Non-coordinating alkylaluminum-free anion-modified almoxane and method thereof

Abstract

This disclosure relates to an almoxane composition having a substantially or completely undetectable alkylaluminum content, a method for forming such an almoxane composition, a catalyst system having an almoxane composition, and a method for polymerizing olefins using a catalyst system having an almoxane composition. In some embodiments, this disclosure relates to an unsupported or supported MAO composition, a method for forming an MAO, a catalyst system having an MAO, and a method for polymerizing olefins using a catalyst system having an MAO. In some embodiments, a method for producing an unsupported or supported MAO having an undetectable or low amount of free trihydrocarbyl aluminum includes the step of introducing an unsupported or supported MAO together with an electron-withdrawing compound to form an unsupported or supported MAO composition having an undetectable or low amount of free trihydrocarbyl aluminum.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims the benefit and priority of U.S. Provisional Patent Application No. 63 / 506543, filed on June 6, 2023, whose disclosure is incorporated herein by reference. This disclosure relates to aluminoxane compositions in which the hydrocarbyl aluminum contents are substantially or completely undetectable, methods for forming such aluminoxane compositions, catalyst systems having aluminoxane compositions, and methods for polymerizing olefins using catalyst systems having aluminoxane compositions. [Background technology]

[0002] Olefin polymerization catalysts are extremely useful in the industry. Therefore, there is considerable interest in discovering novel catalyst systems that increase the commercial utility of catalysts and enable the production of polymers with improved properties. To polymerize monomers to form polyolefins, the catalyst is activated to provide active sites on the catalyst and promote monomer polymerization. Active methylaluminoxane (MAO), obtained from partially hydrolyzed trimethylaluminum (TMA), is effective in activating catalysts of the type known as metallocenes for olefin polymerization. MAO is generally preferred in the industry as an aluminum co-catalyst (also called an activator). MAO is commercially available in the form of an aromatic diluent, usually a 10-30% by mass solution in toluene.

[0003] Considerable effort has been made to improve the effectiveness of catalytic systems for olefin polymerization based on the use of methylaluminoxane or modified methylaluminoxane. For example, WO2009 / 029857 describes the treatment of MAO with a Lewis base in a toluene solution, e.g., tetrahydrofuran, to obtain dimethylaluminum cations (AlMe2) from MAO. + This shows the formation of a Lewis base-stabilized dialkylaluminum cation, e.g., AlMe2 +It can also be derived from sources other than MAO and can be used as a metallocene catalyst activator. See, for example, Klosin et al., WO2000 / 011006, and Organometallics, 2000, v.19, pp.4684-4686. US9090720 shows that ethylenebisindenylzirconium dimethoxide (EtInd2Zr(OMe)2), a metallocene with dimethoxy leaving groups, extracts AlMe2 + from MAO to form the species [EtInd2Zr(μ-OMe)2AlMe2] + which is slowly alkylated to form the fully activated species [EtInd2Zr(μ-Me)2AlMe2] + providing strong evidence for activation by AlMe2 from MAO. The fully activated [EtInd2Zr(μ-Me)2AlMe2] + species is similar to other MAO-activated metallocenes, and MAO-activated metallocenes also form metallocene-dialkylaluminum cationic species such as [Cp2Zr(μ-Me)2AlMe2] + or [Cp2Ti(μ-Me)2AlMe2] + etc., which are examples 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 the activation of zirconocene catalyst precursors by MAO. See also Bryliakov, Talsi, and Bochmann, Organometallics, 2004, v.23, pp. 149-152, which describe the activation of titanocene catalyst precursors by MAO. Although the MAO structure remains unclear, newly prepared active MAO has the empirical formula (Al4O3Me6)4(TMA) described by Sinn and Kaminsky + 1-2 ​This provides evidence of coordination TMA in MAO that is consistent with the observed (Sinn, et al., “Formation, Structure, and Mechanism of Oligomeric Methylaluminoxane”, in Kaminsky (ed.), Metalorg. Cat. for Synth. & Polym., Springer-Verlag, 1999, p. 105). Coordination TMA is thought to be in equilibrium with free TMA. This is because attempts to physically remove all free TMA result in the loss of both free and coordination TMA, and the formation of a more thermally stable MAO gel, which is of very low utility due to its insolubility and unsuitable for forming the final supported catalyst, which is mainly used in both gas-phase and slurry-phase polymerization, or is unusable for solution polymerization. This equilibrium is shown in Scheme 1 using Sinn's fresh MAO formula as an attempt to help understand the gelation process.

[0004] Scheme 1 [ka] Research has shown that the coordination TMA in MAO is actually AlMe2 for precatalytic ionization. + While functioning as a source, free TMA in MAO, in equilibrium with coordinated TMA, was shown to function as an alkylating agent, as shown in Scheme 2. Here, circles are used to represent the MAO structure for clarity of the (Al4O3Me6)4 units (Luo, Jain, and Harlan, INOR 1169, American Chemical Society Priestley Medalist Symposium in Honor of Tobin J. Marks, San Francisco, CA, April 5, 2017; Luo et al., U.S. Patent No. 8575284 (2013) and U.S. Patent No. 9090720 (2015)):

[0005] Scheme 2 [ka] Therefore, maintaining a significant amount of free TMA in the active MAO solution is necessary to stabilize the active MAO composition, for example, to stabilize the MAO molecular structure capped with coordination TMA, thereby reducing the probability of dimerization / oligomerization that forms an insoluble gel, and to reduce the number of active MAO molecules.

[0006] Nevertheless, post-metallocene catalysts, as well as geometrically constrained complex (CGC) catalysts (also known as mono-cyclopentadienyl (mono-Cp) catalysts) containing polar ligands such as oxygen and / or nitrogen donors, present challenges to activation by standard MAO, exhibiting low catalytic activity and short catalytic lifetimes. Without being constrained by theory, the weak activity and short catalytic lifetime are thought to be due to the presence of free TMA in the MAO, which can alkylate the transition metal center of the pre-catalyst bonded to the heteroatom (an example at the Zr center is shown in Scheme 3), similar to the alkylation of metallocenes with dichloride leaving groups in Scheme 2: Scheme 3 [ka]

[0007] There is a need for improved MAOs and methods for forming MAOs that provide high activity and long catalyst lifetime for post-metallocene catalysts and / or CGC catalysts. Examples include solution-type MAOs or supported MAOs that have sufficient coordination TMA but an undetectable or low free TMA content. References cited in the Information Disclosure Statement (37C.FR1.97(h)): US2019 / 0127499; US2009 / 0124486; US6,667,272; US2019 / 0153135; US2013 / 0253155; US2018 / 0142046; US7,193,100; US6,368,999; US8,575,284. [Overview of the project]

[0008] This disclosure relates to active aluminoxane compositions having an undetectable or low free alkylaluminum content, methods for forming such active aluminoxane compositions, catalyst systems comprising such active aluminoxane compositions, and methods for polymerizing olefins using catalyst systems comprising such active aluminoxane compositions. In some embodiments, an aluminoxane composition having an undetectable or low free aluminum alkyl content is an electron-withdrawing group-modified aluminoxane composition containing about 8.5 mol% or less of THF-extractable alkylaluminum relative to the total aluminum content of the aluminoxane composition. In some embodiments, a method for preparing an almoxane composition in which free trialkylaluminum is undetectable or present in low amounts includes the step of introducing an almoxane together with an electron-withdrawing compound containing at least one electron-withdrawing group for forming an electron-withdrawing group-modified almoxane composition. This method includes the step of introducing a hydrocarbylaluminum compound together with an oxygen source at a temperature of about -60°C to about -5°C to form an almoxane composition.

[0009] In some embodiments, an aluminoxane composition having an undetectable or low free trialkylaluminum content is a methylaluminoxane (MAO) composition formed by contacting an electron-withdrawing compound capable of reducing the THF-extractable total trimethylaluminum (TMA) in an unsupported or supported MAO composition to 8.5 mol% or less relative to the total aluminum content of the MAO composition. In some embodiments, the catalyst system comprises a pre-catalyst compound and an MAO composition having an undetectable or low free trialkylaluminum content, the MAO composition having an undetectable or low free TMA content comprising MAO, a hydrocarbyl aluminum compound containing an electron-withdrawing group, and THF-extractable total trialkylaluminum at a concentration of about 8.5 mol% or less relative to the total aluminum content of the MAO composition. In some embodiments, a method for forming an active MAO composition having an undetectable or low free TMA content includes a method of in situ converting THF-extractable TMA in an unsupported or supported MAO to AlMe2X, i.e., a compound capable of acting as an equilibrium blocker (so-called TEB agent) between coordinated TMA and free TMA, using a compound containing at least one electron-withdrawing group X, a so-called electron-withdrawing compound.

[0010] In some embodiments, a method for forming an active MAO composition having an undetectable or low free TMA content includes the step of in situ converting most or all of the THF-extractable TMA in the MAO composition to a TEB agent AlMe2X (wherein X is a fluorine atom or a perfluorinated aryloxy group) by contacting an electron-withdrawing compound containing at least one electron-withdrawing group X with an unsupported or supported MAO composition. In some embodiments, an almoxane composition having an undetectable or low free trialkylaluminum content comprises an almoxane and a TEB agent AlR2X (wherein R is C1-C). 10The almoxane contains a hydrocarbyl group (where the two Rs may be the same or different) and about 2% by mass or less of Al as a free or dimer trihydrocarbyl aluminum compound AlR3 relative to the total aluminum content of the almoxane.

[0011] In some embodiments, the catalyst system comprises a pre-catalyst compound and an aluminoxane composition having an undetectable or low free trialkylaluminum content, wherein the aluminoxane composition having an undetectable or low free trialkylaluminum content comprises an aluminoxane and a TEB agent AlR2X (wherein R is C1-C 10 The almoxane contains a hydrocarbyl group (the two R's may be the same or different) and about 2% by mass or less of Al as a free or dimerized hydrocarbyl aluminum compound AlR3 relative to the total aluminum content of the almoxane.

[0012] In some embodiments, a method for forming a supported or solid MAO composition having an undetectable or low free TMA content includes treatment with a pre-formed AlR2X and a free TMA removal process, such as filtration or decantation. In some embodiments, the electron-withdrawing compound used to form the TEB agent contains at least one Si-F unit. In some embodiments, the method for polymerizing olefins includes using a catalytic system. [Brief explanation of the drawing]

[0013] [Figure 1] This graph shows the ethylene uptake of the final catalyst of post-metallocene complex 6 using the activator of the present invention, according to one embodiment. [Figure 2] This graph shows the ethylene uptake of the final catalyst of post-metallocene complex 6 using a conventional supported MAO activator, according to one embodiment. [Figure 3A]In one embodiment, the ¹H NMR spectra of the activator of the present invention (3A), both using toluene solvent as a reference, are shown in comparison with those of standard MAO (4B), indicating that the activator of the present invention contains less THF-extractable TMA(THF), more AlMe2 + (THF)2, and the inactive species SiMe4 and [(NHAlMe)3]2. [Figure 3B] In one embodiment, the ¹H NMR spectra of the activator of the present invention (3A), both using toluene solvent as a reference, are shown in comparison with those of standard MAO (4B), indicating that the activator of the present invention contains less THF-extractable TMA(THF), more AlMe2 + (THF)2, and the inactive species SiMe4 and [(NHAlMe)3]2. [Figure 4A-4B] The 1H NMR spectra of commercially available 30% MAO solutions after KF treatment are shown. 4A) shows the upper solution phases after 2, 4, 7, and 10 mol% KF treatment, respectively, and 4B) shows the final K+(F-MAO)-clathrate phase (b) and untreated solution-state MAO (a) for comparison. [Figure 5] This graph shows the ethylene-butadiene copolymerization activity in solution of three Group 3 post-metallocene complexes 36, 34, and 35, respectively, when activated with the TMA-free MAO (TF-MAO) of the present invention, according to one embodiment. The graph compares a standard MAO solution with a perfluoroaromatic boron / AliBu2H activator system. [Modes for carrying out the invention]

[0014] definition "Olefin" is also called "alkene," which is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond. For the purposes of this specification and the accompanying claims, where a polymer or copolymer is referred to as containing an olefin, the olefin present in such a polymer or copolymer is a polymerized form of the olefin. For example, where it is stated that a copolymer has a polymerized form of "ethylene" content of 35% to 55% by mass, it is understood that the repeating species units in the copolymer are derived from ethylene in the polymerization reaction product, and that the derived units are present in an amount of 35% to 55% by mass relative to the mass of the copolymer. A "polymer" has two or more identical or different repeating species units. A "homopolymer" is a polymer having the same repeating species units. A "copolymer" is a polymer having two or more repeating species units that are different from each other. A "terpolymer" is a polymer having three different repeating species units. Thus, the definition of copolymer, as used herein, includes terpolymers, etc. When used to refer to repeating species units, "different" means that the repeating species units differ from each other by at least one atom, or that the repeating species units are different isomers. "Ethylene polymer" or "ethylene copolymer" is a polymer or copolymer containing at least 50 mol% ethylene derived units, and "propylene polymer" or "propylene copolymer" is a polymer or copolymer containing at least 50 mol% propylene derived units, and so on. Ethylene should be considered an α-olefin.

[0015] The term "metallocene" refers to a catalytic compound containing two substituted or unsubstituted cyclopentadienyl moieties, either cross-linked or uncross-linked together, wherein the two cyclopentadienyl moieties are directly bonded to a transition metal center, and if this metal center is neutrally charged, it has at least two leaving groups, or if the metal center retains a positive charge, it has at least one leaving group and any weak donors. The term "half-metallocene" refers to a catalytic compound containing one substituted or unsubstituted cyclopentadienyl moiety and a heteroatom-containing ligand, either cross-linked or uncross-linked together, wherein at least one heteroatom on the cyclopentadienyl moiety and the heteroatom-containing ligand is directly bonded to a transition metal center, and if this metal center is neutrally charged, it has at least two leaving groups, or if the metal center retains a positive charge, it has at least one leaving group and any weak donors. This includes so-called "geometrically constrained catalyst" (CGC) compounds. The term "post-metallocene" refers to a catalytic compound that does not contain a cyclopentadienyl moiety and in which a ligand having heteroatoms such as N, O, P, B, or S is directly bonded to the catalytic metal center, and which has at least two leaving groups if the metal center is neutrally charged, or at least one leaving group and any weak donor if the metal center retains a positive charge.

[0016] The terms "aluminoxane" and "alumoxane" are used interchangeably and refer to trialkylaluminum, e.g., C1-C 10 This refers to a composition prepared by the reaction of trialkylaluminum or a mixture thereof with an oxygen source, which may or may not contain coordinated and free trialkylaluminum. The term "MAO" can refer to an MAO composition containing MAO, coordination TMA, free TMA, and gel, for example, the species in Scheme 1, but sometimes it can also refer to only the main molecule of MAO without coordination TMA and free TMA, for example, (Al4O3Me6)4. "Aluminum alkyl or alkylaluminum" means at least one Al-alkyl (Al-R, where R is C1-C) 12 This refers to a compound containing a hydrocarbyl group unit, which may or may not be coordinated to the aluminoxane main structure. When such a compound is not coordinated to the aluminoxane main structure, it is also called an uncoordinated aluminum alkyl or free aluminum alkyl, and it can coordinate with each other to form a dimer, for example, the AlMe3 dimer in Scheme 1.

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

[0018] "Not present" or "does not contain" means undetectable by current analytical methods, such as nuclear magnetic resonance spectroscopy or conventional wet titration. "Contains in low amounts" means 2% by mass or 2 mol% or less relative to the total amount of the same element in the system. For example, "low amount of free TMA" means that the amount of Al in the free TMA content is 2% by mass or 2 mol% or less relative to the total amount of Al in the MAO composition. In some embodiments, "not present" or "does not contain" may include the statement "in low amounts." For example, TMA-free MAO may indicate that the amount of Al in the free TMA content is 2% by mass or 2 mol% or less relative to the total Al content in the MAO. The term "undetectable" means that the quantification of a species obtained by an analytical method, such as an NMR assay or chemical titration, is zero or nearly zero.

