2.5 mL) was added dropwise, resulting in the immediate precipitation of a white solid. The suspension was stirred at room temperature for 1 h. 5-Bromobenzo[c][1,2,5]thiadiazole (215 mg, 1.00 mmol, 1 equiv.) and CPhos G3 precatalyst (8.1 mg, 0.01 mmol, 1 mol%) were added, and the reaction mixture was stirred at room temperature for 18 h. The mixture was removed from the glovebox. The reaction mixture was passed through a plug of silica gel, and the plug was eluted with dichloromethane (2 × 20 mL) to give an amber solution. The solution was concentrated in vacuo. The material was adsorbed onto silica gel and purified by flash column chromatography (40 g, 0.1-2% EtOAc in hexanes) to give the product as a clear oil (286.2 mg, 89% yield). 1 H NMR(400MHz,chloroform-d)δ 7.83(dd,J=9.0,0.7Hz,1H),7.58~7.51(m,1H),7.26(dd,J=9.0,1.7Hz,1H),2.27(s,2H) ),1.38~1.18(m,12H),0.88(t,J=6.8Hz,3H),0.55(dd,J=9.6,5.9Hz,2H),0.01(s,6H). 13 C NMR (101 MHz, chloroform-d) δ 155.55, 153.02, 143.24, 132.51, 120.39, 117.56, 33.55, 31.91, 29.29, 29.22, 26.56, 23.71, 22.66, 14.79, 14.11, −3.49.

[0195] Synthesis of 4-((dimethyl(octyl)silyl)methyl)benzene-1,2-diamine: [ka]

[0196] In a nitrogen-filled glovebox, 5-((dimethyl(octyl)silyl)methyl)benzo[c][1,2,5]thiadiazole (0.2862 g, 0.893 mmol, 1 equiv.) was dissolved in tetrahydrofuran (30 mL). Lithium aluminum hydride (135.5 mg, 3.57 mg, 4 equiv.) was added portionwise over several minutes. The lithium aluminum hydride vial was rinsed with THF (2×5 mL), and the rinse was added to the reaction mixture. The clear, colorless solution turned pink during the addition. The reaction was stirred at room temperature for 2.5 hours, during which time the solution became clear and colorless. The reaction vessel was sealed with a septum, removed from the glovebox, and cooled to 0° C. in an ice bath. The solution was subjected to Fieser workup. Water (0.14 mL), 15% aqueous NaOH (0.14 mL), and water (0.42 mL) were added dropwise via syringe in sequence. The ice bath was removed, and the reaction mixture was stirred at room temperature for 15 minutes, resulting in a pale pink solution. Anhydrous magnesium sulfate was added, and the reaction mixture was stirred for an additional 10 minutes. The solution was filtered and concentrated in vacuo to give the product as a white solid (250.6 mg, 96% yield). 1 H NMR(400MHz,chloroform-d)δ 6.60(d,J=7.5Hz,1H),6.37(d,J=9.3Hz,2H),3.30(s,4H),1.95(s,2H),1.30(s,1 2H),0.92(td,J=7.1,5.9,3.4Hz,3H),0.57~0.43(m,2H),-0.03(t,J=2.1Hz,6H). 13 C NMR (101 MHz, chloroform-d) δ 135.07, 132.59, 130.53, 119.69, 117.31, 116.50, 33.68, 31.98, 29.37, 29.30, 24.51, 23.83, 22.71, 14.87, 14.15, -3.48. 17 H32 HRMS calculated for N2Si[M+1] (ESI): 293.2408, found 293.2403.

