Non-coordinated alkyl aluminum free cation modified aluminoxane and method thereof

Abstract

The present disclosure relates to aluminoxane compositions that are substantially or completely free of non-coordinating hydrocarbyl aluminum content, methods of forming such aluminoxane compositions, catalyst systems having the aluminoxane compositions, and methods of polymerizing olefins using the catalyst systems having the aluminoxane compositions. In some embodiments, the catalyst system includes at least one pre-catalyst compound. The catalyst system includes an unsupported or supported aluminoxane. The aluminoxane includes a monodentate siloxy ligand. In some embodiments, a method of making an aluminoxane includes forming an ionic alkylaluminoxane by reacting a supported or unsupported alkylaluminoxane with a polydentate chelating agent to form a silane alkylaluminoxane complex. The method includes heating or aging a silane alkyl aluminum complex to form a supported or unsupported alkyl aluminoxane comprising a monodentate ligand.

Description

[0001] Inventors: Lubin Luo; Jo-Ann M. Canich; Alexander V. Zabula; Ky Le

[0002] Cross-references to related applications

[0003] This application claims the benefit and priority of U.S. Provisional Application No. 63 / 506541, filed June 6, 2023, the disclosure of which is incorporated herein by reference. Technical Field

[0004] This disclosure relates to aluminum oxane compositions that are substantially or completely free of hydrocarbon aluminum content, methods for forming such aluminum oxane compositions, catalyst systems having said aluminum oxane compositions, and methods for polymerizing olefins using catalyst systems having said aluminum oxane compositions. Background Technology

[0005] Olefin polymerization catalysts are highly useful in industry. Therefore, there is interest in finding new catalyst systems that increase the commercial usefulness of catalysts and allow the production of polymers with improved properties. To polymerize monomers to form polyolefins, the catalyst is activated to provide active sites on the catalyst and promote monomer polymerization. Activated methylaluminoxane (MAO) from partially hydrolyzed trimethylaluminum (TMA) is effective in activating a type of catalyst known as metallocene for olefin polymerization. MAO has become the aluminum co-catalyst (also called activator) of choice in industry. It is commercially available in the form of a 10 wt% to 30 wt% solution in an aromatic diluent (usually toluene).

[0006] Significant efforts have been devoted to improving the effectiveness of catalyst systems for the polymerization of olefins based on methylaluminoxanes or modified methylaluminoxanes. For example, WO 2009 / 029857 demonstrates the formation of dimethylaluminum cations (AlMe2) from MAO after 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 “Ligand Exchange and Alkyl Abstraction Involving (Perfluoroaryl)boranes and -alanes with Aluminum and Gallium Alkyls,” Organometallics, 2000, Vol. 19(23), pp. 4684-4686; US 9090720 shows that metallocene ethylenediindenyl dimethoxyzirconium (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 that also form metallocene-dialkylaluminum cations, such as [Cp2Zr(μ-Me)2AlMe2]. + Or [Cp2Ti(μ-Me)2AlMe2] + For example, 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 Volume 124, pp. 12869-12873 and Sarzotti, DM et al. (2006) “A Kinetic Study of Metallocene-Catalyzed Ethylene Polymerization Using Different Aluminoxane Cocatalysts,” J. Polymer Sci. A The examples in Volume 45, 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 NMR Spectroscopic Study of Titanium(IV) Species Formed by Activation of Cp2TiCl2 and [(Me4C5)SiMe2N t[Bu]TiCl2 with Methylaluminoxane (MAO), "Organometallics," Vol. 23, pp. 149-152, describes the activation of a titanocene catalyst precursor by MAO. Although the structure of MAO remains unclear, freshly prepared activated MAO has shown evidence of coordinated TMA within MAO, consistent with the experimental formula (Al4O3Me6)4(TMA) described by Sinn and Kaminsky. 1-2 (Sinn et al., “Formation, Structure, and Mechanism of Oligomeric Methylalumoxane”, in Kaminsky (ed.)) Metalorg. Cat. for Synth. & Polym., (Springer-Verlag, 1999, p. 105) Consistent. Coordinated TMA is in equilibrium with free TMA, and attempts to physically remove all free TMA result in the formation of a more stable MAO gel with fewer active sites for gas-phase or slurry-phase polymerization due to the loss of coordinated TMA (Equation (1), which makes it difficult to find suitable solvents for solution polymerization or to place on a support (i.e., into the pores of the support).

[0007] Equation (1) .

[0008] 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 equation (2), where circles are used for clarity to represent the main MAO structure, such as the (Al4O3Me6)4 unit (Luo, Jain, and Harlan, INOR 1169, American Chemical Society Priestley Medalist Symposium in Honor of Tobin J. Marks, San Francisco, CA, April 5, 2017; Luo et al., U.S. Patent 8,575,284 (2013) and US 9,090,720 (2015)): Equation (2)

[0009] Therefore, maintaining a large amount of free TMA in the active MAO solution is necessary to stabilize the active MAO composition, for example, to stabilize the MAO molecular structure capped with coordinating TMA to reduce the chance of dimerization / oligomerization of the MAO gel as shown in scheme or equation (1). Thus, physical removal of free TMA may not only lead to MAO gelation, but may also lead to loss of coordinating TMA and result in lower activation efficiency.

[0010] However, post-metallocene catalysts containing polar ligands such as oxygen and / or nitrogen donors and geometrically defined complex (CGC) catalysts (also known as mono-cyclopentadienyl (mono-Cp) catalysts) have shown challenges in activation with conventional MAO, for example, some exhibiting low catalyst activity and some exhibiting short catalyst lifetimes or both. Without being bound by theory, the poor activity and short catalyst lifetime are thought to be due to the presence of free TMA in the MAO, enabling the alkylation of pre-catalyst metal centers bonded to heteroatoms (Scheme 3 or Equation (3), with Zr centers as an example), similar to the alkylation of metallocenes with dichloro-leaching groups in Equation (3): Equation (3) .

[0011] Previous studies have revealed that MAO can be precipitated as a clathrate using the chelating agent octamethyltrisiloxane (OMTS) (Sangokoya et al., WO 2003 / 082879 (2003)). Free TMA can then be separated from the clathrate, with most of the coordinated TMA in MAO being converted to [AlMe2(OMTS)]. + By disrupting the equilibrium between free and coordinated TMA and causing the inclusion phase to precipitate in the original MAO solution, free TMA can be removed from the solution. Unfortunately, the strong chelating effect of the OMTS group, due to its significant positive activation enthalpy, prevents AlMe2 from being removed from the solution. + It is released to efficiently act as an activator of the pre-catalyst.

[0012] Therefore, there is a need for improved MAO and methods for forming MAO that provide high activity and long catalyst lifetime to downstream metallocene catalysts and / or CGCs. For example, solution- or supported MAO with sufficient coordinated TMA drives AlMe2. + However, it contains little or no free TMA, which allows it to maintain its efficiency as an activator.

[0013] References cited in the Disclosure Statement (37 CFR 1.97(h)): WO 2003 / 082879; US2019 / 0127499; US 2009 / 0124486; US 6,667,272; US 2019 / 0153135; US 2013 / 0253155; US2018 / 0142046; US 7,193,100. Summary of the Invention

[0014] This disclosure relates to active cationic modified aluminum oxane compositions that are substantially or completely free of free (non-coordinated) hydrocarbon aluminum, methods for forming such aluminum oxane compositions, catalyst systems having said aluminum oxane compositions, and methods for polymerizing olefins using catalyst systems having said aluminum oxane compositions.

[0015] In some embodiments, the catalyst system includes at least one precatalyst compound and an unsupported or supported aluminoxane containing a monodentate siloxy ligand.

[0016] In some embodiments, the method for preparing aluminum oxanes includes forming ionic alkyl aluminum oxanes by: (1) reacting a supported or unsupported alkyl aluminum oxane with a multidentate chelating agent to form an ionic aluminum oxane composition comprising siloxane chelated alkyl aluminum cations, and (2) heating or aging the ionic aluminum oxane composition comprising siloxane chelated alkyl aluminum cations to form an ionic alkyl aluminum oxane comprising at least one decomposition product of a supported or unsupported alkyl aluminum oxane comprising siloxane chelated cations in a siloxane-modified ionic aluminum oxane composition.

[0017] In some embodiments, the method of preparing an aluminoxane composition includes forming an alkylaluminoxane composition free of noncoordinated alkylaluminum by reacting a supported or unsupported alkylaluminoxane with a silanol to form an alkylaluminoxane composition comprising a supported or unsupported alkylaluminoxane containing a monodentate silanoxy ligand, provided that the noncoordinated alkylaluminum content is based on a total Al content not exceeding 2 wt% Al.

[0018] In some embodiments, the compound is represented by formula (I): (I) in: R 1 R 2 R 3 R 4 R 5 R 6 and R 7 Each of them is independently a hydrogen, hydrocarbon, silyl, or a group containing heteroatoms.

[0019] In some embodiments, the method for preparing the aluminoxane composition includes reacting a supported or solid alkylaluminoxane with a dialkylaluminum silicate to form an alkylaluminum alkylaluminoxane composition, thereby forming an alkylaluminum alkylaluminoxane composition: a) Contacting supported or solid alkylaluminoxanes with dialkylaluminum silicon oxides represented by formula (II): R3SiOAlR2 (II) Where R is independently hydrogen, a hydrocarbon group, or a group containing a non-coordinated or weakly coordinated heteroatom; and b) Separation of noncoordinated alkyl aluminum from siloxane alkylated aluminum oxane compositions.

[0020] In some embodiments, anionic and cationic modified supported or unsupported alkylaluminoxane compositions are provided. Anionic modification is achieved by treating the supported or unsupported alkylaluminoxane with a compound containing at least one electron-withdrawing compound. Cationic modification is achieved by treating the supported or unsupported alkylaluminoxane with a chelating or monodentate siloxane compound, the modification being carried out in any order, followed optionally by heating the anionic and cationic modified supported or unsupported alkylaluminoxane. Attached Figure Description

[0021] Figure 1 A method for synthesizing monodentate ligands according to some implementation schemes is shown.

[0022] Figure 2 A method for synthesizing AlMe2 compositions with monodentate ligand coordination is shown according to some embodiments.

[0023] Figure 3 This is a graph depicting the activity of gas-phase polyethylene polymerization of silica-MAO compared to silica-supported ionic MAO according to some embodiments.

[0024] Figure 4 It is a graph depicting the productivity of TMA-free F-MAO compared to TMA-free ion-MAO according to some implementation schemes.

[0025] Figure 5 It is a graph depicting the catalyst productivity according to some implementation schemes.

[0026] Figure 6 It is based on some implementation schemes and has ionic MAO 1 1H NMR spectrum, where [(OMTS)AlMe2] + One of the decomposition products showed a peak matching the proposed structure, with a Me-Al:SiMe ratio of 4:3.

[0027] definition

[0028] Use such as Chemical and Engineering News The new numbering scheme for the periodic table groups is described in Volume 63(5), page 27 (1985). Thus, “Group 4 metals” are elements from Group 4 of the periodic table, such as Hf, Ti, or Zr, and “Group 3 metals” are elements from Group 3 of the periodic table, such as Sc, Y, or Nd.

[0029] "Olefin," or alternatively "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, based on the weight of the copolymer, when the copolymer is said to have a "ethylene" content of 35 wt% to 55 wt%, it should be understood that the monomer units in the copolymer are derived from ethylene in the polymerization reaction, and said derived units are present in 35 wt% to 55 wt%. 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. Where "different" is used to refer to monomer units, it 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.

[0030] Ethylene should be considered an α-olefin.

[0031] The term "metallocene" refers to a catalyst compound containing two substituted or unsubstituted cyclopentadienyl moieties, either bridged or unbridged, wherein when the metal center is charge-neutral, the two cyclopentadienyl moieties are directly bonded to a metal center having at least two leaving groups, or when the metal center is positively charged, the two cyclopentadienyl moieties are directly bonded to a metal center having at least one leaving group and optionally a weak donor. The term "semi-metallocene" refers to a catalyst compound containing one substituted or unsubstituted cyclopentadienyl moieties, either bridged or unbridged, and a ligand containing a heteroatom, wherein when the metal center is charge-neutral, at least one of the heteroatoms on the cyclopentadienyl moieties and the heteroatom-containing ligand is directly bonded to a metal center having at least two leaving groups, or when the metal center is positively charged, it is directly bonded to a metal center having at least one leaving group and optionally a weak donor, including so-called "defined geometry catalysts" (CGC) compounds. The term "post-metallocene" refers to a catalyst compound that does not contain a cyclopentadienyl structural moiety but contains ligands with heteroatoms such as N, O, P, B, S, etc., where the ligands bind directly to the catalyst metal center with at least two leaving groups when the catalyst metal center is charge-neutral, or directly to the catalyst metal center with at least one leaving group and an optional weak donor when the catalyst metal center is positively charged.

[0032] The term “MAO” can refer to a MAO composition containing MAO, coordinated TMA, free TMA and gel (e.g., the substance in Scheme 1), but sometimes it can refer only to the MAO main molecule, for example, (Al4O3Me6)4, without coordinated TMA and free TMA.

[0033] "Alkyl aluminum" or "alkyl aluminum" means containing at least one Al-alkyl group (Al-R, where R is C1 to C2). 12 Compounds of the (alkyl group) unit can be coordinated with or not coordinated with the main aluminum oxane structure. Such compounds, if not coordinated with the main aluminum oxane structure, are also called uncoordinated alkyl aluminum or free alkyl aluminum, which can coordinate with each other to form dimers, such as the AlMe3 dimer in scheme (1).

[0034] "Non-coordinated alkylaluminum" or "free alkylaluminum" has the same meaning, referring to aluminum compounds having at least one alkyl group (e.g., Me, Et, iBu, Oct) in monomeric or dimer form that is not chemically bonded to the aluminoxane structure. Although free alkylaluminum can become coordinated by exchanging with coordinated alkylaluminum on the aluminoxane structure, the regeneration of free alkylaluminum from the initially coordinated alkylaluminum maintains the free alkylaluminum concentration under the same conditions.

[0035] The terms aluminoxane, alumoxane, alkylaluminoxane, and alkylalumoxane are used interchangeably.

[0036] Sometimes only alkylaluminum is used to indicate free alkylaluminum, for example, TMA means free TMA.

[0037] "Free" or "free of" means undetectable by current analytical methods (such as NMR spectroscopy or conventional wet titration). "Low in" means based on 2 wt% or 2 mol% or less of the total identical elements in the system. For example, "low in" free TMA means that the Al weight (or mol) of free TMA is based on 2 wt% (or mol%) or less of the total Al weight (or mol%) in the MAO composition. In some embodiments, "free" or "free of" includes the description of "low in," for example, TMA-free MAO may indicate that the Al weight or moles of free TMA are based on 2 wt% or 2 mol% or less of the total Al content in the MAO.

[0038] There are two types of TMA-free MAO compositions: 1) cationic modified MAO, which can be a MAO composition modified with a chelating agent to form an ionic MAO composition containing a chelating agent or ligand-stabilized dimethylaluminum cation, which can then be heated to decompose into a monodentate ligand-stabilized cation of the embodiments of this disclosure; cationic modified MAO can also be referred to as ionic MAO; and 2) anionic modified MAO, i.e., a MAO composition modified with the compound AlMe2X, wherein X is an electron-withdrawing group (e.g., pre-formed or in-situ formed AlMe2F or AlMe2(OC6F5), which can replace the coordinating TMA to form a coordinated AlMe2X. When AlMe2 is coordinating with AlMe2X... + When the MAO composition is used to activate the precatalyst, MAO is transformed into (XMAO). - The anion is described in a separate application. MAO modified by both cationic and anionic methods can also yield systems free of non-coordinated alkylaluminum.

[0039] "Chlorinating agent or chelating compound" means a compound having multiple donor groups to form a chelate structure with a dialkylaluminum cation in an alkylaluminumoxane 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.

[0040] "Monodentate agents or monodentate compounds" refers to compounds having a single donor group to form a non-chelate structure with a dialkylaluminum cation in an alkylaluminoxane system. Examples of monodentate agents include, but are not limited to, compounds having a silaneoxy donor group containing a single oxygen atom, such as hexamethyldisiloxane, hexaphenyldisiloxane, hexaethyldisiloxane, dimethylaluminum trimethylsiloxide, diethylaluminum triethylsiloxide, etc.; more preferably, monodentate agents are alkylaluminum modified with silaneoxy donor groups, such as dimethylaluminum trimethylsiloxide, diethylaluminum trimethylsiloxide, diisobutylaluminum trimethylsiloxide, dimethylaluminum triethylsiloxide, diethylaluminum triethylsiloxide, diisobutylaluminum triethylsiloxide, dimethylaluminum tripropylsiloxide, diethylaluminum tripropylsiloxide, diisobutylaluminum tripropylsiloxide, dimethylaluminum triphenylsiloxide, diethylaluminum triphenylsiloxide, diisobutylaluminum triphenylsiloxide, etc.; most preferably, monodentate agents are those generated in situ by decomposition of MAO compositions treated with chelating agents, such as heating OMTS-treated MAO to produce dimethylaluminum trimethylsiloxide, as in Scheme 4, I- b to I- a As shown.

[0041] In this document, ionic aluminum oxanes or ionic MAOs refer to charge-neutral aluminum oxane or MAO compositions containing coordinated alkyl aluminum or TMAs, following electron-donating ligand or compound treatment to form an ionic composition containing an aluminum oxane anion or MAO anion and an electron-donating ligand or compound-stabilized dialkyl aluminum cation or dimethyl aluminum cation. Phase separation of the ionic composition from the mother solution may or may not occur, depending on the solubility of the ionic composition. For example, ionic higher alkyl (e.g., C4-C8) modified MAO products (such as MMAO from Nouryon after ionization) may have better solubility in common concentration ranges such as 10 wt%–30 wt%; on the other hand, ionic MAO at common concentrations may precipitate as a heavier liquid phase (or inclusion phase) to separate from the mother solution. Depending on the aging of the MAO, ionic MAO from fresher MAO products may be more soluble than products that have been aged for a longer period. Highly diluted solutions can dissolve all ionic MAOs.

[0042] Unless otherwise stated, the term "C" is used in conjunction with other terms. n "This refers to a hydrocarbon (one or more) with n carbon atoms (one or more) per molecule, where n is a positive integer."

[0043] The term "hydrocarbon" refers to a class of compounds containing hydrogen atoms bonded to carbon, and includes (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and / or unsaturated), including mixtures of hydrocarbon compounds 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.

[0044] The terms “group”, “radical”, and “substituent” are used interchangeably.

[0045] The terms "hydrocarbyl radical," "hydrocarbyl group," or "hydrocarbyl" are used interchangeably and are defined as meaning 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, is 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.

[0046] Unless otherwise specified (e.g., the definition of "substituted hydrocarbon group", "substituted aromatic compound", etc.), the term "substituted" means that at least one hydrogen atom has been replaced by at least one non-hydrogen group, such as a hydrocarbon group, a heteroatom, or a group containing a heteroatom, such as a halide (such as Br, Cl, F, or I), or at least one functional group, such as -NR. 2. -OR -SeR -TeR -PR 2. -AsR 2. -SbR 2. -SR -BR 2, -SiR 3. -GeR 3. -SnR 3. -PbR 3, where each R It is independently a hydrocarbon group or a haloalkyl group, and has two or more R groups. They can be joined together to form substituted or unsubstituted fully saturated, partially unsaturated, or aromatic ring or polycyclic structures, or in which at least one heteroatom has been inserted into the hydrocarbon ring.

[0047] The term "substituted hydrocarbon group" refers to a hydrocarbon group in which at least one hydrogen atom of the hydrocarbon group has been replaced by at least one heteroatom (such as a halogen group, e.g., Br, Cl, F, or I) or a heteroatom-containing group (such as a functional group, e.g., -NR). 2. -OR -SeR -TeR -PR 2. -AsR 2. -SbR 2. -SR -BR 2, -SiR 3. -GeR 3. -SnR 3. -PbR 3, where each R It is independently a hydrocarbon group or a haloalkyl group, and has two or more R groups. They can be joined together to form substituted or unsubstituted fully saturated, partially unsaturated, or aromatic ring or polycyclic structures, where at least one heteroatom has been inserted into the hydrocarbon ring.

[0048] The term "aryl" or "aryl group" refers to an aromatic ring and its substituted variants, such as phenyl, 2-methyl-phenyl, xylyl, and 4-bromo-xylyl. Similarly, "heteroaryl" refers to an aryl group in which a ring carbon atom (or two or three ring carbon atoms) has been replaced by a heteroatom such as N, O, or S. As used herein, the term "aromatic" also refers to a pseudoaromatic heterocycle, which is a heterocyclic substituent having properties and structure (almost planar) similar to aromatic heterocyclic ligands, but is not an aromatic compound by definition; similarly, the term aromatic compound also refers to a substituted aromatic compound.

[0049] The term "substituted aromatic compound" refers to 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.

[0050] 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 have been replaced by at least one non-hydrogen group, which is such as a hydrocarbon group, a heteroatom or heteroatom-containing group, such as a halogen (such as Br, Cl, F, or I), or at least one functional group, such as -NR. 2. -OR -SeR -TeR -PR 2. -AsR 2. -SbR 2. -SR -BR 2, -SiR 3. -GeR 3. -SnR 3. -PbR 3, where each R It is independently hydrogen, alkyl, or haloalkyl, and has 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, where R^ 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:

[0051] Where R 18 It is hydrogen, C1-C 40 Hydrocarbon groups (such as 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 of the elements is independently selected from hydrogen, C1-C 40 Hydrocarbon groups (such as 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 21Two 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 salt groups are bonded to the rest of the catalyst compound.

[0052] "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 have been substituted by at least one alkyl group, such as C1 to C6. 40 Alternatives C2 to C 20 Alternatives C3 to C 12 Alkyl groups, such as methyl, ethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, adamantyl, etc., including their substituted analogues.

[0053] "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 have been substituted by at least one aryl group, such as C1 to C6. 40 Alternatives C2 to C 20 Alternatives C3 to 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.

[0054] The term "ring atom" refers to an atom that is part of a ring structure. By this definition, benzyl has six ring atoms, and tetrahydrofuran has five ring atoms.

[0055] A heterocyclic ring, also known as a heterocycle, is a ring structure containing heteroatoms, as opposed to a "heteroatom-substituted ring" where hydrogen atoms on the ring atoms are replaced by heteroatoms. For example, tetrahydrofuran is a heterocycle, while 4-N,N-dimethylamino-phenyl is a heteroatom-substituted ring. A substituted heterocycle refers to a heterocycle in which one or more hydrogen groups are replaced by hydrocarbon groups, substituted hydrocarbon groups, heteroatoms, or heteroatom-containing groups.

[0056] A substituted hydrocarbon ring refers to a ring containing carbon and hydrogen atoms in which one or more hydrogen groups are replaced by a hydrocarbon group, a substituted hydrocarbon group, a heteroatom, or a heteroatom-containing group.

[0057] 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 (such as Br, Cl, F or I), or at least one functional group, such as -NR. 2. -OR -SeR -TeR -PR 2. -AsR 2. -SbR 2. -SR -BR 2, -SiR 3. -GeR 3. -SnR 3. -PbR 3, where each R It is independently hydrogen, alkyl, or haloalkyl, and has two or more R groups. They can be joined together to form substituted or unsubstituted fully saturated, partially unsaturated, or aromatic ring or polycyclic structures, or in which at least one heteroatom has been inserted into the hydrocarbon ring.

[0058] A tertiary hydrocarbon group has a carbon atom 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 represented by the following formula: , Where R A R B and R C Independently, these are hydrocarbon groups or substituted hydrocarbon groups that can optionally bond to each other, and the wavy lines indicate the positions where tertiary hydrocarbon groups form bonds with other groups.

[0059] 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. When the hydrocarbon group is an alkyl group, the cyclic tertiary hydrocarbon group is also called a cyclic tertiary alkyl group or an alicyclic tertiary alkyl group. 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. A cyclic tertiary hydrocarbon group can be represented by formula B: (B), Where R A It is a hydrocarbon group or a substituted hydrocarbon group, each R D Independently, it is a hydrogen or 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.

[0060] 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.

[0061] The terms "alkyl radical" 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, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and their substituted analogs. A substituted alkyl group is one in which at least one hydrogen atom of the alkyl group has been replaced by at least one non-hydrogen group, such as a hydrocarbon group, a heteroatom or heteroatom-containing group, such as a halogen (such as Br, Cl, F or I), or at least one functional group, such as -NR. 2. -OR -SeR -TeR -PR 2. -AsR 2. -SbR 2. -SR -BR 2, -SiR 3. -GeR 3. -SnR 3. -PbR 3, where each R It is independently hydrogen, alkyl, or haloalkyl, and has two or more R groups. They can be joined together to form substituted or unsubstituted fully saturated, partially unsaturated, or aromatic or polycyclic structures, or in which at least one heteroatom has been inserted into the hydrocarbon ring.

