Solution catalyst systems and their use

Abstract

This disclosure relates to catalyst systems containing catalyst compounds and activators, and their use. In some embodiments, the solution catalyst system comprises a solution of aluminoxane containing either an anionically modified alkylaluminoxane and / or a cationically modified alkylaluminoxane, wherein the alkylaluminoxane composition is determined by titration of the alkylaluminoxane composition with tetrahydrofuran, and contains 0% to about 2% by mass of Al derived from an uncoordinated trihydrocarbyl aluminum compound relative to the total aluminum content of the alkylaluminoxane composition. The catalyst system comprises a compound represented by formula (I).

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims the benefit and priority of U.S. Provisional Patent Application No. 63 / 506536, filed on June 6, 2023, whose disclosure is incorporated herein by reference. This disclosure relates to a catalytic system containing a catalytic compound and an activator, as well as its use. [Background technology]

[0002] Copolymers of olefins and conjugated dienes have demonstrated beneficial properties in the tire industry, such as aging resistance, puncture resistance, repairability, rolling resistance, and wear resistance. Copolymers formed from ethylene and butadiene monomers have been shown to improve these properties when incorporated into one or more components of a tire. However, copolymerization of ethylene and butadiene is a challenging task due to the differing reaction mechanisms and relative reactivity between these two monomers, making it difficult to develop highly efficient methods for producing high molecular weight ethylene-butadiene random copolymers. To overcome these problems, efforts are currently focused on developing methods for implementing catalytic systems that are resistant to both monomers and capable of copolymerizing both monomers within the same process window. Exemplary catalytic systems based on halogenated complexes of transition metals, such as titanium, provide copolymerization of ethylene and conjugated dienes. Japanese Patent Specifications JP'10237131A, JP'09316118A, and JP'11171930A disclose copolymers of ethylene and butadiene, in which butadiene can be inserted in the form of cyclopentyl linkages. These copolymers are obtained by catalytic systems comprising dimethylsilyl (pentamethylcyclopentadienyl)(t-butylamide)titanium dichloride and methylaluminoxane. Activated methylaluminoxanes (MAOs), obtained from partially hydrolyzed trimethylaluminum (TMA), are effective in activating catalysts of the type known as metallocenes for olefin polymerization. MAOs have become a generally preferred aluminum co-catalyst (also called an activator) in the industry. MAOs are commercially available in the form of aromatic diluents, usually in 10% to 30% by mass solution in toluene.

[0003] Considerable effort has been made to improve the effectiveness of catalytic systems for olefin polymerization based on the use of methylaluminoxane or modified methylaluminoxane. For example, WO2009 / 029857 describes how MAO can be converted into dimethylaluminum cations (AlMe2) by treating it with a Lewis base in a toluene solution, such as tetrahydrofuran. + This indicates that it is formed from MAO. Lewis base-stabilized dialkylaluminum cations, e.g., AlMe2 + It can also be derived from non-MAO sources and used as a metallocene catalyst activator; see, for example, Klosin et al. WO2000 / 011006 and Klosin, J. et al. (2000) “Ligand Exchange and Alkyl Abstraction Involving (Perfluoroaryl)boranes and -alanes with Aluminum and Gallium Alkyls,” Organometallics, v.19(23), pp. 4684-4686. US9090720 states that ethylenebisindenylzirconium dimethoxide (EtInd2Zr(OMe)2), a metallocene with a dimethoxy leaving group, is derived from MAO and AlMe2 + Extract [EtInd2Zr(μ-OMe)2AlMe2] + It forms a seed, which is slowly alkylated to become a fully activated seed [EtInd2Zr(μ-Me)2AlMe2]. + It has been shown that this forms AlMe2 from MAO. +It has been strong evidence of activation. Completely activated [EtInd2Zr(μ-Me)2AlMe2] + species is similar to other metallocenes activated by MAO, and these metallocenes are described in Babushkin, D. E. et al. (2002) “Activation of Dimethyl Zirconocene by Methylaluminoxane (MAO)Size Estimate for Me-MAO- Anions by Pulsed Field-Gradient NMR,” J. Am. Chem. Soc., v.124(43), pp. 12869-12873, and Sarzotti, D. M. et al., (2007) “A kinetic study of metallocene-catalyzed ethylene polymerization using different aluminoxane cocatalysts,” J. Polymer Sci. A, v.45(9), pp. 1677-1690 for the activation of zirconocene catalyst precursors by MAO, such as, for example, [Cp2Zr(μ-Me)2AlMe2] + or [Cp2Ti(μ-Me)2AlMe2] + is also formed. Also described in Bryliakov, K. P. et al. (2004) “ 1 H and 13 C NMR Spectroscopic Study of Titanium(IV) Species Formed by Activation of Cp2TiCl2and [(Me4C5)SiMe2N tSee also “Bu]TiCl2 with Methylaluminoxane (MAO),” Organometallics, v.23(1), pp. 149-152. While the MAO structure remains unclear, a newly synthesized active MAO is described by Sinn and Kaminsky (1999) (Sinn, et al., “Formation, Structure, and Mechanism of Oligomeric Methylaluminoxane”, in Kaminsky (ed.), Metalorg. Cat. for Synth. & Polym., Springer-Verlag, p. 105) with the empirical formula (Al4O3Me6)4(TMA). 1-2 This provides evidence that TMA is coordinated in MAO, consistent with the formula. The coordinated TMA is in equilibrium with the free TMA, and attempts to physically remove all the free TMA result in the formation of a more stable, inert MAO gel. Without wishing to be constrained by theory, Scheme 1 is based on the Sinn / Kaminsky MAO formula (Al4O3Me6)4(TMA) 1-2 The proposed graph structure, based on the above, is constructed solely to help better understand the gelation process. Actual MAO structures may differ.

[0004] [ka]

[0005] TMA coordinated in MAO is used for precatalytic ionization of AlMe2 +While it does indeed function as a source, studies have shown that free TMA in MAO, in equilibrium with coordinated TMA, also functions as an alkylating agent, as shown in Scheme 2 (circles are used to show the main structure of MAO for clarity) (Luo, Jain, and Harlan, INOR 1169, American Chemical Society Priestley Medalist Symposium in Honor of Tobin J. Marks, San Francisco, CA, April 5, 2017; Luo et al., U.S. Patent No. 8575284 (2013) and U.S. Patent No. 9090720 (2015)): [ka]

[0006] Therefore, without being constrained by theory, maintaining a significant amount of free TMA in the active MAO solution is considered necessary to stabilize the active MAO composition, for example, by stabilizing the MAO molecular structure capped with coordination TMA, thereby reducing the probability of dimerization / oligomerization that ultimately forms a low-activity or inactive gel (Al:O:Me around 1:1:1) in Scheme 1. Consequently, the physical removal of free TMA not only forms a low-solubility MAO gel that is difficult to support in solution polymerization or find a suitable solvent for, thus limiting its use, but also leads to the loss of coordination TMA, reducing the number of active MAO molecules and resulting in decreased activation efficiency. Nevertheless, post-metallocene catalysts and geometrically constrained complex (CGC) catalysts containing polar ligands, such as oxygen and / or nitrogen donors, exhibit low catalytic activity and short catalytic lifetimes, posing a challenge to activation by standard MAO. Without being constrained by theory, this weak activity and short catalytic lifetime is thought to be due to the presence of free TMA in the MAO, which can alkylate pre-catalyst transition metal centers bonded to heteroatoms (Scheme 3 shows a Zr center as an example). This is analogous to the alkylation of metallocenes with dichloride leaving groups in Scheme 2:

[0007] [ka] There is a need for improved catalytic systems having complementary catalyst-activator pairs that provide commercially scalable polymerization (e.g., high activity under mild conditions) by providing high-activity polymerization of monoolefins and conjugated dienes (e.g., within the same process window).

[0008] The references cited in the Disclosure Statement (37C.FR1.97(h)) include: U.S. Patent Nos. 5,191,052; 8,962,744; 9,139,680; 10,030,092; 9,181,376; 9,670,302; 9,056,936; 8,969,496; 10,45 No. 7,765; No. 10,844,149; No. 10,822,475; No. 8,039,565; No. 11,155,656; No. 11,136,422; No. 11,254 ,804;No. 11,286,369;No. 7,547,654;No. 10,752,712;US Patent Publication No. 2017 / 0073450;2022 / 0135717;PC T Public WO2021 / 155168;WO2021 / 155158;WO2017 / 097831;WO2022 / 112699;WO2022 / 106769;WO2021 / 053294;WO2021 / 023924;WO2020 / 128249;WO2022 / 112700;WO2022 / 112692;WO2022 / 112690; WO2022 / 112691;WO2020 / 070443;Foreign patent: CN113174401;CN113307901;EP3988583;FR3108610;JP 5656686;JP5675434;JP2013155360;JP2013147567;JP5612511;JP2013159626;Academic journal article:Reddy, A. et al. (2021) “Block Copolymers beneath the Surface: Measuring and Modeling Complex Morphology at the Subdomain Scale,” Macromolecules, v.54, (20), pp. 9445-9451. [Overview of the Initiative]

[0009] This disclosure relates to catalysts containing catalytic compounds and activators, and to the use thereof. In some embodiments, the solution catalyst system is 1) Anionically modified alkylaluminoxanes and / or cationically modified alkylaluminoxanes, wherein when the solution catalyst system is determined by titration of the solution catalyst system using tetrahydrofuran, the solution catalyst system contains 0% to about 2% by mass of Al derived from non-coordinating trialkylaluminum compounds relative to the total aluminum content, and 2) Equation (I):

[0010] [ka] [In the formula, M is a group 3 transition metal or lanthanide metal. E and E' are, independently, oxygen, sulfur, or NR. A And R A Independently, hydrogen, C1-C 40 Hydrocarbyl, substituted C1-C 40 A hydrocarbyl or heteroatom-containing group, Q is a group 14 atom, a group 15 atom, or a group 16 atom. A 1 QA 1 ' is part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms, and A is formed via a triatomic bridge with Q as the central atom of the triatomic bridge. 2 to A 2’ It is connected to, A 1 and A 1 Each of these is independently carbon, nitrogen, or C(R) B ) and R B is hydrogen, C1-C 20 Hydrocarbyl and substituted C1-C 20 Selected from hydrocarbil,

[0011] [ka] It is a divalent group containing 2 to 40 non-hydrogen atoms, and via a two-atom bridge, A 1This is linked to the E-bonded aryl group shown in formula (I), and A 3 and A 2 They combine to form a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocycle, or an unsubstituted heterocycle, each having 5, 6, 7, or 8 ring atoms, and substituents on the rings can bond to form additional rings. [ka] It is a divalent group containing 2 to 40 non-hydrogen atoms, and via a two-atom bridge, A 1 ' is linked to the E' bonded aryl group shown in formula (I), A 3 'and A 2 These combine to form a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocycle, or an unsubstituted heterocycle, each having 5, 6, 7, or 8 ring atoms, and substituents on the rings can bond to form additional rings. Each L is independently a Lewis base. X' is an anionic ligand, Any two L groups may be bonded together to form a bidentate Lewis base. The X' group may be bonded to the L group to form a monoanionic bidentate group. n is 1, m is 0, 1, or 2. n+m does not exceed 3. R 1 , R 2 , R 3 , R 4 , R 1 ', R 2 ', R 3 ', and R 4 Each of these is independently hydrogen, C1-C 40 Hydrocarbyl, substituted C1-C 40 Hydrocarbyl, heteroatom, or heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 1 'and R2 ', R 2 'and R 3 ', R 3 'and R 4 One or more of these may bond to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, and substituents on the rings may bond to form additional rings. Compounds represented by This includes. In some embodiments, the Disclosure provides a polymerization process comprising the step of contacting one or more olefin monomers with a catalytic system comprising an electron-withdrawing alkylaluminoxane activator and a catalyst of formula (I) of the Disclosure.

[0012] In some embodiments, the Disclosure provides a polymerization process comprising the step of contacting one or more olefin monomers with a catalytic system comprising a siloxide donor group-modified alkylaluminoxane activator and a catalyst of formula (I) of the Disclosure. [Brief explanation of the drawing]

[0013] [Figure 1] This is a 1H NMR spectrum of a commercially available MAO solution in THF-d8 according to some embodiments. [Figure 2A] Figure 2A shows the 1H NMR spectra of commercially available 30% MAO solutions after KF treatment. The upper solution phases after 2, 4, 7, and 10 mol% KF treatments are shown, respectively. [Figure 2B] Figure 2B shows the 1H NMR spectrum of a commercially available 30% MAO solution after KF treatment. The final K+(F-MAO)-clathrate phase and the untreated MAO solution for comparison are shown. [Modes for carrying out the invention]

[0014] definition An "anionically modified alkylaluminoxane" refers to an alkylaluminoxane after a specific treatment with at least one novel element or at least one electron-withdrawing group. For example, the introduction of an F atom or a C6F5 group into the alkylaluminoxane structure yields MAO fluoride. Therefore, reagents used to convert standard alkylaluminoxanes to anionically modified alkylaluminoxanes are called anionic modifiers, and for example, (NH4)2SiF6 is called an anionic modifier because of its ability to convert standard MAO to MAO fluoride. Terms such as "anionically modified alkylaluminoxane," "anionically modified aluminoxane," "electron-withdrawing group modified alkylaluminoxane," or "electron-withdrawing group modified aluminoxane" are used interchangeably.

[0015] "Cationally modified alkylaluminoxane" refers to an alkylaluminoxane in which, after a specific treatment, the cation is stabilized by at least one electron-donating compound, such as octamethyltrisiloxane (OMTS), forming an ionic alkylaluminoxane. Therefore, reagents used to convert standard alkylaluminoxanes to cationally modified alkylaluminoxanes are called cation modifiers; for example, OMTS is called a cation modifier due to its ability to convert standard MAO to ionic MAO. However, OMTS is a dialkylaluminum cation complex [AlMe2(OMTS)] stabilized with a very stable chelation donor, as shown in Scheme 4I-b. + This chelating agent is capable of forming a dialkylaluminum cation stabilized with a monodentate donor containing a "siloxy donor group" by heating with at least one free TMA molecule. For example, scheme 4I-a shows AlMe2 +A trimethylsiloxide donor group is used to facilitate the release of the siloxide donor group and increase the activation efficiency. The siloxide donor group may also be introduced via other reactions; for example, Me3SiOH can be reacted with TMA in MAO to form Me3SiOAlMe2 in situ.

[0016] [ka]

[0017] Terms such as "cationically modified alkylaluminoxane," "cationically modified aluminoxane," "siloxy donor group modified alkylaluminoxane," "siloxy donor group modified aluminoxane," "ionic alkylaluminoxane," and "ionic aluminoxane" are used interchangeably. "Uncoordinated alkylaluminum" or "free alkylaluminum" have the same meaning as aluminum compounds having at least one alkyl group, e.g., Me, Et, iBu, Oct, in either monomer or dimer form that is not chemically bonded to the aluminoxane structure. Free alkylaluminum can become coordinated by exchange with alkylaluminum coordinated on the aluminoxane structure, but the concentration of free alkylaluminum is maintained under the same conditions because free alkylaluminum is regenerated from the originally coordinated alkylaluminum. Terms such as aluminoxane, almoxane, alkylaluminoxane, and alkylalmoxane are used interchangeably. Sometimes, only alkylaluminum is used to indicate free alkylaluminum; for example, TMA means free TMA.

[0018] "Not present" or "does not contain" means undetectable by current analytical methods, such as nuclear magnetic resonance spectroscopy or conventional wet titration. "Contains in low amounts" means 2% by mass or 2 mol% or less relative to the total amount of the same element in the system. For example, "low amount of free TMA" means that the amount of Al in the free TMA content is 2% by mass or 2 mol% or less relative to the total amount of Al in the MAO composition. In some embodiments, "not present" or "does not contain" may include the statement "in low amounts." For example, TMA-free MAO may indicate that the amount of Al in the free TMA content is 2% by mass or 2 mol% or less relative to the total Al content in the MAO. For convenience, "F-MAO" refers to anionically modified MAO that does not contain free TMA or has a low free TMA content, while "ionic MAO" refers to cationically modified MAO that does not contain free TMA or has a low free TMA content.

[0019] An "electron-withdrawing group" is an X group on a compound (wherein R = C1-C8 hydrocarbyl group) that can react with an aluminum alkyl compound to form an AlR2X compound in situ. This group is a so-called equilibrium-blocking agent between coordinated alkylaluminum and free alkylaluminum, capable of completely or partially blocking the equilibrium between coordinated alkylaluminum and free alkylaluminum in the alkylaluminoxane solution by replacing the coordinated alkylaluminum in the alkylaluminoxane composition. Examples of X include, but are not limited to, F, C6F5, and OC6F5. Therefore, the term "electron-withdrawing compound" may also refer to a compound containing at least one electron-withdrawing group X that can react with an aluminum alkyl compound to form an AlR2X compound (wherein R = C1-C8 hydrocarbyl group), which is a so-called coordinated TMA-free TMA equilibrium blocker that can replace coordinating alkylaluminum in MAO, such as coordinating TMA, and completely or partially block the equilibrium between coordinating TMA and free TMA in MAO solution. For example, (NH4)2SiF6, SiF4, HOC6F5, etc. can be used to react with AlMe3, AlEt3, and AlOct3 to form AlMe2F, AlEt2F, AlOct2F, AlMe2(OC6F5), AlEt2(OC6F5), and AlOct2(OC6F5), respectively, in situ in an MAO composition.

[0020] "Chelating agent or compound" means a compound having multiple donor groups for forming a chelate structure with a dialkylaluminum cation in an alkylaluminoxane system. Preferred chelating agents or compounds contain multiple siloxy donor groups, for example, octamethyltrisiloxane (OMTS). Examples of chelating agents, but not limited to these, include linear or cyclic polysiloxanes, such as octamethyltrisiloxane (OMTS), octamethylcyclotetrasiloxane, decamethyltetrasiloxane, hexamethylcyclotrisiloxane, and hexaphenylcyclotrisiloxane. "Monoceptive drugs or compounds" refers to compounds having a single donor group that forms a non-chelate structure with a dialkylaluminum cation in an alkylaluminoxane system. Examples of monocephalic agents include, but are not limited to, compounds having a single oxygen-containing siloxidizer group, such as hexamethyldisiloxane, hexaphenyldisiloxane, hexaethyldisiloxane, dimethylaluminum trimethylsiloxide, and diethylaluminum triethylsiloxide. More preferred monocephalic agents are siloxidizer-modified alkylaluminum compounds, such as dimethylaluminum trimethylsiloxide, diethylaluminum trimethylsiloxide, diisobutylaluminum trimethylsiloxide, dimethylaluminum triethylsiloxide, diethylaluminum triethylsiloxide, diisobutylaluminum triethylsiloxide, dimethylaluminum triphenylsiloxide, diethylaluminum triphenylsiloxide, and diisobutylaluminum triphenylylsiloxide. The most preferred monocephalic agents are those derived in situ via the decomposition of chelating agent-treated MAO compositions, for example, by heating OMTS-treated MAO to produce dimethylaluminum trimethylsiloxide from Ib to Ia, as shown in Scheme 4.

[0021] "Olefin" is also called "alkene," which is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond. For the purposes of this specification and the accompanying claims, where a polymer or copolymer is referred to as containing an olefin, the olefin present in such a polymer or copolymer is a polymerized form of the olefin. For example, where a copolymer is said to have an "ethylene" content of 35% to 55% by mass, it is understood that the repeating species units in the copolymer are derived from ethylene in the polymerization reaction product, and that the derived units are present in an amount of 35% to 55% by mass relative to the mass of the copolymer. A "polymer" has two or more identical or different repeating species units. A "homopolymer" is a polymer having the same repeating species units. A "copolymer" is a polymer having two or more repeating species units that are different from each other. A "terpolymer" is a polymer having three different repeating species units. Thus, the definition of copolymer, as used herein, includes terpolymers, etc. When used to refer to repeating species units, "different" means that the repeating species units differ from each other by at least one atom, or that the repeating species units are different isomers. "Ethylene polymer" or "ethylene copolymer" is a polymer or copolymer containing at least 50 mol% ethylene derived units, and "propylene polymer" or "propylene copolymer" is a polymer or copolymer containing at least 50 mol% propylene derived units, and so on.

[0022] Ethylene should be considered an α-olefin. Unless otherwise specified, "C n The term "hydrocarbon" refers to a hydrocarbon having n carbon atoms per molecule (where n is a positive integer). The term "hydrocarbon" refers to one class of compounds containing hydrogen atoms bonded to carbon, and includes (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and / or unsaturated) and mixtures of hydrocarbon compounds having different n values. Similarly, "Cm -C y A group or compound refers to a group or compound containing carbon atoms such that the total number of carbon atoms is in the range of m to y. Therefore, C1-C 50 An alkyl group refers to an alkyl group containing a total of 1 to 50 carbon atoms. The "group," "radical," and "substituent" can be used interchangeably.

[0023] The terms "hydrocarbyl radical," "hydrocarbyl group," or "hydrocarbyl" can be used interchangeably and are defined as meaning a group consisting only of hydrogen and carbon atoms. Hydrocarbyl is C1-C 100 The radical may be linear, branched, or cyclic, and if cyclic, it may be aromatic or non-aromatic. Examples of such radicals, but are not limited to, include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl, and aryl groups such as phenyl, benzyl, and naphthalenyl. Unless otherwise noted, the term "substituted" means that at least one hydrogen atom is replaced by at least one nonhydrogen group, e.g., a hydrocarbyl group, a heteroatom, or a heteroatom-containing group, e.g., a halide (e.g., Br, Cl, F, or I) or at least one functional group, e.g., -NR * 2, -OR * ,-SeR * ,-TeR * ,-PR * 2, -AsR * 2, -SbR * 2, -SR * ,-BR * 2, -SiR * 3, -GeR * 3, -SnR * 3, -PbR * 3 (in the formula, each R *is, independently, a hydrocarbyl or halocarbyl radical, and two or more Rs * may be joined together to form a substituted or unsubstituted, fully saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), or at least one heteroatom is inserted into the hydrocarbyl ring.

[0024] The term "substituted hydrocarbyl" means a hydrocarbyl radical in which at least one hydrogen atom of the hydrocarbyl radical is replaced by at least one heteroatom (e.g., a halide, e.g., Br, Cl, F or I) or a heteroatom-containing group (e.g., a functional group, e.g., -NR * 2, -OR * , -SeR * , -TeR * , -PR * 2, -AsR * 2, -SbR * 2, -SR * , -BR * 2, -SiR * 3, -GeR * 3, -SnR * 3, -PbR * (wherein each R * is, independently, a hydrocarbyl or halocarbyl radical, and two or more Rs * may be joined together to form a substituted or unsubstituted, fully saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), or at least one heteroatom is inserted into the hydrocarbyl ring.