[0019] The terms "anionically modified alkylaluminoxane," "anionically modified aluminoxane," "electron-withdrawing alkylaluminoxane," "electron-withdrawing aluminoxane," and "F-MAO" have similar meanings and are used interchangeably. The term "electron-withdrawing group" (EWG) can refer to an atom or group X capable of withdrawing electrons from an atom to which it is directly bonded, as defined in organic chemistry. Here, an EWG may be more specifically: if any Al-X bond formed at the Al moiety on the MAO to which coordination TMA is coordinated is stronger than the Al-C bond between the same Al moiety on the MAO and the cohesive CH3 group of coordination TMA, both being 3-center, 2-electron bonds, and coordination TMA can be partially or completely substituted by an AlR2X compound (where R = C1-C8 hydrocarbyl group) formed in situ or pre-formed, then such an X is called an EWG. For example, X is -F or -OC6F5 (see Scheme 5).

[0020] The term "electron-withdrawing compound" (EWC) can refer to a compound containing at least one electron-withdrawing group X that can react with an aluminum alkyl compound to form an AlR2X compound (wherein R = C1-C8 hydrocarbyl group), which is a so-called coordinated TMA-free TMA equilibrium blocker or TEB agent (see below) that can completely or partially block the equilibrium between coordinated TMA and free TMA in a supported or unsupported (solution or solid) MAO composition. For example, (NH4)2SiF6, SiF4, HOC6F5, etc., can be reacted with AlMe3, AlEt3, AlOct3 to form AlMe2F, AlEt2F, AlOct2F, AlMe2(OC6F5), AlEt2(OC6F5), and AlOct2(OC6F5), respectively. These can be formed in situ or ex situ in the MAO composition, and then the MAO composition may be added. KF, NaF, K(OC6F5), Na(OC6F5), etc., can be reacted with AlMe2Cl, AlMe2Br, etc., to form AlMe2F, AlMe2(OC6F5), respectively. These can then be separated from metal by-products, such as KCl or NaCl, before being added to the aluminoxane composition.

[0021] The term "TEB (Telekinetic Blocker) between Coordinated TMA and Free TMA" can refer to compounds having the formula AlR2X (wherein R = C1-C8 hydrocarbyl group and X is the electron-withdrawing group defined above). Such compounds can replace coordinated TMA in MAO compositions, and therefore AlR2 can be the active site. + While maintaining the ability to provide, the conversion of coordination TMA to free TMA is eliminated or limited (e.g., Scheme 4). The TEB can be formed in situ or pre-formed by contacting a so-called electron-withdrawing compound, as defined above, with an AlR3 component in an aluminoxane composition, or with a solvent-free AlR3 or AlR2Y compound (where Y is a halide other than fluorine, e.g., Cl, Br).

[0022] Unless otherwise specified, "C n The term "hydrocarbon" refers to a hydrocarbon having n carbon atoms per molecule (where n is a positive integer). The term "hydrocarbon" refers to a certain class of compounds containing hydrogen bonded to carbon, encompassing (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 carbon atoms such that the total number of carbon atoms is in the range of my. Therefore, C1-C 50 An alkyl group refers to an alkyl group containing a total of 1 to 50 carbon atoms. The terms “group,” “radical,” and “substituent” can be used interchangeably. The terms "hydrocarbyl radical," "hydrocarbyl group," or "hydrocarbyl" can be used interchangeably and are defined as meaning a group consisting only of hydrogen and carbon atoms. Hydrocarbyl is C1-C 100 The radical may be linear, branched, or cyclic, and if cyclic, it may be aromatic or non-aromatic. Examples of such radicals, but are not limited to, include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl, and aryl groups such as phenyl, benzyl, and naphthalenyl.

[0023] Unless otherwise noted (except for definitions such as "substituted hydrocarbyl" and "substituted aromatic"), the term "substituted" means that at least one hydrogen atom is replaced by at least one non-hydrogen group, e.g., a hydrocarbyl group, a heteroatom, or a heteroatom-containing group, e.g., a halide (e.g., Br, Cl, F, or I) or at least one functional group, e.g., -NR * 2, -OR * ,-SeR * ,-TeR * ,-PR * 2, -AsR * 2, -SbR * 2, -SR * ,-BR * 2, -SiR * 3, -GeR * 3, -SnR * 3, -PbR * 3 (in the formula, each R * These are independently hydrocarbyl or halocarbyl radicals, and two or more R * This means that the atoms are bonded together and replaced by (which may form a substituted or unsubstituted, fully saturated, partially unsaturated, aromatic cyclic or polycyclic ring structure), or that at least one heteroatom is inserted into the hydrocarbyl ring. The term "substituted hydrocarbyl" refers to a hydrocarbyl radical in which at least one hydrogen atom of the hydrocarbyl radical is at least one heteroatom (e.g., a halide, e.g., Br, Cl, F, or I) or a heteroatom-containing group (e.g., a functional group, e.g., -NR). * 2, -OR * ,-SeR * ,-TeR * ,-PR * 2, -AsR * 2, -SbR * 2, -SR * ,-BR * 2, -SiR * 3, -GeR * 3, -SnR * 3, -PbR * 3 (in the formula, each R *These are independently hydrocarbyl or halocarbyl radicals, and two or more R * This means that the atoms are bonded together and substituted (may form a substituted or unsubstituted, fully saturated, partially unsaturated, aromatic cyclic or polycyclic ring structure), or that at least one heteroatom is inserted into the hydrocarbyl ring.

[0024] The terms "aryl" or "aryl group" refer to aromatic rings and their substitutional variations, such as phenyl, 2-methylphenyl, xylyl, and 4-bromo-xylyl. Similarly, "heteroaryl" refers to an aryl group in which one or two or three ring carbon atoms are 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 that has similar properties and structure (nearly flat) to an aromatic heterocyclic ligand but is not aromatic by definition. Similarly, the term aromatic also refers to a substituted aromatic. The term "substituted aromatic" refers to an aromatic group in which one or more hydrogen groups are replaced by a hydrocarbyl, a substituted hydrocarbyl, a heteroatom, or a heteroatom-containing group.

[0025] A "substituted phenolate" is defined as a group in which at least one, two, three, four, or five hydrogen atoms are located at positions 2, 3, 4, 5, and / or 6, and are associated with at least one non-hydrogen group, such as a hydrocarbyl group, a heteroatom, or a heteroatom-containing group, such as a halogen (e.g., Br, Cl, F, or I), or at least one functional group, such as -NR. * 2, -OR * ,-SeR * ,-TeR * ,-PR * 2, -AsR * 2, -SbR * 2, -SR * ,-BR * 2, -SiR * 3, -GeR * 3, -SnR * 3, -PbR * 3 (in the formula, each R* These are independently hydrogen, hydrocarbyl, or halocarbyl radicals, and two or more R * A phenolate group that is bonded together with other groups (which may form a substituted or unsubstituted, fully saturated, partially unsaturated, aromatic cyclic or polycyclic ring structure), and the 1-position is a phenolate group (Ph-O-, Ph-S-, and Ph-N(R ^ ) is a group, and R^ is hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 It is a substituted hydrocarbyl, heteroatom, or heteroatom-containing group. For example, the "substituted phenolate" group of the catalyst compounds described herein is of formula:

[0026] [ka] [In the formula, R 18 is hydrogen, C1-C 40 Hydrocarbyl (e.g., C1-C) 40 Alkyl) or C1-C 40 A substituted hydrocarbyl, heteroatom, or heteroatom-containing group, E 17 is oxygen, sulfur, or NR 17 And R 17 , R 19 , R 20 , and R 21 Each of them independently produces hydrogen, C1-C 40 Hydrocarbyl (e.g., C1-C) 40 Alkyl) or C1-C 40 Selected from substituted hydrocarbyl groups, heteroatoms, or heteroatom-containing groups, or R 18 , R 19 , R 20 , and R 21 Two or more of these are joined together, C4-C 62 [The compound is represented as a cyclic or polycyclic ring structure, or a combination thereof, with the dashed line indicating the position where the substituted phenolate group forms a bond with the rest of the catalyst compound.]

[0027] "Alkyl-substituted phenolate" means that at least one, two, three, four, or five hydrogen atoms are located at the 2-, 3-, 4-, 5-, and / or 6-positions and are replaced by at least one alkyl group, such as a C1-C 40 , alternatively a C2-C 20 , alternatively a C3-C 12 alkyl, such as methyl, ethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, adamantyl, etc., and further including their substituted analogs, is a phenolate group replaced thereby.

[0028] "Aryl-substituted phenolate" means that at least one, two, three, four, or five hydrogen atoms are located at the 2-, 3-, 4-, 5-, and / or 6-positions and are replaced by at least one aryl group, such as a C1-C 40 , alternatively a C2-C 20 , alternatively a C3-C 12 aryl group, such as phenyl, 4-fluorophenyl, 2-methylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, mesityl, 2-ethylphenyl, naphthalenyl, etc., and further including their substituted analogs, is a phenolate group replaced thereby. The term "ring atom" means an atom that is part of a cyclic ring structure. By this definition, the benzyl group has six ring atoms and tetrahydrofuran has five ring atoms. A heterocyclic ring, also called a hetero ring, is a ring having a hetero atom within the ring structure, in contrast to a "hetero atom-substituted ring" in which hydrogen on the ring atom is replaced by a hetero atom. For example, tetrahydrofuran is a heterocyclic ring and 4-N,N-dimethylamino-phenyl is a hetero atom-substituted ring. A substituted heterocyclic ring means a heterocyclic ring in which one or more hydrogen groups are replaced by a hydrocarbyl, substituted hydrocarbyl, hetero atom, or hetero atom-containing group.

[0029] A substituted hydrocarbyl ring is a ring composed of carbon and hydrogen atoms, in which one or more hydrogen groups are replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom-containing group. For the purposes of the present disclosure, in connection with a catalyst compound (e.g., a substituted bis(phenolate) catalyst compound), the term "substituted" means that a hydrogen group is a hydrocarbyl group, heteroatom or heteroatom-containing group, such as a halogen (e.g., Br, Cl, F or I) or at least one functional group, such as -NR * 2, -OR * , -SeR * , -TeR * , -PR * 2, -AsR * 2, -SbR * 2, -SR * , -BR * 2, -SiR * 3, -GeR * 3, -SnR * 3, -PbR * 3 etc. (wherein each R * is independently hydrogen, a hydrocarbyl or halocarbyl radical, and two or more R * may be joined together to form a substituted or unsubstituted, fully saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), or means that at least one heteroatom is inserted into the hydrocarbyl ring.

[0030] A tertiary hydrocarbyl group has a carbon atom bonded to three other carbon atoms. When the hydrocarbyl group is an alkyl group, the tertiary hydrocarbyl group is also called a tertiary alkyl group. Examples of tertiary hydrocarbyl groups include tert-butyl, 2-methylbutan-2-yl, 2-methylhexan-2-yl, 2-phenylpropan-2-yl, 2-cyclohexylpropan-2-yl, 1-methylcyclohexyl, 1-adamantyl, bicyclo[2.2.1]heptan-1-yl, etc. A tertiary hydrocarbyl group has the formula:

[0031]

Chemical formula

[0032] The cyclic tertiary hydrocarbyl group is defined as a tertiary hydrocarbyl group forming at least one alicyclic (non-aromatic) ring. The cyclic tertiary hydrocarbyl group is also called an alicyclic tertiary hydrocarbyl group. When the hydrocarbyl group is an alkyl group, the cyclic tertiary hydrocarbyl group is also called a cyclic tertiary alkyl group or an alicyclic tertiary alkyl group. Examples of the cyclic tertiary hydrocarbyl group include 1-adamantyl, 1-methylcyclohexyl, 1-methylcyclopentyl, 1-methylcyclooctyl, 1-methylcyclodecyl, 1-methylcyclododecyl, bicyclo[3.3.1]nonan-1-yl, bicyclo[2.2.1]heptan-1-yl, bicyclo[2.3.3]hexan-1-yl, bicyclo[1.1.1]pentan-1-yl, bicyclo[2.2.2]octan-1-yl, etc. The cyclic tertiary hydrocarbyl group has the formula (B):

[0033] [Chemical formula] [Wherein, R A is a hydrocarbyl group or a substituted hydrocarbyl group, each R D is independently hydrogen or a hydrocarbyl group or a substituted hydrocarbyl group, w is an integer from 1 to about 30, and R A and one or more R D and / or two or more R D may be bonded to each other to form an additional ring] can be represented by If a cyclic tertiary hydrocarbyl group contains one or more alicyclic rings, it can be called a polycyclic tertiary hydrocarbyl group, or if the hydrocarbyl group is an alkyl group, it can be called a polycyclic tertiary alkyl group.

[0034] The terms “alkyl radical” and “alkyl” are used interchangeably throughout this disclosure. For the purposes of this disclosure, “alkyl radical” means a C1-C chain which may be linear, branched, or cyclic. 100 Alkyl radicals are defined as alkyl radicals. Examples of such radicals include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl, hexyl, octylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and other radicals including their substituted analogs. A substituted alkyl radical is defined as an alkyl radical in which at least one hydrogen atom of the alkyl radical is replaced by at least one non-hydrogen group, such as a hydrocarbyl group, a heteroatom or heteroatom-containing group, such as a halogen (e.g., Br, Cl, F, or I), or at least one functional group, such as -NR * 2, -OR * -SeR * ,-TeR * ,-PR * 2, -AsR * 2, -SbR * 2, -SR * ,-BR * 2, -SiR * 3, -GeR * 3, -SnR * 3, -PbR * 3 etc (in the formula, each R * These are independently hydrogen, hydrocarbyl, or halocarbyl radicals, and two or more R * The radical is one in which the atoms are bonded together and substituted (may form a substituted or unsubstituted, fully saturated, partially unsaturated, aromatic cyclic or polycyclic ring structure), or in which at least one heteroatom is inserted into the hydrocarbyl ring.

[0035] If isomers of a named alkyl, alkenyl, alkoxide, or aryl group exist (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl), then when an alkyl, alkenyl, alkoxide, or aryl group is mentioned without specifying a particular isomer (e.g., butyl), this explicitly discloses all isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl). Where used herein, Mn is the number-average molecular weight, Mw is the mass-average molecular weight, Mz is the z-average molecular weight, mass% is the mass percentage, and mole% is the mole percentage. The molecular weight distribution (MWD), also known as the polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise specified, all molecular weight units (e.g., Mw, Mn, Mz) are expressed in g / moles (g moles). -1 ) The following abbreviations may be used herein: Me is methyl, Et is ethyl, MAO is MAO, TMS is trimethylsilyl, Oct is octyl, Bu is butyl, iPr is isopropyl, Bn is benzyl (i.e., CH2Ph), THF (also called thf) is tetrahydrofuran, RT is room temperature (23°C unless otherwise noted), tol is toluene, Cp is cyclopentadienyl, NMR is nuclear magnetic resonance, and TMA is trimethylaluminum.

[0036] A “catalytic system” is a combination of at least one pre-catalyst compound, an activator, an optional co-activator, and an optional support material. When “catalytic system” is used to describe such a pair before activation, the catalytic system means the unactivated catalytic complex (pre-catalyst), the activator, and optionally the co-activator together. When used to describe such a pair after activation, the catalytic system means the activated complex and the activator or other charge equilibrium portion. The catalytic compound may be neutral, as in the case of a pre-catalyst, or it may be a charged species with counterions, as in the case of an activated catalytic system. For the purposes of this disclosure and the claims relating thereto, when a catalytic system is described as including a neutral, stable form of its components, it will be well understood by those skilled in the art that the ionic form of these components is a form that reacts with monomers to produce polymers. A polymerization catalytic system is a catalytic system capable of polymerizing monomers into polymers. Furthermore, catalytic compounds and activators (including support-bound activators) represented by the formulas herein encompass both the neutral and ionic forms of the catalytic compounds and activators.