[0062] In the presence of the named alkyl, alkenyl, alkoxy, or aryl isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl), or in the absence of a specific isomer (e.g., butyl), a reference to alkyl, alkenyl, alkoxy, or aryl explicitly discloses all isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl).

[0063] 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 mol% is the molar 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 ).

[0064] The following abbreviations may be used in this document: Me is methyl, MAO is methylaluminoxane (or methylalumoxane), OMTS is octamethyltrisiloxane, TMS is trimethylsilyl or tetramethylsilane (depending on whether it is a group (the former) or a compound (the latter)), Bn is benzyl (i.e., CH2Ph), THF (also known as thf) is tetrahydrofuran, RT is room temperature (and 23°C unless otherwise specified), tol is toluene, Cp is cyclopentadienyl, NMR is nuclear magnetic resonance, and TMA is trimethylaluminum.

[0065] A “catalyst system” is a combination of at least one precatalyst compound, an activator, an optional co-activator, and an optional support material. When “catalyst system” is used to describe such a combination prior to activation, it means the unactivated catalyst complex (precatalyst) together with the activator and, optionally, the co-activator. When used to describe such a combination after activation, it means the activated complex and the activator or other charge-balanced structural component. The catalyst compound may be neutral, as in the precatalyst, or charged with counterions, as in the activated catalyst system. For the purposes of this disclosure and its claims, when a catalyst system is described as comprising a neutral, stable form of a component, those skilled in the art will fully understand 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 both neutral and ionic forms of the catalyst compound and the activator.

[0066] In this specification, a catalyst may be described as a catalyst, catalyst precursor, precatalyst compound, catalyst compound, or metal compound, and these terms are used interchangeably.

[0067] 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, hydroido, amidinate, amidate, and phenyl. Two anionic donors can combine to form a dianionic group.

[0068] 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.

[0069] For the purposes of this disclosure and its claims, phenol salt donors may include Ph-O-, Ph-S-, and Ph-N(R) ^ )- group, where R^ is hydrogen, C1-C 40 Hydrocarbon group, C1-C 40 A substituted hydrocarbon group, heteroatom, or heteroatom-containing group, and Ph is optionally a substituted phenyl group.

[0070] The lanthanide metals (La-Lu) include La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. Detailed Implementation

[0071] This disclosure relates to active ionic aluminum oxanes that are free from or depleted of noncoordinated alkyl aluminum, methods for forming active ionic aluminum oxanes that are free from or depleted of noncoordinated alkyl aluminum, catalyst systems having said active ionic aluminum oxanes, and methods for polymerizing olefins using catalyst systems derived from said active ionic aluminum oxanes.

[0072] In some embodiments, a method for preparing ionic aluminum oxanes that are free of or depleted of noncoordinated alkyl aluminum includes introducing an aluminum oxane with a chelating agent compound to form an ionic aluminum oxane, followed by steps including: separating the noncoordinated alkyl aluminum and heating the ionic aluminum oxane.

[0073] In some embodiments, a method for preparing ionic aluminum oxanes that are free of or depleted of noncoordinated alkyl aluminum includes introducing an aluminum oxane with a chelating agent to form an ionic aluminum oxane, followed by steps including: separating the noncoordinated alkyl aluminum and heating the ionic aluminum oxane. This method includes introducing a hydrocarbon aluminum compound with an oxygen source at a temperature of about -60°C to about 100°C to form an aluminum oxane.

[0074] In some implementations, the catalyst system comprises a precatalyst compound and an ionic aluminum oxane or a heated ionic aluminum oxane derivative that is free of or depleted of noncoordinated alkyl aluminum.

[0075] In some embodiments, the method of polymerizing olefins includes using a catalyst system having: a precatalyst compound, an ionic aluminum oxane that is free of or depleted of noncoordinated alkyl aluminum, or a heated ionic aluminum oxane derivative.

[0076] The method may further include forming alkylaluminoxanes for subsequent treatment with silanols or multidentate silanes. For example, the method may include introducing trimethylaluminum with an oxygen source (optionally in a support) at a temperature of about -60°C to about 100°C prior to ion treatment to form a conventional MAO composition.

[0077] In some embodiments, the preparation of alkylaluminoxanes (e.g., TMA-free MAO) (i.e., "ionic alkylaluminoxanes") involves treating the alkylaluminoxane in unsupported or supported form with a monodentate compound (e.g., Me3SiOH) capable of converting total alkylaluminum (e.g., free and coordinated TMA) into at least partially dialkylaluminum cations stabilized with monodentate ligands (e.g., [AlMe2(µ-O(SiMe3))AlMe2]). + Compositions of monodentate ligand-stabilized dialkylaluminum cations. Monodentate ligand-stabilized dialkylaluminum cations can be formed by treating aluminum oxanes (e.g., MAO) with silanols (e.g., as...). Figure 2 As shown), the silanol reacts with free alkyl aluminum (e.g., TMA) to form ionic aluminum oxane (e.g., Figure 2 (B). Without being bound by theory, it is thought that silanols and free alkylaluminum-derived compounds abstract dialkylaluminum cations from the coordinated alkylaluminum on the aluminoxane to form monodentate ligand-stabilized dialkylaluminum cations, while the MAO host structure becomes a counter anion. The precatalyst can be activated by treating ionic aluminoxane compositions derived from monodentate compounds containing no or low levels of non-coordinated alkylaluminum with a polymerization precatalyst (e.g., metallocene, semi-metallocene, or post-metallocene precatalysts) comprising a precatalyst containing at least one non-leaving polar group.

[0078] Alternatively, ionic aluminum oxane compositions containing monodentate ligands can be formed by treating an alkylaluminum oxane having free alkylaluminum with a polydentate (e.g., bidentate) siloxane to form a chelated siloxane-stabilized dialkylaluminum cation with an aluminum oxane counterion, or a chelated ionic aluminum oxane composition. The chelated ionic aluminum oxane composition can be heated for a certain period of time to form a composition containing a monodentate ligand derived from the decomposed chelate ligand. The catalyst can be activated after treatment of the ionic aluminum oxane composition containing monodentate ligands with a polymerization pre-catalyst (e.g., a metallocene catalyst).

[0079] Alternatively, ionic aluminum oxane compositions containing monodentate ligands can be formed by treating an alkylaluminum oxane (e.g., MAO) with free alkylaluminum (e.g., TMA) with a polydentate (e.g., bidentate) siloxane to form a chelated siloxane-stabilized dialkylaluminum cation with an aluminum oxane counterion, or chelated ionic aluminum oxane composition, which can precipitate as an inclusion phase. A separation process can then be performed to separate the free alkylaluminum from the ionic aluminum oxane composition. The chelated ionic aluminum oxane composition can be heated for a certain period of time to form a composition containing monodentate ligands derived from the decomposed chelate ligands. Treatment of the ionic aluminum oxane composition containing monodentate ligands with a polymerization precatalyst (e.g., a semi-metallocene or post-metallocene precatalyst) can further enhance catalyst activation.

[0080] It has been found that MAO can be treated with multidentate siloxanes to form ionic complexes containing chelated siloxane-stabilized dimethyl cations and aluminoxane counteranions, for example, [AlMe2(OMTS)]. + (MeMAO) - Its activity is generally lower than that of untreated aluminum oxanes or MAOs, but it becomes more active after heating, possibly due to the decomposition of chelating ligands to form less stable monodentate ligand-derived ionic alkyl aluminum oxanes or MAOs (such as [AlMe2(µ-O(SiMe3))AlMe2]). + (MeMAO) - This readily releases dialkylaluminum cations or dimethylaluminum cations for more efficient pre-catalyst activation. Without being bound by theory, for pre-catalyst activation, ionic aluminum oxane compositions containing chelated siloxane-stabilized dialkylaluminum cations exhibit lower activity without heat treatment than heated ionic aluminum oxane compositions due to the energy difference between bond breaking and bond formation reactions, where scheme (1) for chelated ligands is less active than scheme (2) for monodentate ligands:

[0081] Option (1)

[0082] Option (2)

[0083] It has also been found that the need for phase separation to remove free TMA and heating can be eliminated by directly forming monodentate ligand-stabilized dialkylaluminum cations through the reaction of silanols with free TMA in MAO. However, the resulting compositions are less active than monodentate complexes derived from chelate complexes, such as those from [AlMe2(OMTS)] by heating. + (MeMAO) - [AlMe2(µ-O(SiMe3))AlMe2] + (MeMAO) - This may be because the active OH groups react not only with free TMA but also with coordinated TMA (active sites) to form a barrier against AlMe2. + Departing strong bridge O (structure) a (Scheme (3), using trimethylsilanol as an example).

[0084]

[0085] Option (3)

[0086] A slightly better way to overcome silanol poisoning at the active sites of MAO is to use a pre-formed product from the reaction of free alkylaluminum with silanols (such as free TMA with trimethylsilanol): Me3SiOH + AlMe3 = Me3SiOAlMe2 + CH4. However, this route is only suitable for supported or solid aluminoxanes to obtain systems free of coordinated alkylaluminum, as the conversion of coordinated alkylaluminum to free alkylaluminum and its separation from the solution system becomes challenging. In the case of supported or solid alkylaluminoxane systems such as silica-supported MAO or solid MAO, more practical separation processes can be applied, such as filtration or decantation, or, for lower boiling point free alkylaluminum such as free TMA, vacuum drying (with the option of heating).

[0087] The most efficient approach is the chelating agent treatment approach, which can be OMTS treatment of supported or unsupported MAO, followed by phase separation processes for solution-based aluminoxane systems or filtration / decantation processes for supported or solid aluminoxane systems (or vacuum / heating processes for the removal of low-boiling-point alkyl aluminum).

[0088] TMA-free ionic aluminum oxane compositions similarly reduce or eliminate side reactions of oxygen and nitrogen donors in non-leaving heteroatom-coordinated precatalyst compounds such as semi-metallocenes (e.g., defined geometry catalysts (CGCs)) and post-metallocenes, thereby promoting improved catalyst activity and lifetime.

[0089] Furthermore, aluminum oxanes can be formed, allowing free TMA in solution to remain in the upper solution phase and be removed from the ionic MAO by phase separation of the inclusion compound and the solution phase. In some embodiments, free TMA can be retained in the supernatant phase of the supported ionic MAO composition and can be removed by filtration or decantation and washing. After removal, the resulting solution or supported ionic activator can therefore be used for the activation of single-site catalyst precursors containing TMA reactive groups (e.g., O and / or N donors on post-metallocene catalysts and CGC semi-metallocene families).

[0090] Following heat treatment, the monodentate ligand-stabilized dimethylaluminum cations derived from the chelate-treated MAO, which provide more dimethylaluminum cations for pre-catalyst activation, can be detected by NMR spectroscopy. Furthermore, by using silanol compounds, if the ratio of silanoxy to alkylaluminum compound is approximately 1:1, the amount of free trialkylaluminum compounds (such as trimethylaluminum) present in the catalyst system can be reduced or eliminated. This reduces the decomposition reaction of oxygen-containing and / or nitrogen-containing catalyst compounds with oxygen- or nitrogen-reactive trialkylaluminum in the catalyst system. For example, the presence of monodentate ligands can convert the most reactive primary trialkylaluminum (e.g., the dimer form of AlMe3 or TMA) into less reactive secondary dialkylaluminum (e.g., as [Al2Me4(OSiMe3)]). + Or SiMe3(OAlMe2)2).

[0091] Furthermore, without being bound by theory, the presence of monodentate ligands in treated MAO similarly reduces or eliminates the chance of forming free TMA, as shown in the conventional MAO free TMA and coordinated TMA balance scheme (4), and thus reduces or eliminates free TMA-related side reactions of oxygen-containing catalyst compounds and / or nitrogen-containing catalyst compounds, thereby promoting improved catalyst activity and lifetime.

[0092]

[0093] Option (4)

[0094] In some embodiments, ionic MAOs free of noncoordinate TMA can be formed by reacting a heated chelating agent-stabilized ionic MAO composition to produce a chelating agent-derived compound comprising at least one monodentate ligand. For bis(phenolate)-containing Group 3 and lanthanide metal catalyst precursors, ionic MAOs free of noncoordinate TMA can be superior to conventional MAO activators or N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate (D4) / diisobutylaluminum hydride (DIBAH) activators. Furthermore, TMA-free ionic MAOs can be more efficient in activating some post-metallocene catalyst precursors, while TMA-free anionic modified activators, such as MAOs modified with electron-withdrawing groups (e.g., TMA-free fluorinated MAO or F-MAO), have shown lower activation efficiencies. Typically, ionic MAO (or cationic modified MAO) without non-coordinated TMA can broaden the activation range of post-metallocene precatalysts containing O and / or N and CGC semi-metallocene precatalysts (where anionic modified MAO without non-coordinated TMA exhibits limited activation). Therefore, more polyolefin products with desired plastic properties based on semi-metallocene or post-metallocene precatalysts can be produced at the required production rate and with lower operating costs.

[0095] Unsupported aluminum oxanes and supported aluminum oxanes

[0096] Aluminoxanes are oligomers containing —Al(R)—O— or —Al(R)2—O— subunits, where R is an alkyl group, typically C1 to C2. 12 Alkyl groups, such as the inactive MAO gel shown in scheme (1). According to Imhoff, DW et al. (1998), “Characterization of Methylaluminoxanes and Determination of Trimethylaluminum Using Proton NMR,” Organometallics Volume 17(10), pp. 1941-1945, examples of available aluminoxanes include soluble active methylaluminoxanes (MAOs) with a Me:Al ratio in the range of 1.4 to 1.5 based on elemental valence balance (corresponding to an O:Al ratio in the range of 0.8 to 0.75), such as the Sinn / Kaminsky fresh MAO formula (Al4O3Me6)4(TMA). 1-2 Where O:Al = 0.75, excluding, for example, Organometallics The method illustrates the coordination TMA, as well as other modified MAOs, for example, those containing C1 to C2. 10MAO modified with alkyl-based high-alkyl aluminum, carbocation agents, dialkyl aluminum cationic precursors, or containing elements / groups other than Al, Me, and O, such as F, Cl, large aryloxy groups, perfluorinated aryloxy groups (e.g., -OC6F5). Therefore, fresh soluble active MAO from the reaction of a large excess of TMA with water at a sufficiently low temperature can have an Al:O ratio of 1:0.75, and oxygen can be increased, for example, in Grace 30% MAO solution after the removal of a large excess of TMA to form a product containing about 85 mol% MAO and about 15 mol% total TMA (Imhoff et al.). Organometallics , 1998, Vol. 17 (10), p. 1941. Even under cooling, the gelation process may begin after the preparation of the solution MAO. Therefore, the composition of the solution MAO can vary over time, for example, by observing that the oxygen content in the main MAO structure increases with increasing free TMA and decreasing coordinated TMA. In some embodiments, solution MAO with similar aging under similar storage conditions can be used. In some embodiments, solution MAO with aging of less than 6 months under low-temperature storage (e.g., below -10°C, more preferably below -20°C, most preferably below -30°C) can be used. In some embodiments, solution MAO with aging of less than one week under cooling (e.g., below -10°C, more preferably below -20°C, most preferably below -30°C) can be used.

[0097] There are various methods for preparing MAO and modified MAO, such as U.S. Patent No. 4,542,199 and Chen, E. et al. (2000) "Cocatalysts for Metal-Catalyzed Olefin Polymerization: Activators, Activation Processes, and Structure-Activity Relationships," Chem. Rev.,The method described in Volume 100(4), pages 1391-1434. For example, MAO can be modified for various purposes, such as increasing activity or solubility. Examples of available MAO include MAO derived from TMA and oxygen-containing compounds (e.g., WR Grace MAO derived from TMA and water, or Nouryon PMAO derived from TMA and an organic oxygen source, or Tosoh solid MAO), MAO modified with higher alkyl groups (e.g., Nouryon MMAO), MAO modified with carbocation agents (US 9090720), MAO modified with dialkylaluminum cationic precursor agents (US 8575284), MAO modified with halogens (US 7355058), etc.

[0098] Active MAO can be formed under suitable reaction conditions by contacting a large excess of TMA with an oxygen source (such as water, metal salt coordinated water, CO2, methacrylic acid, benzoic acid, or other organic compounds containing reactive oxygen).

[0099] The active unsupported MAOs disclosed herein are commercially available or synthesized. Unsupported active MAOs include solution MAOs (e.g., 30% MAO solutions in toluene from WR Grace, Lanxess, or Nouryon) and solid MAOs (solid MAO products derived from solution MAO after solvent removal, such as solid MAOs sold by Tosoh FineChem Corporation). The active solution or solid MAOs of this disclosure can be prepared in situ by contacting a hydrocarbon aluminum compound with an oxygen source (e.g., TMA with water) in an aliphatic or aromatic diluent at temperatures less than 0°C to -60°C (e.g., -10°C to -50°C, such as -15°C to -30°C).

[0100] The supported MAO of this disclosure can be prepared by conventional methods, such as contacting a pre-formed MAO solution with a support (e.g., silica). For example, the solution MAO can be added to a solid support or a support slurry, or added in reverse, followed optionally by heating to form the supported MAO. The supported MAO of this disclosure can also be prepared in situ by contacting an aluminum hydroxyl compound with an oxygen source supported on a support. These operations are typically carried out in a suitable inert liquid phase, such as in a liquid hydrocarbon diluent such as a liquid aromatic hydrocarbon or aliphatic hydrocarbon. For example, water preloaded in a slurry or solid form in an aliphatic or aromatic diluent (e.g., silica) can be added, optionally with cooling, to a TMA solution cooled to below 0°C to -60°C (e.g., -10°C to -50°C, such as -15°C to -30°C), followed by a heating process, as described in US 11,161,922 and WO 2022 / 108974A1; or a non-hydrolyzable organic oxygen-containing compound can be mixed with TMA at cooling (e.g., at temperatures below 0°C to -60°C, such as -10°C to -50°C, such as -15°C to -30°C) to form a pre-MAO composition, and then the carrier (e.g., silica) can be mixed, followed by a heating process to obtain a supported MAO, as described in US 11,021,552.

[0101] For solution-supported MAO, a suitable diluent for forming the support slurry (e.g., silica slurry) is capable of dissolving the MAO to ensure good distribution of the MAO within the pores of the support; diluents such as toluene, benzene, or xylene are suitable. In some embodiments, the supported catalyst can be prepared, for example, by contacting or mixing a supported ionic aluminum oxyalkoxide with a metal catalyst compound or complex. For in-situ supported MAO, a suitable diluent is a material in which the reactants (e.g., hydrocarbon aluminum such as TMA, non-hydrolyzable organic oxygen-containing compounds, and derivatives of both) are at least partially soluble and are liquid at the reaction temperature. A non-limiting example diluent is one having the formula C n H (2n+2) Noncyclic alkanes, wherein n = 4 to 30, such as isobutene, butane, isopentane, hexane, n-heptane, octane, nonane, decane, etc., having the formula C n H 2n-2 Cycloalkanes, wherein n = 5 to 30, such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and mixtures thereof. Suitable aromatic diluents may include toluene, benzene, or xylene.

[0102] Various ratios of supported ionic aluminoxane to metal catalyst compound can be used. For example, ratios in the range of about 1:1 to about 2000:1, such as about 10:1 to about 300:1, or even about 100:1 to about 150:1, can be used. When contacting the supported aluminoxane and the pre-catalyst, temperatures in the range of about 0°C to about 80°C can be used.

[0103] Hydrocarbon aluminum compounds for alkylaluminoxanes and modified alkylaluminoxanes

[0104] Active aluminum oxane compositions (such as MAO) can be formed using only trimethylaluminum (TMA), but other aluminum alkyl compounds (also known as alkyl aluminum compounds) can be used to modify MAO. The alkyl aluminum compound used for aluminum oxane modification can be an alkyl aluminum compound, such as a trialkyl aluminum compound. For example, the alkyl substituent can be an alkyl group having up to 10 carbon atoms, such as octyl, isobutyl, ethyl, or methyl. Therefore, suitable alkyl aluminum compounds can include trimethylaluminum, triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri(2-methylpentyl)aluminum, trihexylaluminum, tri-n-octylaluminum, and tri-n-decylaluminum. In some embodiments, the alkyl aluminum compound is trimethylaluminum and tri-n-octylaluminum. In some embodiments, the alkyl aluminum compound is represented by the formula R3Al, where each R is independently a hydrocarbon containing 1 to 30 carbon atoms.

[0105] In some embodiments, the hydrocarbon aluminum compound is one or more of a trialkylaluminum mixture, such as dimethylethylaluminum or methyldiethylaluminum from a mixture of AlMe3 and AlEt3, diethylisobutylaluminum or ethyldiisobutylaluminum from a mixture of AlEt3 and AliBu3, etc.

[0106] Oxygen source for the formation of alkylaluminoxanes

[0107] The method may further include forming an alkylaluminoxane for subsequent treatment with a silanol or a multidentate silane. For example, the method may include introducing a hydrocarbon aluminum compound (such as trimethylaluminum) with an oxygen source (optionally in a support) at a temperature of about -60°C to about 100°C prior to ion treatment to form a conventional MAO composition.

[0108] Preferred oxygen sources are water, including ice or water absorbed or distributed on inorganic or organic matter. However, suitable oxygen sources may also include any oxygen source in which one or more oxygen atoms can react with a hydrocarbon-based aluminum compound to form a new Al-O bond. In at least one embodiment, the oxygen source may be or include water, such as pure water or water in a metal hydrate. In some embodiments, the oxygen source may be one or more compounds containing a hydroxyl or carbonyl group, 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 the following: carbon dioxide, carboxylic acids, ketones, aldehydes, esters, acid anhydrides, alcohols, or combinations thereof.

[0109] 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 of these groups is independently hydrogen, alkyl, alkenyl, aryl, or a heteroatom-containing group, and R 3 It is an alkyl, alkenyl, aryl, or heteroatom-containing group.

[0110] In at least one embodiment of this disclosure, the oxygen source is included in 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 including 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 mixtures of the listed compounds.

[0111] The initial charge molar ratio of Al:O (where O is the active oxygen in a compound containing active oxygen) can be 100:1, 60:1, 30:1, 10:1, 1:1, or 0.9:1 to form a desired MAO composition with or without an excess of free alkyl aluminum compounds. In some embodiments, the Al:O molar ratio can be from about 0.9:1 to about 100:1, such as from about 1:1 to about 10:1, or alternatively from about 10:1 to about 60:1, such as from about 30:1 to about 60:1. If one or more unwanted 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 a chelating agent of this disclosure. It should be understood that the above Al:O ratios are starting material (or preparation end) ratios. Because the reaction of TMA with some oxygen sources is extremely rapid and exothermic (e.g., with water), the order of addition can vary significantly with the "preparation end ratio" in terms of the actual reagent ratio. For example, when water is added slowly as needed to avoid overheating or an explosive reaction, the ratio of TMA to initial water (e.g., the first drop) in the reactor approaches infinity at the end of the reaction. Furthermore, in continuous processes, Al:O ratios greater than 1000:1 can be used because unreacted TMA can be recycled for reuse in the reaction. Therefore, an Al:O ratio >1000:1 may still be feasible.

[0112] In some implementations, the oxygen source is water in any form, including adducts.

[0113] In some implementations, the oxygen source is one or more of the following: carbon dioxide, carboxylic acid, ester, acid anhydride, alcohol, or a combination thereof.

[0114] In some embodiments, the oxygen source is one or more of the following: carbon dioxide, carboxylic acid, ester, acid anhydride and alcohol or a combination thereof, optionally containing water.

[0115] In some implementations, the oxygen source is R 1 R 2 C═CR 3 CO2H, where R 1 and R 2 Each of these groups is independently hydrogen, alkyl, alkenyl, aryl, or a heteroatom-containing group, and R 3 It is an alkyl, alkenyl, aryl, or heteroatom-containing group.

[0116] In some implementations, the oxygen source is methacrylic acid.

[0117] In at least one embodiment of this disclosure, the oxygen source is a hydrocarbylboroxine as described in Welborn’s U.S. Patent No. 5,001,244 (incorporated herein by reference).