[0197] Synthesis of 6-((dimethyl(octyl)silyl)methyl)-1H-benzo[d]imidazole: [ka]

[0198] A round-bottom flask was charged with 4-((dimethyl(octyl)silyl)methyl)benzene-1,2-diamine (250.6 mg, 0.857 mmol, 1 equiv.), triethyl orthoformate (0.17 mL, 1.03 mmol, 1.2 equiv.), acetonitrile (3 mL), and dichloromethane (3 mL). Iodine (21.7 mg, 0.0806 mmol, 10 mol%) was added, and the reaction was stirred at room temperature for 7 h. The solution changed from brown to dark green and then back to brown again. The solution was concentrated in vacuo to give a brown oil. The material was adsorbed onto Celite and then purified by flash column chromatography. A silica gel column cartridge was first flushed with 60 mL of 10% triethylamine in hexanes. The column was then equilibrated with 0.1% MeOH in dichloromethane, and typical flash column chromatography (24 g silica gel, 0.1–7% MeOH in dichloromethane) was performed to give a brown oil (191.1 mg, 74% yield). 1 H NMR(400MHz,chloroform-d)δ 12.31~11.89(m,1H),8.14(d,J=2.8Hz,1H),7.58(dd,J=8.3,1.3Hz,1H),7.32(s,1H),6.99(dd,J=8.4,1.5Hz ,1H),2.23(s,2H),1.29(d,J=15.7Hz,12H),0.90(t,J=6.8Hz,3H),0.55(dd,J=9.6,5.7Hz,2H),-0.01(s,6H). 13C NMR (101 MHz, chloroform-d) δ 140.13, 137.40, 135.64, 135.59, 123.90, 115.42, 113.26, 33.66, 31.95, 29.36, 29.27, 25.69, 23.82, 22.69, 14.87, 14.14, -3.51. 18 H 30 HRMS calculated for N2Si[M+1] (ESI): 303.2251, found: 303.2242.

[0199] Example 3: Synthesis of activator 3 [ka]

[0200] In a nitrogen-filled glovebox, a reaction vial was charged with 6-((dimethyl(octyl)silyl)methyl)-1H-benzo[d]imidazole (35.4 mg, 0.117 mmol, 1 equiv.), tris(pentafluorophenyl)borane (119.8 mg, 0.234 mmol, 2 equiv.), Armeen M2HT (62.7 mg, 0.117 mmol, 1 equiv.), and toluene (2 mL). The reaction was stirred at 100 °C for 18 h. The solution was passed through a 0.45 μm syringe filter in-line with a 0.2 μm syringe filter. The filter cake was washed with toluene (2 × 0.5 mL). The combined filtrates were concentrated in vacuo to give a cloudy oil. The oil was triturated with hexane (5 mL). The material was concentrated in vacuo to give a pale yellow solid. The solid was triturated with hexane (5 mL). All volatiles were removed in vacuo to give a yellow solid (207.1 mg, 95% yield). 1 H NMR (500MHz, toluene-d8)δ 8.39(s,1H),7.56(d,J=8.5Hz,1H),7.37(s,1H),6.72(d,J=8.6Hz,1H),2.15~2.04(m,4H), 1.95(d,J=13.1Hz,2H),1.84(s,3H),1.46-0.79(m,85H),0.45~0.31(m,2H),-0.18(s,6H). 11B NMR (160 MHz, toluene-d8) δ -8.66 (br). 19 F NMR (470MHz, toluene-d8, 25℃) δ-127.08~-128.89(m),-129.34,-130.41,-131. 60~-133.29(m),-133.51~-134.86(m),-135.58(d,J=24.3Hz),-135.66~-137 .13(m),-157.13,-157.85~-159.33(m),-159.76(t,J=20.5Hz),-161.19~-16 2.04(m),-163.73~-164.30(m),-164.47~-164.83(m),-165.06~-165.93(m). 19 F NMR (470 MHz, toluene-d8, 90 °C) δ -132.15 (br s), -158.82 (br s), -165.28 (br s). C 37 H 78 HRMS calculated for N[M+1] (ESI): 536.6129, found: 536.6117. 54 H 29 B2F 30 Calculated for N2Si[M-]: 1325.1813, found: 1325.1810.