[0037] In this specification, catalysts may also be referred to as catalysts, catalyst precursors, pre-catalyst compounds, catalyst compounds, or transition metal compounds, and these terms are used interchangeably. An "anionic ligand" is a load ligand that provides one or more pairs of electrons to a metal ion. The term "anionic donor" is used interchangeably with "anionic ligand." Examples of anionic donors, but not limited to these, include methyl, chloride, fluoride, alkoxide, aryl oxide, alkyl, alkenyl, thiolate, carboxylate, amide, benzyl, hydride, amidinate, amidate, and phenyl. Two anionic donors can combine to form a dianionic group.

[0038] A "neutral Lewis base" or "neutral donor group" is an uncharged (neutral) group that donates one or more pairs of electrons to a metal ion. Non-limiting examples of neutral Lewis bases include ethers, thioethers, amines, phosphines, ethyl ethers, tetrahydrofurans, dimethyl sulfides, triethylamines, pyridines, alkenes, alkynes, allenes, and carbenes. Lewis bases can combine to form bidentate or tridentate Lewis bases. For the purposes of this disclosure and the claims relating thereto, the phenolate donor is Ph-O-, Ph-S-, and Ph-N(R ^ )-group, (wherein R^ is hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 It may contain a substituted hydrocarbyl, a heteroatom, or a heteroatom-containing group, where the pH is phenyl, which may be substituted.

[0039] Detailed explanation This disclosure relates to an almoxane, a method for forming an almoxane, a catalyst system having an almoxane, and a method for polymerizing an olefin using a catalyst system having an almoxane. In some embodiments, a method for producing an electron-withdrawing group-modified almoxane includes the step of introducing an almoxane together with an electron-withdrawing group to form an almoxane. In some embodiments, a method for producing low-trialkylaluminum almoxanes includes the step of introducing an almoxane together with an electron-withdrawing compound to form an almoxane modified with a strongly electron-withdrawing atom or group. This method includes the step of introducing a hydrocarbylaluminum compound together with an oxygen source at a temperature of about -60°C to about 0°C to form an almoxane.

[0040] In some embodiments, the electron-withdrawing group-modified almoxane includes an almoxane, an electron-withdrawing group-containing hydrocarbyl aluminum compound, and Al derived from the free or dimer hydrocarbyl aluminum compound in an amount of about 2% by mass or less relative to the total aluminum content of the almoxane composition. In some embodiments, the catalyst system includes a catalyst compound and an electron-withdrawing group-modified almoxane. The electron-withdrawing group-modified almoxane includes an almoxane, an electron-withdrawing group-containing hydrocarbyl aluminum compound, and Al derived from the free or dimer hydrocarbyl aluminum compound in an amount of about 2% by mass or less relative to the total aluminum content of the almoxane composition. In some embodiments, the method for polymerizing olefins includes the use of a catalyst system.

[0041] It has been found that treating an almoxane with a compound containing electron-withdrawing groups forms an electron-withdrawing-modified aluminum species, which coordinates to the almoxane to form a more reactive aluminum species, and that this almoxane promotes catalytic activity and catalyst lifetime. Without being constrained by theory, it is thought that the presence of electron-withdrawing components in the treated almoxane provides more aluminum cations associated with the almoxane. In addition, when the ratio of the strongly electron-withdrawing atom to the hydrocarbyl aluminum compound is approximately 1:1, the amount of free hydrocarbyl aluminum compound (e.g., trimethylaluminum) present in the catalytic system can be reduced or eliminated, thereby reducing side reactions between aluminum in the catalytic system and oxygen-containing catalytic compounds and / or nitrogen-containing catalytic compounds. For example, the presence of a strongly electron-withdrawing atom (e.g., as Al(CH3)2F) reduces the formation of stable hydrocarbyl aluminum dimers (e.g., dimer Al(CH3)3) that may form in the absence of the strongly electron-withdrawing atom. Instead, the presence of strongly electron-withdrawing atoms leads to the formation of more active aluminum cations.

[0042] In addition, the presence of electron-withdrawing compounds in the treated almoxane similarly reduces or eliminates side reactions of oxygen-containing catalytic compounds and / or nitrogen-containing catalytic compounds, thereby promoting improved catalytic activity and lifetime. In addition, hydrocarbyl aluminum compounds containing electron-withdrawing atoms can be formed in situ during the formation of almoxanes. The in situ formation of hydrocarbyl aluminum compounds containing electron-withdrawing atoms offers numerous advantages, such as eliminating the need to purchase such compounds, which are very expensive even if available (for example, there is no commercially available method for producing AlF(CH3)2). Furthermore, electron-withdrawing compounds can provide multiple electron-withdrawing atoms (e.g., (NH4)2SiF6) for multiple available aluminum atoms, thus improving atomic economy. Many such electron-withdrawing compounds are commercially available and relatively inexpensive. The use of such electron-withdrawing compounds reduces the cost and atomic economy of the entire catalyst system formation, and thus similarly improves the cost and atomic economy of the polymers produced from such catalyst systems.

[0043] In addition, the almoxanes of this disclosure may be supported on one or more support particles (e.g., silica) or unsupported. Although fluoride supports are known, it has been found that the fluorine atoms are not completely converted to aluminum-fluorine type almoxanes. Instead, calcination of the fluoride support has been shown to form significant amounts of HF and SiF4 gases, which are difficult to control. In contrast, the almoxanes and methods of this disclosure do not form HF and / or SiF4 gases because the bond strength of the aluminum-fluorine atoms is very strong.

[0044] In some embodiments, the present disclosure relates to a TMA-free active MAO composition, a method for forming such an MAO composition, a catalyst system having a TMA-free active MAO, and a method for polymerizing an olefin using a catalyst system having a TMA-free active MAO, wherein the TMA-free MAO has zero or nearly zero free TMA content in the MAO, while AlMe2 is polymerized through treatment with a so-called coordination TMA-free TMA-neutralizing agent (TEB agent). +It means that the MAO active site that can be provided is maintained or increased. Different from the physical removal of free TMA in MAO that causes loss of activity, a TMA-free active MAO composition with maintained or improved activity becomes possible. Without being bound by theory, both silica fluoride or an electron-withdrawing compound (e.g., (NH4)2SiF6) containing Si-F units can convert free TMA in MAO into AlMe2F, and then this AlMe2F replaces the coordinated TMA in MAO to form a new active site. This active site not only blocks the equilibrium between coordinated TMA and free TMA, but also releases more AlMe2 + for pre-catalyst ionization, and it is also possible to increase the activity of individual active molecules by reducing the ion pair interaction due to the electron-withdrawing effect of F atoms (Scheme 4):

[0045] Scheme 4

Chemical Structure

[0046] Without being bound by theory, the substitution of coordinated TMA with AlMe2F converts the equilibrium in Scheme 1 (Scheme 5a) to Scheme 5b, thus efficiently blocking the equilibrium between free TMA and coordinated TMA. This is probably because the presence of strong electron-withdrawing F atoms makes it energetically unfavorable to break one strong Al-F bond and one weak Al-Me bond to form two weak Al-Me bonds (Scheme 5b). Therefore, a TMA-free system can be obtained by corresponding Si-F units to all TMA (both free and coordinated TMA) in MAO.

[0047] Scheme 5

Chemical Structure

[0048] In some embodiments, a method for producing TMA-free MAO involves treating the MAO, in solution or supported form, with an electron-withdrawing compound that can convert all TMA (free TMA and coordinated TMA) to AlMe2F as the main derivative, and further convert it to any trace amount of non-fluorinated inert aluminum alkyl derivative, depending on the electron-withdrawing compound structure used. In some embodiments, a method for preparing a TMA-free MAO composition in solution or supported form includes the step of introducing a solution or supported MAO composition containing free TMA and coordination TMA, and an electron-withdrawing compound containing at least one strongly electron-withdrawing atom or group X capable of converting free TMA to AlMe2X, to form a modified MAO composition having an undetectable or low free TMA content. The method includes the step of introducing a hydrocarbyl aluminum compound, optionally in a support at a temperature of about -60°C to about 0°C, together with an oxygen source, to form a standard MAO composition, prior to the fluorination treatment. In some embodiments, the TMA-free MAO composition comprises an electron-withdrawing group-modified MAO in solution or supported form, and contains a THF-extractable trihydrocarbyl aluminum compound in an amount of about 8.5 mol% or less relative to the total aluminum content of the MAO.

[0049] In some embodiments, the catalyst system comprises a catalyst compound and a TMA-free MAO composition in solution or supported form, the TMA-free MAO composition comprising an electron-withdrawing group modified MAO in solution or supported form, and containing a THF-extractable trihydrocarbyl aluminum compound in an amount of about 8.5 mol% or less relative to the total aluminum content of the MAO. In some embodiments, a method for preparing a TMA-free supported MAO composition includes a filtration step to remove excess free TMA, followed by treatment of the supported MAO with an electron-withdrawing compound and trialkylaluminum. In some embodiments, the method for preparing a TMA-free supported MAO composition includes treating the support with an electron-withdrawing compound before supporting the MAO, and then adjusting the reactive fluorine atoms on the support to correspond to the total amount of TMA in the MAO supported on the support, thereby obtaining the TMA-free supported MAO composition. In some embodiments, the method for polymerizing olefins includes the use of a catalyst system.

[0050] It has been found that when MAO is treated with an electron-withdrawing compound, electron-withdrawing modified alkylaluminum species are formed, which can coordinate to MAO to form a more reactive aluminum species MAO, and that this MAO promotes catalytic activity and catalyst lifetime. Without being constrained by theory, it is thought that the presence of electron-withdrawing content in the treated MAO provides more aluminum cations associated with the MAO, as shown in Scheme 4. In addition, when the ratio of strongly electron-withdrawing atoms or groups to the hydrocarbyl aluminum compound is about 1:1, the amount of free trihydrocarbyl aluminum compound (e.g., trimethylaluminum) present in the catalytic system can be reduced or eliminated, and therefore the decomposition reaction between oxygen or nitrogen-reactive trihydrocarbyl aluminum in the catalytic system and oxygen-containing catalytic compounds and / or nitrogen-containing catalytic compounds is reduced. For example, the presence of a fluorine atom converts the most reactive primary trihydrocarbyl aluminum (e.g., the dimer form of AlMe3) to the less reactive secondary dihydrocarbyl aluminum (e.g., as Al(CH3)2F), thereby reducing or eliminating the formation of primary trihydrocarbyl aluminum, which in the absence of a fluorine atom could form as an equilibrium reaction of coordination TMA in the standard MAO shown in Scheme 5, as an equilibrium reaction of coordination AlMe2F in the MAO composition shown in Scheme 5. The presence of a fluorine atom instead forms more aluminum cations, as shown in Scheme 4, and further weakens ion-pair interactions, leading to the formation of more reactive ion pairs.

[0051] In addition, the presence of fluorine in the treated MAO similarly reduces or eliminates the probability of forming free TMA in equilibrium with standard MAO free TMA and coordination TMA, thereby reducing or eliminating side reactions of oxygen-containing catalytic compounds and / or nitrogen-containing catalytic compounds, thereby promoting improved catalytic activity and lifetime. In addition, fluorine-containing hydrocarbyl aluminum compounds can be formed in situ by the reaction of TMA in the MAO composition with an electron-withdrawing compound, thus converting primary aluminum alkyl TMA to secondary aluminum alkyl AlMe2F. Furthermore, secondary aluminum alkyl, such as AlMe2F, can also be formed ex situ and added to the supported MAO composition following a step to remove free TMA, such as filtration and washing. However, adding secondary aluminum alkyl, such as AlMe2F, to solution-type MAO is not very preferable because it is difficult to remove free TMA in the solution system.

[0052] In addition, the MAO of this disclosure may be supported on one or more carrier particles (e.g., silica) or unsupported. Although fluorinated carriers are known, carrier fluorination processes, such as the process described in WO2000 / 12565, have been found to generate HF and SiF4 gases that corrode the equipment, and furthermore, uncontrollable fluorine losses make it difficult to obtain an accurate fluorine input. In contrast, the MAO and method of this disclosure do not form HF and / or SiF4 gases because the bond strength between the aluminum and strongly electron-withdrawing atoms or groups is very strong, and therefore the fluorine input can be controlled more precisely.

[0053] Unsupported almoxanes and supported almoxanes Almoxanes are -Al(R)-O- or -Al(R)2-O- subunits (wherein R is an alkyl group, usually C1-C) 12The oligomeric compound contains an alkyl group, for example, the inert MAO gel shown in Scheme 1. Examples of useful almoxanes include methyl almoxane (MAO), modified methyl almoxane (MMAO), ethyl almoxane, triethyl almoxane, triisobutyl almoxane, tetraethyl dialmoxane, and diisobutyl almoxane. Unsupported MAO can refer to solution-type MAO, such as commercially available MAO solution products produced by WRGrace, Tosoh, or Noryon, or solid MAO, such as that produced by Tosoh. Unsupported solid MAO can be prepared by removing the solvent from solution-type MAO products, and controlled particle sizes can be formed using different solidification methods, such as spray drying.

[0054] Various methods exist for preparing MAO and modified MAO, such as those described in U.S. Patent No. 4,542,199 and Chen and Marks, 100 Chem. Rev. 1391 (2000). MAO can also be modified for different purposes, such as increasing activity or solubility. Examples of useful MAOs include TMA-derived MAO with an oxygen donor (e.g., WRGrace MAO from TMA with water, or PMAO from Nouryon or solid MAO from Tosoh from TMA with an organic source), higher alkyl-modified MAO (e.g., MMAO from Nouryon), MAO modified with carbocation agents (US9090720), MAO modified with dialkylaluminum cation precursors (US8575284), and halogen-modified MAO (US7355058).

[0055] Activated MAO is formed by contacting a significantly excess amount of TMA with an oxygen source (e.g., water, water coordinated with a metal salt, CO2, methylacylic acid, benzoic acid, or other reactive oxygen-containing organic matter) under appropriate reaction conditions. The active MAOs of this disclosure can be commercially available or synthesized. The active MAOs of this disclosure can be prepared in situ by contacting a hydrocarbyl aluminum compound with an oxygen source, for example, by contacting TMA with water in an aliphatic or aromatic diluent 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.

[0056] The supported MAOs of this disclosure can be prepared by conventional methods, for example, by contacting a pre-formed MAO solution with a support (e.g., silica). For example, a solution of MAO can be added to a solid support or support slurry or back-addition, and then optionally heated to form supported MAOs. The supported MAOs of this disclosure can also be prepared in situ by contacting a hydrocarbyl aluminum compound with an oxygen source supported on a support. For example, following the heating process described in US11,161,922, water pre-supported on 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, e.g., -10°C to -50°C, e.g., -15°C to -30°C, in the form of a slurry in an aliphatic or aromatic diluent, or in any cooled solid form, to obtain the supported MAO described in US11,021,552. Alternatively, a non-hydrolyzable organic oxygen donor can be mixed with TMA under cooling conditions at a temperature of less than 0°C to -60°C, e.g., -10°C to -50°C, e.g., -15°C to -30°C to form the preceding MAO composition, then mixed with a carrier (e.g., silica), and subsequently subjected to the heating process.

