Anion-modified aluminoxanes free of non-coordinating alkylaluminium and methods thereof

Abstract

The present disclosure relates to aluminoxane compositions having a substantially or completely non-detectable alkyl aluminum content, methods of of forming such aluminoxane compositions, catalyst systems having the aluminoxane compositions, and methods of of polymerizing olefins using catalyst systems having the aluminoxane compositions. In some embodiments, the present disclosure relates to an unsupported or supported MAO composition, process of forming MAO, catalyst system with MAO, and process of polymerizing olefins using catalyst system with MAO. In some embodiments, the method of making an unsupported or supported MAO having an undetectable or low free trihydrocarbyl aluminum includes introducing an electron withdrawing compound to the unsupported or supported MAO with an electron withdrawing compound to form an unsupported or supported MAO composition having an undetectable or low free trihydrocarbyl aluminum.

Description

[0001] Cross-references to related applications

[0002] This application claims the benefit and priority of U.S. Provisional Application No. 63 / 506543, filed June 6, 2023, the disclosure of which is incorporated herein by reference. Technical Field

[0003] This disclosure relates to aluminum oxane compositions having substantially undetectable or completely undetectable 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

[0004] Olefin polymerization catalysts have wide applications in industry. Therefore, there is great interest in finding new catalyst systems that can increase the commercial use of catalysts and produce polymers with improved performance. For monomers to polymerize into polyolefins, the catalyst needs to be activated to provide active sites on the catalyst and promote monomer polymerization. Activated methylaluminoxane (MAO), prepared from partially hydrolyzed trimethylaluminum (TMA), can effectively activate a catalyst used for olefin polymerization known as metallocene. MAO has become the industry's preferred aluminum co-catalyst (also known as an activator). It is commercially available in the form of a 10 to 30% by weight solution in an aromatic diluent (typically toluene).

[0005] Significant efforts have been devoted to improving the effectiveness of olefin polymerization catalyst systems based on or modified with methylaluminoxanes. For example, WO2009 / 029857 demonstrates the formation of dimethylaluminum cations (AlMe2) from MAO by treatment with Lewis bases such as 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., WO2000 / 011006 and Organometallics, 2000, Vol. 19, pp. 4684-4686; US9090720 demonstrates a metallocene compound with a dimethoxy leaving group, namely ethylene bisindenyl dimethoxyzirconium (EtInd2Zr(OMe)2), which abstracts AlMe2 from MAO. + This forms [EtInd2Zr(μ-OMe)2AlMe2] + The species is slowly alkylated to form the fully activated species [EtInd2Zr(μ-Me)2AlMe2]. + This strongly suggests that AlMe2 from MAO +Activation. The fully activated [EtInd2Zr(μ-Me)2AlMe2] + The species is similar to other MAO-activated metallocenes, such as [Cp2Zr(μ-Me)2AlMe2], which also form metallocene-dialkylaluminum cation species. + Or [Cp2Ti(μ-Me)2AlMe2] + Examples can be found in Babushkin and Brintzinger, J. Am. Chem. Soc., 2002, v. 124, pp. 12869-12873 and Sarzotti et al., J. Polymer Sci. A, 2007, v. 45, pp. 1677-1690 (which describe examples of activating zirconium catalyst precursors via MAO); see also Bryliakov, Talsi, and Bochmann, Organometallics, 2004, v. 23, pp. 149-152 (which describes activating titanocene catalyst precursors via MAO). Although the structure of MAO remains unclear, newly prepared activated MAO has shown evidence of coordinated TMA in 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 Methylaluminoxane”, in Kaminsky (ed.), Metalorg. Cat. for Synth. & Polym., Springer-Verlag, 1999, p. 105). It is believed that coordinated TMA exists in equilibrium with free TMA, because attempts to physically remove all free TMA result in the loss of both free and coordinated TMA, forming a more thermally stable MAO gel. This gel becomes less useful due to its insolubility, making it unsuitable for loading into supported finished catalysts primarily used for gas-phase and slurry-phase polymerization, or for solution polymerization. Route 1 uses Sinn's fresh MAO formula to illustrate this equilibrium, aiming to aid in understanding the gelation process.

[0006] Route 1

[0007]

[0008] Studies show that the coordinated TMA in MAO is actually used as AlMe2 for pre-catalyst ionization. +The source, while the free TMA in MAO in equilibrium with the coordinated TMA, is used as an alkylating agent, as shown in Route 2, where the MAO structure is represented by a circle because the (Al4O3Me6)4 unit is for clarity (Luo, Jain, and Harlan, INOR 1169, American Chemical Society Priestley Medalist Symposium in Honor of Tobin J. Marks, San Francisco, CA, April 5, 2017; Luo, et al., US Patents 8575284 (2013) and 9090720 (2015)):

[0009] Route 2

[0010]

[0011] Therefore, it is necessary to maintain a large amount of free TMA in the active MAO solution in order to stabilize the active MAO composition, such as stabilizing the MAO molecular structure capped by coordinated TMA, to reduce the chance of dimerization / oligomerization reactions that form a gel, which will become insoluble and reduce the number of active MAO molecules.

[0012] Nevertheless, post-metallocene catalysts containing polar ligands such as oxygen and / or nitrogen donors and confined geometry complex (CGC) catalysts (also known as monocyclopentadienyl (mono-Cp) catalysts) exhibit challenges when activated with conventional MAO, displaying low catalyst activity and short catalyst lifetime. Unbound by theory, it is believed that the poor activity and short catalyst lifetime are due to the presence of free TMA in the MAO, which can alkylate the procatalytic transition metal center bonded to heteroatoms (Zr center as an example in route 3), similar to the alkylation of metallocenes with two chloride-leaving groups in route 2.

[0013] Route 3

[0014] .

[0015] There is a need for improved MAO that can impart high activity and long catalyst lifetime to post-metallocene and / or CGC catalysts, as well as methods for preparing MAO, such as solutions or supported MAO containing sufficient coordinated TMA but with undetectable or low free TMA content.

[0016] References used in the disclosure statement (37 CFR 1.97(h)): US 2019 / 0127499; US 2009 / 0124486; US 6,667,272; US 2019 / 0153135; US 2013 / 0253155; US 2018 / 0142046; US 7,193,100; US 6,368,999; US 8,575,284. Invention Overview

[0018] This disclosure relates to active aluminum oxane compositions having undetectable or low free alkyl aluminum content, methods for forming such active aluminum oxane compositions, catalyst systems comprising such active aluminum oxane compositions, and methods for polymerizing olefins using catalyst systems comprising such active aluminum oxane compositions.

[0019] In some embodiments, the aluminoxane composition having undetectable or low free alkyl aluminum content is an electron-withdrawing group modified aluminoxane composition containing about 8.5 mol% or less of THF-extractable alkyl aluminum, based on the total aluminum content of the aluminoxane composition.

[0020] In some embodiments, a method for preparing an aluminum oxane composition having undetectable or low levels of free trialkylaluminum comprises introducing an electron-withdrawing compound containing at least one electron-withdrawing group into the aluminum oxane to form an electron-withdrawing group-modified aluminum oxane composition. The method includes introducing an oxygen source into the hydrocarbon aluminum compound at a temperature of about -60°C to about -5°C to form the aluminum oxane composition.

[0021] In some embodiments, the aluminum oxane composition having undetectable or low free trialkylaluminum content is a methylaluminoxane (MAO) composition formed by contacting an electron-withdrawing compound capable of reducing THF-extractable total trimethylaluminum (TMA) in unsupported or supported MAO compositions to 8.5 mol% or less, based on the total aluminum content of the MAO composition.

[0022] In some embodiments, the catalyst system comprises a precatalyst compound and a MAO composition having an undetectable or low free trialkylaluminum content, wherein the MAO composition having an undetectable or low free TMA content comprises MAO, an electron-withdrawing alkylaluminum compound, and about 8.5 mol% or less of THF-extractable total trialkylaluminum, based on the total aluminum content of the MAO composition.

[0023] In some embodiments, the method of forming the active MAO composition having undetectable or low free TMA content includes a method of in-situ conversion of THF-extractable TMA in unloaded or loaded MAO into AlMe2X using a compound containing at least one electron-withdrawing group X (i.e., a so-called electron-withdrawing compound), said AlMe2X compound being capable of acting as a TMA and free TMA balance blocker (a so-called TEB agent).

[0024] In some embodiments, the method of forming the active MAO composition having undetectable or low free TMA content includes: converting most or all of the THF extractable TMA in the MAO composition in situ into a TEB agent AlMe2X by contacting an electron-withdrawing compound containing at least one electron-withdrawing group X with an unloaded or loaded MAO composition, wherein X is a fluorine atom or a perfluoroaryloxy group.

[0025] In some embodiments, the aluminum oxane composition having undetectable or low free trialkylaluminum content comprises an aluminum oxane, a TEB agent AlR2X (where R is C1 to C2), and a TEB agent AlR2X. 10 The total aluminum content of the aluminoxane is based on the total aluminum content of the aluminoxane, and the two Rs may be the same or different. The aluminoxane contains about 2 wt% or less of Al in the form of free or dimeric trialkyl aluminum compounds AlR3.

[0026] In some embodiments, the catalyst system comprises a pre-catalyst compound and an aluminum oxane composition having an undetectable or low free trialkylaluminum content, wherein the aluminum oxane composition having an undetectable or low free trialkylaluminum content comprises an aluminum oxane, a TEB agent AlR2X (where R is C1 to C2), and a TEB agent AlR2X (where R is C1 to C2). 10 The aluminum oxane contains about 2 wt% or less of Al in the form of a free or dimerized alkyl aluminum compound AlR3, based on the total aluminum content of the aluminum oxane.

[0027] In some embodiments, the method of forming the supported or solid MAO composition having undetectable or low free TMA content includes a pre-formed AlR2X treatment and a free TMA removal process, such as a filtration or decanting step.

[0028] In some embodiments, the electron-withdrawing compound used to form the TEB agent contains at least one Si-F unit.

[0029] In some implementations, the method of polymerizing olefins includes the use of a catalyst system. Brief description of the attached figures

[0030] Figure 1This is a schematic diagram of ethylene absorption using a post-metallocene complex 6 finished catalyst with the activator of the present invention according to one embodiment.

[0031] Figure 2 This is a schematic diagram of ethylene absorption using a post-metallocene complex 6 finished catalyst with a conventional supported MAO activator according to one implementation scheme.

[0032] Figure 3A -B illustrates a scenario where less THF can extract TMA (THF) and more AlMe2, according to one embodiment. + The activator of the present invention (3A) and conventional MAO (4B) of (THF)2 and inert species SiMe4 and [(NHAlMe)3]2. 1 Both 1H NMR spectra were obtained with toluene solvent as a reference.

[0033] Figure 4A Figure B illustrates the effect of 30% commercially available MAO solution on KF treatment. 1 1H NMR spectra; where 4A) shows the upper solution phases after treatment with 2, 4, 7 and 10 mol% KF, respectively; and 4B) shows the final KF... + (F-MAO) - The inclusion phase (b) and the untreated solution MAO (a) used for comparison.

[0034] Figure 5 This is a graph showing the activity of solutions of three Group 3 post-metallocene complexes 36, 34, and 35 activated with the TMA-free MAO (TF-MAO) of the present invention for ethylene-butadiene copolymerization according to one embodiment, compared with conventional MAO solutions and perfluoroarylboron / Al solutions. i Comparison of Bu2H activator systems.

[0035] definition

[0036] "Olefin" (or "olefin") is a straight-chain, branched, or cyclic compound of carbon and hydrogen having at least one double bond. 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 a polymer or copolymer is in a polymerized form of said olefin. For example, when a copolymer is said to have a "ethylene" content of 35 wt% to 55 wt%, it should be understood that the chain unit in said copolymer is derived from ethylene in a polymerization reaction, and the amount of said derived unit is 35 wt% to 55 wt%, based on the weight of said copolymer. "Polymer" has two or more identical or different chain units. "Homopolymer" is a polymer having identical chain units. "Copolymer" is a polymer having two or more different chain units. "Terpolymer" is a polymer having three different chain units. Therefore, the definition of copolymer used herein includes terpolymers, etc. "Different" as used to refer to chain units means that the chain units differ from each other by at least one atom or are isomers. "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.

[0037] Ethylene should be considered an α-olefin.

[0038] The term "metallocene" refers to a catalyst compound containing two substituted or unsubstituted cyclopentadienyl moieties (bridged or unbridged together), wherein when the metal center is electrically neutral, the two cyclopentadienyl moieties are directly bonded to a transition 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 transition metal center having at least one leaving group and an optional weak donor. The term "semi-metallocene" refers to a catalyst compound containing one substituted or unsubstituted cyclopentadienyl moieties and a heteroatom-containing ligand (bridged or unbridged together), wherein when the metal center is electrically neutral, the cyclopentadienyl moieties and at least one heteroatom on the heteroatom-containing ligand are directly bonded to a transition metal center having at least two leaving groups; or when the metal center is positively charged, the cyclopentadienyl moieties and at least one heteroatom on the heteroatom-containing ligand are directly bonded to a transition metal center having at least one leaving group and an optional weak donor. The term "semi-metallocene" includes so-called "confined geometry catalysts" (CGC) compounds. The term "post-metallocene" refers to catalyst compounds that do not contain a cyclopentadienyl moiety but contain ligands with heteroatoms such as N, O, P, B, S, etc., which are directly bonded to a catalyst metal center having at least two leaving groups (when the metal center is electrically neutral) or having at least one leaving group and an optional weak donor (when the metal center is positively charged).

[0039] The terms "aluminoxane" and "aluminoxane" are used interchangeably, referring to trialkylaluminum compounds such as C1-C2. 10 Compositions prepared by reacting trialkylaluminum or mixtures thereof with an oxygen source, which may or may not contain coordinated and free trialkylaluminum.

[0040] The term "MAO" can refer to a MAO composition containing MAO, coordinated TMA, free TMA, and gels such as those in Route 1, but sometimes it can refer only to the MAO main molecule, such as (Al4O3Me6)4, without containing coordinated TMA and free TMA.

[0041] "Aluminum alkylate" or "alkylaluminum" refers to a compound containing at least one Al-alkyl group (Al-R, where R is C1-C2). 12 Compounds with a hydrocarbon group (H2O) unit can be coordinated or uncoordinated to the main aluminum oxane structure. If the H2O unit is not coordinated to the main aluminum oxane structure, such compounds are also called uncoordinated aluminum alkylates or free aluminum alkylates, and they can coordinate with each other to form dimers, such as the AlMe3 dimer in route 1.

[0042] "Non-coordinated alkylaluminum" or "free alkylaluminum" has the same meaning, referring to an aluminum compound having at least one alkyl group such as Me, Et, iBu, or Oct, which is in monomeric or dimer form and is not chemically bonded to an aluminoxane structure. Although free alkylaluminum can exchange with coordinated alkylaluminum on an aluminoxane structure to become coordinated alkylaluminum, under the same conditions, the concentration of free alkylaluminum is maintained from the regeneration of the initially coordinated alkylaluminum.

[0043] The terms aluminumoxane, aluminumoxane, alkylaluminoxane, and alkylaluminoxane are used interchangeably.

[0044] Sometimes, only alkylaluminum is used to represent free alkylaluminum; for example, TMA refers to free TMA.

[0045] "Free from" or "does not contain" means that it is undetectable by existing analytical methods such as NMR spectroscopy or conventional wet titration. "Low content" means 2 wt% or 2 mol% or less based on the total amount of the same element in the system. For example, low free TMA content means that the Al weight (or moles) of free TMA contained is 2 wt% (or mol%) or less, based on the total Al weight (or moles) of the MAO composition. In some embodiments, "free from" or "does not contain" includes the "low content" description. For example, a TMA-free MAO may specify that the Al weight or moles of free TMA contained is 2 wt% or 2 mol% or less, based on the total Al content in the MAO.

[0046] The term "undetectable" refers to a substance whose quantitative result obtained by analytical methods (such as nuclear magnetic resonance measurement or chemical titration) is zero or close to zero.

[0047] The terms “anionic modified alkylaluminoxane,” “anionic modified aluminumoxane,” “electron-withdrawing group modified alkylaluminoxane,” “electron-withdrawing group modified aluminumoxane,” and “F-MAO” have similar meanings and can be used interchangeably.

[0048] The term “electron-withdrawing group” (EWG) can refer to an atom or group X that is capable of withdrawing electrons from an atom directly bonded to it, as defined in organic chemistry. In this paper, the definition of EWG can be more specific: if any Al-X bond formed at an Al site on a MAO coordinated to a coordinating TMA is stronger than the Al-C bond (both 3-center 2-electron bonds) between the same Al site on the MAO and the shared CH3 group of the coordinating TMA, then such an X is called an EWG; for example, X is -F or -OC6F5 (see route 5).

[0049] The term “electron-withdrawing compound” (EWC) can refer to a compound containing at least one electron-withdrawing group X, which can react with alkylaluminum compounds to form AlR2X compound, where R = C1-C8 hydrocarbon group. The AlR2X compound can completely or partially block the balance of coordinated TMA and free TMA in supported or unsupported (solution or solid) MAO compositions, and is a so-called coordination and free TMA balance blocker or TEB agent (see below for details). For example, (NH4)2SiF6, SiF4, HOC6F5, etc. can be used to react with AlMe3, AlEt3, AlOct3 to form AlMe2F, AlEt2F, AlOct2F, AlMe2(OC6F5), AlEt2(OC6F5), and AlOct2(OC6F5), respectively. They can be formed either in situ or ex-situ in the MAO composition and then added to the MAO composition. KF, NaF, K(OC6F5), Na(OC6F5), etc. can be used to react with AlMe2Cl and AlMe2Br to form AlMe2F and AlMe2(OC6F5), respectively. They can then be separated from byproduct metal salts such as KCl or NaCl and then added to the aluminoxane composition.

[0050] The term "coordination and free TMA equilibrium inhibitor" (TEB) can refer to a compound of the formula AlR2X, where R = C1-C8 hydrocarbon group and X is an electron-withdrawing group as defined above. Such compounds can substitute for coordinated TMA in MAO compositions, thereby eliminating or limiting the conversion of coordinated TMA to free TMA, while retaining AlR2 as an active site. + The ability (e.g., route 4). The TEB can be formed in situ or pre-formed by contacting the so-called electron-withdrawing compound defined above with the AlR3 component in the aluminum oxane composition or pure AlR3 or AlR2Y compound, wherein Y is a non-fluorinated halogen, such as Cl or Br.

[0051] Unless otherwise specified, the term "C" n "" refers to one or more hydrocarbons with n carbon atoms per molecule, where n is a positive integer.

[0052] 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..." 50Alkyl groups are alkyl groups containing a total number of carbon atoms ranging from 1 to 50.

[0053] The terms “group”, “free radical” and “substituent” are used interchangeably.

[0054] The terms "hydrocarbon radical," "hydrocarbon group," or "hydrocarbon" are used interchangeably and are defined as groups consisting only of hydrogen and carbon atoms. Hydrocarbon groups can be C1-C. 100 Free radicals can be straight-chain, branched, or cyclic, and when cyclic, they can be aromatic or non-aromatic. Examples of such free radicals 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.