[0118] Cationic modified (or ionic) aluminoxane

[0119] Stable chelating agents or monodentate agents (such as silanols and derived dialkylaluminosilicates or polydentate siloxanes) can be used as starting materials in the production of ionic aluminum oxanes. A wide variety of organic, inorganic, or organometallic compounds can be used to form ionic aluminum oxanes. In some embodiments, various aluminum oxanes can be used to form stable alkyl aluminum oxanes, such as methyl aluminum oxanes. In the formation of stable ionic aluminum oxanes, the denser lower liquid phase (or inclusion phase) can be easily separated from the upper solution phase using conventional separation techniques such as phase splitting, decantation, or draining.

[0120] chelating agent-derived ionic MAO In some embodiments, the starting material may be a chelating agent dissolved in a hydrocarbon solvent such as an aromatic solvent. For example, the starting material may include a hydrocarbon aluminoxane (e.g., an alkylaluminoxane) and a chelating agent (which is a hydrocarbon polysiloxane, such as a hydrocarbon trisiloxane). In some embodiments, the chelated hydrocarbon polysiloxane compound may have at least three silicon atoms separated from each other by oxygen atoms in the molecule, 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 individually by a monovalent hydrocarbon group. The hydrocarbon 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 groups such as alkyl, cycloalkyl, aryl, aralkyl, etc.

[0121] 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.

[0122] Non-limiting examples of such polysiloxanes include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, octamethyltrisiloxane (OMTS), decamethyltetrasiloxane, dodecylpentasiloxane, tetradecylmethylhexasiloxane, 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 substituent containing a heteroatom on a polydentate compound).

[0123] In some embodiments, a dialkylaluminum cation stabilized with a chelating ligand (e.g., [AlMe2(OMTS))) can be used. + Ionic alkylaluminoxanes (e.g., ionic MAO) become more active upon heating, which may be achieved by heating after (e.g., AlMe2) + This forms a more unstable monodentate complex, which readily releases dialkylaluminum cations, such as those formed by... 1 Structure I- indicated by H-NMR a : (I- a ) Monodentate-derived ionic MAO Alternatively, ionic aluminum oxanes can be formed in situ by converting free alkyl aluminum (such as TMA) in an aluminum oxane composition (e.g., a MAO composition) using silanol SiR3OH to form a monodentate coordination compound AlR2OSiR3 (e.g., as...). Figure 2 As shown, where R = Me, it is formed to act as a dialkylaluminum cationic stabilizer and to eliminate or reduce free alkylaluminum, which is desirable for solution aluminum oxane systems due to the challenging process of removing free alkylaluminum in solution systems. The R group of a silanol having the formula HO-SiR3, wherein each R is independently hydrogen, alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl), alkenyl, aryl, or a group containing heteroatoms. In some embodiments, each R is methyl.

[0124] In some embodiments, the monodentate coordination compound AlR2OSiR3 (Formula II) can be pre-formed and applied to a solid or supported aluminoxane system, followed by a free alkylaluminum separation process (e.g., filtration or decantation to reduce or eliminate free alkylaluminum in the system). Optionally, if the removal of low-boiling-point free alkylaluminum (such as free TMA) is desired, a heating process with optional vacuum drying can be applied to the supported or solid aluminoxane system.

[0125] In some embodiments, the ionic aluminum oxanes that do not contain non-coordinated alkylaluminum are those formed in aromatic hydrocarbons (such as benzene, toluene, one or more xylenes, ethylbenzene, cumene, etc.), wherein the reactants are alkylaluminoxanes and at least one chelating agent or monodentate agent, most preferably methylaluminoxane and octamethyltrisiloxane.

[0126] In some embodiments where multidentate siloxanes are used, aromatic or aliphatic solvents (such as benzene, toluene, xylene, ethylbenzene) or other aromatic solvents (such as mixtures of two or more liquid aromatic hydrocarbons) or C3-C4 solvents can be used. 12 Aluminoxanes (e.g., those containing siloxane alkyl aluminum complexes) thoroughly washed (before heating) with saturated hydrocarbon solvents (such as isobutylene, isohexane, isopentane, isohexane, heptane, octane, etc.) containing siloxane alkyl aluminum complexes. Figure 1 (A) and when using low-boiling-point solvents (e.g., isobutylene), cooling and / or a closed environment may be required to limit solvent escape. Alternatively or alternatively, aromatic or aliphatic solvents (such as benzene, toluene, xylene, ethylbenzene) or other aromatic solvents (such as mixtures of two or more liquid aromatic hydrocarbons) or C3-C4 solvents may be used. 12 The ionic aluminum oxane (e.g., formed by thorough washing with a saturated hydrocarbon solvent (such as isobutylene, isohexane, isopentane, isohexane, heptane, octane, etc.) or an aromatic or aliphatic solvent or a mixture of two or more aliphatic solvents) is formed. Figure 1 B or Figure 2 (B) The volume of solvent relative to the initial aluminoxane can vary as long as a stirable solution is produced. After each wash, a two-phase liquid system can be formed, and the less dense upper phase can be separated from the denser lower phase, for example, by decantation (which removes residual free alkylaluminum). Such washing can be carried out at ambient temperature or at temperatures that are suitably lowered or raised, for example, in the range of about 10°C to about 100°C, but higher or lower temperatures may still be used. In some embodiments, washing is carried out at one or more temperatures in the range of about 20°C to about 80°C. In some embodiments, washing is carried out at room temperature. In some embodiments, stirring can be used to agitate the mixture formed after washing. Washing can result in the formation of a relatively dense or oily washing liquid aluminoxane composition. An inert liquid non-solvent can then be added to the aluminoxane to form a precipitated solid, which may have a reduced neutral aluminoxane content.

[0127] In some embodiments, a non-solvent can force the solvent contained in the aluminoxane to detach from the aluminoxane to produce a new composition in solid form, resulting in precipitation. Various inert non-solvents can be used, such as C3-C... 12Aliphatic hydrocarbon solvents, such as one or more isobutylene, isopentane, isohexane, heptane, octane, nonane, or decane isomers, cyclopentane, one or more liquid alkylcyclopentanes, cyclohexane, one or more liquid alkylcyclohexanes, and any mixture of two or more such hydrocarbons. Non-solvents may be added at ambient room temperature or at a suitably lowered or raised temperature (e.g., from about 20°C to about 100°C).

[0128] Washing with dialkylaluminum cations stabilized by chelated polysiloxanes (e.g., Figure 1 A) or monodentate dialkylaluminum silicon oxide stabilized dialkylaluminum cations (e.g., Figure 1 B or Figure 2 The precipitated solids produced by the ionic aluminum oxane of (B) can be recovered in solid form, for example, by filtration, centrifugation, decantation, or similar techniques. In some embodiments, the recovered solids are washed with fresh non-solvent.

[0129] In some embodiments where a multidentate siloxane is used as a chelating agent, the solid is then dissolved in any suitable liquid, such that dissolution occurs, and the mixture is heated at an elevated temperature to convert the polysiloxane alkylaluminum complex in the ionic aluminoxane composition into at least one decomposed chelating ligand fragment to form a more active ionic MAO composition, which may have a monodentate ligand-stabilized dialkylaluminum cation (e.g., Figure 1 (B) Once a pre-catalyst is present, it becomes more unstable to readily release cations. The heating process can be carried out within a certain temperature range, such as from about 70°C to about 110°C, or from about 85°C to about 95°C, for a certain period of time, such as from about 0.1 to about 5 hours, or from about 1 hour.

[0130] Alternatively, the solid can be aged at room temperature to convert the aluminoxane with multidentate reagents into aluminoxanes with monodentate ligands (to form a less stable cation) for a period of time, such as from about 1 to about 12 months, like about 5 months. The resulting inclusion complexes with monodentate or chelate ligands can have higher conductivity than the nonionic aluminoxanes in the mother solution, exhibiting a stronger ionic character.

[0131] The monodentate or chelate ligands formed by the methods of this disclosure can be hydrocarbon monosilyl alkoxy groups having at least one oxygen atom in the molecule, wherein the remaining valence bonds of the three bonds of the silicon atom are satisfied individually by a monovalent hydrocarbon group. The monovalent hydrocarbon group of the hydrocarbon monosilyl alkoxy group can each independently contain up to about 18 carbon atoms and can be such a group as alkyl, cycloalkyl, aryl, or a group containing heteroatoms. Non-limiting examples of such monodentate ligands include [Me2Al(µ-OSiMe3)SiMe2] + (For example, Figure 1A) or [Me2Al(µ-OSiMe3)AlMe2] + (For example, Figure 1 B).

[0132] In some implementations, the monodentate ligand is represented by formula (I): (I) Where R 1 R 2 R 3 R 4 R 5 R 6 and R 7 Each of them is independently a hydrogen, hydrocarbon, silyl, or heteroatom-containing group.

[0133] In some implementation schemes, R 1 R 2 R 3 R 4 R 5 R 6 and R 7 Each of these is independently an alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl), alkenyl, or aryl. In some embodiments, R 1 R 2 R 3 R 4 R 5 R 6 and R 7 Each of them is a methyl group.

[0134] As discussed above, there are at least three main methods to obtain unsupported or supported aluminum oxane systems that do not contain non-coordinated alkyl aluminum: 1) Free or uncoordinated alkyl aluminum compounds (or their dimers) as desired components in conventional unsupported or supported alkyl aluminum oxane compositions (e.g., commercial MAO toluene solution, solid MAO, supported conventional MAO, or in-situ supported MAO) can be removed after the unsupported or supported aluminum oxane composition has been treated with a chelating agent to form an ionic alkyl aluminum oxane composition, so as to separate from the unsupported or supported aluminum oxane (either as a lighter phase in the case of solution MAO, or in the case of solid MAO or supported MAO in the case of supernatant) to achieve an unsupported or supported aluminum oxane system free of coordinated alkyl aluminum oxanes.

[0135] 2) Aluminoxane systems without non-coordinated alkylaluminum can be obtained through silanol treatment, where the non-coordinated alkylaluminum can be pre-quantified to match the silanol used. The main advantage of this method is that it eliminates the need for a free alkylaluminum separation process. A disadvantage is that the activation of the derived system is less efficient than in method 1), likely because the silanol reacts not only with the free alkylaluminum but also with the coordinated alkylaluminum (e.g., free TMA and coordinated TMA) to block AlMe2. + Release from the coordinated TMA (active site), as shown in scheme (4).

[0136] 3) Aluminoxane systems without non-coordinated alkylaluminum can also be obtained by treatment with a pre-formed silanol-derived compound R3SiOAlR2 (formula (II), where R is independently hydrogen, hydrocarbon, non-coordinated or weakly coordinated heteroatom-containing group) to avoid silanol poisoning of the coordinated alkylaluminum, as shown in 2). However, this method is more suitable for solid or supported MAO due to the higher solubility of the resulting ionic MAO, making phase separation in solution more challenging and thus more difficult to remove free alkylaluminum. This method has better activation efficiency, but not as good as the method in 1), because, without being bound by theory, deactivated substances, such as those from the coordinated alkylaluminum, are replaced by R3SiOAlR2, which makes AlR2... + It is more difficult to leave the coordinated R3SiOAlR2.

[0137] In some embodiments, for solution, solid, or supported aluminoxane (e.g., MAO) compositions, monodentate ligands are formed in situ by treating the MAO composition with a chelating agent or a monodentate agent (i.e., a polydentate siloxane or a silanol or a silanol-derived dialkylaluminum compound).

[0138] In some embodiments, the amount of chelating agent (e.g., OMTS) applied to the alkylaluminoxane composition can be determined by titrating the target alkylaluminoxane with the chelating agent; for example, an excess of a known amount of OMTS (W) can be used. i It is placed in an alkylaluminoxane solution, and the noncoordinate (neutral) OMTS relative to [AlMe2(OMTS)] can be determined using proton NMR. + The ratio of reactive OMTS can be used to calculate the percentage of reactive OMTS; for example, reactive OMTS% = ([AlMe2(OMTS)] + / ([AlMe2(OMTS)] + + Neutral OMTS)) x 100. Therefore, the total reactive OMTS amount is calculated as W. i x Reactivity OMTS%, see Experimental Examples section for details. Although the amount of chelating agent is most preferably equal to W ix Reactivity OMTS%, but more or less loading is still acceptable, for example, more than W i x Reactivity OMTS% more or less 20%, compared to W i x Reactivity OMTS% more or less 10%, or more than W i x Reactivity OMTS% more or less 5%.

[0139] In some embodiments, the silanol SiR3OH may be loaded based on the free alkyl aluminum in the aluminoxane composition (e.g., free TMA in the MAO composition). The method for determining the free alkyl aluminum (e.g., free TMA) is described in the Experimental Examples section below. Although the amount of silanol is most preferably equal to the amount of free alkyl aluminum in the alkylaluminoxane composition (mol:mol), more or less loading is still acceptable, for example, 20 mol% more or less than the free alkyl aluminum, 10% more or less than the free alkyl aluminum, or 5% more or less than the free alkyl aluminum.

[0140] In some embodiments, the pre-formed silanol (SiR3OH)-derived SiR3OAlR2 can be loaded based on a coordinating alkylaluminum in the aluminoxane composition (e.g., a coordinating TMA in an MAO composition). The method for determining the coordinating alkylaluminum (e.g., coordinating TMA) is described in the Experimental Examples section. While the amount of SiR3OAlR2 is most preferably equal to the amount of coordinating alkylaluminum in the alkylaluminoxane composition (mol:mol), more or less loading is still acceptable, for example, 20 mol% more or less than the coordinating alkylaluminum, 10% more or less than the coordinating alkylaluminum, or 5% more or less than the coordinating alkylaluminum.

[0141] The chelation or monodentate ligand-stabilized dialkylaluminum cation formation reaction can be carried out at any suitable temperature, such as about 0°C to about 100°C, about 10°C to about 30°C, about 20°C, or ambient temperature. The reaction can be carried out in pure substance form (e.g., solid-solid) or using any suitable diluent. In some embodiments, the diluent can be an organic diluent, such as an aliphatic or aromatic diluent. An aliphatic diluent can be a substance having the formula C... n H (2n+2) Acyclic alkanes, wherein n = 4 to 30, such as isobutane, butane, isopentane, hexane, n-heptane, octane, nonane, or decane, having the formula C n H 2n-2The cycloalkanes, wherein n = 5 to 30, include cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and mixtures thereof. Aromatic diluents may include benzene, toluene, or xylene. For chelated ligand-derived ionic alkylaluminoxane compositions, a heating process can be applied to improve the pre-catalyst activation efficiency. The heating temperature can be 60°C to 120°C, more preferably 80°C to 110°C, and most preferably 90°C to 100°C. Heating can be carried out in an open system at 1 atmosphere or in a closed system with a corresponding safety pressure rating at reduced pressure or high pressure (such as 0.1 atm to 15 atm, 0.5 atm to 10 atm, or 0.9 atm to 5 atm).

[0142] Following treatment with a monodentate or chelating agent and an optional free alkylaluminum separation process, the alkylaluminoxane, such as MAO (unsupported or supported), may have a total aluminum content based on MAO of about 2 wt% or less, such as about 1.5 wt% or less, such as about 1 wt% or less, such as about 0.5 wt% or less, such as about 0.25 wt% or less, such as about 0.1 wt% to about 2 wt%, such as about 0.1 wt% to about 1.5 wt%, such as about 0.2 wt% to about 1 wt%, such as about 0.3 wt% to about 0.7 wt%, and alternatively, about 0.1 wt% to about 0.5 wt% of free alkylaluminum compound. The method for determining free alkylaluminum is described in the following Experimental Examples section.

[0143] Optional carrier material

[0144] The carrier material can be a porous carrier material, such as talc and inorganic oxides. Other carrier materials include zeolite, clay, organoclay, or another organic or inorganic carrier material, or mixtures thereof.

[0145] The support material can be an inorganic oxide. The inorganic oxide can be in a finely crushed form. Suitable inorganic oxide materials for the catalyst system used herein can include Group 2, 4, 13, and 14 metal oxides, such as silica, alumina, and mixtures thereof. Other inorganic oxides that can be used alone or in combination with silica or alumina can be magnesium oxide, titanium dioxide, or zirconium oxide. However, other suitable support materials can be used, for example, finely crushed functionalized polyolefins, such as finely crushed polyethylene. Examples of suitable supports can include magnesium oxide, titanium dioxide, zirconium oxide, montmorillonite, phyllosilicates, zeolite, talc, and clay. Additionally, combinations of these support materials can be used, such as silica-chromium, silica-alumina, and silica-titanium dioxide. In at least one embodiment, the support material is selected from Al2O3, ZrO2, SiO2, SiO2 / Al2O3, SiO2 / TiO2, silica-clay, silica / clay, or mixtures thereof.

[0146] Carrier materials, such as inorganic oxides, can have a thickness of approximately 10 μm. 2 / g to approximately 800 m 2 / g surface area, approximately 0.1cm 3 / g to approximately 4.0 cm 3 The pore volume is approximately 3 μm to approximately 300 μm, and the average particle size is approximately 3 μm to approximately 300 μm. The surface area of ​​the support material can be approximately 50 m². 2 / g to approximately 500 m 2 / g, pore volume approximately 0.5 cm³ 3 / g to approximately 3.5 cm 3 / g and an average particle size of approximately 10 μm to approximately 200 μm. For example, the surface area of ​​the support material can be approximately 100 m². 2 / g to approximately 400 m 2 / g, pore volume approximately 0.8 cm³ 3 / g to approximately 3.0 cm 3 / g and the average particle size can be from about 5 μm to about 100 μm. The average pore size of the support material that can be used in this disclosure can be from about 50 Å to about 1000 Å, such as from about 60 Å to about 500 Å, and such as from about 75 Å to about 350 Å. In at least one embodiment, the support material is amorphous silica with a high surface area (e.g., a surface area of ​​about 300 m² / g). 2 / gm; pore volume approximately 1.65 cm³ 3 / gm). For example, suitable silica may be silica sold under the trade names DAVISON™ 952 or DAVISON™ 955 (Davison Chemical Division of WR Grace and Company). In other embodiments, DAVISON™ 948 is used. Alternatively, the silica may be ES-70, ES70X, ES757, PD17062, PD16042, PD16043, or PD14024 silica (Ecovyst, formerly PQ Corporation, Malvern, Pennsylvania), DM L403, DM-L303, D60-120A, D150-60A (AGC Chemicals Company, Japan), CARiACT G-10, P-10, P-6, or Q-10 silica (Fuji Silysia Chemical LTD), Sipernat 310, or Sipernat 50 (Evonik), which has been calcined, for example, at 200°C, 400°C, 600°C, or 875°C.

[0147] For pre-formed MAO loadings, the support material should be dry, i.e., free of or substantially free of absorbed water. However, for in-situ MAO loadings, calcination may be unnecessary when water is used as the oxygen source. The amount of hydroxyl groups on the pore surface of the support material can be controlled by heating or calcining at different temperatures (e.g., from about 100°C to about 1000°C, such as at least about 600°C). When the support material is silica, it is heated to at least about 150°C, such as from about 200°C to about 850°C, and such as at about 400°C–600°C; and for a duration of about 30 minutes to about 100 hours, about 4 hours to about 72 hours, or about 24 hours to about 60 hours. The calcined support material must possess at least some reactive hydroxyl groups (OH) to produce the supported catalyst system of this disclosure.

[0148] The formation of supported ionic aluminumoxanes and derived finished catalysts without non-coordinated alkyl aluminum.

[0149] In embodiments herein, the catalyst system may include a support material as described above. For example, the support material may be contacted with a pre-formed solution of aluminum oxane (e.g., commercial solution MAO) to form a supported MAO, and subsequently contacted with a monodentate agent (e.g., silanol SiR3OH or silanol-derived SiR3OAlR2 compounds) and optionally AlR3 or a chelating agent (e.g., polysiloxane, such as OMTS) to form a monodentate or chelated ligand-stabilized dialkylaluminum cation in situ, or with a pre-formed monodentate agent of this disclosure (e.g., Figure 1A, Figure 1 and Figure 2 Contact with B) (such as dialkylaluminum silicon oxide), followed by free alkylaluminum separation processes such as filtration, decantation, or, in the case of low-boiling-point free alkylaluminum (such as in the case of free TMA), vacuum extraction to remove free alkylaluminum (such as free TMA). To increase the amount from the chelating agent... Figure 1 The activation efficiency of chelating substance A can be improved by applying a heating process. Figure 1 At least a portion of the chelating substance A is converted into Figure 1 Monodentate substance B. For example, 20 mol% of substance A, 40 mol% of substance A, or >70 mol% of substance A, or even undetectable substance A.

[0150] Alternatively, the support material can be contacted with an aluminum oxane (e.g., an ionic MAO without non-coordinated TMA) of the present disclosure to form a supported activator, and then the supported activator can be contacted with a pre-catalyst compound.

[0151] Alternatively, the precatalyst compound can be contacted with MAO that does not contain non-coordinated TMA to form a solution catalyst system, and then the solution catalyst system can be contacted with a support material to form a supported catalyst system.

[0152] Alternatively, the support material can be loaded with an oxygen source (e.g., water), and the oxygen-loaded support is then added in solid form or as a slurry (cooled or uncooled) to a cold TMA solution (optionally heated) to form a supported MAO composition. The chelating agent is then treated with optional AlR3 and a free alkylaluminum separation process (such as filtration, decantation) is performed, or, in the case of free TMA, a vacuum pumping process is performed to remove the free TMA to form a coordinated alkylaluminum-supported alkylaluminoxane system, followed by contact with a pre-catalyst to form the finished catalyst.

[0153] Alternatively, the support material can be loaded with an oxygen source (e.g., water), and the oxygen-loaded support is then added in solid form or as a slurry (cooled or uncooled) to a cold TMA solution (optionally heated) to form a supported MAO composition. The in-situ formed monodentate SiR3OAlR2 compound is then treated by contacting the supported MAO with silanol SiR3OH and optionally AlR3 along with an optional filtration / washing process, or by treating the pre-formed monodentate SiR3OAlR2 compound with the necessary filtration / washing process to form a supported MAO free of non-coordinated TMA, and then a pre-catalyst is contacted to form the finished catalyst.

[0154] Depending on the specific process, a support material with reactive surface groups (such as hydroxyl groups) may be contacted, either as a nonpolar solvent slurry or as a solid, with at least one precatalyst compound in solid or solution form and a MAO-based activator in any order (including the order mentioned above), provided that if the precatalyst has a non-leaving heteroatom donor (e.g., O and / or N), it should be contacted with the MAO-based activator after the MAO has been converted into an ionic MAO without non-coordinating TMA. In at least one embodiment, the support material is first contacted with a pre-formed activator solution (e.g., conventional MAO or ionic MAO without non-coordinating TMA) for a period of about 0.5 hours to about 24 hours, about 2 hours to about 16 hours, or about 4 hours to about 8 hours. In the case of conventional MAO loading, the supported conventional MAO is converted into a supported ionic MAO without non-coordinating TMA using the method described above. Then, the solution or solid form of the precatalyst compound is contacted with a supported activator without non-coordinating TMA. In at least one embodiment, the supported MAO for the catalyst system is generated in situ. In alternative embodiments, the slurry of supported MAO without non-coordinated TMA is contacted with the pre-catalyst compound for a period of about 0.5 hours to about 24 hours, about 1 hour to about 16 hours, or about 2 hours to about 8 hours. In more alternative embodiments, in the slurry preparation process or the initial wet preparation process, a pre-formed ionic MAO solution without non-coordinated TMA is first mixed with at least one pre-catalyst before contact with the support material.

[0155] A mixture of one or more catalysts, one or more activators, and a support is stirred at about 0°C to about 100°C, such as about 23°C to about 60°C, such as at room temperature. The contact time can be about 0.5 hours to about 24 hours, such as about 2 hours to about 16 hours, or about 4 hours to about 8 hours. The ratio of insoluble matter (insoluble silica, supported MAO, activated pre-catalyst, and one or more additives) to solvent can be any practical ratio, such as 3:97, 10:90, 30:70, 50:50 (wt:wt), depending on the specific process used. For example, for continuous processes, lower insoluble matter:solvent ratios, such as 3:97, 1:99, or lower, can be used; for initial wet processes, higher insoluble matter:solvent ratios, such as 60:40 or higher, can be used.

[0156] A suitable nonpolar diluent is a material in which all reactants used herein (e.g., activators and precatalyst compounds) are at least partially soluble and are liquid at the reaction temperature. Nonpolar diluents for in-situ MAO loading can be alkanes such as isopentane, hexane, isohexane, n-heptane, octane, nonane, and decane, although a variety of other materials may also be used, including cycloalkanes such as cyclohexane, aromatic compounds such as benzene, toluene, and ethylbenzene, and for pre-formed MAO loading, aromatic compounds such as benzene, toluene, and ethylbenzene may be used.