[0201] Example 4 - Polymerization Results [ka]

[0202] The polymerization was carried out in a continuous stirred tank reactor, the procedure of which is described in the Continuous Reactor section.

[0203] Each of bimetallic activators 1, 2, and 3, and comparative activator C1 (herein "Comparative C1"), was mixed with procatalyst A to form four catalyst systems. Comparative C1, Comparative C2, Comparative C3, Comparative C4, and Comparative C5 contained 1,2-dichloro-2,3-dichloro-2,4-dichloro-2,5-dichloro-2,6-dichloro-2,7-dichloro-2,8-dichloro-2,9-dichloro-2,9-dichloro-2,10-dichloro-2,11-dichloro-2,12-dichloro-2,13-dichloro-2,14-dichloro-2,15-dichloro-2,16-dichloro-2,17-dichloro-2,18-dichloro-2,19-dichloro-2,19-dichloro-2,10-dichloro-2,11-dichloro-2,12-dichloro-2,13-dichloro + N(H)(Me)(C 18 H 37 )2. Comparative C1 has been successfully used as an activator in industrial-scale olefin polymerization reactions.

[0204] Expanded borates have previously been reported as useful activators in U.S. Patent Application Publication No. 6,395,671 (B2), but unsubstituted imidazole-based borates such as Comparative C5 have low solubility in aliphatic hydrocarbon solvents, preventing their use in systems that cannot tolerate aromatic residues or where more complex slurry-based delivery systems are not applicable. [Table 1]

[0205] The efficiencies of inventive activators 1, 2, and 3, and comparatives C1-C3, as well as the polymer characteristics of the polymers obtained from inventive activators 1, 2, and 3, and comparative C1, were measured. The results are summarized in Table 1. Comparative C1 has a proven track record in industrial applications. [Table 2] a Efficiency is grams of polymer per gram of metal (g of poly / g of metal). b For each activator, based on the efficiency of comparative C4 obtained under identical reaction conditions, The relative efficiency was calculated. [Table 3] [Table 4]

[0206] Substitution of the central imidazole moiety at the R1 position (as shown in activator comparisons C2 and C3) resulted in increased solubility of the activators in aliphatic hydrocarbons. 1 Substitutions at positions appear to have affected the potency of the activators (as shown in Table 2).

[0207] In comparison, the R of imidazole 3 or R2 Substitution at the R position (as shown for activators 1, 2, and 3) increases the solubility of the activators in aliphatic hydrocarbons compared to comparative C5, while substitution at the R 1 This improves catalytic efficiency compared to substitutions at positions C2 and C3. [Table 5]

[0208] Activator 1 and Activator 2 produced polymers in catalyst systems containing Procatalyst A that had substantially reduced conductivity compared to the polymer produced by Procatalyst A and Activator Comparative C1. Equipment standards

[0209] 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 passage through activated alumina and, in some cases, Q-5 reactants. Solvents used in experiments conducted in a nitrogen-filled glovebox were further dried by storage over activated 4 Å molecular sieves. Moisture-sensitive reaction glassware was dried overnight in an oven before use. NMR spectra were recorded on Varian 400-MR and VNMRS-500 spectrometers. LC-MS analysis was performed using a Waters e2695 separations module coupled with a Waters 2424 ELS detector, a Waters 2998 PDA detector, and a Waters 3100 ESI mass detector. LC-MS separation is performed on an XBridge C18 3.5 μm 2.1 × 50 mm column using a 5:95 to 100:0 gradient of acetonitrile and water (containing 0.1% formic acid as the ionizing agent). HRMS analysis is performed using an Agilent 1290 Infinity LC equipped with a Zorbax Eclipse Plus C18 1.8 μm 2.1 × 50 mm column coupled to an Agilent 6230 TOF mass spectrometer equipped with electrospray ionization. 1H NMR data are reported as follows: chemical shifts (multiplicities (br = broad line, s = singlet, d = doublet, t = triplet, q = quartet, p = quintet, sex = sextet, sept = septet, and m = multiplet), integrals, and assignments). 1 Chemical shifts for H NMR data are reported as ppm downfield from internal tetramethylsilane (TMS, δ scale) using residual protons in the deuterated solvent as the reference. 13 C NMR data is 1 Determined using H decoupling, chemical shifts are reported as ppm downfield from tetramethylsilane (TMS, δ scale) using residual carbon in deuterated solvent as the reference. The dielectric constant and dissipation factor were measured using a Haefely 2830 / 2831 Precision Dielectric Analyzer and a Haefely 2914 Solid Test Cell. Volume resistivity was measured using a Keithley 6517B Electrometer and a Keithley 8009 Resistivity Test Fixture.