[0057] For a solution-type MAO support, a suitable diluent for forming a support slurry, such as a silica slurry, such as toluene, benzene, or xylene, can dissolve the MAO to ensure that the MAO is well distributed within the pores of the support. For in situ-supported MAO, a suitable diluent is a liquid material in which the reactants, such as aluminum hydrocarbyl, such as TMA, a non-hydrolyzable organic oxygen donor, and derivatives of the two reagents, are at least partially dissolved at the reactant temperature. A non-limiting example of a diluent is a material of formula C n H (2n+2) Acyclic alkanes having formula C (where n=4 to 30), such as isobutene, butane, isopentane, hexane, n-heptane, octane, nonane, decane, etc. n H 2n-2 The compounds include cycloalkanes (wherein n=5 to 30), such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and mixtures thereof. Suitable aromatic diluents include toluene, benzene, or xylene.

[0058] Hydrocarbyl aluminum compounds for MAO and modified MAO Active almoxane compositions (e.g., MAOs) can be formed exclusively with trimethylaluminum (TMA), but other aluminum alkyl compounds can also be used to modify MAOs. Hydrocarbylaluminum compounds used for modifying almoxanes can be alkylaluminum compounds, such as trialkylaluminum compounds. For example, the alkyl substituent can be an alkyl group with up to 10 carbon atoms, such as octyl, isobutyl, ethyl, or methyl. Thus, suitable hydrocarbylaluminum compounds may include trimethylaluminum, triethylaluminum, tripropylaluminum, tri-n-butylaluminum, tri-isobutylaluminum, tri(2-methylpentyl)aluminum, trihexylaluminum, tri-n-octylaluminum, and tri-n-decylaluminum. In some embodiments, the hydrocarbylaluminum compounds are trimethylaluminum and tri-n-octylaluminum. In some embodiments, the hydrocarbylaluminum compound is represented by the formula R3Al (wherein each R is independently a hydrocarbon containing between 1 and 30 carbon atoms).

[0059] In some embodiments, the hydrocarbyl aluminum compound is one or more of the trialkylaluminum mixtures, for example, dimethylethylaluminum or methyldiethylaluminum obtained from a mixture of AlMe3 and AlEt3, or diethylisobutylaluminum or ethyldiisobutylaluminum obtained from a mixture of AlEt3 and AliBu3.

[0060] Oxygen supply A suitable oxygen source is any oxygen source in which one or more oxygen atoms can react with the hydrocarbyl aluminum compound to form a novel Al-O bond. In at least one embodiment, the oxygen source may be water, for example, pure water or water in a metal salt hydrate, or may contain water. In some embodiments, the oxygen source may be, for example, an alcohol, CO or CO2, acetone, or one or more hydroxy or carbonyl compounds such as carboxylic acids. In at least one embodiment of the present disclosure, the oxygen source is one or more of carbon dioxide, carboxylic acids, ketones, aldehydes, esters, anhydrides, alcohols, or a combination thereof.

[0061] In at least one embodiment of the present disclosure, the oxygen source is of formula R 1 R 2 C=CR 3 CO2H (in the formula, R 1 and R 2 Each of these is independently a hydrogen, alkyl, alkenyl, aryl, or heteroatom-containing group, and R 3 (where is an alkyl, alkenyl, aryl, or heteroatom-containing group). In at least one embodiment of the present disclosure, the oxygen source is contained within a hydrocarbyl aluminum compound, for example, a reaction product of TMA with an alcohol, ketone, ester, or organic acid. Examples of hydrocarbyl aluminum compounds containing an oxygen source include dimethylaluminum methoxide, dimethylaluminum ethoxide, dimethylaluminum isopropoxide, dimethylaluminum n-butoxide, dimethylaluminum isobutoxide, pentamethyldialuminum-t-butoxide, tetramethyldialuminum di-t-butoxide, pentamethyldialuminum-i-propoxide, tetramethyldialuminum di-i-propoxide, or mixtures of the listed compounds. Regardless of the presence or absence of excess free hydrocarbyl aluminum compound, the initial molar ratio of Al:O (wherein O is the reactive oxygen species in the reactive oxygen species-containing compound) for forming the desired MAO composition can be 100:1, 60:1, 30:1, 10:1, 1:1, or 0.9:1. In some embodiments, the molar ratio of Al:O can be about 0.9:1 to about 100:1, e.g., about 1:1 to about 10:1, or instead about 10:1 to about 60:1, e.g., about 30:1 to about 60:1. If an unwanted excess of hydrocarbyl aluminum compound is present, it can be removed, for example, by filtration, then washing with an aliphatic diluent, and / or treatment with the fluorine compounds of this disclosure.

[0062] In some embodiments, the oxygen source is one or more of carbon dioxide, carboxylic acids, esters, anhydrides, and alcohols, or a combination thereof. In some embodiments, the oxygen source is one or more of carbon dioxide, carboxylic acids, esters, anhydrides, and alcohols, or a combination thereof, and optionally contains water. In some embodiments, the oxygen source is R 1 R 2 C=CR 3 CO2H (in the formula, R 1 and R 2 Each of these is independently a hydrogen, alkyl, alkenyl, aryl, or heteroatom-containing group, and R 3 (These are alkyl, alkenyl, aryl, or heteroatom-containing groups.) In some embodiments, the oxygen source is methacrylic acid. In at least one embodiment of the present disclosure, the oxygen source is hydrocarbylboroxine, as described in Welborn's US Patent No. 5,001,244.

[0063] Electron-withdrawing compounds and processes for introducing electron-withdrawing compounds into almoxanes TMA reacts rapidly with hydrolyzable compounds, such as the alcohol ROH, to form AlMe (3-n) (OR) n(n≦3) can be formed, in which case the n value and the position of OR depend on ROH reactivity, steric hindrance, and reactant conditions. Small R groups, for example, MeOH, EtOH, and t BuOH is toxic to MAO. This is because, without being constrained by theory, the small R group converts both free TMA and coordinated TMA to form a very stable oxygen bridge structure, RO - This is because the group is a strong electron-donating group that destabilizes the MAO anion (Scheme 6):

[0064] Scheme 6 [ka] Sterically hindered alcohols, such as 3,5-di-t-butyl-4-hydroxytoluene (BHT), form terminal OR groups, but due to the equilibrium in Scheme 7, a significant excess may be required for a nearly TMA-free system, without being constrained by theory: Scheme 7 [ka]

[0065] For example, Ijpeij et al. (US7,956,140) used MAO treatment with BHT:Al in a ratio of 0.5:1-2 to activate a CGC catalyst precursor containing a nitrogen donor ligand. Such systems may contain a large amount of neutral BHT, which is undesirable in some final products. This is because MAO is usually used in a significantly excessive amount to ensure efficient activation, and the amount of coordinating TMA (active site) can also be reduced by the equilibrium between coordinating TMA and free TMA (Scheme 1).

[0066] As shown in Schemes 4 and 5, compounds containing highly reactive electron-withdrawing atoms or groups, such as compounds containing Si-F moieties, such as silica fluoride supports and silica fluorinating agents (NH4)2SiF6, have been found to be able to convert free TMA in MAO to AlMe2F, and this AlMe2F can function as a TEB agent (TEB agent) to block the equilibrium between coordinated TMA and free TMA. The TEB agent can then replace the coordinated TMA (which becomes free TMA), as shown in Scheme 4, and thus not only eliminate the equilibrium between coordinated TMA and free TMA, but also allow more AlMe2 for precatalytic ionization. + This provides, and furthermore, the introduction of strongly electron-withdrawing atoms onto the MAO anions allows for the dispersion of more MAO anion charges, weakening the interaction of active ion pairs and thus increasing the activity of the system. Therefore, the conversion of all TMA in MAO to TEB agents is a much more efficient method for obtaining a system suitable for activating precatalysts constructed with ligands containing TMA-reactive heteroatom donors, such as N, O, S, and / or P donors, in ligands for post-metallocene and CGC half-metallocene precatalysts, by removing free TMA in MAO while maintaining or improving activation efficiency.

[0067] In some embodiments, the electron-withdrawing compound is of formula (I): A m B (u) X n (I) The inorganic compound has the following characteristics: [wherein A is an ammonium cation with m=0, 1, or 2, where if m=0, B is H, a group 3, 4, 5, 6, 7, 13, 14, 15, 16, or 17 element; if m is not zero, B is a group 3, 4, 5, 13, 14, or 15 element; u is the valence state of element B, which can be 1, 2, 3, or 4; X is an electron-withdrawing atom or group, n=m+u]. In some embodiments, the inorganic fluorine-containing compound having 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. Among these, ammonium fluorosilicate ions may be preferred due to their high fluorine efficiency.

[0068] In some embodiments, the electron-withdrawing compound is of formula (II): R o M (u) X (u-o) (II) [In the formula, R is C1-C 10 This is an organic compound having a hydrocarbyl group, where M is a group 13 or group 14 element, o=1 for group 13 elements, o=2 for group 13 elements other than Al groups, and o=1, 2, or 3 for group 14 elements, X is an electron-withdrawing atom or group, and u is the valence state of element M. In some embodiments, the organofluorine compound having formula (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, and MeAl(OC6F5)2.

[0069] Formation of equilibrium blockers (TEB agents) of coordination and free hydrocarbyl aluminum and free to Hi Use of dorocarbyl aluminum to obtain undetectable solution, solid, or supported aluminumoxane In some embodiments, the TEB agent has the formula AlR2X (R = C1-C8 hydrocarbyl group, where X is an electron-withdrawing group) for a solution, solid, or supported almoxane (e.g., MAO) composition, and this TEB agent 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 trihydrocarbyl aluminum compound (e.g., TMA) in the MAO can be controlled so that little or no free trihydrocarbyl aluminum compound (or its dimer) remains after the TEB agent is formed and replaces the coordinating trihydrocarbyl aluminum compound (e.g., coordinating TMA) in the MAO. For example, in some embodiments, the ratio of the number of active strongly electron-withdrawing atoms (e.g., F) or groups (e.g., C6F5O-) in the strongly electron-withdrawing compound to the hydrocarbyl 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 instead, based on the number of strongly electron-withdrawing atoms or groups in the strongly electron-withdrawing compound relative to the number of moles of the hydrocarbyl aluminum compound. For example, in the case of (NH4)SiF6 and Al(CH3)3, the molar ratio is 8:1, but based on the number of fluorine atoms in the strongly electron-withdrawing compound relative to the number of moles of the hydrocarbyl aluminum compound, it becomes a 6:6 ratio (i.e., a 1:1 ratio). Furthermore, TMA and TMA-reactive NH4 possibly form an inert compound having the formula (Al3Me3N3H3)2. + The ratio is 2:2 (i.e., a 1:1 ratio).

[0070] In some embodiments, the amount of free trihydrocarbyl aluminum compound (or its dimer) is determined after the formation of the solution, solid, or supported MAO composition. For example, commercially produced or obtained unsupported or supported MAO samples are treated with tetrahydrofuran (THF) as shown in Scheme 8 to remove both free and coordinated TMA from the MAO, resulting in TMA-THF adducts, THF-MAO adducts, and AlMe2+ -Can be converted to THF2 adducts:

[0071] Scheme 8 [ka]

[0072] The relative amounts of each adduct can be determined by nuclear magnetic resonance (NMR) spectroscopy. Once the total amounts of the free and coordinated trihydrocarbyl aluminum compounds are determined, an amount of the strongly electron-withdrawing compound can be introduced into the MAO based on a predetermined ratio of the strongly electron-withdrawing electron-withdrawing groups to the free trihydrocarbyl aluminum in the MAO. For example, in some embodiments, the ratio of the strongly electron-withdrawing atoms or groups in the strongly electron-withdrawing compound to the total trihydrocarbyl aluminum compound 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 instead based on the number of strongly electron-withdrawing atoms or groups in the strongly electron-withdrawing compound relative to the number of moles of the trihydrocarbyl aluminum compound (for example, in the case of (NH4)2SiF6 and Al(CH3)3, the molar ratio is 8:1, but based on the number of fluorine atoms in the strongly electron-withdrawing compound relative to the number of moles of the trihydrocarbyl aluminum compound, the ratio becomes 6:6, and furthermore, TMA and TMA-reactive NH4 which probably form an inert compound having the formula (Al3Me3N3H3)2 + The ratio is 2:2). Atomic economics can be further improved by determining the amount of free hydrocarbyl aluminum compound (or its dimer) after MAO formation. This is because a lower amount of fluorine compound can be used compared to a process that uses a certain amount of fluorine compound relative to the total amount of hydrocarbyl aluminum compound used to form the MAO.

[0073] The reaction for TEB formation (reaction of an electron-withdrawing compound with a free hydrocarbyl aluminum compound (or its dimer)) can proceed at any suitable temperature, e.g., about 0°C to about 100°C, e.g., about 10°C to about 30°C, e.g., about 20°C, e.g., ambient temperature. The reaction can proceed under solvent-free conditions (e.g., solid-solid) or with any suitable diluent. In some embodiments, the diluent may be an organic diluent, e.g., an aliphatic diluent or an aromatic diluent. Aliphatic diluents are those of formula C n H (2n+2) Acyclic alkanes having formula C (wherein n=4 to 30), for example isobutane, butane, isopentane, hexane, n-heptane, octane, nonane, or decane, formula C n H 2n-2 The aromatic diluent may be a cycloalkane (wherein n=5 to 30), such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and mixtures thereof. The aromatic diluent may contain benzene, toluene, or xylene.

[0074] After treatment with an electron-withdrawing compound, MAO (unsupported or supported) may contain an amount of Al of about 2% by mass or less, for example, about 1.5% by mass or less, for example, about 1% by mass or less, for example, about 0.5% by mass or less, for example, about 0.25% by mass or less, for example, about 0.1% to about 2% by mass, for example, about 0.1% to about 1.5% by mass, for example, about 0.2% to about 1% by mass, for example, about 0.3% to about 0.7% by mass, relative to the total aluminum content of MAO derived from the free hydrocarbyl aluminum compound. In some embodiments, the TEB agent is formed on a solid or supported MAO composition after a free TMA removal step, such as filtration or decanting, has been performed based on the chemical reaction of Scheme 9 below, without the need to quantify the TMA, in order to remove free TMA, before being added to the solid or supported MAO composition:

[0075] Scheme 9 [ka]

[0076] Methods for preparing pre-formed TEB agents include, but are not limited to, the following: 1) AlR3 (wherein R is a C1-C8 hydrocarbyl group or a mixture thereof, for example, Me, Et, i Bu (or Oct, preferably a Me group) is brought into contact with a strongly electron-withdrawing compound to form an AlR2X compound in situ as the main product. 2) AlR2Y (wherein R is 1, and Y is a non-fluorine halide, e.g., Cl, Br, or I) is an electron-withdrawing salt of formula (III): MX u (III) (In the formula, M is a Group 1 or Group 2 metal, X is an electron-withdrawing group as defined in the section on strongly electron-withdrawing compounds, and u is the valence state of the metal M) is brought into contact with the metal. The stoichiometry of the reaction is shown in Scheme 10: Scheme 10 AlR2Y+1 / uMX u =AlR2X+1 / uMY u Here MY u As solid waste, it can be removed, for example, by filtration.

[0077] In some embodiments, AlR2Y is AlMe2Cl, AlMe2Br, AlMe2I, AlEt2Cl, AlEt2Br, AlEt2I, Al i Bu2Cl, Al i Bu2Br, Al i Bu2I, AlOct2Cl, AlOct2Br, AlOct2I, AlMe2CN, AlEt2CN, Al i Select from Bu2CN, AlOct2CN, etc. uThe ion is 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 it is also possible to form AlMe2OC6F5 + MgCl2 using, for example, AlMe2Cl + ClMgOC6F5, such as ClMgOC6F5. For better solid separation from the desired AlMe2F or AlMe2OC6F5 product, MgCl2 can be oligomerized using a MgCl2 flocculant, such as dioxolane.