[0157] In at least one embodiment, the supported activator is a supported ionic MAO that does not contain non-coordinated TMA, which is MAO supported on silica (e.g., ES70 silica calcined at 400°C) that is free of or depleted of free TMA after physical (e.g., by phase separation, filtration / decantation, or vacuum pumping) or chemical (e.g., by reaction with silanols).

[0158] Embodiments of this disclosure include a method for preparing a finished catalyst system, comprising contacting a solid MAO or supported MAO that does not contain noncoordinated TMA with at least one precatalyst compound having group 3 to group 12 metal atoms or lanthanide metal atoms in an organic diluent.

[0159] In at least one embodiment, solid MAO or supported MAO that does not contain non-coordinated TMA is heated before contacting with the precatalyst compound. In at least one embodiment, solid MAO or supported MAO is heated after contacting with the precatalyst compound.

[0160] Solution catalyst formation

[0161] Embodiments of this disclosure include a method for preparing a solution or homogeneous catalyst system, comprising contacting an ionic liquid MAO (TF-iMAO) free of noncoordinate TMA with at least one precatalyst compound having Group 3 to Group 12 metal atoms or lanthanide metal atoms in an organic diluent.

[0162] In at least one embodiment, TF-iMAO is heated, for example, at 50°C to 120°C, at 80°C to 110°C, or at 90°C to 100°C for 0.5 hours to 24 hours, for 1 to 10 hours, or for 2 to 5 hours, before being contacted with the pre-catalyst compound.

[0163] TF-iMAO can be solvated in an organic diluent and the resulting mixture can be contacted with a solution of at least one precatalyst compound. Alternatively, the precatalyst compound can be added as a solid to the mixture of the organic diluent and TF-iMAO. In at least one embodiment, the mixture of TF-iMAO is contacted with the precatalyst compound for a period of about 0.02 hours to about 24 hours, such as 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, before being contacted with one or more olefin monomers for polymerization.

[0164] Before contacting one or more olefin monomers for polymerization, the mixture of the precatalyst compound and TF-iMAO can be heated to a temperature of approximately 0°C to approximately 70°C (such as approximately 23°C to approximately 60°C, e.g., room temperature).

[0165] A suitable organic diluent is a material in which some or all of the reactants used herein (e.g., TF-iMAO and the precatalyst compound) are at least partially soluble and preferably liquid at the reaction temperature. A non-limiting example diluent is one having the formula C n H (2n+2) Noncyclic 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.

[0166] The diluent can be loaded into the reactor, followed by the TF-iMAO. The catalyst, such as a solution of the catalyst in the organic diluent or as a solid, can then be loaded into the reactor. The mixture can be stirred at a temperature such as room temperature. Additional diluents can be added to the mixture to form a mixture with a desired consistency, such as a slurry having about 2 cc / g of silica to about 20 cc / g of silica, or about 4 cc / g of 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. To heat the mixture, any suitable temperature that evaporates the aliphatic diluent can be used. It should be understood that, depending on the reactor pressure, depressurization under vacuum will lower the boiling point of the aliphatic diluent. The diluent removal temperature can be about 10°C to about 200°C, such as about 60°C to about 140°C, such as about 60°C to about 120°C, such as about 100°C or lower, such as about 90°C or lower. In at least one embodiment, removing the diluent includes applying heat, applying a vacuum, and applying nitrogen gas by bubbling nitrogen gas through the mixture from the bottom of the container. The mixture is then dried.

[0167] Precatalyst compounds

[0168] The terms “catalyst,” “catalyst compound,” “catalyst complex,” “metal complex,” “metal compound,” “precatalyst compound,” and “precatalyst complex” are used interchangeably to describe transition metal complexes or lanthanide metal complexes that, when combined with suitable activators, form olefin polymerization catalysts.

[0169] 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 to 12 metal atom, such as a group 3 to 10 metal atom, or a lanthanide atom. The catalyst compound having a group 3 to 12 metal atom may be monodentate or multidentate, such as bidentate, tripentate, or tetradentate, wherein a heteroatom of the catalyst, such as 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 to 12 metal atom is selected from group 5, group 6, group 8, or group 10 metal atom. In at least one embodiment, the group 3 to 10 metal atom is selected from Cr, Sc, Ti, Zr, Hf, V, Nb, Ta, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, and Ni. In at least one embodiment, the metal atom is selected from group 4, 5, and 6 metal atom. In at least one embodiment, the metal atom is a Group 4 metal atom selected from Ti, Zr, or Hf. The oxidation state of the metal atom can be in the range of 0 to +7, for example +1, +2, +3, +4, or +5, such as +2, +3, or +4. The catalyst compound disclosed herein can be rhenium or a rhenium-based catalyst, scandium or a scandium-based catalyst, or chromium or a chromium-based catalyst.

[0170] Chromium-based catalysts include chromium oxide (CrO3) and silyl chromate catalysts. Chromium catalysts have been a subject of much development in the field of continuous fluidized bed gas-phase polymerization for the production of polyethylene polymers. Such catalysts and polymerization methods have been described, for example, in U.S. Patent Application Publication No. 2011 / 0010938 and U.S. Patent Nos. 7,915,357, 8,129,484, 7,202,313, 6,833,417, 6,841,630, 6,989,344, 7,504,463, 7,563,851, 8,420,754, and 8,101,691.

[0171] The single-Cp catalyst precursor compounds that can be used in this disclosure have at least one polar atom in a cyclopentadienyl (Cp) ligand (which includes isolobal ligands similar to cyclopentadienyl) and at least one non-Cp ligand, which is either bridged or unbridged with the Cp ligand and directly bonded to the precatalyst metal center.

[0172] In at least one embodiment, the single-Cp precatalyst compound of this disclosure is represented by formula (MC-I): T y Cp m MG n X q (MC-I) Where Cp is independently a substituted or unsubstituted cyclopentadienyl ligand or a substituted or unsubstituted ligand similar to the cyclopentadienyl isovalence, such as indenyl, fluorenyl, tetrahydro- s -Indexing the glycosides and tetrahydrogen- as -Indexed by the provincial base. M is a group 4 transition metal, such as Hf, Ti, or Zr. G is derived from formula JR. z The heteroatomic group is represented, where J is N, P, O, or S, and R is... Is it a straight chain, branched chain, or cyclic C1-C? 20 Hydrocarbon group. z is 1 or 2. T is a bridging group. y is 0 or 1. X is a leaving group. m = 1, n = 1, 2 or 3, q ​​= 0, 1, 2 or 3, and the sum of m + n + q equals the oxidation state of the transition metal, such as 2, 3 or 4, such as 4.

[0173] In at least one embodiment, J is N, and R It is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, cyclooctyl, cyclododecyl, decyl, undecyl, dodecyl, adamantyl, or isomers thereof. Example JR z The groups include tert-butylamino and cyclododecylamino.

[0174] Examples of bridging groups T include CH2, CH2CH2, SiMe2, SiPh2, SiMePh, Si(CH2)3, Si(CH2)4, O, S, NPh, PPh, NMe, PMe, NET, NPr, NBu, PEt, PPr, Me2SiOSiMe2, and PBu. In at least one embodiment, T is derived from the formula ER. d 2 or (ER) d 2)2 represents, where E is C, Si, or Ge, and each R d Independently, it is hydrogen, halogen, C1 to C20 hydrocarbon group (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) or C1 to C20 substituted hydrocarbon group, or two R d It can form cyclic structures, including aromatic, partially saturated, or saturated cyclic or fused ring systems.

[0175] Each X is independently selected from the group consisting of hydrocarbon, aryl, hydride, amide, alkoxy, sulfide, phosphide, halide, diene, amine, phosphine, ether, and combinations thereof having 1 to 20 carbon atoms (two Xs may form a fused ring or part of a cyclic system), such as each X being independently selected from halogen, aryl, and C1 to C5 alkyl, such as each X being phenyl, methyl, ethyl, propyl, butyl, pentyl, or chlorinated.

[0176] In at least one embodiment, the single-Cp catalyst precursor compound of formula (MC-I) is selected from: Dimethylsilanediyl(2,3,4,5-tetramethylcyclopentadienyl)(cyclododecylamino)M(R)2; Dimethylsilanediyl(2,3,4,5-tetramethylcyclopentadienyl)(cycloundecylamino)M(R)2; Dimethylsilanediyl(2,3,4,5-tetramethylcyclopentadienyl)(cyclodecylamino)M(R)2; Dimethylsilanediyl(2,3,4,5-tetramethylcyclopentadienyl)(tert-butylamino)M(R)2; Dimethylsilanediyl(cyclopentadienyl)(1-adamantylamino)M(R)2; Dimethylsilanediyl(3-tert-butylcyclopentadienyl)(1-adamantylamino)M(R)2; Dimethylsilanediyl(tetramethylcyclopentadienyl)(1-adamantylamino)M(R)2; Dimethylsilanediyl(tetramethylcyclopentadienyl)(1-adamantylamino)M(R)2; Dimethylsilanediyl(tetramethylcyclopentadienyl)(1-adamantylamino)M(R)2; Dimethylsilanediyl(tetramethylcyclopentadienyl)(1-tert-butylamino)M(R)2; Dimethylsilanediyl(fluorenyl)(1-tert-butylamino)M(R)2; Dimethylsilanediyl(tetramethylcyclopentadienyl)(1-cyclododecylamino)M(R)2; µ-(C6H5)2C(tetramethylcyclopentadienyl)(1-cyclododecylamino)M(R)2; Dimethylsilanediol ( η 5 -2,6,6-trimethyl-1,5,6,7-tetrahydro- s -Index-1-yl)(tert-butylamino)M(R)2; Wherein M is selected from Ti, Zr, and Hf; and each R is selected from halogens or C1 to C5 alkyl groups (such as chlorine, bromine, methyl, ethyl, propyl, butyl, pentyl, or isomers thereof). In at least one embodiment, M is Ti and each R is methyl.

[0177] The single-Cp precatalyst compounds disclosed herein can be synthesized as described in US 5,621,126 and US 5,547,675 (which are incorporated herein by reference).

[0178] The single-Cp precatalyst compound may also include a structure represented by formula (MC-II), preferably having C s or pseudo-C s Symmetrical compounds: (MC-II) in: M stands for zirconium; L 1 It is an unsubstituted fluorenyl, heterocyclopentacyclopentadienyl, or heterofluorenyl ligand, or a substituted fluorenyl, heterocyclopentacyclopentadienyl, or heterofluorenyl ligand having one or more symmetrical or pseudo-symmetrical substituents, each substituent group being independently a group as a hydrocarbon group, a substituted hydrocarbon group, a halocarbyl group, a substituted halocarbyl group, a silylcarbyl group, or a germylcaryl group, and optionally two or more adjacent substituents may be joined to form a substituted or unsubstituted, saturated, partially unsaturated, or aromatic, cyclic, or polycyclic substituent; G is a bridging group; J is a heteroatom from group 15, such as N or P, such as N; R' is a group that is a hydrocarbon group, a substituted hydrocarbon group, a halohydrocarbon group, or a substituted halohydrocarbon group; L' is a neutral Lewis base and w represents the number of L's bonded to M, where w is 0, 1, or 2, and optionally any L' and any X can bond to each other; X can be independently a hydrogen group, a hydrocarbon group, a substituted hydrocarbon group, a halohydrocarbon group, a substituted halohydrocarbon group, a silylhydrocarbon group, a substituted silylhydrocarbon group, a germanylhydrocarbon group, or a substituted germanylhydrocarbon group; or two X groups can be combined and bonded to a metal atom to form a metal ring containing about 3 to about 20 carbon atoms; or both can be olefin, diene, or aryynylene ligands; the two X groups can be independently halogens, alkoxy groups, aryloxy groups, amino groups, phosphoro groups, or other monovalent anionic ligands, or the two X groups can be combined to form an anionic chelate ligand.

[0179] In equation (MC-II), L 1It is a fluorenyl or substituted fluorenyl group, such as fluorenyl, 2,7-dimethylfluorenyl, 2,7-diethylfluorenyl, 2,7-dipropylfluorenyl, 2,7-dibutylfluorenyl, 2,7-diphenylfluorenyl, 2,7-dichlorofluorenyl, 2,7-dibromofluorenyl, 3,6-dimethylfluorenyl, 3,6-diethylfluorenyl, 3,6-dipropylfluorenyl, 3,6-dibutylfluorenyl, 3,6-diphenylfluorenyl, 3,6-dichlorofluorenyl, 3,6-dibromofluorenyl, or 1,1,4,4,7,7,10,10-octamethyl-octahydrodibenzo[a] Fluorenyl, such as fluorenyl, 2,7-dimethylfluorenyl, 2,7-diethylfluorenyl, 2,7-dipropylfluorenyl, 2,7-dibutylfluorenyl, 3,6-dimethylfluorenyl, 3,6-diethylfluorenyl, 3,6-dipropylfluorenyl, 3,6-dibutylfluorenyl, or 1,1,4,4,7,7,10,10-octamethyl-octahydrodibenzofluorenyl, such as 2,7-di-tert-butylfluorenyl, 3,6-di-tert-butylfluorenyl, 1,1,4,4,7,7,10,10-octamethyl-octahydrodibenzofluorenyl, or fluorenyl. G is methylene, dimethylmethylene, diphenylmethylene, dimethylmethylenesilyl, methylphenylmethylenesilyl, diphenylmethylenesilyl, di(4-triethylmethylsilylphenyl)methylenesilyl, ethylene, such as diphenylmethylene, diphenylmethylenesilyl, methylphenylmethylenesilyl, and dimethylmethylenesilyl; such as dimethylmethylenesilyl. A suitable J can be nitrogen. R' is a hydrocarbon group or a halogenated hydrocarbon group, such as C3-C 20 Hydrocarbon groups, such as propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, benzyl, phenyl, and all isomers of substituted phenyl groups (including cyclic and polycyclic), such as tert-butyl, neopentyl, benzyl, phenyl, diisopropylphenyl, adamantyl, norbornyl, cyclohexyl, cyclooctyl, cyclodecyl, and cyclododecyl, such as tert-butyl, adamantane-1-yl, norborn-2-yl, cyclohexyl, cyclooctyl, and cyclododecyl. X is a hydrocarbon group or a halo group, such as methyl, benzyl, fluorine, or chlorine, such as methyl or chlorine; w is zero (L' is not present); M is zirconium.

[0180] Examples of single-Cp catalyst compounds having one or more polar donors include, but are not limited to:

[0181] Monocerometallic precatalyst compounds can also be selected from: Dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamino)dimethyltitanium; Dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamino)titanium dichloride; Dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamino)dimethyltitanium; Dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamino)titanium dichloride; M is selected from Ti, Zr and Hf; and R is selected from halogens or C1 to C5 alkyl groups.

[0182] In some embodiments, the precatalyst of this disclosure may be a "post-metallocene" catalyst having one or more oxygen and / or nitrogen atoms. For example, the catalyst of this disclosure may be a metal complex having: a metal selected from Groups 3-10 or lanthanides, and a tridentate, monoanionic, or dianionic ligand containing one or two anionic donor groups and two or one neutral Lewis base donor, wherein the one or two neutral Lewis base donors are covalently bonded between the two anionic donors, and wherein the metal ligand complex has a pair of 4-, 5-, 6-, 7-, or 8-membered metal rings or a pair of mixed-membered metal rings (such as a mixture of 4- and 5-membered rings, a mixture of 5- and 6-membered rings, a mixture of 6- and 7-membered rings, a mixture of 5- and 7-membered rings, or a mixture of 7- and 8-membered rings).

[0183] The catalyst complexes disclosed herein comprise metals selected from Groups 3-10 of the periodic table or lanthanides, containing a tripentate bianotic ligand with 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 phenolate donors, and the tripentate ligand is coordinated with the metal center to form two octetary rings.

[0184] In some embodiments, the heterocyclic Lewis base donor of the catalyst compound is characterized as 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.

[0185] The anion donor of the tripentate bidentate ligand can be an aryl hydrocarbon thio group, a phenolate, or an aniline. 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 dual axis of rotational symmetry; 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).

[0186] The catalyst compound disclosed herein can be a bis(arylphenolate)pyridine complex. The bis(arylphenolate)pyridine complex can have a tripentate bis(arylphenolate)pyridine ligand that coordinates with a Group 4 transition metal, resulting in the formation of two eight-membered rings. In some embodiments, the bis(arylphenolate)pyridine complex comprises a transition metal complex characterized by a central neutral donor group and two phenolate donors, with the tripentate ligand coordinated with the metal center to form two eight-membered rings; for example, the post-metallocene catalyst can be an 8-8 catalyst. In this type of complex, it is advantageous for the central neutral donor to be a heterocyclic group. It is advantageous for the heterocyclic group to lack hydrogen at the α-position of the heteroatom. 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.

[0187] In some embodiments, the bis(phenolate) ligand can be a tripentate bianionic ligand that coordinates with metal M in such a way as to form an 8-membered metal ring pair. The bis(phenolate) ligand surrounds the metal to form a complex with a twofold 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 effective catalyst components for the production of polyolefins, particularly isotactic poly(α-olefins). If the ligand and metal coordinate in such a way as to give the complex a mirror-like (C2) symmetry, the complex will exhibit a more pronounced symmetry. s If the coordination is symmetrical, the catalyst will be expected to produce only random polymers (α-olefins); Golisz, SR et al. (2009) "Synthesis of Early Transition Metal Bisphenolate Complexes and Their Use as Olefin Polymerization Catalysts," Macromolecules These symmetry-reactivity concepts are summarized in Volume 42(22), pp. 8751-8762. The 8-membered metal ring pairs of catalyst compounds are also a significant feature, which are advantageous for temperature stability and isotactic selectivity of monomer insertion. Related Group 4 complexes characterized by smaller 6-membered metal rings are known ( Macromolecules (2009), Vol. 42, pp. 8751-8762) When used in olefin polymerization, it forms C2 and C3. s A mixture of symmetrical complexes, and therefore not well-suited for the production of highly isotactic poly(α-olefins).

[0188] The bis(phenolate) ligand containing the oxygen donor group (i.e., E = E' = oxygen in formula (PM-I)) can be substituted with alkyl, substituted alkyl, aryl, or other groups. Advantageously, each phenolate group may be substituted at the ring position adjacent to the oxygen donor atom. For example, the substitution at the position adjacent to the oxygen donor atom may be an alkyl group containing 1-20 carbon atoms. The substitution at the position immediately adjacent to the oxygen donor atom may be a non-aromatic cyclic alkyl group having one or more five- or six-membered rings. The substitution at the position immediately adjacent to the oxygen donor atom may be a cyclic tertiary alkyl group. In some embodiments, the substitution at the position immediately adjacent to the oxygen donor atom is adamantane-1-yl or a substituted adamantane-1-yl group.

[0189] A neutral heterocyclic Lewis base donor is covalently bonded between two anion donors (e.g., between two phenolic salt groups) via a "linking group" that connects the heterocyclic Lewis base to the anion donor. The "linking group" in formula (PM-I) is composed of (A... 3 A 2 ) and (A 2’ A 3’ The choice of each linker group can affect catalyst performance, such as the stereoregularity of the produced poly(α-olefin). Each linker 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-long linking groups. When one or both linking groups are phenylene, the alkyl substituents on the phenylene can be selected to optimize catalyst performance. Typically, one or both phenylene groups can be unsubstituted or can be independently separated by C1 to C2. 20 Alkyl substitution, such as substitution by 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.

[0190] In some implementations, the catalyst compound is represented by the formula (PM-I): (PM-I) in: M is a transition metal from Group 3, 4, 5, 6, or 7, or a lanthanide element (such as Hf, Zr, or Ti). E and E' are each independently O, S, or NR. 9 , where R 9 Independently, it is hydrogen, C1-C 40 Hydrocarbon group, C1-C 40Substituted hydrocarbon groups, or heteroatom-containing groups, such as O, such as E and E', both of which are O; Q is a group 14, 15, or 16 atom that forms a coordinate bond with metal M. For example, Q is C, O, S, or N. 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 with Q as the central atom. 2 With A 2 Connection (with connection A) 1 and A 1 A of the curve combination 1 QA 1 (representing a heterocyclic Lewis base). A 1 and A 1' Each of them is independently C, N, or C(R) 22 ), where R 22 Selected from hydrogen, C1-C 20 Hydrocarbon groups and C1-C 20 Substituted hydrocarbon groups (e.g., A) 1 and A 1' Each of them is C); It is a divalent group containing 2 to 40 non-hydrogen atoms, which connects A atoms via a 2-atom bridge. 1 Aromatic groups attached to an E-bonded group, such as o-phenylene, substituted o-phenylene, o-aromatic, substituted o-aromatic, idolene, substituted idolene, benzothiophene, substituted benzothiophene, pyrrolene, substituted pyrrolene, thiophene, substituted thiophene, 1,2-ethylene (-CH2CH2-), substituted 1,2-ethylene, 1,2-vinylene (-HC=CH-), or substituted 1,2-vinylene, such as It is a divalent hydrocarbon group; It is a divalent group containing 2 to 40 non-hydrogen atoms, which connects A atoms via a 2-atom bridge. 1'Aromatic groups attached to an E'-bonded group, such as o-phenylene, substituted o-phenylene, o-aromatic, substituted o-aromatic, idolene, substituted idolene, benzothiophene, substituted benzothiophene, pyrrolene, substituted pyrrolene, thiophene, substituted thiophene, 1,2-ethylene (-CH2CH2-), substituted 1,2-ethylene, 1,2-vinylene (-HC=CH-), or substituted 1,2-vinylene, such as It is a divalent hydrocarbon group; Each L is independently a Lewis base; Each X is an anionic ligand independently; n is 1, 2, or 3; m is 0, 1, or 2; n+m is not greater than 4; R 1 R 2 R 3 R 4 R 1' R 2' R 3' and R 4' Each of them is independently hydrogen, C1-C 40 Hydrocarbon group, C1-C 40 Substituted hydrocarbon groups, heteroatoms, or heteroatom-containing groups (such as R...) 1' and R 1 Independently, it is a cyclic group, such as a cyclic tertiary alkyl group, or R 1 and R 2 R 2 and R 3 R 3 and R 4 R 1' and R 2' R 2' and R 3' R 3' and R 4' One or more 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 substitutions on the rings may join to form additional rings. Any two L groups can bond together to form a bidentate Lewis base; The X group can bind to the L group to form a monoanionic bidentate group; and Any two X groups can join together to form a bianionic ligand group.

[0191] Metal M is selected from elements in Groups 3, 4, 5, 6, or 7, such as Group 4. For example, metal M is zirconium or hafnium.

[0192] The donor atom Q of a neutral heterocyclic Lewis base (in formula (PM-I)) can be nitrogen, carbon, or oxygen. In some embodiments, Q is nitrogen.

[0193] Non-limiting examples of neutral heterocyclic Lewis base groups include derivatives of pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, and their substituted variants. Heterocyclic Lewis base groups may include derivatives of pyridine, pyrazine, thiazole, and imidazole.

[0194] A heterocyclic Lewis base of formula (PM-I) 1 and A 1' Each of them is independently C, N, or C(R) 22 ), where R 22 Selected from hydrogen, C1-C 20 Hydrocarbon groups and C1-C 20 Substituted hydrocarbon group. In some embodiments, A 1 and A 1’ Each of them is carbon. When Q is carbon, A 1 and A 1' Each of them can be selected from nitrogen and C(R) 22 When Q is nitrogen, A 1 and A 1' Each of these 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 (PM-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 atoms at those positions may undergo undesirable decomposition reactions that reduce the stability of the catalytically active material.

[0195] By and joining A 1 and A 1' A of the curve combination 1 QA 1' The heterocyclic Lewis base represented by (formula (PM-I)) 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 groups and C1-C 20 Substituted alkyl groups.

[0196]

[0197] In some implementations, by connection A 1 and A1' A of the curve combination 1 QA 1' The heterocyclic Lewis base represented by formula (PM-I) 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 is formed by bonding with A. 1 and A 1' A of the curve combination 1 QA 1' The heterocyclic Lewis base represented by (formula (PM-I)) is not a six-membered ring containing two or more cyclic heteroatoms.

[0198] In some implementations of formula (PM-I), Q is C, N, or O, such as Q being N.

[0199] In some implementations of formula (PM-I), A 1 and A 1' Each of these elements is independently carbon, nitrogen, or C(R) 22 ), where R 22 Selected from hydrogen, C1-C 20 Hydrocarbon group, substituted C1-C 20 Hydrocarbon group. In some implementations, A 1 and A 1’ Each one in it is carbon.

[0200] In some implementations of formula (PM-I), A of formula (PM-I) 1 QA 1' It is part of a heterocyclic Lewis base (such as pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, or substituted variants thereof).