[0025] The term "aryl" or "aryl group" means an aromatic ring and its approximate substitution variants, such as phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl. Similarly, "heteroaryl" means an aryl group in which one or two or three ring carbon atoms are replaced by heteroatoms, such as N, O, or S. As used herein, the term "aromatic" also refers to pseudoaromatic heterocycles, which are heterocyclic substituents that have properties and structures (nearly flat) similar to those of aromatic heterocyclic ligands but are not aromatic by definition. Similarly, the term "aromatic" also refers to substituted aromatics.

[0026] The term "substituted aromatic" means an aromatic group in which one or more hydrogen groups are replaced by hydrocarbyl, substituted hydrocarbyl, heteroatoms or heteroatom-containing groups. "Substituted phenolate" means that at least one, two, three, four or five hydrogen atoms are in the 2-position, 3-position, 4-position, 5-position, and / or 6-position, and are replaced by at least one non-hydrogen group, such as a hydrocarbyl group, a heteroatom or a heteroatom-containing group, such as a halogen (e.g., Br, Cl, F or I) or at least one functional group, such as -NR * 2, -OR * , -SeR * , -TeR * , -PR * 2, -AsR * 2, -SbR * 2, -SR * , -BR * 2, -SiR * 3, -GeR * 3, -SnR * 3, -PbR * 3 (where each R * is independently hydrogen, a hydrocarbyl or a halocarbyl radical, and two or more R *A phenolate group that is bonded together with (which may form a substituted or unsubstituted fully saturated, partially unsaturated, aromatic cyclic or polycyclic ring structure), where the 1-position is a phenolate group (Ph-O-, Ph-S-, and Ph-N(R^) group, where R^ is hydrogen, C1-C4 hydrocarbyl, C1-C4 substituted hydrocarbyl, heteroatom, or heteroatom-containing group). For example, the "substituted phenolate" group of the catalyst compounds described herein is given by formula: [ka] [In the formula, R 18 is hydrogen, C1-C 40 Hydrocarbyl (e.g., C1-C) 40 Alkyl) or C1-C 40 A substituted hydrocarbyl, heteroatom, or heteroatom-containing group, E 17 is oxygen, sulfur, or NR 17 And R 17 , R 19 , R 20 , and R 21 Each of them independently produces hydrogen, C1-C 40 Hydrocarbyl (e.g., C1-C) 40 Alkyl) or C1-C 40 Selected from substituted hydrocarbyl groups, heteroatoms, or heteroatom-containing groups, or R 18 , R 19 , R 20 , and R 21 Two or more of these are joined together, C4-C 62 [Forms a cyclic or polycyclic ring structure, or a combination thereof; the wavy line indicates the position where the substituted phenolate group forms a bond with the rest of the catalyst compound.] It is represented as R 18 , R 19 , R 20 , and / or R 21 At least one of them is not hydrogen.

[0027] "Alkyl-substituted phenolates" are defined as having at least one, two, three, four, or five hydrogen atoms at the 2nd, 3rd, 4th, 5th, and / or 6th positions, with at least one alkyl group, for example, C1-C 40 , instead C2-C 20 , instead C3-C 12 These are phenolate groups that are replaced by alkyl groups, such as methyl, ethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl, hexyl, octylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, adamantyl, and their substituted analogs. "Aryl-substituted phenolates" are defined as having at least one, two, three, four, or five hydrogen atoms at the 2nd, 3rd, 4th, 5th, and / or 6th positions, with at least one aryl group, for example, C1-C 40 , instead C2-C 20 , instead C3-C 12 These are phenolate groups that have been replaced with aryl groups, such as phenyl, 4-fluorophenyl, 2-methylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, mesityl, 2-ethylphenyl, naphthalenyl, and their substituted analogs.

[0028] The term "ring atom" refers to an atom that is part of the ring structure of a cyclic compound. By this definition, the benzyl group has six ring atoms, and tetrahydrofuran has five ring atoms. A heterocycle, also called a heteroring, is a ring that contains a heteroatom within its ring structure, in contrast to a heteroatom-substituted ring where a hydrogen atom on a ring atom is replaced by a heteroatom. For example, tetrahydrofuran is a heterocycle, and 4-N,N-dimethylaminophenyl is a heteroatom-substituted ring. A substituted heterocycle refers to a heterocycle in which one or more hydrogen groups are replaced by a hydrocarbyl, a substituted hydrocarbyl, a heteroatom, or a heteroatom-containing group. A substituted hydrocarbyl ring is a ring composed of carbon and hydrogen atoms in which one or more hydrogen groups are replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group.

[0029] For the purposes of this disclosure, in relation to catalyst compounds (e.g., substituted bis(phenolate) catalyst compounds), the term “substituted” means that the hydrogen group is a hydrocarbyl group, a heteroatom or heteroatom-containing group, e.g., a halogen (e.g., Br, Cl, F or I) or at least one functional group, e.g., -NR * 2, -OR * ,-SeR * ,-TeR * ,-PR * 2, -AsR * 2, -SbR * 2, -SR * ,-BR * 2, -SiR * 3, -GeR * 3, -SnR * 3, -PbR * 3 etc (in the formula, each R * These are independently hydrogen, hydrocarbyl, or halocarbyl radicals, and two or more R * This means that the atoms are bonded together and replaced by (which may form a substituted or unsubstituted, fully saturated, partially unsaturated, aromatic cyclic or polycyclic ring structure), or that at least one heteroatom is inserted into the hydrocarbyl ring.

[0030] A tertiary hydrocarbyl group has a carbon atom bonded to three other carbon atoms. When the hydrocarbyl group is an alkyl group, it is also called a tertiary alkyl group. Examples of tertiary hydrocarbyl groups include tert-butyl, 2-methylbutan-2-yl, 2-methylhexane-2-yl, 2-phenylpropane-2-yl, 2-cyclohexylpropane-2-yl, 1-methylcyclohexyl, 1-adamantyl, and bicyclo[2.2.1]heptan-1-yl. The formula for a tertiary hydrocarbyl group is: [ka] [In the formula, R A , R B and R C These are independently hydrocarbyl groups or substituted hydrocarbyl groups that may be bonded to each other, and the wavy lines indicate the positions where tertiary hydrocarbyl groups form bonds to other groups. This can be shown as follows.

[0031] A tertiary hydrocarbyl group can be a cyclic tertiary hydrocarbyl group. A cyclic tertiary hydrocarbyl group is defined as a tertiary hydrocarbyl group that forms at least one alicyclic (non-aromatic) ring. A cyclic tertiary hydrocarbyl group is also called an alicyclic tertiary hydrocarbyl group. If the hydrocarbyl group is an alkyl group, a cyclic tertiary hydrocarbyl group is also called a cyclic tertiary alkyl group or an alicyclic tertiary alkyl group. Examples of cyclic tertiary hydrocarbyl groups include 1-adamantyl, 1-methylcyclohexyl, 1-methylcyclopentyl, 1-methylcyclooctyl, 1-methylcyclodecyl, 1-methylcyclododecyl, bicyclo[3.3.1]nonane-1-yl, bicyclo[2.2.1]heptan-1-yl, bicyclo[2.3.3]hexane-1-yl, dicyclic[1.1.1]pentan-1-yl, and dicyclic[2.2.2]octan-1-yl. The cyclic tertiary hydrocarbyl group is represented by formula (B): [ka]

[0032] [In the formula, R A is a hydrocarbyl group or a substituted hydrocarbyl group, and each R D R is independently a hydrogen atom, a hydrocarbyl group, or a substituted hydrocarbyl group, w is an integer from 1 to about 30, and R A and one or more R D and / or two or more R D They may be joined to each other to form an additional ring. This can be shown by: If a cyclic tertiary hydrocarbyl group contains one or more alicyclic rings, this cyclic tertiary hydrocarbyl group can be called a polycyclic tertiary hydrocarbyl group, or if the hydrocarbyl group is an alkyl group, this cyclic tertiary hydrocarbyl group can be called a polycyclic tertiary alkyl group.

[0033] The terms “alkyl radical” and “alkyl” are used interchangeably throughout this disclosure. For the purposes of this disclosure, “alkyl radical” means a C1-C chain which may be linear, branched, or cyclic. 100 Alkyl radicals are defined as alkyl radicals. Examples of such radicals include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl, hexyl, octylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and other radicals including their substituted analogs. A substituted alkyl radical is defined as an alkyl radical in which at least one hydrogen atom is replaced by at least a non-hydrogen group, such as a hydrocarbyl group, a heteroatom or heteroatom-containing group, such as a halogen (e.g., Br, Cl, F, or I), or at least one functional group, such as -NR * 2, -OR * ,-SeR * ,-TeR * ,-PR * 2, -AsR * 2, -SbR * 2, -SR * ,-BR * 2, -SiR * 3, -GeR * 3, -SnR * 3, -PbR * 3 etc (in the formula, each R * These are independently hydrogen, hydrocarbyl, or halocarbyl radicals, and two or more R * The radical is one in which the atoms are bonded together and substituted (may form a substituted or unsubstituted, fully saturated, partially unsaturated, aromatic cyclic or polycyclic ring structure), or in which at least one heteroatom is inserted into the hydrocarbyl ring.

[0034] If isomers of a named alkyl, alkenyl, alkoxide, or aryl group exist (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl), then when an alkyl, alkenyl, alkoxide, or aryl group is mentioned without specifying a particular isomer (e.g., butyl), this explicitly discloses all isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl). Where used herein, Mn is the number-average molecular weight, Mw is the mass-average molecular weight, Mz is the z-average molecular weight, mass% is the mass percentage, and mole% is the mole percentage. The molecular weight distribution (MWD), also known as the polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise specified, all molecular weight units (e.g., Mw, Mn, Mz) are expressed in g / moles (g moles). -1 ) The following abbreviations may be used herein: Me is methyl, Et is ethyl, iBu is isobutyl, Oct is octyl, MAO is methylaluminoxane, Bn is benzyl (i.e., CH2Ph), THF (also called thf) is tetrahydrofuran, RT is room temperature (and 23°C unless otherwise noted), tol is toluene, Cp is cyclopentadienyl, NMR is nuclear magnetic resonance, and TMA is trimethylaluminum.

[0035] A “catalytic system” is a combination of at least one catalytic compound, an activator, an optional activator, and an optional support material. When “catalytic system” is used to describe such a pair before activation, the catalytic system means the unactivated catalytic complex (pre-catalyst), the activator, and optionally a co-activator together. When used to describe such a pair after activation, the catalytic system means the activated complex and the activator or other charge equilibrium portion. The catalytic compound may be neutral, as in the case of the pre-catalyst, or it may be a charged species with counterions, as in the case of the activated catalytic system. For the purposes of this disclosure and the claims relating thereto, when a catalytic system is described as including a neutral, stable form of its components, it will be well understood by those skilled in the art that the ionic form of these components is a form that reacts with monomers to produce polymers. A polymerization catalytic system is a catalytic system capable of polymerizing monomers into polymers. Furthermore, catalytic compounds and activators (including support-bound activators) represented by the formulas herein encompass both the neutral and ionic forms of the catalytic compounds and activators. In this specification, catalysts may also be referred to as catalysts, catalyst precursors, pre-catalyst compounds, catalyst compounds, or transition metal compounds, and these terms are used interchangeably.

[0036] An "anionic ligand" is a load ligand that provides one or more pairs of electrons to a metal ion. The term "anionic donor" is used interchangeably with "anionic ligand." Examples of anionic donors, but not limited to these, include methyl, chloride, fluoride, alkoxide, aryl oxide, alkyl, alkenyl, thiolate, carboxylate, amide, benzyl, hydride, amidinate, amidate, and phenyl. Two anionic donors can combine to form a dianionic group. A "neutral Lewis base" or "neutral donor group" is an uncharged (neutral) group that donates one or more pairs of electrons to a metal ion. Non-limiting examples of neutral Lewis bases include ethers, thioethers, amines, phosphines, ethyl ethers, tetrahydrofurans, dimethyl sulfides, triethylamines, pyridines, alkenes, alkynes, allenes, and carbenes. Lewis bases can combine to form bidentate or tridentate Lewis bases. For the purposes of this disclosure and the claims relating thereto, the phenolate donor is Ph-O-, Ph-S-, and Ph-N(R ** )-group (wherein, R ** is hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 It may contain a substituted hydrocarbyl, a heteroatom, or a heteroatom-containing group, where the pH is phenyl, which may be substituted.

[0037] This disclosure relates to a catalyst system of the present disclosure comprising a rare earth element-based bis(phenolate) type catalyst in combination with an alkylaluminum-free aluminoxane (e.g., TMA-free aluminoxane), wherein the alkylaluminum-free aluminoxane is defined as having 0% to about 2% by mass of Al derived from a non-coordinating trialkylaluminum compound relative to the total Al metal mass in the system, and can be used to produce copolymers of ethylene and butadiene with high conversion rates under mild conditions. Such an improved catalyst system provides commercially scalable polymerization (e.g., high activity under mild conditions) by providing a complementary catalyst-activator pair that brings about high activity (e.g., within the same process window) in the polymerization of monoolefins and conjugated dienes. The catalyst system of the present disclosure is an interesting option for introduction into industrial-scale processes for high-throughput production of copolymer materials, e.g., copolymers derived from ethylene and butadiene monomers, which have tunable physical properties, polymer backbone structures, and different functional group moieties. In addition, polar side chain groups can be incorporated into the polymer chain during the copolymerization process. Such functionalized polymers can be desirable for the tire industry when used as tire materials, due to the enhancement between the copolymer and the fillers present.

[0038] In addition, copolymers formed using the catalyst system of this disclosure may have a plurality of 1,2-cyclopentane units distributed along the polymer backbone. Since these units are substantially uniformly distributed throughout the polymer backbone, they prevent crystallization (e.g., polyethylene blockage). Without being constrained by theory, substantially uniformly distributed 1,2-cyclopentane units throughout the polymer backbone disrupt intra-chain and inter-chain interactions, thereby reducing the crystallization ability of the polymer system (this is demonstrated by a lower Tm value compared to polyethylene homopolymers). The activators of this disclosure can provide copolymers having a higher 1,2-cyclopentane unit content than copolymers prepared using conventional activators. The 1,2-cyclopentane units can impart higher rigidity to the copolymer, which may be beneficial for the use of copolymers in tires. This disclosure is, 1) Anionically modified alkylaluminoxanes and / or cationically modified alkylaluminoxanes, wherein when the alkylaluminoxane composition is determined by titration of the alkylaluminoxane composition using tetrahydrofuran, the anionically modified alkylaluminoxanes and / or cationically modified alkylaluminoxanes have 0% to about 2% by mass of non-coordinating trialkylaluminum compounds relative to the total aluminum content of the alkylaluminoxane composition, and 2) Equation (I):

[0039] [ka] [In the formula, M is a group 3 transition metal or lanthanide metal. E and E' are, independently, oxygen, sulfur, or NR. A And R A Independently, hydrogen, C1-C 40 Hydrocarbyl, substituted C1-C 40 A hydrocarbyl or heteroatom-containing group, Q is a group 14 atom, a group 15 atom, or a group 16 atom. A1 QA 1 ' is part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms, and A is formed via a triatomic bridge with Q as the central atom of the triatomic bridge. 2 to A 2’ It is connected to, A 1 and A 1 Each of these is independently carbon, nitrogen, or C(R) B ) and R B is hydrogen, C1-C 20 Hydrocarbyl and substituted C1-C 20 Selected from hydrocarbil,

[0040] [ka] It is a divalent group containing 2 to 40 non-hydrogen atoms, and via a two-atom bridge, A 1 This is linked to the E-bonded aryl group shown in formula (I), and A 3 and A 2 They combine to form a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocycle, or an unsubstituted heterocycle, each having 5, 6, 7, or 8 ring atoms, and substituents on the rings can bond to form additional rings.

[0041] [ka] It is a divalent group containing 2 to 40 non-hydrogen atoms, and via a two-atom bridge, A 1 ' is linked to the E' bonded aryl group shown in formula (I), A 3 'and A 2 These combine to form a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocycle, or an unsubstituted heterocycle, each having 5, 6, 7, or 8 ring atoms, and substituents on the rings can bond to form additional rings. Each L is independently a Lewis base. X' is an anionic ligand, Any two L groups may be bonded together to form a bidentate Lewis base. The X' group may be bonded to the L group to form a monoanionic bidentate group. n is 1, m is 0, 1, or 2. n+m does not exceed 3. R 1 , R 2 , R 3 , R 4 , R 1 ', R 2 ', R 3 ', and R 4 Each of these is independently hydrogen, C1-C 40 Hydrocarbyl, substituted C1-C 40 Hydrocarbyl, heteroatom, or heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 1 'and R 2 ', R 2 'and R 3 ', R 3 'and R 4 One or more of these may bond to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, and substituents on the rings may bond to form additional rings. Compounds represented by This relates to catalyst systems that include [specific components / systems].

[0042] In some embodiments, the present disclosure relates to a method for polymerizing an olefin using a catalyst system having a trialkylaluminum-free alkylaluminoxane composition, where the trialkylaluminum-free alkylaluminoxane composition means that the free trialkylaluminum content in the alkylaluminoxane composition is zero or nearly zero, for example, 2% by mass or 2 mol% or less, but Al(alkyl)2 +This invention relates to a method for maintaining or increasing the active sites of alkylaluminoxanes capable of providing a coordinating trialkylaluminum through treatment with an anionic or cationic modifier. Unlike the physical removal of free trialkylaluminum in alkylaluminoxanes, which causes loss of catalytic activity, active alkylaluminoxane compositions free of trialkylaluminum, produced via anionic or cationic modifiers, maintain or improve catalytic activity for a wide range of precatalysts. Without being constrained by theory, it is thought that an alkylaluminoxane solution treated with either an anionic modifier (e.g., (NH4)2SiF6) or a cationic modifier (e.g., OMTS) converts all trialkylaluminum to Al(alkyl)2X (X = electron-withdrawing group) which can be replaced by coordinating trialkylaluminum, thereby eliminating equilibrium between coordinating trialkylaluminum and free trialkylaluminum, or enabling ionization of the alkylaluminoxane and precipitation as a clathrate phase, allowing for physical separation from free trialkylaluminum. Free trialkylaluminum is also called uncoordinating alkylaluminum or uncoordinating trialkylaluminum.

[0043] In some embodiments, this disclosure relates to a method for polymerizing olefins using a catalyst system having a TMA-free alkylaluminoxane composition comprising a TMA-free MAO, wherein the TMA-free MAO means that the free TMA content in the MAO is zero or nearly zero, for example, 2% by mass or 2 mol% or less, and simultaneously AlMe2 +The MAO active sites capable of providing this activity are maintained or increased through treatment with anionic or cationic modifiers. Unlike the physical removal of free TMA from the MAO, which causes a loss of activity, TMA-free active MAO compositions produced via anionic or cationic modifiers maintain or improve catalytic activity for a wide range of precatalysts. Without being constrained by theory, it is believed that an MAO solution treated with either an anionic modifier (e.g., (NH4)2SiF6, illustrated as Si-F in Scheme 4) or a cationic modifier (e.g., OMTS) converts the total TMA into AlMe2X (X = electron-withdrawing group, F in Scheme 4), which can replace the coordinating TMA, thereby eliminating the equilibrium between coordinating TMA and free TMA (see Scheme 1), or allows the ionization of the MAO composition, allowing it to precipitate as a clathrate phase and enabling physical separation from free TMA (Scheme 4). Free TMA is also called uncoordinating TMA.

[0044] In some embodiments, a method for producing anionically modified alkylaluminoxanes (also called trialkylaluminum-free alkylaluminoxanes) includes the step of treating an alkylaluminoxane solution with an anionic modifier, such as an electron-withdrawing compound that can be converted to Al(alkyl)2X (X = electron-withdrawing group), depending on the structure of the electron-withdrawing compound used, as a derivative present in large quantities and an optional trace amount of non-fluorinated inert aluminum alkyl derivative. The anionically modified alkylaluminoxane contains an electron-withdrawing group X. In some embodiments, a method for producing an anionically modified alkylaluminoxane includes the step of forming an alkylaluminoxane composition that does not contain free trialkylaluminum or has a low free trialkylaluminum content by introducing an alkylaluminoxane composition containing free trialkylaluminum and coordinating trialkylaluminum, and a fluorine-containing compound capable of converting most of both free and coordinating trialkylaluminum to Al(alkyl)2F or Al(alkyl)2(OC6F5). The anionically modified alkylaluminoxane contains an electron-withdrawing group, and the electron-withdrawing group contains F or an OC6F5 group.

[0045] In some embodiments, a method for producing TMA-free MAO (also called anionically modified MAO) includes treating the MAO solution with an anionic modifier, such as an electron-withdrawing compound that can be converted to AlMe2X (X = electron-withdrawing group), depending on the electron-withdrawing compound structure used, as a derivative present in large quantities and an optional trace amount of a non-fluorinated, inert aluminum alkyl derivative. The TMA-free MAO contains the electron-withdrawing group X. In some embodiments, a method for preparing a TMA-free solution MAO composition includes the step of forming an anionically modified MAO composition that is free of free TMA or has a low free TMA content by introducing a solution MAO composition containing free TMA and coordination TMA, and a fluorine-containing compound that can convert most of both free TMA and coordination TMA to AlMe2F or AlMe2(OC6F5). The TMA-free MAO contains electron-withdrawing groups, and the electron-withdrawing groups contain F or OC6F5 groups. In some embodiments, a method for producing a cationically modified alkylaluminoxane (also called a trialkylaluminoxane-free alkylaluminoxane) includes the steps of: treating an alkylaluminoxane solution with a cationic modifier, such as a chelating agent or a monodentate ligand agent, to form an ionic alkylaluminoxane composition; followed by a physical separation process to isolate the majority of the free trialkylaluminum content; and a heating process to partially or completely convert the chelating ligand to a monodentate ligand; and any additional steps of adding free alkylaluminum. The cationically modified alkylaluminoxane contains a portion of the chelating agent.

[0046] In some embodiments, a method for producing a cationically modified alkylaluminoxane includes the steps of: treating an alkylaluminoxane solution with a cationic modifier, such as OMTS, to form an ionic alkylaluminoxane composition; subsequently, a physical separation process to isolate the majority of the free trialkylaluminum content, for example, by phase separation; and heating the clathrate phase to partially or completely convert the OMTS ligand to dialkylaluminum trimethylsiloxide in the presence of remaining free trialkylaluminum or additional amounts of free trialkylaluminum. The cationically modified alkylaluminoxane contains a portion of a chelating agent, the chelating agent including a siloxide donor, such as dimethylaluminum trialkylsiloxide. In some embodiments, a method for producing TMA-free MAO (also called cation-modified MAO) includes the steps of: treating a solution of MAO with a chelating agent or monodentate agent to form an ionic MAO composition; a physical separation process to isolate the majority of the free TMA content; a heating process to partially or completely convert the chelating ligand to a monodentate ligand; and any additional steps of adding free alkylaluminum, such as trimethylaluminum, triethylaluminum, or triisobutylaluminum.