[0055] Unless otherwise specified (e.g., regarding the definition of "substituted hydrocarbon group", "substituted aromatic compound", etc.), the term "substituted" means that at least one hydrogen atom has been substituted by at least one non-hydrogen group (e.g., hydrocarbon group, heteroatom or heteroatom-containing group such as halogen (e.g. Br, Cl, F or I) or at least one functional group such as -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*3, -GeR*3, -SnR*3, -PbR*3, wherein each R* is independently a hydrocarbon group or a halocarbon group, and two or more R* may be linked together to form a substituted or unsubstituted, fully saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure), or wherein at least one heteroatom has been inserted into the hydrocarbon ring.

[0056] The term "substituted hydrocarbon group" refers to a hydrocarbon radical in which at least one hydrogen atom is replaced by at least one heteroatom (e.g., a halogen such as Br, Cl, F, or I) or a heteroatom-containing group (e.g., a functional group such as -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*3, -GeR*3, -SnR*3, -PbR*3, wherein each R* is independently a hydrocarbon group or a halocarbon group, and two or more R* can be linked together to form a substituted or unsubstituted fully saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), or wherein at least one heteroatom is inserted into the hydrocarbon ring.

[0057] The term “aryl” or “aryl group” refers to an aromatic ring and its substituted variants, such as phenyl, 2-methylphenyl, xylyl, and 4-bromoxylyl. Similarly, “heteroaryl” refers to an aryl group in which one (or two or three) ring carbon atoms have been replaced by a heteroatom such as N, O, or S. As used herein, the term “aromatic” also refers to a pseudoaromatic heterocycle, which is a heterocyclic substituent with properties and structure similar to aromatic heterocyclic ligands (almost planar), but is not aromatic by definition. Likewise, the term “aromatic” also refers to substituted aromatics.

[0058] Similarly, the term "substituted aromatic" 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.

[0059] "Substituted phenolic radical" is a phenolic radical group in which at least one, two, three, four, or five hydrogen atoms at positions 2, 3, 4, 5, and / or 6 are replaced by at least one non-hydrogen group such as a hydrocarbon group, a heteroatom, or a heteroatom-containing group such as a halogen (e.g., Br, Cl, F, or I) or at least one functional group such as -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*3, -GeR*3, -SnR*3, -PbR*3, etc., wherein each R* is independently hydrogen, a hydrocarbon group, or a carboxylated group, and two or more R* can be linked together to form a substituted or unsubstituted fully saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure, wherein position 1 is the phenolic radical 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, in the catalyst compounds described herein, the "substituted phenol group" is represented by the following formula:

[0060]

[0061] Where R 18 It is hydrogen, C1-C 40 Hydrocarbon groups (e.g., C1-C) 40 Alkyl) or C1-C 40 Substituted hydrocarbon groups, heteroatoms, or heteroatom-containing groups, E 17 Is it oxygen, sulfur, or NR? 17 And R 17 R 19 R 20 and R 21 Each of them is independently selected from hydrogen, C1-C 40 Hydrocarbon groups (e.g., C1-C)40 Alkyl) or C1-C 40 Substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 18 R 19 R 20 and R 21 Two or more of them are connected together to form C4-C 62 A cyclic or polycyclic ring structure, or a combination thereof, and the wavy line shows the positions where the substituted phenolic radical group forms bonds with the remainder of the catalyst compound.

[0062] "Alkyl-substituted phenol group" is a phenol group in which at least one, two, three, four, or five hydrogen atoms at positions 2, 3, 4, 5, and / or 6 are replaced by at least one alkyl group such as C1-C6. 40 Alkyl or C2-C 20 Alkyl or C3-C 12 Alkyl groups, such as methyl, ethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, adamantyl, etc. (including their substituted analogues).

[0063] "Aryl-substituted phenol group" is a phenol group in which at least one, two, three, four, or five hydrogen atoms at positions 2, 3, 4, 5, and / or 6 are replaced by at least one aryl group, such as C1-C6. 40 aryl group or C2-C 20 aryl group or C3-C 12 Aryl groups, such as phenyl, 4-fluorophenyl, 2-methylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-ethylphenyl, naphthyl, etc. (including their substituted analogs), are substituted.

[0064] The term "ring atom" refers to an atom that is part of a ring structure. According to this definition, benzyl has six ring atoms and tetrahydrofuran has five ring atoms.

[0065] A heterocycle is a ring with a heteroatom in its ring structure, as opposed to a "heteroatom-substituted ring" in which hydrogen atoms on the ring atoms are replaced by heteroatoms. For example, tetrahydrofuran is a heterocycle, while 4-N,N-dimethylaminophenyl is a heteroatom-substituted ring. A substituted heterocycle is a heterocycle in which one or more hydrogen groups are replaced by a hydrocarbon group, a substituted hydrocarbon group, a heteroatom, or a heteroatom-containing group.

[0066] A substituted hydrocarbon ring is a ring consisting of carbon and hydrogen atoms, wherein one or more hydrogen groups are replaced by hydrocarbon groups, substituted hydrocarbon groups, heteroatoms, or heteroatom-containing groups.

[0067] For the purposes of this disclosure, with respect to catalyst compounds (e.g., substituted di(phenol) catalyst compounds), the term "substituted" means that the hydrogen group has been replaced by a hydrocarbon group, a heteroatom or a heteroatom-containing group such as a halogen (e.g., Br, Cl, F or I) or at least one functional group such as -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*3, -GeR*3, -SnR*3, -PbR*3, etc., wherein each R* is independently a hydrogen, hydrocarbon or halocarbon radical, and two or more R* may be linked together to form a substituted or unsubstituted fully saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure, or wherein at least one heteroatom has been inserted into the hydrocarbon ring.

[0068] A tertiary hydrocarbon group has three carbon atoms bonded to three other carbon atoms. When the hydrocarbon group is an alkyl group, the tertiary hydrocarbon group is also called a tertiary alkyl group. Examples of tertiary hydrocarbon groups include tert-butyl, 2-methylbut-2-yl, 2-methylhex-2-yl, 2-phenylprop-2-yl, 2-cyclohexylprop-2-yl, 1-methylcyclohexyl, 1-adamantyl, bicyclo[2.2.1]heptane-1-yl, etc. Tertiary hydrocarbon groups can be illustrated by the following diagram:

[0069] ,

[0070] Where R A R B and R C The groups are either hydrocarbon groups or substituted hydrocarbon groups, which may optionally be bonded to each other, and the wavy lines indicate the positions where the tertiary hydrocarbon groups form bonds with other groups.

[0071] 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]nonane-1-yl, bicyclo[2.2.1]heptane-1-yl, bicyclo[2.3.3]hexane-1-yl, bicyclo[1.1.1]pentane-1-yl, bicyclo[2.2.2]octane-1-yl, etc. Cyclic tertiary hydrocarbon groups can be illustrated by the diagram of formula (B):

[0072] (B),

[0073] Where R A It is a hydrocarbon group or a substituted hydrocarbon group, each RD Independently, it is a hydrogen or a hydrocarbon group or a substituted hydrocarbon group, w is an integer from 1 to about 30, and R A and one or more R D and / or two or more R D They can optionally bond to each other to form another ring.

[0074] 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.

[0075] The terms "alkyl radical" and "alkyl" are used interchangeably throughout this disclosure. For the purposes of this disclosure, "alkyl radical" is defined as C1-C 100 Alkyl groups, which can be straight-chain, branched, or cyclic. Examples of such free radicals 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 radical is a radical in which at least one hydrogen atom of the alkyl radical has been replaced by at least one non-hydrogen group such as a hydrocarbon group, a heteroatom or a heteroatom-containing group such as a halogen (e.g., Br, Cl, F or I) or at least one functional group such as -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*3, -GeR*3, -SnR*3, -PbR*3, etc., wherein each R* is independently a hydrogen, hydrocarbon or halocarbon radical, and two or more R* may be linked together to form a substituted or unsubstituted fully saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure, or wherein at least one heteroatom has been inserted into the hydrocarbon ring.

[0076] If isomers of the alkyl, alkenyl, ol, or aryl mentioned exist (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl), then mentioning the alkyl, alkenyl, ol, or aryl without specifying a particular isomer (e.g., butyl) clearly discloses all isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl).

[0077] In this document, Mn is the number-average molecular weight, Mw is the weight-average molecular weight, Mz is the z-average molecular weight, wt% is weight percent, and mol% is mole percent. 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 ).

[0078] The following abbreviations may be used in this document: Me is methyl, Et is ethyl, MAO is methylaluminoxane, TMS is trimethylsilyl, Oct is octyl, Bu is butyl, iPr is isopropyl, Bn is benzyl (i.e., CH2Ph), THF (also known as thf) is tetrahydrofuran, RT is room temperature (unless otherwise specified, 23°C), tol is toluene, Cp is cyclopentadienyl, NMR is nuclear magnetic resonance, and TMA is trimethylaluminum.

[0079] A “catalyst system” is a combination of at least one pre-catalyst compound, an activator, an optional co-activator, and an optional support material. When “catalyst system” is used to describe such a pair before activation, it refers to the unactivated catalyst complex (pre-catalyst) and the activator and optional co-activator. When it is used to describe such a pair after activation, it refers to the activated complex and the activator or other charge-balanced structural portion. The catalyst compound can be neutral (as in the pre-catalyst) or a charged substance with counterions (as in the activated catalyst system). For the purposes of this disclosure and its claims, when the catalyst system is described as comprising a neutral, stable form of the components, those skilled in the art will fully understand that the ionic form of the components is the form in which they react with monomers to produce a polymer. A polymerization catalyst system is a catalyst system capable of polymerizing monomers into polymers. Furthermore, catalyst compounds and activators (including activators combined with a support) represented by the formulas herein include both neutral and ionic forms of the catalyst compounds and activators.

[0080] In the description herein, a catalyst may be described as a catalyst precursor, a precatalyst compound, a catalyst compound, or a transition metal compound, and these terms are used interchangeably.

[0081] 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, aryl, alkenyl, thiol, carboxyl, amino, benzyl, hydride, amidine, amide, and phenyl groups. Two anionic donors can combine to form a dianionic group.

[0082] 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, alenes, and carbenes. Lewis bases can link together to form bidentate or tripentate Lewis bases.

[0083] For the purposes of this disclosure and its claims, phenolic donors may include Ph-O-, Ph-S-, and Ph-N(R)-. ^ )- group, where R^ is hydrogen, C1-C 40 Hydrocarbon group, C1-C 40 The substituted hydrocarbon group, heteroatom or heteroatom-containing group, and Ph is optionally a substituted phenyl group.

[0084] Detailed description

[0085] This disclosure relates to aluminum oxanes, methods for forming aluminum oxanes, catalyst systems having aluminum oxanes, and methods for polymerizing olefins using catalyst systems having aluminum oxanes.

[0086] In some embodiments, the method for preparing electron-withdrawing group modified aluminoxanes includes introducing electron-withdrawing groups into the aluminoxane to form the aluminoxane.

[0087] In some embodiments, a method for preparing low-trialkylaluminum aluminum oxanes includes introducing an electron-withdrawing compound into the aluminum oxane to form an aluminum oxane modified with strongly electron-withdrawing atoms or groups. The method includes introducing an oxygen source into a hydrocarbon-based aluminum compound at a temperature of about -60°C to about 0°C to form the aluminum oxane.

[0088] In some embodiments, the electron-withdrawing group modified aluminoxane comprises an aluminoxane, an electron-withdrawing group-containing hydrocarbon aluminum compound, and about 2 wt% or less Al from a free or dimer hydrocarbon aluminum compound, based on the total aluminum content of the aluminoxane composition.

[0089] In some embodiments, the catalyst system comprises a catalyst compound and an electron-withdrawing group-modified aluminoxane. The electron-withdrawing group-modified aluminoxane comprises an aluminoxane, an electron-withdrawing group-containing hydrocarbon aluminum compound, and about 2 wt% or less Al from a free or dimer hydrocarbon aluminum compound, based on the total aluminum content of the aluminoxane composition.

[0090] In some implementations, the method of polymerizing olefins includes the use of a catalyst system.

[0091] It has been found that when aluminoxanes are treated with compounds containing electron-withdrawing groups, electron-withdrawing group-modified aluminum species can be formed and coordinated with the aluminoxane, thereby forming more reactive aluminum species of the aluminoxane. These aluminum species have been found to improve catalyst activity and catalyst lifetime. Without being bound by theory, it is believed that the presence of electron-withdrawing group-containing substances in the treated aluminoxane provides more aluminum cations that associate with the aluminoxane. Furthermore, if the ratio of strong electron-withdrawing atoms to hydrocarbon aluminum compounds is approximately 1:1, the amount of free hydrocarbon aluminum compounds (e.g., trimethylaluminum) present in the catalyst system can be reduced or eliminated, which reduces side reactions between oxygen-containing and / or nitrogen-containing catalyst compounds and aluminum in the catalyst system. For example, the presence of strong electron-withdrawing atoms (e.g., in the form of Al(CH3)2F) reduces the formation of stable hydrocarbon aluminum dimers (e.g., dimer Al(CH3)3) that would form in the absence of strong electron-withdrawing atoms. Instead, the presence of strong electron-withdrawing atoms forms more reactive aluminum cations.

[0092] In addition, the presence of electron-withdrawing compounds in the treated aluminoxane also reduces or eliminates side reactions of oxygen-containing catalyst compounds and / or nitrogen-containing catalyst compounds, promoting improved catalyst activity and lifetime.

[0093] Furthermore, during the formation of aluminoxanes, alkyl aluminum compounds with electron-withdrawing atoms can be formed in situ. The in-situ formation of alkyl aluminum compounds with electron-withdrawing atoms offers several advantages, such as eliminating the need to purchase such compounds, which, even if available, are very expensive (e.g., there is no commercial method for producing AlF(CH3)2). Additionally, electron-withdrawing compounds can provide multiple electron-withdrawing atoms from multiple available aluminum atoms (e.g., (NH4)2SiF6), promoting atom economy. Many such electron-withdrawing compounds are commercially available and quite inexpensive. Using such electron-withdrawing compounds improves the cost and atom economy of forming a monolithic catalyst system, which in turn improves the cost and atom economy of polymers produced from such catalyst systems.

[0094] Furthermore, the aluminum oxanes of this disclosure can be supported on one or more support particles (e.g., silica) or unsupported. While fluorinated supports are known, it has been found that fluorine atoms are not completely converted into aluminum-fluorine type aluminum oxanes. Instead, calcination of fluorinated supports generates significant amounts of HF and SiF4 gases, which have proven difficult to control. In contrast, due to the very strong bond strength between aluminum and fluorine atoms, the aluminum oxanes and methods of this disclosure do not form HF and / or SiF4 gases.

[0095] In some embodiments, this disclosure relates to TMA-free active MAO compositions, methods for forming such MAO compositions, catalyst systems having TMA-free active MAO, and methods for polymerizing olefins using catalyst systems having TMA-free active MAO, wherein TMA-free MAO refers to MAO with zero or near-zero free TMA content, while being able to provide AlMe2. + The active sites of MAO can be maintained or increased through treatment with so-called coordination and free TMA balance blockers (TEB agents). Unlike the physical removal of free TMA from MAO that leads to activity loss, TMA-free active MAO compositions with maintained or increased activity become possible, unbound from theory, in which fluorinated silica containing Si-F units or electron-withdrawing compounds (e.g., (NH4)2SiF6) can convert free TMA in MAO into AlMe2F, which then replaces the coordinated TMA in MAO to form new active sites. This not only disrupts the balance between coordinated and free TMA but also releases more AlMe2F. + Used for pre-catalyst ionization, and to reduce ion pair interactions due to the electron-withdrawing effect of F atoms to increase the activity of individual active molecules (Route 4):

[0096] Route 4

[0097] .

[0098] Unbound by theory, replacing the coordinated TMA with AlMe₂F transforms the equilibrium of Route 1 (Route 5a) into Route 5b, effectively disrupting the balance between free and coordinated TMA. This is likely due to the presence of strongly electron-withdrawing F atoms, making it energy-infeasible to break one strong Al-F bond and one weak Al-Me bond to form two weak Al-Me bonds (Route 5b). Therefore, by matching the total TMA (both free and coordinated TMA) in MAO with the Si-F unit, a TMA-free system can be obtained.

[0099] Route 5

[0100]

[0101] In some embodiments, the method for preparing TMA-free MAO includes treating MAO in solution or on a loaded form with an electron-withdrawing compound capable of converting total TMA (free TMA and coordinated TMA) into the major derivative AlMe2F and optional minor derivatives nonfluorinated inert aluminum alkylates (depending on the structure of the electron-withdrawing compound used).

[0102] In some embodiments, a method for preparing a TMA-free MAO composition in solution or supported form includes introducing an electron-withdrawing compound containing at least one strongly electron-withdrawing atom or group X capable of converting free TMA into AlMe2X into a solution or supported MAO composition containing free TMA and coordinated TMA, to form a modified MAO composition having undetectable or low free TMA content. The method includes introducing an oxygen source, optionally in the support, into a hydrocarbon-based aluminum compound at a temperature of about -60°C to about 0°C prior to the fluorination treatment to form a conventional MAO composition.

[0103] In some embodiments, the TMA-free MAO composition comprises an electron-withdrawing group modified MAO in solution or loaded form, having about 8.5 mol% or less of a THF-extractable trialkylaluminate compound based on the total aluminum content of the MAO.

[0104] In some embodiments, the catalyst system comprises a catalyst compound and a TMA-free MAO composition in solution or supported form, wherein the TMA-free MAO composition comprises an electron-withdrawing group modified MAO in solution or supported form having about 8.5 mol% or less of a THF-extractable trialkylaluminate compound based on the total aluminum content of the MAO.

[0105] In some embodiments, the method for preparing the TMA-free supported MAO composition includes treating the supported MAO with an electron-withdrawing compound and trialkylaluminum and then filtering to remove excess free TMA.

[0106] In some embodiments, the method for preparing the TMA-free supported MAO composition includes adjusting the reactive fluorine atoms on the support to match the total TMA in the MAO subsequently loaded onto the support before MAO loading, and treating the support with an electron-withdrawing compound to obtain the TMA-free supported MAO composition.

[0107] In some implementations, the method of polymerizing olefins includes the use of a catalyst system.

[0108] It has been found that when MAO is treated with electron-withdrawing compounds, electron-withdrawing group-modified alkylaluminum species can form and coordinate with the MAO, thereby forming more reactive aluminum species of the MAO, which has been found to improve catalyst activity and catalyst lifetime. Without being bound by theory, it is believed that the presence of electron-withdrawing groups in the treated MAO provides more aluminum cations that associate with the MAO, as shown in route 4. Furthermore, if the ratio of strong electron-withdrawing atoms or groups to alkylaluminum compounds is approximately 1:1, the amount of free trialkylaluminum compounds (such as trimethylaluminum) present in the catalyst system can be reduced or eliminated, which thus reduces the decomposition reactions of oxygen-containing and / or nitrogen-containing catalyst compounds with oxygen- or nitrogen-reactive trialkylaluminum in the catalyst system. For example, the presence of fluorine atoms transforms the most reactive primary trialkylaluminum (e.g., the dimer form of AlMe3) into the less reactive secondary dialkylaluminum (e.g., in the form of Al(CH3)2F), thereby reducing or eliminating the formation of primary trialkylaluminum, which is a result of the equilibrium reaction of coordinated AlMe2F in the MAO composition shown in Route 5. Otherwise, in the absence of fluorine atoms, primary trialkylaluminum would form due to the equilibrium reaction of coordinated TMA in conventional MAO, as shown in Route 5. The presence of fluorine atoms instead leads to the formation of more aluminum cations and more reactive ion pairs due to weaker ion-pair interactions, as shown in Route 4.

