Solution catalyst system and use thereof

Abstract

The present disclosure relates to catalyst systems containing catalyst compounds and activators and uses thereof. In some embodiments, the solution catalyst system includes an aluminoxane solution comprising an anionically modified alkylaluminoxane and / or a cationically modified alkylaluminoxane, as determined by titration of the alkylaluminoxane composition with tetrahydrofuran, based on the total aluminum content of the alkylaluminoxane composition, the total aluminum content of the alkylaluminoxane composition is determined by titration of the alkylaluminoxane composition with tetrahydrofuran, and the total aluminum content of the alkylaluminoxane composition is determined by titration of the alkylaluminoxane composition with tetrahydrofuran. The alkylaluminoxane composition has from 0 wt% to about 2 wt% of Al from a non-coordinating trihydrocarbyl aluminum compound. The catalyst system includes a compound represented by formula (I).

Description

[0001] Inventors: Alexander V.Zabula, Torin Dupper, Lubin Luo, Jo Ann M.Canich, Michelle E.Titone, Georgy P.Goryunov, Dmitry V.Uborsky, AlexanderZ.Voskoboynikov

[0002] Cross-reference to related applications

[0003] This application claims the benefit and priority of U.S. Provisional Application No. 63 / 506536, filed June 6, 2023, the disclosure of which is incorporated herein by reference. Technical Field

[0004] This disclosure relates to catalyst systems containing catalyst compounds and activators, and their uses. Background Technology

[0005] Copolymers of olefins and conjugated dienes exhibit beneficial properties in the tire industry, such as aging resistance, puncture resistance, repairability, rolling resistance, and abrasion resistance. Copolymers formed from ethylene and butadiene monomers have shown improvements in these properties when incorporated into one or more components of a tire. However, copolymerization of ethylene and butadiene can be challenging due to the differences in reaction mechanisms and relative reactivity between the two monomers, making it difficult to develop efficient methods for producing high molecular weight ethylene-butadiene random copolymers.

[0006] To overcome these difficulties, current efforts focus on developing methods for achieving catalyst systems that are tolerant of both monomers and capable of copolymerizing them within the same process window. Example catalyst systems based on halide complexes of transition metals, such as titanium, have provided for the copolymerization of ethylene and conjugated dienes. Japanese Patent Specifications JP'10237131A, JP'09316118A, and JP'11171930A disclose copolymers of ethylene and butadiene, wherein butadiene can be inserted in the form of cyclopentyl linkages. These copolymers are obtained via catalytic systems comprising dimethylsilyl(pentamethylcyclopentadienyl)(tert-butylamino)titanium dichloride and methylaluminoxane.

[0007] Activated methylaluminoxane (MAO) derived from partially hydrolyzed trimethylaluminum (TMA) can effectively activate a type of catalyst called metallocene used in olefin polymerization. MAO has become the industry's preferred aluminum co-catalyst (also known as an activator). It is commercially available in the form of a 10% to 30% by weight solution in an aromatic diluent (usually toluene).

[0008] Significant efforts have been devoted to improving the effectiveness of catalyst systems based on methylaluminoxanes or modified methylaluminoxanes for olefin polymerization. For example, WO 2009 / 029857 demonstrates the formation of dimethylaluminum cations (AlMe2) from MAO by treatment with a Lewis base (e.g., tetrahydrofuran) in toluene solution. + Lewis base-stabilized dialkylaluminum cations, such as AlMe2 + It can also be derived from non-MAO sources and used as an activator for metallocene catalysts; see, for example, Klosin et al., WO 2000 / 011006 and Klosin, J. et al. (2000) “Ligand Exchange and AlkylAbstraction Involving (Perfluoroaryl)boranes and -alanes with Aluminum and Gallium Alkyls,” Organometallics Volume 19(23), pp. 4684-4686; US 9090720 shows that metallocene ethylene diindene zirconium dimethoxylate (EtInd2Zr(OMe)2) with a dimethoxy leaving group abstracts AlMe2 from MAO. + To form [EtInd2Zr(μ-OMe)2AlMe2] + The substance is slowly alkylated to form the fully activated substance [EtInd2Zr(μ-Me)2AlMe2]. + AlMe2 from MAO + Strong evidence of activation. Fully activated [EtInd2Zr(μ-Me)2AlMe2] + The substance is similar to other MAO-activated metallocenes, and it also forms metallocene-dialkylaluminum cations, such as [Cp2Zr(μ-Me)2AlMe2]. + Or [Cp2Ti(μ-Me)2AlMe2] + , such as Babushkin, DE 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., Vol. 124(43), pp. 12869-12873 and Sarzotti, DM et al., (2007) “A kinetic study of metallocene-catalyzed ethylene polymerization using different aluminoxanecocatalysts,” J. Polymer Sci. A Examples in Volume 45(9), pp. 1677-1690, describe the activation of zirconium diazophora catalyst precursors by MAO; see also Bryliakov, KP et al. (2004) " 1 H and 13 C NMRSpectroscopic Study of Titanium(IV) Species Formed by Activation of Cp2TiCl2and [(Me4C5)SiMe2N t Bu]TiCl2 with Methylaluminoxane (MAO),” Organometallics Volume 23(1), pp. 149-152, describes the activation of a titanium diacene catalyst precursor via MAO. Although the structure of MAO remains unclear, freshly prepared activated MAO shows evidence of coordinated TMA in MAO, consistent with Sinn and Kaminsky (1999) (Sinn, et al., “Formation, Structure, and Mechanism of Oligomeric Methylaluminoxane”, in Kaminsky (ed.), Metalorg. Cat. for Synth. & Polym., The experimental formula (Al4O3Me6)4(TMA) described in Springer-Verlag, page 105 1-2 Consistent. The coordinated TMA and free TMA are in equilibrium, and the attempt to physically remove all free TMA leads to the formation of a more stable, inactive MAO gel. Not wanting to be bound by theory, but merely to aid in a better understanding of the gelation process, this study uses a Sinn / Kaminsky-based MAO formula (Al₄O₃Me₆)₄(TMA). 1-2 Scheme 1 is constructed using the proposed diagrammatic structure. The actual MAO structure may differ.

[0009] Option 1

[0010]

[0011] Studies have shown that the coordinated TMA in MAO actually acts as a pre-catalyst for the ionization of AlMe2. + The source, while the free TMA in MAO in equilibrium with the coordinated TMA acts as an alkylating agent, as shown in Scheme 2. For clarity, the main structure of MAO is represented by circles (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. Patents 8,575,284 (2013) and 9,090,720 (2015)):

[0012] Option 2

[0013] .

[0014] Unbound by theory, it is believed that a significant amount of free TMA needs to be maintained in the active MAO solution to stabilize the active MAO composition, for example, to stabilize the MAO molecular structure capped with coordinated TMA, thereby reducing the chance of dimerization / oligomerization to ultimately form the less active or inactive gel of Scheme 1 (Al:O:Me close to 1:1:1). Therefore, the physical removal of free TMA not only results in poorly soluble MAO gels, limited by the difficulty in loading or finding solvents for solution polymerization, but also leads to the loss of coordinated TMA, a reduction in the number of active MAO molecules, and consequently, lower activation efficiency.

[0015] Nevertheless, post-metallocene catalysts containing polar ligands, such as oxygen and / or nitrogen donors, and restricted geometry complex (CGC) catalysts have shown challenges in activation with conventional MAO, exhibiting low catalyst activity and short catalyst lifetime. Unbound by theory, the poor activity and short catalyst lifetime are believed to be due to the presence of free TMA in MAO, which can alkylate pre-catalyst transition metal centers bonded to heteroatoms (Scheme 3, using Zr centers as an example), similar to the alkylation of metallocenes with dichloride leaving groups in Scheme 2.

[0016] Option 3

[0017] .

[0018] There is a need for improved catalyst systems with complementary catalyst-activator pairs that enable the polymerization of monoolefins and conjugated dienes with high activity (e.g., within the same process window) to provide commercially scalable polymerization (e.g., high activity under mild conditions).

[0019] References used in the disclosure statement (37 CFR 1.97(h)) may 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; 10,457,765; 10,844,149; 10,822,475; 8,039,565; 11,155,656; 11,136,422; 11,254,804; 11,286,369; 7,547,654; 10,752,712; US Patent Publication Nos.: 2017 / 0073450; 2022 / 0135717; PCT Publications: WO 2021 / 155168; WO 2021 / 155158; WO 2017 / 097831; WO 2022 / 112699; WO 2022 / 106769; WO 2021 / 053294; ​​WO 2021 / 023924; WO2020 / 128249; WO 2022 / 112700; WO 2022 / 112692; WO 2022 / 112690; WO 2022 / 112691; WO 2020 / 070443; Foreign Patent: CN113174401; CN113307901; EP3988583; FR3108610;JP5656686; JP5675434; JP2013155360; JP2013147567; JP5612511; JP2013159626; Journal Article: Reddy, A. et al. (2021) “Block Copolymers beneath the Surface: Measuring and Modeling Complex Morphology at the Subdomain Scale,” Macromolecules Volume 54(20), pages 9445-9451. Summary of the Invention

[0020] This disclosure relates to catalyst systems containing catalyst compounds and activators, and their uses.

[0021] In some implementations, the solution catalyst system comprises:

[0022] 1) Anionic modified alkylaluminoxanes, and / or

[0023] Cationic modified alkylaluminoxanes, wherein, based on the total aluminum content of the solution catalyst system determined by titration with tetrahydrofuran, the solution catalyst system has 0 wt% to approximately 2 wt% Al from noncoordinated trialkylaluminum compounds; and

[0024] 2) The compound shown in formula (I):

[0025] (I)

[0026] in:

[0027] M is a group 3 transition metal or a lanthanide metal;

[0028] E and E' are independently oxygen, sulfur, or NR. A , where R A Independently, it is hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups or groups containing heteroatoms;

[0029] Q is a group 14 atom, a group 15 atom, or a group 16 atom;

[0030] A 1 QA 1 It is part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms, which connects A via a 3-atom bridge. 2 Connect to A 2 , where Q is the central atom of the 3-atom bridge;

[0031] A 1 and A 1 Each independently is carbon, nitrogen, or C(R) B ), where R B Selected from hydrogen, C1-C 20 Hydrocarbon groups and substituted C1-C 20 hydrocarbon group;

[0032] It is a divalent group containing 2 to 40 non-hydrogen atoms, which connects A atoms via 2-atom bridges. 1 Linked to the E-bonded aryl group shown in formula (I), and A 3 and A 2 They can be combined to form substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, wherein the substituents on the rings can be joined to form additional rings.

[0033] It is a divalent group containing 2 to 40 non-hydrogen atoms, which connects A atoms via 2-atom bridges.1 Linked to the E′-bonded aryl group shown in formula (I), and A 3 and A 2 They can be combined to form substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, wherein the substituents on the rings can be joined to form additional rings.

[0034] L is an independent Lewis base;

[0035] X′ is an anionic ligand;

[0036] Any two L groups can bond together to form a bidentate Lewis base;

[0037] The X' group can combine with the L group to form a monoanionic bidentate group;

[0038] n is 1;

[0039] m is 0, 1, or 2;

[0040] n+m is not greater than 3; and

[0041] R 1 R 2 R 3 R 4 R 1 ′、R 2 ′、R 3 ′ and R 4 Each is independently hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon group, 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 pairs of rings may join to form one or more substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, and wherein the substituents on the rings may join to form additional rings. In some embodiments, this disclosure provides a polymerization method comprising contacting one or more olefin monomers with a catalyst system comprising an electron-withdrawing group-modified alkylaluminoxane activator and a catalyst of formula (I) of this disclosure.

[0042] In some embodiments, this disclosure provides a polymerization method comprising contacting one or more olefin monomers with a catalyst system comprising an alkylaluminoxane activator modified with a siloxy donor group and a catalyst of formula (I) of this disclosure. Attached Figure Description

[0043] Figure 1 It is a commercial MAO solution in THF-d8 according to some implementation schemes. 1 H NMR spectrum.

[0044] Figure 2A -B is a 30% commercially available MAO solution after KF treatment. 1 H NMR spectrum; Figure 2A The upper solution phases after treatment with 2, 4, 7, and 10 mol% KF are shown respectively; and Figure 2B The final K is shown + (F-MAO) - The clathrate phase and the untreated solution MAO used for comparison. Detailed Implementation

[0045] definition

[0046] "Anionic modified alkylaluminoxanes" refers to alkylaluminoxanes that have undergone certain treatments with at least one new element or at least one electron-withdrawing group. For example, introducing an F atom or a C6F5 group into the structure of an alkylaluminoxane yields fluorinated MAO. Therefore, reagents used to convert conventional alkylaluminoxanes into anionic modified alkylaluminoxanes are called anionic modifiers; for example, (NH4)2SiF6 is called an anionic modifier because of its ability to convert conventional MAO into fluorinated MAO.

[0047] The terms “anion-modified alkylaluminoxane”, “anion-modified aluminumoxane”, “electron-withdrawing group-modified alkylaluminoxane”, or “electron-withdrawing group-modified aluminumoxane” are used interchangeably.

[0048] "Catonic-modified alkylaluminoxanes" refers to alkylaluminoxanes that have undergone certain treatments, wherein ionic alkylaluminoxanes are formed when the cation is stabilized by at least one electron-donating compound, such as a chelating agent, for example, octamethyltrisiloxane (OMTS). Therefore, reagents used to convert conventional alkylaluminoxanes into catonic-modified alkylaluminoxanes are called catonic modifiers; for example, OMTS is called a catonic modifier because of its ability to convert conventional MAO into ionic MAO. However, OMTS is such a chelating agent that it can form a very stable dialkylaluminum cationic complex [AlMe2(OMTS)] stabilized by a chelating donor. + As shown in scheme 4I-b, it can be heated together with at least one free TMA molecule to decompose into monodentate donor-stabilized dialkylaluminum cations containing a "silanoxy donor group" (e.g., scheme 4I-a, using a trimethylsilanoxy donor group as an example), to more easily release AlMe2. + To improve activation efficiency. Silyl oxy donor groups can also be introduced through other reactions, such as the reaction of Me3SiOH with TMA in MAO to form Me3SiOAlMe2 in situ.

[0049] Option 4

[0050]

[0051] The terms “cationically modified alkylaluminoxane”, “cationically modified aluminumoxane”, “silanoxy-donor group modified alkylaluminoxane”, “silanoxy-donor group modified aluminumoxane”, “ionic alkylaluminoxane” and “ionic aluminumoxane” are used interchangeably.

[0052] "Non-coordinated alkylaluminum" or "free alkylaluminum" has the same meaning to refer to aluminum compounds in monomeric or dimer form that are not chemically bonded to the aluminoxane structure and contain at least one alkyl group (e.g., Me, Et, iBu, Oct). Although free alkylaluminum can become coordinated by exchanging with a coordinated alkylaluminum on the aluminoxane structure, the concentration of free alkylaluminum is maintained by regeneration from the original coordinated alkylaluminum under the same conditions.

[0053] The terms aluminoxane, alumoxane, alkylaluminoxane, and alkylalumoxane are used interchangeably.

[0054] Sometimes only alkylaluminum is used to indicate free alkylaluminum, for example, TMA means free TMA.

[0055] "None" or "Contains no" means that it is undetectable by current analytical methods (e.g., NMR spectroscopy or conventional wet titration). "Low content" means 2 wt% or 2 mol% or less of the total identical elements in the system. For example, low free TMA means that the free TMA content in Al weight (or mol) is 2 wt% (or mol%) or less of the total Al weight (or mol%) in the MAO composition. In some embodiments, "none" or "Contains no" includes the description "low content". For example, MAO without TMA may refer to free TMA content in Al weight or 2 mol% or less of the total Al content in the MAO.

[0056] For convenience, "F-MAO" refers to anion-modified MAO with little or no free TMA content, while ionic MAO refers to cationic-modified MAO with little or no free TMA content.

[0057] An "electron-withdrawing group" is a group X on a compound that can react with an alkylaluminum compound to form an AlR2X compound in situ, where R = C1-C8 is a hydrocarbon group. This group can replace the coordinating alkylaluminum in the alkylaluminoxane composition to completely or partially block the coordination and free alkylaluminum balance in the alkylaluminoxane solution, i.e., a so-called coordination and free alkylaluminum balance blocker. Examples of X include, but are not limited to, F, C6F5, OC6F5, etc. Therefore, the term "electron-withdrawing compound" can refer to a compound containing at least one electron-withdrawing group X, which can react with an alkylaluminum compound to form an AlR2X compound, where R = C1-C8 is a hydrocarbon group. This group can replace the coordinating alkylaluminum, such as the coordinating TMA in MAO, to completely or partially block the coordination and free TMA balance in the MAO solution, i.e., a so-called coordination and free TMA balance blocker. For example, (NH4)2SiF6, SiF4, HOC6F5, etc. can be used to react with AlMe3, AlEt3, and AlOct3 in MAO compositions to form AlMe2F, AlEt2F, AlOct2F, AlMe2(OC6F5), AlEt2(OC6F5), and AlOct2(OC6F5) in situ, respectively.

[0058] "Chlorinating agent or compound" means a compound having multiple donor groups to form a chelate structure with dialkylaluminum cations in an alkylaluminoxane system. Preferred chelating agents or compounds contain multiple silanoxy donor groups, such as octamethyltrisiloxane (OMTS). Examples of chelating agents include, but are not limited to, linear or cyclic polysiloxanes, such as octamethyltrisiloxane (OMTS), octamethylcyclotetrasiloxane, decamethyltetrasiloxane, hexamethylcyclotrisiloxane, hexaphenylcyclotrisiloxane, etc.

[0059] "Monodentate reagents or compounds" means compounds that have a single donor group to form a non-chelate structure with dialkylaluminum cations in alkylaluminoxane systems. Examples of monodentate reagents include, but are not limited to, compounds having a silaneoxy donor group containing a single oxygen atom, such as hexamethyldisiloxane, hexaphenyldisiloxane, hexaethyldisiloxane, dimethylaluminumtrimethylsiloxane, diethylaluminumtriethylsiloxane, etc.; more preferably, monodentate reagents are alkylaluminum modified with silaneoxy donor groups, such as dimethylaluminumtrimethylsiloxane, diethylaluminumtrimethylsiloxane, diisobutylaluminumtrimethylsiloxane, dimethylaluminumtriethylsiloxane, diethylaluminumtriethylsiloxane, diisobutylaluminumtriethylsiloxane, dimethylaluminumtripropylsiloxane, diethylaluminumtripropylsiloxane, diisobutylaluminumtripropylsiloxane, dimethylaluminumtriphenylsiloxane, diethylaluminumtriphenylsiloxane, diisobutylaluminumtriphenylsiloxane, etc.; most preferably, monodentate reagents are those generated in situ by decomposition of MAO compositions treated with chelating agents, such as heating OMTS-treated MAO to produce dimethylaluminumtrimethylsiloxane, as shown in Ib to Ia of Scheme 4.

[0060] "Olefin," optionally referred to as "alkene," is a straight-chain, branched, or cyclic compound having at least one double bond between carbon and hydrogen. For the purposes of this specification and the appended claims, when a polymer or copolymer is referred to as containing an olefin, the olefin present in such polymer or copolymer is a polymeric form of an olefin. For example, when a copolymer is referred to as having an "ethylene" content of 35% to 55% by weight, it should be understood that the monomer units in the copolymer are derived from ethylene in the polymerization reaction, and that said derived units are present at 35% to 55% by weight based on the weight of the copolymer. A "polymer" has two or more identical or different monomer units. A "homopolymer" is a polymer having identical monomer units. A "copolymer" is a polymer having two or more monomer units that are different from each other. A "terpolymer" is a polymer having three monomer units that are different from each other. Thus, as used herein, the definition of a copolymer includes terpolymers, etc. The term "different" used to refer to monomer units means that the monomer units differ from each other by at least one atom or are isomerically different. "Ethylene polymer" or "ethylene copolymer" is a polymer or copolymer containing at least 50 mol% ethylene-derived units, "propylene polymer" or "propylene copolymer" is a polymer or copolymer containing at least 50 mol% propylene-derived units, and so on.

[0061] Ethylene should be considered an α-olefin.

[0062] Unless otherwise stated, the term "C" is used in conjunction with other terms. n "This means a hydrocarbon (one or more) with n carbon atoms (one or more) per molecule, where n is a positive integer."