[0201] In some implementations of formula (PM-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 with Q as the central atom. 2 With A 2' Connection. In some implementations, each A 1 and A 1' It is a carbon atom and A 1 QA 1' The fragment forms part of pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, or a variant thereof, or a variant thereof.

[0202] In at least one embodiment of formula (PM-I), Q is carbon and A 1 and A 1' Each of them 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 such embodiments, 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.

[0203] In some implementations of formula (PM-I), It is a divalent group containing 2 to 20 non-hydrogen atoms, which connects A atoms via 2-atom bridges. 1 Linked to an E-bonded aryl group, wherein It is a straight-chain alkyl group or a cyclic group (such as optionally substituted o-phenylene or o-aryl) or a variant thereof.

[0204] It is a divalent group containing 2 to 20 non-hydrogen atoms, which connects A atoms via 2-atom bridges. 1 'Linked to E'-bonded aryl group, where It is a straight-chain alkyl group or a cyclic group (such as optionally substituted o-phenylene or o-aryl) or a variant thereof.

[0205] In some implementations of formula (PM-I), M is Zr or Hf, Q is nitrogen, and A is... 1 and A 1 Both are carbon, E and E' are both oxygen, and R 1 and R 1' Both are C4-C 20 Cyclic tertiary alkyl groups.

[0206] In some implementations of formula (PM-I), M is Zr or Hf, Q is nitrogen, and A is... 1 and A 1 Both are carbon, E and E' are both oxygen, and R 1 and R 1 Both are adamantane-1-yl or substituted adamantane-1-yl.

[0207] In some implementations of formula (PM-I), M is Zr or Hf, Q is nitrogen, and A is... 1 and A 1 Both are carbon, E and E' are both oxygen, and R 1 and R 1 Both are C6-C 20 Aryl.

[0208] In some implementations, the catalyst compound is represented by formula (PM-II): (PM-II) in: M is a group 3, 4, 5, 6, or 7 transition metal or a lanthanide element (such as a group 4 transition metal as Hf, Zr, or Ti). E and E' are each independently O, S, or NR. 9 , where R 9 Independently, it is hydrogen, C1-C 40 Hydrocarbon group, C1-C 40 Substituted hydrocarbon groups, or heteroatom-containing groups, such as O, such as E and E', both of which are O; Each L is independently a Lewis base; Each X is an anionic ligand independently; n is 1, 2, or 3; m is 0, 1, or 2; n+m is not greater than 4; R 1 R 2 R 3 R 4 R 1' R 2' R 3' and R 4' Each of them is independently hydrogen, C1-C 40 Hydrocarbon group, C1-C 40 Substituted hydrocarbon groups, heteroatoms, or heteroatom-containing groups, 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 substitutions on the rings may join to form additional rings. Any two L groups can bond together to form a bidentate Lewis base; The X group can bind to the L group to form a monoanionic bidentate group; Any two X groups can join together to form a bianionic ligand group; R 5 R6 R 7 R 8 R 5 '、R 6 '、R 7 '、R 8 '、R 10 R 11 and R 12 Each of them is independently hydrogen, C1-C 40 Hydrocarbon group, C1-C 40 Substituted hydrocarbon groups, heteroatoms, or heteroatom-containing groups, 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 substitutions on the rings may join to form additional rings.

[0209] In formula (PM-I) or (PM-II), E and E' are each selected from oxygen or NR. 9 , where R 9 Independently, it is hydrogen, C1-C 40 Hydrocarbon group, C1-C 40 Substituted hydrocarbon groups or heteroatom-containing groups. In some embodiments, E and E' are oxygen. When E and / or E' is NR 9 At that time, R 9 Can be selected from C1 to C 20 Hydrocarbon group, alkyl group, or aryl group. In one embodiment, E and E' are each selected from O, S, or N (alkyl) or N (aryl), wherein the alkyl group can be C1 to C2. 20 Alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, etc., and aryl groups are C6 to C6. 40 Aryl groups, such as phenyl, naphthyl, benzyl, methylphenyl, etc.

[0210] In some implementation schemes, and Independently, it is a divalent hydrocarbon group, such as C1 to C2. 12 Hydrocarbon group.

[0211] In some embodiments of the catalyst compound of formula (PM-I) or (PM-II), when E and E' are oxygen, each phenolic salt group may be substituted at the position immediately adjacent to the oxygen atom (i.e., R in formula (PM-I) and (PM-II)). 1 and R 1 Therefore, when E and E' are oxygen, R 1 and R 1' Each of them is independently C1-C 40 Hydrocarbon group, C1-C 40 Substituted hydrocarbon groups, heteroatoms, or heteroatom-containing groups, such as R 1 and R 1' Each of them is independently a non-aromatic cyclic alkyl group having one or more five- or six-membered rings (such as cyclohexyl, cyclooctyl, adamantyl, or 1-methylcyclohexyl, or substituted adamantyl), such as a non-aromatic cyclic tertiary alkyl group (such as 1-methylcyclohexyl, adamantyl, or substituted adamantyl).

[0212] In some embodiments of the catalyst compound of formula (PM-I) or (PM-II), R 1 and R 1' Each of these is independently a tertiary hydrocarbon group. In other embodiments of formula (PM-I) or (PM-II), R 1 and R 1' Each of these is independently a cyclic tertiary hydrocarbon group. In other embodiments of the catalyst compound of formula (PM-I) or (PM-II), R 1 and R 1' Each of them is independently a polycyclic tertiary hydrocarbon group.

[0213] In some embodiments of the catalyst compound of formula (PM-I) or (PM-II), R 1 and R 1' Each of these is independently a tertiary hydrocarbon group. In other embodiments of the catalyst compound of formula (PM-I) or (PM-II), R 1 and R 1' Each of these is independently a cyclic tertiary hydrocarbon group. In other embodiments of the catalyst compound of formula (PM-I) or (PM-II), R 1 and R 1' Each of them is independently a polycyclic tertiary hydrocarbon group.

[0214] Linking group (i.e., in formula (PM-I)) and Each of the radicals can be an ortho-phenylene, such as a substituted ortho-phenylene group. Preferably, R of formula (PM-II) is... 7 and R 7 The position is hydrogen or C1 to 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. For applications involving polymers with high stereoregularity, R of formula (PM-II) is preferred. 7 and R 7 The location is C1 to C 20 Alkyl groups, such as R 7 and R 7 Both are C1 to C3 alkyl groups.

[0215] In some embodiments of formula (PM-I) or (PM-II), M is a Group 4 metal, such as Hf or Zr.

[0216] In some implementations of formulas (PM-I) and (PM-II), each of E and E' is O.

[0217] In some implementations of formulas (PM-I) and (PM-II), R 1 R 2 R 3 R 4 R 1' R 2' R 3' and R 4' Each of them is independently hydrogen, C1-C 40 Hydrocarbon group, C1-C 40 Substituted hydrocarbon groups, heteroatoms, or heteroatom-containing groups, 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 substitutions on the rings may join to form additional rings, such as hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or isomers thereof.

[0218] In some implementations of formulas (PM-I) and (PM-II), R 1 R 2 R 3 R 4 R 1' R 2' R 3' and R 4' Each of the following is independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, triadecyl, phenyl, substituted phenyl (such as methylphenyl and dimethylphenyl), benzyl, substituted benzyl (such as methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl and their isomers.

[0219] In some implementations of formulas (PM-I) and (PM-II), R 4 and R 4' Each of them is independently a hydrogen or a C1 to C3 hydrocarbon group, such as methyl, ethyl or propyl.

[0220] In the implementation schemes of formulas (PM-I) and (PM-II), R 9 It is hydrogen, C1-C 40 Hydrocarbon group, C1-C 40 Substituted hydrocarbon groups, or heteroatom-containing groups, such as hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or their isomers. In some embodiments, R 9 It is a C1 to C6 alkyl (such as methyl, ethyl, propyl, or butyl), phenyl, 2-methylphenyl, 2,6-dimethylphenyl, or 2,4,6-trimethylphenyl.

[0221] In embodiments of formulas (PM-I) and (PM-II), each X is independently selected from the group consisting of hydrocarbon groups (such as alkyl or aryl), hydrazine, amino, alkoxy, thio, phosphorus, halogen, alkyl sulfonate, and combinations thereof having 1 to 20 carbon atoms (two or more X may form a fused ring or part of a ring system), such as each X being independently selected from halogen, aryl, and C1 to C5 alkyl, such as each X being independently hydrazine, dimethylamino, diethylamino, methyltrimethylsilyl, neopentyl, phenyl, benzyl, methyl, ethyl, propyl, butyl, pentyl, fluorine, iodine, bromine, or chlorine groups.

[0222] Alternatively, each X can be independently a halogenated, hydrogenated, alkylated, or alkenylated group.

[0223] In some embodiments of formulas (PM-I) and (PM-II), each L is a Lewis base, independently selected from ethers, thioethers, amines, nitriles, imines, pyridines, haloalkanes, and phosphines, such as the group consisting of ethers, thioethers, or combinations thereof. Optionally, two or more Ls may form part of a fused ring or a ring system, such as each L being independently selected from an ether or thioether group, such as each L being a diethyl ether, tetrahydrofuran, butyl ether, or dimethyl thioether group.

[0224] In some implementations of formulas (PM-I) and (PM-II), R 1 and R 1' Each of them is independently a cyclic tertiary alkyl group.

[0225] In some implementations of formulas (PM-I) and (PM-II), n is 1, 2, or 3, such as 2.

[0226] In some implementations of formulas (PM-I) and (PM-II), m is 0, 1, or 2, such as 0.

[0227] In some implementations of formulas (PM-I) and (PM-II), R 1 and R 1' Each of them is not hydrogen.

[0228] In some implementations of formulas (PM-I) and (PM-II), M is Hf or Zr, and each of E and E' is O; R 1 and R 1' Each of them 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 of them 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' R3' and R 4' One or more pairs of X 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 substitutions on the rings may join to form additional rings; each X is independently selected from the group consisting of hydrocarbon groups (such as alkyl or aryl), hydroxyl, amino, alkoxy, thiol, phospho, halogen, and combinations thereof having 1 to 20 carbon atoms (two or more X may form a fused ring or part of a ring system); each L is independently selected from the group consisting of ethers, thioethers, and haloalkanes (two or more L may form a fused ring or part of a ring system).

[0229] In some implementations of formula (PM-II), R 5 R 6 R 7 R 8 R 5' R 6' R 7' R 8' R 10 R 11 and R 12 Each of them is independently hydrogen, C1-C 40 Hydrocarbon group, substituted C1-C 40 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 substitutions on the rings may join to form additional rings.

[0230] In some implementations of formula (PM-II), R 5 R 6 R 7 R 8 R 5' R 6' R 7' R 8' R 10 R 11 and R 12 Each of them is independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof.

[0231] In some implementations of formula (PM-II), R 5 R 6 R 7 R 8 R 5' R 6' R 7' R8’ R 10 R 11 and R 12 Each of the following is independently selected from 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, heptadecanyl, octadecyl, nonadecanyl, triadecyl, phenyl, substituted phenyl (such as methylphenyl and dimethylphenyl), benzyl, substituted benzyl (such as methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, or isomers thereof.

[0232] In some implementations of formula (PM-II), M is Hf or Zr, and each of E and E' is O; R 1 and R 1’ Each of them is independently C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon group, heteroatom or group containing heteroatom; R 1 R 2 R 3 R 4 R 1' R 2' R 3' and R 4' Each of them 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 substitutions on the rings may join to form additional rings. R 9 It is hydrogen, C1-C 20 Hydrocarbon group, C1-C 20 Substituted hydrocarbon groups or heteroatom-containing groups, such as hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or their isomers; Each X is independently selected from the group consisting of hydrocarbon groups (such as alkyl or aryl), hydrogen groups, amino groups, alkoxy groups, thio groups, phosphoro groups, halogen groups, dienes, amines, phosphines, ethers, and combinations thereof having 1 to 20 carbon atoms (two or more Xs may form a fused ring or part of a ring system). 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 of them is independently hydrogen, C1-C 20 Hydrocarbon group, C1-C 20 Substituted hydrocarbon groups, heteroatoms, or heteroatom-containing groups, 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 substitutions 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 of the following is independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, triadecyl, phenyl, substituted phenyl (such as methylphenyl and dimethylphenyl), benzyl, substituted benzyl (such as methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl and their isomers.

[0233] In some implementations of formula (PM-II), M is Zr or Hf, E and E ’ Both are oxygen, and R 1 and R 1' Both are C4-C 20 Cyclic tertiary alkyl groups.

[0234] In some implementations of formula (PM-II), M is Zr or Hf, E and E ' Both are oxygen, and R 1 and R 1' Both are adamantane-1-yl or substituted adamantane-1-yl.

[0235] In some implementations of formula (PM-II), M is Zr or Hf, E and E ' Both are oxygen, and R 1 R 1' R 3 and R 3’ Each of them is adamantane-1-yl or a substituted adamantane-1-yl.

[0236] In some implementations of formula (PM-II), M is Zr or Hf, E and E ' Both are oxygen, and R 1 and R 1' Both are C4-C 20 Cyclic tertiary alkyl groups, and R 7 and R 7' Both are C1-C 20 alkyl.

[0237] In some embodiments, the catalyst compound is one or more of the following: dimethylzirconium [2',2'''-(pyridin-2,6-diyl)bis(3-adamantane-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenolic salt], dimethylhafnium [2',2'''-(pyridin-2,6-diyl)bis(3-adamantane-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenolic salt] [-2-phenol salt], dimethylzirconium [6,6'-(pyridin-2,6-diylbis(benzo[b]thiophene-3,2-diyl))bis(2-adamantane-1-yl)-4-methylphenol salt)], dimethylhafnium [6,6'-(pyridin-2,6-diylbis(benzo[b]thiophene-3,2-diyl))bis(2-adamantane-1-yl)-4-methylphenol salt)], dimethylzirconium [2',2'''- (pyridin-2,6-diyl)bis(3-((3r,5r,7r)-adamantane-1-yl)-5-methyl-[1,1'-biphenyl]-2-phenolate)], dimethylhafnium[2',2'''-(pyridin-2,6-diyl)bis(3-((3r,5r,7r)-adamantane-1-yl)-5-methyl-[1,1'-biphenyl]-2-phenolate)], dimethylzirconium[2',2'''- (pyridin-2,6-diyl)bis(3-((3r,5r,7r)-adamantane-1-yl)-4',5-dimethyl-[1,1'-biphenyl]-2-phenolate)], dimethylhafnium[2',2'''-(pyridin-2,6-diyl)bis(3-((3r,5r,7r)-adamantane-1-yl)-4',5-dimethyl-[1,1'-biphenyl]-2-phenolate)], or combinations thereof.

[0238] In some embodiments, the catalyst compound is represented by formula (PM-III), formula (PM-IV), or formula (PM-V): (PM-III), (PM-IV) (PM-V) in: In formulas (PM-III), (PM-IV), or (PM-V), M represents Sc, Y, or La-Lu lanthanide metals; Q' in formula (PM-III), formula (PM-IV) or formula (PM-V) is a group 15 heteroatom, preferably N and P, most preferably N; X in formula (PM-III), formula (PM-IV) or formula (PM-V) is an anionic ligand; Each L in formula (PM-III), formula (PM-IV), or formula (PM-V) is independently a Lewis base; Any two or more L groups of formula (PM-III), formula (PM-IV) or formula (PM-V) can be joined together to form a polydentate (e.g., bidentate) Lewis base; The X group of formula (PM-III), formula (PM-IV) or formula (PM-V) can be bonded to the L group to form a monoanionic bidentate group; In formulas (PM-III), (PM-IV), or (PM-V), n is 1; In formulas (PM-III), (PM-IV), or (PM-V), m is 0, 1, or 2; In formulas (PM-III), (PM-IV), or (PM-V), n+m is no greater than 3; R of formula (PM-III), formula (PM-IV) or formula (PM-V) 1 R 2 R 3 R 4 R 1' R 2' R 3' and R 4' Each of them 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 substitutions on the rings may join to form additional rings; and R of formula (PM-III), formula (PM-IV) or formula (PM-V) 5 R 6 R 7 R 8 R 5' R 6' R 7' R8' R 10 R 11 and R 12 Each of them 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 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 substitutions on the rings may join to form additional rings; and Each G in formula (PM-III), formula (PM-IV), or formula (PM-V) is a group 15 or 16 heteroatom or heteroatomic group, such as S, O, NR', PR', where R' is selected from hydrogen and C1-C. 40 Hydrocarbon group or substituted hydrocarbon group.

[0239] In some embodiments of the catalyst compound of formula (PM-I-PM-II), when E and E' are oxygen, each phenolic salt group can be substituted at the position immediately adjacent to the oxygen atom (i.e., R in formula (PM-I-PM-II)). 1 and R 1' Therefore, when E and E' are oxygen, R 1 and R 1' Each of them is independently C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups, heteroatoms, or groups containing heteroatoms, such as R 1 and R 1' Each of them is independently a non-aromatic cyclic alkyl group having one or more five- or six-membered rings (such as cyclohexyl, cyclooctyl, adamantyl, or 1-methylcyclohexyl, or substituted adamantyl), such as a non-aromatic cyclic tertiary alkyl group (such as 1-methylcyclohexyl, adamantyl, or substituted adamantyl).

[0240] In some embodiments of the catalyst compound of formula (PM-III-PM-V), each phenolic salt group may be substituted at the position immediately adjacent to the oxygen atom (i.e., R in formula (PM-III-PM-V)). 1 and R 1' Therefore, R 1 and R 1' Each of them is independently C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups, heteroatoms, or groups containing heteroatoms, such as R 1 and R 1' Each of them is independently a non-aromatic cyclic alkyl group having one or more five- or six-membered rings (such as cyclohexyl, cyclooctyl, adamantyl, or 1-methylcyclohexyl, or substituted adamantyl), such as a non-aromatic cyclic tertiary alkyl group (such as 1-methylcyclohexyl, adamantyl, or substituted adamantyl).

[0241] In some embodiments of the catalyst compound of formula (PM-I-PM-V), R 1 and R 1' Each of these is independently a tertiary hydrocarbon group. In other embodiments of formula (PM-I-PM-V), R 1 and R 1' Each of these is independently a (substituted or unsubstituted) cyclic tertiary hydrocarbon group. In other embodiments of the catalyst compound of formula (PM-I-PM-V), R 1 and R 1' Each of them is independently a (substituted or unsubstituted) polycyclic tertiary hydrocarbon group.

[0242] In some embodiments of the catalyst compound of formula (PM-I-PM-II), when E and E' are oxygen, each phenate group can be substituted at the para position of the oxygen atom (i.e., R in formula (PM-I-PM-II)). 3 and R 3' Therefore, when E and E' are oxygen, R 3 and R 3' Each of them is independently C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups, heteroatoms, or groups containing heteroatoms, such as R 3 and R 3' Each of them 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 of them is independently a non-aromatic cyclic alkyl group having one or more five- or six-membered rings (such as cyclohexyl, cyclooctyl, adamantyl, or 1-methylcyclohexyl, or substituted adamantyl), such as a non-aromatic cyclic tertiary alkyl group (such as 1-methylcyclohexyl, adamantyl, or substituted adamantyl).

[0243] In some embodiments of the catalyst compound of formula (PM-III-PM-V), each phenolic salt group may be substituted at the para position of the oxygen atom (i.e., R in formula (PM-III-PM-V)). 3 and R 3' Therefore, R 3 and R 3' Each of them is independently C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon groups, heteroatoms, or groups containing heteroatoms, such as R 3 and R 3' Each of them 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 of them is independently a non-aromatic cyclic alkyl group having one or more five- or six-membered rings (such as cyclohexyl, cyclooctyl, adamantyl, or 1-methylcyclohexyl, or substituted adamantyl), such as a non-aromatic cyclic tertiary alkyl group (such as 1-methylcyclohexyl, adamantyl, or substituted adamantyl).

[0244] In some embodiments of the catalyst compound of formula (PM-I-PM-V), R 3 and R 3' Each of them 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 (PM-I-PM-V), R 3 and R 3' Each of these is independently a (substituted or unsubstituted) acyclic tertiary hydrocarbon group. In other embodiments of formula (PM-I-PM-V), R 3 and R 3' Each of them is independently tert-butyl.

[0245] In some implementations, the R of formula (PM-II-PM-V) 1 R 2 R 3 R 4 R 1' R2' 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 to C2. 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 their isomers, such as isopropyl.

[0246] In some implementations of formula (PM-I-PM-V), M is a Group 3 metal, such as Sc, Y, La, Lu, or Nd.

[0247] In some implementations of formulas (PM-I) and (PM-II), each of E and E' is O.

[0248] In some implementations of formula (PM-I-PM-V), R 1 R 2 R 3 R 4 R 1' R 2' R 3' and R 4' Each of the following is independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, 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, adamantyl, and their isomers.

[0249] In embodiments of formula (PM-I-PM-V), X is selected from hydrocarbon groups (such as alkyl or aryl), hydride groups, amino groups, alkoxy groups, thio groups, phosphorus groups, halogen groups, alkyl sulfonates, etc., having 1 to 20 carbon atoms. X is selected from halogen groups, aryl groups, and C1 to C5 alkyl groups. X is selected from hydride groups, dimethylamino groups, diethylamino groups, bis(dimethylsilyl)amino groups, bis(trimethylsilyl)amino groups, methylenetrimethylsilyl groups, neopentyl groups, phenyl groups, benzyl groups, methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, fluorine groups, iodine groups, bromine groups, or chlorine groups. In some embodiments, X is selected from bis(dimethylsilyl)amino groups, bis(trimethylsilyl)amino groups, and methylenetrimethylsilyl groups.

[0250] Alternatively, X can be a halogenated, hydrogenated, alkyl, or alkenyl group.

[0251] In some embodiments of formula (PM-I-PM-V), 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 a ring system, such as each L being independently selected from an ether or thioether group, such as each L being a diethyl ether, tetrahydrofuran, butyl ether, or dimethyl thioether group.

[0252] In some implementations of formula (PM-I-PM-V), R 1 and R 1' Each of them is independently a cyclic tertiary alkyl group.

[0253] In some implementations of formula (PM-I-PM-V), m is 0, 1, or 2, such as 0.

[0254] In some implementations of formula (PM-I-PM-V), R 1 and R 1' Each of them is not hydrogen.

[0255] In some implementations of formula (PM-I-PM-V), R 3 and R 3' Each of them is not hydrogen.

[0256] In some implementations of formulas (PM-I) and (PM-II), M is Sc, Y, La, Lu, or Nd, and each of E and E' is O; R 1 and R 1' Each of them 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 of them is independently hydrogen, C1-C 20 Hydrocarbon group, or substituted C1-C 20 Hydrocarbon group.

[0257] In some implementations of formula (PM-III-PM-V), M is Sc, Y, La, Lu, or Nd, R 1 and R 1' Each of them 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 of them is independently hydrogen, C1-C 20 Hydrocarbon group, or substituted C1-C 20 Hydrocarbon group.

[0258] In some implementations of formula (PM-II-PM-V), R 5 R 6 R 7 R 8 R 5' R 6' R 7' R 8' R 10 R 11 and R 12 Each of them is independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof.

[0259] In some implementations of formula (PM-II-PM-V), R 5 R 6 R 7 R 8 R 5' R 6' R 7' R 8’ R 10 R 11 and R 12Each of the following 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, or isomers thereof.

[0260] In some implementations of formula (PM-II), M is Sc, Y, La, Lu, or Nd, and each of E and E' is O; R 1 and R 1’ Each of them is independently C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon group, heteroatom or heteroatom-containing group; R 3 and R 3' Each of them is independently C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon group, heteroatom or heteroatom-containing group; R 1 R 2 R 4 R 1' R 2' and R 4' Each of them 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 substitutions on the rings may join to form additional rings; X is selected from the group consisting of substituted or unsubstituted groups of: hydrocarbon groups (such as alkyl or aryl), hydrazine, amino, alkoxy, thio, phosphine, halogen, diene, amine, phosphine, ether; n is 1; m is 1; and R 5 R 6R 7 R 8 R 5' R 6' R 7' R 8’ R 10 R 11 and R 12 Each of them 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 substitutions 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 of the following 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.

[0261] In some implementations of formula (PM-IV-PM-V), Q' is N.

[0262] In some implementations of formula (PM-III-PM-V), M is Sc, Y, La, Lu, or Nd; R 1 and R 1’ Each of them is independently C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon group, heteroatom or heteroatom-containing group; R 3 and R 3' Each of them 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 of them 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 substitutions on the rings may join to form additional rings; X is selected from the group consisting of substituted or unsubstituted groups of: hydrocarbon groups (such as alkyl or aryl), hydrazine, amino, alkoxy, thio, phosphine, halogen, diene, amine, phosphine, ether; n is 1; m is 1; and R 5 R 6 R 7 R 8 R 5' R 6' R 7' R 8’ R 10 R 11 and R 12 Each of them 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 substitutions 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 12Each of the following 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.