[0109] In addition, the presence of fluorine in treated MAO also reduces or eliminates the possibility of free TMA forming in the balance between free TMA and coordinated TMA in conventional MAO, thereby reducing or eliminating side reactions of oxygen-containing catalyst compounds and / or nitrogen-containing catalyst compounds, and promoting improved catalyst activity and lifetime.

[0110] In addition to the in-situ formation of primary aluminum alkylates (TMA) from the reaction of TMA in the MAO composition with electron-withdrawing compounds to convert primary aluminum alkylates (TMA) into secondary aluminum alkylates (AlMe2F), secondary aluminum alkylates such as AlMe2F can also be formed ex-situ and added to the supported MAO composition, followed by free TMA removal (e.g., filtration and washing). However, since free TMA is difficult to remove from solution systems, adding secondary aluminum alkylates such as AlMe2F to solution MAO is less preferred.

[0111] Furthermore, the MAO of this disclosure can be supported or unsupported using one or more support particles (e.g., silica). While fluorinated supports are known, it has been found that support fluorination processes, such as those described in WO 2000 / 12565, generate HF and SiF4 gases that corrode equipment, and that accurate fluorine loading is difficult to achieve due to uncontrollable F loss. In contrast, the MAO and method of this disclosure do not form HF and / or SiF4 gases due to the very strong bond strength between aluminum and strong electron-withdrawing atoms or groups, thus allowing for more precise control of fluorine loading.

[0112] Unsupported aluminum oxanes and supported aluminum oxanes

[0113] Aluminoxanes are oligomers containing either —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 inert MAO gel shown in Route 1. Examples of useful aluminoxanes include methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, triethylaluminoxane, triisobutylaluminoxane, tetraethyldialuminoxane, and diisobutylaluminoxane.

[0114] Unsupported MAO can refer to solution MAO, such as commercially available MAO solution products manufactured by WR Grace, Tosoh, or Nouryon, or solid MAO, such as solid MAO manufactured by Tosoh. Unsupported solid MAO can be prepared by removing the solvent from solution MAO products and using different solid-forming methods such as spray drying to form controlled particle sizes.

[0115] Various methods exist for preparing and modifying MAO, such as those described in U.S. Patent Nos. 4,542,199 and Chen and Marks, 100 Chem. Rev. 1391 (2000). MAO can also be modified for various purposes, such as increasing activity or solubility. Examples of useful MAOs include MAOs 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), higher alkyl-modified MAOs (e.g., Nouryon MMAO), carbocation-modified MAOs (US9090720), dialkylaluminum cationic precursor-modified MAOs (US 8575284), halogen-modified MAOs (US 7355058), etc.

[0116] Active MAO is formed by the contact of a large excess of TMA with an oxygen source (such as water, water coordinated with metal salts, CO2, methacrylic acid, benzoic acid, or other reactive oxygen-containing organic compounds) under suitable reaction conditions.

[0117] The active MAO disclosed herein is commercially available or can be synthesized. The active MAO disclosed herein can be prepared in situ by contacting a hydrocarbon aluminum compound with an oxygen source (e.g., TMA and water) in an aliphatic or aromatic diluent at a temperature less than 0°C to −60°C, for example −10°C to −50°C, for example −15°C to −30°C.

[0118] 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, solution-type MAO can be added to a solid support or a support slurry, or vice versa, and then optionally heated to form the supported MAO. The supported MAO of this disclosure can also be prepared in situ by contacting a hydrocarbon-based aluminum compound with an oxygen source supported on a support. For example, with optional cooling, water in the form of a slurry in an aliphatic or aromatic diluent or in solid form, preloaded in a carrier material (e.g., silica), can be added to a TMA solution cooled to a temperature of less than 0°C to −60°C, for example −10°C to −50°C, for example −15°C to −30°C, and then heated, as described in US11,161,922; or a non-hydrolyzable organic oxygen-containing compound can be mixed with TMA at a temperature of less than 0°C to −60°C, for example −10°C to −50°C, for example −15°C to −30°C to form a pre-MAO composition, and then the carrier (e.g., silica) is mixed and then heated to obtain a supported MAO, as described in US11,021,552.

[0119] Regarding solution-loaded MAO, a suitable diluent for forming a support slurry, such as a silica slurry, is capable of dissolving MAO to ensure good MAO distribution within the pores of the support; for example, diluents such as toluene, benzene, or xylene. Regarding in-situ loaded MAO, suitable diluents are reactants such as the hydrocarbon-based aluminum (e.g., TMA), the non-hydrolyzable organic oxygen-containing compounds, and derivatives of the two reagents, in which at least partial soluble material is present and which is liquid at the reaction temperature. A non-limiting exemplary diluent is: Formula C n H (2n+2) Noncyclic alkanes, where n = 4-30, such as isobutene, butane, isopentane, hexane, n-heptane, octane, nonane, decane, etc.; Formula C n H 2n-2Cycloalkanes, where n = 5-30, such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, etc.; and mixtures thereof. Suitable aromatic diluents may include toluene, benzene, or xylene.

[0120] Hydrocarbon aluminum compounds for MAO and modified MAO

[0121] Active aluminum oxane compositions (e.g., MAO) can be formed using only trimethylaluminum (TMA), but other alkylaluminum compounds can be used to modify MAO. The alkylaluminum compound used for aluminum oxane modification can be an alkylaluminum compound, such as a trialkylaluminum compound. For example, the alkyl substituent can be an alkyl group with up to 10 carbon atoms, such as octyl, isobutyl, ethyl, or methyl. Therefore, suitable alkylaluminum 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 alkylaluminum compound is trimethylaluminum and tri-n-octylaluminum. In some embodiments, the alkylaluminum compound is represented by the formula R3Al, where each R is independently a alkyl group containing 1-30 carbon atoms.

[0122] In some embodiments, the alkyl aluminum compound is one or more of a trialkyl aluminum mixture, such as dimethyl ethyl aluminum or methyl diethyl aluminum from a mixture of AlMe3 and AlEt3, diethyl isobutyl aluminum or ethyl diisobutyl aluminum from a mixture of AlEt3 and AliBu3, etc.

[0123] oxygen source

[0124] A suitable oxygen source is 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 hydroxyl or carbonyl groups, such as alcohols, CO or CO2, acetone, or carboxylic acids. In at least one embodiment of this disclosure, the oxygen source is one or more of carbon dioxide, carboxylic acids, ketones, aldehydes, esters, acid anhydrides, alcohols, or combinations thereof.

[0125] 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.

[0126] In at least one embodiment of this disclosure, the oxygen source includes 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 dimethylaluminum methyl oxyoxide, dimethylaluminum ethoxide, dimethylaluminum isopropoxide, dimethylaluminum n-butoxide, dimethylaluminum isobutoxide, pentamethylaluminum tert-butoxide, tetramethylaluminum ditert-butoxide, pentamethylaluminum isopropoxide, tetramethylaluminum diisopropoxide, or mixtures of the listed compounds, etc.

[0127] The initial feed molar ratio Al:O (where O is the active oxygen in the active oxygen-containing compound) 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, for example, from about 1:1 to about 10:1, or from about 10:1 to about 60:1, for example, from about 30:1 to about 60:1. If an undesirable excess of one or more alkyl aluminum compounds is present, it (they) can be removed, for example, by filtration and then washing with an aliphatic diluent and / or treatment with one or more fluorine compounds disclosed herein.

[0128] In some implementations, the oxygen source is one or more of carbon dioxide, carboxylic acid, ester, acid anhydride, alcohol, or combinations thereof.

[0129] In some embodiments, the oxygen source is one or more of carbon dioxide, carboxylic acids, esters, acid anhydrides, and alcohols, or combinations thereof, optionally containing water.

[0130] 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.

[0131] In some implementations, the oxygen source is methacrylic acid.

[0132] In at least one embodiment of this disclosure, the oxygen source is a hydrocarbon boronoxane as described in Welborn’s US5,001,244.

[0133] Electron-withdrawing compounds and methods for introducing electron-withdrawing compounds into aluminoxanes

[0134] TMA can react with hydrolytic compounds such as alcohol ROH to rapidly form AlMe.(3-n) (OR) n (n≤3), where n and the position of OR depend on the reactivity, steric hindrance, and reaction conditions of the ROH. Small R groups such as MeOH, EtOH, and t BuOH is a MAO poison because it is not bound by theory; the small R group will transform both free TMA and coordinated TMA to form a very stable oxygen bridge structure, and the RO- group is a strong electron-donating group, which makes the MAO anion unstable (route 6).

[0135] Route 6

[0136] .

[0137] Stericly hindered alcohols, such as 3,5-di-tert-butyl-4-hydroxytoluene (BHT), form terminal OR groups, but for systems containing almost no TMA, a large excess may be required, which is not theoretically constrained due to the equilibrium in route 7:

[0138] Route 7

[0139]

[0140] For example, Ijpeij et al. (US7,956,140) used a BHT:Al ratio of 0.5:(1-2) for MAO treatment to provide activation of CGC catalyst precursors containing nitrogen-donor ligands. Such systems may contain a large amount of neutral BHT, which is undesirable in some end products because MAO is often used in large excess amounts to ensure effective activation, and the amount of coordinated TMA (active sites) may also be reduced due to the balance between coordinated TMA and free TMA (route 1).

[0141] As shown in routes 4 and 5, compounds containing one or more highly reactive electron-withdrawing atoms or groups (e.g., compounds containing Si-F structural moieties, such as fluorinated silica supports and silica fluorinators (NH4)2SiF6) have been found to convert free TMA in MAO into AlMe2F, which can be used as a coordination and free TMA equilibrium blocker (TEB agent). The TEB agent can then replace the coordinated TMA (which becomes free TMA), thereby eliminating the equilibrium between coordinated and free TMA and providing more AlMe2 for pre-catalyst ionization. +Furthermore, the more dispersed MAO anion charge weakens the active ion pair interactions (due to the introduction of strong electron-withdrawing atoms onto the MAO anion as shown in Route 4), thereby enhancing the system's activity. Therefore, converting total TMA in MAO into a TEB agent is a far more efficient method for removing free TMA from MAO while maintaining or improving activation efficiency to obtain a system suitable for activating a pre-catalyst constructed using ligands containing TMA-reactive heteroatom donors, such as N, O, S, and / or P donors in ligands used in post-metallocene and CGC semi-metallocene pre-catalysts.

[0142] In some embodiments, the electron-withdrawing compound is an inorganic compound of formula (I):

[0143] A m B (u) X n (I)

[0144] Where A is an ammonium cation; m = 0, 1, or 2, provided that when m = 0, B is H, an element in group 3, 4, 5, 6, 7, 13, 14, 15, 16, or 17, and when m is not zero, B is an element in group 3, 4, 5, 13, 14, or 15; u is the valence state of element B, and can be 1, 2, 3, or 4; X is an electron-withdrawing atom or group; n = m + u.

[0145] In some embodiments, the inorganic fluorine-containing compound of formula (I) is selected from NH4BF4, (NH4)2SiF6, NH4PF6, NH4F, (NH4)2TaF7, NH4NbF4, (NH4)2GeF6, (NH4)2SmF6, (NH4)2TiF6, (NH4)2ZrF6, MoF6, ReF6, GaF3, SO2ClF, F2, SiF4, SF6, ClF3, ClF5, BrF5, IF7, NF3, HF, BF3, B(OC6F5)3, AlF3, Al(OC6F5)3, NHF2, and NH4HF2. Of course, ammonium hexafluorosilicate may be preferred due to its high F-efficiency.

[0146] In some embodiments, the electron-withdrawing compound is an organic compound of formula (II):

[0147] R o M (u) X (u-o) (II)

[0148] Where R is C1-C 10Hydrocarbon group; M is a group 13 or 14 element; if M is a group 13 element, then o=1; if M is a group 13 non-Al element, then o=2; and if M is a group 14 element, then o=1, 2 or 3; X is an electron-withdrawing atom or group; and u is the valence state of element M.

[0149] In some embodiments, the organofluorine compound of formula (II) is selected from Me3SiF, Me2SiF2, MeSiF3, Et3SiF, Et2SiF2, EtSiF3, Ph3SiF, Ph2SiF2, PhSiF3, Me3CF, Me2CF2, MeCF3, Et3CF, Et2CF2, EtCF3, Ph3CF, Ph2CF2, PhCF3, Me2BF, MeBF2, MeAlF2, Et2BF, EtBF2, EtAlF2, Ph2BF, PhBF2, Me3Si(OC6F5), Me2Si(OC6F5)2, MeSi(OC6F5)3, Me3C(OC6F5), Ph3C(OC6F5), Me2B(OC6F5), MeB(OC6F5)2, MeAl(OC6F5)2.

[0150] The formation of coordination and free trialkyl aluminum equilibrium blockers (TEB agents) and the use thereof to obtain solution, solid or supported aluminoxanes with undetectable free trialkyl aluminum.

[0151] In some embodiments, for solution, solid, or supported aluminoxane (e.g., MAO) compositions, the TEB agent has the formula AlR2X (R = C1 to C8 hydrocarbon groups, and X is an electron-withdrawing group), which is formed in situ by treating the MAO composition with an electron-withdrawing inorganic or organic compound. The amount of the electron-withdrawing compound relative to the trialkylaluminum compound (e.g., TMA) in the MAO can be controlled such that after the TEB agent forms and replaces the coordinated trialkylaluminum compound (e.g., coordinated TMA) in the MAO, little or no free trialkylaluminum compound (or its dimer) remains. For example, in some embodiments, the ratio of the number of active electron-withdrawing atoms (e.g., F) or groups (e.g., C6F5O-) in the strong electron-withdrawing compound to the hydrocarbon aluminum compound is about 1.5:1 to about 1:1.5, for example, about 1.3:1 to about 1:1.3, for example, about 1.2:1 to about 1:1.2, for example, about 1.1:1 to about 1:1.1, for example, about 1.05:1 to about 1:1.05. In some embodiments, the ratio is a molar ratio, or based on the number of electron-withdrawing atoms or groups in the strong electron-withdrawing compound relative to the molar number of the hydrocarbon aluminum compound, for example, (NH4)SiF6 and Al(CH3)3 is an 8:1 molar ratio, but based on the number of fluorine atoms in the strong electron-withdrawing compound relative to the molar number of the hydrocarbon aluminum compound, it is a 6:6 ratio (i.e., 1:1 ratio), plus the TMA and TMA reactive NH4. + (Its formation is presumed to be an inert compound with the formula (Al3Me3N3H3)2) in a 2:2 ratio (i.e., a 1:1 ratio).

[0152] In some embodiments, the amount of free trialkylaluminum compound (or its dimer) is determined after the formation of a solution, solid, or supported MAO composition. For example, samples of unsupported or supported MAO produced or commercially available can be treated with tetrahydrofuran (THF) to convert the free or coordinated TMA in the MAO into TMA-THF adducts, THF-MAO adducts, and AlMe2. + -THF2 adducts, as shown in route 8:

[0153] Route 8

[0154] .

[0155] The relative amounts of each adduct can be determined by nuclear magnetic resonance (NMR) spectroscopy. Once the total amount of free and coordinated trialkylaluminum compounds is determined, a certain amount of the strong electron-withdrawing compound is introduced into the MAO according to a predetermined ratio of electron-withdrawing groups in the strong electron-withdrawing compound to free trialkylaluminum in the MAO. For example, in some embodiments, the ratio of strong electron-withdrawing atoms or groups in the strong electron-withdrawing compound to the total trialkylaluminum compounds in the MAO is about 1.5:1 to about 1:1.5, for example about 1.3:1 to about 1:1.3, for example about 1.2:1 to about 1:1.2, for example about 1.1:1 to about 1:1.1, for example about 1.05:1 to about 1:1.05. In some embodiments, the ratio is a molar ratio, or based on the number of strongly electron-withdrawing atoms or groups in the strongly electron-withdrawing compound relative to the molar number of the trialkylaluminum compound (e.g., (NH4)SiF6 and Al(CH3)3 is an 8:1 molar ratio, but based on the number of fluorine atoms in the strongly electron-withdrawing compound relative to the molar number of the trialkylaluminum compound, it is a 6:6 ratio, plus the reactivity of TMA with NH4. + (Its formation is presumably based on an inert compound of formula (Al3Me3N3H3)2) in a 2:2 ratio. Determining the amount of free hydrocarbon aluminum compound (or its dimer) after MAO formation further improves atom economy because this method can use less fluorine compound compared to processes in which a certain amount of fluorine compound is used relative to the total amount of hydrocarbon aluminum compound used to form MAO.

[0156] The reaction of the electron-withdrawing compound with the free alkyl aluminum compound (or its dimer) to form a TEB agent can be carried out at any suitable temperature, such as from about 0°C to about 100°C, from about 10°C to about 30°C, or from about 20°C, or at ambient temperature. The reaction can be carried out under solvent-free conditions (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 of formula C... n H (2n+2) Noncyclic alkanes, where n = 4-30, such as isobutane, butane, isopentane, hexane, n-heptane, octane, nonane, or decane, formula C n H 2n-2 Cycloalkanes, where n = 5-30, such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, etc., and mixtures thereof. Aromatic diluents may include benzene, toluene, or xylene.

[0157] After treatment with electron-withdrawing compounds, MAO (unloaded or loaded) may have about 2 wt% or less, for example about 1.5 wt% or less, for example about 1 wt% or less, for example about 0.5 wt% or less, for example about 0.25 wt% or less, for example about 0.1 wt% to about 2 wt%, for example about 0.1 wt% to about 1.5 wt%, for example about 0.2 wt% to about 1 wt%, for example about 0.3 wt% to about 0.7 wt% of Al from free hydrocarbon-based aluminum compounds, based on the total aluminum content of MAO.

[0158] In some embodiments, for solid or supported MAO compositions, based on the chemical process of route 9 below, the TEB agent is first formed, then added to the solid or supported MAO composition, followed by a free TMA removal step such as filtration or decantation to remove free TMA, without requiring TMA quantification:

[0159] Route 9

[0160]

[0161] Methods for preparing pre-formed TEB agents include, but are not limited to:

[0162] 1) Make AlR3 (where R is a C1 to C8 hydrocarbon group or a mixture thereof, such as Me, Et, i Bu (oct, preferably Me group) is contacted with a strong electron-withdrawing compound to form an AlR2X compound in situ as the main product.

[0163] 2) Contact AlR2Y (where R is as defined in 1, and Y is a non-fluorinated halogen such as Cl, Br, or I) with an electron-withdrawing salt of formula (III):

[0164] MX u (III)

[0165] Where M is a Group 1 or 2 metal; X is an electron-withdrawing group defined in the strongly electron-withdrawing compound moiety; and u is the valence state of said metal M. The stoichiometric ratios of the reaction are shown in route 10:

[0166] Route 10

[0167] AlR2Y + 1 / u MX u = AlR2X + 1 / u MY u

[0168] Among them MY u It can be removed as solid waste, for example, by filtration.