[0063] The term "hydrocarbon" refers to a class of compounds containing hydrogen bound to carbon, and encompasses (i) saturated hydrocarbons, (ii) unsaturated hydrocarbons, and (iii) mixtures of hydrocarbons (saturated and / or unsaturated), including mixtures of hydrocarbons with different n values. Similarly, "C m -C y "A group or compound refers to a group or compound containing a total number of carbon atoms ranging from m to y. Therefore, C1-C..." 50 Alkyl groups are alkyl groups that contain a total number of carbon atoms ranging from 1 to 50.

[0064] The terms "group", "radical", and "substituent" are used interchangeably.

[0065] The terms "hydrocarbyl radical," "hydrocarbyl group," or "hydrocarbyl" are used interchangeably and are defined as a group consisting only of hydrogen and carbon atoms. Hydrocarbyl groups can be C1-C. 100 A functional group, which can be straight-chain, branched, or cyclic, and when cyclic, can be aromatic or non-aromatic. Examples of such functional groups include, but are not limited to, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, etc.; and aryl groups such as phenyl, benzyl, naphthyl, etc.

[0066] Unless otherwise specified (e.g., the definition of "substituted hydrocarbon group", "substituted aromatic group", etc.), the term "substituted" means that at least one hydrogen atom has been substituted by at least one non-hydrogen group, such as a hydrocarbon group, a heteroatom or heteroatom-containing group, such as a halogen group (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 R Each is independently a hydrocarbon group or a haloalkyl group, and there are two or more R groups. They can be joined together to form substituted or unsubstituted, fully saturated, partially unsaturated, or aromatic cyclic or polycyclic structures, or at least one heteroatom of which has been inserted into the hydrocarbon ring.

[0067] The term "substituted hydrocarbon group" means a hydrocarbon group in which at least one hydrogen atom has been substituted by: at least one heteroatom (e.g., a halogen group, such as Br, Cl, F, or I) or a heteroatom-containing group (e.g., a 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 R Each is independently a hydrocarbon group or a haloalkyl group, and there are two or more R groups. They can be joined together to form substituted or unsubstituted, fully saturated, partially unsaturated, or aromatic cyclic or polycyclic structures, or in which at least one heteroatom has been inserted into the hydrocarbon ring.

[0068] The term “aryl” or “aromatic group” means an aromatic ring and its substituted 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 have been replaced by a heteroatom, such as N, O, or S. As used herein, the term “aromatic compound” also refers to a pseudoaromatic heterocycle, which is a heterocyclic substituent having properties and structure (almost planar) similar to aromatic heterocyclic ligands, but which, by definition, is not an aromatic compound; similarly, the term aromatic compound also refers to a substituted aromatic compound.

[0069] The term "substituted aromatic" means an aromatic group in which one or more hydrogen groups are replaced by a hydrocarbon group, a substituted hydrocarbon group, a heteroatom, or a heteroatom-containing group.

[0070] A "substituted phenolate" is a phenolate group in which at least one, two, three, four, or five hydrogen atoms at positions 2, 3, 4, 5, and / or 6 are replaced by at least one non-hydrogen group, such as a hydrocarbon 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. Substitution, where R Each is independently hydrogen, alkyl, or haloalkyl, and contains two or more R groups. They can be joined together to form substituted or unsubstituted, fully saturated, partially unsaturated, or aromatic cyclic or polycyclic structures, wherein the 1-position is a phenolic salt group (Ph-O-, Ph-S-, and Ph-N(R)). ^ )- group, wherein R ^ It is hydrogen, C1-C 40 Hydrocarbon group, C1-C 40 (Substituted hydrocarbon groups, heteroatoms, or heteroatom-containing groups). For example, the "substituted phenolic salt" group in the catalyst compounds described herein is represented by the following formula:

[0071]

[0072] Where R 18 It is hydrogen, C1-C 40 Hydrocarbon groups (e.g., C1-C) 40 Alkyl) or C1-C 40 Substituted hydrocarbon groups, heteroatoms, or heteroatom-containing groups, E 17 Is it oxygen, sulfur, or NR? 17 And R 17 R 19 R 20 and R 21 Each is independently selected from hydrogen, C1-C 40 Hydrocarbon groups (e.g., C1-C) 40 Alkyl) or C1-C 40 Substituted hydrocarbon groups, heteroatoms, or heteroatom-containing groups, or R 18 R 19 R 20 and R 21 Two or more of them join together to form C4-C 62 Cyclic or polycyclic structures, or combinations thereof, and the wavy lines indicate the positions where the substituted phenolic groups bond with the remainder of the catalyst compound. R 18 R 19 R 20 and / or R 21At least one of them is not hydrogen.

[0073] "Alkyl-substituted phenolic salts" are phenolic salt groups in which at least one, two, three, four, or five hydrogen atoms at positions 2, 3, 4, 5, and / or 6 are replaced by at least one alkyl group, such as C1-C6. 40 Or C2-C 20 Or C3-C 12 Alkyl groups, such as methyl, ethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, adamantyl, etc., including their substituted analogues.

[0074] "Aryl-substituted phenolic salts" are phenolic salt groups in which at least one, two, three, four, or five hydrogen atoms at positions 2, 3, 4, 5, and / or 6 are replaced by at least one aryl group, such as C1-C6. 40 Or C2-C 20 Or C3-C 12 Aryl groups, such as phenyl, 4-fluorophenyl, 2-methylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, mesitylene, 2-ethylphenyl, naphthyl, etc., including their substituted analogs.

[0075] The term "ring atom" refers to an atom that is part of a ring structure. According to this definition, benzyl has 6 ring atoms, and tetrahydrofuran has 5 ring atoms.

[0076] A heterocyclic ring, also known as a heterocycle, is a ring containing heteroatoms in its ring structure, as opposed to a "heteroatom-substituted ring" where hydrogen atoms on the ring atoms are replaced by heteroatoms. For example, tetrahydrofuran is a heterocycle, and 4-N,N-dimethylamino-phenyl is a heteroatom-substituted ring. A substituted heterocycle is defined as a heterocycle in which one or more hydrogen groups are replaced by hydrocarbon groups, substituted hydrocarbon groups, heteroatoms, or heteroatom-containing groups.

[0077] A substituted hydrocarbon ring is a ring composed of carbon and hydrogen atoms, wherein one or more hydrogen groups are replaced by a hydrocarbon group, a substituted hydrocarbon group, a heteroatom, or a heteroatom-containing group.

[0078] For the purposes of this disclosure, with respect to catalyst compounds (e.g., substituted bis(phenolic) catalyst compounds), the term "substituted" means that the hydrogen group has been replaced by a hydrocarbon 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 3rd grade, of which R Each is independently hydrogen, alkyl, or haloalkyl, and contains two or more R groups. They can be joined together to form substituted or unsubstituted, fully saturated, partially unsaturated, or aromatic cyclic or polycyclic structures, or in which at least one heteroatom has been inserted into the hydrocarbon ring.

[0079] A tertiary hydrocarbon group has three carbon atoms bonded to three other carbon atoms. When the hydrocarbon group is an alkyl group, the tertiary hydrocarbon group is also called a tertiary alkyl group. Examples of tertiary hydrocarbon groups include tert-butyl, 2-methylbut-2-yl, 2-methylhex-2-yl, 2-phenylprop-2-yl, 2-cyclohexylprop-2-yl, 1-methylcyclohexyl, 1-adamantyl, bicyclo[2.2.1]hept-1-yl, etc. A tertiary hydrocarbon group can be described by the following formula:

[0080] ,

[0081] Where R A R B and R C Independently, there are hydrocarbon groups or substituted hydrocarbon groups that may optionally bond to each other, and the wavy lines indicate the positions where tertiary hydrocarbon groups form bonds with other groups.

[0082] A tertiary hydrocarbon group can be a cyclic tertiary hydrocarbon group. A cyclic tertiary hydrocarbon group is defined as a tertiary hydrocarbon group that forms at least one alicyclic (non-aromatic) ring. Cyclic tertiary hydrocarbon groups are also called alicyclic tertiary hydrocarbon groups. In the case where the hydrocarbon group is an alkyl group, cyclic tertiary hydrocarbon groups are also called cyclic tertiary alkyl groups or alicyclic tertiary alkyl groups. Examples of cyclic tertiary hydrocarbon groups include 1-adamantyl, 1-methylcyclohexyl, 1-methylcyclopentyl, 1-methylcyclooctyl, 1-methylcyclodecyl, 1-methylcyclododecyl, bicyclo[3.3.1]non-1-yl, bicyclo[2.2.1]hept-1-yl, bicyclo[2.3.3]hex-1-yl, bicyclo[1.1.1]pent-1-yl, bicyclo[2.2.2]oct-1-yl, etc. Cyclic tertiary hydrocarbon groups can be described by formula (B):

[0083] (B),

[0084] Where R A It is a hydrocarbon group or a substituted hydrocarbon group, R DEach is independently hydrogen or a hydrocarbon group or a substituted hydrocarbon 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 can optionally bond to each other to form another ring.

[0085] When a cyclic tertiary hydrocarbon group contains more than one alicyclic ring, it can be called a polycyclic tertiary hydrocarbon group, or if the hydrocarbon group is an alkyl group, it can be called a polycyclic tertiary alkyl group.

[0086] The terms "alkyl group" and "alkyl" are used interchangeably throughout this disclosure. For the purposes of this disclosure, "alkyl" is defined as a C1-C group that can be straight-chain, branched, or cyclic. 100 Alkyl groups. Examples of such groups may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, etc., including their substituted analogs. A substituted alkyl group is a group in which at least one hydrogen atom of the alkyl group has been substituted by at least a non-hydrogen group, such as a hydrocarbon 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 3rd grade, of which R Each is independently hydrogen, alkyl, or haloalkyl, and contains two or more R groups. They can be joined together to form substituted or unsubstituted, fully saturated, partially unsaturated, or aromatic cyclic or polycyclic structures, or in which at least one heteroatom has been inserted into the hydrocarbon ring.

[0087] When the alkyl, alkenyl, alkoxy, or aryl isomers mentioned (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl) are present, all isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl) are explicitly disclosed when the alkyl, alkenyl, alkoxy, or aryl isomers are mentioned without specifying a particular isomer (e.g., butyl).

[0088] As used herein, Mn is the number-average molecular weight, Mw is the weight-average molecular weight, and Mz is the z-average molecular weight; wt% is the weight percentage, and mole% is the mole percentage. 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 in g / mol (g mol) -1 ).

[0089] The following abbreviations may be used in this article: Me is methyl, Et is ethyl, iBu is isobutyl, Oct is octyl, MAO is methylaluminoxane, Bn is benzyl (i.e., CH2Ph), THF (also known as thf) is tetrahydrofuran, RT is room temperature (23°C unless otherwise specified), tol is toluene, Cp is cyclopentadienyl, NMR is nuclear magnetic resonance, and TMA is trimethylaluminum.

[0090] "Catalyst system" is a combination of at least one catalyst compound, an activator, an optional co-activator, and an optional support material. When "catalyst system" is used to describe such a combination before activation, it means an unactivated catalyst complex (pre-catalyst) together with an activator and an optional co-activator. When it is used to describe such a combination after activation, it means an activated complex and an activator or other charge-balanced structural component. The catalyst compound may be neutral, as in the pre-catalyst, or charged, as in the activated catalyst system, with counterions. For the purposes of this disclosure and its claims, when a catalyst system is described as comprising a neutral, stable form of a component, it is fully understood by those skilled in the art that the ionic form of the component is the form in which it reacts with the monomer to produce a polymer. A polymerization catalyst system is a catalyst system that can polymerize monomers into polymers. Furthermore, catalyst compounds and activators (including support-bonded activators) represented by the formulas herein include catalyst compounds and activators in both neutral and ionic forms.

[0091] In the description herein, a catalyst may be described as a catalyst, catalyst precursor, precatalyst compound, catalyst compound, or transition metal compound, and these terms may be used interchangeably.

[0092] An anionic ligand is a negatively charged ligand that donates one or more pairs of electrons to a metal ion. The terms "anionic donor" and "anionic ligand" are used interchangeably. Examples of anionic donors include, but are not limited to, methyl, chloride, fluoride, alkoxide, aryloxide, alkyl, alkenyl, thiolate, carboxyl, amino, benzyl, hydrogen, amidinate, amidate, and phenyl. Two anionic donors can combine to form a dianionic group.

[0093] 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, phosphine, diethyl ether, tetrahydrofuran, dimethyl sulfide, triethylamine, pyridine, alkenes, alkynes, alene, and carbene. Lewis bases can bond together to form bidentate or tripentate Lewis bases.

[0094] For the purposes of this disclosure and its claims, phenol salt donors may include Ph-O-, Ph-S-, and Ph-N-. )- group, in which It is hydrogen, C1-C 40 Hydrocarbon group, C1-C 40 A substituted hydrocarbon group, heteroatom, or heteroatom-containing group, and Ph is an optionally substituted phenyl group.

[0095] This disclosure relates to a catalyst system comprising a combination of a rare-earth-based bis(phenolate) catalyst and an alkylaluminum-free aluminoxane (e.g., a TMA-free aluminoxane), wherein the alkylaluminum-free aluminoxane is defined as having 0 wt% to about 2 wt% Al from a non-coordinated trialkylaluminum compound based on the total Al metal weight in the system. This catalyst system can be used to produce copolymers of ethylene and butadiene at high conversion rates under mild conditions. This improved catalyst system provides a complementary catalyst-activator pair that provides highly active (e.g., within the same process window) polymerization of monoolefins and conjugated dienes to provide commercially scalable polymerization (e.g., high activity under mild conditions). The catalyst system of this disclosure is an attractive option for implementation into industrial-scale processes to produce copolymer materials (e.g., copolymer materials derived from ethylene and butadiene monomers) with customizable physical properties, polymer backbone structure, and different functional structural moieties at high throughput. Furthermore, polar side-chain structural moieties can be incorporated into the polymer chain during copolymerization. Such functionalized polymers can be desirable for the tire industry due to the enhanced interaction between the copolymer and one or more fillers present with the copolymer during its use as a tire material.

[0096] Furthermore, copolymers formed using the catalyst system of this disclosure can have a plurality of 1,2-cyclopentane units distributed along the polymer backbone. These units can be substantially uniformly distributed along the polymer backbone, which prevents crystallization (e.g., polyethylene blocks). Unbound from theoretical constraints, the substantially uniform distribution of 1,2-cyclopentane units along the polymer backbone can disrupt intra- and inter-chain interactions, thereby reducing the crystallinity of the polymer system (as demonstrated by the lower Tm value compared to polyethylene homopolymers). The activator of this disclosure can provide copolymers with a higher content of 1,2-cyclopentane units than copolymers prepared using conventional activators. The 1,2-cyclopentane units can provide increased stiffness to the copolymer, which can be beneficial for its use in tires.

[0097] This disclosure relates to catalyst systems, which include:

[0098] 1) Anionic modified alkylaluminoxanes, and / or

[0099] Cationic modified alkylaluminoxanes, wherein, as determined by titration of the alkylaluminoxane composition with tetrahydrofuran, the alkylaluminoxane composition has 0% to about 2% by weight of a noncoordinated trialkylaluminum compound based on the total aluminum content of the alkylaluminoxane composition; and

[0100] 2) The compound shown in formula (I):

[0101] (I)

[0102] in:

[0103] M is a group 3 transition metal or a lanthanide metal;

[0104] E and E' are independently oxygen, sulfur, or NR. A , where R A Independently, it is hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups or groups containing heteroatoms;

[0105] Q is a group 14 atom, a group 15 atom, or a group 16 atom;

[0106] A 1 QA 1' It is part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms, which connects A via a 3-atom bridge. 2 Connect to A 2' , where Q is the central atom of the 3-atom bridge;

[0107] A 1 and A 1' Each independently is carbon, nitrogen, or C(R) B), where R B Selected from hydrogen, C1-C 20 Hydrocarbon groups and substituted C1-C 20 hydrocarbon group;

[0108] It is a divalent group containing 2 to 40 non-hydrogen atoms, which connects A atoms via 2-atom bridges. 1 Linked to the E-bonded aryl group shown in formula (I), and A 3 and A 2 They can be combined to form substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, wherein the substituents on the rings can be joined to form additional rings.

[0109] It is a divalent group containing 2 to 40 non-hydrogen atoms, which connects A atoms via 2-atom bridges. 1 Linked to the E′-bonded aryl group shown in formula (I), and A 3 and A 2 They can be combined to form substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, wherein the substituents on the rings can be joined to form additional rings.

[0110] L is an independent Lewis base;

[0111] X′ is an anionic ligand;

[0112] Any two L groups can bond together to form a bidentate Lewis base;

[0113] The X' group can combine with the L group to form a monoanionic bidentate group;

[0114] n is 1;

[0115] m is 0, 1, or 2;

[0116] n+m is not greater than 3; and

[0117] R 1 R 2 R 3 R 4 R 1′ R 2′ R 3′ and R 4′ Each is independently hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon group, heteroatom or heteroatom-containing group, or R 1and 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 pairs of rings may join to form one or more substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocycles or unsubstituted heterocycles, each having 5, 6, 7 or 8 ring atoms, and wherein the substituents on the rings may join to form additional rings.

[0118] In some embodiments, this disclosure relates to a method for polymerizing olefins using a catalyst system having a trialkylaluminum-free alkylaluminoxane composition, wherein the trialkylaluminum-free alkylaluminoxane composition means that the free trialkylaluminum content in the alkylaluminoxane composition is zero or close to zero, for example, 2% by weight or 2 mol% or less, while being able to provide Al(alkyl)2 + The active sites of alkylaluminoxanes can be maintained or increased through treatment with anionic or cationic modifiers. Unlike the physical removal of free trialkylaluminum from alkylaluminoxanes that causes catalytic activity loss, active alkylaluminoxane compositions without trialkylaluminum produced via anionic or cationic modifiers maintain or improve the catalytic activity of various precatalysts. Unbound by theory, it is believed that alkylaluminoxane solutions treated with anionic modifiers (e.g., (NH4)2SiF6) or cationic modifiers (e.g., OMTS) convert all trialkylaluminum to Al(alkyl)2X (X = electron-withdrawing group), which can replace the coordinated trialkylaluminum to eliminate the balance between coordinated and free trialkylaluminum, or enable the alkylaluminoxane to ionize as an inclusion phase precipitate, thereby allowing physical separation from the free trialkylaluminum. Free trialkylaluminum is also called non-coordinated alkylaluminum or non-coordinated trialkylaluminum.

[0119] In some embodiments, this disclosure relates to a method for polymerizing olefins using a catalyst system having a TMA-free alkylaluminoxane composition (including TMA-free MAO), wherein TMA-free MAO means that the content of free TMA in the MAO is zero or close to zero, for example, 2% by weight or 2% by mol% or less, while being able to provide AlMe2 +The active sites of MAO can be maintained or increased through treatment with anionic or cationic modifiers. Unlike the physical removal of free TMA from MAO that causes a loss of activity, TMA-free active MAO compositions produced via anionic or cationic modifiers maintain or improve the catalytic activity of various precatalysts. Unbound by theory, it is believed that MAO solutions treated with anionic modifiers (e.g., (NH4)2SiF6, shown as Si-F in Scheme 4) or cationic modifiers (e.g., OMTS) will convert all TMA into AlMe2X (X = electron-withdrawing group, F in Scheme 4), which can replace coordinated TMA to eliminate the coordination and free TMA equilibrium (see Scheme 1), or enable the MAO composition to ionize as an inclusion phase precipitate, thereby allowing physical separation from free TMA (Scheme 4). Free TMA is also known as non-coordinated TMA.

[0120] In some embodiments, methods for preparing anionicly modified alkylaluminoxanes (also known as trialkylaluminum-free alkylaluminoxanes) include treating an alkylaluminoxane solution with an anionic modifier, such as an electron-withdrawing compound, capable of converting all trialkylaluminum (free and coordinated trialkylaluminum) into Al(alkyl)₂X (X = electron-withdrawing group) as the major derivative and optionally minor non-fluorinated inert alkylaluminum derivatives, depending on the structure of the electron-withdrawing compound used. Anionicly modified alkylaluminoxanes contain the electron-withdrawing group X.

[0121] In some embodiments, the method for preparing anionic modified alkylaluminoxanes includes introducing an alkylaluminoxane composition containing free trialkylaluminum and coordinated trialkylaluminum, and a fluorinated compound capable of converting most of the free and coordinated trialkylaluminum into Al(alkyl)₂F or Al(alkyl)₂(OC₆F₅) to form a modified alkylaluminoxane composition containing little or no free trialkylaluminum. The anionic modified alkylaluminoxane contains electron-withdrawing groups, and these electron-withdrawing groups include F or OC₆F₅ groups.