[0047] In some embodiments, a method for producing TMA-free MAO, as shown in Scheme 4, includes the steps of: treating a solution MAO with OMTS to form an ionic MAO composition; subsequently, a physical separation process to isolate the majority of the free TMA content, for example, by phase separation; and heating the clathrate phase in the presence of remaining free TMA or additional amounts of free TMA to partially or completely convert the OMTS ligand to a trimethylsiloxy ligand. The TMA-free MAO contains a portion of a chelating agent, the chelating agent being a siloxy donor, for example, dimethylaluminum trimethylsiloxy. In some embodiments, the Disclosure provides a polymerization process comprising the step of contacting one or more olefin monomers with a pre-catalyst of the Disclosure.

[0048] Formation of a non-coordinating alkylaluminum-free activator system As described above, non-coordinating alkylaluminum (or free alkylaluminum) (where "free" includes the statement "in low amounts"), for example, TMA-free MAO may indicate that the amount of free TMA relative to the total Al content in the MAO is 2% by mass or 2 mol% or less, and the method for quantifying free alkylaluminum is described in the experimental section. Such non-coordinating alkylaluminum-free systems can be prepared by one or both of the two methods described below:

[0049] A) in situ anionically modified aluminoxane (also called anionically modified aluminoxane) A standard MAO solution, such as WRGrace's 30% MAO product containing free TMA, is treated with an electron-withdrawing compound as shown in Scheme 4 Ic to introduce an electron-withdrawing group into the MAO composition, converting the free TMA to AlMe2X (X = electron-withdrawing group), thereby enhancing the function of coordinated TMA, namely, as an activator of AlMe2X. +Free TMA can be removed by replacing the coordinating TMA while still maintaining the supply of the coordinating TMA. Therefore, electron-withdrawing compounds can also be called anionic modifiers. As shown in Scheme 4, strongly electron-withdrawing compounds, such as compounds containing highly reactive electron-withdrawing atoms or groups, such as fluorine-containing compounds or pentafluorophenoxy (C6F5O-)-containing compounds, have been found to be able to convert free TMA in MAO to AlMe2F or AlMe2(OC6F5) in situ, and these AlMe2F or AlMe2(OC6F5) can function as a TEB agent (TEB agent) that breaks the equilibrium between coordinating TMA and free TMA. The TEB agent can replace the coordinating TMA (which becomes free TMA), and thus eliminate the equilibrium of coordinating TMA with respect to free TMA, as well as more AlMe2 + By providing a charge to ionize the precatalyst and providing a more dispersed charge on the MAO anion, the interaction between active ion pairs is weakened by introducing a strongly electron-withdrawing atom or group onto the MAO anion (as shown in Scheme 4). The overall result is the removal of free TMA and an increase in the activity of the catalytic system. Therefore, converting all TMA in MAO to a TEB agent is a much more efficient way to remove free TMA from MAO while maintaining or improving the activation efficiency to obtain a system suitable for activating precatalysts constructed with TMA-reactive heteroatom donors, e.g., ligands containing N, O, S, and / or P donors (e.g., ligands for post-metallocene type precatalysts). A method for quantifying total TMA in the MAO composition is described in the experimental section.

[0050] In some embodiments, the electron-withdrawing compound is of formula (A'): A m B (u) X n (A') This is an inorganic compound having [wherein A in formula (A') is a cation, m is 0, 1, or 2, except that if m is 0, B is H or an element of Group 3, 4, 5, 6, 7, 13, 14, 15, 16, or 17; if m is not zero, B is an element of Group 3, 4, 5, 13, 14, or 15; u is the valence state of element B; X is an electron-withdrawing atom or group; and n = m + u]. In some embodiments, the inorganic fluorine-containing compound having formula (A') is selected from NH4BF4, (NH4)2SiF6, NH4PF6, NH4F, (NH4)2TaF7, NH4NbF4, (NH4)2GeF6, (NH4)2SmF6, (NH4)2TiF6, (NH4)2ZrF6, MoF6, ReF6, GaF3, SO2ClF, F2, SiF4, SF6, ClF3, ClF5, BrF5, IF7, NF3, HF, BF3, B(OC6F5)3, AlF3, Al(OC6F5)3, NHF2, and NH4HF2. Of these, ammonium hexafluorosilicate may be preferred due to its high fluorination efficiency.

[0051] In some embodiments, the electron-withdrawing compound is of formula (B'): R o M (u) X (u-o) (B') [In the formula, R is C1-C 10 It is an organometallic compound having a hydrocarbyl group, where M is an element of group 13 or group 14, and if M is Al, a group 13 element, then o is 1; if M is not Al, a group 13 element, then o is 1 or 2; if M is a group 14 element, then o is 1, 2, or 3; X is an electron-withdrawing atom or group, and u is the valence state of element M. In some embodiments, the organofluorine compound having formula (B') is selected from Me3SiF, Me2SiF2, MeSiF3, Et3SiF, Et2SiF2, EtSiF3, Ph3SiF, Ph2SiF2, PhSiF3, Me3CF, Me2CF2, MeCF3, Et3CF, Et2CF2, EtCF3, Ph3CF, Ph2CF2, PhCF3, Me2BF, MeBF2, MeAlF2, Et2BF, EtBF2, EtAlF2, Ph2BF, PhBF2, Me3Si(OC6F5), Me2Si(OC6F5)2, MeSi(OC6F5)3, Me3C(OC6F5), Ph3C(OC6F5), Me2B(OC6F5), MeB(OC6F5)2, and MeAl(OC6F5)2. In some embodiments, the anionically modified alkylaluminoxane (including anionically modified MAO) contains an electron-withdrawing group, and the electron-withdrawing group contains -F or -OC6F5.

[0052] B) Cationally modified aluminoxane (also called ionic aluminoxane) Chelating agents, such as polysiloxanes or monodentate agents, such as silanols and dialkylaluminum siloxides derived therefrom, can be used as cationic modifiers to produce aluminoxane compositions free of uncoordinated trialkylaluminum. Chelating agents such as OMTS can precipitate aluminoxanes such as MAO as ionic aluminoxanes (e.g., clathrates), enabling their separation from free alkylaluminum. Various organic or organometallic compounds may be suitable for forming ionic aluminoxanes, enabling their separation from free alkylaluminum. In some embodiments, various aluminoxanes can be used to form stable ionic alkylaluminoxanes, such as methylaluminoxane. When forming stable ionic aluminoxanes, the denser lower liquid phase (or clathrate phase) can be easily separated from the upper solution phase by conventional separation techniques, such as phase separation, decantation, or discharge.

[0053] Ionic MAO derived from chelating agent: In some embodiments, the starting material may be a chelating agent dissolved in a hydrocarbon solvent such as an aromatic solvent. For example, the starting material may include a chelating agent that is a hydrocarbyl aluminoxane, e.g., alkyl aluminoxane, and a hydrocarbyl polysiloxane, e.g., hydrocarbyl trisiloxane. In some embodiments, the chelated hydrocarbyl polysiloxane compound may have at least three silicon atoms in the molecule, separated from each other by oxygen atoms such that there is a linear, branched, or cyclic skeleton of alternating Si and oxygen atoms, and the remaining four valence bonds of each of these silicon atoms are individually filled by monovalent hydrocarbyl groups. The hydrocarbyl polysiloxane may have as many as 18 or more silicon atoms in the molecule. Each monovalent hydrocarbyl group of the polysiloxane may independently contain up to about 18 carbon atoms and can be alkyl, cycloalkyl, aryl, arylalkyl, and the like. In some embodiments, the chelating agent is of the formula R(SiR2O) n The formula may include a polydentate siloxane having SiR3 (wherein each R is independently hydrogen, alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl), alkenyl, aryl, or heteroatom-substituted hydrocarbyl group, n=2 to 8). In some embodiments, each R is methyl. In some embodiments, the chelating agent is of the formula (SiR2O) n (wherein R is independently a hydrogen, an alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl), an alkenyl, an aryl, or a heteroatom-substituted hydrocarbyl group, and n=3 to 6) cyclic polydentate siloxane may also be included.

[0054] Non-limiting examples of such polysiloxanes include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, octamethyltrisiloxane (OMTS), decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane (as an example of an alkenyl substituent on a polydentate compound), and 1,3,5,7-tetrakis(3,3,3-trifluoropropyl)1,3,5,7-tetramethylcyclosiloxane (as an example of a heteroatom-containing substituent on a polydentate compound). In some embodiments, the ionic alkylaluminoxane, for example, the ionic MAO, contains a dialkylaluminum cation stabilized with a chelate ligand, for example, [AlMe2(OMTS)] + It can be heated to become more active, and this is probably due to the formation of dialkylaluminum cations, AlMe2, after heating. + This is due to the formation of unstable monodentate complexes that readily release the material, for example, 1 Structure Ia containing a siloxy (trimethylsiloxy) group has been observed by 1H nuclear magnetic resonance spectroscopy:

[0055] [ka] The heating temperature may be approximately 40°C to 130°C, for example, approximately 60°C to 110°C, or for example, approximately 80°C to 100°C. The heating time may be approximately 30 minutes to 24 hours, for example, approximately 2 hours to 12 hours, or for example, approximately 4 hours to 8 hours. Aging at ambient temperature can also decompose the chelated complex and increase the activation efficiency, but this can take a very long time, for example, 24 hours, 2 days, or more than a week.

[0056] Ionic MAO derived from monodentate agents: Alternatively, ionic aluminoxanes may be formed by using silanol SiR3OH to in situ convert free alkylaluminum in alkylaluminoxanes to, for example, TMA in the MAO composition, thereby forming a monodentate coordination compound R3SiOAlR2 (e.g., R=Me) which functions as a dialkylaluminum cation stabilizer and can eliminate or reduce free alkylaluminum, which is desirable for solution aluminoxane systems because processes for removing free alkylaluminum in solution systems are difficult. The R group of the silanol having the formula HO-SiR3 is independently hydrogen, alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl), alkenyl, aryl, or heteroatom-containing group. In some embodiments, each of R is methyl. Heating processes are optional for processing monodentate agents. Precatalytic compounds The terms "catalyst," "catalytic compound," "catalytic complex," "transition metal complex," "transition metal compound," "precatalytic compound," and "precatalytic complex" are used interchangeably to describe transition metal or lanthanide metal complexes that form an olefin polymerization catalyst when combined with an appropriate activator.

[0057] In at least one embodiment, the disclosure provides a catalyst system comprising a catalyst compound having a metal atom. The catalyst compound may be a metallocene catalyst compound. The metal may be a group 3 transition metal or a lanthanide metal. The catalyst compound may be a group 3 transition metal or lanthanide metal having a monodentate or polydentate ligand, e.g., a bidentate, tridentate, or tetradentate ligand, and a heteroatom of the catalyst, e.g., phosphorus, oxygen, nitrogen, or sulfur, is chelated to the metal atom of the catalyst. A non-limiting example is bis(phenolate). In at least one embodiment, the group 3 transition metal or lanthanide metal atom is selected from Sc, Y, and La. The catalysts of the present disclosure may be “post-metallocene” catalysts having oxygen and / or nitrogen atoms. For example, the catalysts of the present disclosure may be metal complexes having a metal selected from group 3 or lanthanide metals and a tridentate dianionic ligand containing two anionic donor groups and a neutral Lewis base donor, wherein the neutral Lewis base donor is covalently bonded between the two anionic donors, and the metal-ligand complex is characterized by a pair of eight-membered metallocycle rings. The catalyst complex of this disclosure comprises a metal selected from a Group 3 metal or lanthanide metal of the periodic table and a tridentate dianionic ligand containing two anionic donor groups and a neutral heterocyclic Lewis base donor, the heterocyclic donor being covalently bonded between the two anionic donors. In some embodiments, the dianionic tridentate ligand is characterized by a central heterocyclic donor group and two phenolate donors, the tridentate ligand coordinating to the metal center to form two eight-membered rings.

[0058] In some embodiments, the heterocyclic Lewis base donor of the catalytic compound is characterized by a nitrogen or oxygen donor atom. For example, the heterocyclic group includes pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, and derivatives of these substitutional forms. In some embodiments, the heterocyclic Lewis base does not have a hydrogen atom at the alpha position relative to the donor atom. In some embodiments, the heterocyclic Lewis base donor includes pyridine, trisubstituted pyridine, and tetrasubstituted pyridine. The anionic donor of the tridentate dianionic ligand may be an aryl thiolate, phenolate, or anilide. In some embodiments, the anionic donor is a phenolate. The tridentate dianionic ligand coordinates to a metal center to form a complex that may lack a plane of mirror symmetry. In some embodiments, the tridentate dianionic ligand coordinates to a metal center to form a complex with a twofold rotational symmetry axis. When determining the symmetry of a bis(phenolate) complex, only the metal and the dianionic tridentate ligand are considered (i.e., the remaining ligands are ignored).

[0059] The catalytic compounds of this disclosure may be bis(arylphenolate)pyridine complexes. The bis(arylphenolate)pyridine complex may have a tridentate bis(arylphenolate)pyridine ligand, which coordinates to a group 3 transition metal or lanthanide metal to form two 8-membered rings. In some embodiments, the bis(arylphenolate)pyridine complex includes a dianionic tridentate ligand transition metal complex characterized by a central neutral donor group and two phenolate donors, where the tridentate ligand coordinates to the metal center to form two 8-membered rings, for example, a post-metallocene catalyst may be an 8-8 catalyst. In this type of complex, it is advantageous that the central neutral donor is a heterocyclic group. It is also advantageous that the heterocyclic group does not have a hydrogen atom at the alpha position relative to the heteroatom. In some embodiments, the bis(phenolate) ligand can be a tridentate dianionic ligand that coordinates to the metal M in such a way that a pair of eight-membered metallocycle rings are formed. The bis(phenolate) ligand encapsulates the metal, forming a complex with a double rotation axis, thereby giving symmetry to the complex C2. The C2 shape and the eight-membered metallocycle rings are features that make these complexes effective as catalytic components for polyolefin production.

[0060] Bis(phenolates), anilides, and / or arylthiolate ligands containing a donor group (e.g., oxygen, nitrogen, or sulfur, respectively) can be substituted with alkyl, substituted alkyl, aryl, or other groups. It may be advantageous for each phenolate group to be substituted at a ring position adjacent to the donor atom on the ring structure. For example, the substituent adjacent to the donor atom may be an alkyl group containing 1 to 20 carbon atoms. In this type of complex, it may also be advantageous for the phenolate to be substituted with one or more alkyl substituents (e.g., ortho and / or para relative to the oxygen of the phenolate). In some embodiments, the substituent adjacent to the donor atom may be a non-aromatic cyclic alkyl group having one or more five-membered or six-membered rings. In this type of complex, it may also be advantageous for the phenolate to be substituted with one or more cyclic tertiary alkyl substituents. The use of tertiary cyclic alkyl-substituted phenolates can improve the ability of these catalysts to produce high molecular weight polymers. In some embodiments, the substituent adjacent to the oxygen donor atom is adamantane-1-yl or substituted adamantane-1-yl. In some embodiments, the substitution adjacent to the oxygen donor atom is tert-butyl or substituted tert-butyl.

[0061] A neutral heterocyclic Lewis base donor is covalently bonded between two anionic donors (e.g., between two phenolate groups) via a "linker group" that attaches the heterocyclic Lewis base to the anionic donor. For example, the "linker group" is (A in formula (I) 3 A 2 ) and (A 2’ A 3’ The following is more detailed, as indicated by the following: The selection of each linker group may affect catalytic performance. Each linker group is a C2-C2 group with a length of 2 atoms. 40It can be a divalent group. One or both linker groups may independently be phenylene, substituted phenylene, heteroaryl, vinylene, or acyclic two-carbon linker groups. In some embodiments, one or both phenylenes may be unsubstituted, or independently C1-C 20 Alkyl compounds, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, or their isomers, such as isopropyl. In some embodiments, the catalyst compound is of formula (I): [ka]

[0062] [In the formula, M is a group 3 transition metal or lanthanide metal (e.g., Sc, Y, or La), E and E' are, independently, O, S, or NR. A And R A Independently, hydrogen, C1-C 40 Hydrocarbyl, substituted C1-C 40 A hydrocarbyl or heteroatom-containing group, for example, O, and for example, E and E' are both O. Q is a group 14, group 15, or group 16 atom, for example Q is C, O, S, or N, for example Q is C, N, or O, for example Q is N, A 1 QA 1’ It is part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms, and A is connected via a triatomic bridge with Q as the central atom of the triatomic bridge. 2 to A 2’ It is connected to (A 1 QA 1’ is, A 1 and A 1’ (Together with the curve showing the bond, it represents a heterocyclic Lewis base.) A 1and A 1’ Each of these is independently C, N, or C(R) B ) and R B is hydrogen, C1-C 20 Hydrocarbyl and substituted C1-C 20 Selected from hydrocarbil (for example, A 1 and A 1’ Each of them is C),

[0063] [ka] A is formed via a two-atom bridge. 1 It is a divalent group containing 2 to 40 non-hydrogen atoms linked to an E-bonded aryl group, and A 3 and A 2 They combine to form a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocycle, or an unsubstituted heterocycle, each having 5, 6, 7, or 8 ring atoms, and substituents on the ring can bond to form additional rings, for example, A 3 and A 2 These combine to form ortho-phenylene, substituted ortho-phenylene, ortho-arene, substituted ortho-arene, indolene, substituted indolene, benzothiophene, substituted benzothiophene, pyrrolene, substituted pyrrolene, thiophene, and substituted thiophene.

[0064] [ka] A is formed via a two-atom bridge. 1’ A divalent group containing 2 to 40 non-hydrogen atoms linked to an E' bonded aryl group, 3’ and A 2’ They combine to form a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocycle, or an unsubstituted heterocycle, each having 5, 6, 7, or 8 ring atoms, and substituents on the ring can bond to form additional rings, for example, A 3’ and A 2’These combine to form, for example, ortho-phenylene, substituted ortho-phenylene, ortho-arene, substituted ortho-arene, indolene, substituted indolene, benzothiophene, substituted benzothiophene, pyrolene, substituted pyrolene, thiophene, substituted thiophene, Each L is independently a Lewis base. X' is an anionic ligand, Any two L groups may be bonded together to form a polydentate (for example, a bidentate) Lewis base. The X' group may be bonded to the L group to form a monoanionic bidentate group. n is 1, m is 0, 1, or 2. n+m does not exceed 3. R 1 , R 2 , R 3 , R 4 , R 1 ', R 2 ', R 3 ', and R 4 Each of these is independently hydrogen, C1-C 40 Hydrocarbyl, substituted C1-C 40 Hydrocarbyl, heteroatom, or heteroatom-containing group (e.g., R 1 'and R 1 This is independently a hydrocarbyl group, e.g., a tertiary alkyl group, or a cyclic hydrocarbyl group, e.g., a cyclic tertiary alkyl group), or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 1’ and R 2’ , R 2’ and R 3’ , R 3’ and R 4’ One or more of these may bond to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, and substituents on the rings may bond to form additional rings. It is represented as follows.

[0065] Metal M is selected from Group 3 elements or lanthanide elements. For example, metal M is Sc, Y, or La. The donor atom Q (in formula (I)) of a neutral heterocyclic Lewis base can be nitrogen, sulfur, or oxygen. In some embodiments, Q is nitrogen. Non-limiting examples of neutral heterocyclic Lewis bases include pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, and their substituted variations. In some embodiments, the heterocyclic Lewis base may include pyridine, pyrazine, thiazole, or imidazole.

[0066] In some embodiments, A 1 and A 1’ Each of these is independently C, N, or C(R) 22 ) and R 22 is hydrogen, C1-C 20 Hydrocarbyl and substituted C1-C 20 Selected from hydrocarbyl. In some embodiments, A 1 and A 1’ Each of them is carbon. If Q is carbon, then A 1 and A 1’ Each of them independently contains nitrogen and C(R) 22 ) can be selected from. If Q is nitrogen, then A 1 and A 1’ Each of them can be carbon. In some embodiments, Q = nitrogen and A 1 =A 1’ = Carbon. If Q is nitrogen or oxygen, then in the heterocyclic Lewis base of formula (I), either hydrogen atom is A. 1 Or A 1’ The hydrogen atoms do not necessarily have to be bonded to an atom, and in some cases, this is preferable. This is because hydrogen atoms at these positions may undergo undesirable decomposition reactions that reduce certain stability of catalytic activity. In at least one embodiment of formula (I), Q is carbon, and A 1 and A 1’Each of these is N or C(R 22 ) and R 22 is hydrogen, C1-C 20 Hydrocarbyl, substituted C1-C 20 Selected from hydrocarbyl, heteroatom, or heteroatom-containing group. In such embodiments, A 1 QA 1’ The fragments form part of a cyclic carbene, an N-heterocyclic carbene, a cyclic aminoalkyl carbene, or a substituted variant thereof.

[0067] A 1 and A 1’ Together with the curves that connect them, A 1 QA 1’ The heterocyclic Lewis base represented by (formula (I)) can be selected from the following, and each R 23 The group consists of hydrogen, heteroatoms, and C1-C atoms. 20 Alkyl, C1-C 20 Alkoxide, C1-C 20 Amides, and substituted C1-C 20 Selected from alkyl groups. [ka]

[0068] In some embodiments, A 1 and A 1’ Together with the curves that connect them, A 1 QA 1’ A heterocyclic Lewis base represented by (formula (I)) is a six-membered ring containing zero or one ring heteroatom, or a five-membered ring containing zero, one, two, or three ring heteroatoms. Alternatively, A 1 and A 1’ Together with the curves that connect them, A 1 QA 1’ The heterocyclic Lewis base represented by (formula (I)) is not a six-membered ring containing two or more ring heteroatoms. In some embodiments of formula (I), A 1 QA 1’ It is part of a heterocyclic Lewis base containing 2 to 20 non-hydrogen atoms, and A is connected via a triatomic bridge with Q as the central atom of the triatomic bridge.2 to A 2’ It is connected to A. In some embodiments, each A 1 and A 1’ A is a carbon atom, 1 QA 1’ The fragments form pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, or substituted forms thereof, or part of a substituted form thereof.

[0069] In some embodiments of formula (I), M is Sc, Y, or La, Q is nitrogen, and A 1 and A 1 ' is carbon, E and E' are both oxygen, R 1 and R 1 'Both are independently, C4-C 20 It is a cyclic tertiary alkyl group. In some embodiments of formula (I), M is Sc, Y, or La, Q is nitrogen, and A 1 and A 1’ Both are carbon, E and E ’ Both are oxygen, and R 1 and R 1’ Both are independently adamantane-1-yl or substituted adamantane-1-yl. In some embodiments of formula (I), M is Sc, Y, or La, Q is nitrogen, and A 1 and A 1’ Both are carbon, E and E ’ Both are oxygen, and R 1 and R 1’ Both are independently acyclic tertiary alkyl groups.