[0169] In some implementations, AlR2Y is selected from AlMe2Cl, AlMe2Br, AlMe2I, AlEt2Cl, AlEt2Br, AlEt2I, Al i Bu2Cl, Al i Bu2Br, Al i Bu2I, AlOct2Cl, AlOct2Br, AlOct2I, AlMe2CN, AlEt2CN, Al i Bu2CN, AlOct2CN, etc.; and MX u The polymers are selected from LiF, NaF, KF, MgF2, CaF2, BaF2, LiOC6F5, NaOC6F5, KOC6F5, Mg(OC6F5)2, Ca(OC6F5)2, Ba(OC6F5)2, etc. It should be understood that ClMgOC6F5 can also be used, for example, AlMe2Cl + ClMgOC6F5 to form AlMe2OC6F5 + MgCl2. MgCl2 agglomerating agents such as dioxolane can be used to oligomerize MgCl2 to achieve better solid-state separation, forming the desired AlMe2F or AlMe2OC6F5 products.

[0170] Optional carrier materials and derived supported aluminum oxanes without trialkylaluminum

[0171] In some embodiments of this disclosure, the catalyst system may include a support material. For example, the support material may be contacted with a pre-formed solution-type aluminoxane, such as commercially available solution-type MAO, to form a supported MAO, and then the supported MAO may be contacted with a strong electron-withdrawing compound to form the TEB agent of this disclosure or a pre-formed TEB agent in situ. Alternatively, the support material may be contacted with a TMA-free MAO of this disclosure to form a supported activator, and then the supported activator may be contacted with a pre-catalyst compound. Alternatively, the pre-catalyst compound may be contacted with a TMA-free MAO to form a solution-type catalyst system, and then the catalyst system may be contacted with the support material to form a supported catalyst system. Alternatively, the supported material can be loaded with an oxygen source, such as water, and then the oxygen-loaded support, in solid or slurry form, is added to a cold TMA solution with or without cooling, optionally heated, to form a supported MAO composition. The supported MAO is then treated with an in-situ formed TEB agent by contacting it with a strong electron-withdrawing compound and optionally AlR3 and optionally filtering / washing, or by pre-formed TEB agent treatment followed by necessary filtration / washing steps to form a TMA-free supported MAO, which is then contacted with a pre-catalyst to form the finished catalyst.

[0172] The carrier material can be a porous carrier material, such as talc and inorganic oxides. Other carrier materials include zeolites, clay, organoclay or other organic or inorganic carrier materials, or mixtures thereof.

[0173] The support material can be an inorganic oxide. The inorganic oxide can be in a finely fractionated form. Suitable inorganic oxide materials used in the catalyst system 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, and zirconium oxide. However, other suitable support materials can be used, such as finely fractionated functionalized polyolefins like finely fractionated polyethylene. Examples of suitable supports can include magnesium oxide, titanium dioxide, zirconium oxide, montmorillonite, pisilicates, zeolites, talc, and clay. Furthermore, 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.

[0174] Carrier materials such as inorganic oxides can have approximately 10 μm 2 / g to approximately 800m 2 / g surface area, approximately 0.1cm 3 / g to approximately 4.0cm 3 The pore volume is approximately 3 μm to approximately 300 μm, and the average particle size is approximately 50 μm. 2 / g to approximately 500m 2 / g surface area, approximately 0.5cm² 3 / g to approximately 3.5cm 3 Pore ​​volume of approximately 10 μm to approximately 200 μm and average particle size of approximately 10 μm to approximately 200 μm. For example, the support material can have a pore volume of approximately 100 μm. 2 / g to approximately 400m 2 / g surface area, approximately 0.8cm² 3 / g to approximately 3.0cm 3 The pore volume is approximately 5 μm to approximately 100 μm, and the average particle size is approximately 5 μm to approximately 100 μm. The average pore size of the support material useful in this disclosure can be approximately 50 Å to approximately 1000 Å, for example, approximately 60 Å to approximately 500 Å, for example, approximately 75 Å to approximately 350 Å. In at least one embodiment, the support material is amorphous silica with a high surface area (surface area = 300 m² / g). 2 / gm; pore volume = 1.65cm³ 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 some 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 have been calcined at, for example, 200°C, 400°C, 600°C or 875°C.

[0175] For pre-formed MAO loads, the support material should be dry, i.e., free of or substantially free of absorbed water. However, for in-situ MAO loads, the support material may be uncalcined when water is used as the oxygen source. The support material can be dried by heating or calcining at about 100°C to about 1000°C, for example, at least about 600°C. When the support material is silica, it is heated to at least 200°C, for example, about 200°C to about 850°C, for example, about 600°C; and for 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 have at least some reactive hydroxyl (OH) groups for producing the supported catalyst system of this disclosure. The calcined support material is then contacted with at least one polymerization catalyst comprising at least one catalyst compound and an activator.

[0176] The support material having reactive surface groups such as hydroxyl groups is slurried in a nonpolar diluent. When using a pre-formed TMA-free MAO, the resulting slurry is contacted in any order with a pre-catalyst compound in solid or solution form and the MAO. When using a pre-formed conventional MAO, the resulting slurry is first contacted with the MAO and then treated with an in-situ formed TEB agent or a pre-formed TEB agent and other necessary steps to obtain a TMA-free supported MAO before contacting it with the pre-catalyst compound. In at least one embodiment, the slurry of the support material is first contacted with an activator (e.g., a TMA-free MAO) for a period ranging from about 0.5 hours to about 24 hours, about 2 hours to about 16 hours, or about 4 hours to about 8 hours. The pre-catalyst compound, in solution or solid form, is then contacted with the supported activator. In at least one embodiment, the supported catalyst system is generated in situ. In some alternative embodiments, the slurry of supported MAO without TMA is first contacted with the pre-catalyst compound for a period of time ranging from about 0.5 hours to about 24 hours, from about 1 hour to about 16 hours, or from about 2 hours to about 8 hours.

[0177] A mixture of one or more catalysts, one or more activators, and a support is heated to about 0°C to about 70°C, for example to about 23°C to about 60°C, or for example to room temperature. The contact time can be about 0.5 hours to about 24 hours, for example about 2 hours to about 16 hours or about 4 hours to about 8 hours.

[0178] A suitable nonpolar diluent is a material in which all reactants used herein, such as activators and precatalyst compounds, are at least partially soluble and are liquid at the polymerization temperature. Nonpolar diluents for in-situ MAO loading can be alkanes, such as isopentane, hexane, isohexane, n-heptane, octane, nonane, and decane, although various other materials can also be used, including cycloalkanes such as cyclohexane, aromatics such as benzene, toluene, and ethylbenzene. For pre-formed MAO loading, aromatics such as benzene, toluene, and ethylbenzene can be used.

[0179] In at least one embodiment, the supported activator is a supported TMA-free MAO (TF-MAO), which is a silica-supported MAO (e.g., ES70 silica calcined at 400°C), wherein the total TMA in the MAO is partially or completely converted into a TEB agent to form a coordinating TEB agent on the main MAO structure and optionally undergoes a free TMA removal step, resulting in undetectable or low levels of free TMA.

[0180] Catalyst system formation

[0181] Embodiments of this disclosure include a method for preparing a catalyst system, the method comprising contacting an unsupported MAO (a TMA-free solution) or a supported MAO (a TMA-free support) with at least one precatalyst compound having group 3 to group 12 metal atoms or lanthanide metal atoms in an organic diluent. Alternatively, a TMA-free solution-type MAO may be first contacted with at least one precatalyst compound, and then contacted with a support.

[0182] In at least one embodiment, the unsupported MAO or supported MAO is heated before it comes into contact with the catalyst compound.

[0183] Unsupported or supported MAO can be solvated or slurried in an organic diluent, and the resulting mixture can then be contacted with a solution of at least one catalyst compound. Alternatively, the catalyst compound can be added in solid form to the mixture of the organic diluent and MAO. In at least one embodiment, the mixture of MAO is contacted with the catalyst compound for a period ranging from about 0.02 hours to about 24 hours, for example, from about 0.1 hours to about 1 hour, from about 0.2 hours to about 0.6 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours.

[0184] The mixture of catalyst compound and MAO can be heated to about 0°C to about 70°C, for example, about 23°C to about 60°C, such as room temperature. The contact time can be about 0.02 hours to about 24 hours, for example, about 0.1 hours to about 1 hour, about 0.2 hours to about 0.6 hours, about 2 hours to about 16 hours, or about 4 hours to about 8 hours.

[0185] A suitable organic diluent is a material in which some or all of the reactants used herein, such as MAO and the catalyst compound, are at least partially soluble (or, in the case of a solid support, suspended) and are liquid at the reaction temperature. A non-limiting exemplary diluent is of formula C. n H (2n+2) Acyclic alkanes, where n is 4-30, such as isobutane, butane, isopentane, hexane, n-heptane, octane, nonane, decane, etc., and those of formula C n H (2n-2) Cycloalkanes, where n is 5-30, such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and mixtures thereof. Aromatic diluents may include benzene, toluene, or xylene.

[0186] The diluent can be added to the reactor, followed by the addition of MAO. A catalyst, such as a catalyst solution in an organic diluent or in solid form, can then be added to the reactor. The mixture can be stirred at a temperature such as room temperature. Additional diluent can be added to the mixture to form a mixture with a desired consistency, for example, having about 2 cc / g silica to about 20 cc / g silica, or, for example, a slurry of about 4 cc / g. The diluent can then be removed. Removing the diluent dries the mixture and can be carried out under vacuum, by purging with an inert atmosphere, by heating the mixture, or a combination thereof. Regarding heating the mixture, any suitable temperature that evaporates the aliphatic diluent can be used. It should be understood that the reduced pressure under vacuum will lower the boiling point of the aliphatic diluent, depending on the reactor pressure. The temperature for diluent removal can be about 10°C to about 200°C, for example, about 60°C to about 140°C, for example, about 60°C to about 120°C, for example, about 80°C or lower, for example, about 70°C or lower. In at least one embodiment, diluent removal includes heating, applying a vacuum, and applying nitrogen purging from the bottom of the container by bubbling nitrogen gas through the mixture. The mixture is then dried.

[0187] Precatalyst compounds

[0188] The terms “catalyst,” “catalyst compound,” “catalyst complex,” “transition metal complex,” “transition metal compound,” “precatalyst compound,” and “precatalyst complex” are used interchangeably to describe transition metal or lanthanide metal complexes that, when combined with a suitable activator, form olefin polymerization catalysts.

[0189] 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 Group 12 metal atom, such as a Group 3 to Group 10 metal atom or a lanthanide atom. The catalyst compound having a Group 3 to Group 12 metal atom may be monodentate or multidentate, such as bidentate, tripentate, or tetradentate, wherein the heteroatom of the catalyst, such as phosphorus, oxygen, nitrogen, or sulfur, chelates with the metal atom of the catalyst. Non-limiting examples include bis(phenol) compounds. In at least one embodiment, the Group 3 to Group 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 Group 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.

[0190] The catalyst compounds disclosed herein may be chromium or chromium-based catalysts. Chromium-based catalysts include chromium oxide (CrO3) and silyl chromate catalysts. Chromium catalysts are the subject of much development work in the field of continuous fluidized bed gas-phase polymerization for the production of polyethylene polymers. Such catalysts and polymerization processes 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.

[0191] The useful single-Cp catalyst precursor compounds of this disclosure have a cyclopentadienyl (Cp) ligand (which includes ligands isoelectronic with the cyclopentadienyl) directly bonded to the metal center of the precursor catalyst and at least one polar atom in at least one non-Cp ligand that is either bridged or not bridged to the Cp ligand.

[0192] In at least one embodiment, the single Cp precatalyst compound of this disclosure is represented by formula (MC-I):

[0193] T y Cp m MG n X q (MC-I)

[0194] Cp is independently a substituted or unsubstituted cyclopentadienyl ligand or a substituted or unsubstituted isovalenced ligand of cyclopentadienyl such as indenyl, fluorenyl, tetrahydro-s-indaneyl, and tetrahydro-as-indecenyl. M is a group 4 transition metal, such as Hf, Ti, or Zr. G is formed by the formula JR*. z The heteroatomic group represented by J is N, P, O, or S, and R* is a straight-chain, branched, or cyclic C1-C group. 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, for example 2, 3 or 4, such as 4.

[0195] In at least one embodiment, J is N, and R* is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, cyclooctyl, cyclododecyl, decyl, undecyl, dodecyl, adamantyl, or isomers thereof. Exemplary JR* z The groups include tert-butylamino and cyclododecylamino.

[0196] 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-C20 hydrocarbon group (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) or a C1-C20 substituted hydrocarbon group, or two R groups. d It can form cyclic structures, including aromatic, partially saturated or saturated cyclic or fused ring systems.

[0197] Each X is independently selected from the group consisting of: hydrocarbon radicals having 1-20 carbon atoms, aryl, hydrogen, amino, alcohol, thiols, phosphides, halogens, dienes, amines, phosphines, ethers, and combinations thereof (two Xs may form a fused ring or part of a ring system), for example, each X is independently selected from halogens, aryl and C1 to C5 alkyl groups, for example, each X is phenyl, methyl, ethyl, propyl, butyl, pentyl or chlorinated.

[0198] In at least one embodiment, the single Cp catalyst precursor compound of formula (MC-I) is selected from:

[0199] Dimethylsilyldi(2,3,4,5-tetramethylcyclopentadienyl)(cyclododecylamino)M(R)2;

[0200] Dimethylsilyldi(2,3,4,5-tetramethylcyclopentadienyl)(cycloundecylamino)M(R)2;

[0201] Dimethylsilyldi(2,3,4,5-tetramethylcyclopentadienyl)(cyclodecylamino)M(R)2;

[0202] Dimethylsilyldi(2,3,4,5-tetramethylcyclopentadienyl)(tert-butylamino)M(R)2;

[0203] Dimethylsilyl(cyclopentadienyl)(l-adamantylamino)M(R)2;

[0204] Dimethylsilyldi(3-tert-butylcyclopentadienyl)(1-adamantylamino)M(R)2;

[0205] Dimethylsilyldi(tetramethylcyclopentadienyl)(1-adamantylamino)M(R)2;

[0206] Dimethylsilyldi(tetramethylcyclopentadienyl)(1-adamantylamino)M(R)2;

[0207] Dimethylsilyldi(tetramethylcyclopentadienyl)(1-adamantylamino)M(R)2;

[0208] Dimethylsilyl(tetramethylcyclopentadienyl)(1-tert-butylamino)M(R)2;

[0209] Dimethylsilyl(fluorenyl)(1-tert-butylamino)M(R)2;

[0210] Dimethylsilyl(tetramethylcyclopentadienyl)(1-cyclododecylamino)M(R)2;

[0211] µ-(C6H5)2C(tetramethylcyclopentadienyl)(1-cyclododecylamino)M(R)2;

[0212] Dimethylsilyldimethyl(η) 5 -2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indargen-1-yl)(tert-butylamino)M(R)2;

[0213] Wherein M is selected from Ti, Zr, and Hf; and each R is selected from a halogen or a C1 to C5 alkyl group (e.g., chlorine, bromine, methyl, ethyl, propyl, butyl, pentyl, or isomers thereof). In at least one embodiment, M is Ti, and each R is methyl.

[0214] The single Cp precatalyst compounds disclosed herein can be synthesized as described in US5,621,126 and US5,547,675, which are incorporated herein by reference.

[0215] The single Cp precatalyst compound may also include compounds having a structure represented by formula (MC-II), which preferably has C s Or a fake C s symmetry:

[0216] (MC-II)

[0217] in:

[0218] M stands for zirconium;

[0219] L 1 It is an unsubstituted fluorenyl, heterocyclopentapentalenyl, or heterofluorenyl ligand, or a substituted fluorenyl, heterocyclopentapentalenyl, or heterofluorenyl ligand having one or more symmetrical or pseudo-symmetrical substituents, each substituent being independently a free radical, which is a hydrocarbon, substituted hydrocarbon, carbohalide, substituted carbohalide, silylcarbyl, or germanium carbohalide, and optionally two or more adjacent substituents may be linked to form a substituted or unsubstituted saturated, partially unsaturated, or aromatic cyclic or polycyclic substituent;

[0220] G is a bridging group;

[0221] J is a heteroatom of group 15, such as N or P, such as N;

[0222] R' is a free radical, which can be a hydrocarbon group, a substituted hydrocarbon group, a carbide group, or a substituted carbide group;

[0223] 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 be bonded to each other;

[0224] X can be independently a hydrogen radical, a hydrocarbon radical, a substituted hydrocarbon radical, a carbohalide radical, a substituted carbohalide radical, a silane radical, a substituted silane radical, a germanium radical, or a substituted germanium radical; or two Xs can be linked together and bonded to a metal atom to form a metal heterocycle containing about 3 to about 20 carbon atoms; or both can be alkene, diene, or aryynylene ligands; the two Xs can be independently halogens, alkoxy groups, aryloxy groups, amino groups, phosphoryl groups, or other monovalent anionic ligands, or the two Xs can also be linked together to form an anionic chelate ligand.

[0225] In (MC-II), L 1 It 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-octamethyloctahydrofluorenyl. Benzo[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-octamethyloctahydrodibenzo[a]fluorenyl, such as 2,7-di-tert-butylfluorenyl, 3,6-di-tert-butylfluorenyl, 1,1,4,4,7,7,10,10-octamethyloctahydrodibenzo[a]fluorenyl or fluorenyl. G is methylene, dimethylmethylene, diphenylmethylene, dimethylmethylenesilyl, methylphenylmethylenesilyl, diphenylmethylenesilyl, di(4-triethylmethylsilylphenyl)methylenesilyl, ethylene, such as diphenylmethylene, diphenylmethylenesilyl, methylphenylmethylenesilyl, and dimethylmethylenesilyl; for example, dimethylmethylenesilyl. A suitable J can be nitrogen. R' is a hydrocarbon group or a halogenated carbonyl group, such as C3-C. 20 Hydrocarbon group, 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 halogenated, such as methyl, benzyl, fluorine, or chlorine, such as methyl or chlorine; w is zero (L' is not present); M is zirconium.

[0226] Non-limiting examples of single-Cp catalyst compounds having one or more polar donors include, but are not limited to:

[0227] The monometallic precatalyst compound may also be selected from:

[0228] Dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamino)titanium dimethylate;

[0229] Dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamino)titanium dichloride;

[0230] Dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamino)titanium dimethylate; or

[0231] Dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamino)titanium dichloride.

[0232] In some embodiments, the pre-catalyst 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 tripentate monodentate or di-anionic 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 is characterized by 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.

[0233] The catalyst complexes disclosed herein comprise metals selected from Groups 3-10 of the periodic table or lanthanides, containing a tripentate bianionic ligand with two anionic donor groups and a neutral heterocyclic Lewis base donor, wherein the heterocyclic donor is covalently bonded between the two anionic donors. In some embodiments, the tripentate bianionic ligand is characterized by a central heterocyclic donor group and two phenolic donors, and the tripentate ligand is located at the center of the metal to form two octet rings.

[0234] In some embodiments, the heterocyclic Lewis base donor of the catalyst compound is characterized by a nitrogen or oxygen donor atom. For example, the heterocyclic group includes pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, and derivatives of their substituted variants. In some embodiments, the heterocyclic Lewis base does not have a hydrogen atom 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.

[0235] The anion donor of the tripentate bianion ligand can be an arylsulfide, a phenolic group, or an aniline group. In some embodiments, the anion donor is a phenolic group. The tripentate bianion ligand is aligned with the metal center to form a complex, which may not have a symmetry mirror. In some embodiments, the tripentate bianion ligand is aligned with the metal center to form a complex having a dual symmetry rotation axis; when determining the symmetry of the bis(phenolic) complex, only the metal and the bianionate tripentate ligand are considered (i.e., the remaining ligands are ignored).