[0078] Any carrier material and derived from it Hi aluminum-free supported aluminum In embodiments of this specification, the catalyst system may include a support material. For example, the support material may be contacted with a pre-formed solution almoxane, such as a commercially available solution MAO, to form a supported MAO, and subsequently the supported MAO may be contacted with a strongly electron-withdrawing compound to form a TEB agent in situ, or it may be contacted with the pre-formed TEB agent of this disclosure. Alternatively, the support material may be contacted with the TMA-free MAO of this disclosure to form a supported activator, and subsequently the supported activator may be contacted with a pre-catalyst compound. Alternatively, the pre-catalyst compound may be contacted with the TMA-free MAO to form a solution catalyst system, and subsequently the catalyst system may be contacted with the support material to form a supported catalyst system. Alternatively, the supported material may be supported on an oxygen source, such as water, and the oxygen-supported carrier may then be added to a cooled TMA solution, either in solid form or slurry, with or without cooling, and optionally heated, to form a supported MAO composition. This can then be treated with a TEB agent formed in situ via contact between the supported MAO and a strongly electron-withdrawing compound, optionally treated with AlR3, optionally subjected to a filtration / washing step, or treated with a pre-formed TEB agent, subjected to the necessary filtration / washing steps, to form a TMA-free supported MAO before contact with the pre-catalyst, thereby forming the final catalyst.

[0079] The carrier material can be a porous carrier material, such as talc and inorganic oxides. Other carrier materials include zeolite, clay, organoclay, or other organic or inorganic carrier materials, or mixtures thereof.

[0080] The carrier material can be an inorganic oxide. The inorganic oxide can also be in a finely divided form. Suitable inorganic oxide materials for use in the catalyst systems herein include metal oxides of Group 2, Group 4, Group 13, and Group 14, such as silica, alumina, and mixtures thereof. Other inorganic oxides that can be used alone or in combination with silica or alumina include magnesium, titania, and zirconia. However, other suitable carrier materials can be, for example, finely divided functionalized polyolefins, such as finely divided polyethylene. Examples of suitable carriers include magnesium, titania, zirconia, montmorillonite, phyllosilicate, zeolite, talc, and clay. Combinations of these carrier materials can also be used, for example, silica-chromium, silica-alumina, and silica-titania. In at least one embodiment, the support material is selected from Al2O3, ZrO2, SiO2, SiO2 / Al2O3, SiO2 / TiO2, silica clay, silicon dioxide / clay, or a mixture thereof.

[0081] The carrier material, for example, an inorganic oxide, is approximately 10 m 2 / g~about 800m 2 Surface area per g: approximately 0.1 cm² 3 / g ~ approx. 4.0cm 3 It can have a pore volume of 1 / g and an average particle size of approximately 3 μm to 300 μm. The surface area of ​​the carrier material is approximately 50 m². 2 / g~about 500m 2 It can be / g, and the pore volume is approximately 0.5 cm³. 3 / g ~ approx. 3.5cm 3 It can be / g, and the average particle size can be approximately 10 μm to approximately 200 μm. For example, the surface area of ​​the carrier material is approximately 100 m². 2 / g~about 400m2 It can be / g, and the pore volume is approximately 0.8 cm³. 3 / g~approx.3.0cm 3 The particle size can be approximately 5 μm to approximately 100 μm, and the average particle size can be approximately 5 μm to approximately 100 μm. The average pore size of the carrier 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 carrier material has a high surface area, amorphous silica (surface area = 300 m²). 2 / gm, 1.65cm 3 This is the pore volume per gm. For example, suitable silica can be silica commercially available under the trademark names Daviso® 952 or Davison® 955 (Davison Chemical Division of WRGrace and Company). In other embodiments, DAVISON® 948 is used. Alternatively, the silica can be ES-70, ES70X, ES757, PD17062, PD16042, PD16043, or PD14024 silica (Ecovyst, formerly PQ Corporation, Malvern, Pennsylvania), DML403, 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 are calcined at, for example, 200°C, 400°C, 600°C, or 875°C.

[0082] The support material should be dried for the support of the pre-formed MAO, i.e., free from or substantially free from absorbed water, although calcination is not required for in situ MAO support if water is used as an oxygen source. Drying of the support material may be affected by heating or calcination at temperatures of about 100°C to about 1000°C, for example, at least about 600°C. If the support material is silica, it is heated to at least 200°C, for example, at about 200°C to about 850°C, for example, about 600°C, for a period of about 30 minutes to about 100 hours, about 4 hours to about 72 hours, or about 24 hours to about 60 hours. The calcined support material must have at least some reactive hydroxyl (OH) groups to produce the supported catalyst system of the present disclosure. The calcined support material is then brought into contact with at least one polymerization catalyst comprising at least one catalyst compound and an activator.

[0083] A carrier material having reactive surface groups such as hydroxyl groups is slurryed in a non-polar diluent, and the resulting slurry is contacted with a pre-catalyst compound and MAO in solid or solution form, either in any order if a pre-formed TMA-free MAO is present, or if a pre-formed standard MAO is present, it is first contacted with the standard MAO, and then the supported MAO is treated with a TEB agent formed in situ or a pre-formed TEB agent, and after other necessary steps to obtain a TMA-free supported MAO are performed, it is contacted with the pre-catalyst compound. In at least one embodiment, the carrier material slurry is first contacted with an activator (e.g., TMA-free MAO) for about 0.5 to about 24 hours, about 2 to about 16 hours, or about 4 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 produced in situ. In an alternative embodiment, the TMA-free supported MAO slurry is first brought into contact with the pre-catalyst compound for a period of time such as about 0.5 hours to about 24 hours, about 1 hour to about 16 hours, or about 2 hours to about 8 hours. The mixture of catalyst, activator, and support is heated to approximately 0°C to approximately 70°C, for example, approximately 23°C to approximately 60°C, for example, at room temperature. The contact time can be approximately 0.5 hours to approximately 24 hours, for example, approximately 2 hours to approximately 16 hours, or approximately 4 hours to approximately 8 hours.

[0084] A suitable nonpolar diluent is a material that is liquid at the polymerization temperature and to which all reactants used herein, e.g., activators and precatalytic compounds, are at least partially soluble. Nonpolar diluents for in situ MAO loading can be alkanes, e.g., isopentane, hexane, isohexane, n-heptane, octane, nonane, and decane, but a variety of other materials can also be used, including cycloalkanes, e.g., cyclohexane, aromatics, e.g., benzene, toluene, and ethylbenzene, on the other hand, aromatics, e.g., benzene, toluene, and ethylbenzene can be used for pre-formed MAO loadings. In at least one embodiment, the supported activator is a supported TMA-free MAO (TF-MAO), which is an MAO supported on silica (e.g., ES70 silica calcined at 400°C) and has an undetectable or low amount of free TMA after performing the steps of partially or completely converting all TMA in the MAO into a TEB agent, forming a coordinating TEB agent on the main MAO structure, and optionally removing free TMA.

[0085] Formation of a catalytic system Embodiments of the present disclosure include a method for preparing a catalyst system, which comprises contacting an unsupported MAO (TMA-free solution) or a supported MAO (TMA-free support) with at least one pre-catalyst compound having a group 3 to 12 metal atom or a lanthanide metal atom in an organic diluent. Alternatively, the TMA-free solution of MAO may be first contacted with at least one pre-catalyst compound, and then with a support. In at least one embodiment, the unsupported or supported MAO is heated before being brought into contact with the catalyst compound. Unsupported or supported MAO can be solvated or slurryed in an organic diluent, and the resulting mixture is brought into contact with a solution of at least one catalyst compound. The catalyst compound may also be added as a solid to the mixture of the organic diluent and MAO. In at least one embodiment, the MAO mixture is brought into contact with the catalyst compound for a period of time ranging from 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.

[0086] The mixture of the catalyst compound and MAO can be heated to a temperature of about 0°C to about 70°C, for example, about 23°C to about 60°C, for example, room temperature. The contact time may be about 0.02 hours to about 24 hours, for example, about 0.1 hours to about 1 hour, about 0.2 hours to about 0.6 hours, about 2 hours to about 16 hours, or about 4 hours to about 8 hours.

[0087] A suitable organic diluent is a material that is liquid at the reaction temperature, in which some or all of the reactants used herein, such as MAO and catalyst compounds, are at least partially soluble (or suspended in the case of a solid carrier). A non-limiting example of a diluent is a material of formula C n H (2n+2) Acyclic alkanes having formula C (wherein n is 4 to 30), such as isobutane, butane, isopentane, hexane, n-heptane, octane, nonane, decane, etc., and formula C n H (2n-2) The compounds include cycloalkanes (wherein n is 5 to 30), such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and mixtures thereof. Aromatic diluents may include benzene, toluene, or xylene.

[0088] The diluent can be added to the reactor, followed by the addition of MAO. The catalyst can then be added to the reactor, for example, as a catalyst solution in an organic diluent or as a solid. The mixture can be stirred at a temperature such as room temperature. Additional diluents can be added to the mixture to form a slurry with a desired viscosity, for example, about 2 cc / g silica to about 20 cc / g silica, or for example, about 4 cc / g silica. The diluent can then be removed. Removal of the diluent can be done by drying the mixture, carrying it out under a vacuum, purging it under an inert atmosphere, and heating the mixture, or a combination thereof. For heating the mixture, any suitable temperature can be used to evaporate the aliphatic diluent. It is understood that reducing the pressure under vacuum will lower the boiling point of the aliphatic diluent depending on the reactor pressure. The temperature at which the diluent is removed can be about 10°C to about 200°C, for example, about 60°C to about 140°C, for example, about 60°C to about 120°C, for example, about 80°C or lower, for example, about 70°C or lower. In at least one embodiment, removing the diluent includes applying a nitrogen purge from the bottom of the container by applying heat, applying a vacuum, and bubbling nitrogen through the mixture. The mixture becomes dry.

[0089] Precatalytic compounds The terms "catalyst," "catalytic compound," "catalytic complex," "transition metal complex," "transition metal compound," "precatalytic compound," and "precatalytic complex" are used interchangeably to describe transition metal or lanthanide metal complexes that form an olefin polymerization catalyst when combined with an appropriate activator. In at least one embodiment, the disclosure provides a catalytic system comprising a catalytic compound having a metal atom. The catalytic compound may be a metallocene catalytic compound. The metal may be a group 3 to group 12 metal atom, for example, a group 3 to group 10 metal atom, or a lanthanide group atom. The catalytic compound having a group 3 to group 12 metal atom may be monodentate or polydentate, for example, bidentate, tridentate, or tetradentate, and a heteroatom of the catalyst, for example, phosphorus, oxygen, nitrogen, or sulfur, is chelated to the catalytic metal atom. A non-limiting example is bis(phenolate). 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 atoms. In at least one embodiment, the Group 3 to Group 10 metal atoms are 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, Group 5, and Group 6 metal atoms. 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, for example, +2, +3, or +4.

[0090] The catalyst compounds of this disclosure may be chromium or chromium-based catalysts. Examples of chromium-based catalysts include chromium oxide (CrO3) and silyl chromate catalysts. Chromium catalysts have been a subject of extensive development in the field of continuous fluidized bed vapor polymerization for the production of polyethylene polymers. Such catalysts and polymerization processes are described, for example, in U.S. Patent Publication No. 2011 / 0010938, as well as U.S. Patents No. 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. A mono-Cp catalyst precursor compound useful in this disclosure has one cyclopentadienyl (Cp) ligand (including an isoglobal ligand to cyclopentadienyl) and at least one non-Cp ligand, each having at least one polar atom directly bonded to the metal center of the pre-catalyst, either bridged or unbridged to the Cp ligand.

[0091] In at least one embodiment, the monoCp precatalyst compound of the present disclosure is of formula (MC-I): T y Cp m MG n X q (MC-I) [In the formula, Cp is independently a substituted or unsubstituted cyclopentadienyl ligand, or an isoglobal substituted or unsubstituted ligand to cyclopentadienyl, such as indenyl, fluorenyl, tetrahydro-s-indacenyl, and tetrahydro-as-indecenyl. M is a group 4 transition metal, such as Hf, Ti, or Zr. G is a group JR * z A heteroatom group represented by (wherein J is N, P, O or S, and R * C1-C is a linear, branched, or cyclic C1-C 20 (It is hydrocarbyl). 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 is equal to the oxidation state of the transition metal, e.g., 2, 3 or 4, e.g., 4).

[0092] In at least one embodiment, J is N and R * These are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, cyclooctyl, cyclododecyl, decyl, undecyl, dodecyl, adamantyl, or isomers thereof. Exemplary JR * z Examples of bases include t-butylamide and cyclododecylamide. Examples of crosslinking 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 a crosslinking group of the formula ER d 2 or (ER d 2)2(wherein E is C, Si, or Ge, and each R d These are independently hydrogen, halogen, C1-C20 hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) or C1-C20 substituted hydrocarbyl, or two R d It can be represented as an aromatic, partially saturated or saturated, cyclic, or fused-ring cyclic structure.

[0093] Each X is independently selected from the group consisting of hydrocarbyl radicals having 1 to 20 carbon atoms, aryls, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and combinations thereof (two Xs may form part of a fused ring or ring system). For example, each X is independently selected from halides, aryls, and C1-C5 alkyl groups, for example, each X is a phenyl, methyl, ethyl, propyl, butyl, pentyl, or chloro group.

[0094] In at least one embodiment, the monoCp catalyst precursor compound of formula (MC-I) is Dimethylsilanediyl (2,3,4,5-tetramethylcyclopentadienyl)(cyclododecylamide) M(R)2; Dimethylsilanediyl (2,3,4,5-tetramethylcyclopentadienyl)(cycloundecylamide) M(R)2; Dimethylsilanediyl (2,3,4,5-tetramethylcyclopentadienyl)(cyclodecylamide) M(R)2; Dimethylsilanediyl (2,3,4,5-tetramethylcyclopentadienyl)(t-butylamide)M(R)2; Dimethylsilanediyl(cyclopentadienyl)(1-adamantylamide)M(R)2; Dimethylsilanediyl (3-tert-butylcyclopentadienyl) (1-adamantylamide) M(R)2; Dimethylsilanediyl(tetramethylcyclopentadienyl)(1-adamantylamide)M(R)2; Dimethylsilanediyl(tetramethylcyclopentadienyl)(1-adamantylamide)M(R)2; Dimethylsilanediyl(tetramethylcyclopentadienyl)(1-adamantylamide)M(R)2; Dimethylsilanediyl(tetramethylcyclopentadienyl)(1-tert-butylamide)M(R)2; Dimethylsilanediyl (fluorenyl) (1-tert-butylamide) M(R)2; Dimethylsilanediyl(tetramethylcyclopentadienyl)(1-cyclododecylamide)M(R)2; μ-(C6H5)2C(tetramethylcyclopentadienyl)(1-cyclododecylamide)M(R)2; Dimethylsilanediyl (η 5 -2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indasen-1-yl)(tert-butylamide)M(R)2; A selection is made from, where M is selected from Ti, Zr, and Hf, and each R is selected from halogens or C1-C5 alkyl groups (e.g., chloro, bromo, methyl, ethyl, propyl, butyl, pentyl, or their isomers). In at least one embodiment, M is Ti and each R is methyl.

[0095] The mono-Cp precatalyst compounds of this disclosure can be synthesized as described in US5,621,126 and US5,547,675, which are incorporated herein by reference.