[0070] In some embodiments, the catalyst compound is of formula (II): [ka] [In the formula, M is a group 3 metal or lanthanide metal (e.g., Sc, Y, or La), E and E' are, independently, O, S, or NR.A And R A Independently, hydrogen, C1-C 40 Hydrocarbyl, substituted C1-C 40 A hydrocarbyl or heteroatom-containing group, for example, E and E ’ Both are O, Each L is independently a Lewis base. X' is an anionic ligand, Two or more L groups may be bonded together to form a polydentate (for example, a bidentate) Lewis base. The X' group may be bonded to the L group to form a monoanionic bidentate group. n is 1, m is 0, 1, or 2. n+m does not exceed 3. R 1 , R 2 , R 3 , R 4 , R 1’ , R 2’ , R 3’ , and R 4’ Each of them independently produces hydrogen, C1-C 40 Hydrocarbyl, substituted C1-C 40 Hydrocarbyl, heteroatom, or heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 1’ and R 2’ , R 2’ and R 3’ , R 3’ and R 4’ One or more of these may bond to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, and substituents on the rings may bond to form additional rings. R 5 , R 6 , R 7 , R 8 , R 5’ , R 6’, R 7’ , R 8’ , R 10 , R 11 , and R 12 Each of them independently produces hydrogen, C1-C 40 Hydrocarbyl, substituted C1-C 40 Hydrocarbyl, heteroatom, or heteroatom-containing group, or R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 5’ and R 6’ , R 6’ and R 7’ , R 7’ and R 8’ , R 10 and R 11 , or R 11 and R 12 One or more of these may bond to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, and substituents on the rings may bond to form additional rings. It is represented as follows.

[0071] In equation (II), E and E' are, independently, oxygen or NR. A Selected from, R A Hydrogen, C1-C 40 Hydrocarbyl, substituted C1-C 40 It is a hydrocarbyl or heteroatom-containing group. In some embodiments, E and E' are oxygen. E and / or E' are NR A In the case of R A C1-C 20 It can be selected from hydrocarbyl, alkyl, or aryl. In one embodiment, E and E' are each independently selected from O, S, N(alkyl), or N(aryl), and this alkyl is C1-C 20 Alkyls can be, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, etc., and aryls are C6-C40 Examples of aryl groups include phenyl, naphthalenyl, benzyl, and methylphenyl. In some embodiments of the catalytic compounds of formula (I) or (II), when E and E' are oxygen, each phenolate group is located at the position adjacent to the oxygen atom (i.e., R in formulas (I) and (II)). 1 and R 1’ ) can be substituted. Therefore, if E and E' are oxygen, R 1 and R 1 Each of these is independently C1-C 40 Hydrocarbyl, substituted C1-C 40 A hydrocarbyl, heteroatom, or heteroatom-containing group, for example, R 1 and R 1 Each of the elements is independently a non-aromatic cyclic alkyl group having one or more five-membered or six-membered rings (e.g., cyclohexyl, cyclooctyl, adamantyl, or 1-methylcyclohexyl, or substituted adamantyl), for example, a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, adamantyl, or substituted adamantyl).

[0072] In some embodiments of the catalyst compound of formula (I) or (II), R 1 and R 1 Each of the ' is independently a tertiary hydrocarbyl group. In other embodiments of formula (I) or (II), R 1 and R 1 Each of the ' is independently a (substituted or unsubstituted) cyclic tertiary hydrocarbyl group. In other embodiments of the catalyst compound of formula (I) or (II), R 1 and R 1 Each of these is independently a (substituted or unsubstituted) polycyclic tertiary hydrocarbyl group. In some embodiments of the catalytic compounds of formula (I) or (II), when E and E' are oxygen, each phenolate group is in the para position relative to the oxygen atom (i.e., R in formula (I) or (II)). 3 and R 3’ ) can be substituted. Therefore, if E and E' are oxygen, R 3and R 3’ Each of these is independently C1-C 40 Hydrocarbyl, substituted C1-C 40 A hydrocarbyl, heteroatom, or heteroatom-containing group, for example, R 3 and R 3’ Each of these is independently C1-C 20 Alkyl, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or isomers thereof. Alternatively, R 3 and R 3’ Each of these is independently a non-aromatic cyclic alkyl group having one or more five-membered or six-membered rings (e.g., cyclohexyl, cyclooctyl, adamantyl, or 1-methylcyclohexyl, or substituted adamantyl), for example, a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, adamantyl, or substituted adamantyl).

[0073] In some embodiments of the catalyst compound of formula (I) or (II), R 3 and R 3’ Each of these independently corresponds to (substitutive or non-substitutive) C1-C 20 Alkyl, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or their isomers. In some embodiments of the catalyst compound of formula (I) or (II), R 3 and R 3’ Each of these is independently an acyclic tertiary hydrocarbyl group (substituted or unsubstituted). In other embodiments of formula (I) or (II), R 3 and R 3’ Each of them is independently tert-butyl. In some embodiments, R of formula (II) 1 , R 2 , R 3 , R 4 , R 1’ , R 2’ , R 3’ , R 4’ , R 5 , R 6 , R 7 , R 8 , R5’ , R 6’ , R 7’ , R 8’ , R 10 , R 11 , or R 12 One or more of these are independently hydrogen or C1-C 20 These are alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, or their isomers, such as isopropyl. In some embodiments of formula (I) or (II), M is a group 3 metal, such as Sc, Y, or La.

[0074] In some embodiments of formulas (I) and (II), E and E' are each O. In some embodiments of formulas (I) and (II), R 1 , R 2 , R 3 , R 4 , R 1 ', R 2 ', R 3 ', and R 4 Each of the following is independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthalenyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and their isomers.

[0075] In embodiments of formulas (I) and (II), each X' is independently selected from hydrocarbyl radicals (e.g., alkyl or aryl) having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, alkyl sulfonates, and combinations thereof. For example, each X' is independently selected from halides, aryls, and C1-C5 alkyl groups. For example, each X' is independently a hydride, dimethylamide, diethylamide, bis(dimethylsilyl)amide, bis(trimethylsilyl)amide, methylenetrimethylsilyl, neopentyl, phenyl, benzyl, methyl, ethyl, propyl, butyl, pentyl, fluoro, iodine, bromo, or chloro group. In some embodiments, each X' is independently selected from bis(dimethylsilyl)amide, bis(trimethylsilyl)amide, and methylenetrimethylsilyl. Alternatively, each X' may independently be a halide, hydride, alkyl group, or alkenyl group. In some embodiments of formulas (I) and (II), each L is independently a Lewis base selected from ethers, thioethers, amines, nitriles, imines, pyridines, halocarbons, and phosphines, for example, an ether, a thioether, or a combination thereof, and optionally two or more Ls may form part of a fused ring or ring system, for example, each L is independently selected from an ether or thioether group, for example, each L is an ethyl ether, tetrahydrofuran, dibutyl ether, or dimethyl sulfide group.

[0076] In some embodiments of formulas (I) and (II), R 1 and R 1’ Each of them is independently a cyclic tertiary alkyl group. In some embodiments of formulas (I) and (II), m is 0, 1, or 2, for example, 0. In some embodiments of formulas (I) and (II), R 1 and R 1’ None of them are hydrogen. In some embodiments of formulas (I) and (II), R 3 and R 3’None of them are hydrogen. In some embodiments of formulas (I) and (II), M is Sc, Y, or La, and E and E' are each O, R 1 and R 1 Each of these is independently C1-C 40 Hydrocarbyl, substituted C1-C 40 Hydrocarbyl, heteroatom, or heteroatom-containing group, R 2 , R 3 , R 4 , R 2 ', R 3 ', and R 4 Each of these is independently hydrogen, C1-C 20 Hydrocarbyl, or substituted C1-C 20 It is hydrocarbil.

[0077] In some embodiments of formula (II), R 5 , R 6 , R 7 , R 8 , R 5 ', R 6 ', R 7 ', R 8 ' 、 R 10 , R 11 and R 12 Each of these is independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof. In some embodiments of formula (II), R 5 , R 6 , R 7 , R 8 , R 5 ', R 6 ', R 7 ', R 8 ' 、 R 10 , R 11 and R 12Each of these is independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthalenyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, or isomers thereof.

[0078] In some embodiments of formula (II), M is Sc, Y, or La, and E and E' are each O, R 1 and R 1 Each of these is independently C1-C 40 Hydrocarbyl, substituted C1-C 40 Hydrocarbyl, heteroatom, or heteroatom-containing group, R 3 and R 3 Each of these is independently C1-C 40 Hydrocarbyl, substituted C1-C 40 Hydrocarbyl, heteroatom, or heteroatom-containing group, R 1 , R 2 , R 4 , R 1 ', R 2 ', and R 4 Each of these is independently hydrogen, C1-C 20 Hydrocarbyl, substituted C1-C 20 Hydrocarbyl, heteroatom, or heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 1 'and R 2 ', R 2 'and R 3 ', R 3 'and R 4One or more of these may bond to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, and substituents on the rings may bond to form additional rings. Each X' is independently selected from the group consisting of substituted or unsubstituted: hydrocarbyl radicals having 1 to 20 carbon atoms (e.g., alkyl or aryl), hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and combinations thereof (two or more X' may form part of a fused ring or ring system), where n is 2, m is 0, and R 5 , R 6 , R 7 , R 8 , R 5 ', R 6 ', R 7 ', R 8 ' 、 R 10 , R 11 and R 12 Each of them independently produces hydrogen, C1-C 20 Hydrocarbyl, substituted C1-C 20 It may be a hydrocarbyl, a heteroatom, or a heteroatom-containing group, or one or more adjacent R groups may bond to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, and substituents on the ring may bond to form additional rings, for example, R 5 , R 6 , R 7 , R 8 , R 5 ', R 6 ', R 7 ', R 8 ' 、 R 10 , R 11 and R 12Each of these is independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and their isomers.

[0079] In some embodiments of formula (II), M is Sc, Y, or La, and E and E' are both oxygen, and R 1 and R 1 'Both are independently, C4-C 20 It is a cyclic tertiary alkyl, R 3 and R 3 'Both are independently, C1-C 10 It is alkyl. In some embodiments of formula (II), M is Sc, Y, or La, and E and E' are both oxygen, and R 1 and R 1 ' is either adamantane-1-yl or substituted adamantane-1-yl, R 3 and R 3 'Both are independently, C1-C 10 It is alkyl. In some embodiments of formula (II), M is Sc, Y, or La, and E and E' are both oxygen, and R 1 , R 1 ', R 3 and R 3 Each of these is independently adamantane-1-yl or substituted adamantane-1-yl.

[0080] In some embodiments, the catalyst compound is of formula (III): [ka] [In the formula, M is a group 3 metal or lanthanide metal (for example, M is Sc, Y, or La), E and E' are, independently, O, S, or NR. A And R A Independently, hydrogen, C1-C 40 Hydrocarbyl, substituted C1-C 40 A hydrocarbyl, or heteroatom-containing group, for example, O, where both E and E' are O. Each L is independently a Lewis base. Each X' is independently an anionic ligand. Any two L groups may be bonded together to form a bidentate Lewis base. The X' group may be bonded to the L group to form a monoanionic bidentate group. n is 1, m is 0, 1, or 2. n+m does not exceed 3. R 1 , R 2 , R 3 , R 4 , R 1 ', R 2 ', R 3 ', and R 4 Each of these is independently hydrogen, C1-C 40 Hydrocarbyl, substituted C1-C 40 Hydrocarbyl, heteroatom, or heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 1 'and R 2 ', R 2 'and R 3 ', or R 3 'and R 4One or more of these may bond to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, and substituents on the rings may bond to form additional rings. R 5 , R 6 , R 7 , R 8 , R 5 ', R 6 ', R 7 ', R 8 ', R 10 , R 11 , and R 12 Each of them independently produces hydrogen, C1-C 40 Hydrocarbyl, substituted C1-C 40 Hydrocarbyl, heteroatom, or heteroatom-containing group, or R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 5 'and R 6 ', R 6 'and R 7 ', R 7 'and R 8 ', R 10 and R 11 , or R 11 and R 12 One or more of these may bond to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, and substituents on the rings may bond to form additional rings. It is represented as follows.

[0081] In equation (III), E and E' are oxygen or NR, respectively. A Selected from, R A Independently, hydrogen, C1-C 40 Hydrocarbyl, substituted C1-C 40 It is a hydrocarbyl or heteroatom-containing group. In some embodiments, E and E' are oxygen. E and / or E' are NRA If R A is C1~C 20 Hydrocarbyl, alkyl, or aryl can be selected. In one embodiment, E and E' are selected from O, S, N(alkyl), or N(aryl), respectively, and the alkyl is C1-C 20 Alkyls can be, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, etc., and aryls are C6-C 40 Examples of aryl groups include phenyl, naphthalenyl, benzyl, and methylphenyl. In some embodiments of the catalytic compound of formula (III), when E and E' are oxygen, each phenolate group is located at a position adjacent to the oxygen atom (i.e., R of formula (III)). 1 and R 1 ) can be substituted. Therefore, if E and E' are oxygen, R 1 and R 1 Each of these is independently C1-C 40 Hydrocarbyl, substituted C1-C 40 A hydrocarbyl, heteroatom, or heteroatom-containing group, R 1 and R 1 ' is independently, C1-C 20 Alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl. Alternatively, R 1 and R 1 Each of the elements is independently a non-aromatic cyclic alkyl group having one or more five-membered or six-membered rings (e.g., cyclohexyl, cyclooctyl, adamantyl, or 1-methylcyclohexyl, or substituted adamantyl), for example, a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, adamantyl, or substituted adamantyl).

[0082] In some embodiments of the catalyst compound of formula (III), R 1 and R 1Each of the ' is independently an acyclic tertiary hydrocarbyl group (substituted or unsubstituted). In other embodiments of formula (III), R 1 and R 1 Each of these is independently tert-butyl. In some embodiments, R 1 and R 1 Each of the elements is independently a non-aromatic cyclic alkyl group having one or more five-membered or six-membered rings (e.g., cyclohexyl, cyclooctyl, adamantyl, or 1-methylcyclohexyl, or substituted adamantyl), for example, a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, adamantyl, or substituted adamantyl). In some embodiments of the catalyst compound of formula (III), R 1 and R 1 Each of the ' is independently a tertiary hydrocarbyl group. In other embodiments of formula (III), R 1 and R 1 Each of the ' is independently a cyclic tertiary hydrocarbyl group. In other embodiments of the catalytic compound of formula (III), R 1 and R 1 Each of these is independently a polycyclic tertiary hydrocarbyl group.

[0083] In some embodiments of the catalytic compound of formula (III), when E and E' are oxygen, each phenolate group is in a para position relative to the oxygen atom (i.e., R in formula (III)). 3 and R 3 Substitution is possible in '). Therefore, if E and E' are oxygen, R 3 and R 3 Each of these is independently C1-C 40 Hydrocarbyl, substituted C1-C 40 A hydrocarbyl, heteroatom, or heteroatom-containing group, for example, R 3 and R 3 Each of these is independently C1-C 20Alkyl, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or isomers thereof. Alternatively, R 3 and R 3 Each of the elements is independently a non-aromatic cyclic alkyl group having one or more five-membered or six-membered rings (e.g., cyclohexyl, cyclooctyl, adamantyl, or 1-methylcyclohexyl, or substituted adamantyl), for example, a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, adamantyl, or substituted adamantyl). In some embodiments of the catalyst compound of formula (III), R 3 and R 3 Each of these is independently (substitutive or non-substitutive) C1-C 20 Alkyl, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or isomers thereof. In some embodiments of the catalytic compound of formula (III), R 3 and R 3 Each of the ' is independently an acyclic tertiary hydrocarbyl group (substituted or unsubstituted). In some embodiments of formula (III), R 3 and R 3 Each of these is independently tert-butyl.

[0084] In some embodiments, R of formula (III) 1 , R 2 , R 3 , R 4 , R 1 ', R 2 ', R 3 ', R 4 ', R 5 , R 6 , R 7 , R 8 , R 5 ', R 6 ', R 7 ', R 8 ', R 10 , R 11 , or R 12 One or more of these are independently hydrogen or C1-C 20These are alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, or their isomers, such as isopropyl. In some embodiments of formula (III), M is a group 3 metal, such as Sc, Y, or La. In some embodiments of equation (III), E and E' are each O. In some embodiments of formula (III), R 1 , R 2 , R 3 , R 4 , R 1 ', R 2 ', R 3 ', and R 4 Each of these is independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthalenyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and their isomers.

[0085] In the embodiment of formula (III), R A is hydrogen, C1-C 40 Hydrocarbyl, substituted C1-C 40 A hydrocarbyl or heteroatom-containing group, for example, R A These are hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or isomers thereof. In embodiments of formula (III), each X' is independently selected from hydrocarbyl radicals (e.g., alkyl or aryl) having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, alkyl sulfonates, and combinations thereof (two or more X' may form part of a condensed ring or ring system). For example, each X' is independently selected from halides, aryls, and C1-C5 alkyl groups. For example, each X' is independently a hydride, dimethylamide, diethylamide, bis(dimethylsilyl)amide, bis(trimethylsilyl)amide, methylenetrimethylsilyl, neopentyl, phenyl, benzyl, methyl, ethyl, propyl, butyl, pentyl, fluoro, iodo, bromo, or chloro group. In some embodiments, each X' is independently selected from bis(dimethylsilyl)amide, bis(trimethylsilyl)amide, and methylenetrimethylsilyl. Alternatively, each X' may independently be a halide, hydride, alkyl group, or alkenyl group.

[0086] In some embodiments of formula (III), each L is independently a Lewis base selected from ethers, thioethers, amines, nitriles, imines, pyridines, halocarbons, and phosphines, for example, an ether, a thioether, or a combination thereof, and optionally two or more Ls may form part of a fused ring or ring system, for example, each L is independently selected from an ether or thioether group, for example, each L is an ethyl ether, tetrahydrofuran, dibutyl ether, or dimethyl sulfide group. In some embodiments of formula (III), R 1 and R 1 Each of these is independently a tertiary alkyl group. In some embodiments of equation (III), m is 0, 1, or 2, for example, 0. In some embodiments of formula (III), R 1 and R 1 Each of these is not hydrogen. In some embodiments of formula (III), R 3 and R3 Each of these is not hydrogen.

[0087] In some embodiments of formula (III), M is Sc, Y, or La, and E and E' are each O, and R 1 and R 1 Each of these is independently C1-C 40 Hydrocarbyl, substituted C1-C 40 Hydrocarbyl, heteroatom, or heteroatom-containing group, R 2 , R 3 , R 4 , R 2 ', R 3 ', and R 4 Each of these is independently hydrogen, C1-C 20 Hydrocarbyl, or substituted C1-C 20 It is hydrocarbil. In some embodiments of formula (III), R 5 , R 6 , R 7 , R 8 , R 5 ', R 6 ', R 7 ', R 8 ' 、 R 10 , R 11 and R 12 Each of these is independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof.

[0088] In some embodiments of formula (III), R 5 , R 6 , R 7 , R 8 , R 5 ', R 6 ', R 7 ', R 8 ' 、 R 10 , R 11 and R 12Each of these is independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthalenyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, or isomers thereof.

[0089] In some embodiments of formula (III), M is Sc, Y, or La, and E and E' are each O, and R 1 and R 1 Each of these is independently C1-C 40 Hydrocarbyl, substituted C1-C 40 Hydrocarbyl, heteroatom, or heteroatom-containing group, R 3 and R 3 Each of these is independently C1-C 40 Hydrocarbyl, substituted C1-C 40 A hydrocarbyl, heteroatom, or heteroatom-containing group, R 1 , R 2 , R 4 , R 1 ', R 2 ', and R 4 Each of these is independently hydrogen, C1-C 20 Hydrocarbyl, substituted C1-C 20 Hydrocarbyl, heteroatom, or heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 1 'and R 2 ', R 2 'and R 3 ', R 3 'and R 4One or more of these may bond to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, and substituents on the rings may bond to form additional rings. Each X' is independently selected from the group consisting of substituted or unsubstituted hydrocarbyl radicals (e.g., alkyl or aryl) having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and combinations thereof (where two or more X' may form part of a fused ring or ring system). n is 2, m is 0, R 5 , R 6 , R 7 , R 8 , R 5 ', R 6 ', R 7 ', R 8 ' 、 R 10 , R 11 and R 12 Each of them independently produces hydrogen, C1-C 20 Hydrocarbyl, substituted C1-C 20 The group may be a hydrocarbyl, a heteroatom, or a heteroatom-containing group, or one or more adjacent R groups may bond to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, wherein substituents on the ring can bond to form additional rings, for example, R 5 , R 6 , R 7 , R 8 , R 5 ', R 6 ', R 7 ', R 8 ' 、 R 10 , R 11 and R 12Each of these is independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and their isomers.

[0090] In some embodiments of formula (III), M is Sc, Y, or La, and both E and E' are oxygen, and R 1 and R 1 'Both are independently, C4-C 20 It is a tertiary alkyl (e.g., tert-butyl), and R 3 and R 3 'Both are independently, C1-C 10 It is alkyl. In some embodiments of formula (III), M is Sc, Y, or La, and both E and E' are oxygen, and R 1 and R 1 ' is either tert-butyl or substituted tert-butyl, R 3 and R 3 'Both are independently, C1-C 10 It is alkyl. In some embodiments of formula (III), M is Sc, Y, or La, and both E and E' are oxygen, and R 1 , R 1 ', R 3 and R 3 Each of these is independently methyl, substituted methyl, tert-butyl, substituted tert-butyl, adamantan-1-yl, or substituted adamantan-1-yl.

[0091] MAO solution useful as a starting reagent for preparing anionically modified alkylaluminoxanes and / or cationically modified alkylaluminoxanes. Aluminoxanes are -Al(R)-O- or -Al(R)2-O- subunits (wherein R is an alkyl group, usually C1-C). 12 These are oligomeric compounds containing alkyl groups (for example, the inert MAO gel shown in Scheme 1). Examples of useful aluminoxanes include methyl aluminoxane (MAO), modified methyl aluminoxane (MMAO), ethyl aluminoxane, triethyl aluminoxane, triisobutyl aluminoxane, tetraethyldialuminoxane, and di-isobutyl aluminoxane.

[0092] One fresh active MAO solution obtained from the reaction of a significantly excess of TMA with water at a sufficiently low temperature is given by formula (Al4O3Me6)4(TMA) 1-2The number of coordinated TMAs depends on the surrounding TMA concentration (Sinn, et al., “Formation, Structure, and Mechanism of Oligomeric Methylaluminoxane”, in Kaminsky (ed.), Metalorg. Cat. for Synth. & Polym., Springer-Verlag, 1999, p. 105). Therefore, fresh active MAO has an Al:O ratio of 1:0.75, and oxygen may increase after aging or removal of free TMA in equilibrium with coordinated TMA (Scheme 1). For example, in Grace's 30% MAO solution, after removing a significant excess of TMA, the ratio becomes approximately 1:0.78, forming a product containing approximately 85 mol% MAO and approximately 15 mol% total TMA (Imhoff, et al., Organometallics, 1998, 17 (10), p. 1941). The gelation process also starts under cooling after the MAO solution is prepared. Therefore, the MAO solution composition may change over time, for example, an increase in free TMA and a decrease in coordination TMA, along with an increase in oxygen content in the main MAO structure. Preferably, MAO solutions with similar elapsed times under similar storage conditions should be used. More preferably, MAO solutions with an elapsed time of less than 6 months should be used at low temperature storage, e.g., below -10°C, more preferably below -20°C, and most preferably below -30°C. Most preferably, MAO solutions with an elapsed time of less than 1 week should be used under cooling, e.g., below -10°C, e.g., below -20°C, e.g., below -30°C.