[0236] The catalyst compound disclosed herein can be a di(arylphenol)pyridine complex. The di(arylphenol)pyridine complex can have a tripentate di(arylphenol)pyridine ligand coordinated to a Group 4 transition metal to form two eight-membered rings. In some embodiments, the di(arylphenol)pyridine complex comprises a transition metal complex with a bianionic tripentate ligand characterized by a central neutral donor group and two phenolic donors, wherein the tripentate ligand is coordinated to 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 that the heterocyclic group does not have hydrogen at the α-position of the heteroatom. In this type of complex, it may also be advantageous for the phenolic group to be substituted with one or more cyclic tertiary alkyl substituents. Using cyclic tertiary alkyl-substituted phenolic groups can improve the ability of these catalysts to produce high molecular weight polymers.

[0237] In some embodiments, the bis(phenol) ligand can be a tripentate bianionic ligand that coordinates to metal M in such a manner as to form a pair of 8-membered metal rings. The bis(phenol) ligand forms a complex around the metal with a double rotation axis, thereby giving the complex C2 symmetry. This C2 geometry and 8-membered metal rings are characteristics of these complexes, making them effective catalyst components for the production of polyolefins, particularly isotactic poly(α-olefins). If the ligand coordinates such that the complex has a mirror-like (C2) symmetry... sIf the symmetry of the metal coordination is such that the catalyst is expected to generate only random polymerization (α-olefins), then these symmetry-reactivity concepts are summarized by Bercaw, JE in Macromolecules, v.42, pp.8751-8762 (2009). The pair of 8-membered metal rings in the catalyst compound is also a significant feature, which benefits temperature stability and isomeric selectivity for monomer chaining. Related Group 4 complexes with smaller 6-membered metal rings (Macromolecules 2009, v.42, pp.8751-8762) are known to form C2 and C3 complexes when used in olefin polymerization. s It is a mixture of symmetrical coordination compounds, and therefore not well-suited for the production of higher isotactic polymers (α-olefins).

[0238] The bis(phenol) ligand containing an oxygen donor group (i.e., E=E'=oxygen in formula (I)) can be substituted with alkyl, substituted alkyl, aryl, or other groups. It may be advantageous for each phenol group to be substituted at a ring position adjacent to the oxygen donor atom. For example, the substituent at the position adjacent to the oxygen donor atom can be an alkyl group containing 1-20 carbon atoms. The substituent at the position adjacent to the oxygen donor atom can be a non-aromatic cyclic alkyl group having one or more five- or six-membered rings. The substituent at the position adjacent to the oxygen donor atom can be a cyclic tertiary alkyl group. In some embodiments, the substituent at the position adjacent to the oxygen donor atom is adamantane-1-yl or a substituted adamantane-1-yl group.

[0239] The neutral heterocyclic Lewis base donor is covalently bonded between the two anion donors (e.g., between two phenolic groups) via a "linking group," which binds the heterocyclic Lewis base to the anion donor. In formula (PM-I), the "linking group" is formed by (A... 3 A 2 ) and (A 2’ A 3’ The choice of each linking group can affect catalyst performance, such as the stereoregularity of the produced poly(α-olefin). Each linking group can be a C2-C group with a length of two atoms. 40 Divalent groups. One or both linking groups can be independently phenylene, substituted phenylene, heteroaryl, vinylene, or acyclic two-carbon linking groups. When one or both linking groups are phenylene, the alkyl substituents on the phenylene group 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. 20Alkyl 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, etc.

[0240] In some implementations, the catalyst compound is represented by formula (PM-I):

[0241] (PM-I)

[0242] in:

[0243] M is a transition metal from Group 3, 4, 5 or 6, or a lanthanide metal (e.g., Hf, Zr or Ti);

[0244] E and E' are each independently O, S, or NR. 9 , where R 9 It is hydrogen on its own, C1-C 40 Hydrocarbon group, C1-C 40 Substituted hydrocarbon groups or heteroatom-containing groups such as O, for example, E and E' are both O;

[0245] 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.

[0246] A 1 QA 1’ It is part of a heterocyclic Lewis base containing 4-40 non-hydrogen atoms, which connects A via a 3-atom bridge including Q. 2 With A 2’ Connection, Q is the central atom (A) of the 3-atom bridge 1 QA 1’ With connection A 1 and A 1’ The curves together represent the heterocyclic Lewis base;

[0247] 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' Both are C);

[0248] A is connected via a 2-atom bridge 1A divalent group containing 2-40 non-hydrogen atoms attached to the aryl group bonded to the E, such as o-phenylene, substituted o-phenylene, o-arylene, substituted o-arylene, indoleyl, substituted indoleyl, benzothiophene, substituted benzothiophene, pyrroleyl, substituted pyrroleyl, thiophene, substituted thiophene, 1,2-ethylene (-CH2CH2-), substituted 1,2-ethylene, 1,2-vinylene (-HC=CH-), or substituted 1,2-vinylene, for example... It is a divalent hydrocarbon group;

[0249] A is connected via a 2-atom bridge 1' A divalent group containing 2-40 non-hydrogen atoms attached to the aryl group bonded to the E', such as o-phenylene, substituted o-phenylene, o-arylene, substituted o-arylene, indoleyl, substituted indoleyl, benzothiophene, substituted benzothiophene, pyrroleyl, substituted pyrroleyl, thiophene, substituted thiophene, 1,2-ethylene (-CH2CH2-), substituted 1,2-ethylene, 1,2-vinylene (-HC=CH-), or substituted 1,2-vinylene, for example... It is a divalent hydrocarbon group;

[0250] Each L is independently a Lewis base;

[0251] Each X is an anionic ligand independently;

[0252] n is 1, 2, or 3;

[0253] m can be 0, 1, or 2;

[0254] n+m is not greater than 4;

[0255] R 1 R 2 R 3 R 4 R 1' R 2' R 3' and R 4' Each of them is a hydrogen atom, C1-C 40 Hydrocarbon group, C1-C 40 Substituted hydrocarbon groups, heteroatoms, or heteroatom-containing groups (e.g., 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 R1' and R 2' R 2’ and R 3' R 3' and R 4' One or more groups can be linked to form one or more substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocycles or unsubstituted heterocycles, each ring having 5, 6, 7 or 8 ring atoms, and wherein the substituents on the rings can be linked to form additional rings;

[0256] Any two L groups can be linked together to form a bidentate Lewis base;

[0257] The X group can be attached to the L group to form a monoanionic bidentate group; and

[0258] Any two X groups can be linked together to form a bianionic ligand group.

[0259] The metal M is selected from elements in Groups 3, 4, 5, or 6, such as elements in Group 4. For example, the metal M is zirconium or hafnium.

[0260] The donor atom Q of the neutral heterocyclic Lewis base (in formula (PM-I)) can be nitrogen, carbon, or oxygen. In some embodiments, Q is nitrogen.

[0261] 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.

[0262] A heterocyclic Lewis base of formula (PM-I) 1 and A 1’ Each is independently C, N, or C(R) 22 ), where R 22 Selected from hydrogen, C1-C 20 Hydrocarbon groups and C1-C 20 Substituted hydrocarbon group. In some embodiments, A 1 and A 1' Both are 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 A1’ Atomic bonded hydrogen atoms are likely preferred because hydrogen at these positions is believed to undergo undesirable decomposition reactions, reducing the stability of catalytically active species.

[0263] By A 1 QA 1’ and connection A 1 and A 1’ The heterocyclic Lewis bases (of formula (PM-I)) represented by the curves together can be selected from the following group:

[0264] ,

[0265] Each R 23 The radical group is selected from hydrogen, heteroatoms, C1-C. 20 Alkyl, C1-C 20 alcohol radical, C1-C 20 Amides, and C1-C 20 Substituted alkyl groups.

[0266] In some implementation schemes, by A 1 QA 1’ and connection A 1 and A 1’ The curves together represent heterocyclic Lewis bases (of formula (PM-I)) that are six-membered rings containing zero or one cyclic heteroatom or five-membered rings containing zero, one, two, or three cyclic heteroatoms. Alternatively, from A... 1 QA 1’ and connection A 1 and A 1’ The curves together represent heterocyclic Lewis bases (of formula (PM-I)) that are not six-membered rings containing two or more cyclic heteroatoms.

[0267] In some implementations of formula (PM-I), Q is C, N, or O, for example, Q is N.

[0268] In some implementations of formula (PM-I), A 1 and A 1' Each of them 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’ They're all carbon.

[0269] In some implementations of formula (PM-I), A in 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 their substituted variants.

[0270] In some implementations of formula (PM-I), A 1 QA 1’ It is part of a heterocyclic Lewis base containing 2-20 non-hydrogen atoms, which connects A via a 3-atom bridge. 2 Connect to A 2’ Where Q is the central atom of the 3-atom bridge. In some embodiments, A 1 and A 1' They are all carbon atoms, and A 1 QA 1’ The fragment forms pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, or a substituted variant group thereof, or part of a substituted variant thereof.

[0271] 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 an embodiment, A 1 QA 1’ The fragment forms part of a cyclic carbene, an N-heterocyclic carbene, a cyclic aminoalkyl carbene, or a substituted variant thereof.

[0272] In some implementations of formula (PM-I), A is connected via a 2-atom bridge 1 A divalent group containing 2-20 non-hydrogen atoms attached to the aryl group bonded to the E, wherein... It is a straight-chain alkyl group or a cyclic group (e.g., optionally substituted o-phenylene or o-aryl groups) or a variant thereof.

[0273] A is connected via a 2-atom bridge 1' A divalent group containing 2-20 non-hydrogen atoms attached to the aryl group bonded to E', wherein... It is a straight-chain alkyl group or a cyclic group (e.g., optionally substituted o-phenylene group or o-aryl group) or a substituted variant thereof.

[0274] 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 ’ Both are oxygen, and R 1 and R 1’ Both are C4-C 20 Cyclic tertiary alkyl groups.

[0275] 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 ’ Both are oxygen, and R 1 and R 1’ They are all adamantane-1-yl or substituted adamantane-1-yl.

[0276] 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 ’ Both are oxygen, and R 1 and R 1’ Both are C6-C 20 Aryl.

[0277] In some implementations, the catalyst compound is represented by formula (PM-II):

[0278] (PM-II)

[0279] in:

[0280] M is a transition metal from Group 3, 4, 5 or 6 or a lanthanide metal (e.g., a Group 4 transition metal, i.e., Hf, Zr or Ti);

[0281] E and E' are each independently O, S, or NR. 9 , where R 9 It is hydrogen on its own, C1-C 40 Hydrocarbon group, C1-C 40 Substituted hydrocarbon groups or heteroatom-containing groups, such as O, for example, E and E' are both O;

[0282] Each L is independently a Lewis base;

[0283] Each X is an anionic ligand independently;

[0284] n is 1, 2, or 3;

[0285] m can be 0, 1, or 2;

[0286] n+m is not greater than 4;

[0287] R 1 R 2 R 3 R 4 R 1' R 2' R 3' and R 4' Each of them is a hydrogen atom, C1-C 40 Hydrocarbon group, C1-C 40 Substituted 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 groups can be linked to form one or more substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocycles or unsubstituted heterocycles, each ring having 5, 6, 7 or 8 ring atoms, and wherein the substituents on the rings can be linked to form additional rings;

[0288] Any two L groups can be linked together to form a bidentate Lewis base;

[0289] The X group can be attached to the L group to form a monoanionic bidentate group;

[0290] Any two X groups can be linked together to form a bianion ligand group;

[0291] 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 a hydrogen atom, C1-C 40 Hydrocarbon group, C1-C 40 Substituted 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’ R6’ and R 7’ R 7’ and R 8’ R 10 and R 11 Or R 11 and R 12 One or more groups can be linked to form one or more substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocycles, or unsubstituted heterocycles, each ring having 5, 6, 7, or 8 ring atoms, and wherein the substituents on the rings can be linked to form additional rings.

[0292] In formula (PM-I) or (PM-II), E and E' are each selected from oxygen or NR. 9 , where R 9 It is hydrogen on its own, C1-C 40 Hydrocarbon group, C1-C 40 A substituted hydrocarbon group or a heteroatom-containing group. 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 A hydrocarbon group, alkyl, or aryl. In one embodiment, E and E' are each selected from O, S, N (alkyl), or N (aryl), wherein the alkyl group can be C1 to C2. 20 Alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, etc., and aryl groups are C6-C. 40 Aryl groups, such as phenyl, naphthyl, benzyl, methylphenyl, etc.

[0293] In some implementation schemes, and Independently, it is a divalent hydrocarbon group, such as C1-C. 12 Hydrocarbon group.

[0294] In some embodiments of the catalyst compound of formula (PM-I) or (PM-II), when E and E' are oxygen, each phenolic radical group can be substituted at a position adjacent to the oxygen atom (i.e., R in formulas (PM-I) and (PM-II)). 1 and R 1’ Therefore, when E and E' are oxygen, R 1 and R 1' Each is independently C1-C 40 Hydrocarbon group, C1-C 40 Substituted hydrocarbon groups, heteroatoms, or heteroatom-containing groups, such as R 1 and R 1'Each is independently a non-aromatic cyclic alkyl group having one or more five- or six-membered rings (e.g., cyclohexyl, cyclooctyl, adamantyl, or 1-methylcyclohexyl or substituted adamantyl), such as a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, adamantyl or substituted adamantyl).

[0295] In some embodiments of the catalyst compound of formula (PM-I) or (PM-II), R 1 and R 1' Each is an independent tertiary hydrocarbon group. In some other embodiments of formula (PM-I) or (PM-II), R 1 and R 1' Each is independently a cyclic tertiary hydrocarbon group. In some other embodiments of the catalyst compound of formula (PM-I) or (PM-II), R 1 and R 1' Each is an independent polycyclic tertiary hydrocarbon group.

[0296] In some embodiments of the catalyst compound of formula (PM-I) or (PM-II), R 1 and R 1' Each is independently a tertiary hydrocarbon group. In some other embodiments of the catalyst compound of formula (PM-I) or (PM-II), R 1 and R 1' Each is independently a cyclic tertiary hydrocarbon group. In some other embodiments of the catalyst compound of formula (PM-I) or (PM-II), R 1 and R 1' Each is an independent polycyclic tertiary hydrocarbon group.

[0297] The linking group (i.e., in formula (PM-I)) and Each of the groups can be a substituted phenyl group, such as a substituted phenyl group. R in formula (PM-II) 7 and R 7’ The position is hydrogen or C1-C. 20 Alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, or their isomers such as isopropyl, are preferred. For applications targeting polymers with high stereoregularity, R in formula (PM-II) is preferred. 7 and R 7’ The location is C1 to C 20 Alkyl (e.g., R) 7 and R 7’ (All are C1 to C3 alkyl groups) are preferred.

[0298] In some embodiments of formula (PM-I) or (PM-II), M is a Group 4 metal, such as Hf or Zr.

[0299] In some implementations of formulas (PM-I) and (PM-II), E and E' are both O.

[0300] 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 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 groups may be linked to form one or more substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocycles, or unsubstituted heterocycles, each ring having 5, 6, 7, or 8 ring atoms, and wherein the substituents on the rings may be linked to form additional rings, such as hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or their isomers.

[0301] 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 these 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 (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl and their isomers.

[0302] In some implementations of formulas (PM-I) and (PM-II), R 4 and R 4' Each is independently hydrogen or a C1 to C3 hydrocarbon group, such as methyl, ethyl, or propyl.

[0303] In some implementations of formulas (PM-I) and (PM-II), R 9 It is hydrogen, C1-C 40 Hydrocarbon group, C1-C 40 A substituted hydrocarbon group, or a heteroatom-containing group, such as hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or their isomers. In some embodiments, R 9 It is a C1-C6 alkyl (e.g., methyl, ethyl, propyl, or butyl), phenyl, 2-methylphenyl, 2,6-dimethylphenyl, or 2,4,6-trimethylphenyl.

[0304] In embodiments of formulas (PM-I) and (PM-II), each X is independently selected from the group consisting of hydrocarbon radicals (e.g., alkyl or aryl) having 1-20 carbon atoms, hydride, amino, alcohol, thiol, phosphide, halogen, alkyl sulfonate, and combinations thereof (two or more X may form a fused ring or part of a ring system), for example, each X is independently selected from halogen, aryl, and C1 to C5 alkyl groups, for example, each X is independently a hydride, dimethylamino, diethylamino, methyltrimethylsilyl, neopentyl, phenyl, benzyl, methyl, ethyl, propyl, butyl, pentyl, fluorine, iodine, bromine, or chlorine groups.

[0305] Alternatively, each X can be independently a halogen, a hydride, an alkyl group, or an alkenyl group.

[0306] In some embodiments of formulas (PM-I) and (PM-II), each L is a Lewis base, independently selected from the group consisting of ethers, thioethers, amines, nitriles, imines, pyridines, halogenated carbons, and phosphines, such as ethers, thioethers, or combinations thereof. Optionally, two or more Ls may form a fused ring or part of a ring system, for example, each L is independently selected from ethers or thioethers, such as each L being diethyl ether, tetrahydrofuran, dibutyl ether, or dimethyl thioether.

[0307] 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.

[0308] In some implementations of formulas (PM-I) and (PM-II), n is 1, 2, or 3, for example, 2.

[0309] In some implementations of formulas (PM-I) and (PM-II), m is 0, 1, or 2, for example, 0.

[0310] In some implementations of formulas (PM-I) and (PM-II), R 1 and R 1' Neither of them are hydrogen.

[0311] In some implementations of formulas (PM-I) and (PM-II), M is Hf or Zr, and E and E' are both O; R 1 and R 1’ Each is independently C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon group, heteroatom or group containing heteroatom, R 2 R 3 R 4 R 2' R 3' and R 4' Each is independently hydrogen, C1-C 20 Hydrocarbon group, substituted C1-C 20 Hydrocarbon group, heteroatom or heteroatom-containing group, or R 1 and R 2 R 2 and R 3 R 3 and R 4 R 1' and R 2' R 2’ and R 3' R 3' and R 4'One or more groups can be linked to form one or more substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocycles, or unsubstituted heterocycles, each ring having 5, 6, 7, or 8 ring atoms, and wherein substituents on the rings can be linked to form additional rings; each X is independently selected from the group consisting of: hydrocarbon radicals (e.g., alkyl or aryl) having 1-20 carbon atoms, hydrides, amides, alkoxides, thiols, phosphides, halogens, and combinations thereof (two or more Xs can form a fused ring or part of a ring system); each L is independently selected from the group consisting of: ethers, thioethers, and halocarbons (two or more Ls can form a fused ring or part of a ring system).

[0312] 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 a heteroatom-containing group, or one or more adjacent R groups may be connected to form one or more substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocycles or unsubstituted heterocycles, each ring having 5, 6, 7 or 8 ring atoms, and wherein substituents on the rings may be connected to form additional rings.

[0313] 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.

[0314] 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 these 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 (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, or isomers thereof.