[0122] In some embodiments, a method for preparing TMA-free MAO (also known as anion-modified MAO) involves treating an MAO solution with an anion modifier, said anion modifier being, for example, an electron-withdrawing compound capable of converting all TMA (free and coordinated TMA) into AlMe2X (X = electron-withdrawing group) as the main derivative and optionally a minor non-fluorinated inert alkyl aluminum derivative, depending on the structure of the electron-withdrawing compound used. TMA-free MAO contains the electron-withdrawing group X.

[0123] In some embodiments, a method for preparing a TMA-free solution MAO composition includes introducing a solution MAO composition containing free TMA and coordinated TMA, and a fluorinated compound capable of converting most of the free and coordinated TMA into AlMe2F or AlMe2 (OC6F5), to form an anion-modified MAO composition with no or low free TMA content. The TMA-free MAO contains electron-withdrawing groups, and these electron-withdrawing groups include F or OC6F5 groups.

[0124] In some embodiments, the method for preparing cationic modified alkylaluminoxanes (also known as trialkylaluminum-free alkylaluminoxanes) includes treating an alkylaluminoxane solution with a cationic modifier, such as a chelating agent or a monodentate reagent, to form an ionic alkylaluminoxane composition, followed by a physical separation process to separate most of the free trialkylaluminum content, and a heating process to partially or completely convert the chelated ligands into monodentate ligands (one or more) with an optional additional free alkylaluminum charge. The cationic modified alkylaluminoxanes contain a portion of the chelating agent.

[0125] In some embodiments, the method for preparing cationic modified alkylaluminoxanes includes treating an alkylaluminoxane solution with a cationic modifier, such as OMTS, to form an ionic alkylaluminoxane composition, followed by a physical separation process to separate most of the free trialkylaluminum content, for example by phase separation, and heating the inclusion phase to partially or completely convert the OMTS ligand into dialkylaluminum trimethylsiloxide with residual free trialkylaluminum or an additional amount of free trialkylaluminum. The cationic modified alkylaluminoxane contains a portion of a chelating agent, and the chelating agent contains a silaneoxy group donor, such as dimethylaluminum trialkylsiloxide.

[0126] In some embodiments, a method for preparing TMA-free MAO (also known as cationic modified MAO) includes treating a solution of MAO with a chelating agent or a monodentate reagent to form an ionic MAO composition, followed by a physical separation process to separate most of the free TMA content, and a heating process to partially or completely convert the chelating ligand into one or more monodentate ligands with an optional additional free alkyl aluminum load, such as trimethylaluminum, triethylaluminum, or triisobutylaluminum.

[0127] In some embodiments, the method for preparing TMA-free MAO includes treating a solution of MAO with OMTS to form an ionic MAO composition, followed by a physical separation process to separate most of the free TMA content, such as by phase separation and heating the inclusion phase to partially or completely convert the OMTS ligand into a trimethylsilyloxy ligand with residual free TMA or an additional amount of free TMA, as shown in Embodiment 4. The TMA-free MAO contains a portion of a chelating agent, and the chelating agent contains a silyloxy donor, such as dimethylaluminumtrimethylsiloxane.

[0128] In some embodiments, this disclosure provides a polymerization method comprising contacting one or more olefin monomers with a precatalyst of this disclosure.

[0129] Formation of activator systems without non-coordinated alkyl aluminum

[0130] As described above, non-coordinated alkylaluminum (or free alkylaluminum), where "free" includes descriptions of "poor content," for example, MAO free of TMA can refer to the Al weight or moles of free TMA content based on 2 wt% or 2 mol% or less of the total Al content in the MAO, wherein the quantitative method for free alkylaluminum is described in the experimental section. Such a system free of non-coordinated alkylaluminum can be prepared by any one or two of the following methods:

[0131] A) In-situ anion-modified aluminum oxane, also known as anion-modified aluminum oxane.

[0132] Electron-withdrawing compounds can be used to treat conventional MAO solutions, such as WRGrace 30% MAO products containing free TMA, to introduce electron-withdrawing groups into the MAO composition. This is achieved by removing free TMA by converting it to AlMe2X (X = electron-withdrawing group) and replacing the coordinated TMA, while still maintaining the function of the coordinated TMA, i.e., providing AlMe2. + As an activator, as shown in Ic of Scheme 4. Therefore, electron-withdrawing compounds can also be called anionic modifiers. As shown in Scheme 4, strongly electron-withdrawing compounds have been found, such as compounds containing one or more highly reactive electron-withdrawing atoms or groups, such as compounds containing fluorine atoms or compounds containing pentafluorophenoxy (C6F5O-), which can convert free TMA in MAO in situ to AlMe2F or AlMe2 (OC6F5), and can act as a blocking agent (TEB agent) for the coordination and free TMA equilibrium. The TEB agent can replace the coordinated TMA (which becomes free TMA), thereby eliminating the coordination and free TMA equilibrium and providing more AlMe2 for pre-catalyst ionization. + Furthermore, the introduction of strongly electron-withdrawing atoms or groups onto the MAO anion provides a more dispersed MAO anionic charge, thereby weakening the active ion-pair interactions (as shown in Scheme 4). The overall result is the removal of free TMA and an improvement in the activity of the catalyst system. Therefore, converting all TMA in MAO to a TEB agent is a much more efficient method for removing free TMA from MAO while maintaining or improving activation efficiency, to obtain systems suitable for activating precatalysts constructed with ligands containing TMA-reactive heteroatom donors (e.g., N, O, S, and / or P donors in the ligands of post-metallocene precatalysts). The quantitative method for total TMA in the MAO composition is described in the Experimental Section.

[0133] In some implementations, the electron-withdrawing compound is an inorganic compound having the formula (A'):

[0134] A m B (u) X n (A')

[0135] In formula (A'), A is a cation; m is 0, 1, or 2, provided that when m is 0, B is H or an element of group 3, 4, 5, 6, 7, 13, 14, 15, 16, or 17, and when 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.

[0136] In some embodiments, the inorganic fluorinated 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. Ammonium hexafluorosilicate is preferred due to its high fluorination efficiency.

[0137] In some embodiments, the electron-withdrawing compound is an organometallic compound having the formula (B'):

[0138] R o M (u) X (u-o) (B')

[0139] Where R is C1-C 10 Hydrocarbon group; M is a group 13 or 14 element; when M is an Al group 13 element, o is 1; when M is a non-Al group 13 element, o is 1 or 2; and when M is a group 14 element, o is 1, 2 or 3; X is an electron-withdrawing atom or group; and u is the valence state of element M.

[0140] 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, MeAl(OC6F5)2.

[0141] In some embodiments, the anion-modified alkylaluminoxane (including anion-modified MAO) contains an electron-withdrawing group, and the electron-withdrawing group contains -F or -OC6F5.

[0142] B) Cationic modified aluminum oxanes, also known as ionic aluminum oxanes

[0143] Chelating agents, such as polysiloxanes or monodentate reagents, such as silanols and derived dialkylaluminum silicates, can be used as cationic modifiers to produce aluminoxane compositions free of non-coordinated trialkylaluminum. Chelating agents, such as OMTS, can precipitate aluminoxanes, such as MAO, as ionic aluminoxanes (e.g., inclusion complexes) to allow their separation from free alkylaluminum. Various organic or organometallic compounds are suitable for forming ionic aluminoxanes to allow separation from free alkylaluminum. In some embodiments, various aluminoxanes can be used to form stable ionic alkylaluminoxanes, such as methylaluminoxanes. In the formation of stable ionic aluminoxanes, the denser lower liquid phase (or inclusion complex phase) can be readily separated from the upper solution phase by conventional separation techniques, such as phase splitting, decantation, or drainage.

[0144] Chelating agent-derived ionic MAOIn 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 hydrocarbon-based aluminum oxane, such as an alkyl aluminum oxane, and a chelating agent, said chelating agent being a hydrocarbon-based polysiloxane, such as a hydrocarbon-based trisiloxane. In some embodiments, the chelated hydrocarbon-based polysiloxane compound may have at least three silicon atoms in the molecule, separated from each other by oxygen atoms, such that there is a straight, branched, or cyclic backbone with alternating Si and oxygen atoms, wherein the remaining portion of the four valence bonds of each silicon atom is satisfied by a monovalent hydrocarbon group. The hydrocarbon-based polysiloxane may have up to 18 or more silicon atoms in the molecule. The monovalent hydrocarbon groups of the polysiloxane may each independently contain up to about 18 carbon atoms and may be, for example, alkyl, cycloalkyl, aryl, arylalkyl, etc.

[0145] In some embodiments, the chelating agent may include an agent having the formula R(SiR2O). n SiR3 is a multidentate siloxane, wherein each R is independently hydrogen, an alkyl group (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl), an alkenyl, an aryl, or a heteroatom-substituted hydrocarbon group, and n = 2-8. In some embodiments, each R is methyl. In some embodiments, the chelating agent may include a compound having the formula (SiR2O). n Cyclic polydentate siloxanes, wherein R is independently hydrogen, alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl), alkenyl, aryl, or heteroatom-substituted hydrocarbon group, and n = 3-6.

[0146] Non-limiting examples of such polysiloxanes include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, octamethyltrisiloxane (OMTS), decamethyltetrasiloxane, dodecylpentasiloxane, tetradecylhexasiloxane, 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-tetra(3,3,3-trifluoropropyl)1,3,5,7-tetramethylcyclosiloxane (as an example of a heteroatom-containing substituent on a polydentate compound).

[0147] In some implementations, it contains a chelating ligand (e.g., [AlMe2(OMTS)]). + Stabilized dialkylaluminum cations in ionic alkylaluminoxanes (e.g., ionic MAO) can be heated to become more reactive, presumably by forming less stable monodentate complexes upon heating to facilitate the release of dialkylaluminum cations (e.g., AlMe2). + ), such as through 1 Structure Ia containing a silanoxy (trimethylsilanoxy) group, as observed by H-NMR spectroscopy:

[0148] (Ia).

[0149] The heating temperature can be from about 40°C to about 130°C, for example from about 60°C to about 110°C, or from about 80°C to about 100°C. The heating time can be from about 30 minutes to about 24 hours, for example from about 2 hours to about 12 hours, or from about 4 hours to about 8 hours. Aging in an environment can also decompose the chelated complex to improve activation efficiency, but it will take longer, for example, 24 hours, 2 days, or 1 week or longer.

[0150] Ionic MAO derived from monodentate reagent Alternatively, ionic aluminum oxanes can be formed by in-situ conversion of free alkyl aluminum in alkyl aluminum oxanes, such as TMA in MAO compositions, using silanol SiR3OH to form a monodentate coordination compound R3SiOAlR2 (e.g., R=Me) to act as a dialkyl aluminum cation stabilizer and to eliminate or reduce free alkyl aluminum. This is necessary for solution aluminum oxane systems because the process of removing free alkyl aluminum in solution is challenging. 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 a heteroatom-containing group. In some embodiments, R is each methyl. Heating is optional for monodentate reagent treatment.

[0151] Precatalyst compounds

[0152] The terms “catalyst,” “catalyst compound,” “catalyst complex,” “transition metal complex,” “transition metal compound,” “precatalyst compound,” and “precatalyst complex” are used interchangeably to describe transition metal or lanthanide metal complexes that, when combined with a suitable activator, form olefin polymerization catalysts.

[0153] In at least one embodiment, this 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 a lanthanide metal having monodentate or polydentate ligands (e.g., bidentate, tripentate, or tetradentate ligands), wherein a heteroatom of the catalyst (e.g., phosphorus, oxygen, nitrogen, or sulfur) is chelated with a metal atom of the catalyst. Non-limiting examples include bis(phenolic salts). In at least one embodiment, the Group 3 transition metal or lanthanide metal atom is selected from Sc, Y, and La.

[0154] The catalyst disclosed herein may be a "post-metallocene" catalyst having one or more oxygen and / or nitrogen atoms. For example, the catalyst disclosed herein may be a metal complex having a metal selected from Group 3 or lanthanides, and a tripentate bianion ligand containing two anion donor groups and a neutral Lewis base donor, wherein the neutral Lewis base donor is covalently bonded between the two anion donors, and wherein the metal-ligand complex is characterized by a pair of 8-membered metal rings.

[0155] The catalyst complexes disclosed herein comprise a metal selected from Group 3 of the periodic table or lanthanides, a tripentate bianotic ligand containing two anion donor groups and a neutral heterocyclic Lewis base donor, wherein the heterocyclic donor is covalently bonded between the two anion donors. In some embodiments, the tripentate bianotic ligand is characterized by a central heterocyclic donor group and two phenolic salt donors, and the tripentate ligand is coordinated with the metal center to form two octetary rings.

[0156] In some embodiments, the heterocyclic Lewis base donor of the catalyst compound is characterized by a nitrogen or oxygen donor atom. For example, the heterocyclic group includes derivatives of pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, and their substituted variants. In some embodiments, the heterocyclic Lewis base lacks one or more hydrogen atoms at the α-position of the donor atom. In some embodiments, the heterocyclic Lewis base donor includes pyridine, 3-substituted pyridine, and 4-substituted pyridine.

[0157] The anion donor for the tridentate bidentate ligand can be an aryl hydrocarbon thio group, a phenolate, or an N-acetanilide. In some embodiments, the anion donor is a phenolate. The bidentate bidentate ligand coordinates with the metal center to form a complex that may lack a symmetry mirror. In some embodiments, the bidentate bidentate ligand coordinates with the metal center to form a complex with a twofold rotational symmetry axis; when determining the symmetry of the bis(phenolate) complex, only the metal and the bidentate bidentate ligand are considered (i.e., the remaining ligands are ignored).

[0158] The catalyst compound disclosed herein can be a bis(arylphenolate)pyridine complex. The bis(arylphenolate)pyridine complex may have a tripentate bis(arylphenolate)pyridine ligand that coordinates with a Group 3 transition metal or a lanthanide metal to form two eight-membered rings. In some embodiments, the bis(arylphenolate)pyridine complex comprises a transition metal complex with a bianionic tripentate ligand characterized by a central neutral donor group and two phenolate donors, wherein the tripentate ligand coordinates with the metal center to form two eight-membered rings; for example, the 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 advantageous that the heterocyclic group lacks a hydrogen at the α-position of the heteroatom.

[0159] In some embodiments, the bis(phenolate) ligand can be a tripentate bianionic ligand coordinated to metal M in a manner forming an 8-membered metal ring pair. The bis(phenolate) ligand encapsulates the metal to form a complex with a double rotation axis, thereby endowing the complex with C2 symmetry. The C2 geometry and the 8-membered metal ring are characteristics of these complexes, making them efficient catalyst components for the production of polyolefins.

[0160] Bis(phenolate), N-aniline, and / or aryl thioligands containing donor groups (e.g., oxygen, nitrogen, or sulfur, respectively) can be substituted with alkyl, substituted alkyl, aryl, or other groups. Advantageously, each phenolate group is substituted at a ring position adjacent to the donor atom in the ring structure. For example, the substituent at the position adjacent to the donor atom can be an alkyl group containing 1-20 carbon atoms. In this type of complex, it is also advantageous for the phenolate to be substituted with one or more alkyl substituents (e.g., ortho and / or para positions of the oxygen atom in the phenolate). In some embodiments, the substituent ortho to the donor atom can be a non-aromatic cyclic alkyl group having one or more five- or six-membered rings. In this type of complex, it is also advantageous for the phenolate to be substituted with one or more cyclic tertiary alkyl substituents. Using cyclic tertiary alkyl-substituted phenolates can improve the ability of these catalysts to produce high molecular weight polymers. In some embodiments, the substituent ortho to the oxygen donor atom is adamantane-1-yl or a substituted adamantane-1-yl. In some implementations, the substituent at the position adjacent to the oxygen donor atom is tert-butyl or a substituted tert-butyl.

[0161] A neutral heterocyclic Lewis base donor is covalently bonded between two anion donors (e.g., between two phenol salts) via a "linking group" that attaches the heterocyclic Lewis base to the anion donor. For example, the "linking group" is formed by (A) in formula (I). 3 A 2 ) and (A 2' A 3' The following describes the process in more detail. The choice of each linking group can affect catalyst performance. Each linking group can be a C2-C group with a length of two atoms. 40 Divalent groups. One or both linking groups can be independently phenylene, substituted phenylene, heteroaryl, vinylene, or acyclic two-carbon linking groups. In some embodiments, one or both phenylene groups can be unsubstituted or can be independently C1-C2 linked groups. 20 Alkyl substitution, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl or isomers thereof, such as isopropyl.

[0162] In some implementations, the catalyst compound is represented by formula (I):

[0163] (I)

[0164] in:

[0165] M is a group 3 transition metal or a lanthanide metal (e.g., Sc, Y, or La);

[0166] E and E' are each independently O, S, or NR. A , where R A Independently, it is hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups or groups containing heteroatoms, such as O, for example E and E' are both O;

[0167] Q is a group 14, 15, or 16 atom, for example, Q is C, O, S, or N, for example, Q is C, N, or O, for example, Q is N;

[0168] A 1 QA 1' It is part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms, which connects A via a 3-atom bridge. 2 Connect to A 2' Where Q is the central atom of the 3-atom bridge (A) 1 QA 1' With the shown joints A1 and A 1' The curve combination represents a heterocyclic Lewis base;

[0169] A 1 and A 1' Each is independently C, N, or C(R) B ), where R B Selected from hydrogen, C1-C 20 Hydrocarbon groups and substituted C1-C 20 Hydrocarbon group (e.g., A) 1 and A 1' Each is C);

[0170] It is a divalent group containing 2 to 40 non-hydrogen atoms, which connects A atoms via 2-atom bridges. 1 Linked to an E-bonded aryl group, and A 3 and A 2 These can be combined to form substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, wherein the substituents on the rings can join to form additional rings, such as A. 3 and A 2Combined to form o-phenylene, substituted o-phenylene, o-arene, substituted o-arene, indolene, substituted indolene, benzothiophene, substituted benzothiophene, pyrrolene, substituted pyrrolene, thiophene, substituted thiophene;

[0171] It is a divalent group containing 2 to 40 non-hydrogen atoms, which connects A atoms via 2-atom bridges. 1′ Linked to the E′-bonded aryl group, and A 3′ and A 2′ These can be combined to form substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, wherein the substituents on the rings can join to form additional rings, such as A. 3′ and A 2′ Combined to form, for example, o-phenylene, substituted o-phenylene, o-aromatic, substituted o-aromatic, indoleyl, substituted indoleyl, benzothiophene, substituted benzothiophene, pyrrolyl, substituted pyrrolyl, thiophene, substituted thiophene;

[0172] L is an independent Lewis base;

[0173] X' is an anionic ligand;

[0174] Any two L groups can bond together to form a polydentate (e.g., bidentate) Lewis base;

[0175] The X' group can combine with the L group to form a monoanionic bidentate group;

[0176] n is 1;

[0177] m is 0, 1, or 2;

[0178] n+m is not greater than 3; and

[0179] R 1 R 2 R 3 R 4 R 1′ R 2′ R 3′ and R 4′ Each is independently hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon group, heteroatom or heteroatom-containing group (e.g., R) 1′ and R 1 Independently, it is a hydrocarbon group, such as a tertiary alkyl group, or a cyclic hydrocarbon group, such as a cyclic tertiary alkyl group, or R 1 and R 2 R 2 and R3 R 3 and R 4 R 1′ and R 2′ R 2′ and R 3′ R 3′ and R 4′ One or more pairs of rings may join to form one or more substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocycles or unsubstituted heterocycles, each having 5, 6, 7 or 8 ring atoms, and wherein the substituents on the rings may join to form additional rings.

[0180] Metal M is selected from Group 3 elements or lanthanides. For example, metal M is Sc, Y, or La.

[0181] The donor atom Q of the neutral heterocyclic Lewis base (in formula (I)) can be nitrogen, sulfur, or oxygen. In some embodiments, Q is nitrogen.

[0182] Non-limiting examples of neutral heterocyclic Lewis base groups include pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, and substituted variants thereof. In some embodiments, the heterocyclic Lewis base group may include pyridine, pyrazine, thiazole, or imidazole.

[0183] In some implementation schemes, A 1 and A 1' Each is independently C, N, or C(R) 22 ), where R 22 Selected from hydrogen, C1-C 20 Hydrocarbon groups and substituted C1-C 20 Hydrocarbon group. In some implementations, A 1 and A 1' Each is carbon. When Q is carbon, A... 1 and A 1' Each can be independently selected from nitrogen and C(R) 22 When Q is nitrogen, A 1 and A 1' Each can be carbon. In some implementations, Q = nitrogen and A 1 =A 1' =Carbon. When Q is nitrogen or oxygen, the heterocyclic Lewis base of formula (I) may not have any affinity for A. 1 Or A 1' Hydrogen atoms in atomic bonds are preferred because it is believed that hydrogen at those positions can undergo undesirable decomposition reactions that reduce the stability of the catalytically active substance.