[0096] The monoCp precatalyst compound is also preferably C s or pseudo-C s Equation (MC-II) exhibits symmetry:

[0097] [ka] [In the formula, M is zirconium, L 1 is an unsubstituted fluorenyl, heterocyclopentapentalenyl, or heterofluorenyl, or a substituted fluorenyl, heterocyclopentapentalenyl, or heterofluorenyl ligand having one or more symmetric or pseudosymmetric substituents, where each substituent is independently a radical group that is hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or gelmylcarbyl, and optionally two or more adjacent substituents may bond to form substituted or unsubstituted, saturated, partially unsaturated, or aromatic, cyclic, or polycyclic substituents. G is a crosslinking group, J is a heteroatom of Group 15, for example, N or P, for example, N. R' is a radical group that is a hydrocarbyl, substituted hydrocarbyl, halocarbyl, or substituted halocarbyl. L' is a neutral Lewis base, and w indicates the number of L's bonded to M, where w is 0, 1, or 2, and any L' may be bonded to any X. The compounds may include a structure represented by [X independently being a hydride radical, a hydrocarbyl radical, a substituted hydrocarbyl radical, a halocarbyl radical, a substituted halocarbyl radical, a silylcarbyl radical, a substituted silylcarbyl radical, a gelmylcarbyl radical, or a substituted gelmylcarbyl radical], or both X may bond to a metal atom to form a metalacycle ring containing about 3 to about 20 carbon atoms, or both together may be an olefin, diolefin, or ane ligand, and both X may independently be a halogen, alkoxide, aryloxide, amide, phosphide, or other monovalent anionic ligand, or both X may also bond to form an anionic chelate ligand].

[0098] In equation (MC-II), L 1 Fluorenyl or substituted fluorenyl, for example, fluorenyl, 2,7-dimethylfluorenyl, 2,7-diethylfluorenyl, 2,7-dipropylfluorenyl, 2,7-dibutylfluorenyl, 2,7-diphenylfluorenyl, 2,7-dichlorofluorenyl, 2,7-dibromofluorenyl, 3,6-dimethylfluorenyl, 3,6-diethylfluorenyl, 3,6-dipropylfluorenyl, 3,6-dibutylfluorenyl, 3,6-diphenylfluorenyl, 3,6-dichlorofluorenyl, 3,6-dibromofluorenyl, or 1,1,4,4,7,7,10,10-octamethyl-octahydrodibenzofluorenyl Olenyl, for example, fluorenyl, 2,7-dimethylfluorenyl, 2,7-diethylfluorenyl, 2,7-dipropylfluorenyl, 2,7-dibutylfluorenyl, 3,6-dimethylfluorenyl, 3,6-diethylfluorenyl, 3,6-dipropylfluorenyl, 3,6-dibutylfluorenyl, or 1,1,4,4,7,7,10,10-octamethyl-octahydrodibenzofluorenyl, for example, 2,7-di-tert-butylfluorenyl, 3,6-di-tert-butylfluorenyl, 1,1,4,4,7,7,10,10-octamethyl-octahydrodibenzofluorenyl, or fluorenyl. G is methylene, dimethylmethylene, diphenylmethylene, dimethylsilylene, methylphenylsilylene, diphenylsilylene, di(4-triethylsilylphenyl)silylene, ethylene, e.g., diphenylmethylene, diphenylsilylene, methylphenylsilylene, and dimethylsilylene, e.g., dimethylsilylene. A suitable J can be nitrogen. R' is a hydrocarbil or halocarbil, e.g., C3-C 20It is a hydrocarbyl, for example, all isomers (including cyclic and polycyclic) of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, benzyl, phenyl, and substituted phenyl, for example, tert-butyl, neopentyl, benzyl, phenyl, diisopropylphenyl, adamantyl, norbornyl, cyclohexyl, cyclooctyl, cyclodecyl, and cyclododecyl, for example, tert-butyl, adamanto-1-yl, norborn-2-yl, cyclohexyl, cyclooctyl, and cyclododecyl. X is a hydrocarbyl or halo, for example, methyl, benzyl, fluoro(floro), or chloro, for example, methyl or chloro, w is zero (L' does not exist), and M is zirconium.

[0099] Examples of mono-Cp catalyst compounds with polar donors, but not limited to these, include:

[0100] [Table 1-1] [Table 1-2]

[0101] Monometallocene precatalytic compounds are also, Dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamide)titaniumdimethyl; Dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamide)titanium dichloride; Dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamide)titaniumdimethyl; or Dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamide)titanium dichloride; You may choose from the following.

[0102] In some embodiments, the pre-catalyst of the Disclosure may be a “post-metallocene” catalyst having an oxygen atom and / or a nitrogen atom. For example, the catalyst of the Disclosure may be a metal complex having a metal selected from Group 3 to 10 or lanthanide metals and a tridentate monovalent anionic ligand or divalent 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 the metal ligand complex is characterized by a pair of 4-membered, 5-membered, 6-membered, 7-membered, or 8-membered metallocycle rings, or a pair of mixed members, for example, a mix of a 4-membered and a 5-membered ring, a mix of a 5-membered and a 6-membered ring, a mix of a 6-membered and a 7-membered ring, a mix of a 5-membered and a 7-membered ring, or a mix of a 7-membered and an 8-membered ring.

[0103] The catalyst complexes of the present disclosure comprise a tridentate dianionic ligand containing a metal selected from groups 3 to 10 of the periodic table or lanthanide metals, two anionic donor groups, and a neutral heterocyclic Lewis base donor, the heterocyclic donor being covalently bonded between the two anionic donors. In some embodiments, the dianionic tridentate ligand is characterized by a central heterocyclic donor group and two phenolate donors, the tridentate ligand coordinating to the metal center to form two eight-membered rings. In some embodiments, the heterocyclic Lewis base donor of the catalytic compound is characterized by a nitrogen or oxygen donor atom. For example, the heterocyclic group includes pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan derivatives, and their substituted variations. In some embodiments, the heterocyclic Lewis base does not have hydrogen at the alpha position relative to the donor atom. In some embodiments, the heterocyclic Lewis base donor includes pyridine, 3substituted pyridine, and 4substituted pyridine.

[0104] The anionic donor of the tridentate dianionic ligand may be an aryl thiolate, phenolate, or anilide. In some embodiments, the anionic donor is a phenolate. The tridentate dianionic ligand coordinates to a metal center to form a complex that may not have mirror plane symmetry. In some embodiments, the tridentate dianionic ligand coordinates to a metal center to form a complex with a two-fold rotational symmetry axis. When determining the symmetry of the bis(phenolate) complex, only the metal and the dianionic tridentate ligand are considered (i.e., the remaining ligands are ignored).

[0105] The catalytic compounds of this disclosure may be bis(arylphenolate)pyridine complexes. The bis(arylphenolate)pyridine complex may have a tridentate bis(arylphenolate)pyridine ligand, which coordinates to a group 4 transition metal to form two 8-membered rings. In some embodiments, the bis(arylphenolate)pyridine complex includes a dianionic, tridentate ligand transition metal complex characterized by a central neutral donor group and two phenolate donors, which coordinate to a metal center to form two 8-membered rings, for example, a post-metallocene catalyst may be an 8-8 catalyst. In this type of complex, it is advantageous that the central neutral donor is a heterocyclic group. It is advantageous that the heterocyclic group does not have hydrogen at the alpha position relative to the heteroatom. In this type of complex, it may also be advantageous that the phenolate is substituted with one or more cyclic tertiary alkyl substituents. The use of cyclic tertiary alkyl-substituted phenolates can improve the ability of these catalysts to produce high molecular weight polymers.

[0106] In some embodiments, the bis(phenolate) ligand can be a tridentate dianionic ligand that coordinates to the metal M in a manner that forms a pair of eight-membered metallocycle rings. The bis(phenolate) ligand encapsulates the metal to form a complex with a two-fold rotation axis, thus conferring C2 symmetry to the complex. The C2 shape and eight-membered metallocycle rings are characteristic features of these complexes, which make them effective catalytic components for the production of polyolefins, particularly isotactic poly(alphaolefins). When the ligand coordinates to the metal in a manner that the complex has mirror (Cs) symmetry, the catalyst is expected to produce only atactic poly(alphaolefins). These symmetry-reactivity concepts are summarized in Bercaw, JE (2009) in Macromolecules, v.42, pp. 8751-8762. The pair of eight-membered metallocycle rings in the catalytic compound is also a noteworthy feature that is advantageous for temperature stability and isoselectivity of the monomer chain. Related Group 4 complexes, characterized by smaller 6-membered metallocycle rings, exhibit C2 symmetry and C when used in olefin polymerization. s It is known to form a mixture of symmetrical complexes (Macromolecules 2009, v.42, pp.8751-8762), and therefore is not well-suited for the formation of highly isotactic poly(alphaolefins).

[0107] The bis(phenolate) ligand containing an oxygen donor group (i.e., E=E'=oxygen in formula (I)) can be substituted with an alkyl, substituted alkyl, aryl, or other group. It may be advantageous for each phenolate group to be substituted at a ring position adjacent to the oxygen donor atom. For example, the substitution adjacent to the oxygen donor atom can be an alkyl group containing 1 to 20 carbon atoms. The substitution adjacent to the oxygen donor atom can be a non-aromatic cyclic alkyl group having one or more 5-membered or 6-membered rings. The substitution adjacent to the oxygen donor atom can be a cyclic tertiary alkyl group. In some embodiments, the substitution adjacent to the oxygen donor atom is adamantane-1-yl or substituted adamantane-1-yl.

[0108] A neutral heterocyclic Lewis base donor is covalently bonded between two anionic donors (for example, between two phenolate groups) via a "linker group" that binds the heterocyclic Lewis base to an anionic donor. The "linker group" is (A in formula (PM-I) 3 A 2 ) and (A 2’ A 3’ ) is shown. The selection of each linker group can affect the catalytic performance, for example, the stereoregularity of the resulting poly(alphaolefin). Each linker group is a C2-C with a length of 2 atoms. 40 It can be a divalent group. One or both linker groups may independently be phenylene, substituted phenylene, heteroaryl, vinylene, or acyclic two-carbon linker groups. If one or both linker groups are phenylene, alkyl substituents on the phenylene group may be selected to optimize catalytic performance. Typically, one or both phenylenes may be unsubstituted or independently C1-C 20 Alkyl compounds, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, or their isomers, such as isopropyl, may be substituted.

[0109] In some embodiments, the catalyst compound is of formula (PM-I): [ka] [In the formula, M is a transition metal or lanthanide from Group 3, Group 4, Group 5, or Group 6 (e.g., Hf, Zr, or Ti), E and E' are, independently, O, S, or NR. 9 And R 9 Independently, hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 Substituted hydrocarbyl or heteroatom-containing group, for example, O, where both E and E' are O, Q is an atom of Group 14, Group 15, or Group 16 that forms a coordinate bond with metal M. For example, Q is C, O, S, or N. For example, Q is C, N, or O. For example, Q is N. A 1 QA 1’ It is part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms, and A is connected via a triatomic bridge with Q as the central atom of the triatomic bridge. 2 to A 2’ It is connected to (A 1 QA 1’ is, A 1 and A 1’ (Together with the curve showing the bond, it represents a heterocyclic Lewis base.) A 1 and A 1 Each of these is independently C, N, or C(R) 22 ) and R 22 is hydrogen, C1-C 20 Hydrocarbyl, and C1-C 20 Selected from substituted hydrocarbyls (e.g., A 1 and A 1 Each of these is C), [ka] A is formed via a two-atom bridge. 1A divalent group containing 2 to 40 nonhydrogen atoms linked to an E-bonded aryl group, for example, ortho-phenylene, substituted ortho-phenylene, ortho-arene, substituted ortho-arene, indolene, substituted indolene, benzothiophene, substituted benzothiophene, pyrolene, substituted pyrolene, thiophene, substituted thiophene, 1,2-ethylene (-CH2CH2-), substituted 1,2-ethylene, 1,2-vinylene (-HC=CH-), or substituted 1,2-vinylene, for example, [ka] It is a divalent hydrocarbyl group, [ka] A is formed via a two-atom bridge. 1 A divalent group containing 2 to 40 nonhydrogen atoms linked to an aryl group with an E bond, for example, ortho-phenylene, substituted ortho-phenylene, ortho-arene, substituted ortho-arene, indolene, substituted indolene, benzothiophene, substituted benzothiophene, pyrolene, substituted pyrolene, thiophene, substituted thiophene, 1,2-ethylene (-CH2CH2-), substituted 1,2-ethylene, 1,2-vinylene (-HC=CH-), or substituted 1,2-vinylene, for example, [ka] It is a divalent hydrocarbyl group, Each L is independently a Lewis base. Each X is independently an anionic ligand. n is 1, 2, or 3. m is 0, 1, or 2. n+m does not exceed 4. R 1 , R 2 , R 3 , R 4 , R 1’ , R 2’ , R 3’ , and R 4’ Each of them independently produces hydrogen, C1-C 40Hydrocarbyl, C1-C 40 Substituted hydrocarbyl, heteroatom, or heteroatom-containing group (e.g., R 1’ and R 1 These are independently cyclic groups (e.g., cyclic tertiary alkyl groups) or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 1’ and R 2’ , R 2’ and R 3’ , R 3’ and R 4’ One or more of these may bond to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, and the substitutions on the rings can bond to form additional rings. Any two L groups may be bonded together to form a bidentate Lewis base. The X group may be bonded to the L group to form a monoanionic bidentate group. This can be expressed as: [Any two X groups may bond together to form a dianionic ligand group.]

[0110] The metal, M, is selected from elements of Group 3, Group 4, Group 5, or Group 6, for example, from Group 4. For example, the metal, M, is zirconium or hafnium. The donor atom Q (in formula (PM-I)) of a neutral heterocyclic Lewis base can be nitrogen, carbon, or oxygen. In some embodiments, Q is nitrogen. Non-limiting examples of neutral heterocyclic Lewis bases include derivatives of pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, and furan, as well as their substituted forms. Heterocyclic Lewis bases can include derivatives of pyridine, pyrazine, thiazole, and imidazole.

[0111] A of heterocyclic Lewis bases 1 and A 1’Each of these (formula (PM-I)) is independently C, N, or C(R 22 ) and R 22 is hydrogen, C1-C 20 Hydrocarbyl, and C1-C 20 Selected from substituted hydrocarbyls. In some embodiments, A 1 and A 1’ Each of them is carbon. If Q is carbon, then A 1 and A 1’ Each of them is nitrogen and C(R) 22 ) can be selected from. If Q is nitrogen, then A 1 and A 1’ Each of them can be carbon. In some embodiments, Q = nitrogen and A 1 =A 1’ = carbon. If Q is nitrogen or oxygen, the heterocyclic Lewis base in formula (PM-I) is A 1 Or A 1’ The atom may not have any hydrogen atoms bonded to it, and in some cases, it may even be preferable that it does not have any hydrogen atoms. This is because hydrogen atoms at these positions are thought to be capable of causing undesirable decomposition reactions that reduce certain stability of catalytic activity. A 1 and A 1’ Together with the curves that connect them, A 1 QA 1’ The heterocyclic Lewis base represented by (formula (PM-I)) can be selected from the following, and each R 23 The group consists of hydrogen, heteroatoms, and C1-C atoms. 20 Alkyl, C1-C 20 Alkoxide, C1-C 20 Amides, and C1-C 20 Selected from substituted alkyl groups.

[0112] [ka]

[0113] In some embodiments, A 1 and A 1’ Together with the curves that connect them, A 1 QA1’ A heterocyclic Lewis base represented by (formula (PM-I)) is a six-membered ring containing zero or one ring heteroatom, or a five-membered ring containing zero, one, two, or three ring heteroatoms. Alternatively, A 1 and A 1’ Together with the curves that connect them, A 1 QA 1’ The heterocyclic Lewis base represented by (formula (PM-I)) is not a six-membered ring containing two or more ring heteroatoms.

[0114] In some embodiments of formula (PM-I), Q is C, N, or O, for example, Q is N. In some embodiments of formula (PM-I), A 1 and A 1’ Each of them independently contains carbon, nitrogen, or C(R) 22 ) and R 22 is hydrogen, C1-C 20 Hydrocarbyl, substituted C1-C 20 Selected from hydrocarbyl. In some embodiments, A 1 and A 1’ Each of them is carbon. In some embodiments of formula (PM-I), A of formula (PM-I) 1 QA 1’ These are heterocyclic Lewis bases, such as pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, or their substituted variations.