[0315] In some implementations of formula (PM-II), M is Hf or Zr, and E and E' are both O; R 1 and R 1' Each is independently C1-C 40 Hydrocarbon group, substituted C1-C 40 Hydrocarbon group, heteroatom or group containing heteroatoms;

[0316] 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 groups can be linked to form one or more substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocycles or unsubstituted heterocycles, each ring having 5, 6, 7 or 8 ring atoms, and wherein the substituents on the rings can be linked to form additional rings;

[0317] R 9 It is hydrogen, C1-C 20 Hydrocarbon group, C1-C 20Substituted hydrocarbon groups or heteroatom-containing groups, such as hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or their isomers;

[0318] Each X is independently selected from the following group: hydrocarbon radicals (e.g., alkyl or aryl) having 1-20 carbon atoms, hydride, amide, alcohol, thiol, phosphide, halogen, diene, amine, phosphine, ether, and combinations thereof (two or more X may form a fused ring or part of a ring system).

[0319] 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 be linked to form one or more substituted hydrocarbon rings, unsubstituted hydrocarbon rings, substituted heterocycles, or unsubstituted heterocycles, each ring having 5, 6, 7, or 8 ring atoms, and wherein substituents on the rings may be linked to form additional rings, such as R... 5 R 6 R 7 R 8 R 5' R 6' R 7' R 8' 、 R 10 R 11 and R 12 Each is independently selected from 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, triacontyl, phenyl, substituted phenyl (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl and their isomers.

[0320] In some implementations of formula (PM-II), M is Zr or Hf, E and E ’ Both are oxygen, and R1 and R 1’ Both are C4-C 20 Cyclic tertiary alkyl groups.

[0321] In some implementations of formula (PM-II), M is Zr or Hf, E and E ’ Both are oxygen, and R 1 and R 1’ They are all adamantane-1-yl or substituted adamantane-1-yl.

[0322] 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.

[0323] In some implementations of formula (PM-II), M is Zr or Hf, E and E ’ It's all oxygen, 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.

[0324] 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-phenol salt)], dimethylzirconium [6,6'-(pyridin-2,6-diyldi(benzo[b]thiophene-3,2-diyl))di(2-adamantane-1-yl)-4-methylphenol salt)], dimethylhafnium [6,6'-(pyridin-2,6-diyldi(benzo[b]thiophene-3,2-diyl))di(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'''-( Pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantane-1-yl)-4',5-dimethyl-[1,1'-biphenyl]-2-phenol)], dimethylhafnium[2',2'''-(pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantane-1-yl)-4',5-dimethyl-[1,1'-biphenyl]-2-phenol)] or combinations thereof.

[0325] In some embodiments, the precatalyst compound is one or more of the following Group 4-based precatalysts:

[0326]

[0327]

[0328] .

[0329] In some embodiments, the precatalyst compound is one or more of the following Group 3-based precatalysts:

[0330] In some embodiments, TMA-free (or trialkylaluminum-free) solution-type aluminum oxanes (e.g., MAO), solid-type aluminum oxanes (e.g., MAO), or supported aluminum oxanes (e.g., MAO) can also be used in dual-Cp metallocene pre-catalyst compounds without polar donors to control polymer properties, such as by restricting free aluminum alkyl groups in the system that could cause chain transfer from the catalytic metal center to the free aluminum alkyl group, thereby adjusting the polymer molecular weight and molecular weight distribution. The metallocene pre-catalyst compounds 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 unbridged metallocene catalyst compounds represented by formula (BC-I):

[0331] Cp A Cp B M'X' n (BC-I)

[0332] Where Cp A and Cp B Each is independently selected from cyclopentadienyl ligands and ligands isovalve to cyclopentadienyl, Cp A and Cp B One or both may contain heteroatoms, and Cp A and Cp B One or both may be substituted by one or more R” groups. M’ is selected from Groups 3 to 12 and lanthanides. 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, aralkyl, arylene alkyl, alkylaryl, alkylene aryl, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocyclic, heteroaryl, heteroatom-containing group, hydrocarbon, lower hydrocarbon, substituted hydrocarbon, heterohydrocarbon, silyl, boranyl, phosphin, phosphine, amino, amine, ether, and thioether.

[0333] In at least one implementation, Cp A and Cp B Each is independently selected from cyclopentadienyl, indole, fluorenyl, cyclopentenylphenanthrene, benzo[a]indole, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentenylcyclododecenyl, phenanthreneindole, 3,4-benzofluorenyl, 9-phenylfluorenyl, 8-H-cyclopentenyl[a]acenaphthenyl, 7-H-dibenzofluorenyl, indole[1,2-9]anthracene, thieno[a]indole, thieno[a]fluorenyl, and their hydrogenated variants.

[0334] The catalyst compound can be a bridged metallocene catalyst compound represented by formula (BC-II):

[0335] Cp A (A)Cp B M'X' n (BC-II)

[0336] Where Cp A and Cp B Each is independently selected from cyclopentadienyl ligands and ligands isovalent with cyclopentadienyl. Cp A and Cp B One or both may contain heteroatoms, and Cp A and Cp B One or both may be substituted 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 lower alkenyl, divalent substituted alkenyl, divalent heteroalkenyl, divalent alkoxy, divalent lower alkoxy, divalent aryloxy, divalent alkylthio, divalent lower alkylthio, divalent arylthio, divalent aryl, divalent substituted aryl, divalent heteroaryl, divalent arylalkyl, divalent arylalkylene, divalent arylalkylene, divalent arylalkylene, divalent haloalkyl, divalent haloalkenyl, divalent haloalkynyl, divalent heteroalkyl, divalent heterocyclic, divalent heteroaryl, divalent Groups containing heteroatoms, divalent hydrocarbon groups, divalent lower hydrocarbon groups, divalent substituted hydrocarbon groups, divalent heteroalkyl groups, divalent silyl groups, divalent boranyl groups, divalent phosphin groups, divalent phosphine groups, divalent amino groups, divalent amine groups, divalent ether groups, and divalent thioether groups. "R" is selected from alkyl groups, lower alkyl groups, substituted alkyl groups, heteroalkyl groups, alkenyl groups, lower alkenyl groups, substituted alkenyl groups, heteroalkenyl groups, alkynyl groups, lower alkenylyl groups, aryloxy groups, alkathioyl groups, lower alkathioyl groups, aryloxyyl groups, substituted aryl groups, heteroaryl groups, arylalkyl groups, arylene alkyl groups, alkane aryl groups, alkane aryl groups, haloalkyl groups, haloalkenyl groups, haloalkynyl groups, heteroalkyl groups, heterocyclic groups, heteroaryl groups, groups containing heteroatoms, hydrocarbon groups, lower hydrocarbon groups, substituted hydrocarbon groups, heteroalkyl groups, silyl groups, boranyl groups, phosphinyl groups, phosphine groups, amino groups, amine groups, germanium groups, ether groups, and thioether groups.

[0337] In at least one implementation, Cp A and Cp B Each of the following is 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.

[0338] 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 the process described herein takes place. Using the same transition metal compound with an activator may be preferable; however, two different activators may also be used in combination, such as the TMA-free supported or unsupported MAO of this disclosure and a strong Lewis acid activator (e.g., trifluoroarylborane) or a noncoordinated or weakly coordinated anionic activator (e.g., N,N-dimethylanilineon or triphenylmethyltetrafluoroarylborate). If one or more transition metal compounds contain an X group that is not hydrogen, a hydrocarbon group, or a substituted hydrocarbon group, the MAO may be contacted with the transition metal compound before the addition of the noncoordinated anionic activator.

[0339] The two transition metal compounds (pre-catalysts) can be used in any ratio. In some embodiments, the molar ratio (A:B) of the (A) and (B) transition metal compounds is in the range of 1:1000 to 1000:1, or 1:100 to 500:1, or 1:10 to 200:1, or 1:1 to 100:1, or 1:1 to 75:1, or 5:1 to 50:1. The specific ratio chosen will depend on the specific pre-catalyst, activation method, and desired end product selected. In one specific embodiment, when two precatalysts are used, wherein the two precatalysts are activated by the same activator, the useful molar percentage ratio, depending on the molecular weight of the precatalysts, is 10% to 99.9% A to 0.1% to 90% B, or 25% to 99% A to 0.5% to 50% B, or 50% to 99% A to 1% to 25% B, or 75% to 99% A to 1% to 10% B.

[0340] In some embodiments, the leaving group of the aforementioned precatalyst is preferably pre-alkylated, for example, by methylation, ethylation, benzylation, or trimethylsilylmethyleneization, because the alkylating agent in the MAO, such as free TMA, has been significantly removed. However, the non-alkylated precatalyst can still be used with mild alkylating agents such as high-carbon trialkylaluminum (e.g., trioctylaluminum) or secondary aluminum alkylates (e.g., AlMe2BHT or AlEt2BHT), or if the solution, solid, or supported MAO system has sufficient low TMA or trialkylaluminum residues to alkylate the precatalyst, then a mild alkylating agent is not required.

[0341] Polymerization process

[0342] This disclosure also relates to polymerization processes in which monomers (e.g., ethylene, propylene) and optionally one or more comonomers are contacted with a catalyst system prepared by one of the methods described in this disclosure in a single polymerization reactor or multiple polymerization reactors in series, according to a corresponding polymerization process, to obtain a desired polymer product including single-phase polymers or copolymers and multiphase copolymers, for example in a single reactor for solution, slurry, and gas-phase polymerization and copolymerization, and in multiple reactors, for example, for sequential copolymerization in solution, slurry, and gas phases. The pre-catalyst compound and activator can be combined in any suitable order. The pre-catalyst compound and activator can be combined before contact with the monomer, for example, by first forming a finished catalyst system by combining the pre-catalyst compound and a TMA-free silica-supported MAO, 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.

[0343] Monomers may include substituted or unsubstituted C2-C. 40 α-olefins, such as C2-C 20 α-olefins, such as C2-C 12 α-olefins, such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and their isomers. In at least one embodiment, the monomer comprises ethylene and optionally a comonomer, comprising one or more C3-C... 40 Alkenes, such as C4-C 20 Alkenes, such as C6-C 12 Olefins. The C3-C 40 Olefin monomers can be linear, branched, or cyclic. The C3-C... 40 Cyclic olefins can be strained or unstrained monocyclic or polycyclic, and may optionally include heteroatoms and / or one or more functional groups. In another embodiment, the monomer comprises propylene and optional comonomers, including one or more ethylene or C4-C... 40 Alkenes, such as C4-C 20 Alkenes, such as C6-C 12 Olefins. The C4-C 40 Olefins can be linear, branched, or cyclic. The C4-C... 40 Cyclic olefins can be strained or strain-free monocyclic or polycyclic, and may optionally include heteroatoms and / or one or more functional groups.

[0344] Exemplary C2-C 40Olefin monomers and optional comonomers may include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, ethylene-imide norbornene, vinyl norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxa norbornene, 7-oxa norbornadiene, their substituted derivatives, and their isomers, such as hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene, and their respective homologues and derivatives, such as norbornene, norbornadiene, and dicyclopentadiene. For certain precatalysts, formula C n H (n-2) Conjugated or non-conjugated dienes (n=4-30) can also be used as comonomers, such as butadiene, 2-methylbutadiene, 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.

[0345] The polymerization process disclosed herein can be carried out in any suitable manner. Any suitable suspension, homogeneous, bulk, solution, slurry, or gas-phase polymerization process can be used. Such processes can be carried out in batch, semi-batch, or continuous modes. Homogeneous polymerization processes (defined as processes in which at least 90 wt% of the product is soluble in the reaction medium) and slurry processes can be used. Homogeneous polymerization processes can be bulk homogeneous processes (defined as processes in which the monomer concentration in all feeds to the reactor is 70 vol% or higher). Alternatively, no diluent is present or added to the reaction medium (except for a small amount of diluent used as a carrier for the catalyst system or other additives, or except for the amount of diluent typically found in the monomer (e.g., propane in propylene)). In another embodiment, the process is a slurry process. The term "slurry polymerization process" as used herein refers to a polymerization process in which a supported catalyst is used and the monomer is polymerized on particles of said supported catalyst. At least 95 wt% of the polymer product derived from said supported catalyst is in particulate form, as solid particles (not dissolved in the diluent).

[0346] Suitable diluents for polymerization include noncoordinate inert liquids. Examples of diluents for polymerization 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., Isopars). ); perhalogenated hydrocarbons, such as perfluorinated C4-C 10 Alkanes; chlorobenzenes; and aromatic and alkyl-substituted aromatic compounds, such as benzene, toluene, 1,3,5-trimethylbenzene, and xylene. Suitable diluents may also include liquid olefins that can be used 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 said 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, said diluent is not aromatic, for example, an aromatic hydrocarbon is present in said diluent in an amount of less than 1 wt%, for example less than 0.5 wt%, for example 0 wt%, based on the weight of the diluent.

[0347] In at least one embodiment, the feed concentration of the monomer and comonomer used for polymerization is 60 vol% solvent or less, for example 40 vol% or less, for example 20 vol% or less, based on the total volume of the feed stream. In at least one embodiment, the polymerization is carried out using a bulk method.

[0348] In at least one embodiment, the feed concentration of the monomers and comonomers used for polymerization in the feed stream leading to the reactor is 60 vol% diluent or less, for example, 40 vol% or less, for example, 20 vol% or less, based on the total volume of the feed stream. In at least one embodiment, the polymerization is carried out in a bulk process.

[0349] Polymerization can be carried out at any temperature and / or pressure suitable for obtaining the desired polymer. For solution polymerization, suitable temperatures include about 50°C to about 200°C, for example about 60°C to about 180°C, for example about 65°C to about 160°C, for example about 80°C to about 150°C, for example about 85°C to about 140°C. For slurry or gas-phase polymerization, suitable temperatures include about 50°C to about 120°C, for example about 60°C to about 110°C, for example about 65°C to about 100°C, for example about 70°C to about 85°C, for example about 75°C to about 80°C. Polymerization can be carried out at pressures of about 0.1 MPa to about 25 MPa, for example about 0.45 MPa to about 6 MPa, or about 0.5 MPa to about 4 MPa.

[0350] In a suitable polymerization process, the run time of the reaction can be up to about 300 minutes, for example, from about 5 minutes to about 250 minutes, from about 10 minutes to about 120 minutes, from about 20 minutes to about 90 minutes, or from about 30 minutes to about 60 minutes. In a continuous process, the run time can be the average residence time of the reactor. In at least one embodiment, the run time of the reaction is up to about 45 minutes. In a continuous process, the run time can be the average residence time of the reactor.

[0351] 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-345 kPa), for example about 0.01 psig to about 25 psig (0.07 kPa-172 kPa), for example about 0.1 psig to about 10 psig (0.7 kPa-70 kPa).

[0352] In at least one embodiment, the hydrogen content is from about 0.0001 ppm to about 2,000 ppm, for example from about 0.0001 ppm to about 1,500 ppm, for example from about 0.0001 ppm to about 1,000 ppm, for example from about 0.0001 ppm to about 500 ppm. Alternatively, hydrogen may be present in an amount of 0 ppm.

[0353] In at least one embodiment, MAO may be present in an amount of 0 mol%p, or the amount of MAO present may be such that the molar ratio of aluminum to transition metal is less than 500:1, for example less than 300:1, for example less than 100:1, for example less than 1:1.

[0354] Unless otherwise specified, “catalyst productivity” is a measure of the number of grams of polymer (P) produced using a polymerization catalyst containing W g of catalyst (cat) over a time period T hours, and can be expressed by the formula: P / (T x W), in gP / gcat⁻¹hr⁻¹. Unless otherwise specified, “catalyst activity” is a measure of how active the catalyst is, and is reported as the mass of product polymer (P) produced per mole of catalyst (cat) used (kgP / molcat) (for solution-derived MAO catalyst systems), or as the mass of product polymer (P) produced per unit mass of catalyst (cat) used (kgP / gcat or gP / gcat) (for solution, solid, or supported MAO catalyst systems). Catalyst activity can also be expressed as the elapsed time T (hours) and is reported as the mass of product polymer (P) produced per mole or millimole of catalyst (cat) used, in gP / mmolcat for solution or solid MAO activators. -1 hr -1 For solution, solid, or supported MAO activators, the unit is kgPgcat. -1 hr -1 .

[0355] In at least one embodiment, according to this disclosure, a solution catalyst system using a TMA-free solution-type MAO activator has a catalyst activity greater than about 10 to 1,000 kg Pgcat-1hr-1, for example greater than about 20 kg Pgcat-1hr-1, for example greater than about 30 kg Pgcat-1hr-1; for example, about 100 kg Pgcat-1hr-1 to about 300 kg Pgcat-1hr-1; and a TMA-free supported MAO-derived finished catalyst system used in slurry or gas-phase polymerization has a catalyst activity greater than about 3 to 30 kg Pgcat-1hr-1, for example about 4 kg Pgcat-1hr-1 to about 20 kg Pgcat-1hr-1, for example about 6 kg Pgcat-1hr-1 to about 15 kg Pgcat-1hr-1. The catalyst activity is approximately 8 kg Pgcat-1hr-1 to approximately 10 kg Pgcat-1hr-1; and the activity of the solid MAO self-supported catalyst system without TMA is between that of the above solution polymerization and supported catalyst polymerization (slurry and gas phase polymerization).

[0356] 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, for example from about 20 minutes to about 90 minutes, or for example 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, for example from about 20 minutes to about 90 minutes, or for example from about 30 minutes to about 60 minutes; for supported catalyst polymerization, such as slurry or gas-phase polymerization, the catalyst residence time in the reactor can be from about 10 minutes to about 240 minutes, for example from about 30 minutes to about 120 minutes, or for example from about 60 minutes to about 90 minutes; and for catalyst systems derived from supported MAO, the residence time in the slurry or gas-phase polymerization reactor is similar to that of the supported catalyst system.

[0357] In at least one embodiment, the polymerization: 1) at about 0°C to about 300°C (e.g., from about 25°C to about 250°C, from about 50°C to about 160°C, from about 80°C to about 140°C); 2) carried out at an ambient pressure of about 10 MPa (e.g., from about 0.35 MPa to about 10 MPa, from about 0.45 MPa to about 6 MPa, from about 0.5 MPa to about 4 MPa); 3) carried out without an aliphatic hydrocarbon diluent, for example in a gas-phase reactor; or carried out using a monomer as a diluent, for example in a slurry reactor using propylene as both monomer and diluent; or for solution or slurry polymerization, in an aliphatic hydrocarbon diluent (e.g., 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; for example, wherein the amount of aromatic hydrocarbons present in the diluent is less than 1% by weight based on the weight of the diluent, for example less than 0.5% by weight, e.g.) The polymerization is carried out in a manner that is 0% by weight; 4) wherein the catalyst system used in the polymerization contains less than 0.5 mol%, for example, MAO is present at a level of less than 500:1, for example less than 300:1, for example less than 100:1, for example less than 1:1; 5) the polymerization occurs in at least one reaction zone; 6) optionally a scavenger (e.g., a trialkylaluminum compound) is absent (e.g., present at 0 mol%, or the scavenger is present at a scavenger metal to transition metal molar ratio of less than 100:1, for example less than 50:1, for example less than 15:1, for example less than 10:1); and 7) optionally hydrogen is present in the polymerization reactor at a partial pressure of about 0.001 psig to about 50 psig (0.007 kPa-345 kPa) (e.g., about 0.01 psig to about 25 psig (0.07 kPa-172 kPa), for example about 0.1 psig to about 10 psig (0.7 kPa-70 kPa)). In at least one embodiment, the catalyst system used in the polymerization comprises more than one precatalyst compound. A “reaction zone” (also referred to as a “polymerization zone”) is a vessel in which polymerization occurs, such as a stirred tank reactor or a loop reactor. When multiple reactors are used in a continuous polymerization process, each reactor is considered a separate polymerization zone. For multi-stage polymerization in a batch polymerization process, each polymerization stage is considered a separate polymerization zone. In at least one embodiment, polymerization occurs in one or more reaction zones. The room temperature is 23°C unless otherwise specified.