[0184] In at least one embodiment of formula (I), Q is carbon and A 1 and A 1' Each is N or C(R)22 ), where R 22 Selected from hydrogen, C1-C 20 Hydrocarbon group, substituted C1-C 20 Hydrocarbon group, heteroatom, or heteroatom-containing group. In this embodiment, A 1 QA 1' The fragment forms part of a cyclic carbene, an N-heterocyclic carbene, a cyclic aminoalkyl carbene, or a substituted variant thereof.

[0185] By A 1 QA 1' With joint A 1 and A 1' The heterocyclic Lewis bases (formula (I)) represented by the curve combination can be selected from the following, wherein each R 23 The radical group is selected from hydrogen, heteroatom, C1-C 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 Amino and substituted C1-C 20 alkyl.

[0186]

[0187] In some implementation schemes, by A 1 QA 1' With joint A 1 and A 1' The curve combination represents a heterocyclic Lewis base (formula (I)) that is a six-membered ring containing zero or one cyclic heteroatom or a five-membered ring containing zero, one, two, or three cyclic heteroatoms. Alternatively, it can be represented by A. 1 QA 1' With joint A 1 and A 1' The curve combination represents a heterocyclic Lewis base (formula (I)) that is not a six-membered ring containing two or more cyclic heteroatoms.

[0188] In some implementations of formula (I), A 1 QA 1' It is part of a heterocyclic Lewis base containing 2 to 20 non-hydrogen atoms, which connects A via a 3-atom bridge. 2 Connect to A 2' Where Q is the central atom of the 3-atom bridge. In some embodiments, A 1 and A 1' Each is a carbon atom, and A 1 QA 1' The fragment forms pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan or a substituted variant group or a portion thereof.

[0189] In some embodiments of formula (I), M is Sc, Y, or La, Q is nitrogen, and A is... 1 and A 1' Both are carbon, E and E ' Both are oxygen, and R 1 and R 1' They are all independently C4-C 20 Cyclic tertiary alkyl groups.

[0190] In some embodiments of formula (I), M is Sc, Y, or La, Q is nitrogen, and A is... 1 and A 1' Both are carbon, E and E ' Both are oxygen, and R 1 and R 1' They are all independently adamantane-1-yl or substituted adamantane-1-yl.

[0191] In some embodiments of formula (I), M is Sc, Y, or La, Q is nitrogen, and A is... 1 and A 1' Both are carbon, E and E ' Both are oxygen, and R 1 and R 1' They are all independently acyclic tertiary alkyl groups.

[0192] In some implementations, the catalyst compound is represented by formula (II):

[0193] (II)

[0194] in:

[0195] M is a Group 3 metal or a lanthanide metal (e.g., Sc, Y, or La);

[0196] E and E' are each independently O, S, or NR. A , where R A It is hydrogen on its own, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups or groups containing heteroatoms, such as E and E', are both O;

[0197] L is an independent Lewis base;

[0198] X′ is an anionic ligand;

[0199] Any two or more L groups can join together to form a polydentate (e.g., bidentate) Lewis base;

[0200] The X′ group can combine with the L group to form a monoanionic bidentate group;

[0201] n is 1;

[0202] m is 0, 1, or 2;

[0203] n+m is not greater than 3;

[0204] R 1 R 2 R 3 R 4 R 1′ R 2′ R 3′ and R 4′ Each independently is hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon group, 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 pairs of rings may join to form one or more substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, and wherein the substituents on the rings may join to form additional rings; and

[0205] R 5 R 6 R 7 R 8 R 5′ R 6′ R 7′ R 8′ R 10 R 11 and R 12 Each is independently hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon group, 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 R12 One or more pairs of rings may join to form one or more substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocycles or unsubstituted heterocycles, each having 5, 6, 7 or 8 ring atoms, and wherein the substituents on the rings may join to form additional rings.

[0206] In equation (II), E and E' are each independently selected from oxygen or NR. A , where R A Independently, it is hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon group or heteroatom-containing group. In some embodiments, E and E' are oxygen. When E and / or E' is NR A At that time, R A Optional from C1-C 20 Hydrocarbon, alkyl, or aryl. In one embodiment, E and E' are each independently selected from O, S, N (alkyl), or N (aryl), wherein the alkyl group can be C1-C2. 20 Alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, etc., and the aryl group is C6-C. 40 Aryl groups, such as phenyl, naphthyl, benzyl, methylphenyl, etc.

[0207] In some embodiments of the catalyst compound of formula (I) or (II), when E and E' are oxygen, each phenolic salt group may be substituted at the ortho position of the oxygen atom (i.e., R in formula (I) and (II)). 1 and R 1' Therefore, when E and E' are oxygen, R 1 and R 1' Each is independently C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon group, heteroatom or heteroatom-containing group, such as R 1 and R 1' Each is independently a non-aromatic cyclic alkyl group having one or more five- or six-membered rings (e.g., cyclohexyl, cyclooctyl, adamantyl, or 1-methylcyclohexyl or substituted adamantyl), such as a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, adamantyl or substituted adamantyl).

[0208] In some embodiments of the catalyst compound of formula (I) or (II), R 1 and R 1' Each is independently a tertiary hydrocarbon group. In other embodiments of formula (I) or (II), R 1 and R 1' Each is independently a (substituted or unsubstituted) cyclic tertiary hydrocarbon group. In other embodiments of the catalyst compound of formula (I) or (II), R1 and R 1' Each is an independent (substituted or unsubstituted) polycyclic tertiary hydrocarbon group.

[0209] In some embodiments of the catalyst compound of formula (I) or (II), when E and E' are oxygen, each phenate group may be substituted at the para position of the oxygen atom (i.e., R in formula (I) and (II)). 3 and R 3' Therefore, when E and E' are oxygen, R 3 and R 3' Each is independently C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon group, heteroatom or heteroatom-containing group, such as R 3 and R 3' Each is independently C1-C 20 Alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or their isomers. Alternatively, R 3 and R 3' Each is independently a non-aromatic cyclic alkyl group having one or more five- or six-membered rings (e.g., cyclohexyl, cyclooctyl, adamantyl, or 1-methylcyclohexyl or substituted adamantyl), such as a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, adamantyl or substituted adamantyl).

[0210] In some embodiments of the catalyst compound of formula (I) or (II), R 3 and R 3' Each is independently (substituted or unsubstituted) C1-C 20 Alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or isomers thereof. In some embodiments of the catalyst compound of formula (I) or (II), R 3 and R 3' Each is independently a (substituted or unsubstituted) acyclic tertiary hydrocarbon group. In other embodiments of formula (I) or (II), R 3 and R 3' Each is an independent tert-butyl.

[0211] In some implementations, R in formula (II) 1 R 2 R 3 R 4 R 1' R 2' R 3' R 4' R 5 R 6 R 7 R 8R 5' R 6' R 7' ;R 8' R 10 R 11 Or R 12 One or more of them are independently hydrogen or C1-C 20 Alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl or isomers thereof, such as isopropyl.

[0212] In some embodiments of formula (I) or (II), M is a Group 3 metal, such as Sc, Y, or La.

[0213] In some implementations of equations (I) and (II), E and E' are each O.

[0214] In some implementations of formulas (I) and (II), R 1 R 2 R 3 R 4 R 1′ R 2′ R 3′ and R 4′ Each is independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, nonadecanyl, triadecyl, phenyl, substituted phenyl (such as methylphenyl and dimethylphenyl), benzyl, substituted benzyl (such as methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl and their isomers.

[0215] In embodiments of formulas (I) and (II), X' is each independently selected from hydrocarbon groups (e.g., alkyl or aryl), hydrides, amides, alkoxy groups, thio groups, phospho groups, halides, alkyl sulfonates, and combinations thereof having 1 to 20 carbon atoms. For example, X' is each independently selected from halides, aryl groups, and C1-C5 alkyl groups. For example, X' is each independently selected from hydrides, dimethylamino, diethylamino, bis(dimethylsilyl)amino, bis(trimethylsilyl)amino, methylenetrimethylsilyl, neopentyl, phenyl, benzyl, methyl, ethyl, propyl, butyl, pentyl, fluoro, iodo, bromo, or chloro. In some embodiments, X' is each independently selected from bis(dimethylsilyl)amino, bis(trimethylsilyl)amino, and methylenetrimethylsilyl.

[0216] Alternatively, X' can be a halogen, hydrogen, alkyl, or alkenyl group, each independently.

[0217] In some embodiments of formulas (I) and (II), each L is a Lewis base, independently selected from ethers, thioethers, amines, nitriles, imines, pyridines, haloalkanes, and phosphines, such as ethers, thioethers, or combinations thereof. Optionally, two or more Ls may form part of a fused ring or ring system, for example, each L is independently selected from ether or thioether groups, such as each L is a diethyl ether, tetrahydrofuran, dibutyl ether, or dimethyl thioether group.

[0218] In some implementations of formulas (I) and (II), R 1 and R 1' Each is an independent cyclic tertiary alkyl group.

[0219] In some implementations of equations (I) and (II), m is 0, 1, or 2, for example, 0.

[0220] In some implementations of formulas (I) and (II), R 1 and R 1' Neither of them is hydrogen.

[0221] In some implementations of formulas (I) and (II), R 3 and R 3' Neither of them is hydrogen.

[0222] In some embodiments of equations (I) and (II), M is Sc, Y, or La, and E and E' are each O; R 1 and R 1' Each is independently C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon group, heteroatom or heteroatom-containing group, R 2 R 3 R 4 R2' R 3' and R 4' Each is independently hydrogen, C1-C 20 Hydrocarbon group or substituted C1-C 20 Hydrocarbon group.

[0223] In some implementations 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 is independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl or its isomers.

[0224] In some implementations 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 is independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, nonadecanyl, triadecyl, phenyl, substituted phenyl (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl or isomers thereof.

[0225] In some implementations of formula (II), M is Sc, Y, or La, and E and E' are each O; R 1 and R 1' Each is independently C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon group, heteroatom or heteroatom-containing group; R 3 and R 3' Each is independently C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon group, heteroatom or heteroatom-containing group; R 1 R2 R 4 R 1' R 2' and R 4' Each is independently hydrogen, C1-C 20 Hydrocarbon group, substituted C1-C 20 Hydrocarbon group, 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 pairs of rings may join to form one or more substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocycles or unsubstituted heterocycles, each having 5, 6, 7 or 8 ring atoms, and wherein the substituents on the rings may join to form additional rings.

[0226] X' is independently selected from substituted or unsubstituted groups: hydrocarbon groups (e.g., alkyl or aryl), hydroxyl, amino, alkoxy, thiol, phosphoyl, halogen, diene, amine, phosphine, ether, and combinations thereof (two or more X' may form a fused ring or part of a ring system); 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 is independently hydrogen, C1-C 20 Hydrocarbon group, substituted C1-C 20 A hydrocarbon group, a heteroatom or heteroatom-containing group, or one or more adjacent R groups may join to form one or more substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocycles or unsubstituted heterocycles, each having 5, 6, 7 or 8 ring atoms, and wherein the substituents on the rings may join to form additional rings, such as R... 5 R 6 R 7 R 8 R 5' R 6' R 7' R 8′ R 10 R 11and R 12 Each is independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, nonadecanyl, triadecyl, phenyl, substituted phenyl (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl and their isomers.

[0227] In some implementations of formula (II), M is Sc, Y, or La, and E and E ' It's all oxygen, R 1 and R 1' They are all independently C4-C 20 Cyclic tertiary alkyl groups, and R 3 and R 3' They are all independently C1-C 10 alkyl.

[0228] In some embodiments of formula (II), M is Sc, Y, or La, E and E' are both oxygen, and R 1 and R 1' All are adamantane-1-yl or substituted adamantane-1-yl, and R 3 and R 3' They are all independently C1-C 10 alkyl.

[0229] In some embodiments of formula (II), M is Sc, Y, or La, E and E' are both oxygen, and R 1 R 1' R 3 and R 3' Each is independently adamantane-1-yl or a substituted adamantane-1-yl.

[0230] In some embodiments, the catalyst compound is represented by formula (III):

[0231] (III)

[0232] in:

[0233] M is a Group 3 metal or a lanthanide metal (e.g., M is Sc, Y, or La);

[0234] E and E′ are each independently O, S, or NR. A , where R A It is hydrogen on its own, C1-C 40 Hydrocarbon group, substituted C1-C40 Hydrocarbon groups or groups containing heteroatoms, such as O, for example E and E' are both O;

[0235] L is an independent Lewis base;

[0236] X' is an anionic ligand independently;

[0237] Any two L groups can bond together to form a bidentate Lewis base;

[0238] The X' group can combine with the L group to form a monoanionic bidentate group;

[0239] n is 1;

[0240] m is 0, 1, or 2;

[0241] n+m is not greater than 3;

[0242] R 1 R 2 R 3 R 4 R 1' R 2' R 3' and R 4' Each is independently hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon group, 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 4' One or more pairs of rings may join to form one or more substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, and wherein the substituents on the rings may join to form additional rings; and

[0243] R 5 R 6 R 7 R 8 R 5' R 6' R 7' R 8′ R 10 R 11 and R 12 Each is independently hydrogen, C1-C 40Hydrocarbon group, substituted C1-C 40 Hydrocarbon group, 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 pairs of rings may join to form one or more substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocycles or unsubstituted heterocycles, each having 5, 6, 7 or 8 ring atoms, and wherein the substituents on the rings may join to form additional rings.

[0244] In equation (III), E and E' are each selected from oxygen or NR. A , where R A Independently, it is hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon group or heteroatom-containing group. In some embodiments, E and E' are oxygen. When E and / or E' is NR A At that time, R A Optional from C1-C 20 Hydrocarbon, alkyl, or aryl. In one embodiment, E and E' are each selected from O, S, N (alkyl), or N (aryl), wherein the alkyl group can be C1-C2. 20 Alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, etc., and the aryl group is C6-C. 40 Aryl groups, such as phenyl, naphthyl, benzyl, methylphenyl, etc.

[0245] In some embodiments of the catalyst compound of formula (III), when E and E' are oxygen, each phenolic salt group may be substituted at the ortho position of the oxygen atom (i.e., R in formula (III)). 1 and R 1’ Therefore, when E and E' are oxygen, R 1 and R 1' Each is independently C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon group, heteroatom or heteroatom-containing group, R 1 and R 1' Independently, it is C1-C 20Alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl. Alternatively, R 1 and R 1' Each is independently a non-aromatic cyclic alkyl group having one or more five- or six-membered rings (e.g., cyclohexyl, cyclooctyl, adamantyl, or 1-methylcyclohexyl or substituted adamantyl), such as a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, adamantyl or substituted adamantyl).

[0246] In some embodiments of the catalyst compound of formula (III), R 1 and R 1' Each is independently a (substituted or unsubstituted) acyclic tertiary hydrocarbon group. In other embodiments of formula (III), R 1 and R 1' Each is an independent tert-butyl.

[0247] In some implementation schemes, R 1 and R 1' Each is independently a non-aromatic cyclic alkyl group having one or more five- or six-membered rings (e.g., cyclohexyl, cyclooctyl, adamantyl, or 1-methylcyclohexyl or substituted adamantyl), such as a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, adamantyl or substituted adamantyl).

[0248] In some embodiments of the catalyst compound of formula (III), R 1 and R 1' Each is independently a tertiary hydrocarbon group. In other embodiments of formula (III), R 1 and R 1' Each is independently a cyclic tertiary hydrocarbon group. In other embodiments of the catalyst compound of formula (III), R 1 and R 1' Each is an independent polycyclic tertiary hydrocarbon group.

[0249] In some embodiments of the catalyst compound of formula (III), when E and E' are oxygen, the phenoxide groups can each be substituted at the para position of the oxygen atom (i.e., R in formula (III)). 3 and R 3' Therefore, when E and E' are oxygen, R 3 and R 3' Each is independently C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon group, heteroatom or heteroatom-containing group, such as R 3 and R 3' Each is independently C1-C 20Alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or their isomers. Alternatively, R 3 and R 3' Each is independently a non-aromatic cycloalkyl group having one or more five- or six-membered rings (e.g., cyclohexyl, cyclooctyl, adamantyl, or 1-methylcyclohexyl or substituted adamantyl), such as a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, adamantyl or substituted adamantyl).

[0250] In some embodiments of the catalyst compound of formula (III), R 3 and R 3' Each is independently (substituted or unsubstituted) C1-C 20 Alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or isomers thereof. In some embodiments of the catalyst compound of formula (III), R 3 and R 3' Each is independently a (substituted or unsubstituted) acyclic tertiary hydrocarbon group. In some embodiments of formula (III), R 3 and R 3' Each is an independent tert-butyl.

[0251] In some implementations, R in equation (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 them are independently hydrogen or C1-C 20 Alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl or isomers thereof, such as isopropyl.

[0252] In some embodiments of formula (III), M is a Group 3 metal, such as Sc, Y, or La.

[0253] In some implementations of equation (III), E and E' are each O.

[0254] In some implementations of formula (III), R 1 R 2 R 3 R 4 R 1' R 2' R 3' and R 4' Each is independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, nonadecanyl, triadecyl, phenyl, substituted phenyl (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl and their isomers.

[0255] In the implementation of formula (III), R A It is hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups or groups containing heteroatoms, such as R A It is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl or its isomers.

[0256] In embodiments of formula (III), each X' is independently selected from hydrocarbon groups (e.g., alkyl or aryl), hydrazine, amino, alkoxy, thio, phospho, halogen, alkyl sulfonate, and combinations thereof having 1 to 20 carbon atoms (two or more X's may form a fused ring or part of a ring system). For example, each X' is independently selected from halogen, aryl, and C1-C5 alkyl groups. For example, each X' is independently selected from hydrazine, dimethylamino, diethylamino, bis(dimethylsilyl)amino, bis(trimethylsilyl)amino, methylenetrimethylsilyl, neopentyl, phenyl, benzyl, methyl, ethyl, propyl, butyl, pentyl, fluoro, iodo, bromo, or chloro. In some embodiments, each X' is independently selected from bis(dimethylsilyl)amino, bis(trimethylsilyl)amino, and methylenetrimethylsilyl.

[0257] Alternatively, each of X' can be independently a halogen, hydrogen, alkyl, or alkenyl group.

[0258] In some embodiments of formula (III), each L is a Lewis base, independently selected from ethers, thioethers, amines, nitriles, imines, pyridines, haloalkanes and phosphines, such as ethers, thioethers or combinations thereof. Optionally, two or more L's may form part of a fused ring or ring system, for example, each L is independently selected from ether or thioether groups, such as each L is a diethyl ether, tetrahydrofuran, dibutyl ether or dimethyl thioether group.

[0259] In some implementations of formula (III), R 1 and R 1' Each is an independent tertiary alkyl group.

[0260] In some implementations of formula (III), m is 0, 1, or 2, for example, 0.

[0261] In some implementations of formula (III), R 1 and R 1' Neither of them is hydrogen.

[0262] In some implementations of formula (III), R 3 and R 3' Neither of them is hydrogen.

[0263] In some implementations of equation (III), M is Sc, Y, or La, and E and E' are each O; R 1 and R 1' Each is independently C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon group, heteroatom or heteroatom-containing group, R 2 R 3 R 4 R 2' R 3' and R 4' Each is independently hydrogen, C1-C 20 Hydrocarbon group or substituted C1-C 20 Hydrocarbon group.

[0264] In some implementations 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 is independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl or its isomers.

[0265] In some implementations of formula (III), R5 R 6 R 7 R 8 R 5' R 6' R 7' R 8' R 10 R 11 and R 12 Each is independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, nonadecanyl, triadecyl, phenyl, substituted phenyl (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl or isomers thereof.

[0266] In some implementations of equation (III), M is Sc, Y, or La, and E and E' are each O; R 1 and R 1' Each is independently C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon group, heteroatom or heteroatom-containing group; R 3 and R 3' Each is independently C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon group, heteroatom or group containing heteroatom;

[0267] R 1 R 2 R 4 R 1' R 2' and R 4' Each is independently hydrogen, C1-C 20 Hydrocarbon group, substituted C1-C 20 Hydrocarbon group, 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 pairs of rings may join to form one or more substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocycles or unsubstituted heterocycles, each having 5, 6, 7 or 8 ring atoms, and wherein the substituents on the rings may join to form additional rings.