[0263] In some implementations of formula (PM-II), M is Sc, Y, La, Lu, or Nd, and E and E ’ Both are oxygen, R 1 and R 1’ Both are C4-C independently. 20 Cyclic tertiary alkyl groups, and R 3 and R 3' Both are C1-C independently. 10 alkyl.

[0264] In some implementations of formula (PM-III-PM-V), M is Sc, Y, La, Lu, or Nd; R 1 and R 1' Both are C4-C independently. 20 Cyclic tertiary alkyl groups, and R 3 and R 3' Both are C1-C independently. 10 alkyl.

[0265] In some implementations of formula (PM-II), M is Sc, Y, La, Lu, or Nd, and E and E ' Both are oxygen, R 1 and R 1' Both are adamantane-1-yl or substituted adamantane-1-yl, and R 3 and R 3' Both are C1-C independently. 10 alkyl.

[0266] In some implementations of formula (PM-III-PM-V), M is Sc, Y, La, Lu, or Nd; R 1 and R 1' Both are adamantane-1-yl or substituted adamantane-1-yl, and R 3 and R 3' Both are C1-C independently. 10 alkyl.

[0267] In some implementations of formula (PM-II), M is Sc, Y, La, Lu, or Nd, and E and E ' Both are oxygen, and R 1 R 1' Each of them is independently adamantane-1-yl or a substituted adamantane-1-yl, and R 3 and R 3' Both are methyl or tert-butyl, respectively.

[0268] In some implementations of formula (PM-III-PM-V), M is Sc, Y, La, Lu, or Nd; R 1 R 1 Each of ' is independently adamantane-1-yl or a substituted adamantane-1-yl, and R 3 and R 3' Both are methyl or tert-butyl, respectively.

[0269] In some embodiments of formula (PM-IV-PM-V), G is S, O, NR', PR', where R' is selected from hydrogen and hydrocarbon groups or substituted hydrocarbon groups.

[0270] In some implementations of formula (PM-IV-PM-V), G is S or O, more preferably S.

[0271] In some embodiments of formula (PM-IV-PM-V), G is NR', PR', where R' is selected from hydrogen atoms and C1-C 20 Hydrocarbon groups and substituted hydrocarbon groups.

[0272] In some embodiments of formula (PM-IV-PM-V), G is NR', PR', and R' is selected from hydrogen or methyl.

[0273] In some implementations of formula (PM-III), M is Sc, Y, La, Lu, or Nd; R 1 R 1' Each of them is adamantane-1-yl or substituted adamantane-1-yl, R 3 and R 3' Both are tert-butyl or methyl, and R 2 R 2' R 4 R 4' R 5 R 5' R 6 R 6' R 7 R 7' R 8 R 8' R 10R 11 and R 12 It is hydrogen.

[0274] In some implementations of formula (PM-III), M is Sc, Y, La, Lu, or Nd; R 1 R 1' Each of them is tert-butyl, R 3 and R 3' Both are tert-butyl or methyl, and R 2 R 2' R 4 R 4' R 5 R 5' R 6 R 6' R 7 R 7' R 8 R 8' R 10 R 11 and R 12 It is hydrogen.

[0275] In some implementations of formula (PM-V), M is Sc, Y, La, Lu, or Nd; G is S, R 1 R 1' Both are tert-butyl, R 3 and R 3' Both are methyl groups, and R 2 R 2' R 4 R 4' R 5 R 5' R 6 R 6' R 7 R 7' R 8 R 8' R 10 R 11 and R 12 It is hydrogen.

[0276] In some implementations of formula (PM-V), M is Sc, Y, La, Lu, or Nd; G is S, R 1 R 1' Both are adamantane-1-yl or substituted adamantane-1-yl, R 3 and R 3' Both are methyl or tert-butyl, and R 2 R 2' R 4 R 4' R5 R 5' R 6 R 6' R 7 R 7' R 8 R 8' R 10 R 11 and R 12 It is hydrogen.

[0277] In some implementations, the catalyst compound is one or more of the following: .

[0278] In some embodiments, for the purpose of controlling polymer properties, such as to regulate polymer molecular weight and molecular weight distribution by limiting free alkylaluminum in the system that may cause transfer from the catalytic metal center to the free alkylaluminum chain, solution aluminum oxanes (e.g., MAO), solid aluminum oxanes (e.g., MAO), or supported aluminum oxanes (e.g., MAO) without TMA (or without trialkylaluminum) can also be used for bis-Cp metallocene precatalyst compounds that do not have polar donors. Metallocene precatalyst compounds as used herein include metallocenes comprising Group 3 to Group 10 metal complexes, preferably Group 4 to Group 6 metal complexes, such as Group 4 metal complexes. The metallocene catalyst compounds of the catalyst systems disclosed herein can be non-bridging metallocene catalyst compounds represented by formula (BC-I): Cp A Cp B M'X' n (BC-I) Each Cp A and Cp B Independently selected from cyclopentadienyl ligands and ligands isovalve-like with cyclopentadienyl, Cp A and Cp B One or two of them may contain heteroatoms, and Cp A and Cp BOne or both of them may be replaced by one or more R'' groups. M' is selected from group 3 to 12 atoms and lanthanide atoms. X' is an anion leaving group. n is 0 or an integer from 1 to 4. R'' is selected from alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, lower alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, alkylthio, lower alkylthio, aryl, substituted aryl, heteroaryl, aryl, arylalkyl, arylenealkyl, alkylaryl, arylenealkyl, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocyclic, heteroaryl, group containing heteroatom, hydrocarbon, lower hydrocarbon, substituted hydrocarbon, heterohydrocarbon, silyl, boryl, phosphin, phosphine, amino, amine, ether, and thioether.

[0279] In at least one implementation, each Cp A and Cp B Independently selected from cyclopentadienyl, indole, fluorenyl, cyclopentaphenanthreneyl, benzo[a]indole, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, phenanthreneyl, 3,4-benzofluorenyl, 9-phenylfluorenyl, 8-H-cyclopenta[a]acenaphthylenyl, 7-H-dibenzofluorenyl, indole[1,2-9]anthraene, thienenodole, thienenofluorenyl and their hydrogenated forms.

[0280] Metallocene catalyst compounds can be bridging metallocene catalyst compounds represented by formula (BC-II): Cp A (A)Cp B M'X' n (BC-II) Each Cp A and Cp B Independently selected from cyclopentadienyl ligands and ligands isovalve similar to cyclopentadienyl ligands. Cp A and Cp B One or two of them may contain heteroatoms, and Cp A and Cp BOne or both of them may be replaced by one or more R'' groups. M' is selected from group 3 to 12 atoms and lanthanides. X' is an anion leaving group. n is 0 or an integer from 1 to 4. (A) is selected from divalent alkyl, divalent lower alkyl, divalent substituted alkyl, divalent heteroalkyl, divalent alkenyl, divalent lower alkenyl, divalent substituted alkenyl, divalent heteroalkenyl, divalent alkoxy, divalent lower alkoxy, divalent aryloxy, divalent alkylthio, divalent lower alkoxy, divalent arylthio, divalent aryl, divalent substituted aryl, divalent heteroaryl, divalent alkylthio Aryl alkyl, divalent arylene alkyl, divalent alkylaryl, divalent alkylene aryl, divalent haloalkyl, divalent haloalkenyl, divalent haloalkynyl, divalent heteroalkyl, divalent heterocyclic, divalent heteroaryl, divalent group containing heteroatoms, divalent hydrocarbon group, divalent lower hydrocarbon group, divalent substituted hydrocarbon group, divalent heterohydrocarbon group, divalent silyl alkyl, divalent boryl alkyl, divalent phosphinyl, divalent phosphine, divalent amino, divalent amine, divalent ether, divalent sulfide. R'' is selected from alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, lower alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, alkylthio, lower alkylthio, aryl, substituted aryl, heteroaryl, aralkyl, arylene alkyl, alkylaryl, alkylene aryl, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocyclic, heteroaryl, group containing heteroatoms, hydrocarbon, lower hydrocarbon, substituted hydrocarbon, heterohydrocarbon, silyl, boryl, phosphonyl, phosphine, amino, amine, germanium, ether and thioether.

[0281] In at least one implementation, each Cp A and Cp B Independently selected from cyclopentadienyl, n-propylcyclopentadienyl, indenyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, and n-butylcyclopentadienyl. (A) can be CR'2 or SiR'2, wherein each R' is independently hydrogen or C1-C. 20 Hydrocarbon group.

[0282] In some embodiments, two or more different precatalyst compounds are present in the catalyst system used herein. In some embodiments, two or more different precatalyst compounds are present in the reaction zone in which one or more methods described herein occur. It is preferable to use the same activator for the catalyst compounds; however, two different activators (such as TMA-free supported or unsupported MAO and strong Lewis acid activators (e.g., trifluoroaromatic boranes) from this disclosure) or noncoordinated or weakly coordinated anionic activators (e.g., N,N-dimethylaniline, tetrafluoroaromatic borate, or triphenyl methyl tetrafluoroaromatic borate) may be used in combination. If one or more catalyst compounds contain an X group that is not hydrogen-based, hydrocarbon-based, or a substituted hydrocarbon-based group, the MAO may be contacted with the catalyst compound before the addition of the noncoordinated anionic activator.

[0283] These two catalyst compounds (precatalysts) can be used in any ratio. In some embodiments, the molar ratio of catalyst compound (A) to catalyst compound (B) falls within the range of (A:B) 1:1000 to 1000:1, alternatively 1:100 to 500:1, alternatively 1:10 to 200:1, alternatively 1:1 to 100:1, and alternatively 1:1 to 75:1, and alternatively 5:1 to 50:1. The specific ratio chosen will depend on the exact precatalyst selected, the activation method, and the desired end product. In specific implementations, when using both precatalysts (where both are activated with the same activator), the available molar percentages, based on the molecular weight of the precatalysts, are 10% to 99.9% A to 0.1% to 90% B, alternatively 25% to 99% A to 0.5% to 50% B, alternatively 50% to 99% A to 1% to 25% B, and alternatively 75% to 99% A to 1% to 10% B.

[0284] In some embodiments, the leaving groups of the precatalyst described above are preferably pre-alkylated, such as by methylation, ethylation, benzylation, or trimethylsilylmethyleneation, because the alkylating agent (e.g., free TMA) in the MAO has been significantly removed. However, non-alkylated precatalysts can still be used with mild alkylating agents (such as high-carbon trialkylaluminum (e.g., trioctylaluminum) or secondary alkylaluminum (e.g., AlMe2BHT or AlEt2BHT)) or without mild alkylating agents (if the solution, solid, or supported MAO system has sufficient low TMA or trialkylaluminum residues for alkylation of the precatalyst).

[0285] Aggregation methods

[0286] This disclosure also relates to polymerization methods in which monomers (e.g., ethylene; propylene) and optionally one or more comonomers are contacted in a single polymerization reactor or multiple polymerization reactors with a catalyst system prepared by one of the methods described in this disclosure in a sequence following the corresponding polymerization method to obtain a desired polymer product, including single-phase polymers or copolymers and multiphase copolymers, such as for solution, slurry, and gas-phase polymerization and copolymerization in a single reactor, such as for solution, slurry, and gas-phase continuous copolymerization in multiple reactors. The pre-catalyst compound and activator can be combined in any suitable order. The pre-catalyst compound and activator can be combined prior to contact with the monomer, for example, the finished catalyst system can be formed by first combining the pre-catalyst compound with a silica-supported MAO without TMA and then feeding it into the polymerization reactor for contact with the monomer. Alternatively, the pre-catalyst compound and activator can be introduced separately into the polymerization reactor, wherein the pre-catalyst compound and activator subsequently react to form an active catalyst.

[0287] Monomers may include substituted or unsubstituted C2 to C3 groups. 40 α-olefins, such as C2 to C 20 α-olefins, such as C2 to 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 comprising one or more C3 to C4 groups. 40 Alkenes, such as C4 to C4 20 Olefins, such as C6 to C6 12 Olefins. C3 to C 40 Olefin monomers can be straight-chain, branched, or cyclic. (C3 to C4) 40 Cycloolefins 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 comprising one or more ethylene or C4 to C64 propylene monomers. 40 Alkenes, such as C4 to C4 20 Olefins, such as C6 to C6 12 Alkenes. C4 to C 40 Olefin monomers can be straight-chain, branched, or cyclic. (C4 to C5) 40 Cycloolefins can be tensioned or untensioned, monocyclic or polycyclic, and may optionally include heteroatoms and / or one or more functional groups.

[0288] Examples C2 to C 40Olefin monomers and optional comonomers may include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, ethylidene norbornene, vinyl norbornene, norbornediene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxa norbornene, 7-oxa norbornediene, 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, norbornediene and their respective homologues and derivatives, such as norbornene, norbornediene and dicyclopentadiene. For some precatalysts, having the formula C n H (n-2) Conjugated or non-conjugated dienes (n = 4 to 30) can also act as comonomers, such as butadiene, 2-methyl-butadiene, 1,3-pentadiene, 1,4-pentadiene, 2-methyl-1,4-pentadiene, 3-methyl-1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 5-methyl-1,4-hexadiene, 2-methyl-1,5-hexadiene, 1,4-heptadiene, 1,5-heptadiene, 1,6-heptadiene, 5-methyl-1,4-heptadiene, 6-methyl-1,5-heptadiene, 2-methyl-1,6-heptadiene, etc.

[0289] The polymerization method disclosed herein can be carried out in any suitable manner. Any suitable 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 wt% of the product is soluble in the reaction medium.) Homogeneous polymerization 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 vol% or higher.) Alternatively, a diluent may be absent or added to the reaction medium (except for a small amount used as a carrier for the catalyst system or other additives, or an amount present with the monomer; e.g., propane in propylene). 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 wt% of the polymer product derived from the supported catalyst is in particulate form as solid particles (insoluble in the diluent).

[0290] Suitable diluents for polymerization may include noncoordinate inert liquids. Examples of diluents for polymerization may 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 those commercially available (e.g., Isopar™); and perhalogenated hydrocarbons, such as perfluorinated C4 to C5 hydrocarbons. 10 Alkanes, chlorobenzenes, and aromatic and alkyl-substituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene. Suitable diluents may 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 at least one embodiment, an aliphatic hydrocarbon diluent is used as the diluent, 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 diluent is not aromatic, such as an aromatic compound present in the diluent at less than 1 wt%, such as less than 0.5 wt%, such as 0 wt%, based on the weight of the diluent.

[0291] In at least one embodiment, the feed stream entering the reactor has a feed concentration of 60% by volume or less diluent, such as 40% by volume or less, and such as 20% by volume or less monomer and comonomer for polymerization, based on the total volume of the feed stream. In at least one embodiment, the polymerization is carried out using a bulk method.

[0292] The polymerization can be operated at any temperature and / or pressure suitable for obtaining the desired polymer. Suitable temperatures for solution polymerization include about 50°C to about 200°C, such as about 60°C to about 180°C, such as about 65°C to about 160°C, such as about 80°C to about 150°C, and such as about 85°C to about 140°C. Suitable temperatures for slurry-phase or gas-phase polymerization include about 50°C to about 120°C, such as about 60°C to about 110°C, such as about 65°C to about 100°C, such as about 70°C to about 85°C, and such as about 75°C to about 80°C. The polymerization can be operated at pressures of about 0.1 MPa to about 25 MPa, such as about 0.45 MPa to about 6 MPa, or about 0.5 MPa to about 4 MPa.

[0293] In suitable polymerization, the reaction run time can be up to about 300 minutes, such as about 5 minutes to about 250 minutes, such as about 10 minutes to about 120 minutes, such as about 20 minutes to about 90 minutes, such as 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 45 minutes. In continuous processes, the run time can be the average residence time of the reactor.

[0294] 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), such as about 0.01 psig to about 25 psig (0.07 kPa to 172 kPa), such as about 0.1 psig to about 10 psig (0.7 kPa to 70 kPa).

[0295] In at least one embodiment, the hydrogen content is from about 0.0001 ppm to about 2,000 ppm, such as from about 0.0001 ppm to about 1,500 ppm, such as from about 0.0001 ppm to about 1,000 ppm, such as from about 0.0001 ppm to about 500 ppm. Alternatively, hydrogen may be present at zero ppm.

[0296] In at least one embodiment, MAO may be present at zero mol%, or alternatively, MAO may be present at a molar ratio of aluminum to catalyst metal of less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1.

[0297] Unless otherwise specified, “catalyst productivity” is a measure of how many grams of polymer (P) are produced over a time period of T hours using a polymerization catalyst containing W g of catalyst (cat); and can be expressed by the formula: P / (T×W), where gPgcat -1 hr -1 The units are expressed as follows. Unless otherwise specified, “catalyst activity” is a measure of how active the catalyst is, and for solution-derived MAO catalyst systems, it is reported as the mass of product polymer (P) produced per mole of catalyst (cat) used (kgP / molcat) or for solution, solid, or supported MAO catalyst systems, it is reported as the mass of product polymer (P) produced per mass of catalyst (cat) used (kgP / gcat or gP / gcat). Catalyst activity can also be expressed over a time period T (hours), and for solution or solid MAO as an activator, it is reported as the mass of product polymer (P) produced per mole or millimole of catalyst (cat) used and expressed in gP / mmolcat.-1 hr -1 Units are expressed as kgPgcat for solution, solid, or supported MAO as an activator. -1 hr -1 Expressed in units.

[0298] In at least one embodiment, according to this disclosure, a solution catalyst system having a TMA-free solution of MAO as an activator has a concentration greater than about 10 to 1,000 kg Pgcat. -1 hr -1 Such as Pgcat larger than approximately 20 kg -1 hr -1 Such as Pgcat larger than approximately 30 kg -1 hr -1 Such as approximately 100 kg of Pgcat -1 hr -1 Approximately 300 kg Pgcat -1 hr -1 Catalytic activity; the finished product catalyst system of supported MAO without TMA used in slurry polymerization or gas-phase polymerization has a catalytic activity greater than approximately 3 to 30 kg Pgcat. -1 hr -1 Such as approximately 4 kg of Pgcat -1 hr -1 Approximately 20 kg Pgcat -1 hr -1 Such as approximately 6 kg of Pgcat -1 hr -1 Approximately 15 kg Pgcat -1 hr -1 Such as approximately 8 kg of Pgcat -1 hr -1 Approximately 10 kg Pgcat -1 hr -1 The catalyst activity; and a TMA-free solid MAO self-supported catalyst system with activity between solution polymerization and supported catalyst polymerization (slurry polymerization and gas phase polymerization).

[0299] In at least one embodiment, for solution polymerization, the catalyst residence time in the reactor can be from about 10 minutes to about 120 minutes, such as from about 20 minutes to about 90 minutes, such as from about 30 minutes to about 60 minutes; for solution polymerization, the catalyst residence time in the reactor can be from about 10 minutes to about 120 minutes, such as from about 20 minutes to about 90 minutes, such as from about 30 minutes to about 60 minutes; for supported catalyst polymerization, such as slurry-phase or gas-phase polymerization, the catalyst residence time in the reactor can be from about 10 minutes to about 240 minutes, such as from about 30 minutes to about 120 minutes, such as from about 60 minutes to about 90 minutes; and for catalyst systems derived from supported MAO; the residence time in the slurry-phase or gas-phase polymerization reactor is similar to that of the supported catalyst system.

[0300] In at least one embodiment, 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 the absence of an aliphatic hydrocarbon diluent, such as in a gas-phase reactor, or in the presence of the monomer also acting as a diluent, such as in a slurry reactor using propylene as both monomer and diluent, or in the presence of aliphatic hydrocarbon diluents 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 where the aromatic compound is present in an amount less than 1g by weight of the diluent used for solution or slurry polymerization. 4) The catalyst system used in the polymerization contains less than 0.5 mol%, such as MAO in a molar ratio of less than 500:1, less than 300:1, less than 100:1, or less than 1:1 of aluminum to catalyst metal; 5) The polymerization is carried out in at least one reaction zone; 6) Optionally, no scavenger (such as a trialkylaluminum compound) is present (e.g., in zero mol%, or alternatively, a scavenger in a molar ratio of less than 100:1, such as less than 50:1, less than 15:1, or less than 10:1 of scavenger metal to catalyst metal); and 7) Optionally, hydrogen is present in a molar ratio of about 0.001 psig to about 50 psig (0.007 kPa to 345 kPa) (such as about 0.01 psig to about 25 psig (0.07 kPa to 172 kPa), such as about 0.1 psig to about 10 psig (0.7 kPa to 345 kPa). A partial pressure of 10 kPa to 70 kPa exists in the polymerization reactor. In at least one embodiment, the catalyst system used in the polymerization comprises no more than one precatalyst compound. A “reaction zone,” also called a “polymerization zone,” is a vessel in which polymerization occurs, such as a stirred tank reactor or a circulating 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 is carried out in one or more reaction zones. Unless otherwise specified, the room temperature is 23°C.

[0301] Other additives may also be used in the polymerization process as needed, such as one or more scavengers, hydrogen, alkylaluminum, or chain transfer agents, such as higher alkyl-modified MAO, compounds represented by the formula AlR3 or ZnR2 (where each R is independently a C1-C8 aliphatic group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, or isomers thereof) or combinations thereof, such as diethylzinc, MAO, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or combinations thereof. Other additives, such as reactor electrostatic precipitators or antifouling agents, such as Evonik S202 or Atmer, may also be used. TM Antistatic agents can also be added to catalyst preparation, post-catalyst treatment, or during or after polymerization.

[0302] Polyolefin products

[0303] This disclosure also relates to compositions of substances produced by the methods described herein. The methods described herein can be used to produce polymers of olefins or mixtures of olefins. Polymers that can be prepared include polyethylene, polypropylene, and C4-C4 polymers. 20 Homopolymers of olefins, C4-C 20 Copolymers of olefins, ethylene and C3-C 20 Copolymers of olefins, propylene and C4-C 20 Copolymers of olefins, C4-C 20 terpolymers of olefins, ethylene and propylene with C4-C 20Terpolymers of olefins and terpolymers of ethylene and propylene with 5-ethylidene-2-norbornene. Polymers such as HDPE, MDPE, LDPE, or LLDPE can be produced using the methods described herein, wherein butene, hexene, or octene serves as a comonomer to induce a polymer density transition; such as iPP, sPP, or aPP derived from different stereo or regio-regular precatalysts; such as random copolymer plastics derived from propylene-rich ethylene copolymers having no more than 30% ethylene content or ethylene-rich propylene copolymers having no more than 30% propylene content; ethylene-propylene elastomers (rubbers), i.e., EP rubbers, wherein ethylene and propylene are approximately 50:50, such as 30:70, 40:60, 50:50, 60: 40, or 70:30, such as ethylene-butadiene copolymers from solution polymerization; such as impact-resistant copolymers, for example, biphase copolymers of iPP-EPR, iPP-EBR (ethylene-butene rubber), and iPP-EHR (ethylene-hexene rubber) prepared by reactor polymerization with supported catalysts; such as EPDM (curable ethylene-propylene-diene terpolymer), EBDM (curable ethylene-butene-diene terpolymer), and EHDM (curable ethylene-hexene-diene terpolymer) from solution polymerization; or such curable iPP-EPDM, iPP-EBDM, and iPP-EHDM biphase copolymers prepared by reactor polymerization. Multiphase copolymers with more than two phases can be obtained from more reaction zones, such as PE-RCP-EPR or iPP-RCP-EPR triphase copolymers.

[0304] In some implementations, where the measurement methods are similar to those described in standards ASTM D1238 and ISO 1133, the melt index (MI) of PE-based polymers is from 0.01 to about 50 g / 10 min, such as 0.1 to 10 g / 10 min, such as 0.5 to 5 g / 10 min, such as 1-2 g / 10 min; or the melt flow rate or mass flow rate (MFR) of PP-based polymers is from 0.01 to 2000 g / 10 min, such as 0.05 to 1000 g / 10 min, such as 0.1 to 500 g / 10 min, such as 0.5 to 100 g / 10 min, such as 2-50 g / 10 min.

[0305] In some embodiments, the weight-average molecular weight (Mw) of the polymer product, as measured by GPC, is in the range of 10k to 2000k, such as 50k to 1000k, such as 60k to 500k, such as 100k to 300k; and the molecular weight distribution (MWD) or polydispersity index (PDI) is 1.5 to 30, such as 2 to 10, such as 2.5 to 9, which may have a unimodal or multimodal distribution, for example, a bimodal distribution from a two-stage polymerization process in two different reaction zones or from a one-stage polymerization process in a reaction zone having a catalyst system containing two different precatalyst compounds.