[0093] Various methods exist for preparing MAO and modified MAO, such as those described in U.S. Patent No. 4,542,199 and Chen and Marks, 100 Chem. Rev. 1391 (2000). MAO may also be modified for different purposes, for example, to increase activity or solubility. Examples of useful MAOs include MAOs obtained from TMA and oxygen donors (e.g., MAO of WRGrace obtained from TMA and water, or PMAO of Nouryon obtained from TMA and an organic oxygen source, or solid MAO of Tosoh), higher alkyl-modified MAOs (e.g., MMAO of Nouryon), MAOs modified with carbocation agents (U.S. Patent No. 9,090,720), MAOs modified with dialkylaluminum cation precursors (U.S. Patent No. 8,575,284), and halogen-modified MAOs (U.S. Patent No. 7,355,058). Activated MAO can also be formed by contacting a significantly excess of TMA with a non-hydrolyzable oxygen source (e.g., CO2, methylacylic acid, benzoic acid, or other organic compounds containing reactive oxygen) under appropriate reaction conditions.

[0094] The active MAOs of this disclosure can be obtained commercially or synthetically. The active MAOs of this disclosure can be prepared in situ by contacting TMA with water in an oxygen source and, for example, an aliphatic or aromatic diluent, at a temperature of less than 0°C to about -60°C, for example, about -10°C to about -50°C, for example, about -15°C to about -30°C. Hydrocarbyl aluminum compounds for MAO and modified MAO. Active aluminoxane compositions (e.g., MAO) can be formed using trimethylaluminum (TMA) alone, but other aluminum alkyl compounds can also be used to modify MAO. Hydrocarbyl aluminum compounds used for aluminoxane modification can be alkylaluminum compounds, such as trialkylaluminum compounds. For example, the alkyl substituent can be an alkyl group with up to 10 carbon atoms, such as octyl, isobutyl, ethyl, or methyl. Thus, suitable hydrocarbyl aluminum compounds include trimethylaluminum, triethylaluminum, tripropylaluminum, tri-n-butylaluminum, tri-isobutylaluminum, tri(2-methylpentyl)aluminum, trihexylaluminum, tri-n-octylaluminum, and tri-n-decylaluminum. In some embodiments, the hydrocarbyl aluminum compounds are trimethylaluminum and tri-n-octylaluminum. In some embodiments, the hydrocarbyl aluminum compound is represented by the formula R3Al (wherein each R is independently a hydrocarbon containing between 1 and 30 carbon atoms).

[0095] In some embodiments, the hydrocarbyl aluminum compound is one or more of the trialkylaluminum mixtures, such as dimethylethylaluminum or methyldiethylaluminum derived from an AlMe3 and AlEt3 mixture, or diethylisobutylaluminum or ethyldiisobutylaluminum derived from an AlEt3 and AliBu3 mixture. Oxygen source. Suitable oxygen sources for forming alkylaluminoxanes of the present disclosure include any oxygen source in which one or more oxygen atoms can react with the hydrocarbylaluminum compound to form a novel Al-O bond. In at least one embodiment, the oxygen source may be water or contain water, for example, pure water or water in a metal salt hydrate. In some embodiments, the oxygen source may be one or more compounds containing hydroxyl or carbonyl, for example, alcohol, CO or CO2, acetone, or carboxylic acid. In at least one embodiment of the present disclosure, the oxygen source is one or more of carbon dioxide, carboxylic acids, ketones, aldehydes, esters, anhydrides, alcohols, or combinations thereof.

[0096] In at least one embodiment of the present disclosure, the oxygen source is of formula R 1 R 2 C=CR 3 CO2H (in the formula, R 1 and R 2 Each of these is independently a hydrogen, alkyl, alkenyl, aryl, or heteroatom-containing group, and R 3 (where is an alkyl, alkenyl, aryl, or heteroatom-containing group). In at least one embodiment of the present disclosure, the oxygen source comprises a reaction product of a hydrocarbyl aluminum compound, such as TMA, with an alcohol, ketone, ester, or organic acid. Examples of hydrocarbyl aluminum compounds comprising an oxygen source include dimethylaluminum methoxide, dimethylaluminum ethoxide, dimethylaluminum isopropoxide, dimethylaluminum n-butoxide, dimethylaluminum isobutoxide, pentamethyldialuminum-t-butoxide, tetramethyldialuminum di-t-butoxide, pentamethyldialuminum-i-propoxide, tetramethyldialuminum di-i-propoxide, or combinations thereof.

[0097] Regardless of the presence or absence of excess free hydrocarbyl aluminum compound, the initial molar ratio of Al:O (wherein O is the reactive oxygen species in the reactive oxygen species-containing compound) for forming a desired MAO composition can be about 100:1, about 60:1, about 30:1, about 10:1, about 1:1, or about 0.9:1. In some embodiments, the molar ratio of Al:O may be about 0.9:1 to about 100:1, for example, about 1:1 to about 10:1, or instead about 10:1 to about 60:1, for example, about 30:1 to about 60:1. If an unwanted excess of hydrocarbyl aluminum compound is present, the excess hydrocarbyl aluminum compound may be removed, for example, by filtration, then washed with an aliphatic diluent, and / or treated with the fluorine compounds of this disclosure. In some embodiments, the oxygen source is one or more of carbon dioxide, carboxylic acids, esters, anhydrides, alcohols, or combinations thereof. In some embodiments, the oxygen source is one or more of carbon dioxide, carboxylic acids, esters, anhydrides, and alcohols, or combinations thereof, and optionally contains water. In some embodiments, the oxygen source is R 1 R 2 C=CR 3 CO2H (in the formula, R 1 and R 2 Each of these is independently a hydrogen, alkyl, alkenyl, aryl, or heteroatom-containing group, and R 3 (The group is an alkyl, alkenyl, aryl, or heteroatom-containing group.) In some embodiments, the oxygen source is methacrylic acid. In at least one embodiment of the present disclosure, the oxygen source is hydrocarbylboroxine as described in Welborn's U.S. Patent No. 5,001,244.

[0098] Formation of a catalytic system The catalyst systems of this disclosure may comprise one or more pre-catalysts and activators (alkylaluminoxane-free alkylaluminoxanes) as described above, and the catalyst compounds of this disclosure may be formed by combining the activators with any known method obtained from the literature, which may include combining them with a support such as silica. The catalyst systems may also be added to or generated in solution polymerization or bulk polymerization (in monomers). The catalyst systems of this disclosure may comprise one or more activators and one, two or more pre-catalysts. An activator is defined as any compound capable of activating any one of the pre-catalyst compounds described above by converting a neutral metal compound into a catalytically active metal compound cation. The terms “co-catalyst” and “activator” are used interchangeably herein. In at least one embodiment, the catalyst system comprises an activator and a pre-catalyst compound of formula (I), formula (II), formula (III), or a combination thereof.

[0099] Embodiments of the present disclosure include a method for preparing a catalyst system, comprising the step of contacting an unsupported anionically modified MAO or a cationically modified MAO (TMA-free solution) or a supported anionically modified MAO or cationically modified MAO (TMA-free support) with at least one pre-catalyst compound having a group 3 atom or a lanthanide metal atom in an organic diluent. Alternatively, the anionically modified MAO or cationically modified MAO is first contacted with at least one pre-catalyst compound before contacting the support. In at least one embodiment, an unsupported anionically modified MAO or a cationically modified MAO, or a supported anionically modified MAO or cationically modified MAO, is heated before contact with the catalyst compound. Unsupported anionically modified MAO or cationically modified MAO, or supported anionically modified MAO or cationically modified MAO, can be solvated or slurried in an organic diluent, and the resulting mixture is brought into contact with a solution of at least one catalyst compound. The catalyst compound may also be added as a solid to the mixture of the organic diluent and the anionically modified MAO or cationically modified MAO. In at least one embodiment, the mixture of anionically modified MAO or cationically modified MAO is brought into contact with the catalyst compound for a period of about 0.02 hours to about 24 hours, for example, about 0.1 hours to about 1 hour, about 0.2 hours to about 0.6 hours, about 2 hours to about 16 hours, or about 4 hours to about 8 hours.

[0100] The mixture of the catalyst compound and the anionically modified MAO or cationically modified MAO may be heated to a temperature of about 0°C to about 70°C, for example, about 23°C to about 60°C, for example, room temperature. The contact time may be about 0.02 hours to about 24 hours, for example, about 0.1 hours to about 1 hour, about 0.2 hours to about 0.6 hours, about 2 hours to about 16 hours, or about 4 hours to about 8 hours. A suitable organic diluent is a material in which some or all of the reactants used herein, such as anionically modified MAO or cationically modified MAO and catalyst compounds, are at least partially soluble (or suspended in the case of a solid support) and are liquid at the reaction temperature. A non-limiting example of a diluent is formula C n H (2n+2) Acyclic alkanes of formula C (where n is 4-30), such as isobutane, butane, isopentane, hexane, n-heptane, octane, nonane, decane, etc., and formula C n H (2n-2) The formulas include cycloalkanes (wherein n is 5 to 30), such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and mixtures thereof. Aromatic diluents may include benzene, toluene, or xylene.

[0101] A diluent can be added to the reactor, followed by anion-modified MAO or cationic-modified MAO. The catalyst can then be added to the reactor, for example, as a catalyst solution in an organic diluent or as a solid. The mixture can be stirred at room temperature or similar temperatures. Additional diluents may be added to the mixture to form a slurry with a desired viscosity, e.g., approximately 2 cc / g silica to approximately 20 cc / g silica, e.g., approximately 4 cc / g. The diluent can then be removed. Removing the diluent involves drying the mixture, which may be done under a vacuum, by purging with an inert atmosphere, by heating the mixture, or a combination thereof. For heating the mixture, any suitable temperature that evaporates the aliphatic diluent can be used. It should be understood that under reduced pressure in a vacuum, the boiling point of the aliphatic diluent decreases depending on the pressure in the reactor. The diluent removal temperature can be about 10°C to about 200°C, for example, about 60°C to about 140°C, for example, about 60°C to about 120°C, for example, about 80°C or less, for example, about 70°C or less. In at least one embodiment, removing the diluent includes applying heat, applying a vacuum, and applying a nitrogen purge by bubbling nitrogen through the mixture from the bottom of the container. The mixture is dried.

[0102] Polymerization process This disclosure relates to a polymerization process in which monomers (e.g., ethylene; propylene) and optionally comonomers are brought into contact with a catalytic system comprising the activators described above and at least one precatalytic compound. The precatalytic compound and the activator can be combined in any suitable order. The precatalytic compound and the activator can be combined before contact with the monomer. Alternatively, the precatalytic compound and the activator can be introduced separately into the polymerization reactor and subsequently reacted to form an active catalyst. As monomers, substituted or unsubstituted C2-C 40 Alpha-olefins, for example, C2-C 20 Alpha-olefins, for example, C2-C 12Alpha-olefins include, for example, ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene and their isomers. In at least one embodiment, the monomer is ethylene and one or more C3-C3 molecules. 40 Olefins, for example, C4-C 20 Olefins, for example, C6-C 12 Contains any comonomer including olefins. C3-C 40 Olefin monomers may be linear, branched, or cyclic. C3-C 40 The cyclic olefin may be strained or unstrained, monocyclic or polycyclic, and may optionally contain heteroatoms and / or one or more functional groups. In another embodiment, the monomer is propylene and one or more ethylenes or C4-C 40 Olefins, for example, C4-C 20 Olefins, for example, C6-C 12 Contains any comonomer including olefins. C4-C 40 The olefin monomer may be linear, branched, or cyclic. C4-C 40 The cyclic olefin may be strained or not, may be monocyclic or polycyclic, and may optionally contain heteroatoms and / or one or more functional groups.

[0103] Exemplary C2~C 40Olefin monomers and optional comonomers include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, ethylidene norbornene, vinyl norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, their substituted derivatives, and their Isomers include, for example, hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene, and their respective homologs and derivatives, such as norbornene, norbornadiene, and dicyclopentadiene. The polymerization described herein may include copolymerization of butadiene and ethylene. Generally, copolymerization of ethylene and butadiene on an industrial scale is considered a difficult process because the polymerization reaction mechanism and the relative reactivity of the monomers are thought to be different. The polymerization process described herein has been shown to reduce the manufacturing and processing problems associated with such polymers and has been shown to produce high molecular weight polymers with higher catalytic activity.

[0104] In some embodiments, the polymerization process is carried out by contacting a monomer composition comprising ethylene and one or more conjugated dienes with a catalytic system having one or more catalyst compounds and activators as described above. The catalyst compounds and activators may be combined in any order, and are usually combined before contact with the monomers. Exemplary conjugated diene monomers are any hydrocarbon structures, for example, C4-C having at least two adjacent unsaturated bonds. 30This may include: Examples of conjugated dienes include isoprene, 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene, 1,3-nonadien, 1,3-decadien, cyclopentadiene, dicyclopentadiene, or higher rings containing diolefins with or without substituents at various ring positions.

[0105] The polymerization process can be carried out by any suitable method known in the art. Any suspension, homogeneous, bulk, solution, slurry, or gas-phase polymerization process can be used. Such processes can be operated in batch, semi-batch, or continuous mode. Homogeneous polymerization processes and slurry processes can be utilized. (A homogeneous polymerization process is defined as a process in which at least 90% by mass of the product is soluble in the reaction medium.) A homogeneous process can be a bulk homogeneous process. (A bulk process is defined as a process in which the monomer concentration of all feeds to the reactor is 70% by volume or more.) Alternatively, no solvent or diluent is present or added in the reaction medium (except for small amounts used as a support for the catalyst system or other additives, or amounts normally present in the monomer). In another embodiment, the process is a slurry process. As used herein, the term “slurry polymerization process” means a polymerization process in which a supported catalyst is utilized and monomers are polymerized on supported catalyst particles. At least 95% by mass of the polymer product derived from the supported catalyst is in granular form as solid particles (not dissolved in a diluent).

[0106] Suitable diluents / solvents for polymerization include non-coordinating, inert liquids. Examples include linear and branched hydrocarbons, e.g., isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, e.g., cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, e.g., commercially available (Isopar®); and perhalogenated hydrocarbons, e.g., perfluorinated C 4-10 Examples include alkanes, chlorobenzenes, and aromatic and alkyl-substituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene. Suitable solvents also include liquid olefins that can act as monomers or comonomers, including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, and mixtures thereof. In preferred embodiments of the present invention, aliphatic hydrocarbon solvents used as solvents are, for example, isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons are, for example, cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. In another embodiment, the solvent is not aromatic, and preferably, aromatics are present in the solvent in amounts of less than 1% by mass, preferably less than 0.5% by mass, and preferably less than 0% by mass, relative to the mass of the solvent.

[0107] In at least one embodiment, the feed concentrations of monomers and comonomers for polymerization in the feed stream to the reactor are such that the diluent is 60% by volume or less, for example, 40% by volume or less, for example, 20% by volume or less, relative to the total volume of the feed stream. In at least one embodiment, polymerization is carried out in a bulk process. Polymerization can be carried out at any temperature and / or pressure suitable for obtaining the desired polymer. Suitable temperatures and / or pressures include temperatures of about 0°C to about 300°C, for example, about 20°C to about 200°C, for example, about 35°C to about 160°C, for example, about 80°C to about 160°C, for example, about 85°C to about 140°C. Polymerization can be carried out at pressures of about 0.1 MPa to about 25 MPa, for example, about 0.45 MPa to about 6 MPa, or about 0.5 MPa to about 4 MPa. In a suitable polymerization, the reaction operation time can be up to about 1,500 minutes, for example, about 1,200 minutes, for example, about 300 minutes, for example, about 5 minutes to about 250 minutes, for example, about 10 minutes to about 120 minutes, for example, about 20 minutes to about 90 minutes, for example, about 30 minutes to about 60 minutes. In a continuous process, the operation time can be the average residence time of the reactor. In at least one embodiment, the reaction operation time is up to about 180 minutes. In a continuous process, the operation time may be the average residence time of the reactor.

[0108] In at least one embodiment, hydrogen is present in the polymerization reactor at partial pressures of approximately 0.001 psig to approximately 50 psig (0.007 kPa to 345 kPa), for example, approximately 0.01 psig to approximately 25 psig (0.07 kPa to 172 kPa), for example, approximately 0.1 psig to approximately 10 psig (0.7 kPa to 70 kPa). In at least one embodiment, the hydrogen content is approximately 0.0001 ppm to approximately 2,000 ppm, for example, approximately 0.0001 ppm to approximately 1,500 ppm, for example, approximately 0.0001 ppm to approximately 1,000 ppm, for example, approximately 0.0001 ppm to approximately 500 ppm. Alternatively, hydrogen can be present at zero ppm. In at least one embodiment, the aluminoxane may be present in zero mol%, or alternatively, the aluminoxane may be present in a molar ratio of less than 500:1, e.g., less than 300:1, e.g., less than 100:1, e.g., less than 1:1, to a group 3 rare earth metal or lanthanide of aluminum.

[0109] In at least one embodiment, polymerization is carried out 1) at a temperature of about 0°C to about 300°C (e.g., about 25°C to about 250°C, e.g., about 50°C to about 160°C, e.g., about 80°C to about 140°C); 2) at atmospheric pressure up to about 10 MPa (e.g., about 0.35 MPa to about 10 MPa, e.g., about 0.45 MPa to about 6 MPa, e.g., about 0.5 MPa to about 4 MPa); and 3) with an aliphatic hydrocarbon diluent (e.g., isobutane, butane, pentane, isope). 4) Polymerization is carried out in a diluent (e.g., less than 1% by mass, e.g., less than 0.5% by mass, e.g., less than 0500:1 by molar ratio of aluminum to transition metal (e.g., less than 300:1 by molar ratio, e.g., less than 300:1 by molar ratio, e.g., less than 100:1 by molar ratio, e.g., less than 1:1, e.g., less than 1:1, e.g., less than 1:1, e.g., less than 500:1 by molar ratio of aluminum to transition metal, e.g., less than 500:1 by molar ratio, e.g., less than 300:1 by molar ratio, e.g., less than 100:1 by molar ratio, e.g., less than 1:1, e.g., less than 1:1, e.g., less than 500:1 by molar ratio, e.g., less than 500:1 by molar ratio, e.g., less than 500:1 by molar ratio, e.g., less 7) Hydrogen is present in the polymerization reactor at a molar ratio of less than 100:1 to the transfer metal, e.g., less than 50:1, e.g., less than 15:1, e.g., less than 10:1; and optionally, hydrogen is present in the polymerization reactor at a partial pressure of about 0.001 psig to about 50 psig (0.007 kPa to 345 kPa) (e.g., about 0.01 psig to about 25 psig (0.07 kPa to 172 kPa), e.g., about 0.1 psig to about 10 psig (0.7 kPa to 70 kPa)). In at least one embodiment, the catalyst system used for polymerization includes one or fewer catalyst compounds. The “reaction zone” is also called the “polymerization zone,” which is the vessel in which polymerization takes place, e.g., a stirred tank reactor or a loop reactor. When multiple reactors are used in a continuous polymerization process, each reactor is considered a separate polymerization zone. For multi-step polymerization in a batch polymerization process, each polymerization step is considered a separate polymerization zone. In at least one embodiment, polymerization occurs in a single reaction zone.The room temperature is 23°C unless otherwise specified.

[0110] If desired, other additives may also be used in polymerization, such as one or more scavengers, hydrogen, aluminum alkyl, or chain transfer agents, such as alkylaluminoxanes, compounds represented by the formula AlR3 or ZnR2 (wherein each R is independently a C1-C8 aliphatic radical, such as methyl, ethyl, propyl, butyl, pentyl, hexyloctyl or isomers thereof), or combinations thereof, such as diethylzinc, methylaluminoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or combinations thereof.

[0111] In some embodiments, the polymerization process is a solution-phase polymerization process. Solution polymerization is a polymerization process in which the polymer is dissolved in a liquid polymerization medium, such as an inert solvent or monomer or a blend thereof. Solution polymerization is usually homogeneous polymerization. Homogeneous polymerization is polymerization in which the polymer product is dissolved in the polymerization medium. Such systems are not turbid, as described in Oliveira, JV et al. (2000) Ind. Eng, Chem. Res. v.29, pg. 4627. Solution polymerization may also include polymerization in a continuous reactor, in which the polymer is formed and the supplied starting monomer and catalyst material is stirred to reduce or avoid a concentration gradient, where the monomer acts as a diluent or solvent, or a hydrocarbon is used as a diluent or solvent. A suitable process can be operated at a temperature of about 0°C to about 250°C, e.g., about 50°C to about 170°C, e.g., about 80°C to about 150°C, and / or at a pressure of about 0.1 MPa or higher, e.g., 0.5 MPa or higher. The upper pressure limit is not strictly restricted, but can be approximately 200 MPa or less, for example, 120 MPa or less, for example, 30 MPa or less. Temperature control within the reactor can be achieved by maintaining equilibrium between the heat of polymerization reaction and the cooling of the reactor by a reactor jacket or cooling coil to cool the reactor contents, self-refrigeration, evaporation of a pre-cooled feed, a liquid medium (diluent, monomer, or solvent), or a combination of all three. Adiabatic reactors with a pre-cooled feed can also be used. The purity, type, and amount of the solvent can be optimized to maximize the catalyst productivity for a particular type of polymerization. The solvent can also be introduced as a catalyst support. The solvent can be introduced as a gas or liquid phase depending on the pressure and temperature. Advantageously, the solvent can be held in the liquid phase and introduced as a liquid. The solvent can be introduced into the feed to the polymerization reactor.

[0112] The processes described herein may be solution polymerization processes that can be carried out in batches (e.g., batches; half-batches) or in continuous processes. Suitable reactor designs include tanks, loops, and tubes. In at least one embodiment, the process is carried out in a continuous form, and a series-configured dual-loop reactor is used. In at least one embodiment, the process is carried out in a continuous form, and a series-configured dual continuous stirred-tank reactor (CSTR) is used. Furthermore, the process can be carried out in a continuous form, and a tube reactor may be used. In another embodiment, the process is carried out in a continuous form, and a single-loop reactor and a single CSTR are used in series. The process can also be carried out in batches, and a single stirred-tank reactor may be used.