[0268] Each X' is independently selected from substituted or unsubstituted groups: hydrocarbon groups (e.g., alkyl or aryl), hydrogen groups, amino groups, alkoxy groups, thio groups, phosphoro groups, halogen groups, dienes, amines, phosphines, ethers, and combinations thereof (two or more X's may form a fused ring or part of a ring system);

[0269] n is 2; m is 0; and R is 0. 5 R 6 R 7 R 8 R 5' R 6' R 7' R 8' R 10 R 11 and R 12 Each is independently hydrogen, C1-C 20 Hydrocarbon group, substituted C1-C 20 A hydrocarbon group, a heteroatom or heteroatom-containing group, or one or more adjacent R groups may join to form one or more substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocycles or unsubstituted heterocycles, each having 5, 6, 7 or 8 ring atoms, and wherein the substituents on the rings may join to form additional rings, such as R... 5 R 6 R 7 R 8 R 5' R 6' R 7' R 8' R 10 R 11 and R 12 Each is independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, nonadecanyl, triadecyl, phenyl, substituted phenyl (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl and their isomers.

[0270] In some embodiments of formula (III), M is Sc, Y, or La, E and E' are both oxygen, and R1 and R 1' They are all independently C4-C 20 Tertiary alkyl groups (e.g., tert-butyl), and R 3 and R 3' They are all independently C1-C 10 alkyl.

[0271] In some embodiments of formula (III), M is Sc, Y, or La, E and E' are both oxygen, and R 1 and R 1' All are tert-butyl or substituted tert-butyl, and R 3 and R 3' They are all independently C1-C 10 alkyl.

[0272] In some embodiments of formula (III), M is Sc, Y, or La, E and E' are both oxygen, and R 1 R 1' R 3 and R 3' Each is independently methyl, substituted methyl, tert-butyl, substituted tert-butyl, adamantane-1-yl, or substituted adamantane-1-yl.

[0273] It can be used as a starting material for the preparation of anionic modified alkylaluminoxanes and / or cationic modified alkylaluminoxanes. MAO solution of the reagent.

[0274] Aluminoxanes are oligomers containing -Al(R)-O- or -Al(R)2-O- subunits, where R is an alkyl group, typically C1-C. 12 Alkyl groups, such as the inactive MAO gel shown in Scheme 1. Examples of useful aluminoxanes include methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, triethylaluminoxane, triisobutylaluminoxane, tetraethyldialuminoxane, and diisobutylaluminoxane.

[0275] One of the freshly reacted MAO solutions from the reaction of a large excess of TMA with water at a sufficiently low temperature has the formula (Al4O3Me6)4(TMA). 1-2 The 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(See Springer-Verlag, 1999, p. 105). Therefore, freshly activated MAO has an Al:O ratio of 1:0.75, and oxygen can increase, for example, in a Grace 30% MAO solution, after removing a large amount of excess TMA to form a product containing approximately 85 mol% MAO and approximately 15 mol% total TMA, to approximately 1:0.78 (Imhoff et al.). Organometallics ,1998, 17 (10), page 1941). Even under cooling, the gelation process begins after the preparation of solution MAO. Therefore, the solution MAO composition can vary over time, for example, by observing an increase in oxygen content in the main MAO structure with increasing free TMA and decreasing coordinated TMA. Preferably, solution MAO with a similar storage time under similar storage conditions should be used; more preferably, solution MAO with a storage time of less than 6 months under low-temperature storage (e.g., below -10°C, more preferably below -20°C, most preferably below -30°C) should be used; and most preferably, solution MAO with a storage time of less than one week under cooling (e.g., below -10°C, below -20°C, below -30°C).

[0276] There are various methods for preparing MAO and modified MAO, such as U.S. Patent No. 4,542,199 and Chen and Marks. 100 Chem.Rev. The method described in 1391 (2000). MAO can also be modified for various purposes, such as improving activity or solubility. Examples of useful MAOs include MAOs derived from TMA with oxygenates (e.g., WRGrace MAO derived from TMA with water, or Nouryon PMAO derived from TMA with an organic oxygen source, or Tosoh solid MAO), higher alkyl-modified MAOs (e.g., Nouryon MMAO), carbocation-modified MAOs (US Patent No. 9,090,720), dialkylaluminum cationic precursor-modified MAOs (US Patent No. 8,575,284), halogen-modified MAOs (US Patent No. 7,355,058), etc.

[0277] Active MAO can also be formed by contacting a large amount of excess TMA with a non-hydrolyzable oxygen source (such as CO2, methacrylic acid, benzoic acid or other organic compounds containing reactive oxygen) under suitable reaction conditions.

[0278] The active MAO disclosed herein can be commercially available or synthesized. The active MAO disclosed herein can be prepared in situ by contacting a hydrocarbon aluminum compound with an oxygen source, such as TMA, and water in an aliphatic or aromatic diluent at a temperature below 0°C to about -60°C, for example about -10°C to about -50°C, for example about -15°C to about -30°C.

[0279] Hydrocarbon aluminum compounds for MAO and modified MAO Active aluminum oxane compositions (e.g., MAO) may be formed using only trimethylaluminum (TMA), but other alkylaluminum compounds may be used to modify MAO. The alkylaluminum compound used for aluminum oxane modification may be an alkylaluminum compound, such as a trialkylaluminum compound. For example, the alkyl substituent may be an alkyl group with up to 10 carbon atoms, such as octyl, isobutyl, ethyl, or methyl. Therefore, suitable alkylaluminum compounds may include trimethylaluminum, triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri(2-methylpentyl)aluminum, trihexylaluminum, tri-n-octylaluminum, and tri-n-decylaluminum. In some embodiments, the alkylaluminum compound is trimethylaluminum and tri-n-octylaluminum. In some embodiments, the alkylaluminum compound is represented by the formula R3Al, where each R is independently a hydrocarbon containing 1 to 30 carbon atoms.

[0280] In some embodiments, the hydrocarbon aluminum compound is one or more of a trialkylaluminum mixture, such as dimethyl ethylaluminum or methyl diethylaluminum from a mixture of AlMe3 and AlEt3, diethyl isobutylaluminum or ethyl diisobutylaluminum from a mixture of AlEt3 and AliBu3, etc.

[0281] oxygen source Suitable oxygen sources for forming the alkylaluminoxanes of this disclosure include any oxygen source in which one or more oxygen atoms are capable of reacting with a hydrocarbon aluminum compound to form a new Al-O bond. In at least one embodiment, the oxygen source may be water or water comprising, for example, pure water or water in a metal hydrate. In some embodiments, the oxygen source may be one or more compounds containing hydroxyl or carbonyl groups, such as alcohols, CO or CO2, acetone, or carboxylic acids. In at least one embodiment of this disclosure, the oxygen source is one or more of carbon dioxide, carboxylic acids, ketones, aldehydes, esters, acid anhydrides, alcohols, or combinations thereof.

[0282] In at least one embodiment of this disclosure, the oxygen source is of formula R 1 R 2 C=CR 3 CO2H represents R, where R 1 and R 2 Each is independently a hydrogen, alkyl, alkenyl, aryl, or heteroatom-containing group, and R 3 It can be an alkyl, alkenyl, aryl, or heteroatom-containing group.

[0283] In at least one embodiment of this disclosure, the oxygen source comprises a hydrocarbon-based aluminum compound, such as the reaction product of TMA with an alcohol, ketone, ester, or organic acid. Examples of hydrocarbon-based aluminum compounds containing an oxygen source include aluminum dimethylmethoxide, aluminum dimethylethanol, aluminum dimethylisopropoxide, aluminum dimethyln-butoxide, aluminum dimethylisobutoxide, aluminum pentamethyltert-butoxide, aluminum tetramethylditert-butoxide, aluminum pentamethylisopropoxide, aluminum tetramethyldiisopropoxide, or combinations thereof.

[0284] The initial charge molar ratio Al:O (where O is the active oxygen in the active oxygen-containing compound) can be about 100:1, about 60:1, about 30:1, about 10:1, about 1:1, or about 0.9:1 to form a desired MAO composition with or without excess free alkyl aluminum compounds. In some embodiments, the Al:O molar ratio can be about 0.9:1 to about 100:1, for example about 1:1 to about 10:1, or about 10:1 to about 60:1, for example about 30:1 to about 60:1. If one or more undesirable excess alkyl aluminum compounds are present, they can be removed, for example by filtration followed by washing with an aliphatic diluent and / or treatment with one or more fluorine compounds of this disclosure.

[0285] In some embodiments, the oxygen source is one or more of carbon dioxide, carboxylic acids, esters, acid anhydrides, alcohols, or combinations thereof. In some embodiments, the oxygen source is one or more of carbon dioxide, carboxylic acids, esters, acid anhydrides, and alcohols, or combinations thereof, optionally containing water. In some embodiments, the oxygen source is R... 1 R 2 C=CR 3 CO2H, where R 1 and R 2 Each is independently a hydrogen, alkyl, alkenyl, aryl, or heteroatom-containing group, and R 3 It is an alkyl, alkenyl, aryl, or heteroatom-containing group. In some embodiments, the oxygen source is methacrylic acid.

[0286] In at least one embodiment of this disclosure, the oxygen source is a hydrocarbylboroxine as described in Welborn, U.S. Patent No. 5,001,244.

[0287] Catalyst system formation

[0288] The catalyst system disclosed herein may include one or more precatalysts and activators (alkylaluminoxanes without alkylaluminoxanes) as described above, and may be formed by combining the catalyst compounds of this disclosure with the activators in any manner known from the literature (including combining them with a support, such as silica). The catalyst system may also be added to or generated in solution polymerization or bulk polymerization (in monomers). The catalyst system disclosed herein may have one or more activators and one, two, or more precatalysts. An activator is defined as any compound that can activate any of the precatalyst 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.

[0289] In at least one embodiment, the catalyst system comprises an activator and a precatalyst compound of formula (I), formula (II), formula (III), or a combination thereof.

[0290] Embodiments of this disclosure include a method for preparing a catalyst system, the method comprising contacting unsupported anionic or cationic modified MAO (a TMA-free solution) or supported anionic or cationic modified MAO (a TMA-free support) with at least one precatalyst compound having Group 3 atoms or lanthanide metal atoms in an organic diluent. Alternatively, the anionic or cationic modified MAO may be contacted with at least one precatalyst compound before contacting with the support.

[0291] In at least one embodiment, the unloaded anionic or cationic modified MAO or the loaded anionic or cationic modified MAO is heated before contacting with the catalyst compound.

[0292] Unloaded anionic or cationic modified MAO, or loaded anionic or cationic modified MAO, can be solvated or slurried in an organic diluent, and the resulting mixture can be contacted with a solution of at least one catalyst compound. The catalyst compound can also be added as a solid to the mixture of the organic diluent and the anionic or cationic modified MAO. In at least one embodiment, the mixture of anionic or cationic modified MAO is contacted with the catalyst compound for a period of about 0.02 hours to about 24 hours, for example, a period of 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.

[0293] The mixture of the catalyst compound and anionic or cationic modified MAO can be heated to a temperature of about 0°C to about 70°C, for example, about 23°C to about 60°C, such as room temperature. The contact time can 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.

[0294] A suitable organic diluent is a material in which some or all of the reactants used herein (e.g., anionic or cationic modified MAO and catalyst compounds) are at least partially soluble (or, in the case of a solid support, suspended) and are liquid at the reaction temperature. Non-limiting examples of diluents are those having the formula C n H (2n+2) Acyclic alkanes, wherein n is 4 to 30, such as isobutane, butane, isopentane, hexane, n-heptane, octane, nonane, decane, etc., and those having the formula C n H (2n-2) Cycloalkanes, wherein n is 5 to 30, such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and mixtures thereof. Aromatic diluents may include benzene, toluene, or xylene.

[0295] A diluent, followed by anionic or cationic modified MAO, can be charged into the reactor. A catalyst can then be charged into the reactor, for example, as a solution of the catalyst in the organic diluent or as a solid. The mixture can be stirred at, for example, room temperature. Additional diluents can be added to the mixture to form a mixture with the desired consistency, for example, a slurry having about 2 cc / g silica to about 20 cc / g silica, or for example, about 4 cc / g silica. The diluent can then be removed. Removing the diluent dries the mixture and can be done under a vacuum atmosphere, by purging with an inert atmosphere, by heating the mixture, or a combination thereof. For heating the mixture, any suitable temperature for evaporating the aliphatic diluent can be used. It should be understood that reduced pressure under vacuum will lower the boiling point of the aliphatic diluent, depending on the reactor pressure. 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 lower, for example, about 70°C or lower. In at least one embodiment, removing the diluent includes applying heat, applying a vacuum, and applying nitrogen gas purging from the bottom of the container (by bubbling the nitrogen gas through the mixture). The mixture is then dried.

[0296] Aggregation methods

[0297] This disclosure relates to a polymerization method in which a monomer (e.g., ethylene; propylene) and optionally a comonomer are contacted with a catalyst system comprising an activator and at least one precatalyst compound, as described above. The precatalyst compound and the activator can be combined in any suitable order. The precatalyst compound and the activator can be combined prior to contact with the monomer. Alternatively, the precatalyst compound and the activator can be introduced separately into the polymerization reactor, where they subsequently react to form an active catalyst.

[0298] Monomers may include substituted or unsubstituted C2-C. 40 α-olefins, such as C2-C 20 α-olefins, such as C2-C 12 α-olefins, such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and their isomers. In at least one embodiment, the monomer comprises ethylene and optionally a comonomer, said comonomer comprising one or more C3-C... 40 Alkenes, such as C4-C 20 Alkenes, such as C6-C 12 Alkenes. C3-C 40 Olefin monomers can be straight-chain, branched, or cyclic. (C3-C) 40 Cyclic olefins can be tensioned or untensioned, monocyclic or polycyclic, and may optionally include heteroatoms and / or one or more functional groups. In another embodiment, the monomer comprises propylene and optionally a comonomer, said comonomer comprising one or more ethylene or C4-C... 40 Alkenes, such as C4-C 20 Alkenes, such as C6-C 12 Alkenes. C4-C 40 Olefin monomers can be straight-chain, branched, or cyclic. (C4-C) 40 Cyclic olefins can be tensioned or untensioned, monocyclic or polycyclic, and may optionally include heteroatoms and / or one or more functional groups.

[0299] Example C2-C 40Olefin monomers and optional comonomers may 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-oxa norbornene, 7-oxa norbornadiene, their substituted derivatives and isomers, such as 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 corresponding homologues and derivatives, such as norbornene, norbornadiene, and dicyclopentadiene.

[0300] The polymerization disclosed herein may include the copolymerization of butadiene and ethylene. Typically, the industrial-scale copolymerization of ethylene and butadiene is considered a difficult process because the reaction mechanisms and the relative reactivity of the monomers are believed to be different. The polymerization methods described herein have been found to reduce manufacturing and processing problems associated with such polymers—the methods have shown increased catalytic activity in producing high molecular weight polymers.

[0301] In some embodiments, the polymerization method is carried out by contacting a monomer composition comprising ethylene and one or more conjugated dienes with a catalyst system having one or more catalyst compounds and activators, as described above. The catalyst compounds and activators can be combined in any order and are typically combined before contact with the monomers.

[0302] Example conjugated diene monomers can include any hydrocarbon structure having at least two adjacent unsaturated bonds, such as C4-C. 30 Examples of conjugated dienes include isoprene, 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene, 1,3-nonadiene, 1,3-decadiene, cyclopentadiene, dicyclopentadiene, or higher cyclic dienes with or without substituents at different ring positions.

[0303] The polymerization method can be carried out in any suitable manner known in the art. Any suspension, homogeneous, bulk, solution, slurry, or gas-phase polymerization method can be used. Such methods can be operated in batch, semi-batch, or continuous modes. Homogeneous polymerization and slurry polymerization methods can be employed. (A homogeneous polymerization method is defined as a method in which at least 90% by weight of the product is soluble in the reaction medium). A homogeneous method can be a bulk homogeneous method. (A bulk method is defined as a method in which the monomer concentration in all feeds entering the reactor is 70% by volume or higher). Alternatively, no solvent or diluent is present or added to the reaction medium (except for small amounts, or amounts typically present with the monomer, used as a support or other additive in the catalyst system). In another embodiment, the method is a slurry method. As used herein, the term "slurry polymerization method" means a polymerization method in which a supported catalyst is used and the monomer is polymerized on supported catalyst particles. At least 95% by weight of the polymer product derived from the supported catalyst is in particulate form, as solid particles (not dissolved in the diluent).

[0304] Suitable diluents / solvents for polymerization include noncoordinate inert liquids. Examples include straight-chain and branched hydrocarbons such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as commercially available (Isopar™); and perhalogenated hydrocarbons such as perfluorinated C42-24 ... 4-10 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 a preferred embodiment of the invention, aliphatic hydrocarbon solvents are used as solvents, such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. In another embodiment, the solvent is not aromatic, and preferably the aromatic compound is present in the solvent at less than 1% by weight, preferably less than 0.5% by weight, and preferably less than 0% by weight based on the weight of the solvent.

[0305] In at least one embodiment, based on the total volume of the feed stream, the feed concentration of monomers and comonomers for polymerization in the feed stream to the reactor is 60 vol% diluent or lower, for example, 40 vol% or lower, for example, 20 vol% or lower. In at least one embodiment, the polymerization is carried out using a bulk method.

[0306] Polymerization can be carried out at any temperature and / or pressure suitable for obtaining the desired polymer. Suitable temperatures and / or pressures include temperatures from about 0°C to about 300°C, for example from about 20°C to about 200°C, for example from about 35°C to about 160°C, for example from about 80°C to about 160°C, for example from about 85°C to about 140°C. Polymerization can be operated at pressures from about 0.1 MPa to about 25 MPa, for example from about 0.45 MPa to about 6 MPa, or from about 0.5 MPa to about 4 MPa.

[0307] In suitable polymerization, the reaction run 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 continuous processes, the run time can be the average residence time of the reactor. In at least one embodiment, the reaction run time is up to about 180 minutes. In continuous processes, the run time can be the average residence time of the reactor.

[0308] In at least one embodiment, 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), for example about 0.01 psig to about 25 psig (0.07 kPa to 172 kPa), for example about 0.1 psig to about 10 psig (0.7 kPa to 70 kPa).

[0309] In at least one embodiment, the hydrogen content is from about 0.0001 ppm to about 2,000 ppm, for example from about 0.0001 ppm to about 1,500 ppm, for example from about 0.0001 ppm to about 1,000 ppm, for example from about 0.0001 ppm to about 500 ppm. Alternatively, hydrogen may be present at zero ppm.

[0310] In at least one embodiment, the aluminum oxane may be present at zero mole percent, or the aluminum oxane may be present at a molar ratio of aluminum to a Group 3 rare earth metal or a lanthanide element of less than 500:1, for example less than 300:1, for example less than 100:1, for example less than 1:1.

[0311] In at least one embodiment, the polymerization is carried out at a temperature of about 0°C to about 300°C (e.g., about 25°C to about 250°C, about 50°C to about 160°C, about 80°C to about 140°C); 2) at a pressure of about atmospheric pressure to about 10 MPa (e.g., about 0.35 MPa to about 10 MPa, about 0.45 MPa to about 6 MPa, about 0.5 MPa to about 4 MPa); 3) in an aliphatic hydrocarbon diluent (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., wherein, based on the weight of the diluent, aromatic hydrocarbons are present in the diluent in an amount of less than 1% by weight, e.g., less than 0.5% by weight, e.g., 0% by weight); 4) wherein the catalyst system used in the polymerization contains less than 0.5 mol%, e.g., about 0 mol% of aluminoxane. Alternatively, the aluminum oxane is present in a molar ratio of aluminum to transition metal of less than 500:1, for example less than 300:1, for example less than 100:1, for example less than 1:1; 5) polymerization is carried out in a reaction zone; 6) optionally, a scavenger (e.g., a trialkylaluminum compound) is absent (e.g., present at zero molar % or the scavenger is present in a molar ratio of scavenger metal to transition metal of less than 100:1, for example less than 50:1, for example less than 15:1, for example less than 10:1); and 7) 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), for example about 0.1 psig to about 10 psig (0.7 kPa to 70 kPa). In at least one embodiment, the catalyst system used in the polymerization comprises no more than one catalyst compound. A "reaction zone," also known as a "polymerization zone," is a container in which polymerization takes place, such as 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-stage polymerization in a batch polymerization process, each polymerization stage is considered a separate polymerization zone. In at least one embodiment, polymerization takes place in one reaction zone. Unless otherwise specified, the room temperature is 23°C.