[0115] In some embodiments of formula (PM-I), A 1 QA 1’ It is part of a heterocyclic Lewis base containing 2 to 20 non-hydrogen atoms, and A is formed via a triatomic bridge with Q as the central atom of the triatomic bridge. 2 to A 2’ It is connected to A. In some embodiments, each A 1 and A 1’ A is a carbon atom, 1 QA 1’The fragments form pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, or substituted forms thereof, or part of a substituted form thereof. In at least one embodiment of formula (PM-I), Q is carbon, and A 1 and A 1’ Each of these is N or C(R 22 ) and R 22 is hydrogen, C1-C 20 Hydrocarbyl, substituted C1-C 20 Selected from hydrocarbyl, heteroatom, or heteroatom-containing group. In such embodiments, A 1 QA 1’ The fragments form part of a cyclic carbene, an N-heterocyclic carbene, a cyclic aminoalkyl carbene, or a substituted variant thereof.

[0116] In some embodiments of formula (PM-I), [ka] It is a divalent group containing 2 to 20 non-hydrogen atoms, and via a two-atom bridge, A 1 It is linked to an E-bonded aryl group, [ka] It is either a linear alkyl group or a part of a cyclic group (for example, an ortho-phenylene group or an ortho-arylene group which may be substituted) or a substituted variant thereof.

[0117] [ka] It is a divalent group containing 2 to 20 nonhydrogen atoms, and A is formed via a two-atom bridge. 1’ It is linked to the E'-bonded aryl group, [ka] This forms a part of a linear alkyl or cyclic group, for example, an ortho-phenylene group which may be substituted, or an ortho-arylene group, or a substituted variant thereof. In some embodiments of formula (PM-I), M is Zr or Hf, Q is nitrogen, and A 1 and A 1’ Both are carbon, E and E ’ Both are oxygen, and R 1 and R 1’ Both are C4-C 20 It is a cyclic tertiary alkyl group.

[0118] In some embodiments of formula (PM-I), M is Zr or Hf, Q is nitrogen, and A 1 and A 1’ Both are carbon, E and E ’ is oxygen, R 1 and R 1’ is adamantane-1-yl or substituted adamantane-1-yl. In some embodiments of formula (PM-I), M is Zr or Hf, Q is nitrogen, and A 1 and A 1’ Both are carbon, E and E ’ Both are oxygen, and R 1 and R 1’ Both are C6-C 20 It is Ariel. In some embodiments, the catalyst compound is of formula (PM-II):

[0119] [ka] [In the formula, M is a transition metal or lanthanide from Group 3, Group 4, Group 5, or Group 6 (for example, a Group 4 transition metal such as Hf, Zr, or Ti). E and E' are, independently, O, S, or NR. 9 And R 9 Independently, hydrogen, C1-C 40 Hydrocarbyl, C1-C 40A substituted hydrocarbyl or heteroatom-containing group, for example, O, and for example, both E and E' are O. Each L is independently a Lewis base. Each X is independently an anionic ligand. n is 1, 2, or 3. m is 0, 1, or 2. n+m does not exceed 4. R 1 , R 2 , R 3 , R 4 , R 1’ , R 2’ , R 3’ , and R 4’ Each of them independently produces hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 A substituted hydrocarbyl, heteroatom, or heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 1’ and R 2’ , R 2’ and R 3’ , R 3’ and R 4’ One or more of these may bond to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, and the substitutions on the rings can bond to form additional rings. Any two L groups may be bonded together to form a bidentate Lewis base. The X group may be bonded to the L group to form a monoanionic bidentate group. Any two of the X groups may bond together to form a dianionic ligand group. R 5 , R 6 , R 7 , R 8 , R 5’ , R 6’ , R 7’ ;R 8’ , R10 , R 11 , and R 12 Each of them independently produces hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 A substituted hydrocarbyl, heteroatom, or heteroatom-containing group, or R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 5’ and R 6’ , R 6’ and R 7’ , R 7’ and R 8’ , R 10 and R 11 , or R 11 and R 12 One or more of these may bond to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, and the substitutions on the rings can bond to form additional rings.

[0120] In formula (PM-I) or (PM-II), E and E' are oxygen or NR, respectively. 9 Selected from, R 9 Independently, hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 It is a substituted hydrocarbyl or heteroatom-containing group. In some embodiments, E and E' are oxygen. E and / or E' are NR 9 In the case of R 9 C1-C 20 Hydrocarbyl, alkyl, or aryl compounds can be selected. In one embodiment, E and E' are each selected from O, S, or N(alkyl) or N(aryl), where alkyl is C1-C 20 Alkyls can be, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, etc., and aryls are C6-C 40Examples of aryl groups include phenyl, naphthalenyl, benzyl, and methylphenyl.

[0121] In some embodiments, [ka] These are independently divalent hydrocarbyl groups, for example, C1-C 12 It is a hydrocarbyl group.

[0122] In some embodiments of the catalytic compounds of formula (PM-I) or (PM-II), when E and E' are oxygen, each phenolate group is located at a position adjacent to the oxygen atom (i.e., R in formulas (PM-I) and (PM-II)). 1 and R 1’ ) can be substituted. Therefore, if E and E' are oxygen, R 1 and R 1’ Each of these is independently C1-C 40 Hydrocarbyl, C1-C 40 A substituted hydrocarbyl, heteroatom, or heteroatom-containing group, for example, R 1 and R 1’ Each of these is independently a non-aromatic cyclic alkyl group having one or more five-membered or six-membered rings (e.g., cyclohexyl, cyclooctyl, adamantyl, or 1-methylcyclohexyl, or substituted adamantyl), for example, a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, adamantyl, or substituted adamantyl).

[0123] In some embodiments of the catalyst compound of formula (PM-I) or (PM-II), R 1 and R 1’ Each of these is independently a tertiary hydrocarbyl group. In other embodiments of formula (PM-I) or (PM-II), R 1 and R 1’ Each of these is independently a cyclic tertiary hydrocarbyl group. In other embodiments of the catalyst compound of formula (PM-I) or (PM-II), R 1 and R 1’Each of these is independently a polycyclic tertiary hydrocarbyl group. In some embodiments of the catalyst compound of formula (PM-I) or (PM-II), R 1 and R 1’ Each of these is independently a tertiary hydrocarbyl group. In other embodiments of the catalyst compound of formula (PM-I) or (PM-II), R 1 and R 1’ Each of these is independently a cyclic tertiary hydrocarbyl group. In other embodiments of the catalyst compound of formula (PM-I) or (PM-II), R 1 and R 1’ Each of these is independently a polycyclic tertiary hydrocarbyl group.

[0124] Linker group (i.e., in formula (PM-I)) [ka] ) can each be a part of an ortho-phenylene group, for example, a substituted ortho-phenylene group. 7 and R 7’ The position is hydrogen or C1-C 20 It is preferable that the alkyl group be alkyl, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, or an isomer thereof, such as isopropyl. For applications targeting polymers with high stereoregularity, the R of formula (PM-II) is preferable. 7 and R 7’ The position is C1-C 20 Being alkyl, for example, R 7 and R 7’ In some cases, it may be preferable for both to be C1-C3 alkyl. In some embodiments of formula (PM-I) or (PM-II), M is a group 4 metal, such as Hf or Zr. In some embodiments of formulas (PM-I) and (PM-II), E and E' are each O. In some embodiments 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 independently produces hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 A substituted hydrocarbyl, heteroatom, or heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 1’ and R 2’ , R 2’ and R 3’ , R 3’ and R 4’ One or more of these may bond to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, and the substitutions on the rings may bond to form additional rings, such as hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or isomers thereof.

[0125] In some embodiments 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, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthalenyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and their isomers.

[0126] In some embodiments of formulas (PM-I) and (PM-II), R 4 and R 4’ Each of these is independently hydrogen or a C1-C3 hydrocarbyl, such as methyl, ethyl, or propyl. In the embodiments of formulas (PM-I) and (PM-II), R 9 is hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 Substituted hydrocarbyl or heteroatom-containing group, such as hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or isomers thereof. In some embodiments, R 9 These are C1-C6 alkyl (e.g., methyl, ethyl, propyl, or butyl), phenyl, 2-methylphenyl, 2,6-dimethylphenyl, or 2,4,6-trimethylphenyl.

[0127] In embodiments of formulas (PM-I) and (PM-II), each X is independently selected from the group consisting of hydrocarbyl radicals having 1 to 20 carbon atoms (e.g., alkyl or aryl), hydrides, amides, alkoxides, sulfides, phosphides, halides, alkyl sulfonates, and combinations thereof (where two or more X may form part of a fused ring or ring system). For example, each X is independently selected from halides, aryls, and C1-C5 alkyl groups. For example, each X is independently a hydride, dimethylamide, diethylamide, methyltrimethylsilyl, neopentyl, phenyl, benzyl, methyl, ethyl, propyl, butyl, pentyl, fluoro, iodo, bromo, or chloro group.

[0128] Alternatively, each X may independently be a halide, hydride, alkyl group, or alkenyl group. In some embodiments of formulas (PM-I) and (PM-II), each L is independently a Lewis base selected from the group consisting of ethers, thioethers, amines, nitriles, imines, pyridines, halocarbons, and phosphines, for example, an ether, a thioether, or a combination thereof, and two or more L may optionally form part of a fused ring or ring system, for example, each L is independently selected from an ether or thioether group, for example, each L is an ethyl ether, tetrahydrofuran, dibutyl ether, or dimethyl sulfide group. In some embodiments of formulas (PM-I) and (PM-II), R 1 and R 1’ Each of them is independently a cyclic tertiary alkyl group. In some embodiments of formulas (PM-I) and (PM-II), n is 1, 2, or 3, for example, 2.

[0129] In some embodiments of formulas (PM-I) and (PM-II), m is 0, 1, or 2, for example, 0. In some embodiments of formulas (PM-I) and (PM-II), R 1 and R 1’ None of them are hydrogen. In some embodiments of formulas (PM-I) and (PM-II), M is Hf or Zr, and E and E' are each O, and R 1 and R 1’ Each of these is independently C1-C 40 Hydrocarbyl, substituted C1-C 40 Hydrocarbyl, heteroatom, or heteroatom-containing group, R 2 , R 3 , R 4 , R 2’ , R 3’ , and R 4’ Each of them independently produces hydrogen, C1-C 20 Hydrocarbyl, substituted C1-C 20 Hydrocarbyl, heteroatom, or heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 1’ and R 2’ , R 2’ and R 3’ , R 3’ and R 4’ One or more of these may bond to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, wherein substitutions on the rings can bond to form additional rings, each X independently selected from the group consisting of hydrocarbyl radicals (e.g., alkyl or aryl) having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, and combinations thereof (where two or more X may form a fused ring or part of a ring system), and each L independently selected from the group consisting of ethers, thioethers, and halocarbons (where two or more L' may form a fused ring or part of a ring system).

[0130] In some embodiments 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 independently produces hydrogen, C1-C 40 Hydrocarbyl, substituted C1-C 40 The group may be a hydrocarbyl, a heteroatom, or a heteroatom-containing group, or one or more adjacent R groups may bond to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, and the substitutions on the rings may bond to form additional rings. In some embodiments 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 these is independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof.

[0131] In some embodiments 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 12Each of these is independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthalenyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, or their isomers.

[0132] In some embodiments of formula (PM-II), M is Hf or Zr, and E and E' are each O, and R 1 and R 1’ Each of these is independently C1-C 40 Hydrocarbyl, substituted C1-C 40 A hydrocarbyl, heteroatom, or heteroatom-containing group, R 1 , R 2 , R 3 , R 4 , R 1’ , R 2’ , R 3’ , and R 4’ Each of them independently produces hydrogen, C1-C 20 Hydrocarbyl, substituted C1-C 20 Hydrocarbyl, heteroatom, or heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 1’ and R 2’ , R 2’ and R 3’ , R 3’ and R 4’One or more of these may bond to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, and the substitutions on the rings can bond to form additional rings. R 9 is hydrogen, C1-C 20 Hydrocarbyl, C1-C 20 A substituted hydrocarbyl or heteroatom-containing group, for example, hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or isomers thereof. Each X is independently selected from the group consisting of hydrocarbyl radicals having 1 to 20 carbon atoms (e.g., alkyl or aryl), hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and combinations thereof (where two or more X may form part of a fused ring or ring system). n is 2, m is 0, R 5 , R 6 , R 7 , R 8 , R 5’ , R 6’ , R 7’ , R 8’ , R 10 , R 11 and R 12 Each of them independently produces hydrogen, C1-C 20 Hydrocarbyl, C1-C 20 The R groups may be substituted hydrocarbyl, heteroatoms, or heteroatom-containing groups, or one or more adjacent R groups may bond to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, and the substitutions on the rings may bond to form additional rings, for example, R 5 , R 6 , R 7 , R 8 , R 5’ , R 6’ , R 7’ , R 8’ , R 10 , R 11 and R12 Each of these is independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and their isomers.

[0133] In some embodiments of formula (PM-II), M is Zr or Hf, and E and E ’ Both are oxygen, and R 1 and R 1’ Both are C4-C 20 It is a cyclic tertiary alkyl group. In some embodiments of formula (PM-II), M is Zr or Hf, and E and E ’ Both are oxygen, and R 1 and R 1’ Both are adamantane-1-yl or substituted adamantane-1-yl. In some embodiments of formula (PM-II), M is Zr or Hf, and E and E ’ Both are oxygen, and R 1 , R 1’ , R 3 and R 3’ Each of these is either adamantane-1-yl or a substituted adamantane-1-yl.

[0134] In some embodiments of formula (PM-II), M is Zr or Hf, and E and E ’ Both are oxygen, and R 1 and R 1’ Both are C4-C 20 It is a cyclic tertiary alkyl, R 7 and R 7’ Both are C1-C 20 It is alkyl. In some embodiments, the catalyst compound is one or more of the following: dimethylzirconium[2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1'-biphenyl]-2-oleate)], dimethylhafnium[2',2'''-(pyridine-2,6-diyl)bis(3-adamantan-1-yl)-5-(tert-butyl)-[1,1' (-biphenyl]-2-oleate), dimethylzirconium[6,6'-(pyridine-2,6-diylbis(benzo[b]thiophene-3,2-diyl))bis(2-adamantan-1-yl)-4-methylphenolate)], dimethylhafnium[6,6'-(pyridine-2,6-diylbis(benzo[b]thiophene-3,2-diyl))bis(2-adamantan-1-yl)-4-methylphenolate)], dimethyl Zirconium [2',2'''-(pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)-5-methyl-[1,1'-biphenyl]-2-oleate)], Dimethylhafnium [2',2'''-(pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)-5-methyl-[1,1'-biphenyl]-2-oleate)], Dimethylzirconium [2',2'''-(pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)-4',5-dimethyl-[1,1'-biphenyl]-2-oleate)], dimethylhafnium[2',2'''-(pyridine-2,6-diyl)bis(3-((3r,5r,7r)-adamantan-1-yl)-4',5-dimethyl-[1,1'-biphenyl]-2-oleate)], or combinations thereof.

[0135] In some embodiments, the precatalytic compound is one or more of the following Group 4-based precatalysts: [ka] JPEG2026520732000031.jpg205156 JPEG2026520732000032.jpg230153

[0136] In some embodiments, the precatalytic compound is one or more Group 3-based precatalysts: [ka]

[0137] In some embodiments, TMA-free (or trihydrocarbyl aluminum-free) solution almoxanes (e.g., MAO), solid almoxanes (e.g., MAO), or supported almoxanes (e.g., MAO) can also be used in bisCp metallocene precatalytic compounds without polar donors for the purpose of controlling the properties of the polymer, for example, by restricting free aluminum alkyl in the system which can cause chain transfer from the catalytic metal center to free aluminum alkyl. When used herein, the metallocene precatalytic compounds include metallocenes comprising group 3 to group 10 metal complexes, preferably group 4 to group 6 metal complexes, for example, group 4 metal complexes. The metallocene catalytic compounds of the catalytic systems of this disclosure are of formula (BC-I): Cp A Cp B M'X' n (BC-I) The non-crosslinked metallocene catalyst compound represented by each Cp may be a non-crosslinked metallocene catalyst compound, and each Cp A and Cp B These are independently selected from cyclopentadienyl ligands and isoglobal ligands to cyclopentadienyl, and Cp A and Cp B One or both of these may contain a heteroatom, Cp A and Cp BOne or both of these may be substituted with one or more R'' groups. M' is selected from group 3 to group 12 atoms and lanthanide group atoms. X' is an anionic 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, arylthio, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene, alkalyl, alkalene, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocyclic, heteroaryl, heteroatom-containing group, hydrocarbyl, lower hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, silyl, boryl, phosphin, phosphine, amino, amine, ether, and thioether.