Claims

1. A process for polymerizing olefins comprising the step of polymerizing ethylene and (C ３ ~C ４０ ) contacting an alpha-olefin comonomer with the bimetallic activator complex, wherein the bimetallic activator complex comprises an anion and a countercation; the anion has a structure according to formula (I), 【Chemical 1】 In formula (I), each M is independently aluminum or boron; R １ is C(H), R ２ But C(R Ｌ ) or N, and each R L is —H; R ３ However, (C １ ~C ３０ ) hydrocarbyl or (C １ ~C ３０ ) heterohydrocarbyl, or R 3 is connected to R 2 to form a ring; Each R ４ is independently substituted with at least three fluorine atoms (C １ ~C ３０ ) selected from the group consisting of alkyl and radicals having the formula (II): 【Chemistry 2】 In formula (II), R ２１ , R ２２ , R ２３ , R ２４ , and R ２５ are independently halogen-substituted (C １ ~C ４０ ) alkyl, halogen-substituted (C ６ ~C ４０ ) aryl, —H, —NR Ｎ ２ , -OR Ｃ , -SR Ｃ or halogen, provided that R ２１～２５ At least three of the halogen-substituted groups are １ ~C ４０ ) alkyl, halogen-substituted (C ６ ~C ４０ ) selected from the group consisting of aryl, and —F; Each R Ｎ and each R Ｃ But independently, (C １ ~C ３０ ) hydrocarbyl or —H; When R 3 is connected to R 2 to form a ring, the anion of the bimetallic activator complex has a structure according to formula (Ia): 【Chemistry 3】 In formula (Ia), R 31 , R 32 , R 33 , and R 34 are independently (C 1 -C 30 )hydrocarbyl, (C 1 -C 30 )heterohydrocarbyl, or —H; R 1 , R 4 , and M are as defined in formula (I); and at least one of R 32 and R 33 is —CH 2 Si(CH 3 ) 2 (R C ), and each R C is independently (C 1 -C 10 )alkyl; process.

2. Each R ４ But, -C ６ F ５ 2. The process of claim 1, wherein

3. 3. The process of claim 1 or 2, wherein each M is boron.

4. R ２ is C(H) and R ３ However, (C １ ~C ２０ ) alkyl or (C １ ~C １０ 4. The process of claim 1, wherein the aryl group is aryl.

5. R ２ is C(H) and R ３ However, (C １ ~C １０ 4. The process of claim 1, wherein the aryl group is aryl.

6. R ２ is C(H) and R ３ The process of any one of claims 1 to 3, wherein is n-octyl or tert-octyl.

7. R ３２ and R ３３ At least one of the groups is —CH ２ Si(CH ３ ) ２ (C ８ H １７ 2. The process of claim 1, wherein 8. The process of claim 1, wherein the procatalyst is a Group IV metal-ligand complex.

9. The process of claim 8, wherein the Group IV metal-ligand complex is a bis-biphenylphenoxy metal-ligand complex.

10. The process of claim 8, wherein the Group IV metal-ligand complex is a constrained geometry metal-ligand complex.

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