[0312] Other additives may also be used in the polymerization as needed, such as one or more scavengers, hydrogen, alkylaluminum or chain transfer agents, such as alkylaluminoxanes, compounds represented by the formula AlR3 or ZnR2 (where R is each independently a C1-C8 aliphatic group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl or isomers thereof) or combinations thereof, such as diethylzinc, methylaluminoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum or combinations thereof.

[0313] In some embodiments, the polymerization method is solution-phase polymerization. Solution polymerization is a polymerization method in which the polymer is dissolved in a liquid polymerization medium, such as an inert solvent or one or more monomers or blends thereof. Solution polymerization is typically homogeneous. Homogeneous polymerization is polymerization in which the polymer product is dissolved in a polymerization medium. Such systems are not turbid, as in Oliveira, JV et al. (2000). Ind. Eng, Chem. Res As described on page 4627 of Volume 29. Solution polymerization can include polymerization in a continuous reactor, wherein the formed polymer, the supplied starting monomer, and the catalyst material are stirred to reduce or avoid concentration gradients, and wherein the monomer acts as a diluent or solvent, or wherein a hydrocarbon is used as a diluent or solvent. Suitable methods can be operated at temperatures from about 0°C to about 250°C, for example from about 50°C to about 170°C, for example from about 80°C to about 150°C, and / or at pressures of about 0.1 MPa or higher, for example 0.5 MPa or higher. The upper limit of pressure is not strictly limited, but can be about 200 MPa or less, for example 120 MPa or less, for example 30 MPa or less. Temperature control in the reactor can be achieved by balancing the heat of polymerization with reactor cooling, which is carried out by cooling the reactor contents through a reactor jacket or cooling coil, automatic refrigeration, pre-cooled feed, evaporation of the liquid medium (diluent, monomer, or solvent), or a combination of all three. An adiabatic reactor with a pre-cooled feed can also be used. The purity, type, and amount of solvent can be optimized for specific types of polymerization to maximize catalyst productivity. Solvents can also be introduced as catalyst supports. Depending on pressure and temperature, solvents can be introduced in the gas or liquid phase. Advantageously, solvents can be maintained in the liquid phase and introduced as liquids. Solvents can be introduced into the polymerization reactor as feed.

[0314] The methods described herein can be solution polymerization methods, which can be carried out in a batch (e.g., batch; semi-batch) or continuous manner. Suitable reactors can include kettle, loop, and tubular designs. In at least one embodiment, the method is carried out continuously and uses a dual loop reactor configured in series. In at least one embodiment, the method is carried out continuously and uses a dual continuous stirred tank reactor (CSTR) configured in series. Furthermore, the method can be carried out continuously and a tubular reactor can be used. In another embodiment, the method is carried out continuously and uses a loop reactor and a CSTR configured in series. The method can also be carried out in a batch manner and a single stirred tank reactor can be used.

[0315] Catalyst activity and polymer properties

[0316] Unless otherwise stated, catalyst activity is a measure of how active a catalyst is and is reported as the mass of product polymer (P) produced per mole of catalyst (cat) used (kgP / molcat) or the mass of product polymer (P) produced per mass of catalyst (cat) used (gP / gcat). The amount of catalyst (moles or mass) refers to the amount (moles or mass) of the metal element in the catalyst. Catalyst activity can also be expressed over a time period of hours T and reported as the mass of product polymer (P) produced per mole or millimole of catalyst (cat) used, in gP / mmolcat. -1 hr -1 The activity of a catalyst used for copolymerizing ethylene and conjugated dienes depends on the catalyst's structure, the activator used, the metal element incorporated into the catalyst, the concentration of the catalyst in the reaction medium, and / or the composition of the copolymerized monomer system. In some embodiments, the catalyst activator is anionic or cationic alkylaluminoxane. In some embodiments, the co-activator is diisobutylaluminum hydride (DIBAL). In some embodiments, the catalyst activity is about 0.01 kg. 聚合物 / mol cat Approximately 350 kg 聚合物 / mol cat For example, about 5 kg 聚合物 / mol cat Approximately 340 kg 聚合物 / mol cat For example, about 10 kg 聚合物 / mol cat Approximately 330 kg 聚合物 / mol cat For example, about 25 kg 聚合物 / mol cat Approximately 320 kg 聚合物 / mol cat For example, about 50 kg 聚合物 / mol cat Approximately 310 kg 聚合物 / mol cat For example, about 100 kg 聚合物 / mol cat Approximately 300 kg 聚合物 / mol cat For example, about 150kg 聚合物 / mol cat Approximately 290 kg 聚合物 / mol cat For example, about 200 kg 聚合物 / mol cat Approximately 275 kg 聚合物 / molcat For example, about 230 kg 聚合物 / mol cat Approximately 250 kg 聚合物 / mol cat In some implementations, the catalyst activity is approximately 0.01 kg. 聚合物 / mol cat Approximately 285 kg 聚合物 / mol cat In some implementations, the catalyst activity is approximately 5.5 kg. 聚合物 / mol cat Approximately 45 kg 聚合物 / mol cat In some implementations, the catalyst activity is approximately 100 kg. 聚合物 / mol cat Approximately 250kg 聚合物 / mol cat For example, about 175 kg 聚合物 / mol cat approximately 225 kg 聚合物 / mol cat In some implementations, the catalyst activity is approximately 20 kg. 聚合物 / mol cat Approximately 350 kg 聚合物 / mol cat For example, approximately 230 kg 聚合物 / mol cat Approximately 260kg 聚合物 / mol cat .

[0317] In some embodiments, the resulting polyolefin product is formed via copolymerization of ethylene and a conjugated diene. Typically, copolymerization of ethylene and a conjugated diene on an industrial scale is considered a difficult process because the monomers have different polymerization mechanisms and relative reactivity. However, the polymerization method disclosed herein has been found to reduce manufacturing and processing problems associated with such polymers—the method shows the production of high molecular weight polymers with increased catalytic activity.

[0318] In some embodiments, the copolymer formed by the copolymerization of ethylene and butadiene is represented by Scheme 5:

[0319] Option 5

[0320]

[0321] A significant aspect of the copolymers includes butadiene units with two adjacent carbon atoms of a cyclopentane ring in the main chain. Some butadiene is incorporated in the trans-1,4 configuration, forming a straight main chain with one degree of unsaturation. Some butadiene can also be incorporated in the cis-1,4 configuration, also forming a straight main chain with one degree of unsaturation, but with both hydrogens associated with the double-bonded carbon on the same side of the double bond. Finally, some butadiene, typically very small to zero, can be incorporated in the 1,2 configuration, leaving dangling vinyl groups as unsaturated branches on the saturated carbon chain. Thus, copolymers with sufficient residual unsaturation in the main chain or side chains can be formed for eventual use in specific applications, such as crosslinking or chemical modification.

[0322] The ethylene copolymers disclosed herein exhibit improved properties in controlling polymer crystallinity, particularly due to the more efficient use of diene comonomers. Specifically, the efficient use of diene comonomers involves improved separation of comonomer molecules along the polyethylene chain, which was not previously achieved for such ethylene copolymers. Therefore, the polymers of this disclosure not only have particularly good applications for those uses previously employed with such polymers, but also exhibit excellent overall physical properties in tires, including improved traction and low rolling resistance, marking a significant improvement over previously available materials. The improved properties of the polymers are caused by the separation and dispersion of the diene comonomers and other comonomers along the polymer molecular sequence.

[0323] In some embodiments, the Mw of the ethylene copolymer of this disclosure is from about 100,000 g / mol to about 2,000,000 g / mol, for example from about 110,000 g / mol to about 500,000 g / mol, for example from about 113,000 g / mol to about 350,000 g / mol.

[0324] In some embodiments, the PDI of the ethylene copolymer of this disclosure is about 1.5 to about 70, for example about 2 to about 10, for example about 3 to about 6.

[0325] In some embodiments, the ethylene copolymer of this 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%.

[0326] In some embodiments, the ethylene copolymer of this disclosure has about 0.01 mol% to about 3 mol% of 1,2-configured butadiene along the main chain of the polymer, for example about 0.1 mol% to about 2 mol%, for example about 0.5 mol% to about 1 mol%.

[0327] In some embodiments, the ethylene copolymer of this disclosure has about 0.01 mol% to about 10 mol% of butadiene in the 1,4-trans configuration along the main chain of the polymer, 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%.

[0328] In some embodiments, the ethylene copolymer of this disclosure has about 1 mol% to about 20 mol% of 1,4-cis configuration butadiene along the main chain of the polymer, 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%.

[0329] In some embodiments, the ethylene copolymer of this disclosure has a Mw / Mn (PDI) value of about 2 to about 65, for example about 5 to about 55, for example about 10 to about 40, for example about 15 to about 35, or about 20 to about 30.

[0330] In some embodiments, the molar ratio of activator to copolymerization precatalyst is from about 10:1 to about 100:1, for example, from about 20:1 to about 60:1. It should be noted that increasing the activator content relative to the catalyst compound leads to increased catalyst activity. Additionally, increasing the activator content relative to the catalyst leads to a decrease in the molecular weight (Mw) of the polymer product, thus allowing for precise control of Mw in the polymerization process. This is consistent with the coordination chain transfer mechanism of copolymerization.

[0331] In some embodiments, the thermal melt temperature (Tm) of the ethylene copolymer is from about 95°C to about 130°C, for example from about 95°C to about 1115°C, for example from about 98°C to about 110°C. In some embodiments, the ethylene copolymer has two thermal melt temperatures simultaneously.

[0332] Novel rare-earth-based bis(phenolate) catalyst systems can be activated with various TMA-free activators to produce ethylene-butadiene copolymers at high conversion rates under mild conditions—a process widely considered difficult due to differences in reaction mechanisms and monomer reactivity ratios. Interestingly, the applicant has found that higher activity can be obtained in reaction mixtures activated with anionic or cationic alkylaluminoxanes (including F-MAO or ionic MAO) compared to the activity obtained with conventional activators (DIMAH-D4 / DIBAL or TMA-free commercial MAO). Without being bound by theory, the increase in activity is believed to be due to a reduction in free TMA in the activator / catalyst system. As previously mentioned, free TMA leads to poor activity and short catalyst lifetime because the free TMA present in MAO can alkylate the transition metal centers of the pre-catalyst, similar to the alkylation of metallocenes with dichloride leaving groups. Activation of the bis(phenolate)-catalyst with the activator disclosed herein yields polyolefin polymer products containing a large amount of 1,2-cyclopentane units, with both monomers incorporated fairly uniformly throughout the polymer chain. In contrast, lanthanide-based metallocene catalysts (e.g., Michelin's Nd-bisfluorene) yield products containing 1,2-cyclohexane segments.

[0333] Unbound 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 to form crystalline domains due to inter- and intra-chain interactions. While crystalline domains can provide benefits to polymer materials, in some cases, the amount of crystalline domains within the polymer system can adversely affect the physical properties of the resulting material (e.g., tensile strength, abrasion resistance, and brittleness). Unbound by theory, the incorporation of 1,2-cyclopentane units along the polymer backbone disrupts the polymer chain's ability to organize into crystalline domains, thereby reducing the percentage of crystallinity within the system. Furthermore, uniform incorporation of 1,2-cyclopentane units along the polymer backbone further ensures that polymer crystallinity is mitigated due to the reduction in ethylene-rich regions within the polymer system. Therefore, unique products are provided in high yields by MAO without TMA and ionic MAO-activated bis(phenolate) catalysts, making these systems highly attractive for industrial applications.

[0334] Polymer functionalization

[0335] In some cases, it may be desirable to incorporate polar groups along the polymer backbone so that subsequent reactions can be carried out after polymerization. In some embodiments, the polymerization described herein further includes the use of a third monomer, which is a metal hydrocarbon alkenyl transfer agent (which is any Group 12 or 13 metal reagent containing at least one transferable group having an allyl end), such as an aluminum vinyl transfer agent, also known as AVTA (which is any aluminum reagent containing at least one transferable group having an allyl end).

[0336] The suitable catalyst systems of this disclosure can have high olefin growth rates and negligible or no chain termination via β-hydrogen elimination, β-methyl elimination or chain transfer to monomers, relative to the rate of chain transfer to AVTA or other chain transfer agents, such as alkylaluminum (if present).

[0337] In at least one embodiment of this disclosure, the aluminum vinyl transfer agent is represented by formula (D):

[0338] Al(R') v (R”) 3-v (D)

[0339] Where R' is a hydrocarbon group containing 1 to 30 carbon atoms, R” is a hydrocarbon alkenyl group containing 4 to 20 carbon atoms with an allyl end, and v is 0.1 to 3, or 1 to 3, or 1.1 to less than 3, or v is 0.5 to 2.9, 1.1 to 2.9, or 1.5 to 2.7, or 1.5 to 2.5, or 1.8 to 2.2. Although from formula Al(R') 3-v (R”) v The appropriate compound to represent this is a neutral substance, but anionic forms can also be conceived, such as those represented by formula (B): [Al(R')4- w (R”) w ]-, where w is 0.1-4, R' is a hydrocarbon group containing 1 to 30 carbon atoms, and R” is a hydrocarbon alkenyl group containing 4 to 20 carbon atoms with an allyl chain end.

[0340] In at least one embodiment of any of the aluminum vinyl transfer agents described herein, R' is independently selected from C1-C1. 30 Hydrocarbon groups (e.g., C1-C) 20 Alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or isomers thereof, and R” is represented by the following formula:

[0341] -(CH2) n CH=CH2

[0342] Where n is an integer from 2 to 18, for example, from 6 to 18, for example, from 6 to 12, for example, 6.

[0343] Aluminum vinyl transfer agents may include one or more of the following: tris(but-3-en-1-yl)aluminum, tris(pent-4-en-1-yl)aluminum, tris(oct-7-en-1-yl)aluminum, tris(non-8-en-1-yl)aluminum, tris(dec-9-en-1-yl)aluminum, tris(dodecyl-11-en-1-yl)aluminum, dimethyl(oct-7-en-1-yl)aluminum, diethyl(oct-7-en-1-yl)aluminum, dibutyl(oct-7-en-1-yl)aluminum, diisobutyl(oct-7-en-1-yl)aluminum, diisobutyl(non-8-en-1-yl)aluminum, dimethyl(dec-9-en-1-yl)aluminum, diethyl(dec-9-en-1-yl)aluminum, dibutyl( Dec-9-en-1-yl)aluminum, diisobutyl(dec-9-en-1-yl)aluminum and diisobutyl(dodec-11-en-1-yl)aluminum, methyl-di(oct-7-en-1-yl)aluminum, ethyl-di(oct-7-en-1-yl)aluminum, butyl-di(oct-7-en-1-yl)aluminum, isobutyl-di(oct-7-en-1-yl)aluminum, isobutyl-di(non-8-en-1-yl)aluminum, methyl-di(dec-9-en-1-yl)aluminum, ethyl-di(dec-9-en-1-yl)aluminum, butyl-di(dec-9-en-1-yl)aluminum, isobutyl-di(dec-9-en-1-yl)aluminum and isobutyl-di(dodec-11-en-1-yl)aluminum.

[0344] In at least one embodiment of this disclosure, particularly useful AVTAs include, but are not limited to, tris(but-3-en-1-yl)aluminum, tris(pent-4-en-1-yl)aluminum, tris(oct-7-en-1-yl)aluminum, tris(non-8-en-1-yl)aluminum, tris(dec-9-en-1-yl)aluminum, dimethyl(oct-7-en-1-yl)aluminum, diethyl(oct-7-en-1-yl)aluminum, dibutyl(oct-7-en-1-yl)aluminum, diisobutyl(oct-7-en-1-yl)aluminum, diisobutyl(non-8-en-1-yl)aluminum, diisobutyl(dec-9-en-1-yl)aluminum, diisobutyl(dodecyl-11-en-1-yl)aluminum, etc. Mixtures of one or more AVTAs may also be used. In some embodiments of this disclosure, isobutyl-di(oct-7-en-1-yl)-aluminum, isobutyl-di(dec-9-en-1-yl)-aluminum, isobutyl-di(non-8-en-1-yl)-aluminum, and isobutyl-di(hept-6-en-1-yl)-aluminum are suitable.

[0345] Aluminum vinyl transfer agents can comprise the product of an organoaluminum compound reaction between an aluminum reagent (AlR3) and an alkyl diene. Suitable alkyl dienes include those having two "α-olefins" as described above at both ends of the carbon chain. Alkyl dienes can be straight-chain or branched alkyl chains and can be substituted or unsubstituted. Exemplary alkyl dienes include, for example, 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-tetracenediene, 1,13-tetradecadiene, 1,14-pentadecadiene, 1,15-hexadecadiene, 1,16-heptadecadiene, 1,17-octadecadiene, 1,18-nonadecadiene, 1,19-eicosadiene, 1,20-teicosadiene, etc. Exemplary aluminum reagents include triisobutylaluminum, diisobutylaluminum hydride, isobutylaluminum dihydride, 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 dihydride, or aluminum hydride (AlH3)) with an alkyl diene and heating to a temperature that causes the release of olefinic byproducts. The use of one or more solvents is not required. However, nonpolar solvents such as hexane, pentane, toluene, benzene, xylene, etc., or combinations thereof, can be used. In at least one embodiment of this disclosure, AVTA is free of coordinating polar solvents such as tetrahydrofuran and diethyl ether. After the reaction is complete, the solvent (if present) can be removed, and the product can be used directly without further purification.

[0346] 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.

[0347] In at least one embodiment of this disclosure, v in formula (D) is about 2, or v is 2.

[0348] In at least one embodiment, v in formula (D) is about 1, or v is 1, for example about 1 to about 2.

[0349] In some implementations, v in equation (D) can be an integer or a non-integer, for example, v is 1.1 to 2.9, for example, about 1.5 to about 2.7, for example, about 1.6 to about 2.4, for example, about 1.7 to about 2.4, for example, about 1.8 to about 2.2, for example, about 1.9 to about 2.1 and all ranges therein.

[0350] In at least one embodiment, R′ is isobutyl, and R″ is each octenyl or decenyl, and v is 1.1 to 2.9, for example about 1.5 to about 2.7, for example about 1.6 to about 2.4, for example about 1.7 to about 2.4, for example about 1.8 to about 2.2, for example about 1.9 to about 2.1.

[0351] The quantity v is described by the following formula: (3-v)+v=3, and Al(R′). v (R″) 3-v , where R″ is a hydrocarbon alkenyl group with 4 to 20 carbon atoms having an allyl end, R′ is a hydrocarbon group with 1 to 30 carbon atoms, and v is 0.1 to 3 (e.g., 1.1 to 3). This formula represents the observed average value of organoaluminum substances present in a mixture (e.g., by means of...). 1 (As determined by H NMR), the mixture may contain any of Al(R′)3, Al(R′)2(R″), Al(R′)(R″)2, and Al(R″)3. On the other hand, based on the weight of AVTA, the aluminum vinyl transfer agent has a dimer present in less than 50% by weight, for example, less than 40% by weight, for example, less than 30% by weight, for example, less than 20% by weight, for example, less than 15% by weight, for example, less than 10% by weight, for example, less than 5% by weight, for example, less than 2% by weight, for example, less than 1% by weight, for example, 0% by weight. Alternatively, the dimer... It exists in amounts of 0.1-50% by weight, or 1-20% by weight, or 2-10% by weight. The dimer is a dimer product of the alkyl diene used in the preparation of AVTA. The dimer can be formed under certain reaction conditions and is formed by inserting the diene molecule into the Al-R bond of AVTA followed by β-hydrogen elimination. For example, if the alkyl diene used is 1,7-octadiene, the dimer is 7-methylenepentadecane-1,14-diene. Similarly, if the alkyl diene is 1,9-decadiene, the dimer is 9-methylenenonadecane-1,18-diene.

[0352] For the polymerization of this disclosure, the molar ratio of AVTA to the catalyst complex can be greater than 5, or greater than 10, or greater than 15, or greater than 20, or greater than 25, or greater than 30.

[0353] In at least one embodiment of this disclosure, the metal hydrocarbon alkenyl chain transfer agent is represented by the following formula: Al(R′) 3-v (R″) v Where R′ are each independently C1-C 30 Each of the hydrocarbon groups, R″, is independently a C4-C group with a terminal vinyl group. 20 The hydrocarbon is alkenyl, and v is 0.1 to 3, for example, R” is independently a C4-C chain with an allyl end. 20 The hydrocarbon is alkenyl, and v is 0.1 to 3, for example, v=2.