[0358] If desired, other additives may also be used in the polymerization, 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, methylaluminoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or combinations thereof. Other additives include reactor electrostatic precipitators or antifouling agents, such as Evonik S202 or Atmer. TM Antistatic agents can also be added to catalyst preparation, post-catalyst treatment, or during or after polymerization.

[0359] Polyolefin products

[0360] This disclosure also relates to material compositions produced by the methods described herein. The processes 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, propylene, and C4-C 20Terpolymers of olefins, and terpolymers of ethylene, propylene, and 5-ethylidene-2-norbornene. The processes described herein can be used to produce polymers such as HDPE, MDPE, LDPE, or LLDPE using butene, hexene, or octene as comonomers to adjust polymer density; iPP, sPP, or aPP produced by different stereo- or regio-regulation of the pre-catalyst; random copolymer plastics derived from propylene-rich ethylene copolymers or ethylene-rich propylene copolymers with an ethylene content not exceeding 30%; ethylene-propylene elastomers (rubbers) with an ethylene-propylene ratio close to 50:50, such as 30:70, 40:60, 50:50, 60:40, or 70:30, i.e., EP. Rubber; for example, ethylene-butadiene copolymers prepared by solution polymerization; impact copolymers, such as iPP-EPR, iPP-EBR (ethylene-butene rubber), and iPP-EHR (ethylene-hexene rubber) biphase copolymers obtained from supported catalyst polymerization and reactor preparation; for example, EPDM (vulcanizable ethylene-propylene diene terpolymer), EBDM (vulcanizable ethylene-butene diene terpolymer), and EHDM (vulcanizable ethylene-hexene diene terpolymer) obtained from solution polymerization; or, for example, vulcanizable iPP-EPDM, iPP-EBDM, and iPP-EHDM biphase copolymers prepared by reactor preparation. 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.

[0361] In some embodiments, the melt index (MI) of the PE-based polymer is from 0.01 to about 50 g / 10 min, for example 0.1-10 g / 10 min, for example 0.5-5 g / 10 min, for example 1-2 g / 10 min; or the melt flow rate or mass flow rate (MFR) of the PP-based polymer is 0.01-2000 g / 10 min, for example 0.05-1000 g / 10 min, for example 0.1-500 g / 10 min, for example 0.5-100 g / 10 min, for example 2-50 g / 10 min, wherein the measurement method is described in similar standards ASTM D1238 and ISO 1133.

[0362] In some embodiments, the weight-average molecular weight (Mw) of the polymer product is in the range of 10k-2000k, for example, in the range of 50k-1000k, for example, in the range of 60k-500k, for example, in the range of 100k-300k, measured by GPC; and the molecular weight distribution (MWD) or polydispersity index (PDI) is 1.5-30, for example, 2-10, for example, 2.5-9, which may have a unimodal or multimodal distribution, for example, derived from a two-stage polymerization process in two different reaction zones or from a bimodal distribution derived from a one-stage polymerization process in one reaction zone using a catalyst system containing two different precatalyst compounds.

[0363] In some embodiments, the comonomer distribution in the polymer product can be a conventional distribution, i.e., the comonomer binding decreases with increasing Mw; it can be a flat distribution, i.e., the comonomer binding is similar under different molecular weight compositions; or it can be a broad orthogonal comonomer distribution, i.e., the comonomer binding increases with increasing Mw.

[0364] experiment

[0365] In studies improving existing technologies (e.g., U.S. Patent 6,368,999), it was found that fluorinated silica supports containing Si-F units react with free TMA in MAO, thereby forming a more active supported MAO. Therefore, fluorinating agents for fluorinated silica, such as (NH4)2SiF6, which also contain Si-F units, were tested and found to react with free TMA in supported or unsupported MAO systems (e.g., solution systems). It has now been demonstrated that by treating the conventional MAO system with compounds containing Si-F units (the fluorinated silica or the fluorinating agent for fluorinated silica) to match the total THF-extractable TMA content of the conventional MAO system with the Si-F units, conventional supported or unsupported MAO systems with the desired free TMA can be converted into active MAO systems with low or undetectable free TMA content without affecting the activation efficiency of the MAO.

[0366] Unless otherwise stated, 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 and deoxygenated and purified according to known procedures. All starting materials were either purchased from Aldrich and purified before use, or prepared according to procedures known to those skilled in the art. Silica ES70 was obtained from PQ (now Ecovyst). MAO was supplied by WR Grace as a 30 wt% MAO solution in toluene (e.g., 13.6 wt% Al or 5.04 mmol Al / g). Deuterated solvents were obtained from Cambridge Isotope Laboratories (Andover, Mass.) and dried with 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.

[0367] Example 1 - Quantification of total THF-extractable TMA content in commercially available MAO solutions

[0368] Treatment with THF solvent, following route 8, converts both coordinated TMA and free TMA into the major product AlMe3(THF) and the minor product AlMe2(THF)2. + This method can quantify the total TMA content, including coordinated TMA and free TMA, in supported or unsupported MAO compositions. Therefore, total TMA is the sum of AlMe3(THF) and AlMe2(THF)2. + The sum (converted back to TMA in the calculation) can be used as follows 1 Quantification is performed using 1H NMR, in which toluene is used as an internal standard for solution MAO, or an added inert compound is used as an internal standard for solution MAO, solid MAO, or supported MAO.

[0369] 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% (from the Certificate of Analysis (COA) of the MAO product), and THF-d8 NMR solvent treated with 3A molecular sieve (Cambridge Isotope).

[0370] If the MAO used for the study is stored at a temperature below -20°C for less than 3 months, the total TMA weight percentage in the MAO product COA can be used without significant error. For MAO solutions stored for longer periods or with frequently changing storage temperatures (e.g., removing some MAO from the refrigerator and then putting it back in), the total THF-extractable TMA content may increase significantly due to the gelation process that releases TMA (Route 1).

[0371] Procedure: In a drying oven, fill a dried 5 mm NMR tube with approximately 0.5 inches of MAO solution, then add approximately 1.5 inches of THF-d8 solvent, shake thoroughly, and then refract the sample using D1=30s, ns=4. 1 1H NMR spectroscopy. A longer relaxation time D1 may be more accurate, but 30 seconds is sufficient to obtain quantitative toluene CH3 and Al-CH3 signals with an error of less than 2wt%. Figure 3 shows the bottom spectrum ( Figure 3B The diagram shows the regions from toluene (Me) to Al-Me. 1 H NMR spectrum.

[0372] Treatment: CH3 peak on p-toluene, total Al-CH3 area, AlMe2(THF)2 + Integrate the peaks and the AlMe3(THF) peak; set the integral value of toluene CH3 to 300 (setting it to 300 instead of 3, i.e., the number of protons in CH3, is to ensure that the printed spectrum output has at least 3 significant digits, because the digits after the decimal point may be truncated), and record the values ​​including MAO, AlMe3(THF), and AlMe2(THF)2. + The integral values ​​for all Al-Me species (350.28), AlMe3(THF) (78.96), and AlMe 2 (THF)2 + The integral value is 7.98; minor species such as processed oils, which are usually present but present in small amounts (e.g., <1 wt%), are ignored. According to COA, the molecular formula of MAO without coordinated TMA is Al1O. 0.78 Me 1.44 The calculated Mw is 61.1. The MAO integral is 350.28 - 78.96 - 7.98 = 263.34. The number of protons in the MAO is 1.44 * 3 = 4.32. AlMe2 + It is included in the TMA because it is generated by the coordination TMA. The calculation results are listed in Table 1.

[0373] Table 1. Calculation of Total THF Extractable TMA

[0374] 1Weight fraction = Mw * integral / number of protons, which is the weight contribution of each species;

[0375] 2 wt% = (Individual weight fraction / Total weight fraction) * 100%;

[0376] 3 AlMe2 + It is derived from the coordination TMA and is therefore converted back to TMA.

[0377] As can be seen, the total TMA content has increased from 4.76 wt% (COA) to 5.33 wt%, indicating a lower degree of gelation.

[0378] Example 2 - Quantitative analysis of TMA in commercially available MAO solutions

[0379] The quantification of coordinated TMA is based on the following reaction (route 11):

[0380] Route 11

[0381] .

[0382] In the above reaction, KF precipitates MAO into an inclusion phase, thereby forming an ionic MAO composition by substituting the coordinated TMA, which is then separated from the solution phase containing free TMA. An excess of a known amount of KF (W1) is then applied. KF ) is applied to MAO solution and the remaining KF(W2) is separated after the reaction. KF The consumption of KF can be calculated as W1. KF – W2 KF This is an indirect quantitative method for the content of coordinated TMA.

[0383] Chemicals: KF (Aldrich), 10 g of KF was placed in a 50 mL round-bottom flask and dried under vacuum in an oil bath at 110°C for 4 hours; the same MAO solution and THF-d8 used in Example 1.

[0384] 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 oven-dried vials (20 mL), followed by the addition of KF (58.1 g / mol) at concentrations of 59.6 mg (2 mol%, based on total Al), 118.9 mg (4 mol%, based on total Al), 207.6 mg (7 mol%, based on total Al), and 298 mg (10 mol%, based on total Al), respectively. The vials were then shaken overnight on a shaker. The vials were removed from the shaker and allowed to settle for 10 hours. KF completely disappeared from the vials treated with 2 mol%, 4 mol%, and 7 mol%, respectively, but residual KF remained in the vial treated with 10 mol%. The supernatant of all four vials was used... 1 Analysis was performed using 1H NMR spectroscopy in THF-d8 NMR solvent, and... Figure 4A The Al-Me region shown in the image, compared with the spectrum, reveals a reduced MAO concentration. The inclusion phase in the sample (vial treated with 10 mmol% KF) from which conventional MAO was completely converted to ionic MAO was also analyzed in THF-d8NMR solvent. 1 Analysis was performed using 1H NMR spectroscopy, and the spectra of the Al-Me region were displayed. Figure 4B The results, when compared with the parent MAO solution, showed that AlMe2 was not present in the ionic MAO. + This species, meaning that all coordinating TMAs were removed by KF, confirms that the coordinating TMAs are AlMe2. + The source of the KF was determined by collecting the remaining KF in the 10 mol% treated vial using a pre-weighed glass frit filter, washing with 3 × 10 mL of dry toluene and 30 mL of dry isohexane, and then weighing to obtain 75.3 mg (2.54 mol% based on total Al), resulting in a coordinated TMA of 10 - 2.5 = 7.5 mol% in the MAO solution. According to Table 1, the total Al% was 13.8 wt%, and the total TMA (free + coordinated) was 5.33 wt%. The total TMA can be converted to 2.00 wt% Al, which is equivalent to 14.5 mol%.

[0385] Example 3 - Treatment of (NH4)2SiF6 with commercially available MAO solution

[0386] This embodiment uses (NH4)2SiF6 as an electron-withdrawing compound to convert most of the total TMA into AlMe2F. NMR reaction stoichiometry studies show that 1 equivalent of (NH4)2SiF6 can consume 8 equivalents of TMA to form 6 equivalents of AlMe2F and a species with 2 equivalents of NH and 2 equivalents of Al-Me, which is likely a species with two 6-membered rings satisfying the 3-coordination of H and the 4-coordination of Al as stable products, although whether it is the exact structure does not affect the reaction stoichiometry (route 12):

[0387] Route 12

[0388] (NH4)2SiF6 + 8AlMe3 (or 4(AlMe3)2) = 6AlMe2F + 2 / 6[(NHAlMe)3]2 + 6CH4 + SiMe4

[0389] Therefore, after quantifying the total TMA, the solution MAO was treated with 1 / 8 equivalent of (NH4)2SiF6 relative to the total TMA content.

[0390] Chemicals: Commercially available MAO solution as described above; (NH4)2SiF6 (Aldrich, vacuum dried overnight at ambient temperature, Mw=178.17).

[0391] Procedure: 40 g of MAO solution (204 mmol aluminum) was placed in a 6 oz flask containing a stir bar. Under vigorous stirring, 0.66 g of (NH4)2SiF6 (3.70 mmol) was slowly added to the MAO solution. After stirring for 1 hour, all solids disappeared. A sample of the solution was taken for further analysis. 1 1H NMR was performed using THF-d8 as the NMR solvent. Figure 3 shows the spectrum of the treated MAO (H NMR). Figure 3A ), and the spectrum of the parent MAO solution ( Figure 3B Comparison in the Al-Me region.

[0392] from Figure 3A -B NMR spectroscopy revealed that after treatment with electron-withdrawing compounds, the integral value of THA (AlMe3(THF)) extractable from THF decreased from 78.96 (3B) to 37.94 (3A), while AlMe2(THF)2... + The species integral value increased from 7.98 (3B) to 15.23 (3A). According to the following reaction (route 13), THF-extractable TMA is believed to originate from coordinated AlMe2F. Route 13 indicates that AlMe2F is a poor source of free TMA in the absence of a donor because the strongly electron-withdrawing group F is unfavorable for bonding to Al, resulting in coordination unsaturation (left-hand reaction).

[0393] Route 13

[0394]

[0395] Route 13 also helps to understand the observed MAO chemical reactions in EWC-treated systems, where monodentate donors such as THF can replace AlMe3 formed by AlMe2 in coordinated AlMe2F, which is directly bonded to Al in coordinated AlMe2F by a neighboring Me, to form TMF-coordinated TMA. Figure 3A AlMe3(THF) in the ligand, as shown in path I; or AlMe2 is captured from the coordinated AlMe2F. + ,form Figure 3A AlMe2 in + (THF)2, as shown in path II. The catalyst precursor with two leaving donor groups, acting as a chelating agent, can only abstract AlMe2 from coordinated AlMe2F. + Formation of a bimetallic cation containing catalyst precursor AlMe2 + The ion pairs of the complex are shown in path III.

[0396] Examples 4-1, 4-2, 4-3 - Small-scale solution propylene polymerization

[0397] Polymerization reagent: A pre-catalyst solution was prepared using a given transition metal complex (ExxonMobil Chemical - anhydrous, stored under N2) (98%) dissolved in toluene, typically at a concentration of 0.5 mmol / L. The complex was activated using various methylaluminoxanes (MAO), including commercially available methylaluminoxanes (cMAO, 10 wt% toluene solution, Albemarle - control) and F-MAO. Complex 6 can be prepared as described in US 11,254,763.

[0398] All MAO is typically used in the form of a 0.2 wt% toluene solution. The MAO micromolar numbers reported below are based on the micromolar number of aluminum in the MAO, with a formula weight of 58.0 g / mol.

[0399] Solvent-polymerized toluene and / or isohexane were supplied by ExxonMobil Chemicals and purified by a series of columns: two tandem 500cc OXYCLEAR columns from Labclear (Oakland, California), followed by two tandem 500cc columns packed with dry 3Å molecular sieves (8-12 mesh; Aldrich Chemical Company), and two tandem 500cc columns packed with dry 5Å molecular sieves (8-12 mesh; Aldrich Chemical Company).

[0400] Polymer-grade propylene was purified by a series of columns: a 2,250cc OXICLEAR column from Labclear, followed by a 2,250cc column packed with 3Å molecular sieves (8-12 mesh; Aldrich Chemical Company), then two tandem 500cc columns packed with 5Å molecular sieves (8-12 mesh; Aldrich Chemical Company), then a 500cc column packed with SELEXSORBCD (BASF), and finally a 500cc column packed with SELEXSORB COS (BASF).

[0401] Reactor Description and Preparation: The polymerization reaction was carried out in an inert atmosphere (N2) drying oven using an autoclave equipped with an external heater for temperature control, a glass liner (reactor internal volume approximately 22.5 ml), a diaphragm inlet, adjustable nitrogen, ethylene, and propylene supplies, and a disposable PEEK mechanical stirrer (800 RPM). The autoclave was prepared as follows: first purging with dry nitrogen at 110°C or 115°C for 5 hours, then purging at 25°C for 5 hours.

[0402] Polypropylene (PP):

[0403] Prepare the reactor as described above, heat to 40°C, and then purge with propylene gas at atmospheric pressure. For MAO activation experiments, add toluene, MAO, propylene (1.0 ml unless otherwise specified 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 specified) while stirring at 800 rpm. Add the pre-catalyst solution to the reactor via syringe under process conditions. Monitor the reactor temperature and typically maintain it within ±1°C. Terminate the polymerization reaction by adding approximately 50 psi of air-gas mixture or CO2 gas to the autoclave for approximately 30 seconds. Unless otherwise specified, the polymerization reaction is quenched according to a predetermined pressure loss of approximately 8 psi (maximum quenching value in psi), or quenched for a polymerization time of up to 30 minutes (unless otherwise specified). Then cool and vent the reactor. Separate the polymer after removing the solvent under vacuum. Report the actual quenching time. A quenching time less than the maximum reaction time indicates that the reaction was quenched due to absorption. The reported yields include the total weight of the polymer and residual catalyst. Catalyst activity is reported as grams of polymer per millimole of complex per hour of reaction time (gP / mmol cat•hr). Examples of propylene homopolymerization, including characterization, are summarized in Table 1 below.

[0404] 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%) for approximately 3 hours in a shaker oven at 165°C. Typical polymer concentrations in the solution ranged from 0.1 to 0.9 mg / ml, and BHT concentrations were 1.25 mg BHT / ml TCB. The samples were cooled to 135°C for testing.

[0405] High-temperature size exclusion chromatography analysis is performed using an automated “rapid GPC” system, as described in US 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). The 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) (sometimes also referred to as polydispersity (PDI)) of the polymer were measured by gel permeation chromatography using a Symyx Technology GPC equipped with an evaporative light scattering detector (ELSD), calibrated with polystyrene standards (Polymer Laboratories: Polystyrene Calibration Kit SM-10: Mp (peak Mw) between 5,000 and 3,390,000). Alternatively, the sample was measured by gel permeation chromatography using a Symyx Technology GPC equipped with a dual-wavelength infrared detector, calibrated with polystyrene standards (Polymer Laboratories: Polystyrene Calibration Kit SM-10: Mp (peak Mw) between 580 and 3,039,000). The sample (250 μL of polymer solution in TCB injected into the system) was run at an elution flow rate of 2.0 mL / min (sample temperature 135°C, chamber / column temperature 165°C) using three tandem PolymerLaboratories PLgel 10 μm Mixed-B 300 x 7.5 mm columns. Column diffusion correction was not performed. Numerical analysis was performed using Epoch® software from Symyx Technologies or Automation Studio software from Freeslate. The resulting molecular weights are relative to linear polystyrene standards. The molecular weight data are reported in the table below, titled Mn, Mw, Mz, and PDI, as defined above.

[0406] 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 melting) and then allowed to cool naturally to room temperature overnight. The sample was then heated to 220°C at a rate of 100°C / min (second melting) and then cooled at a rate of 50°C / min. Melting point data were acquired during heating. The reported values ​​are peak melting temperatures, and are referred to as second melting temperatures for the purposes of this disclosure. The results are presented in the table in heading T. m The report below.