[0306] In some embodiments, the comonomer distribution in the polymer product can be a conventional distribution, i.e., the comonomer incorporation becomes less with increasing Mw; it can be a flat distribution, i.e., different molecular weight compositions have similar incorporation; or it can be a broad orthogonal comonomer distribution, i.e., the comonomer incorporation becomes more with increasing Mw.

[0307] Experimental Examples

[0308] General considerations

[0309] Unless otherwise specified, all reactions were carried out in a CELSTIR reactor under a purified nitrogen atmosphere using a standard glove box, high vacuum, or Schlenk technique. All solvents used were anhydrous, deoxygenated, and purified according to known procedures. All starting materials were purchased from Aldrich and purified or prepared according to procedures known to those skilled in the art prior to use. Silica ES70 was obtained from PQ Corporation (now Ecovyst). MAO as 30 wt% in toluene solution was obtained from WR Grace (e.g., 13.6 wt% Al or 5.04 mmol Al / g). Deuterated solvents were obtained from Cambridge Isotope Laboratories (Andover, Mass.) and dried over 3A molecular sieves. 1 All H NMR data were collected at room temperature (RT) on a Broker AVANCE III 400 MHz spectrometer running Topspin™ 3.0 software.

[0310] Example 1

[0311] Quantitative analysis of the total THF-extractable TMA content in commercial MAO solutions

[0312] According to the reaction scheme (8), both coordinated and free TMA are converted into AlMe3(THF) as the major product and AlMe2(THF)2 as the minor product by THF solvent treatment.+ This allows for the quantification of the total TMA content in supported or unsupported MAO compositions, including both coordinated and free TMA. Therefore, the total TMA is composed of AlMe3(THF) and AlMe2(THF)2. + The sum (converted back to TMA in the calculation) can be used as follows 1 The 1H NMR method is used for quantification, with toluene as the solvent and an added inert compound as the internal standard for solution MAO, solid MAO, or supported MAO.

[0313] Chemicals: WR Grace 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 product) and THF-d8 NMR solvent treated with 3A molecular sieve (Cambridge Isotope).

[0314] If the MAO used for the study is stored at < -20°C for less than 3 months, the total TMA wt% in the MAO product COA can be used without significant error. For MAO solutions stored for longer periods or with frequent temperature changes (e.g., frequently removed from and returned to the freezer), the total THF-extractable TMA content may increase significantly due to the gelation process that releases TMA.

[0315] Procedure: In a drying oven, place ~0.5 inches of MAO solution followed by ~1.5 inches of THF-d8 solvent into a dried 5 mm NMR tube, shake thoroughly, and then acquire the sample using D1 = 30 s, ns = 4. 1 1H NMR spectra. A longer relaxation time D1 can be more accurate, but 30 s is long enough to obtain quantitative toluene CH3 and Al-CH3 signals with an error of <2 wt%. In the region from toluene Me to Al-Me... 1 The H NMR spectrum illustration is from Figure 3 In the bottom spectrum (B).

[0316] Treatment: CH3 peak on p-toluene, total Al-CH3 area, AlMe2(THF)2 + The peaks of MAO and AlMe3(THF) were integrated; the CH3 intoluene was integrated to 300 (the number of protons in CH3 was set to 300 instead of 3 to ensure at least 3 digits of precision in the printed spectrum output, as the digits after the decimal point may be truncated) and the integrals of MAO, AlMe3(THF) and AlMe2(THF)2 were included. +The integral of all Al-Me substances was recorded as 350.28, and the integral of AlMe3(THF) was recorded as 78.96. 2 (THF)2 + The integral was recorded as 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 for uncoordinated TMA is Al1O 0.78 Me 1.44 The Mw concentration was 61.1 g / mol. The MAO integral is 350.28 - 78.96 - 7.98 = 263.34. The number of protons in MAO is 1.44. 3 = 4.32. AlMe2 + It is counted as TMA because it is generated from coordinate TMA. The calculation results are listed in Table 1.

[0317] Table 1. Calculation of Total THF Extractable TMA

[0318] 1 Parts by weight, = Mw The integral / proton# is the weight contribution of a single substance; 2 wt% = Individual parts by weight / Total parts by weight 100%; 3 AlMe2 + It is derived from the coordination TMA and is therefore converted back to TMA.

[0319] It can be seen that the total TMA content has increased from 4.76 wt% (COA) to 5.33 wt%, which is an indication of low-level gelation.

[0320] Example 2

[0321] Quantitative analysis of coordinated TMA in commercial MAO solutions

[0322] The quantification of coordinated TMA is based on the following reaction scheme (5): Option (5) .

[0323] In the above reaction, KF can displace and coordinate TMA, causing MAO to precipitate as an inclusion phase, which is then separated from the solution phase containing free TMA, thereby forming an ionic MAO composition. A large excess of a known amount of KF (W1) is then applied. KF ) was applied to the MAO solution and the remaining KF (W2) was separated after the reaction. KF KF consumption can be calculated as W1 KF– W2 KF It is an indirect quantitative method for coordinating TMA content.

[0324] Chemicals: KF (Aldrich), 10 g in a 50 mL round-bottom flask, dried in an oil bath at 110°C under vacuum for 4 hours; using the same MAO solution and THF-d8 as in Example 1.

[0325] 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 20 mL dried vials, followed by KF (58.1 g / mol) at concentrations of 59.6 mg (based on total Al, 2 mol%), 118.9 mg (based on total Al, 4 mol%), 207.6 mg (based on total Al, 7 mol%), and 298 mg (based on total Al, 10 mol%). The vials were shaken overnight. The vials were removed from the shaker and allowed to stand for 1 hour. KF completely disappeared in the vials treated with 2 mol%, 4 mol%, and 7 mol%, but the vial treated with 10 mol% showed residual KF. The KF was then analyzed in THF-d8 NMR solvent. 1 ¹H NMR spectroscopy was used to analyze all the upper phase solutions of these four vials, and... Figure 5 The comparative spectra shown in Figure A in the Al-Me region indicate a decrease in MAO concentration. Also, in THF-d8 NMR solvent... 1 ¹H NMR spectroscopy analysis was performed on the inclusion phase from a sample (with a vial treated with 10 mmol% KF) where conventional MAO was completely converted to ionic MAO, and the spectra of the Al-Me region were shown in the figure. Figure 5 In B, the parent MAO solution was used for comparison, which showed that the MAO ions did not exist in AlMe2. + The substance means that all coordinated TMAs were removed by KF, because the coordinated TMAs were confirmed to be AlMe2. + The source of the KF was determined. The remaining KF in a 10 mol% treated vial 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 (based on 2.54 mol% of total Al) of unreacted KF, yielding a coordinated TMA of 10⁻².⁵ = 7.5 mol% in MAO solution. The total Al% was 13.8 wt% and the total TMA (free + coordinated) was 5.33 wt%. The total TMA could be converted to 2.00 wt% Al to obtain 14.5 mol%.

[0326] Example 3

[0327] Free TMA estimation

[0328] Based on the weight percentage of total TMA used in Example 1 (Wt) 总TMA Quantification methods for (% of coordinated TMA and free TMA) and the weight percentage (Wt) of coordinated TMA used in Example 2. 配位TMA The quantitative method of % (%) for free TMA content Wt 游离TMA % can be estimated as Wt 游离TMA % = Wt 总TMA % - Wt 配位TMA %.

[0329] Example 4

[0330] OMTS titration

[0331] It can react with OMTS to form AlMe2(OMTS). + The quantification of the MAO active site of the cationic complex was based on the reaction of the following scheme (6), using the Kaminsky active MAO formula with two coordinated TMA molecules as an example.

[0332] Chemicals: Octamethyltrisiloxane (OMTS, from Aldrich, stored overnight with 3A molecular sieves prior to use); use the same MAO solution as in Example 1.

[0333] Procedure: In a drying oven, add 1.0 g (5.0 mmol Al) of 30% MAO solution and 0.236 g of OMTS (1.0 mmol, Al-based, 20 mol%) to a 20 mL vial and mix thoroughly. Shake the mixture on a shaker for 120 minutes at room temperature. Then, slowly mix the mixture with 10 g of dry CDCl3 and shake on a shaker for 10 minutes to obtain a homogeneous solution. Then, take a sample for use. 1 ¹H NMR spectroscopy. Free OMTS: -OSiMe3: 0.20 ppm 18H; =SiMe2: 0.14 ppm 6H. [AlMe2(OMTS)] + : AlMe2: -0.26ppm, 6H; -OSiMe3: 0.61ppm 18H; =SiMe2: 0.94ppm, 6H. [AlMe2(OMTS)] + Quantitative details are summarized in Table 2, using toluene as an internal standard, based on the results of Example 1 (parent MAO, Table 1): Table 2. MAO OMTS titration results

[0334] 1 From Table 1; 2 Wt% divided by substance Mw: toluene 92.1 and TMA 72.1 g / mol; 3 Since there was no change during the reaction in the closed system, the parent MAO toluene was used as an internal standard, and the concentration was set at 0.73 mol% as the parent MAO solution; 4 = (20.0 / 6) / (383.1 / 3) 0.73 = 0.019 mol% Table 2 shows that OMTS can only convert one of the two coordinated TMA molecules on the MAO molecule into AlMe2(OMTS). + KF can replace both, based on a comparison with Example 2, where KF titration consumes twice the amount of KF compared to the amount of OMTS in OMTS titration. This difference is thought to be due to the strong electron-withdrawing group F effectively pulling a negative charge from the MAO molecule, allowing the MAO anion to carry a -2 charge, whereas OMTS and AlMe2... + The complexation gives the Al anion two electron-donating Me groups and two electron-donating O atoms (scheme (6)) or three electron-donating Me groups and one electron-donating O atom (another possibility of the coordinated TMA structure) to make it difficult to acquire a second negative charge on the MAO anion, as shown in scheme (7).

[0335]

[0336] Example 5

[0337] Solution ions MAO (MAO-1 and MAO-2) from OMTS treatment

[0338] Chemicals: WR Grace 30% MAO toluene solution (13.6 wt% Al from WR Grace analytical certificate; total Al based on the method of Example 4, 7.5 mol% coordinated TMA); OMTS (236.5 g / mol, Aldrich, 3A molecular sieve overnight).

[0339] Procedure: 41.5 g MAO (207.5 mmol Al) was placed in a 100 mL round-bottom flask equipped with a stir bar. Based on the OMTS titration results in Table 2 of Example 4, 1.84 g OMTS (7.8 mmol) (based on 3.7 mol% OMTS of total Al) was slowly added to the MAO solution. The mixture was stirred for 45 minutes. The mixture was transferred to a separatory funnel and allowed to stand overnight. Two liquid phases were formed. The bottom phase (product) was collected and weighed. 21 g of oily material was obtained. The boundary between the two phases was discarded. Weight of the top layer: 19.5 g as a standard solution. Bottom phase ions MAO in CDCl31 H NMR: [AlMe2(µ-OSiMe3)2SiMe2] + -MAO region: SiMe2: δ0.92 (6H); SiMe3: δ0.92 (18H); AlMe2: δ-0.29 (6H); Free TMA: δ-6.6 (9H).

[0340] Using [AlMe2(µ-OSiMe3)2SiMe2] + The free TMA content was calculated using the free TMA as an internal standard (3.7 mol% of total Al, AlMe2 integral 59.70) to obtain free TMA (integral 9.70) = (9.70 / 9). 3.7 mol% / (59.70 / 6) = 0.40 mol% (or 0.40 wt%), based on total Al. This ion MAO is labeled I-MAO-1.

[0341] Then, the oily ionic MAO was heated in an oil bath at 90°C for 60 minutes to obtain... 1 H NMR, such as Figure 6 As shown in the figure, new substances containing Al-Me units appear at -0.23 ppm, and this increases with the presence of Si-Me units at 0.56 ppm, maintaining a Si-Me:Al-Me ratio of 3:4. These are attributed to substances I- described in the cationic modified (ionic) MAO section. a As the most likely structure, among 1 The 1H NMR spectrum shows the Si-Me and Al-Me regions as follows. The MAO ion is labeled as I-MAO-2.

[0342] (I- a )

[0343] Experimental evidence shows that each MAO molecule has two coordinating TMAs, but only one can form the OMTS chelate cation [AlMe2(OMTS)]. + Because it is difficult to construct two anionic charges on a single molecule, approximately 3.7 mol% OMTS based on Al is sufficient to precipitate almost all MAO molecules as ionic MAO to separate them from the free TMA remaining in the upper solution phase (which can be removed by phase separation). OMTS can be added either as a pure substance or as a solution.

[0344] Examples (Ex) 6, 7 and 8 and comparative examples (cEx) 1, 2, 3 and 4

[0345] Small-scale aggregation: Polymerization reagents. A pre-catalyst solution was prepared using a given transition metal complex (ExxonMobil Chemical - anhydrous, stored under N2) (98%) typically dissolved in toluene at a concentration of 0.5 mmol / L. The complex was activated using various methylaluminoxanes (MAOs), including commercial methylaluminoxanes (rMAO, 10 wt% in toluene, WR Grace, for reference), TMA-free F-MAO (described in another patent application), or TMA-free I-MAO-2 (from Example 5). Catalyst A could be prepared as described in US 11,254,763.

[0346] All MAO is typically used as a 0.2 wt% toluene solution. The micromolar numbers of MAO reported below are based on the micromolar number of aluminum in the MAO, which has a molecular weight of 58.0 g / mol.

[0347] Solvents, polymerization-grade toluene, and / or isohexane were supplied by ExxonMobil Chemical Co. and purified by passing through a series of columns: two tandem 500 cc OXYCLEAR columns from Labclear (Oakland, California), followed by two tandem 500 cc columns packed with dry 3 Å molecular sieves (8-12 mesh; Aldrich Chemical Company), and two tandem 500 cc columns packed with dry 5 Å molecular sieves (8-12 mesh; Aldrich Chemical Company).

[0348] 1-Octenene (C8; 98%, Aldrich Chemical Company) was dried by overnight stirring on NaK and then filtered through alkaline alumina (Aldrich Chemical Company, Brockman Basic 1).

[0349] Polymer-grade ethylene (C2) was used and further purified by passing it through a series of columns: a 500 cc Oxyclear column from Labclear (Oakland, Calif.), followed by a 500 cc column packed with dry 3 Å molecular sieves (8-12 mesh; Aldrich Chemical Company), and a 500 cc column packed with dry 5 Å molecular sieves (8-12 mesh; Aldrich Chemical Company).

[0350] Polymer-grade propylene was purified by passing it through a series of columns: a 2,250 cc OXICLEAR column from Labclear, followed by a 2,250 cc column packed with 3 Å molecular sieves (8-12 mesh; Aldrich Chemical Company), then two tandem 500 cc columns packed with 5 Å molecular sieves (8-12 mesh; Aldrich Chemical Company), then a 500 cc column packed with SELEXSORB CD (BASF), and finally a 500 cc column packed with SELEXSORB COS (BASF).

[0351] Reactor Description and Preparation: Polymerization was carried out in an inert atmosphere (N2) drying oven using an autoclave equipped with an external heater for temperature control, glass inserts (internal reactor volume = 23.5 mL for C2 / C8; 22.5 mL for C3), a diaphragm inlet, controlled nitrogen, ethylene and propylene supply, and a disposable PEEK mechanical stirrer (800 RPM). The autoclave was prepared by purging with dry nitrogen at 110°C or 115°C for 5 hours and then purging at 25°C for 5 hours.

[0352] Propylene polymer (PP): Prepare the reactor as described above, heat to 40°C, and then purge with propylene gas at atmospheric pressure. For MAO-activated runs, add toluene, MAO, propylene (1.0 ml, unless otherwise listed in the table), and comonomer (if used) via syringe. Then heat the reactor to the process temperature (typically 70°C or 100°C, unless otherwise mentioned) while stirring at 800 RPM. With the reactor under process conditions, add a pre-catalyst solution via syringe. Monitor the reactor temperature, which is typically maintained within + / - 1°C. Stop the polymerization by adding approximately 50 psi of air-gas mixture or CO2 gas to the autoclave for approximately 30 seconds. Unless otherwise specified (maximum quenching value, in psi), the polymerization is quenched based on a predetermined pressure loss of approximately 8 psi, or unless otherwise specified, the polymerization time is a maximum of 30 minutes. Then allow the reactor to cool and vent. After removing the solvent under vacuum, separate the polymer. Report the actual quenching time. A quenching time less than the maximum reaction time indicates that the reaction is quenched with absorption. The reported yields include the total weight of polymer and residual catalyst. Catalyst activity is reported as polymer g / mmol complex / hour reaction time (gP / mmol cat·hr). Examples of propylene homopolymerization, including characterization, are summarized in Table 3 below.

[0353] Ethylene / 1-octene copolymer(EO): The reactor was prepared as described above and then purged with ethylene. For operation with activated MAO, toluene, 1-octene (100 μL), and the activator (MAO) were added via syringe at room temperature and atmospheric pressure. The reactor was then brought to process temperature (100°C) and ethylene was added to process pressure (200 psig = 1480.3 kPa) while stirring at 800 RPM. The pre-catalyst solution was then added to the reactor via syringe under process conditions. During polymerization, ethylene was allowed to enter the autoclave (using a computer-controlled solenoid valve) to maintain the reactor gauge pressure (+ / - 2 psig). The reactor temperature was monitored and typically maintained within + / - 1°C. Polymerization was stopped by adding approximately 50 psi of compressed air to the autoclave for approximately 30 seconds. Polymerization was quenched after the predetermined cumulative amount of ethylene (maximum quenching value of 15 psid) had been added or after a maximum polymerization time of 30 minutes. The reactor was then cooled and discharged. The polymer was separated after the solvent was removed under vacuum. The reported yields include the total weight of polymer and residual catalyst. Catalyst activity is reported as polymer g / mmol transition metal compound / hour reaction time (g / mmol·hr). Examples of ethylene-octene copolymerization are summarized in Table 4.

[0354] Small-scale polymer characterization. For analytical testing, polymer sample solutions were prepared by dissolving the polymer in 1,2,4-trichlorobenzene (TCB, 99+% purity) containing 2,6-di-tert-butyl-4-methylphenol (BHT, Sigma-Aldrich, 99%) at 165°C in a shaking oven for approximately 3 hours. Typical polymer concentrations in the solution ranged from 0.1 to 0.9 mg / ml, with the TCB containing 1.25 mg BHT / ml. Samples were cooled to 135°C for testing.

[0355] High-temperature size exclusion chromatography was performed using an automated “Rapid GPC” system, as described in the following: U.S. Patents 6,491,816; 6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632; 6,175,409; 6,454,947; 6,260,407; and 6,294,388; each of which is incorporated herein by reference. Molecular weight (weight-average molecular weight (Mw), number-average molecular weight (Mn), z-average molecular weight (Mz)) and molecular weight distribution (PDI = MWD = Mw / Mn) (which is sometimes also referred to as the polydispersity (PDI) of the polymer) were measured by gel permeation chromatography using a Symyx Technology GPC equipped with an evaporative light scattering detector (ELSD) and calibrated with polystyrene standards (Polymer Laboratories: Polystyrene Calibration Kit SM-10: Mp (peak Mw) from 5,000 to 3,390,000). Alternatively, the sample was measured by gel permeation chromatography using a Symyx Technology GPC equipped with a dual-wavelength infrared detector and calibrated with polystyrene standards (Polymer Laboratories: Polystyrene Calibration Kit SM-10: Mp (peak Mw) from 580 to 3,039,000). Samples (250 μL of polymer solution in TCB injected into the system) were run using three PolymerLaboratories in tandem: PLgel 10 μm Mixed-B 300 x 7.5 mm columns at an elution flow rate of 2.0 ml / min (sample temperature 135°C, chamber 165°C / column). Column broadening correction was not performed. Numerical analysis was performed using Epoch® software available from Symyx Technologies or Automation Studio software available from Freeslate. The obtained molecular weights are relative to linear polystyrene standards. Molecular weight data are reported in the following tables under the headings Mn, Mw, Mz, and PDI as defined above.

[0356] Differential scanning calorimetry (DSC) measurements were performed on a TA-Q100 instrument to determine the melting point of the polymer. The sample was pre-annealed at 220°C for 15 minutes (first melt) and then allowed to cool to room temperature overnight. The sample was then heated to 220°C at a rate of 100°C / min (second melt) and then cooled at a rate of 50°C / min. Melting points were collected during the heating period. The reported values ​​are peak melting temperatures and are referred to as second melt for the purposes of this disclosure. The results are shown in the table in heading T. m Submit a report.

[0357] FTIR – Samples for infrared analysis are prepared by depositing a stabilized polymer solution onto a silanized wafer. Approximately 0.12 mg to 0.24 mg of polymer is deposited onto the wafer cell using this method. The sample is then analyzed on a Brucker Equinox 55 FTIR spectrometer equipped with a Pikes' MappIR specular reflectance sample attachment. Spectra covering the spectral range of 5000 cm⁻¹ to 500 cm⁻¹ are collected in 32 scans at a resolution of 2 cm⁻¹. For the ethylene-1-octene copolymer, the wt% octene in the copolymer is determined by measuring the methyl deformation band at ~1375 cm⁻¹. The peak height of this band is normalized by combining and overtone bands at ~4321 cm⁻¹, correcting for differences in optical path length. The normalized peak height is compared with that from… 1 Correlating individual calibration curves from the H NMR data to predict octene content in the wt% range of ~2 wt% to 35 wt%. Typically, an R0.98 or greater is obtained. 2 Correlation. These figures are reported in Table 2 under heading C8 (wt%).

[0358] Two precatalysts, including post-metallocene A and hafnium-cadmium B with the following structures, were used for propylene and ethylene polymerization tests, respectively: .

[0359] Table 3 lists examples of propylene polymerization. Standard conditions include 0.015 μmol of catalyst A and the type and amount of activator (Act) indicated in Table 3. 1 ml of propylene and a total of 4.1 ml of solvent were used. The reaction was heated to 70°C or 100°C, stirred at 800 rpm, and quenched after a pressure loss of 8 psi, or after a maximum reaction time of 30 minutes if the quench pressure is not met.

[0360] Table 3: Homopolymerization of propylene using catalyst A

[0361] Table 3 (continued)

[0362] Table 3 shows that, for propylene homopolymerization, by comparing the groups of cEx 1-1 to -3 and Ex 6-1 to -2 at 70°C and the groups of cEx 1-4 and Ex 6-3 to -5 at 100°C, ionic MAO without non-coordinated TMA is inferior to F-MAO without non-coordinated TMA as an activator for post-metallocene precatalysts with zirconium centers. F-MAO also outperforms conventional MAO by comparing cEx 2-1 to -3 and cEx 1-7 to -9. However, for ethylene polymerization (typically using small amounts of higher alkyl olefins such as butane, haxane, or octane as comonomers to obtain lower polymer densities, e.g., LLDPE; octene is used here), in the cases listed in Table 4 below, with the same precatalyst catalyst A as for the propylene polymerization above, and using hafnium diacene precatalyst catalyst B, which is generally difficult to activate with conventional MAO as an activator, ionic MAO is significantly superior to F-MAO. In fact, by comparing cEx 3-1 to -3 with Ex 7-1 to -3 and cEx 4-1 to -3 with Ex 8-1 to -3 respectively, F-MAO showed almost no reactivity for ethylene-octene copolymerization in the case of both precatalyst A and catalyst B. Therefore, it has been shown that both anionic modified MAO (e.g., F-MAO) and cationic modified MAO (e.g., OMTS-treated MAO) without non-coordinated alkylaluminum are needed for the activation of precatalysts containing non-leaving heteroatoms to achieve polymerization or copolymerization of various monomers and copolymers.

[0363] Table 4 lists examples of ethylene-octene copolymerization. Standard conditions include 0.015 μmol of catalyst A or 0.025 μmol of catalyst B and the type and amount of activator (Act) indicated in the table. Octene (0.100 ml) and 4.9 ml of toluene were used. The reaction was heated to 100°C, pressurized with 200 psi ethylene in a semi-continuous feed, and stirred at 800 rpm. The reaction was quenched after absorbing 15 psi ethylene or, if the quenching pressure was not met, a maximum of 30 minutes. This indicates that the octene content is outside the FTIR calibration range.