[0354] This technology can be used to produce intrachain functionalized ethylene / butadiene copolymers. Furthermore, the method disclosed herein allows for intrachain functionalization of ethylene / butadiene copolymers within a single reactor. The aluminum-carbon bond can react with various electrophilic agents (and other reagents), such as oxygen, halogens, and carbon dioxide, to form functionalized vinyl transfer agent units. For example, the aluminum-carbon bond reacts with carbon dioxide to form carbon dioxide-functionalized vinyl transfer agent units.

[0355] tire

[0356] In some embodiments, the copolymers of this disclosure can be used as components of tires. The tire (also referred to herein as a “tire product”) can be any suitable tire, such as a rubber tire having an outer (visible) rubber sidewall layer, wherein the outer sidewall layer comprises the copolymers of this disclosure. The tire can be constructed, shaped, molded to include the outer sidewall (rubber sidewall layer) and cured by various methods clearly visible to those skilled in the art.

[0357] Blends of highly saturated specialty elastomers with highly unsaturated polymers may be required to improve the blend's performance window (e.g., oxygen and ozone resistance, thermal stability, viscosity, etc.). Particularly for tire treads, the tread compound in a tire determines its performance characteristics, such as wear, traction, and rolling resistance. Providing excellent traction and low rolling resistance while offering good tread wear is a technical challenge. The challenge lies in striking a trade-off between wet traction and rolling resistance / tread wear.

[0358] Because the methods and polymers of this disclosure reduce or eliminate the need to introduce fillers into the final tire product, the reduction or absence of fillers in the tire product provides improved wear resistance of the tire product (tire tread), such as reducing or eliminating crack initiation and propagation.

[0359] As used herein, the term "filler" refers to any material used to enhance or alter the physical properties of a composition (as a tire product), impart certain processing properties, or reduce the cost of a tire.

[0360] In some implementations, examples of inorganic fillers include calcium carbonate, clay, mica, silica, silicates, talc, titanium dioxide, alumina, zinc oxide, starch, wood flour, or one or more combinations thereof. The filler can be of any size and range, for example, from 0.0001 μm to 100 μm in the tire industry.

[0361] As used herein, the term "silica" refers to any type or particle size of silica or other silicic acid derivatives or silicic acid processed by solution, pyrolysis, or similar methods, including untreated precipitated silica, crystalline silica, colloidal silica, aluminum silicate or calcium silicate, pyrolytic silica, etc. Precipitated silica can be conventional silica, semi-dispersible silica, or highly dispersed silica. The filler can be supplied by Rhodia under the trade name ZEOSIL. TM Z1165 or ZEOSIL TM 1165MP purchased commercially.

[0362] Because the functionalized copolymers of this disclosure can provide improved interactions between the copolymer and one or more additives, fewer additives (e.g., fillers) can be used compared to conventional tire compositions. In some embodiments, the composition (as a tire product) contains less than 150 phr per 100 parts by weight of rubber (phr), for example, about 10 to about 150 phr of filler (e.g., silica). In another embodiment, the composition (as a tire product) contains about 30 to about 130 phr of filler. In yet another embodiment, the composition contains about 50 to about 90 phr of filler.

[0363] Example

[0364] GPC-4D:

[0365] Unless otherwise stated, the molecular weight distribution and moments (Mw, Mn, Mz, Mw / Mn, etc.) and comonomer content are determined by using an infrared detector IR5 equipped with a multi-channel bandpass filter, specifically an infrared detector assembly IR5 with a multi-channel bandpass filter (which has a coverage of approximately 2700 cm⁻¹). -1 Approximately 3000 cm -1The determination was performed using high-temperature gel permeation chromatography (Polymer Char GPC-IR) with an 18-angle light scattering detector and a viscometer, targeting the band region (representing the saturated CH stretching vibration). Polymer separation was achieved using three Agilent PLgel 10-µm mixed-B LS columns. A reagent-grade 1,2,4-trichlorobenzene (TCB) (from Sigma-Aldrich) containing ~300 ppm of the antioxidant BHT was used as the mobile phase, with a nominal flow rate of ~1.0 mL / min and a nominal injection volume of ~200 μL. The entire system, including the transfer line, columns, and detector, could be contained in an oven maintained at ~145°C. A given sample volume could be weighed and sealed in a standard vial containing ~10 μL of a flow marker (heptane). After loading the vial into the autosampler, oligomers or polymers could be automatically dissolved in the instrument with ~8 mL of added TCB solvent vial after continuous shaking at ~160°C. Sample solution concentrations can range from ~0.2 to ~2.0 mg / ml, with lower concentrations used for higher molecular weight samples. The concentration c at each point in the chromatogram can be obtained by subtracting the baseline from the broadband IR5 signal. I Using the equation: c=α I The mass recovery rate is calculated using a mass constant determined using polyethylene or polypropylene standards, where α is the mass constant. The mass recovery rate can be calculated as the ratio of the integral area of ​​the concentration chromatography within the elution volume to the injection mass (which equals the predetermined concentration multiplied by the injection loop volume). The conventional molecular weight (IR MW) is determined by combining a universal calibration relation with column calibration (using a range of monodisperse polystyrene (PS) standards ranging from 700 to 10 M gm / mol). The MW at each elution volume is calculated using the following equation:

[0366]

[0367] Variables with the subscript "PS" represent polystyrene, while those without subscripts represent the test sample. In this method, α ps =0.67 and K PS =0.000175, α and K for other materials were calculated using GPC ONE™ software (PolymerCharacterization, SA, Valencia, Spain). Unless otherwise specified, concentrations are expressed in g / cm³. 3 The molecular weight is expressed in g / mole, and the intrinsic viscosity (and therefore K in the Mark-Houwink equation) is expressed in dL / g.

[0368] The comonomer composition was determined by the ratio of the IR5 detector intensities of the CH2 and CH3 channels, calibrated using a series of PE and PP homopolymer / copolymer standards (whose nominal values ​​were predetermined by NMR or FTIR). Specifically, this provides the amount of methyl groups per 1000 total carbons as a function of molecular weight (CH3 / 1000TC). The amount of short-chain branching (SCB / 1000TC) as a function of molecular weight was then calculated by applying a chain-end correction to the CH3 / 1000TC function, assuming that each chain is linear and capped at each end with methyl groups. The weight % of comonomers was then obtained by the following expression, where f is 0.3, 0.4, 0.6, 0.8, etc., for comonomers such as C3, C4, C6, and C8, respectively:

[0369]

[0370] The bulk composition of the polymer, as analyzed by GPC-IR and GPC-4D, was obtained by considering the entire signal of the CH3 and CH2 channels between the integration limits of the concentration chromatogram. First, the following ratios were obtained.

[0371]

[0372] Then, the same correction as previously mentioned for obtaining the CH3 / 1000TC as a function of molecular weight is applied to obtain the bulk CH3 / 1000TC. The bulk methyl chain terminus (bulk CH3 terminus / 1000TC) is obtained by weight-average and chain terminus correction within the molecular weight range.

[0373]

[0374]

[0375] And convert the SCB / 1000TC into a physical body in the same way as described above. .

[0376] The LS detector is an 18-angle Wyatt Technology High Temperature DAWN HELEOSII. The LS molecular weight at each point in the chromatogram is... M By using the Zimm model for static light scattering ( Light Scattering from Polymer Solutions (Huglin, MB, Ed.; Academic Press, 1972.) This is used to analyze the LS output to determine:

[0377]

[0378] Here, ΔR(θ) is the excess Rayleigh scattering intensity measured at scattering angle θ, c is the polymer concentration determined by IR5 analysis, A2 is the second virial coefficient, P(θ) is the shape factor of the monodisperse random coil, and K o These are the optical constants of the system:

[0379]

[0380] Where NA is Avogadro's constant, and (dn / dc) is the refractive index increment of the system, with n=1.500 for TCB at 145℃ and λ=665nm. For the analysis of polyethylene homopolymers, ethylene-hexene copolymers, and ethylene-octene copolymers, dn / dc=0.1048 ml / mg and A2=0.0015; for the analysis of ethylene-butene copolymers, dn / dc=0.1048 (1-0.00126 w2) ml / mg and A2 = 0.0015, where w2 is the weight percentage of butene comonomer.

[0381] Specific viscosity is determined using a high-temperature Agilent (or Viscotek Corporation) viscometer, which has four capillaries arranged in a Wheatstone bridge configuration with two pressure sensors. One sensor measures the total pressure drop across the detector, and the other, located between the two sides of the bridge, measures the pressure difference. The specific viscosity η of the solution flowing through the viscometer is calculated from their outputs. S The intrinsic viscosity [η] at each point in the chromatogram is calculated using the equation [η] = ηs / c, where c is the concentration and is determined by the IR5 broadband channel output. The viscosity MW at each point is calculated according to... To calculate, where ps It is 0.67 and K ps It is 0.000175.

[0382] In DSC2500 TM Differential scanning calorimetry (DSC) was performed on a TA Instruments instrument to determine the glass transition temperature (Tg) and melting point (Tm) of the polymer of this disclosure 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 to a final temperature of 150°C at a rate of 10°C / min and held at that temperature for 5 minutes. A second cooling-heating cycle was then performed using the same conditions as above. The events “first melt” and “second melt” from the two cycles were recorded respectively. References to melting point temperature (Tm) and glass transition temperature (Tg) refer to the second melt.

[0383] Catalyst Synthesis

[0384] Option 6

[0385]

[0386] Ln(Me3SiCH2)3(THF)2 (Ln=Sc,Y,Lu) is synthesized from (trimethylsilyl)methyllithium (0.7M in hexane; Acros Organics) and anhydrous LnCl3 (Aldrich), as follows: Chemical Communications As described in 2016, Vol. 52(31), pp. 5425-5427. Ln(N(SiMe2H)2)3(THF) n (Ln=Sc, Y, La) as in the literature ( Organometallics 2013, Volume 32, pp. 1528-1530 and J. Org. Chem. Prepared as described in 2007, 72, Vol. 23, pp. 8648-8655. The ligand precursor 2′,2'''-(pyridin-2,6-diyl)bis(3-(tert-butyl)-5-methyl-[1,1′-biphenyl]-2-phenol) is synthesized as described in WO2020 / 167824. The ligand precursor 6,6′-(pyridin-2,6-diyl)bis(benzo[b]thiophene-3,2-diyl))bis(2-(tert-butyl)-4-methylphenol) is synthesized as described in WO2020 / 167819. The ligand precursor 2′,2'''-(pyridin-2,6-diyl)bis(3-(adamantane-1-yl)-5-(tert-butyl)-[1,1′-biphenyl]-2-phenol) is synthesized as described in US11,254,763. Methylaluminoxane was used as a 30 wt% toluene solution (Grace, 13.5 wt% Al, 5 mmol Al / g). Ammonium hexafluorosilicate (NH4)2SiF6 was purchased from Aldrich and dried under vacuum at ambient temperature for 16 h. Octamethyltrisiloxane (OMTS, Aldrich) was degassed and dried on an activated molecular sieve (3 Å) for 16 h. All other reagents were commercially available, and all solvents were dried and degassed using previously reported conventional methods before use. The metal complex (also known as the catalyst) and pre-catalyst were prepared under an inert atmosphere as shown in Scheme 6.

[0387] Example 1. Synthesis of complex Y-1

[0388]

[0389] In a 20 mL scintillation vial, 182 mg of Y(Me3SiCH2)3(THF)2 (0.368 mmol) was added in a single batch to a suspension of 204 mg (0.368 mmol) of 2′,2'''-(pyridine-2,6-diyl)bis(3-(tert-butyl)-5-methyl-[1,1'-biphenyl]-2-phenol) in 10 mL of hexane at -30 °C. The resulting mixture was stirred at room temperature for 6 hours and the vial was placed in a refrigerator (-30 °C). After 12 hours, the precipitate was filtered out 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 out using a syringe filter (0.45 μm PTFE), and the mother liquor was evaporated to dryness to give 145 mg (49%) of the product as a beige powder. 47 H 58 Analysis and calculation of YNO3Si: C, 70.39; H, 7.29; N, 1.75. Found: 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).

[0390] Example 2. Synthesis of complex Sc-2

[0391]

[0392] In a 20 mL scintillation vial at room temperature, 170 mg (0.255 mmol) of 6,6'-(pyridine-2,6-dimethylbis(benzo[]) bThiophene-3,2-diyl)bis(2-(tert-butyl)-4-methylphenol) was added in a single batch of 115 mg of Sc(Me3SiCH2)3(THF)2 (0.255 mmol) to a suspension in 10 mL of hexane and 0.5 mL of toluene. The resulting solution was stirred at room temperature for 12 hours and the flask was placed in a refrigerator (-30°C). After 12 hours, the precipitate was filtered out using a syringe filter (0.45 μm PTFE), and the mother liquor was returned to the refrigerator. After 12 hours, the precipitate was filtered out again using a syringe filter (0.45 μm PTFE), and the mother liquor was evaporated to dryness to give 127 mg (57%) of the product as a grayish-white solid. 51 H 58 Analytical calculations for ScNS2O3Si: C, 70.39; H, 6.72; N, 1.61. Found: C 70.68; H 6.98; N 1.50. 1 H NMR (400 MHz, benzene-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). 13C NMR (400 MHz, benzene-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.

[0393] Example 3. Synthesis of complex Y-2

[0394]

[0395] In a 20 mL scintillation vial at room temperature, 135 mg (0.202 mmol) of 6,6'-(pyridine-2,6-dimethylbis(benzo[]) was added. b Thiophene-3,2-diyl)bis(2-(tert-butyl)-4-methylphenol) was added in a single batch of 100 mg of Y(Me3SiCH2)3(THF)2 (0.202 mmol) to a suspension in 10 mL hexane and 0.5 mL toluene. The resulting solution was stirred at room temperature for 12 hours and the flask was placed in a refrigerator (-30°C). After 12 hours, the precipitate was filtered out 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 out using a syringe filter (0.45 μm PTFE), and the mother liquor was evaporated to dryness to give 124 mg (67%) of the product as a grayish-white solid. 51 H 58 Analysis and calculation of YNS2O3Si: C, 67.01; H, 6.40; N, 1.53. Found: C 66.85; H 6.65; N 1.31. 1H NMR (400 MHz, benzene-d6): δ7.61 (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, 1.1Hz, 1H), 6.21 (d, J = 7.7 Hz, 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). 13 C NMR (400MHz, 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.

[0396] Example 4. Synthesis of complex Sc-3

[0397]

[0398] In a 20 mL scintillation vial, at room temperature, 294 mg of Sc(CH2SiMe3)3(THF)2 (0.660 mmol) was added in a single batch to a suspension of 526 mg (0.660 mmol) of 2′,2'''-(pyridin-2,6-diyl)bis(3-(adamantane-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) 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 a refrigerator (-30°C). After 12 hours, the precipitate was filtered out using a syringe filter (0.45 μm PTFE), and the mother liquor was returned to the refrigerator. After 12 hours, the precipitate was filtered out again using a syringe filter (0.45 μm PTFE), and the mother liquor was evaporated to give 103 mg (15%) of the product as a grayish-white solid. 65 H 82 Analysis and calculation of ScNO3Si: C, 78.20; H, 8.28; N, 1.40. Found: C 78.42; H 8.61; N 1.26. 1 H NMR (400 MHz, benzene-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). 13C NMR (400 MHz, benzene-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.

[0399] Example 5. Synthesis of complex Y-3

[0400]

[0401] In a 20 mL scintillation vial, at room temperature, 63 mg of Y(Me3SiCH2)3(THF)2 (0.127 mmol) was added in a single batch to a suspension of 101 mg (0.127 mmol) of 2′,2'''-(pyridin-2,6-diyl)bis(3-(adamantane-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) in 20 mL of hexane and 1.5 mL of toluene. The resulting solution was stirred at room temperature for 12 hours, and the vial was placed in a refrigerator (-30°C). After 12 hours, the precipitate was filtered out using a syringe filter (0.45 μm PTFE), and the mother liquor was returned to the refrigerator. After another 12 hours, the precipitate was filtered out again using a syringe filter (0.45 μm PTFE), and the mother liquor was evaporated to give 110 mg (83%) of a product as a grayish-white solid. 65 H 82 Analysis and calculation of YNO3Si: C, 74.90; H, 7.93; N, 1.34. Found: C 75.27; H 8.12; N 1.19. 1H NMR (400 MHz, benzene-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).

[0402] Example 6. Synthesis of the complex Sc-3-N

[0403]

[0404] In a 20 mL scintillation flask, [Sc{N(SiMe2H)2}2]·THF (207 mg, 0.4 mmol) was dissolved in 2 mL of THF. Then, solid 2′,2'''-(pyridin-2,6-diyl)bis(3-(adamantane-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) (312 mg, 0.39 mmol) was slowly added under stirring at ambient temperature. 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 the volatiles were removed under a nitrogen stream. n-Pentane (5 mL) was added to the pale yellow oily residue and evaporated to facilitate the removal of residual THF. This process was repeated twice to obtain a pale yellow powder, which 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. White crystals were decanted and dried under vacuum to give 129 mg (33%) of the desired product. 1 The width of the resonance signal in the H NMR spectrum hinders their accurate integration. 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).

[0405] Example 7. Synthesis of the complex Y-3-N

[0406]

[0407] In a 20 mL scintillation flask, [Y{N(SiMe2H)2}2]·1.5 THF (235 mg, 0.39 mmol) was dissolved in 2 mL of THF. Then, solid 2′,2'''-(pyridin-2,6-diyl)bis(3-(adamantane-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol) (305 mg, 0.38 mmol) was slowly added under stirring at ambient temperature. 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 the volatiles were removed under a nitrogen stream. n-Pentane (5 mL) was added to the pale yellow oily residue and evaporated to facilitate the removal of residual THF. This process was repeated twice to obtain a pale yellow powder, which was dissolved in toluene (1 mL). The resulting solution was separated into layers 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 time). It was then dried under vacuum with gentle heating (below 40 °C) to give 273 mg of white solid product (64%). 1 H NMR (400MHz, benzene-d6): δ7.48-7.33 (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).

[0408] Example 8. Synthesis of the complex La-3-N

[0409]

[0410] In a 20 mL scintillation flask, [La{N(SiMe2H)2}2]·1.5 THF (243 mg, 0.35 mmol) was dissolved in 2 mL of THF. Then, solid 2′,2'''-(pyridin-2,6-diyl)bis(3-(adamantane-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenol (273 mg, 0.34 mmol) was slowly added under stirring at ambient temperature. After addition, the reaction mixture was diluted by adding 3 mL of THF. The resulting mixture was stirred at 60 °C for 2 hours, followed by removal of volatiles under a nitrogen stream and heating at 60 °C. n-Pentane (5 mL) was added to the pale yellow oily residue and evaporated to promote the removal of residual THF and HN(SiMe2H)2. This process was repeated five times, yielding a pale yellow powder, which was washed twice with n-pentane (7 mL each time). The resulting product was dissolved in toluene (3 mL), and the solution was then passed through a glass microfiber filter and a celite stopper. The filtrate was concentrated to about 0.5 mL and separated into layers with n-pentane at -35 °C, yielding a yellow crystalline precipitate. The precipitate was collected by decantation and dried under vacuum for 4 hours to give 297 mg of product (70%). 1 H NMR (400MHz, 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 ( sept, 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).

[0411] Example 9. F-MAO without TMA.

[0412] Reaction: (NH4)2SiF6 + 8AlMe3 = 2 / 6 [(AlMeNH)3]2 + 6AlMe2F + SiMe4 + 6CH4

[0413] Ammonium hexafluorosilicate (NH4)2SiF6 (0.66 g, 3.7 mmol) was slowly added to a commercial solution of MAO in toluene (30 wt% MAO, 40 g, 200 mmol Al). The resulting mixture was shaken for 1 hour to obtain an F-MAO solution.

[0414] Example 10. Ionic MAO without TMA.

[0415]

[0416] Octamethyltrisiloxane (OMTS) (4.80 g, 20.3 mmol) was added to a commercial solution of MAO in toluene (109.0 g, 30 wt% MAO, 545 mmol Al), and the resulting mixture was stirred at ambient temperature for 45 min. The solution was then transferred to a separating funnel and allowed to settle for 16 h, after which the two liquid layers were separated. The bottom layer (51 g, oil) was heated at 90 °C for 1 h to promote the low-activity chelation of AlMe2 (OMTS). + The cation is converted into an active monodentate coordination [(AlMe2)2(OSiMe3)] + Substance. Ionic MAO is also called I-MAO.