[0407] Table 2. Propylene polymerization experiments. Standard conditions include 0.015 μmol of pre-catalyst complex 6 (see above) and the type and amount of activator shown in the table. Use 1 mL of propylene and a total of 4.1 mL of solvent. Heat the reaction to 70°C or 100°C, stir at 800 rpm, and quench the reaction after a pressure loss of 8 psi or a reaction time of up to 30 minutes (if the quenching pressure is not reached).

[0408] Table 2. Propylene homopolymer

[0409] The data in Table 2 show that even with a very short contact time between the pre-catalyst and MAO (see Catalyst Solution and Polymerization Procedure above) and a very short polymerization time (quenching time) to accommodate high-throughput polymerization designs, the activity of TMA-free MAO (TF-MAO) is significantly higher than that of conventional MAO. The difference in activity is even greater if the contact time between the pre-catalyst and MAO is longer, such as in the case of supported catalysts described below. Furthermore, the molecular weight (Mw) of TF-MAO is significantly higher than that of MAO, likely due to the lack of free TMA capable of chain transfer in TF-MAO. This suggests that controlling the concentration of free TMA in MAO-based systems can provide another means of controlling the desired polymer molecular weight.

[0410] Examples 5-7 and Comparative Examples 2-7 - Solution-based ethylene-butadiene copolymerization

[0411] Polymerization vessel: Symyx Discovery Tools TI-6AL-4V high-pressure parallel reactor.

[0412] Chemicals: Complexes 34, 35, and 36 prepared as described in US 11,254,763; iBu2AlH (DIBAL) (pure, Nouryon); [HNMe2Ph] + B(C6F5)4 -(Boulder Scientifics); MAO (WR Grace 30% MAO, Al = 13.5%); TF-MAO (from Example 3); Toluene (Aldrich, treated with 3A molecular sieve overnight); Ethylene (plant production line, purified with standard drying / purification column); Butadiene (BD) (Aldrich, cooled in a drying oven freezer set to -20°C, poured into cold toluene to make a 10wt% solution, and stored overnight with activated alumina).

[0413] Procedure: Add iBu2AlH (DIBAL, 20 equivalents, relative to the previous catalyst metal) and [HNMe2Ph] + B(C6F5)4 - Each precatalyst was activated with either 1.2 equivalents (relative to the precatalyst metal) or MAO (100 equivalents, relative to the precatalyst metal) or TF-MAO (100 equivalents, relative to the precatalyst metal). After stirring the precatalyst and activator for approximately 10 minutes, a butadiene-toluene solution (10 wt%) (approximately 2500 butadiene equivalents / catalyst) was added, and the reactor containing six 20 mL vials was sealed. The reactor was heated to 100°C and stirred at 225 rpm, then pressurized with ethylene (250 psi, Sigma, 99.5%). The reactor was repressurized when the pressure dropped below 240 psi within the first hour. After 4 hours, the reactor was cooled and then depressurized. The polymer product was separated from each vial by precipitation and washing 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.

[0414] via iBu2AlH-[HNMe2Ph] + B(C6F5)4 - No product was formed when the copolymerization reaction mixture was activated with the activator system (Table 3, Comparative Examples 1, 4, and 7). For the reaction mixtures activated with conventional MAO (Experiments 2, 5, and 8), the formation of ethylene-rich copolymers was observed, with lower yields (maximum 43.5 kg product / mol RE). When using TMA-free MAO (TF-MAO) (Experiments 3, 6, and 9), the activity of the three pre-catalysts was significantly increased to a maximum of 239.4 kg product / mol M, as illustrated in the figure. Figure 5 As shown.

[0415] Table 3. Polymerization data for pre-catalyst complexes 34, 35, and 36*

[0416] * Conditions: Approximately 1 g BD, toluene solution, BD:M = 2500; 240 psi ethylene; 100°C; 4 hours; 1.2 equivalents [HNMe2Ph] + B(C6F5)4 - / 20 equivalents of iBu2AlH or 100 equivalents of MAO or 100 equivalents of TF-MAO, relative to the pre-catalyst metal; ** 1,4 or 1,2-intercalation products

[0417] Comparative Example 8 and Examples 8-12

[0418] The examples here use post-metallocene (complex 6) to test TMA-free supported MAO (TF-sMAO) and compare it with conventional supported MAO (sMAO).

[0419] Catalyst preparation:

[0420] Chemicals: Silica ES70 (Ecovyst (formerly PQ), calcined at 400°C); MAO (WR Grace 30% MAO toluene solution, Al = 13.5 wt%); (NH4)2SiF6 (Aldrich, vacuum dried overnight at ambient temperature, Mw = 178.17); solvents toluene (Aldrich, anhydrous, treated with 3A molecular sieve overnight before use) and isohexane (ExxonMobil apparatus solvent, treated with 3A molecular sieve overnight before use); post-metallocene complex 6 (ExxonMobil laboratory preparation, Mw = 945 g / mol).

[0421] Catalyst preparation procedure in Examples 8-12: 2.8 g of MAO solution (14 mmol Al, based on a silica feed rate of 7.0 mmol / g) was slowly added to 2.04 g of silica and 12 g of toluene in a 20 mL vial; the mixture was heated to 100°C for 4 hours. The supernatant was subjected to NMR analysis (no Al-Me species detected); 29.1 mg of (NH4)2SiF6 was added (based on 7 mol% F loaded on Al, i.e., 14 mmol Al x 7% / 6 x 178.12 = 29.1 mg), shaken for 30 minutes, and heated at 70°C for 20 minutes; filtered, and washed with 10 x 2 g toluene and 1 x 20 g iC6, and dried under vacuum for 30 minutes, yield 3.0 g (this step removed most of the free TMA); 1.0 g sMAO was resuspended in 4 g toluene, 31 mg of complex 6 was added, and shaken on a shaker for 1 hour; filtered, washed with 2 x 5 g toluene and 1 x 10 g iC6, and dried under vacuum for 1 hour. Yield: 1.0 g.

[0422] Comparative Example 8 Catalyst Preparation Procedure: The same chemicals and a similar procedure to the above except for the absence of (NH4)2SiF6 treatment.

[0423] Salt bed gas phase PE polymerization

[0424] Chemicals: NaCl (Fisher S271-10, dehydrated at 180°C and subjected to multiple pump / purge cycles, finally passed through a 16-mesh sieve before use); Al supported on ES-70 silica (calcined at 875°C). i Bu3.

[0425] Procedure: Heat a 2L autoclave to 110°C and purge with nitrogen for at least 30 minutes. Add 350 g of dry NaCl and silica-supported Al to the reactor at 105°C. i Add 6 g of Bu3 and stir for 30 minutes. Adjust the temperature to 85°C. Add 2.0 mL of dry, degassed 1-hexene to the reactor using a syringe at 2 psig N2 pressure, then add N2 to the reactor to a pressure of 20 psig. Inject a mixture of H2 and N2 into the reactor (120 SCCM; 10% H2 in N2) while stirring the bed. Inject the catalyst specified in Table 3 into the reactor with ethylene at a pressure of 220 psig; ethylene is continuously introduced throughout the experiment to maintain a constant pressure within 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. The hydrogen to ethylene ratio is measured by online GC analysis. Terminate the polymerization after 1 hour by venting the reactor, cooling to room temperature, and then exposing it to air. Remove the salts by washing twice with water; separate the polymer by filtration, wash simply with acetone, and dry in air for at least two days. The yields of Comparative Example 8 (using the finished catalyst derived from Complex 6 and a conventional supported MAO) and Examples 8-12 (using the finished catalyst derived from Complex 6 and the supported MAO (TF-sMAO) of the present invention) and the activities calculated based on the yields are listed in Table 3.

[0426] Table 3. Results of vapor-phase PE polymerization in a 2L salt bed

[0427]

[0428] The data in Table 3 show that the TF-sMAO-complex 6 catalyst system has higher activity, and the activity can be further increased by adding hexane; its H2 response is not as sensitive as that of metallocene, but its activity increases with the increase of H2 feed amount.

[0429] In summary, the MAO and catalyst system disclosed herein provide improved catalyst activity and catalyst lifetime for post-metallocene and CGC catalysts. Furthermore, hydrocarbon-based aluminum compounds with strong electron-withdrawing atoms or groups can be formed in situ during MAO formation.

[0430] Unless otherwise specified, the phrase "consisting essentially of..." does 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, this phrase does not exclude impurities and variations that typically accompany the elements and materials used.

[0431] For the sake of brevity, only certain ranges are explicitly disclosed herein. However, a range beginning with any lower bound can be combined with any upper bound to describe a range not explicitly mentioned, and a range beginning with any lower bound can be combined with any other lower bound to describe a range not explicitly mentioned. Similarly, a range beginning with any upper bound can be combined with any other upper bound to describe a range not explicitly mentioned. Furthermore, every point or value within a range, even if not explicitly mentioned, can be included. Therefore, each point or value can be used as its own lower or upper bound, combined with any other point or value or any other lower or upper bound to describe a range not explicitly mentioned.

[0432] All documents described herein, including any priority documents and / or test procedures, are incorporated herein by reference to the extent that they are not inconsistent with this document. As will be apparent from the foregoing general description and specific embodiments, various modifications may be made without departing from the spirit and scope of this disclosure, although the form of this disclosure has been illustrated and described. Therefore, this disclosure is not intended to be limited thereto. Similarly, the term “comprising” is considered synonymous with the term “including.” Likewise, when 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, wherein the composition, element, or group of elements is preceded by the transitional phrase “substantially constitutes…,” “consisting of…,” “selected from the group of…,” or “is,” and vice versa.

[0433] Although this disclosure has been described in conjunction with various embodiments and examples, those skilled in the art who benefit from this disclosure will understand that other embodiments can be devised without departing from the scope and spirit of this disclosure.

Claims

1. A method for preparing an aluminumoxane composition, the method comprising: An electron-withdrawing compound is introduced into an unloaded or loaded aluminoxane composition to form an aluminoxane composition, which is determined by titration with tetrahydrofuran to have approximately 0 wt% to 2 wt% Al from free and / or dimer trialkyl aluminum compounds based on the total aluminum content of the aluminoxane composition, wherein the electron-withdrawing compound is: Inorganic compounds of formula (I): A m B (u) X n (I) Where A is an ammonium cation; m = 0, 1, or 2, provided that when m = 0, B is H or an element of group 3, 4, 5, 6, 7, 13, 14, 15, 16, or 17, and when m is not zero, B is an element of group 3, 4, 5, 13, 14, or 15; u is the valence state of element B and can be 1, 2, 3, or 4; X is a halogen or pseudohalogen atom or a haloaryl or aryloxy group; and n = m + u.

2. The method of claim 1, wherein the inorganic compound of formula (I) is selected from the group consisting of: NH4BF4, (NH4)2SiF6, NH4PF6, NH4F, (NH4)2TaF7, NH4NbF4, (NH4)2GeF6, (NH4)2SmF6, (NH4)2TiF6, (NH4)2ZrF6, MoF6, ReF6, GaF3, SO2ClF, F2, SiF4, SF6, ClF3, ClF5, BrF5, IF7, NF3, HF, BF3, B(OC6F5)3, AlF3, Al(OC6F5)3, NHF2, NH4HF2, and combinations thereof.

3. A method for preparing unsupported or supported aluminum oxane compositions, the method comprising: An electron-withdrawing compound is introduced into an unloaded or loaded aluminoxane composition to form an aluminoxane composition, which is determined by titration of the unloaded or loaded aluminoxane composition with tetrahydrofuran to have approximately 0 wt% to 2 wt% Al from free and / or dimer trialkyl aluminum compounds based on the total aluminum content of the aluminoxane composition, wherein the electron-withdrawing compound is: Organic compounds of formula (II): R o M (u) X (u-o) (II) Where R is C1-C 10 Hydrocarbon group; M is a group 13 or 14 element; if M is a group 13 element, o = 1; if M is a group 13 non-Al element, o = 2; and if M is a group 14 element, o = 1, 2 or 3; X is an electron-withdrawing atom or group; u is the valence state of element M, 3 or 4; and X is a halogen, pseudohalogen, or haloaryl or aryloxy group.

4. The method of claim 3, wherein the organic compound of formula (II) is selected from the group consisting of: Me3SiF, Me2SiF2, MeSiF3, Et3SiF, Et2SiF2, EtSiF3, Ph3SiF, Ph2SiF2, PhSiF3, Me3CF, Me2CF2, MeCF3, Et3CF, Et2CF2, EtCF3, Ph3CF, Ph2CF2, PhCF3, M e2BF, MeBF2, MeAlF2, Et2BF, EtBF2, EtAlF2, Ph2BF, PhBF2, Me3Si(OC6F5), Me2Si(OC6F5)2, MeSi(OC6F5)3, Me3C(OC6F5), Ph3C(OC6F5), Me2B(OC6F5), MeB(OC6F5)2, MeAl(OC6F5)2, and combinations thereof.

5. The method of any one of claims 1-4, wherein the trialkylaluminum compound is selected from the group consisting of: AlMe3, AlEt3, Al i Bu3, AlOct3, and their combinations.

6. The method of any one of claims 1-5, further comprising introducing an oxygen source into the trialkylaluminum compound at a temperature of about -60°C to about 0°C to form the aluminum oxane.

7. The method of any one of claims 1-6, further comprising introducing an oxygen-containing carrier slurry into a trialkylaluminate compound solution to form an aluminum oxane in situ on the carrier in the form of a supported aluminum oxane.

8. The method of claim 7, wherein the trialkylaluminum compound is trimethylaluminum.

9. The method of claims 6-8, wherein the oxygen source is water.

10. The method of claims 6-8, wherein the oxygen source is an alcohol or a carboxylic acid.

11. The method of any one of claims 1-10, wherein the ratio of electron-withdrawing group X to the trialkylaluminum compound is about 1.2:1 to about 1:1.2, wherein the ratio is a molar ratio.

12. The method of claim 11, wherein the molar number of the trialkylaluminum compound is the molar number of the trialkylaluminum compound present in the aluminoxane after the aluminoxane is formed.

13. The method of any one of claims 1-12, wherein the aluminum oxane is a solution of methylaluminoxane (MAO), and the step of introducing an electron-withdrawing compound into the solution of MAO is carried out at a temperature of about 10°C to about 100°C.

14. The method of claims 1-12, wherein the aluminum oxane is a supported methylaluminoxane (MAO), and the step of introducing an electron-withdrawing compound into the supported MAO is carried out at a temperature of about 10°C to about 100°C in the presence of a diluent.

15. The method of any one of claims 1-14, further comprising introducing at least one precatalyst compound into the supported or unsupported aluminoxane composition.

16. A composition comprising the following components: 1) Solid or supported aluminoxane compositions; 2) A blocking agent represented by the formula AlR2X, where R is a C1-C8 hydrocarbon group, and X is a halogen atom, a pseudohalogen group, or a haloaryl or aryloxy group; and 3) Al from 0 wt% to about 2 wt% of the trialkyl aluminum compound in free and / or dimer form, based on the total aluminum content of the composition, was determined by titrating the composition with tetrahydrofuran.

17. The composition of claim 16, wherein R is methyl, ethyl, isobutyl or octyl, and X is an F atom or a C6F5O- group.

18. A method including the following steps: A first composition comprising the following components is provided: 1) Solid or supported aluminoxane compositions; 2) A blocking agent represented by the formula AlR2X, where R is a C1-C8 hydrocarbon group, and X is a halogen atom, a pseudohalogen group, or a haloaryl or aryloxy group; and 3) Trialkylaluminum compounds in free and / or dimer form; and The supernatant is separated from the first composition to form a second composition, the second composition comprising: 1) The solid or supported aluminoxane composition; 2) The blocking agent; and 3) The amount of Al from the trialkyl aluminum compound in free and / or dimer form, from 0 wt% to about 2 wt% based on the total aluminum content of the second composition, was determined by titrating the second composition with tetrahydrofuran.

19. A method for preparing an aluminum oxane composition, said aluminum oxane composition comprising: 1) Supported or solid methylaluminoxane (MAO) compositions; 2) Blockers represented by formula (III): AlR2X (III) Where R is a C1-C8 hydrocarbon group, and X is F or OC6F5. The premise is that equation (III) is one of the following two: a) A compound of formula AlR2Y, in which R is a C1-C8 hydrocarbon group and Y is a non-fluorinated halogen or pseudohalogen, is pre-formed by contacting an electron-withdrawing salt represented by formula (IV): MX u (IV) Where M is a group 1 or 2 metal; u is the valence state 1 or 2 of said metal M; and X is F or OC6F5; or b) Pre-formed or in-situ formed by contacting a trialkylaluminum compound AlR3, which is not present in the MAO composition, wherein R is a C1-C8 hydrocarbon group, with an inorganic compound of formula (I) of claim 1 or an organic compound of formula (II) of claim 2; and 3) Remove free trialkylaluminum to obtain the aluminoxane composition having about 0 wt% to 2 wt% Al from free and / or dimer forms of trialkylaluminum compounds based on the total aluminum content of the aluminoxane composition, determined by titrating the aluminoxane composition with tetrahydrofuran.

20. The method of claim 19, wherein the AlR2Y is selected from the group consisting of: AlMe2Cl, AlMe2Br, AlMe2I, AlEt2Cl, AlEt2Br, AlEt2I, Al i Bu2Cl, Al i Bu2Br, Al i Bu2I, AlOct2Cl, AlOct2Br, AlOct2I, AlMe2CN, AlEt2CN, Al i Bu2CN, AlOct2CN, and combinations thereof; the compounds of formula (IV) are selected from the group consisting of LiF, NaF, KF, MgF2, CaF2, BaF2, LiOC6F5, NaOC6F5, KOC6F5, Mg(OC6F5)2, Ca(OC6F5)2, Ba(OC6F5)2, and combinations thereof.

21. The method of claim 19, wherein the supported or solid MAO composition comprises about 0.1 wt% to about 1 wt% of a trialkylaluminum compound in free and / or dimer form, based on the total aluminum content of the supported aluminoxane composition.

22. A catalyst system, comprising: At least one precatalyst compound; and The supported or unsupported aluminum oxane composition according to claim 16.

23. The catalyst system of claim 22, wherein the pre-catalyst 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 with isoelectronic properties to the cyclopentadienyl group; M is a group 4 transition metal; G is derived from formula JR* z The heteroatomic group represented by J is N, P, O, or S, and R* is a straight-chain, branched, or cyclic C1-C group. 20 hydrocarbon group; z is 1 or 2; T-bridging groups; 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.

24. The catalyst system of claim 22, wherein the precatalyst compound is a di(arylphenol)pyridine complex.

25. The catalyst system of claim 24, wherein the di(arylphenol)pyridine complex is selected from the group consisting of: And their combinations.

26. The catalyst system of claim 22, wherein the pre-catalyst compound is selected from the group consisting of: 。 27. A method for producing a polyolefin composition by polymerizing olefins, the method comprising contacting at least one olefin with a catalyst system according to any one of claims 22-26 and obtaining the polyolefin composition from a single-reactor or multi-reactor polymerization apparatus using batch, continuous or sequential solution, slurry or gas-phase polymerization.

28. The method of claim 27, wherein the catalyst system has: for a supported catalyst, a catalyst activity of about 2,000 g Pgcat-1hr-1 to about 30,000 g Pgcat-1hr-1; and for a solution catalyst, a catalyst activity of about 10,000 g Pgcat-1hr-1 to about 1,000,000 g Pgcat-1hr-1.

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