[0113] Catalytic activity and polymer properties Unless otherwise noted, catalytic activity is a measure of the activity of a catalyst and is reported as the mass of product polymer (P) produced per mole of catalyst (cat) used (kgP / mol cat) or as the mass of product polymer (P) produced per gram of catalyst (cat) used (gP / g cat). The amount (moles or mass) of catalyst refers to the amount (moles or mass) of the metal element in the catalyst. Catalytic activity can also be expressed against a given time T and is reported as the mass of product polymer (P) produced per mole or millimoles of catalyst (cat) used, in units of gP / mmol / cat. -1 time -1 This is expressed as follows. The activity of catalysts used in the copolymerization of ethylene and conjugated dienes depends on the catalyst structure, the activator used, the metal elements incorporated into the catalyst, the catalyst concentration in the reaction medium, and / or the composition of the monomer system being copolymerized. In some embodiments, the catalyst activator is anionically or cationically modified alkylaluminoxane. In some embodiments, the co-activator is diisobutylaluminum hydride (DIBAL). In some embodiments, the catalytic activity is approximately 0.01 kg polymer / mol cat ~Approximately 350 kg polymer / mol cat, for example, about 5 kg polymer / mol cat ~ about 340 kg polymer / mol cat , for example, about 10 kg polymer / mol cat ~ about 330 kg polymer / mol cat , for example, about 25 kg polymer / mol cat ~ about 320 kg polymer / mol cat , for example, about 50 kg polymer / mol cat ~ about 310 kg polymer / mol cat , for example, about 100 kg polymer / mol cat ~ about 300 kg polymer / mol cat , for example, about 150 kg polymer / mol cat ~ about 290 kg polymer / mol cat , for example, about 200 kg polymer / mol cat ~ about 275 kg polymer / mol cat , for example, about 230 kg polymer / mol cat ~ about 250 kg polymer / mol cat is. In some embodiments, the catalyst activity is about 0.01 kg polymer / mol cat ~ about 285 kg polymer / mol cat is. In some embodiments, the catalyst activity is about 5.5 kg polymer / mol cat ~ about 45 kg polymer / mol cat is. In some embodiments, the catalyst activity is about 100 kg polymer / mol cat ~ about 250 kg polymer / mol cat is, for example, about 175 kg polymer / mol cat ~ about 225 kg polymer / mol cat is. In some embodiments, the catalyst activity is about 20 kg polymer / mol cat ~ about 350 kg polymer / mol cat is, for example, about 230 kg polymer / mol cat ~ about 260 kg polymer / mol cat is.

[0114] In some embodiments, the resulting polyolefin products are formed via copolymerization of ethylene and a conjugated diene. Generally, copolymerization of ethylene and a conjugated diene on an industrial scale is considered a difficult process due to the differing polymerization mechanisms and relative reactivity of the monomers. However, the polymerization process of this disclosure has been shown to reduce the manufacturing and processing problems associated with such polymers, and this process has been demonstrated to produce high molecular weight polymers with higher catalytic activity. In some embodiments, the copolymer formed by copolymerization between ethylene and butadiene is [ka] This is represented by scheme 5. Notable embodiments of the copolymer include butadiene units having two carbon atoms adjacent to a cyclopentane ring in the main chain. Some butadienes are incorporated in a trans-1,4 configuration, forming a linear main chain with one unsaturated bond. Some butadienes may also be incorporated into the copolymer in a cis-1,4 configuration, which also forms a linear main chain with one unsaturated bond, but both hydrogens are associated with the double bond carbon on the same side of the double bond. Finally, some butadienes may be incorporated in a 1,2 configuration, usually with very little to zero allocation, thereby leaving a pendant vinyl group as an unsaturated branch on a saturated carbon chain. Thus, copolymers can be formed with a sufficient amount of unsaturation remaining in the main chain or side chains for end use in special applications such as crosslinking or chemical modification.

[0115] The ethylene copolymers of this disclosure have improved properties, particularly resulting from the more efficient use of diene comonomers for controlling the crystallinity of the polymer. Specifically, the efficient use of diene comonomers includes improved isolation of comonomer molecules along the polyethylene chain, which had not been previously achieved for such ethylene copolymers. Therefore, the polymers of this disclosure not only have particularly good applications compared to previous uses of such polymers, but also exhibit superior overall physical properties in tires, including improved traction and lower rolling resistance, showing a significant improvement over previously available materials. The improved properties of the polymers arise from the isolation and dispersion of diene comonomers and other comonomers along the arrangement of polymer molecules. In some embodiments, the ethylene copolymers of the present disclosure have a Mw of about 100,000 g / mol to about 2,000,000 g / mol, for example, about 110,000 g / mol to about 500,000 g / mol, for example, about 113,000 g / mol to about 350,000 g / mol.

[0116] In some embodiments, the ethylene copolymers of the present disclosure have a PDI of about 1.5 to about 70, for example, about 2 to about 10, for example, about 3 to about 6. In some embodiments, the ethylene copolymer of the present disclosure has about 0.01 mol% to about 10 mol% of cyclopentane units along the main chain of the polymer, for example, about 0.1 mol% to about 9 mol%, for example, about 1 mol% to about 8 mol%, for example, about 2.5 mol% to about 7.5 mol%, for example, about 4 mol% to about 7 mol% of cyclopentane. In some embodiments, the ethylene copolymer of the present disclosure has, along the main chain of the polymer, in a 1,2 configuration, about 0.01 mol% to about 3 mol% of butadiene, for example, about 0.1 mol% to about 2 mol%, for example, about 0.5 mol% to about 1 mol% of butadiene.

[0117] In some embodiments, the ethylene copolymer of the present disclosure has, along the main chain of the polymer, about 0.01 mol% to about 10 mol% of butadiene in a 1,4-trans configuration, for example, about 1 mol% to about 9 mol%, for example, about 2.5 mol% to about 8 mol%, for example, about 4 mol% to about 7.5 mol%, for example, about 5 mol% to about 6 mol% of butadiene. In some embodiments, the ethylene copolymer of the present disclosure has about 1 mol% to about 20 mol% of butadiene, for example, about 2 mol% to about 19 mol%, for example, about 2.5 mol% to about 15 mol%, for example, about 3 mol% to about 8 mol% of butadiene in a 1,4-cis configuration along the main chain of the polymer. In some embodiments, the ethylene copolymers of the present disclosure have Mw / Mn(PDI) values ​​of about 2 to about 65, e.g., about 5 to about 55, e.g., about 10 to about 40, e.g., about 15 to about 35, or instead about 20 to about 30. In some embodiments, the molar ratio of the activator to the copolymer pre-catalyst is approximately 10:1 to 100:1, for example, approximately 20:1 to 60:1. It has been noted that increasing the activator content relative to the catalyst compound results in increased catalytic activity. Furthermore, increasing the activator content relative to the catalyst leads to a lower Mw of the polymer product, thus enabling precise control of Mw in the polymerization process. This is consistent with the coordination chain transfer mechanism of copolymerization.

[0118] In some embodiments, the ethylene copolymer has a thermal melting temperature (Tm) of approximately 95°C to approximately 130°C, for example, approximately 95°C to approximately 1115°C, for example, approximately 98°C to approximately 110°C. In some embodiments, the ethylene copolymer has two thermal melting temperatures simultaneously. Novel bis(phenolate) catalyst systems based on rare earth elements can be activated with various TMA-free activators to produce copolymers of ethylene and butadiene under mild conditions with high conversion rates. This process has been widely considered difficult due to differences in reaction mechanisms and monomer reactivity ratios. Interestingly, the applicant found that higher activity was achieved in reaction mixtures activated with anionically modified alkylaluminoxanes or cationically modified alkylaluminoxanes containing F-MAO or ionic MAO compared to the activity obtained with conventional activators (DIMAH-D4 / DIBAL or commercially available non-TMA-free MAO). Without being constrained by theory, the increase in activity is thought to be due to a decrease in free TMA in the activator / catalyst system. As previously noted, the presence of free TMA in MAO can alkylate the transition metal center of the pre-catalyst, thus causing weak activity and a short catalyst lifetime. This is analogous to the alkylation of metallocenes with dichloride leaving groups. Activation of a bis(phenolate) catalyst with the activator of this disclosure can yield a polyolefin polymer product containing a substantial amount of 1,2-cyclopentane units, in addition to fairly uniform incorporation of both monomers throughout the polymer chain. In contrast, a lanthanide-based metallocene catalyst (e.g., Michelin's Nd-bisfluorenyl) yields a product containing 1,2-cyclohexane fragments.

[0119] Without being constrained by theory, the amount of 1,2-cyclopentane units along the polymer backbone influences the morphology of the resulting polymer system. For example, polyethylene is well documented as being capable of forming crystalline domains through inter- and intramolecular interactions. While crystalline domains can offer advantages to polymer materials, in some cases, the amount of crystalline domains in the polymer system can negatively affect the physical properties of the resulting material (e.g., tensile strength, abrasion resistance, and brittleness). Without being constrained by theory, the incorporation of 1,2-cyclopentane units along the polymer backbone disrupts the polymer chain's ability to organize crystalline domains, thus reducing the percentage of crystallinity in the system. Furthermore, uniform incorporation of 1,2-cyclopentane units along the polymer backbone further ensures the reduction of polymer crystallization by decreasing ethylene-rich regions in the polymer system. Therefore, activation of bis(phenolate) catalysts with TMA-free MAO and ionic MAO yields high-yielding and unique products, making these systems highly interesting for industrial applicability.

[0120] Polymer functionalization In some cases, it may be desirable to incorporate polar groups along the main chain of the polymer so that subsequent reactions can take place after polymerization. In some embodiments, the polymerization described herein further comprises utilizing a third monomer which is a metal hydrocarbenyl transfer agent (a metal agent of either Group 12 or Group 13 containing at least one movable group having an allyl chain end group), for example, an aluminum vinyl transfer agent also known as AVTA (which is any aluminum agent containing at least one movable group having an allyl chain end group). In suitable catalyst systems of this disclosure, when the olefin growth rate is high and AVTA or other chain transfer agents, such as aluminum alkyl, chain termination via β-hydride elimination, β-methyl elimination, or chain transfer to monomer occurs at a rate less than or no rate than chain transfer to these agents.

[0121] In at least one embodiment of this disclosure, the aluminum vinyl transfer agent is of formula (D): Al(R') v (R) 3-v (D) [In the formula, R' is a hydrocarbyl group containing 1 to 30 carbon atoms, R'' is a hydrocarbenyl group containing 4 to 20 carbon atoms with an allyl chain-terminant group, v is 0.1 to 3, instead 1 to 3, instead 1.1 to less than 3, instead v is 0.5 to 2.9, 1.1 to 2.9, instead 1.5 to 2.7, instead 1.5 to 2.5, instead 1.8 to 2.2] It is represented by the formula Al(R'). 3-v (R) v The appropriate compound represented by is a neutral species, but anionic formulations may also be considered, for example, formula (B):[Al(R') 4-w (R) w ] - An anionic compound represented by the formula (wherein w is 0.1 to 4, R' is a hydrocarbyl group containing 1 to 30 carbon atoms, and R'' is a hydrocarbenyl group containing 4 to 20 carbon atoms with an allyl chain terminal group) may also be considered.

[0122] In at least one embodiment of any of the formulas for aluminum vinyl transport agents described herein, each R' is independently C1 to C 30 Hydrocarbyl group (for example, C1~C 20 Alkyl groups are selected from, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or their isomers), where R is of the formula: -(CH2) n CH=CH2 [In the formula, n is an integer between 2 and 18, e.g., 6 to 18, e.g., 6 to 12, e.g., 6] It is represented as follows.

[0123] Aluminum vinyl transfer agents include tri(buta-3-en-1-yl)aluminum, tri(penta-4-en-1-yl)aluminum, tri(octa-7-en-1-yl)aluminum, tri(nona-8-en-1-yl)aluminum, tri(deca-9-en-1-yl)aluminum, tri(dodeca-11-en-1-yl)aluminum, dimethyl(octa-7-en-1-yl)aluminum, diethyl(octa-7-en-1-yl)aluminum, dibutyl(octa-7-en-1-yl)aluminum, diisobutyl(octa-7-en-1-yl)aluminum, diisobutyl(nona-8-en-1-yl)aluminum, dimethyl(deca-9-en-1-yl)aluminum, diethyl(deca-9-en-1-yl)aluminum, and dibutyl(deca-9-en-1-yl) It may contain one or more of the following: luminium, diisobutyl(deca-9-en-1-yl)aluminum, and diisobutyl(dodeca-11-en-1-yl)aluminum, methyl-di(octa-7-en-1-yl)aluminum, ethyl-di(octa-7-en-1-yl)aluminum, butyl-di(octa-7-en-1-yl)aluminum, isobutyl-di(octa-7-en-1-yl)aluminum, isobutyl-di(nona-8-en-1-yl)aluminum, methyl-di(deca-9-en-1-yl)aluminum, ethyl-di(deca-9-en-1-yl)aluminum, butyl-di(deca-9-en-1-yl)aluminum, isobutyl-di(deca-9-en-1-yl)aluminum, and isobutyl-di(dodeca-11-en-1-yl)aluminum.

[0124] In at least one embodiment of this disclosure, particularly useful AVTAs include, but are not limited to, tri(buta-3-en-1-yl)aluminum, tri(penta-4-en-1-yl)aluminum, tri(octa-7-en-1-yl)aluminum, tri(nona-8-en-1-yl)aluminum, tri(deca-9-en-1-yl)aluminum, dimethyl(octa-7-en-1-yl)aluminum, diethyl(octa-7-en-1-yl)aluminum, dibutyl(octa-7-en-1-yl)aluminum, diisobutyl(octa-7-en-1-yl)aluminum, diisobutyl(nona-8-en-1-yl)aluminum, diisobutyl(deca-9-en-1-yl)aluminum, and diisobutyl(dodeca-11-en-1-yl)aluminum. Mixtures of one or more AVTAs may also be used. In some embodiments of this disclosure, isobutyl-di(octa-7-en-1-yl)-aluminum, isobutyl-di(deca-9-en-1-yl)-aluminum, isobutyl-di(nona-8-en-1-yl)-aluminum, and isobutyl-di(hepta-6-en-1-yl)-aluminum are suitable.

[0125] Examples of aluminum vinyl transfer agents include reaction products of organoaluminum compounds between an aluminum reagent (AlR3) and an alkyldiene. Suitable alkyldienes include those having the two "alphaolefins" mentioned above at the two ends of their carbon chains. The alkyldiene can be a linear or branched alkyl chain and can be substituted or unsubstituted. Examples of exemplary alkyldienes include, but are not limited to, 1,3-butadiene, 1,4-pentadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, 1,14-pentadecadiene, 1,15-hexadecadiene, 1,16-heptadecadiene, 1,17-octadecadiene, 1,18-nonadecadiene, 1,19-aicosadiene, and 1,20-hen'eicosadiene. Examples of exemplary aluminum reagents include triisobutylaluminum, diisobutylaluminum hydride, isobutylaluminum dihydrogen, and aluminum hydride (AlH3). Useful compounds can be prepared by combining an aluminum reagent (e.g., alkylaluminum) having at least one secondary alkyl moiety (e.g., triisobutylaluminum) and / or at least one hydride, e.g., dialkylaluminum hydride, monoalkylaluminum dihydrogen, or aluminum trihydrogen (aluminum hydride, AlH3), with an alkyldiene and heating to a temperature that causes the release of alkylene byproducts. The use of a solvent is not required. However, non-polar solvents, such as hexane, pentane, toluene, benzene, xylene, or combinations thereof, can be used. In at least one embodiment of this disclosure, AVTA does not contain coordinating polar solvents, such as tetrahydrofuran and diethyl ether. After the reaction is complete, any solvent present can be removed, and the product can be used without further purification.

[0126] In at least one embodiment, R'' in formula (D) is butenyl, pentenyl, heptenyl, octenyl, or decenyl, for example, R'' is octenyl or decenyl. R' in formula (D) can be methyl, ethyl, propyl, isobutyl, or butyl, for example, R' is isobutyl. In at least one embodiment of the present disclosure, v in formula (D) is approximately 2, or v is 2. In at least one embodiment, v in equation (D) is about 1, or v is 1, for example, about 1 to about 2. In some embodiments, v in formula (D) can be an integer or a non-integer, for example, v is in the range of 1.1 to 2.9, e.g., about 1.5 to about 2.7, e.g., about 1.6 to about 2.4, e.g., about 1.7 to about 2.4, e.g., about 1.8 to about 2.2, e.g., about 1.9 to about 2.1, and all ranges in between. In at least one embodiment, R' is isobutyl, each R'' is octenyl or decenyl, and v is 1.1 to 2.9, e.g., about 1.5 to about 2.7, e.g., about 1.6 to about 2.4, e.g., about 1.7 to about 2.4, e.g., about 1.8 to about 2.2, e.g., about 1.9 to about 2.1.

[0127] The quantity of v is given by the formula: (3-v)+v=3, and Al(R') v (R) 3-v This is explained using [wherein R'' is a hydrocarbenyl group containing 4 to 20 carbon atoms with an allyl chain terminal group, R' is a hydrocarbyl group containing 1 to 30 carbon atoms, and v is 0.1 to 3 (e.g., 1.1 to 3)]. This formulation is explained using the observed average values ​​of organoaluminum species present in the mixture ( 1This represents the result when measured by 1H NMR, and this mixture may contain any of Al(R')3, Al(R')2(R"), Al(R')(R")2, and Al(R")3. In yet another embodiment, the aluminum vinyl transfer agent contains less than 50% by mass of dimer relative to the mass of AVTA, for example less than 40% by mass, for example less than 30% by mass, for example less than 20% by mass, for example less than 15% by mass, for example less than 10% by mass, for example less than 5% by mass, for example less than 2% by mass, for example less than 1% by mass, for example 0% by mass. Alternatively, the dimer may be 0.1~ It is present at 50% by mass, 1-20% by mass instead, and 2-10% by mass instead. The dimer is a dimer product of the alkyldiene used in the preparation of AVTA. The dimer can be formed under certain reaction conditions by insertion of the diene molecule into the Al-R bond of AVTA, followed by β-hydride elimination. For example, if the alkyldiene used is 1,7-octadiene, the dimer is 7-methylenepentadeca-1,14-diene. Similarly, if the alkyldiene is 1,9-decadiene, the dimer is 9-methylenenonadeca-1,18-diene.

[0128] For polymerization according to the present disclosure, the molar ratio of AVTA to the catalyst complex can be greater than 5, instead greater than 10, instead greater than 15, instead greater than 20, instead greater than 25, instead greater than 30. In at least one embodiment of this disclosure, the metal hydrocarbenyl chain transfer agent is of the formula: Al(R') 3-v (R'') v [In the formula, each R' is independently C1-C 30 It is a hydrocarbyl group, and each R'' independently has a C4-C with a terminal vinyl group. 20 It is a hydrocarbenyl group, where v is 0.1 to 3, for example, each R'' independently has an allyl chain terminal group, C4-C 20 It is a hydrocarbenyl group, and v is between 0.1 and 3, for example, v=2. This technology enables the production of in-chain functionalized ethylene / butadiene copolymers. Furthermore, the process disclosed herein allows for the in-chain functionalization of ethylene / butadiene copolymers in a single reactor. The Al-carbon bond can react with various electrophiles (and other reagents), such as oxygen, halogens, and carbon dioxide, to form functionalized vinyl transfer agent units. For example, the Al-carbon bond reacts with carbon dioxide to form carbon dioxide-functionalized vinyl transfer agent units.

[0129] tire In some embodiments, the copolymers of the Disclosure may be used as components of a tire. The tire (also referred to herein as “tire product”) may be any suitable tire, for example, a rubber tire having an outer (visible) rubber sidewall layer, the outer sidewall layer comprising the copolymers of the Disclosure. The tire may be constructed, molded, or shaped to include the outer sidewall (rubber sidewall layer) and cured by a variety of methods readily apparent to those skilled in the art. Blends of highly saturated specialty elastomers blended with highly unsaturated polymers are sometimes desirable to improve the performance window of the blend (e.g., oxygen and ozone resistance, thermal stability, tackiness, etc.). Regarding tire treads, the tire tread compound, in particular, determines the tire's characteristics, such as wear, traction, and rolling resistance. Achieving good traction and low rolling resistance while providing good tread wear is a technical challenge. This challenge involves a trade-off between wet traction and rolling resistance / tread wear. The methods and polymers disclosed herein reduce or eliminate the need for fillers introduced into the final tire product. As a result, the reduction or absence of fillers in the tire product leads to improved wear resistance of the tire product (tire tread), such as a reduction or elimination of the initiation and growth of cracking.