[0417] Example 11. Quantification of total THF-extractable TMA content in MAO solution According to Scheme 7, the total TMA content in the MAO composition, including both coordinated and free TMA, can be converted into AlMe3(THF) as the major product and AlMe2(THF)2 as the minor product by THF solvent treatment. + To quantify. Therefore, the total TMA is AlMe3(THF) and AlMe2(THF)2. + The sum (converted back to TMA in the calculation), and can be used as follows 1 Quantification is performed using 1H NMR, where toluene is used as an internal standard for solution MAO, or an added inert compound is used as an internal standard for solution MAO, solid MAO, or supported MAO.

[0418] Option 7

[0419]

[0420] Procedure: In a drying oven, fill a dried 5 mm NMR tube with ~0.5 inches of MAO solution, then add ~1.5 inches of THF-d8 solvent, shake thoroughly, and then obtain the sample using D1=30s, ns=4. 11H NMR spectra. A longer relaxation time, D1, might be more accurate, but 30 s is sufficient to obtain quantitative signals for toluene CH3 and Al-CH3 with an error of <2 wt%. Commercial MAO solution (WRGrace MAO 30% toluene solution (Al = 13.6 wt% (5.0 mmol / g), MAO = 26.6 wt%, total TMA (coordinated and free) = 4.76 wt%, Certificate of Analysis (COA) from MAO products)) in the toluene Me to Al-Me region. 1 HNMR spectrum shown Figure 1 middle.

[0421] Treatment: CH3 peak on p-toluene, total Al-CH3 area, AlMe2(THF)2 + Integrate the peaks and AlMe3(THF) peaks; set the integral of CH3 in toluene to 300 (set to 300 instead of CH3 proton number 3 to ensure at least 3 digits of precision in the printed spectrum output, as the decimal places may be truncated), and include MAO, AlMe3(THF) and AlMe2(THF)2. + The integral record for all Al-Me substances is 350.28, the integral for AlMe3(THF) is 78.96, and the integral for AlMe2(THF)2 is... + The integral is 7.98, ignoring minor substances such as processing oils that are typically present but present in small amounts (e.g., <1 wt%). Based on COA, the MAO formula without coordinated TMA is Al1O. 0.78 Me 1.44 The result is Mw 61.1. The MAO integral is 350.28 - 78.96 - 7.98 = 263.34. The number of protons in the MAO is 1.44. 3 = 4.32. AlMe2 + It is counted as TMA because it is generated by coordination TMA. The calculation results are listed in Table 1.

[0422] Table 1. Calculation of Total THF Extractable TMA

[0423]

[0424] 1 Parts by weight = Mw The integral / proton# is the weight contribution of a single substance;

[0425] 2 Weight % = Individual weight parts / Total weight parts 100%;

[0426] 3 AlMe2 + It is derived from the coordination TMA and thus transformed back into the TMA.

[0427] As can be seen, the total TMA content has increased from 4.76% by weight (COA) to 5.33% by weight, indicating a low degree of gelation.

[0428] Example 12. Quantitative analysis of coordinated TMA in commercial MAO solutions

[0429] The quantification of coordinated TMA is based on the following reaction (Scheme 8):

[0430] Option (8)

[0431]

[0432] In the above reaction, KF can displace and coordinate TMA to form an ionic MAO composition, thereby precipitating MAO as an inclusion phase for separation from the solution phase containing free TMA. A large excess of a known amount of KF (W1) is then applied. KF ) is applied to the MAO solution and the remaining KF(W2) is separated after the reaction. KF The KF consumption can be calculated as W1. KF -W2 KF This is an indirect quantitative method for the content of coordinated TMA.

[0433] Chemicals: KF (Aldrich), 10 g in a 50 mL round-bottom flask, vacuum dried in an oil bath at 110 °C for 4 hours; using the same MAO solution and THF-d8 as in Example 11.

[0434] Procedure: In a drying oven, 10.0 g of MAO solution (51.1 mmol Al, calculated based on the results in Table 1) was added to each of four dried flasks (20 mL), followed by 59.6 mg (based on 2 mol% of total Al), 118.9 mg (based on 4 mol% of total Al), 207.6 mg (based on 7 mol% of total Al), and 298 mg (based on 10 mol% of total Al), respectively. The flasks were shaken overnight. The flasks were then removed from the shaker and the inclusion phase was allowed to settle for 10 hours. The KF in the 2 mol%, 4 mol%, and 7 mol% treated flasks completely disappeared, but the 10 mol% treated flask showed residual KF. 1 ¹H NMR spectroscopy was used to analyze all upper phase solutions in four flasks in THF-d8 NMR solvent, and the results were compared. Figure 2A The spectrum shown in the Al-Me region indicates a decreased MAO concentration. Also using... 1The inclusion phase from a sample (with a vial treated with 10 mmol / L KF) that had been completely converted from conventional MAO to ionic MAO was analyzed by 1H NMR spectroscopy in THF-d8 NMR solvent, and the spectra in the Al-Me region were analyzed. Figure 2B The diagram shows that the MAO mother liquor was used for comparison, demonstrating that ionic MAO does not contain AlMe2. + This means that all coordinated TMA is removed by KF, and the coordinated TMA is AlMe2. + Source confirmation. The remaining KF in the 10 mol% treated bottle was collected using a pre-weighed frit filter, washed with 3 × 10 mL of dry toluene and 30 mL of dry isohexane, and then weighed to obtain 75.3 mg (2.54 mol%, based on total Al) of unreacted KF, yielding a coordinated TMA of 10 - 2.5 = 7.5 mol% in the MAO solution. The total Al% was 13.8 wt%, and the total TMA (free + coordinated) was 5.33 wt%. The total TMA can be converted to 2.00 wt% Al, yielding 14.5 mol%.

[0435] Figure 2A -B. 30% commercial MAO solution after KF treatment. 1 H NMR spectrum; Figure 2A The upper solution phases after KF treatment at 2, 4, 7, and 10 mol% are shown respectively; Figure 2B The final K was shown + (F-MAO) - Inclusion phase and untreated solution MAO used for comparison.

[0436] Example 13. Estimation of Free TMA Based on the weight percentage of total TMA in Example 12 (by weight) 总TMA The quantitative method for (% of coordinated TMA and free TMA) and the weight percentage (by weight) of coordinated TMA in Example 13. 配位TMA Quantitative methods for %), free TMA content by weight 游离TMA % can be estimated as weight 游离TMA % = weight 总TMA %-weight 配位TMA %.

[0437] Example 14. Polymerization reaction

[0438] All operations involving air- and moisture-sensitive materials are performed in an inert atmosphere within a N2-ventilated glove box. The catalyst is added... iActivation was performed using Bu2AlH (DIBAL) and dimethylphenylammonium tetra(pentafluorophenyl)borate (DIMAH-D4), or MAO (13 wt% Al in toluene, 100 equivalents), or F-MAO (100 equivalents, Example 9), or ionic MAO (10 equivalents, Example 10). After stirring the catalyst and activator for approximately 10 minutes, a solution of butadiene in toluene (10 wt% - 20 wt%) (~2500 butadiene equivalents / catalyst) was added, and the reactor equipped with six 20 mL bottles was sealed. The reactor was heated to 100°C, stirred at 225 rpm, and then pressurized with ethylene (250 psi, Sigma, 99.5%). Within the first hour, when the pressure dropped below 240 psi, the reactor was repressurized. After 4–14 hours, the reactor was cooled and then depressurized. To separate the polymer product, the contents of each bottle were precipitated and washed with acetone and methanol. The solids were then filtered off and washed with a large amount of acetone and methanol. The polymer sample was then dried in a vacuum oven at 50°C for 18 hours.

[0439] NMR studies:

[0440] 13 C NMR

[0441] The sample was dissolved in deuterated 1,1,2,2-tetrachloroethane (tce-d2) at 140 °C at a concentration of 34 mg / mL. Spectra were recorded at 120 °C using a Bruker NMR spectrometer with at least 600 MHz and a 10 mm cryoprobe. Measurements were performed using a 90° pulse, a 10 s delay, 512 transients, and gated decoupling. 13 C10 NMR spectra. Polymer resonance peaks are referenced to the polyethylene main peak at 29.98 ppm. Spectral assignments are based on the following reference: Llauro et al. Macromolecules , 34,18,(2001), 6304-6311; Makhiyanov Polymer Sci , (2012), 60-90 and Longo et al. . Macromolecules, Volume 36, (2003), pp. 9067-6074.

[0442]

[0443] The composition is calculated using the following signals:

[0444]

[0445] 1 H NMR

[0446] The sample was dissolved in deuterated 1,1,2,2-tetrachloroethane (tce-d2) at 140 °C at a concentration of at least 30 mg / mL. Spectra were recorded at 120 °C using a Bruker NMR spectrometer with at least 600 MHz and a 10 mm cryoprobe. Measurements were performed using a 30° pulse, a 5-second delay, and 512 transients. 1 ¹H NMR. The peak was taken with reference to the residual solvent peak at 5.98 ppm.

[0447]

[0448] The catalyst being tested

[0449]

[0450] The feature is 2- t Bu-4-Me phenol salt fragments and alkyl groups connected to the metal center bis(phenol salt) catalysts Y-1, Sc-2, and Y-2 (Y-1 is derived from formula II, Sc-2 and Y-2 are derived from formula III) were activated by DIMASH-D4 / DIBAL, MAO, and F-MAO. Interestingly, no product was formed when the copolymerization reaction mixture was activated by the DIMASH-D4 / DIBAL activator (Table 2, runs 1, 4, and 7). For the MAO-activated reaction mixture, low yields (up to 43.5 kg) were observed. 产物 / mol RE The formation of ethylene-rich copolymers (runs 2, 5, and 8). When F-MAO is used, the activity of systems Y-1, Sc-2, and Y-2 can be significantly increased to up to 239.4 kg. 产物 / mol M (Run 3, 6 and 9).

[0451] Table 2. Polymerization data for bis(phenolic) catalysts Y-1, Sc-2 and Y-2.

[0452]

[0453] - Conditions: Approximately 1 g of 1,3-butadiene (BD), toluene solution, BD:M = 2500 molar ratio, where M is a Group 3 or lanthanide metal; 250 psi ethylene; 100 °C; 14 hours; 1.5 equivalents of DIMASH-D4 / 44 equivalents of DIBAL or 100 equivalents of MAO or F-MAO.

[0454] Activation of bis(phenolate)-catalysts M-3 and M-3-N (derived from formula II) with alkyl or amino prosthetic groups and a central Group III metal ion via DIMASH-D4 / DIBAL, MAO, and ionic MAO (Table 3). For all M-3 and M-3-N complexes, significantly higher activity was observed when the copolymerization was initiated by ionic MAO. For the scandium complex Sc-3 (with 2-(1-adamantyl)-4- t The highest activity was observed when Bu-phenol salt fragments were combined with ionic MAO (running 3,337 kg). 聚合物 / mol M However, cross-linked polymers are formed as the main polymerization product. It is worth noting that MAO or ionic MAO activators are beneficial for the formation of 1,2-cyclopentane units in the polymer chain.

[0455] Table 3. Polymerization data of catalysts M-3 and M-3-N activated by MAO, ionic MAO and DIMASH-D4.

[0456]

[0457] - Conditions: Approximately 1g BD, toluene solution, BD: M=2500; 250 psi ethylene; 100℃; 14 hours;

[0458] -1,2-cyclopentane.

[0459] If the reaction is carried out in the presence of the chain transfer agent DIBAL, the significant crosslinking during the copolymerization of ethylene and butadiene activated by ionic MAO can be mitigated (Table 4). The molecular weight of the polymer decreases with increasing DIBAL concentration. Overall, the composition of the copolymer remains almost identical for reaction mixtures involving various stoichiometric amounts of DIBAL.

[0460] Table 4. Polymerization data of Sc-3 / ionic MAO system in the presence of various equivalences of DIBAL.

[0461]

[0462] - Conditions: Approximately 1g BD, toluene solution, BD: M=2500; 250 psi ethylene; 100℃; 5 hours.

[0463] In general, the catalyst system disclosed herein, comprising a combination of a rare-earth-based bis(phenolate) catalyst with TMA-free MAO and / or ionic MAO, can be used to produce copolymers of ethylene and butadiene at high conversion rates under mild conditions. The catalyst system disclosed herein is an attractive option for industrial-scale processes implementing, for example, copolymer materials derived from ethylene and butadiene monomers, with customizable physical properties, polymer backbone structure, and different functional structural moieties. Furthermore, polar side-chain structural moieties can be incorporated into the polymer chain during copolymerization. Such functionalized polymers may be desirable for the tire industry due to the enhanced interactions between the copolymer and one or more fillers present with the copolymer during use as tire materials.

[0464] Unless otherwise stated, the terms “consist essentially of” and “consisting essentially of” do not exclude the presence of other steps, elements, or materials, whether or not specifically mentioned in this specification, provided that such steps, elements, or materials do not affect the essential and novel features of this disclosure. In addition, they do not exclude impurities and variations that are generally associated with the elements and materials used.

[0465] For the sake of brevity, this document only explicitly discloses certain ranges. However, a range from any lower bound can be combined with any upper bound to enumerate ranges not explicitly listed, and a range from any lower bound can be combined with any other lower bound to enumerate ranges not explicitly listed, just as a range from any upper bound can be combined with any other upper bound to enumerate ranges not explicitly listed. Furthermore, a range includes every point or individual value between its endpoints, even if not explicitly listed. Therefore, each point or individual value can act as its own lower or upper bound, combined with any other point or individual value or any other lower or upper bound to enumerate ranges not explicitly listed.

[0466] All literature described herein is incorporated herein by reference, including any priority literature and / or testing procedures, provided they do not contradict this document. As will be apparent from the foregoing general description and specific embodiments, while the form of this disclosure has been shown and described, various modifications may be made without departing from the spirit and scope of this disclosure. Therefore, this disclosure is not intended to be limited thereto. Similarly, for purposes of U.S. law, the term “comprising” is considered synonymous with the term “including.” Likewise, whenever a composition, element, or group of elements is preceded by the transitional phrase “comprising,” it should be understood that we also consider the same composition or group of elements preceded by the transitional phrase “consistently composed of,” “composed of,” “selected from,” or “is”, or vice versa.

[0467] While this disclosure has been described with respect to various embodiments and examples, those skilled in the art who benefit from this disclosure will understand that other embodiments can be devised without departing from the scope and spirit of this disclosure.

Claims

1. A solution catalyst system comprising: 1) an anionically modified alkylaluminoxane, and / or a cationically modified alkylaluminoxane, wherein the solution catalyst system has 0 wt% to about 2 wt% Al from a non-coordinating trialkylaluminum compound based on the total aluminum content of the solution catalyst system as determined by titration of the solution catalyst system with tetrahydrofuran; and 2) a compound represented by Formula (I): (I) wherein: M is a Group 3 transition metal or a lanthanide metal; E and E' are each independently oxygen, sulfur or NR A wherein R A is independently hydrogen, C1-C 40 hydrocarbyl, substituted C1-C 40 hydrocarbyl or a 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, which is connected to A 2 via a 3-atom bridge 2 wherein Q is the central atom of the 3-atom bridge A 1 and A 1 each independently carbon, nitrogen or C(R B ), wherein R B is selected from hydrogen, C1-C 20 hydrocarbyl and substituted C1-C 20 hydrocarbyl; is a divalent group containing 2 to 40 atoms other than hydrogen which bridges A 1 to the E-bonded aryl group shown in formula (I), and A 3 and A 2 combine to form a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring each having 5, 6, 7, or 8 ring atoms, and wherein the substituents on the ring can combine to form additional rings; is a divalent group containing 2 to 40 atoms other than hydrogen which bridges A 1 is attached to the E'-bonded aryl group shown in formula (I), and A 3 and A 2 combine to form a substituted hydrocarbyl ring, an unsubstituted hydrocarbyl ring, a substituted heterocyclic ring, or an unsubstituted heterocyclic ring each having 5, 6, 7, or 8 ring atoms, and wherein substituents on the ring can combine to form additional rings; L is each independently a Lewis base; X' is an anionic ligand; any two L groups can be joined together to form a bidentate Lewis base; the X' group can be joined to an L group to form a monoanionic bidentate group; n is 1; m is 0, 1, or 2; n + m is not greater than 3; and R 1 , R 2 , R 3 , R 4 , R 1′ , R 2′ , R 3′ , and R 4′ are each independently hydrogen, a C1-C 40 alkyl group, a substituted C1-C 40 alkyl group, a heteroatom or heteroatom-containing group, or one or more pairs of 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′ may join to form one or more substituted alkyl rings, unsubstituted alkyl rings, substituted heterocyclic rings, or unsubstituted heterocyclic rings each having 5, 6, 7, or 8 ring atoms, and wherein substituents on the ring can join to form additional rings.

2. The catalyst system of claim 1, wherein the anionically modified alkylaluminoxane comprises an electron withdrawing group.

3. The catalyst system of claim 2, wherein the electron withdrawing group comprises -F or -OC6F5.

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

5. The catalyst system of claim 4, wherein the fluorine-containing compound comprises at least one compound selected from the group consisting of 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, AlF3, NHF2, NH4HF2, 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, and PhBF2; and the -OC6F5 containing compound comprises at least one compound selected from the group consisting of HOC6F5, Me3Si(OC6F5), Me2Si(OC6F5)2, MeSi(OC6F5)3, Me3C(OC6F5), Ph3C(OC6F5), Me2B(OC6F5), MeB(OC6F5)2, MeAl(OC6F5)2, Al(OC6F5)3, and B(OC6F5)3.

6. The catalyst system of claim 1, wherein the cationically modified alkylaluminoxane comprises a chelating agent or a monodentate agent.

7. The catalyst system of claim 6, wherein the chelating or monodentate agent comprises a siloxy donor.

8. The catalyst system of claim 7, wherein the siloxy donor comprises a dimethylaluminum trihydrocarbylsiloxy.

9. The catalyst system of claim 7, wherein the siloxy donor is derived from the decomposition of a chelated polymeric siloxane stabilized dialkyl aluminum cation, or is generated in situ from the reaction of a silanol with a free alkyl aluminum in an alkyl aluminum alkoxide composition.

10. The catalyst system of claim 9, wherein the chelated polymeric siloxane 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-tetravinylcyclotetrasiloxane, or the silanol comprises at least one compound selected from trimethylsilanol, triethylsilanol, tripropylsilanol, tributylsilanol, trihexylsilanol, triheptylsilanol, or trioctylsilanol.

11. The catalyst system of claim 1, 2, or 6, wherein the alkyl aluminum oxyalkane of the anionically modified alkyl aluminum oxyalkane and the cationically modified alkyl aluminum oxyalkane is methyl aluminum oxyalkane, and the non-coordinating trialkyl aluminum compound is trimethyl aluminum.

12. The catalyst system of claim 10, wherein the alkyl aluminum oxyalkane composition is obtained by a process comprising a phase separation step to separate an ionic alkyl aluminum oxyalkane phase from a non-coordinating alkyl aluminum solution phase, followed by an ionic alkyl aluminum oxyalkane decomposition step by heating the ionic alkyl aluminum oxyalkane at a temperature selected from 50 °C to 120 °C for 0.5 hours or more, or aging at ambient for 24 hours or more.

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

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

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

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

17. The catalyst system of any one of claims 1 to 16, wherein: A of formula (I) 3 and A 2 together to form a first ortho-phenylene group, and A of formula (I) 3' and A 2' together to form a second ortho-phenylene group.

18. The catalyst system of any one of claims 1 to 17, wherein: A of formula (I) 3 and A 2 to form a first benzothiophene, and A of formula (I) 3' and A 2' to form a second benzothiophene.

19. The catalyst system of claim 18, wherein R 1' and R 1 are each independently selected from adamant-1-yl or substituted adamant-1-yl.

20. The catalyst system of claim 19, wherein R 1' and R 1 are each t-butyl or substituted t-butyl.

21. The catalyst system of claim 20, wherein R 3 and R 3' are each independently methyl or t-butyl.

22. The catalyst system of any one of claims 1 to 21, wherein R 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 are each hydrogen.

23. A method of producing a polymer, the method comprising: polymerization of the alpha-olefin and optional comonomer by introducing the alpha-olefin and 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 with the catalyst system of any one of claims 1 to 23 to form a polymer.

24. A process for the production of an ethylene copolymer, the process comprising: 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 ethylene and a conjugated diene with the catalyst system according to any one of claims 1 to 24, to polymerize the ethylene and the at least one conjugated diene, thereby forming an ethylene copolymer.

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