[0364] Table 4. Ethylene-octene copolymerization using catalyst A and catalyst B (100:1 Al:Zr or Hf)

[0365] Table 4 (continued)

[0366] Example 9 and comparative examples 5, 6 and 7

[0367] Silica-supported MAO (sMAO), cationic modified (OMTS-treated) sMAO, and OMTS-treated with heating Therapeutic sMAO and anion-modified ((NH4)2SiF6 treated) sMAO

[0368] Chemicals: Silica, ES70 (calcined at 600°C); WR Grace 30% MAO toluene solution (13.6wt% Al (COA) or 5.0mmol Al / g); OMTS (236.5g / mol, Aldrich, overnight in 3A molecular sieve); (NH4)2SiF6 (178.2g / mol, Aldrich, vacuum dried at 110°C); Catalyst A (945g / mol, prepared as described above).

[0369] program: 1) sMAO and its derived supported catalyst A (cEx 5): 10.0 g of ES70 silica and 50 g of dry toluene were mixed in a 100 mL CelSir reaction vessel to form a 17 wt% slurry, and the mixture was stirred. 13 g of MAO solution based on 6.5 (mmol Al / g silica) was slowly added to the silica slurry. The mixture was stirred at ambient temperature for 30 minutes, and then the temperature was raised to 100°C and maintained for 4 hours. After cooling to ambient temperature, the supernatant was filtered and washed with dry isohexane. The wet solid was then dried to constant weight under vacuum. Yield: 13.8 g sMAO (~4.7 mmol Al / g).

[0370] 1.0 g sMAO was mixed with 4 g toluene in a 20 mL vial. 38 mg of catalyst A (40 µmol / g) was added to the vial. The mixture was then shaken on a shaker for 2 hours. The solid contents were separated by filtration, washed with isohexane, and dried to constant weight under vacuum. Yield: 1.0 g.

[0371] 2) TMA-free sMAO from OMTS treatment without heating (cEx 6)

[0372] 2.0 g of sMAO from step 1) above was mixed with 8 g of toluene in a 20 mL vial. 223 mg of OMTS (0.94 mmol, based on 10 mol% Al, intentionally in excess) was added to the vial. It should be noted that the main difference between the solution obtained and the supported ionic MAO without noncoordinate TMA is that, in the solution case, most of the excess OMTS remains in the upper solution phase (which can be removed by phase separation); while in the supported case, it remains in the supernatant (which can be removed by filtration or decantation). The mixture was shaken on a shaker for 1 hour, then filtered, washed with isohexane, and dried under vacuum to constant weight. Yield: 2.1 g.

[0373] 1.0 g of OMTS-treated sMAO was slurried in a 20 mL vial in 4 g toluene and 38 mg of catalyst A (40 µmol / g). The vial was shaken on a shaker for 1 hour. The mixture was filtered, washed with isohexane, and dried under vacuum to constant weight. Yield: 1.0 g.

[0374] 3) TMA-free sMAO from heated OMTS treatment (Ex 9)

[0375] 1.0 g of OMTS-treated sMAO from step 2) above was mixed with 4 g of toluene in a 20 mL vial. The vial was loosely capped and placed in an oil bath to heat at 100°C for 3 hours. The mixture was allowed to cool to ambient temperature, 38 mg of catalyst A (40 µmol / g) was added, and the mixture was shaken on a shaker for 1 hour. The mixture was filtered, washed with isohexane, and dried under vacuum to constant weight. Yield: 1.0 g.

[0376] 4) TMA-free anionic modified sMAO from (NH4)2SiF6 treated with heat (cEx 7)

[0377] 2.0 g sMAO was mixed with 8 g toluene in a 20 mL vial. 20 mg (NH4)2SiF6 (based on 7 mol F% of Al in sMAO, 0.11 mmol) and 47 mg pure TMA (to aid in the dissolution of (NH4)2SiF6) were added to the vial, and the mixture was allowed to stir on a shaker for 30 min and heated at 70°C for 20 min. The mixture was then filtered, washed with toluene (this process removes most of the free TMA), and re-slurryed with 3 g toluene. 38 mg of catalyst A (40 µmol / g) was added to the mixture. The mixture was then shaken on a shaker for 2 h. The solid contents were separated by filtration and washed with isohexane, and dried to constant weight under vacuum. Yield: 2.0 g.

[0378] Salt bed gas phase PE polymerization

[0379] Chemicals: NaCl (Fisher S271-10, dehydrated at 180°C and subjected to several pump / purge cycles and finally passed through a 16-mesh sieve before use); TMA loaded with ES-70 silica (calcined at 875°C) as a cleaning agent.

[0380] Procedure: Heat the A2 L autoclave to 110°C and purge with N2 for at least 30 minutes. At 105°C, add 350 g of dry NaCl and silica-supported Al. iAdd 6 g of Bu3 and stir for 30 minutes. Adjust the temperature to 85°C. Add 2.0 mL of dried, degassed 1-hexene to the reactor using a syringe at a pressure of 2 psig N2, then charge the reactor with N2 to a pressure of 20 psig. Simultaneously, allow a mixture of H2 and N2 to flow into the reactor (120 SCCM; 10% H2 in N2). Inject the catalyst and ethylene as indicated in Table 3 into the reactor at a pressure of 220 psig; allow ethylene flow during operation to maintain a constant pressure in the reactor. Feed 1-hexene into the reactor at a flow rate of 0.1 g / g to ethylene. Feed hydrogen into the reactor at a flow rate of 0.5 mg / g to ethylene. Measure the hydrogen to ethylene ratio by online GC analysis. After 1 hour, stop the polymerization by venting the reactor, cooling to room temperature, and then exposing it to air. Remove salts by washing twice with water; separate the polymer by filtration, briefly wash with acetone, and air-dry for at least two days. The yields and activities calculated based on the yields of the comparative example 8 using the finished catalyst derived from complex 6 of conventional supported MAO and examples 8-12 using the finished catalyst derived from complex 6 of the supported MAO (TF-sMAO) of the present invention are listed in Table 5.

[0381] Table 5. Results of vapor-phase PE polymerization in a 2L salt bed

[0382] Table 5 shows that unheated OMTS-treated sMAO is not as good as conventional MAO, and the chelation effect with OMTS makes AlMe2 very stable. +The difficulty in separating the chelate to form a binuclear complex with the precatalyst is consistent with the hypothesis (Scheme 1). Upon heating, it becomes more active, possibly due to the decomposition of the chelate ligands to form monodentate ligands. Conversely, it also indicates that the anionic modified supported MAO (cEx 7) exhibits significantly higher activity than the ionic sMAO form when compared to the solution polymerization results in Table 4, where the solution polymerization results show that the anionic modified MAO is almost inactive (cEx 3-1 to -3 relative to Ex 7-1 to -3 with the same precatalyst, catalyst A). The difficulty in separating the active soluble byproducts from the solution-treated MAO may be a factor influencing the activation of the precatalyst. For example, in solution anion-modified MAO, all TMA molecules (including coordinated and free TMA) are converted to AlMe2F, resulting in an excess of AlMe2F in the system (e.g., ~14.5 mol% of total TMA and ~7.5 mol% of coordinated TMA (Table 2) means that about half of the AlMe2F molecules do not replace coordinated TMA and become free AlMe2F, which may be a poison for some activated pre-catalysts).

[0383] Gas-phase PE polymerization using silica-supported ionic MAO (siMAO-1) activated post-metallocene Zr precatalyst (catalyst A) (2L salt bed reactor, 85°C, 1 hour (H2 charge 120 mL, H2:C2 = 0.5 feed; hexene (C6) = ) 2.5 mL of material, C6 = / C2 = 0.1; 12 mg catalyst) is shown in Figure 3 middle.

[0384] Examples 10 to 16 and Comparative Examples 8 to 21

[0385] Solution polymerization of heated inclusion complexes of ionic MAO (ionic MAO-2) activated by ionic MAO (ionic MAO-2) precatalyst for ethylene-butadiene copolymerization was performed, and the results are shown in Table 6.

[0386] Polymerization vessel: Symyx Discovery Tools TI-6AL-4V high-pressure parallel reactor.

[0387] Chemicals: Complexes 34 to 40 are prepared as described in US 11,254,763; i Bu2AlH (DIBAL) (pure, Nouryon); [HNMe2Ph] + B(C6F5)4 -(Boulder Scientifics); MAO (W. R Grace 30% MAO, Al = 13.5%); Ionic MAO-2 (from Example 5); Toluene (Aldrich, stored overnight with 3A molecular sieve); Ethylene (plant pipeline purified with standard drying / purification column); Butadiene (BD) (Aldrich, cooled in a freezer in a drying oven set at -20°C, poured into cold toluene to prepare a 10 wt% solution and stored overnight with activated alumina).

[0388] Procedure: Each of the pre-catalysts is added i Bu₂AlH (DIBAL, relative to 20 metal equivalents of the pre-catalyst) and [HNMe₂Ph] + B(C6F5)4 - Activation was performed using (D4, 1.2 equivalents of the pre-catalyst metal) or MAO (100 equivalents of the pre-catalyst metal) or TF-MAO (100 equivalents of the pre-catalyst metal). After stirring the pre-catalyst and activator for approximately 10 minutes, a solution of butadiene in toluene (10 wt%) (~2500 butadiene equivalents / catalyst) was added, and the reactor, equipped with six 20 mL vials, was then sealed. The reactor was heated to 100°C, stirred at 225 rpm, and then pressurized with ethylene (250 psi, Sigma, 99.5%). During the first hour, the reactor was repressurized when the pressure dropped below 240 psi. After 4 hours, the reactor was cooled and then depressurized. The polymer product was separated from each vial by precipitation and washed with acetone and methanol. The solids were then filtered off and washed with large amounts of acetone and methanol. The polymer samples were then dried in a vacuum oven at 50°C for 18 hours.

[0389] Table 6. Polymerization of precatalysts 34-40 activated by MAO, ionic MAO and DIMASH-D4.

[0390] - Conditions: Approximately 1 g BD, toluene solution, BD:RE = 2500; 250 psi ethylene; 100°C; 14 hours; -1,2-cyclopentane.

[0391] In some implementations, it is used with conventional MAO and conventional solution activators such as perfluoroaromatic borates (e.g., [HNMe2Ph)). + B(C6F5)4 - (D4) and iCompared to Bu₂AlH (DIBAH), the use of solution ionic MAO (ionic MAO-2) enables more efficient activation of post-metallocene Group 3 precatalysts, as shown in Table 6. The results of another application using TMA-free anion-modified MAO containing Group 3 metal centers were also compared, using conventional MAO, conventional borate systems, and TMA-free fluorinated MAO (F-MAO). Figure 4 As shown in the image.

[0392] Examples 17-18 and Comparative Example 22

[0393] SiMe3(OH) treatment of MAO and catalyst A (Ex 17)

[0394] Chemicals: SiMe3(OH) (90.2 g / mol, pure, Aldrich, stored overnight with 3A molecular sieve before use); 30% MAO toluene solution (13.5 wt% Al, WR Grace).

[0395] Procedure: Place 5.0 g of MAO solution (25 mmol Al) in a 20 mL vial equipped with a stir bar on a stirrer. While stirring vigorously, slowly add 0.169 g of SiMe3OH (1.857 mmol, based on 7.5 mmol% free TMA in MAO, according to Table 2) as a solution (dissolved in 2.0 g toluene). Bubbling is observed. The reaction may require cooling to minimize side reactions. Shake the mixture on a shaker for 15 minutes. The solution weight is 7.14 g (3.50 mmol Al / g solution, presumed no Al loss). The resulting solution was used as a pre-catalyst for the polymerization of 1-hexene as described below, with results summarized in Table 7.

[0396] Solution treated with SiMe3OAlMe2 and catalyst A (Ex 18)

[0397] Chemicals: SiMe3(OH) (90.2 g / mol, pure, Aldrich, stored overnight with 3A molecular sieve before use); TMA (72.1 g / mol, pure, Aldrich, used as is); 30% MAO toluene solution (13.5 wt% Al, WRGrace).

[0398] Procedure: In a 20 mL vial, 0.169 g of SiMe3OH (1.87 mmol) and 1.0 g of toluene were added. In another 20 mL vial, 133.9 mg of TMA (1.86 mmol) and 1.0 g of toluene were added, along with a stir bar, and the vial was placed in a -30°C freezer for 30 minutes. The silanol solution was then slowly added to the cold TMA solution with vigorous stirring. The mixture was shaken on a shaker for 15 minutes. The resulting SiMe3OAlMe2 was mixed with 5.0 g of MAO solution (25 mmol Al) in another 20 mL vial and allowed to be stirred on a shaker for 60 minutes. The solution weight was 7.28 g (3.69 mmol Al / g solution). The resulting solution was used as a pre-catalyst for the polymerization of 1-hexene as described below, with the results summarized in Table 7.

[0399] 1-Hexene polymerization

[0400] Since rapid screening for 1-hexene polymerization in the environment requires rapid activation of the pre-catalyst and rapid polymerization of 1-hexene, ethylene(bis(indenyl))dimethylzirconium is used here.

[0401] Equipment: Equal volumes of MAO Al, toluene solvent, 1-hexene, and ethylene(bis(indenyl))dimethylzirconium (Table 7) were added to a double-jacketed 50 mL round-bottom flask designed to limit heat loss and allow thermocouple immersion in the reaction solution. Thermocouples were used to measure the temperature rise during 1-hexene polymerization as a specification of activity.

[0402] Chemicals: Treated MAO solutions from Ex. 17 and Ex. 18, and untreated MAO solution (5 mmol Al / g) as a reference (cEx 22). 1-Hexene (plant grade, stored overnight with 3A molecular sieves before use). Pre-catalyst ethylene(bis(indenyl))dimethylzirconium (377.6 g / mol).

[0403] Procedure: Add the amounts of MAO, toluene, and 1-hexene, along with a stir bar, as shown in Table 7, to a 50 mL jacketed flask. Stir the mixture at 600 rpm. Record the initial ambient temperature. Then, inject 10.0 mg of ethylene(bis(indenyl))dimethylzirconium solution (in 1.0 g toluene to make a concentration of 10.6 µmol Zr / g solution) into the mixture in the flask as shown in Table 7, while starting a stopwatch. Record the final temperature at the 5-minute mark. After the polymerization test, empty the flask and wash it three times with toluene before using it for the next test. The results are summarized in Table 7.

[0404] Table 7. Polymerization of 1-hexene using catalyst A and treated MAO compared to conventional MAO

[0405] Table 7 only shows that treated MAO can still activate metallocenes. For post-metallocene activation, the performance of the pre-catalyst needs to be compared with the metal center and ligand structures, the type of polymerization using monomers and comonomers, and the conditions (including different residence times, different polymerization temperatures, supported or solution polymerization, etc.).

[0406] Overall, the MAO and catalyst system disclosed herein provide improved catalyst activity and lifetime for certain post-metallocene and CGC precatalysts. Furthermore, the monodentate ligand can be formed in situ during MAO formation and can provide a more active activator compared to that provided by multidentate chelating ligands (as siloxane alkylaluminum complexes). Ionization of MAO with chelating agents such as the OMTS disclosed herein can be gel-free for a longer period than conventional aluminoxanes or even monodentate siloxane-modified alkylaluminoxanes, ensuring stability during storage or transport. Moreover, since siloxane alkylaluminum complexes can be stable, end users can be able to heat the siloxane alkylaluminum complexes to obtain active monodentate ligands for improved efficiency, as the active monodentate ligands can be formed before use as catalyst activators, thus providing improved atom economy / efficiency. The cationic modified alkylaluminoxanes disclosed herein offer numerous benefits, primarily enabling more efficient activation of certain post-metallocene or CGC semi-metallocenes containing O and / or N, especially those with low activation efficiency when using anionic modified MAO, conventional MAO, or boron / borate-based solution activators. Furthermore, the amount of activator (alkylaluminoxane) required for catalyst activation is reduced due to improved efficiency / atom economy. The presence of monodentate or chelate ligands in the treated aluminoxane similarly reduces or eliminates side reactions in another type of MAO system without noncoordinated alkylaluminum, thereby promoting improved catalyst activity and lifetime for better derivatization catalysts and polymer quality control.

[0407] It should be understood that conventional MAO can also be modified by both anionic and cationic modification. For example, MAO can be treated with an electron-withdrawing agent such as (NH4)2SiF6, followed by a chelating agent such as OMTS, with an optional heating process, to form a dual-modified alkylaluminoxane composition that contains no or is depleted of noncoordinated alkylaluminum.

[0408] Unless otherwise stated, the phrases “consists 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. Furthermore, they do not exclude impurities and differences that are generally associated with the elements and materials used.

[0409] 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 single value between its endpoints, even if not explicitly listed. Therefore, each point or single value can act as its own lower or upper bound and be combined with any other point or single value or any other lower or upper bound to enumerate ranges not explicitly listed.

[0410] All references described herein are incorporated herein by reference, including any priority documents and / or test procedures, provided they are not contrary to this document. As will be apparent from the foregoing general description and specific embodiments, while the form of this disclosure has been illustrated and described, various modifications may be made without departing from the spirit and scope of this disclosure. Therefore, it is not intended to limit this disclosure. Similarly, 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 contemplate the same composition or group of elements preceded by the transitional phrases “consistently composed of,” “composed of,” “selected from the group of,” or “is,” and vice versa.

[0411] Although this disclosure has been described with reference to various embodiments and examples, those skilled in the art who benefit from this disclosure will understand that other embodiments can be designed without departing from the scope and spirit of this disclosure.

Claims

1. A catalyst system comprising: At least one precatalyst compound; and Unsupported or supported aluminoxanes containing monodentate siloxy ligands.

2. The catalyst system as described in claim 1, wherein, The precatalyst compound contains at least one non-leaving heteroatom donor chemically bonded to the metal catalytic center of the precatalyst.

3. The catalyst system as described in claim 2, wherein, The unsupported or supported aluminum oxane is substantially free of noncoordinated alkyl aluminum or has no more than 2 wt% Al as noncoordinated alkyl aluminum based on the total Al in the unsupported or supported aluminum oxane composition.

4. The catalyst system according to any one of claims 1 to 3, wherein, The monodentate ligand is represented by formula (I): (I) in: R 1 R 2 R 3 R 4 R 5 R 6 and R 7 Each of them is independently a hydrogen, hydrocarbon, silyl, or a group containing heteroatoms.

5. The catalyst system as described in claim 4, wherein, Each R 1 R 2 R 3 R 4 R 5 R 6 and R 7 Each of them is independently hydrogen, alkyl, or alkenyl.

6. The catalyst system as described in claim 5, wherein, Each R 1 R 2 R 3 R 4 R 5 R 6 and R 7 Each of them is a methyl group.

7. The catalyst system of claim 1, wherein, The aluminum oxane is a supported aluminum oxane.

8. The catalyst system of claim 7, wherein, The support of the supported aluminoxane comprises silicon dioxide and the aluminoxane comprises methylaluminoxane.

9. The catalyst system according to any one of claims 1 to 8, wherein, The precatalyst compound is represented by the following formula: T y Cp m MG n X q in: Cp is independently a substituted or unsubstituted cyclopentadienyl ligand or a substituted or unsubstituted ligand similar to the cyclopentadienyl isovalence, such as indene, fluorenyl and indole. M is a group 4 transition metal; G is derived from formula JR z The heteroatomic group is represented, where J is N, P, O, or S, and R is... Is it a straight chain, branched chain, or cyclic C1-C? 20 hydrocarbon group; z is 1 or 2; T is a bridging group; y is 0 or 1; X is a leaving group; m=1； n = 1, 2, or 3; q = 0, 1, 2 or 3, and The sum of m+n+q equals the oxidation state of the transition metal.

10. The catalyst system of claim 9, wherein, The precatalyst compound is a bis(arylphenol)pyridine complex.

11. The catalyst system of claim 10, wherein, The bis(arylphenol salt)pyridine complex is selected from the group consisting of: Dimethylzirconium [2',2'''-(pyridin-2,6-diyl)bis(3-adamantane-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenolic salt], Dimethylhafnium [2',2'''-(pyridin-2,6-diyl)bis(3-adamantane-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-phenolic salt], Dimethylzirconium [6,6'-(pyridin-2,6-diylbis(benzo[b]thiophene-3,2-diyl))bis(2-adamantane-1-yl)-4-methylphenol salt)] Dimethylhafnium [6,6'-(pyridin-2,6-diylbis(benzo[b]thiophene-3,2-diyl))bis(2-adamantane-1-yl)-4-methylphenol salt)] Dimethylzirconium [2',2'''-(pyridin-2,6-diyl)bis(3-((3r,5r,7r)-adamantane-1-yl)-5-methyl-[1,1'-biphenyl]-2-phenolic salt)], Dimethylhafnium [2',2'''-(pyridin-2,6-diyl)bis(3-((3r,5r,7r)-adamantane-1-yl)-5-methyl-[1,1'-biphenyl]-2-phenolic salt)], Dimethylzirconium [2',2'''-(pyridin-2,6-diyl)bis(3-((3r,5r,7r)-adamantane-1-yl)-4',5-dimethyl-[1,1'-biphenyl]-2-phenolic salt)], Dimethylhafnium [2',2'''-(pyridin-2,6-diyl)bis(3-((3r,5r,7r)-adamantane-1-yl)-4',5-dimethyl-[1,1'-biphenyl]-2-phenolic salt)], and combinations thereof.

12. The catalyst system of claim 1, wherein, The precatalyst compound is selected from the group consisting of: 。 13. The catalyst system of claim 1, wherein, The precatalyst compound is selected from the group consisting of: 。 14. A method for preparing aluminumoxane, comprising: Ionic alkylaluminoxanes are formed through the following: Reaction of supported or unsupported alkylaluminoxanes with a multidentate chelating agent to form an ionic aluminumoxane composition comprising siloxane-chelated alkylaluminum cations; and Heating or aging the ionic aluminum oxane composition containing siloxane chelated alkyl aluminum cations to form an ionic alkyl aluminum oxane containing at least one decomposition product of the siloxane chelated cations in the ionic aluminum oxane composition modified with siloxane, or an unsupported alkyl aluminum oxane.

15. The method of claim 14, wherein, The multidentate chelating agent is a bidentate siloxane.

16. The method of claim 15, wherein, The bidentate siloxane is octamethyltrisiloxane.

17. A method for preparing an aluminoxane composition, comprising: Alkyl aluminum oxane compositions free of non-coordinated alkyl aluminum are formed by the following: Reaction of supported or unsupported alkylaluminoxanes with silanols to form alkylaluminoxane compositions comprising supported or unsupported alkylaluminoxanes containing monodentate silanoxy ligands, provided that the noncoordinated alkylaluminum content is based on a total Al content not exceeding 2 wt% Al.

18. The method of claim 17, wherein, The silanol is represented by the formula HO-SiR3, wherein each R is independently hydrogen, alkyl, alkenyl, aryl, or a group containing heteroatoms.

19. The method of claim 18, wherein, Each R is a methyl group.

20. A compound represented by formula (I): (I) in: R 1 R 2 R 3 R 4 R 5 R 6 and R 7 Each of them is independently a hydrogen, hydrocarbon, silyl, or a group containing heteroatoms.

21. The catalyst system of claim 20, wherein, Each R 1 R 2 R 3 R 4 R 5 R 6 and R 7 Each of them is independently hydrogen, alkyl, or alkenyl.

22. The catalyst system of claim 21, wherein, Each R 1 R 2 R 3 R 4 R 5 R 6 and R 7 Each of them is a methyl group.

23. A method for preparing an aluminoxane composition, comprising: Alkyl aluminum alkyl aluminum oxane compositions are formed by the following: The alkylaluminum alkyloxane composition is formed by reacting supported or solid alkylaluminum oxanes with dialkylaluminum silicon oxides as follows: a) Contact the supported or solid alkylaluminoxane with the dialkylaluminum silicon oxide represented by formula (II): R3SiOAlR2 (II) Where R is independently hydrogen, a hydrocarbon group, or a group containing a non-coordinated or weakly coordinated heteroatom; and b) Separation of noncoordinated alkyl aluminum from siloxane alkylated aluminum oxane compositions.

24. The composition of claim 23, wherein, Each R is a methyl group.

25. An anionic and cationic modified supported or unsupported alkylaluminoxane composition, wherein, Anionic modification is achieved by treating the supported or unsupported alkylaluminoxane with a compound containing at least one electron-withdrawing compound, and cationic modification is achieved by treating the supported or unsupported alkylaluminoxane with a chelated or monodentate siloxane compound, the modification being carried out in any order, followed optionally by heating the anionic and cationic modified supported or unsupported alkylaluminoxane.

26. The composition of claim 25, wherein, The active electron-withdrawing compound is (NH4)2SiF6, a chelated siloxane compound is used and it is octamethyltrisiloxane, and the monodentate siloxane compound is SiMe3OH or SiMe3OAlMe2, and the optional heating temperature is about 60°C to about 110°C.

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