[0130] As used herein, the term "filler" refers to any material used to enhance or modify the physical properties of a composition (as a tire product), to impart certain processing characteristics, or to reduce the cost of a tire. In some embodiments, examples of inorganic fillers include calcium carbonate, clay, mica, silica, silicates, talc, titanium dioxide, alumina, zinc oxide, starch, wood flour, or combinations thereof. The fillers may be of any size and range, for example, in the tire industry they may be 0.0001 μm to 100 μm. As used herein, the term “silica” is intended to refer to silica of any type or particle size, or other silicic acid derivatives, or silicic acid, or any silica processed by methods such as solution or exothermic methods, and includes untreated silica, precipitated silica, crystalline silica, colloidal silica, aluminum or calcium silicate, fumed silica, etc. Precipitated silica may be conventional silica, semi-highly dispersible silica, or highly dispersible silica. The filler may be one of those commercially available from Rhodia Company under the trademark names ZEOSIL® Z1165 or ZEOSIL® 1165MP. The functionalized copolymers of this disclosure can result in improved interaction between the copolymer and additives, allowing for the use of smaller amounts of additives (e.g., fillers) compared to conventional tire compositions. In some embodiments, the composition (as a tire product) contains less than 150 parts by weight (phr) of filler (e.g., silica) per 100 parts by weight of rubber, for example, about 10 to about 150 phr. In another embodiment, the composition (as a tire product) contains about 30 to about 130 phr of filler. In a further embodiment, the composition contains about 50 to about 90 phr of filler. [Examples]

[0131] GPC-4D: Unless otherwise noted, the molecular weight distribution and molecular weight moment (Mw, Mn, Mz, Mw / Mn, etc.) and comonomer content are approximately 2700 cm². -1~about 3000cm -1 The determination is made using high-temperature gel permeation chromatography (Polymer Char GPC-IR) equipped with a multi-channel band filter-based infrared detector IR5, an 18-angle light scattering detector, and a viscometer, with a multi-channel band filter-based infrared detector ensemble IR5 having a band range spanning (representing saturated CH stretching vibration). Polymer separation is obtained using three Agilent PLgel 10-μm Mixed-BLS columns. Reagent-grade 1,2,4-trichlorobenzene (TCB) (Sigma-Aldrich) containing approximately 300 ppm of the antioxidant BHT can be used as the mobile phase at a nominal flow rate of approximately 1.0 mL / min and a nominal injection volume of approximately 200 μL. The entire system, including the mobile line, column, and detector, can be contained in an oven maintained at approximately 145°C. A given amount of sample can be weighed and sealed in a standard vial with approximately 10 μL of flow marker (heptane) added to the sample. After filling the autosampler with vials, the oligomer or polymer can be automatically dissolved in the instrument using approximately 8 mL of TCB solvent added with continuous shaking at approximately 160°C. The sample solution concentration can be approximately 0.2 to 2.0 mg / ml, with lower concentrations used for samples with higher molecular weights. The concentration c at each point in the chromatogram can be calculated from the IR5 broadband signal I, subtracted from the baseline, using the equation: c = αI (where α is the mass constant determined using polyethylene or polypropylene standards). The mass recovery can be calculated from the ratio of the integrated area over the elution volume in concentration chromatography to the injected mass, which is equal to the predetermined concentration multiplied by the injection loop volume. Conventional molecular weight (IR MW) is determined by combining general calibration with column calibration performed using a series of monodisperse polystyrene (PS) standards ranging from 700 to 10 Mgm / mol. The MW at each elution volume is given by the following equation:

[0132]

number

[0133] The comonomer composition is determined by the intensity ratio of the IR5 detector corresponding to the CH2 and CH3 channels, and this intensity ratio is calibrated using a series of PE and PP homo / copolymer standards whose nominal values ​​are defined by NMR or FTIR. In particular, this yields the number of methyl groups per 1000 total carbon atoms (CH3 / 1000TC) as a function of molecular weight. The short-chain branching (SCB) content per 1000TC (SCB / 1000TC) is then calculated as a function of molecular weight by applying a chain end correction to the CH3 / 1000TC function, assuming that each chain is straight and each end is terminated with a methyl group. The mass % of the comonomer is then obtained from the following formula (where f is 0.3, 0.4, 0.6, 0.8, etc. for C3, C4, C6, C8... comonomers, respectively): w2 = f * SCB / 1000TC

[0134] The bulk composition of the polymer from GPC-IR and GPC-4D analysis is obtained by considering the total signals of the CH3 and CH2 channels during the integration interval of the concentration chromatogram. First, the following ratios are obtained:

number

[0135] The LS detector is an 18-angle Wyatt Technology High Temperature DAWN HELEOS II. The LS molecular weight (M) at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering (Light Scattering from Polymer Solutions; Huglin, MB, Ed.; Academic Press, 1972).

number

[0136]

number

[0137] The high-temperature Agilent (or Viscotek Corporation) viscometer has four capillaries arranged in a wheatstone bridge configuration and two pressure transducers, used to determine specific viscosity. One transducer measures the total pressure drop across the entire detector, while the other is positioned between the two sides of the bridge and measures the pressure difference. The specific viscosity, ηs, for the solution flowing through the viscometer is calculated from these outputs. The intrinsic viscosity [η] at each point in the chromatogram is calculated from the equation [η] = ηs / c (where c is the concentration, determined from the IR5 broadband channel output). The viscosity MW at each point is given by M = K PS M α PS +1 / [η](where α ps 0.67, and K ps The calculation is performed assuming that (is 0.000175). Differential scanning calorimetry (DSC) measurements were performed using a DSC2500™ (TA Instruments) to determine the glass transition temperature (Tg) and melting point (Tm) of the polymers disclosed herein, as follows: The polymer sample was cooled to -150°C at a rate of 10°C / min and held for 10 minutes. The sample was then heated at a rate of 10°C / min to a final temperature of 150°C and held at this temperature for 5 minutes. The second cooling-heating cycle was then performed using the same conditions as described above. The events "first melting" and "second melting" from both cycles were recorded, respectively. References to the melting point temperature (Tm) and glass transition temperature (Tg) refer to the second melting.

[0138] Catalyst synthesis [ka]

[0139] Ln(Me3SiCH2)3(THF)2(Ln=Sc,Y,Lu) was synthesized from (trimethylsilyl)methyllithium (0.7M in hexane; Acros Organics) and anhydrous LnCl3 (Aldrich) as described in Chemical Communications 2016, v.52(31), pp. 5425-5427. Ln(N(SiMe2H)2)3(THF) nThe ligand precursor (Ln=Sc, Y, La) was prepared as described in the literature (Organometallics 2013, v.32, pp. 1528-1530 and J. Org. Chem. 2007, 72, v.23, pp. 8648-8655). The ligand precursor, 2',2'''-(pyridine-2,6-diyl)bis(3-(tert-butyl)-5-methyl-[1,1'-biphenyl]-2-ol) was synthesized as described in WO2020 / 167824. The ligand precursor, 6,6'-(pyridine-2,6-diylbis(benzo[b]thiophene-3,2-diyl))bis(2-(tert-butyl)-4-methylphenol) was synthesized as described in WO2020 / 167819. The ligand precursor, 2',2'''-(pyridine-2,6-diyl)bis(3-(adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-ol) was synthesized as described in US11,254,763. Methyl aluminoxane was used in the form of a 30% by mass solution in toluene (Grace, 13.5% by mass of Al, 5 mmol of Al / g). Ammonium hexafluorosilicate (NH4) 2SiF6 was purchased from Aldrich and dried under vacuum at ambient temperature for 16 hours. Octamethyltrisiloxane (OMTS, Aldrich) was degassed and dried on an activated molecular sieve (3 Å) for 16 hours. All other reagents were commercially available, and all solvents were dried and degassed before use using typical methods previously reported. The metal complexes, also called catalysts and pre-catalysts, were prepared under the inert atmosphere shown in Scheme 6.

[0140] (Example 1) Synthesis of complex Y-1 [ka]

[0141] In a 20 ml scintillation vial, 182 mg of Y(Me3SiCH2)3(THF)2 (0.368 mmol) was added at -30°C to a suspension of 2',2'''-(pyridine-2,6-diyl)bis(3-(tert-butyl)-5-methyl-[1,1'-biphenyl]-2-ol) in 10 ml of hexane. The resulting mixture was stirred at room temperature for 6 hours, and the vial was placed in the refrigerator (-30°C). After 12 hours, the precipitate was filtered off using a syringe filter (0.45 μm PTFE), and the mother liquor was returned to the refrigerator. After another 12 hours, the formed precipitate was filtered off using a syringe filter (0.45 μm PTFE), and the mother liquor was evaporated to dryness to obtain 145 mg (49%) of the product as a beige powder. Elemental analysis: C 47 H 58 Calculated values ​​for YNO3Si: C, 70.39; H, 7.29; N, 1.75. Measured values: C 70.65; H 7.68; N 1.51. 1 H NMR (400 MHz, benzene-d6): δ 7.53 (dd, J = 7.5, 1.3 Hz, 1H), 7.18 - 7.38 (m, 6H), 6.94 - 7.06 (m, 4H), 6.88 (dd, J = 7.8, 1.1 Hz, 1H), 6.66 (d, J = 2.3 Hz, 1H), 6.52 (t, J = 7.8 Hz, 1H), 6.32 (dd, J = 7.8, 1.1 Hz, 1H), 3.69 - 3.75 (m, 2H), 3.57 - 3.63 (m, 2H), 2.28 (s, 3H), 2.20 (s, 3H), 1.67 (s, 9H), 1.56 (s, 9H), 1.11 - 1.14 (m, 4H), 0.27 (s, 9H), -0.41 (dd ,J = 11.4, 3.9 Hz, 1H), -2.05 (dd, J = 11.4, 4.0 Hz, 1H).

[0142] (Example 2) Synthesis of complex Sc-2 [ka]

[0143] In a 20 ml scintillation vial, 115 mg of Sc(Me3SiCH2)3(THF)2 (0.255 mmol) was added at room temperature to a suspension of 6,6'-(pyridine-2,6-diylbis(benzo[b]thiophene-3,2-diyl))bis(2-(tert-butyl)-4-methylphenol) in 10 ml of hexane and 0.5 ml of toluene. The resulting solution was stirred at room temperature for 12 hours, and the vial was placed in the refrigerator (-30°C). After 12 hours, the precipitate was filtered off using a syringe filter (0.45 μm PTFE), and the mother liquor was returned to the refrigerator. After 12 hours, the precipitate was filtered off using a syringe filter (0.45 μm PTFE), and the mother liquor was evaporated to dryness to obtain 127 mg (57%) of the product as an off-white solid. Elemental analysis: C 51 H 58 Calculated values ​​for ScNS2O3Si: C, 70.39; H, 6.72; N, 1.61. Measured values: C 70.68; H 6.98; N 1.50. 1H NMR (400 MHz, ベンゼン-d6): δ 7.73 (d, J = 8.0 Hz, 1H), 7.55 (d, J = 8.0 Hz, 1H), 7.51 (d, J = 8.0 Hz, 1H), 7.40 (d, J = 1.7 Hz, 1H), 7.31 (dt, J = 7.2, 1.0 Hz, 1H), 7.15 - 7.21 (m, 2H), 7.00 - 7.14 (m, 5H), 6.91 (dt, J = 8.0, 1.0 Hz, 1H), 6.79 (t, J = 7.8 Hz, 1H), 6.22 (dd, J = 7.7, 1.1 Hz, 1H), 6.11 (d, J = 7.8 Hz, 1H), 4.10 - 4.17 (m, 2H), 3.97 - 4.05 (m, 2H), 2.25 (s, 3H), 2.21 (s, 3H), 1.50 (s, 9H), 1.15 - 1.24 (m, 4H), 0.98 (s, 9H), 0.17 (d, J = 11.3 Hz, 1H), 0.12 (s, 9H), -1.59 (d, J = 11.3 Hz, 1H). 13 C NMR (400 MHz, ベンゼン-d6): δ 162.6, 159.5, 156.9, 154.3, 151.0, 145.0, 142.9, 141.5, 140.0, 139.7, 139.6, 139.1, 136.8, 132.6, 130.6, 130.2, 129.7, 129.6, 126.0, 125.97, 125.6, 125.4, 125.3, 124.9, 124.2, 124.1, 123.6, 123.5, 123.2, 122.8, 122.3, 72.7, 35.9, 35.3, 30.1, 29.5, 25.2, 21.8, 21.3, 4.1.

[0144] (Example 3) Synthesis of wrong body Y-2

change

[0145] In a 20 ml scintillation vial, 100 mg of Y(Me3SiCH2)3(THF)2 (0.202 mmol) was added at room temperature to a suspension of 6,6'-(pyridine-2,6-diylbis(benzo[b]thiophene-3,2-diyl))bis(2-(tert-butyl)-4-methylphenol) in 10 ml of hexane and 0.5 ml of toluene. The resulting solution was stirred at room temperature for 12 hours, and the vial was placed in the refrigerator (-30°C). After 12 hours, the precipitate was filtered off using a syringe filter (0.45 μm PTFE), and the mother liquor was returned to the refrigerator. After 12 hours, the formed precipitate was filtered off using a syringe filter (0.45 μm PTFE), and the mother liquor was evaporated to dryness to yield 124 mg (67%) of the product as an off-white solid. Elemental analysis: C 51 H 58 Calculated values ​​for YNS2O3Si: C, 67.01; H, 6.40; N, 1.53. Measured values: C 66.85; H 6.65; N 1.31. 1 H NMR (400 MHz, benzene-d6): δ 7.61 (d, J = 7.9 Hz, 1H), 7.55 (d, J = 7.9 Hz, 1H), 7.51 (d, J = 7.9 Hz, 1H), 7.36 (d, J = 2.0 Hz, 1H), 7.28 (dt, J = 7.5, 1.1 Hz, 1H), 7.17 - 7.21 (m, 2H), 6.93 - 7.10 (m, 5H), 6.77 (t, J = 7.8 Hz, 1H), 6.28 (dd, J = 7.7, 1.1 Hz, 1H), 6.21 (d, J = 7.7Hz, 1H), 3.80 - 3.93 (m, 4H), 2.26 (s, 3H), 2.22 (s, 3H), 1.48 (s, 9H), 1.09 - 1.15 (m, 4H), 1.05 (s, 9H), 0.19 (s, 9H), -0.59 (dd, J = 11.3, 3.9 Hz, 1H), -2.18 (dd, J = 11.3, 4.0 Hz, 1H). 13¹³C NMR (400 MHz, benzene-d6): δ 162.9, 160.1, 156.9, 153.8, 152.0, 145.8, 142.6, 141.7, 140.2, 139.6, 139.4, 136.9, 130.6, 130.3, 130.1, 130.0, 129.6, 126.2, 125.8, 125.6, 125.5, 124.9, 124.6, 124.3, 123.6, 123.5, 123.2, 123.1, 122.8, 122.7, 122.2, 72.0, 35.8, 35.3, 30.4, 30.2, 29.9, 29.5, 25.2, 21.34, 21.31, 4.6.

[0146] (Example 4) Synthesis of complex Sc-3 [ka]

[0147] In a 20 ml scintillation vial, 294 mg of Sc(CH2SiMe3)3(THF)2 (0.660 mmol) was added at room temperature to a suspension of 2',2'''-(pyridine-2,6-diyl)bis(3-(adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-ol) in 40 ml of hexane and 6.5 ml of toluene. The resulting solution was stirred at room temperature for 12 hours, and the vial was placed in the refrigerator (-30°C). After 12 hours, the precipitate was filtered off using a syringe filter (0.45 μm PTFE), and the mother liquor was returned to the refrigerator. After 12 hours, the precipitate was filtered off using a syringe filter (0.45 μm PTFE), and the mother liquor was evaporated to obtain 103 mg (15%) of the product as an off-white solid. Elemental analysis: C 65 H 82 Calculated values ​​for ScNO3Si: C, 78.20; H, 8.28; N, 1.40. Measured values: C 78.42; H 8.61; N 1.26. 1H NMR (400 MHz, ベンゼン-d6): δ 7.67 (d, J = 7.2 Hz, 1H), 7.66 (d, J = 2.8 Hz, 1H), 7.53 (d, J = 2.7 Hz, 1H), 7.39 - 7.47 (m, 3H), 7.34 (d, J = 7.1 Hz, 1H), 7.30 (d, J = 2.7 Hz, 1H), 7.19 - 7.22 (m, 2H), 7.04 - 7.08 (m, 1H), 6.86 - 6.90 (m, 2H), 6.65 (t, J = 7.8 Hz, 1H), 6.36 (dd, J = 7.7, 1.0 Hz, 1H), 3.98 - 4.06 (m, 2H), 3.68 - 3.74 (m, 2H), 2.66 - 2.73 (m, 3H), 2.43 - 2.63 (m, 6H), 2.30 - 2.39 (m, 6H), 2.27 (br.s, 3H), 2.14 - 2.22 (m, 3H), 1.90 - 2.12 (m, 9H), 1.46 (s, 9H), 1.34 (s, 9H), 1.20 - 1.28 (m, 4H), 0.31 (s, 9H), 0.14 (d, J = 11.4 Hz, 1H), -1.88 (d, J = 11.5 Hz, 1H). 13 C NMR (400 MHz, ベンゼン-d6): δ 161.8, 159.3, 158.3, 158.1, 145.9, 144.5, 138.6, 138.5, 137.7, 137.2, 136.7, 136.0, 135.8, 133.2, 131.7, 131.3, 130.9, 130.8, 130.2, 129.9, 129.7, 127.1, 126.7, 126.0, 125.2, 124.9, 124.0, 123.8, 122.0, 73.1, 42.8, 41.3, 38.7, 38.3, 38.1, 37.8, 34.7, 34.5, 32.5, 32.3, 30.23, 30.18, 25.4, 4.5.

[0148] (Example 5) Synthesis of wrong body Y-3 [ka]

[0149] In a 20 ml scintillation vial, 63 mg of Y(Me3SiCH2)3(THF)2 (0.127 mmol) was added at room temperature to a suspension of 2',2'''-(pyridine-2,6-diyl)bis(3-(adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-ol) in 20 ml of n-hexane and 1.5 ml of toluene. The resulting solution was stirred at room temperature for 12 hours, and the vial was placed in the refrigerator (-30°C). After 12 hours, the precipitate was filtered off using a syringe filter (0.45 μm PTFE), and the mother liquor was returned to the refrigerator. After 12 hours, the precipitate was filtered off using a syringe filter (0.45 μm PTFE), and the mother liquor was evaporated to yield 110 mg (83%) of the product as an off-white solid. Elemental analysis:C 65 H 82 Calculated values ​​for YNO3Si: C, 74.90; H, 7.93; N, 1.34. Measured values: C 75.27; H 8.12; N 1.19. 1H NMR (400 MHz, ベンゼン-d6): δ 7.62 (d, J = 7.6, 1.0 Hz, 1H), 7.52 (d, J = 2.7 Hz, 1H), 7.41 (d, J = 2.7 Hz, 1H), 7.37 (dt, J = 7.5, 1.5 Hz, 1H), 7.25 - 7.34 (m, 5H), 7.23 (d, J = 2.7 Hz, 1H), 6.97 - 7.13 (m, 6H), 6.80 - 6.82 (m, 2H), 6.58 (t, J = 7.8 Hz, 1H), 6.32 (dd, J = 7.8, 1.0 Hz, 1H), 3.65 - 3.72 (m, 2H), 3.42 - 3.50 (m, 2H), 2.60 - 2.67 (m, 3H), 2.49 - 2.56 (m, 3H), 2.34 - 2.41 (m, 3H), 2.16 - 2.28 (m, 9H), 2.04 - 2.11 (m, 3H), 1.85 - 1.93 (m, 9H), 1.38 (s, 9H), 1.26 (s, 9H), 1.04 - 1.11 (m, 4H), 0.26 (s, 9H), -0.63 (dd, J = 11.3, 3.8 Hz, 1H), -2.03 (dd, J = 11.3, 3.9 Hz, 1H).

[0150] (Example 6) Synthesis of wrong body Sc-3-N

change

[0151] In a 20 mL scintillation vial, [Sc{N(SiMe2H)2}2]·THF (207 mg, 0.4 mmol) was dissolved in 2 mL of THF. Then, while stirring at ambient temperature, solid 2',2'''-(pyridine-2,6-diyl)bis(3-(adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-ol) (312 mg, 0.39 mmol) was slowly added. After addition, the reaction mixture was diluted by adding 3 mL of THF. The resulting mixture was stirred at 60°C for 2 hours, and then volatile matter was removed under a nitrogen stream. n-pentane (5 mL) was added to the pale yellow oily residue and evaporated to accelerate the removal of remaining THF. This process was repeated twice to obtain a pale yellow powder. This powder was dissolved in n-pentane (5 mL) and filtered. The filtrate was concentrated to approximately 1 / 5 of its original volume and cooled to -35°C. The white crystals were decanted and removed, and the mixture was dried in vacuum to obtain 129 mg (33%) of the desired product. 1 The broadness of the resonance signals in the 1H NMR spectrum hinders these precise integrations. 1 H NMR (400 MHz, benzene-d6): δ 7.47 (d, J = 2.7 Hz, 2H), 7.43 (d, J = 2.8 Hz, 2H), 7.30-7.11 (m, 6H), 7.01-6.95 (m, 2H), 6.55-6.49 (m, 3H), 4.34 (m, 2H, Si-H), 3.62 (s, 4H, THF), 2.45-2.42 (m, 6H), 2.26-2.21 (m, 12H), 1.97-1.85 (m, 14H), 1.36-1.35 (m, 4H), 1.30 (s, 18 H, C(CH3)3), 0.20 (d, J = 10.8 Hz, 12H, SiMe2).

[0152] (Example 7) Synthesis of complex Y-3-N [ka]

[0153] In a 20 mL scintillation vial, [Y{N(SiMe2H)2}2]·1.5 THF (235 mg, 0.39 mmol) was dissolved in 2 mL of THF. Then, while stirring at ambient temperature, solid 2',2'''-(pyridine-2,6-diyl)bis(3-(adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-ol) (305 mg, 0.38 mmol) was slowly added. After addition, the reaction mixture was diluted by adding 3 mL of THF. The resulting mixture was stirred at 60°C for 2 hours, and then volatile matter was removed under a nitrogen stream. n-pentane (5 mL) was added to the pale yellow oily residue and evaporated to accelerate the removal of remaining THF. This process was repeated twice to obtain a pale yellow powder. This powder was dissolved in toluene (1 mL). The resulting solution was layered with n-pentane and stored at -35°C. The precipitated white solid product was collected by filtration and washed twice with cold n-pentane (0.5 mL each). This was then dried under vacuum while gently heating (below 40°C) to obtain 273 mg of white solid product (64%). 1 H NMR (400 MHz, benzene-d6): δ 7.48-7.33 (m, 5H), 7.25-7.00 (m, 6H), 6.85-6.75 (m, 2H), 6.54 (t, 7.5 Hz, 1H) 6.28 (m, 1H), 4.45 ( s, 2H, SiH), 3.74-3.45 (m, 4H), 2.61-2.44 (m, 6H), 2.26-2.11 (m, 11H), 1.98 (m, 6H), 1.88-1.85 (m, 7H), 1.37-1.15 (m, 22H), 0.26 (dd, J = 18.7 and 2.1 Hz, 12 H, SiMe2).

[0154] (Example 8) Synthesis of the La-3-N complex [ka]

[0155] In a 20 mL scintillation vial, [La{N(SiMe2H)2}2]·1.5 THF (243 mg, 0.35 mmol) was dissolved in 2 mL of THF. Then, while stirring at ambient temperature, solid 2',2'''-(pyridine-2,6-diyl)bis(3-(adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-ol) (273 mg, 0.34 mmol) was slowly added. After addition, the reaction mixture was diluted by adding 3 mL of THF. The resulting mixture was stirred at 60°C for 2 hours, then volatile matter was removed under a stream of nitrogen, and the mixture was heated at 60°C. n-pentane (5 mL) was added to the pale yellow oily residue and evaporated to promote the removal of remaining THF and HN(SiMe2H)2. This process was repeated 5 times to obtain a pale yellow powder. The powder was washed twice with n-pentane (7 ml each). The resulting product was dissolved in toluene (3 ml), and the resulting solution was then passed through a glass microfiber filter and a Celite plug. The filtrate was concentrated to approximately 0.5 mL and layered with n-pentane at -35°C, resulting in the precipitation of yellow crystals. This was collected by decanting and dried under vacuum for 4 hours to obtain 297 mg of product (70%). 1 H NMR (400 MHz, benzene-d6): δ 7.43-7.40 (m, 4H), 7.29-7.11 (m, 6H), 7.06-6.98 (m, 2H), 6.61-6.54 (m, 3H), 4.48 (septet, 2.9 Hz, 2H, SiH), 3.46 (s, 4H, THF), 2.46-2.16 (m, 18H), 2.02-1.99 (m, 6H), 1.90-1.87 (m, 6H), 1.32 (s, 18H, tBu), 1.16-1.13 (m, 4H), 0.26 (dd, J = 22.4 and 3.0 Hz, 12H, SiMe2).

[0156] (Example 9) F-MAO without TMA Reaction: (NH4)2SiF6 + 8AlMe3 = 2 / 6[(AlMeNH)3]2 + 6AlMe2F + SiMe4 + 6CH4 Ammonium hexafluorosilicate (NH4)2SiF6 (0.66 g, 3.7 mmol) was slowly added to a commercially available MAO solution in toluene (30 wt% MAO, 40 g, 200 mmol of Al). The resulting mixture was shaken for 1 hour to obtain a solution of F-MAO.

[0157] (Example 10) Ionic MAO without TMA [Chemical formula] Octamethyltrisiloxane (OMTS) (4.80 g, 20.3 mmol) was added to a commercially available MAO solution in toluene (109.0 g, 30 wt% MAO, 545 mmol of Al), and the resulting mixture was stirred at ambient temperature for 45 minutes. Then, the solution was transferred to a separatory funnel and allowed to settle for 16 hours, separating into two liquid layers. The lower layer (51 g, oil) was heated at 90 °C for 1 hour to obtain a less active chelated AlMe2(OMTS) + The cation was promoted to convert to an active monodentate coordination [(AlMe2)2(OSiMe3)] + species. Ionic MAO is also called I-MAO.

[0158] (Example 11) Quantification of the total content of THF-extractable TMA in the MAO solution. The total TMA content, including coordinated TMA and free TMA in the MAO composition, can be quantified by converting both coordinated TMA and free TMA to AlMe3(THF) as the main product and AlMe2(THF)2 + as the by-product according to Scheme 7 via THF solvent treatment. Thus, the total TMA is the sum of AlMe3(THF) and AlMe2(THF)2 + (re-converted to TMA in calculation), and can be quantified using the following 1 1H NMR method, using solvent toluene as the internal standard for solution MAO, or for solution MAO, solid MAO, or supported MAO, using the added inert compound as the internal standard.

[0159] [ka]

[0160] Procedure: Fill an oven-dried 5mm NMR tube in a dry box with approximately 0.5 inches (12.7 mm) of MAO solution, followed by approximately 1.5 inches (38.1 mm) of THF-d8 solvent, and oscillate thoroughly. Then, use D1=30 seconds and ns=4 to analyze the sample. 1 Obtain a 1H NMR spectrum. A longer relaxation time D1 may yield greater accuracy, but a length of 30 seconds is sufficient to obtain an error of <2 mass% in the quantification of the CH3 and Al-CH3 signals of toluene. 1 The 1H NMR spectrum is for a commercially available MAO solution (WRGrace, MAO 30% toluene solution (Al = 13.6% by mass (5.0 mmol / g), MAO = 26.6% by mass, total TMA (coordination and liberation) = 4.76% by mass, based on the Certificate of Analysis (COA) of the MAO product)) and is shown in Figure 1. Processing: CH3 peak of toluene, total area of ​​Al-CH3, AlMe2(THF)2 + Integrate the peaks of MAO, AlMe3(THF), and AlMe3(THF). Set the integral value of CH3 in toluene to 300 (set to 300 instead of the CH3 proton number 3, because decimal places may be truncated, so this is to ensure at least 3 digits of precision in the spectral output), MAO, AlMe3(THF), and AlMe2(THF)2 + Assuming the integral value for all Al-Me species, including AlMe3, is 350.28, and the integral value for AlMe3(THF) is 78.96, AlMe2(THF)2 + The integral value is recorded as 7.98, and trace amounts of species, such as machining oils that are usually present in small amounts, for example, <1 mass%, are ignored. Based on COA, the MAO formula without coordination TMA is Al1O 0.78 Me 1.44Therefore, Mw 61.1 is obtained. The integral value of MAO is 350.28 - 78.96 - 7.98 = 263.34. The number of protons in MAO is 1.44 * 3 = 4.32. AlMe2 + Since it is generated from the coordination TMA, it is counted as a TMA. The calculation results are listed in Table 1.

[0161] [Table 1] Here, we can see that the total TMA content has increased from 4.76 mass% (COA) to 5.33 mass%, which indicates a low degree of gelation.

[0162] (Example 12) Quantification of coordination TMA in commercially available MAO solutions The quantification of coordination TMA is based on the following reaction (Scheme 8): [ka]

[0163] In the above reaction, KF can form an ionic MAO composition by precipitating MAO as a clathrate phase and separating it from the solution phase containing free TMA via substitution of coordinating TMA. A large excess of known amounts of KF(W1) KF ) is applied to the MAO solution, and the remaining KF(W2) after the reaction is applied. KF By isolating ), the consumption of KF is reduced to W1 KF -W2 KF This can be calculated as follows, and this is an indirect method of quantifying the coordination TMA content. Chemical substance: KF (Aldrich), 10g placed in a 50mL round-bottom flask and dried in an oil bath at 110°C under vacuum for 4 hours. The same MAO solution and THF-d8 as in Example 11 were used.

[0164] Procedure: In a dry box, 10.0 g of MAO solution (51.1 mmol of Al, calculated based on the results in Table 1) was added to each of four oven-dried vials (20 mL). Then, 59.6 mg (2 mol%) of KF (58.1 g / mol) (2 mol%), 118.9 mg (4 mol%) (4 mol%), 207.6 mg (7 mol%) (7 mol%), and 298 mg (10 mol%) of KF (58.1 g / mol) were added, respectively. The vials were placed on a shaker and shaken overnight. The vials were removed from the shaker and the clathrate phase was allowed to settle for 10 hours. All KF in the vials treated with 2 mol%, 4 mol%, and 7 mol% disappeared, but the vial treated with 10 mol% showed that KF remained. All upper phase solutions from the four vials were NMRed in THF-d8 solvent. 1 Figure 2A, which compares the Al-Me region spectra analyzed using 1H nuclear magnetic resonance spectroscopy, shows a decrease in MAO concentration. Similarly, the clathrate phase obtained from a sample (10 mmol% KF treated vial) in which the standard MAO was completely converted to ionic MAO was also analyzed in THF-d8 NMR solvent. 1 The analysis was performed using 1H nuclear magnetic resonance spectroscopy, and the Al-Me region spectrum is shown in Figure 2B along with a comparative MAO mother solution. This spectrum represents AlMe2 in relation to ionic MAO. + This indicates the absence of species, which means that all coordination TMAs have been removed by KF, and that coordination TMAs are AlMe2 + This confirms that it is the source of the substance. The KF remaining in the vial after 10 mol% treatment was collected using a pre-mass-measured frit filter, washed with 3 × 10 mL of dry toluene and 30 mL of dry isohexane, and then mass-measured. The amount of unreacted KF was 75.3 mg (2.54 mol% relative to total Al), and coordinated TMA in MAO solution was obtained as 10 - 2.5 = 7.5 mol%. Total Al% was 13.8 mass%, and total TMA (free + coordinated) was 5.33 mass%. Total TMA can be converted to 2.00 mass% Al to obtain 14.5 mol%.

[0165] Figure 2A-B. Commercial 30% MAO solution after KF treatment. 1These are 1H NMR spectra. Figure 2A shows the upper solution phases after treatment with 2, 4, 7, and 10 mol% KF, respectively, and Figure 2B shows the final KF + (F-MAO) - The image shows the clathrate phase and an untreated MAO solution for comparison. (Example 13) Evaluation of free TMA. Total TMA (Wt) in Example 12 全TMA Quantification method for mass percentage of coordination TMA and free TMA, and mass percentage of coordination TMA (Wt) in Example 13 配位TMA Based on a quantitative method for %), the free TMA content (Wt) 遊離TMA % is Wt 遊離TMA %=Wt 全TMA %-Wt 配位TMA It can be predicted in percentages.

[0166] (Example 14) polymerization reaction All operations involving air and moisture-sensitive materials were carried out under an inert atmosphere in an N2-ventilated glove box. The catalyst was activated by the addition of iBu2AlH(DIBAL) and dimethylanilinium tetrakispentafluorophenyl borate (DIMAH-D4), or MAO (100 equivalents of 13% by mass of Al in toluene), or F-MAO (100 equivalents, Example 9), or ionic MAO (10 equivalents, Example 10). After stirring the catalyst and activator for about 10 minutes, a butadiene solution in toluene (10% to 20% by mass) was added (about 2500 butadiene equivalents / catalyst), and the reactor, containing six 20 mL vials, was then sealed. The reactor was heated to 100°C, stirred at 225 rpm, and then pressurized with ethylene (250 psi, Sigma, 99.5%). If the pressure dropped below 240 psi during the first hour, the reactor was repressurized. After 4–14 hours, the reactor was cooled and then the pressure was reduced. To isolate the polymer product, the contents of each vial were precipitated and washed with acetone and methanol. The solid was then filtered off and washed with large amounts of acetone and methanol. The polymer samples were then dried in a vacuum oven at 50°C for 18 hours.

[0167] NMR research: 13 C NMR The sample was dissolved in deuterated 1,1,2,2-tetrachloroethane (TCE-D2) at a concentration of 34 mg / mL at 140°C. Spectra were recorded at 120°C using a Bruker NMR spectrometer with a 10 mm cryogenic probe and at least 600 MHz. A 90° pulse, 10-second delay, 512 transients, and gated decoupling were used. 13 This was used for measuring 13C NMR spectra. Polymer resonance peaks were aligned to the polyethylene major peak at 29.98 ppm. Spectral attribution is based on the following references: Llauro et.al. Macromolecules, 34,18, (2001), 6304-6311; Makhiyanov Polymer Sci, (2012), 60-90 and Longo et.al. Macromolecules, v.36, (2003), pp. 9067-6074. [ka] The following signals were used to calculate the composition:

[0168] [Table 2]

[0169] 1 1H NMR The sample was dissolved in deuterated 1,1,2,2-tetrachloroethane (TCE-D2) at a concentration of at least 30 mg / mL at 140°C. Spectra were recorded at 120°C using a Bruker NMR spectrometer at at least 600 MHz with a 10 mm cryogenic probe. A 30° pulse, a 5-second delay, and 512 transients were used. 1 It was used for 1H NMR measurements. The peak was aligned to the residual solvent peak at 5.98 ppm. [Table 3]

[0170] Tested catalysts [ka]

[0171] Bis(phenolate) catalysts Y-1, Sc-2, and Y-2 (Y-1 derived from formula II, and Sc-2 and Y-2 derived from formula III), characterized by 2-tBu-4-Me-phenolate fragments and alkyl groups bonded to a metal center, were activated with DIMAH-D4 / DIBAL, MAO, and F-MAO. Interestingly, no products were formed when the copolymer reaction mixture was activated with the DIMAH-D4 / DIBAL activator (Table 2, Experiments 1, 4, and 7). The formation of ethylene-rich copolymers was low in yield (43.5 kg). 生成物 / mol RE (Up to) MAO-activated reaction mixture was observed (Experiments 2, 5 and 8). When F-MAO was used, the activity of the Y-1, Sc-2 and Y-2 systems was 239.4 kg 生成物 / mol M We were able to significantly increase this (Experiments 3, 6, and 9).

[0172] [Table 4]

[0173] Bis(phenolate) catalysts M-3 and M-3-N (derived from formula II), which hold alkyl or amide auxiliary groups and a group III metal ion in the center, were activated with DIMAH-D4 / DIBAL, MAO, and ionic MAO (Table 3). For all M-3 and M-3-N complexes, the activity was particularly higher when the copolymerization reaction was initiated with ionic MAO. Scandium complex Sc-3 (characterized by a 2-(1-adamantyl)-4-tBu-phenolate fragment) was activated with ionic MAO (Experiment 3, 337 kg). ポリマー / mol MWhen combined with ), the highest activity was observed, but a crosslinked polymer was formed as the main polymerization product. It should be noted that MAO or ionic MAO activators prefer the formation of 1,2-cyclopentane units in the polymer chain.

[0174] [Table 5] TIFF2026520731000045.tif92159

[0175] Significant crosslinking during copolymerization of ethylene and butadiene activated by ionic MAO can be mitigated by carrying out the reaction in the presence of the chain transfer agent DIBAL (Table 4). Increasing the concentration of DIBAL reduces the molecular weight of the polymer. Overall, the copolymer composition remains almost identical for reaction mixtures containing various equivalents of DIBAL.

[0176] [Table 6]

[0177] Overall, the catalyst systems of this disclosure, which have rare earth element-based bis(phenolate) type catalysts, can be used in combination with TMA-free MAO and / or ionic MAO to produce ethylene-butadiene copolymers under mild conditions and with high conversion rates. The catalyst systems disclosed herein are of interest for introduction into industrial-scale processes for high-throughput production of copolymer materials derived from ethylene and butadiene monomers, for example, these copolymer materials have tunable physical properties, polymer back-chain structures, and different functional group moieties. In addition, polar side-chain moieties can be incorporated into the polymer chain during the copolymerization process. Such functionalized polymers may be desirable for the tire industry during use as tire materials due to enhanced interactions between the copolymer and fillers present with the copolymer.

[0178] Unless otherwise specified, the phrases “consists essentially of” and “consisting essentially of” do not preclude the presence of other steps, elements, or materials, whether or not they are specifically described herein, provided that such steps, elements, or materials do not further affect the fundamental and novel features of the disclosure, and furthermore, these phrases do not preclude impurities and errors that are typically associated with the elements and materials used.

[0179] For the sake of brevity, only certain ranges are explicitly disclosed herein. However, any range from any lower limit can, in combination with any upper limit, describe ranges not explicitly stated, and similarly, any range from any lower limit can, in combination with any other lower limit, describe ranges not explicitly stated, and likewise, any range from any upper limit can, in combination with any other upper limit, describe ranges not explicitly stated. Furthermore, "within range" includes all points or individual values ​​between their endpoints, even if they are not explicitly stated. Thus, every point or individual value can function as a lower or upper limit itself, in combination with any other point or individual value, or any other lower or upper limit, to describe ranges not explicitly stated.

[0180] All documents described herein, including any priority documents and / or test procedures, are incorporated herein by reference only to the extent that they do not contradict the wording herein. As is evident from the general description and specific embodiments above, while the forms of this disclosure are illustrative and described, various modifications can be made without departing from the spirit and scope of this disclosure. Therefore, this disclosure is not intended to be limited thereto. Similarly, for the purposes of U.S. law, the term “comprising” is considered to have the same meaning as the term “including.” Similarly, when a composition, element, or group of elements is preceded by the transitional phrase “comprising,” it is understood that the same composition or group of elements preceded by the transitional phrase “consisting essentially of,” “consisting of,” “selected from the group consisting of,” or “is,” and vice versa. While this disclosure describes several embodiments and examples, those skilled in the art who are interested in this disclosure will recognize that other embodiments can be devised that do not depart from the scope and spirit of this disclosure.

Claims

1. A solution catalyst system, 1) Anionically modified alkylaluminoxanes and / or cationically modified alkylaluminoxanes, wherein when the solution catalyst system is determined by titration of the solution catalyst system using tetrahydrofuran, the solution catalyst system contains 0% to about 2% by mass of Al derived from a non-coordinating trialkylaluminum compound relative to the total aluminum content of the solution catalyst system, and 2) Equation (I): 【Chemistry 1】 [In the formula, M is a group 3 transition metal or lanthanide metal. E and E' are, independently, oxygen, sulfur, or NR A And R A These are, independently, hydrogen and C 1 -C 40 Hydrocarbyl, substituted C 1 -C 40 A hydrocarbyl or heteroatom-containing group, Q is a group 14 atom, a group 15 atom, or a group 16 atom. A 1 QA 1 ' is part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms, and is linked to A via a three-atom bridge having Q as the central atom of the three-atom bridge 2 to A 2’ and is linked to A 1 and A 1 Each of these is independently carbon, nitrogen, or C(R) B ) and R B is hydrogen, C 1 -C 20 Hydrocarbyl and substituted C 1 -C 20 Selected from hydrocarbil, 【Chemistry 2】 This is a divalent group containing 2 to 40 nonhydrogen atoms, and via a two-atom bridge, A 1 This is linked to the E-bonded aryl group shown in formula (I), A 3 and A 2 They combine to form a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocycle, or an unsubstituted heterocycle, each having 5, 6, 7, or 8 ring atoms, and substituents on the rings can bond to form additional rings. 【Transformation 3】 This is a divalent group containing 2 to 40 nonhydrogen atoms, and via a two-atom bridge, A 1 ' is linked to the E' bonded aryl group shown in formula (I), A 3 'and A 2 These combine to form a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocycle, or an unsubstituted heterocycle, each having 5, 6, 7, or 8 ring atoms, and substituents on the rings can bond to form additional rings. Each L is independently a Lewis base. X' is an anionic ligand, Any two L groups may be bonded together to form a bidentate Lewis base. The X' group may be bonded to the L group to form a monoanionic bidentate group. n is 1, m is 0, 1, or 2. n+m does not exceed 3. R 1 , R 2 , R 3 , R 4 , R 1 ', R 2 ', R 3 ', and R 4 Each of these is independently hydrogen, C 1 -C 40 Hydrocarbyl, substituted C 1 -C 40 Hydrocarbyl, heteroatom, or heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 1 'and R 2 ', R 2 'and R 3 ', R 3 'and R 4 One or more of these may bond to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, and substituents on the rings may bond to form additional rings. Compounds represented by A solution catalyst system including this.

2. The catalyst system according to claim 1, wherein the anionically modified alkylaluminoxane contains an electron-withdrawing group.

3. The electron-withdrawing group is -F or -OC 6 F 5 The catalyst system according to claim 2, including the following:

4. The catalyst system according to claim 3, wherein the non-coordinating trialkylaluminum compound is trimethylaluminum.

5. A fluorine-containing compound is NH 4 BF 4 、(NH 4 ) 2 SiF 6 、NH 4 PF 6 、NH 4 F、(NH 4 ) 2 TaF 7 、NH 4 NbF 4 、(NH 4 ) 2 GeF 6 、(NH 4 ) 2 SmF 6 、(NH 4 ) 2 TiF 6 、(NH 4 ) 2 ZrF 6 、MoF 6 、ReF 6 、GaF 3 、SO 2 ClF、F 2 、SiF 4 、SF 6 、ClF 3 、ClF 5 、BrF 5 、IF 7 、NF 3 、HF、BF 3 、AlF 3 、NHF 2 、NH 4 HF 2 、Me 3 SiF、Me 2 SiF 2 、MeSiF 3 、Et 3 SiF、Et 2 SiF 2 、EtSiF 3 、Ph 3 SiF、Ph 2 SiF 2 、PhSiF 3 、Me 3 CF、Me 2 CF 2 、MeCF 3 、Et 3 CF、Et 2 CF 2 EtCF 3 Ph 3 CF, Ph 2 CF 2 PhCF 3 Me 2 BF, MeBF 2 MeAlF 2 , Et 2 BF, EtBF 2 , EtAlF 2 Ph 2 BF and PhBF 2 It comprises at least one compound selected from the group consisting of -OC 6 F 5 The containing compound is HOC 6 F 5 Me 3 Si(OC) 6 F 5 ), Me 2 Si(OC) 6 F 5 ) 2 MeSi (OC 6 F 5 ) 3 Me 3 C(OC) 6 F 5 ), Ph 3 C(OC) 6 F 5 ), Me 2 B(OC) 6 F 5 ), MeB(OC 6 F 5 ) 2 MeAl(OC 6 F 5 ) 2 Al(OC) 6 F 5 ) 3 , and B(OC 6 F 5 ) 3 The catalyst system according to claim 4, comprising at least one compound selected from the group consisting of the following.

6. The catalyst system according to claim 1, wherein the cation-modified alkylaluminoxane contains a chelating agent or a monocementary agent.

7. The catalyst system according to claim 6, wherein the chelating agent or monocephalic agent contains a siloxidant.

8. The catalyst system according to claim 7, wherein the siloxide donor comprises dimethylaluminum trihydrocarbyl siloxide.

9. The catalyst system according to claim 7, wherein the siloxide donor is derived from the decomposition product of a dialkylaluminum cation stabilized with a chelated polysiloxane, or from in situ formation by the reaction of silanol and free alkylaluminum in an alkylaluminoxane composition.

10. The catalyst system according to claim 9, wherein the chelated polysiloxane comprises at least one compound selected from hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, octamethyltrisiloxane (OMTS), decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, or 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxaneate, or the silanol comprises at least one compound selected from trimethylsilanol, triethylsilanol, tripropylsilanol, tributylsilanol, trihexylsilanol, triheptylsilanol, or trioctylsilanol.

11. The catalyst system according to claim 1, 2, or 6, wherein the alkylaluminoxane of the anionically modified alkylaluminoxane and the cationically modified alkylaluminoxane is methylaluminoxane, and the non-coordinating trialkylaluminum compound is trimethylaluminum.

12. The catalyst system according to claim 10, comprising a phase separation step of isolating an ionic alkylaluminoxane phase from a non-coordinating alkylaluminoxane solution phase, followed by an ionic alkylaluminoxane decomposition step via heating the ionic alkylaluminoxane at a temperature selected from 50°C to 120°C for 0.5 hours or more, or aging it at ambient for 24 hours or more, to obtain an alkylaluminoxane composition.

13. The catalyst system according to any one of claims 1 to 12, wherein M in formula (I) is selected from the group consisting of Sc, Y, or La.

14. The catalyst system according to any one of claims 1 to 13, wherein E and E' in formula (I) are each oxygen.

15. The catalyst system according to any one of claims 1 to 14, wherein Q in formula (I) is nitrogen.

16. A in equation (I) 1 and A 1 The catalyst system according to any one of claims 1 to 15, wherein each of the ' is carbon.

17. A in equation (I) 3 and A 2 They combine to form the first ortho-phenylene, A in equation (I) 3 'and A 2 The catalyst system according to any one of claims 1 to 16, wherein the ' combine to form a second ortho-phenylene.

18. A in equation (I) 3 and A 2 These combine to form the first benzothiophene, A in equation (I) 3 'and A 2 The catalyst system according to any one of claims 1 to 17, wherein the two components combine to form a second benzothiophene.

19. R in equation (I) 1 'and R 1 The catalyst system according to claim 18, wherein each of the is independently selected from the group consisting of adamantan-1-yl or substituted adamantan-1-yl.

20. R in equation (I) 1 'and R 1 The catalyst system according to claim 19, wherein each of the elements is tert-butyl or substituted tert-butyl.

21. R in equation (I) 3 and R 3 The catalyst system according to claim 20, wherein each of the elements is independently methyl or tert-butyl.

22. R in equation (I) 2 , R 4 , R 2 ', R 4 ', R 5 , R 6 , R 7 , R 8 , R 5 ', R 6 ', R 7 ', R 8 ', R 10 , R 11 , and R 12 The catalyst system according to any one of claims 1 to 21, wherein each of the elements is hydrogen.

23. A method for producing a polymer, comprising the step of polymerizing an α-olefin and an optional comonomer in a reactor at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30°C to 230°C, by introducing the α-olefin and optionally the comonomer together with a catalyst system according to any one of claims 1 to 23.

24. A method for producing an ethylene copolymer, comprising the step of polymerizing ethylene and at least one conjugated diene in a reactor at a reactor pressure of 0.05 MPa to 1,500 MPa and a reactor temperature of 30°C to 230°C, by introducing the ethylene and conjugated diene together with a catalyst system according to any one of claims 1 to 24.

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