[0138] In at least one embodiment, each Cp A and Cp B These are independently selected from cyclopentadienyl, indenyl, fluorenyl, cyclopentaphenantrenyl, benzoindenyl, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, phenantrenylindenyl, 3,4-benzofluorenyl, 9-phenylfluorenyl, 8-H-cyclopenta[a]acenaphtyrenyl, 7-H-dibenzofluorenyl, indeno[1,2-9]anthracene, thiophenoindenyl, thiophenofluorenyl, and their hydrogenated versions.

[0139] The metallocene catalyst compound is given by formula (BC-II): Cp A (A)Cp B M'X' n (BC-II) The crosslinked metallocene catalyst compound represented by Cp may be a compound where each Cp A and Cp BThese are independently selected from cyclopentadienyl ligands and ligands isoglobal to cyclopentadienyl. Cp A and Cp B One or both of these may contain a heteroatom, Cp A and Cp B One or both of these may be substituted with one or more R'' groups. M' is selected from group 3 to group 12 atoms and lanthanide group atoms. X' is an anionic leaving group. n is 0 or an integer from 1 to 4. (A) is a divalent alkyl, divalent lower alkyl, divalent substituted alkyl, divalent heteroalkyl, divalent alkenyl, divalent lower alkenyl, divalent substituted alkenyl, divalent heteroalkenyl, divalent alkynyl, divalent lower alkynyl, divalent substituted alkynyl, divalent heteroalkynyl, divalent alkoxy, divalent alkylthio, divalent lower alkylthio, divalent arylthio, divalent aryl, divalent substituted aryl, divalent heteroaryl, divalent aral Selected from: chlorine, divalent aralkylene, divalent alkalil, divalent alkalilene, divalent haloalkyl, divalent haloalkenyl, divalent haloalkynyl, divalent heteroalkyl, divalent heterocycle, divalent heteroaryl, divalent heteroatom-containing group, divalent hydrocarbyl, divalent lower hydrocarbyl, divalent substituted hydrocarbyl, divalent heterohydrocarbyl, divalent silyl, divalent boryl, divalent phosphin, divalent phosphine, divalent amino, divalent amine, divalent ether, and divalent thioether. 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, arylthio, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene, alkalyl, alkalene, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocyclic, heteroaryl, heteroatom-containing group, hydrocarbyl, lower hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, silyl, boryl, phosphin, phosphine, amino, amine, germanium, ether, and thioether.

[0140] In at least one embodiment, Cp A and Cp B Each of these is independently selected from cyclopentadienyl, n-propylcyclopentadienyl, indenyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, and n-butylcyclopentadienyl. (A) may be CR'2 or SiR'2, where each R' is independently hydrogen or C1-C 20 It is hydrocarbil. In some embodiments, two or more different precatalytic compounds are present in the catalytic system used herein. In some embodiments, two or more different precatalytic compounds are present in the reaction zone where the processes described herein occur. While it may be preferable to use the same activator for the transition metal compound, two different activators, for example, a TMA-free supported or unsupported MAO as disclosed herein and a strong Lewis acid activator (e.g., trisperfluoroaromatic borane) or a non-coordinating or weakly coordinating anionic activator (e.g., N,N-dimethylanilinium or trityltetrakisperfluoroaromatic borate), may be used in combination. If one or more transition metal compounds contain an X group that is not a hydride, hydrocarbyl, or substituted hydrocarbyl, the MAO may be brought into contact with the transition metal compound before the addition of the non-coordinating anionic activator.

[0141] Two transition metal compounds (pre-catalysts) can be used in any ratio. In some embodiments, the molar ratio of (A) transition metal compound to (B) transition metal compound falls within the range of (A:B) 1:1000-1000:1, instead of 1:100-500:1, instead of 1:10-200:1, instead of 1:1-100:1, instead of 1:1-75:1, or instead of 5:1-50:1. The specific ratio selected depends on the specific pre-catalyst selected, the activation method, and the desired final product. In certain embodiments, when two pre-catalysts are used and both are activated with the same activator, the useful molar percentages based on the molecular weight of the pre-catalysts are A 10%-99.9% vs B 0.1%-90%, instead of A 25%-99% vs B 0.5%-50%, instead of A 50%-99% vs B 1%-25%, or instead of A 75%-99% vs B 1%-10%.

[0142] In some embodiments, the leaving groups of the pre-catalysts described above are preferably pre-alkylated, for example, by methylation, ethylation, benzylation, or trimethylsilylmethyleneation, because the alkylating agent in the MAO, such as free TMA, has been significantly removed. However, non-alkylated pre-catalysts may still be used with a mild alkylating agent, such as a higher carbon trialkylaluminum (e.g., trioctylaluminum) or a secondary aluminum alkyl (e.g., AlMe2BHT or AlEt2BHT), or without a mild alkylating agent if the solution, solid, or supported MAO system has a low amount of TMA or trihydrocarbylaluminum residues sufficient for alkylation of the pre-catalyst.

[0143] Polymerization process This disclosure also relates to a polymerization process to obtain desired polymer products, including single-phase polymers or copolymers and multi-phase copolymers, obtained, for example, in a single reactor or in multiple reactors for sequential copolymerization of solution polymerization, slurry polymerization, and gas-phase polymerization, and obtained in a single reactor for copolymerization, and for example, in multiple reactors for sequential copolymerization of solution polymerization, slurry polymerization, and gas-phase polymerization, according to a corresponding polymerization process. 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 supplying the pre-catalyst compound and TMA-free silica-supported MAO to the polymerization reactor and combining them first before contact with the monomer to form the final catalyst system. Alternatively, the pre-catalyst compound and activator can be introduced separately into the polymerization reactor, where they are subsequently reacted to form an active catalyst.

[0144] The monomer is a substituted or unsubstituted C2-C group. 40 Alpha-olefins, for example, C2-C 20 Alpha-olefins, for example, C2-C 12 Alpha-olefins may include, for example, ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene and their isomers. In at least one embodiment, the monomer is ethylene and one or more C3-C3 molecules. 40 Olefins, for example, C4-C 20 Olefins, for example, C6-C 12 Contains any comonomer including olefins. C3-C 40 Olefin monomers may be linear, branched, or cyclic. C3-C 40 The cyclic olefin may be strained or unstrained, monocyclic or polycyclic, and may optionally contain heteroatoms and / or one or more functional groups. In another embodiment, the monomer is propylene and one or more ethylenes or C4-C40 Olefins, for example, C4-C 20 Olefins, for example, C6-C 12 Contains any comonomer including olefins. C4-C 40 Olefin monomers may be linear, branched, or cyclic. C4-C 40 The cyclic olefin may be strained or not, may be monocyclic or polycyclic, and may optionally contain heteroatoms and / or one or more functional groups.

[0145] Exemplary C2-C 40 Olefin monomers and any comonomers include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, ethylidenenorbornene, vinylnorbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, 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 homologs and derivatives, such as norbornene, norbornadiene, and dicyclopentadiene, may also be included. For some pre-catalysts, formula C n H (n-2) Conjugated or unconjugated dienes having (n=4~30), such as butadiene, 2-methyl-butadiene, 1,3-pentadiene, 1,4-pentadiene, 2-methyl-1,4-pentadiene, 3-methyl-1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 5-methyl-1,4-hexadiene, 2-methyl-1,5-hexadiene, 1,4-heptadiene, 1,5-heptadiene, 1,6-heptadiene, 5-methyl-1,4-heptadiene, 6-methyl-1,5-heptadiene, and 2-methyl-1,6-heptadiene, can also function as comonomers.

[0146] The polymerization process of this disclosure can be carried out in any suitable manner. Any suitable suspension polymerization, homogeneous polymerization, bulk polymerization, solution polymerization, slurry polymerization, or gas-phase polymerization process can be used. Such processes can be operated in batch, semi-batch, or continuous mode. Homogeneous polymerization processes and slurry processes are available. (A homogeneous polymerization process is defined as a process in which at least 90% by mass of the product is dissolved in the reaction medium.) A homogeneous polymerization process can also be a bulk homogeneous process. (A bulk process is defined as a process in which the monomer concentration in all feeds to the reactor is 70% by volume or more.) In another possibility, no diluent is present in the reactant medium or added (except for small amounts used as a support for the catalyst system or other additives, or amounts found in the monomer, such as propane in propylene). In another embodiment, the process is a slurry process. As used herein, the term “slurry polymerization process” means a polymerization process in which a supported catalyst is utilized and monomers are polymerized on supported catalyst particles. At least 95% by mass of the polymer product derived from the supported catalyst is in the form of granular solid particles (not dissolved in the diluent).

[0147] Diluents suitable for polymerization may include non-coordinating, inert liquids. Examples of diluents for polymerization include linear and branched hydrocarbons, e.g., isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, e.g., cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, e.g., commercially available ones (e.g., Isopar®); perhalogenated hydrocarbons, e.g., perfluorinated C4-C 10Examples of suitable diluents include alkanes, chlorobenzenes, and aromatic and alkyl-substituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene. Suitable diluents may also contain liquid olefins that can act as monomers or comonomers, including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, and mixtures thereof. In at least one embodiment, aliphatic hydrocarbon diluents, such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof, as well as cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, are used as diluents. In another embodiment, the diluent is non-aromatic, for example, aromatics are present in less than 1% by mass, e.g., less than 0.5% by mass, e.g., less than 0% by mass, relative to the mass of the diluent.

[0148] In at least one embodiment, the feed stream to the reactor has a feed concentration of polymerization monomers and comonomers such that the diluent concentration is 60% by volume or less, for example, 40% by volume or less, for example, 20% by volume or less, relative to the total volume of the feed stream. In at least one embodiment, polymerization is carried out in a bulk process. Polymerization can be carried out at any temperature and / or pressure suitable for obtaining the desired polymer. Suitable temperatures for solution polymerization include approximately 50°C to approximately 200°C, for example, approximately 60°C to approximately 180°C, for example, approximately 65°C to approximately 160°C, for example, approximately 80°C to approximately 150°C, for example, approximately 85°C to approximately 140°C. Suitable temperatures for slurry polymerization or gas-phase polymerization include approximately 50°C to approximately 120°C, for example, approximately 60°C to approximately 110°C, for example, approximately 65°C to approximately 100°C, for example, approximately 70°C to approximately 85°C, for example, approximately 75°C to approximately 80°C, etc. Polymerization can be carried out at pressures of approximately 0.1 MPa to approximately 25 MPa, for example, approximately 0.45 MPa to approximately 6 MPa, or approximately 0.5 MPa to approximately 4 MPa.

[0149] In a suitable polymerization, the reaction operation time can be up to about 300 minutes, for example, about 5 minutes to about 250 minutes, for example, about 10 minutes to about 120 minutes, for example, about 20 minutes to about 90 minutes, for example, about 30 minutes to about 60 minutes. In a continuous process, the operation time can be the average residence time of the reactor. In at least one embodiment, the reaction operation time is up to about 45 minutes. In a continuous process, the operation time may be the average residence time of the reactor. In at least one embodiment, hydrogen is present in the polymerization reactor at partial pressures of approximately 0.001 psig to approximately 50 psig (0.007 kPa to 345 kPa), for example, approximately 0.01 psig to approximately 25 psig (0.07 kPa to 172 kPa), for example, approximately 0.1 psig to approximately 10 psig (0.7 kPa to 70 kPa). In at least one embodiment, the hydrogen content is approximately 0.0001 ppm to approximately 2,000 ppm, for example, approximately 0.0001 ppm to approximately 1,500 ppm, for example, approximately 0.0001 ppm to approximately 1,000 ppm, for example, approximately 0.0001 ppm to approximately 500 ppm. Alternatively, hydrogen can be present at zero ppm.

[0150] In at least one embodiment, MAO may be present in zero mol%, or instead, MAO may be present in an aluminum-to-transition metal molar ratio of less than 500:1, e.g., less than 300:1, e.g., less than 100:1, e.g., less than 1:1. Unless otherwise noted, "catalytic productivity" is a measure of how much polymer (P) is produced (in grams) over a period of time T using a polymerization catalyst containing Wg catalyst (cat), and can be expressed by the formula: P / (T×W), where gPgcat -1 time -1It is expressed in units of . Unless otherwise noted, "catalytic activity" is a measure of the degree of activity of a catalyst, and for catalyst systems derived from solution MAO, it is reported as the mass of polymer product (P) produced per mole of catalyst (cat) used (kgP / mol cat), or for catalyst systems derived from solution, solid, or supported MAO, it is reported as the mass of polymer product (P) produced per mass of catalyst (cat) used (kgP / gcat or gP / gcat). Catalytic activity is also expressed in terms of a period of T time, and is reported as the mass of polymer product (P) produced per mole or millimol of catalyst (cat) used, and for solution or solid MAO as an activator, it is expressed as gPmmolcat. -1 time -1 It is expressed in units of kgPgcat for solutions, solids, or supported MAO as activators. -1 time -1 It may also be expressed in units of [unit name].

[0151] In at least one embodiment, a solution catalyst system having TMA-free solution-form MAO as an activator, according to the present disclosure, is provided in a volume of approximately 10 to 1,000 kg Pgcat -1 time -1 For example, approximately 20kg Pgcat -1 time -1 For example, over 30kg Pgcat -1 time -1 For example, a Pgcat exceeding 100 kg -1 time -1 ~Approximately 300kg Pgcat -1 time -1 The final catalyst system, derived from TMA-free supported MAO and possessing catalytic activity, used in slurry polymerization or gas-phase polymerization, has a catalytic output of approximately 3 to 30 kg Pgcat. -1 time -1 For example, about 4kg Pgcat -1 time -1 ~Approximately 20kg Pgcat -1 time -1 For example, about 6kg Pgcat -1 time -1 ~Approximately 15kg Pgcat -1 time -1For example, about 8kg Pgcat -1 time -1 ~approximately 10kg Pgcat -1 time -1 The catalytic activity of the TMA-free solid MAO self-supported catalyst system is intermediate between solution polymerization and supported catalytic polymerization (slurry polymerization and gas-phase polymerization).

[0152] In at least one embodiment, for solution polymerization, the catalyst residence time in the reactor can be about 10 minutes to about 120 minutes, for example, about 20 minutes to about 90 minutes, for example, about 30 minutes to about 60 minutes; for solution polymerization, the catalyst residence time in the reactor can be about 10 minutes to about 120 minutes, for example, about 20 minutes to about 90 minutes, for example, about 30 minutes to about 60 minutes; for supported catalyst polymerization, for example, slurry polymerization or gas-phase polymerization, the catalyst residence time in the reactor can be about 10 minutes to about 240 minutes, for example, about 30 minutes to about 120 minutes, for example, about 60 minutes to about 90 minutes; and for a self-supported MAO-derived catalyst system, the residence time in the slurry polymerization reactor or gas-phase polymerization reactor is similar to that of a supported catalyst system.

[0153] In at least one embodiment, polymerization is carried out as follows: 1) at a temperature of about 0°C to about 300°C (e.g., about 25°C to about 250°C, e.g., about 50°C to about 160°C, e.g., about 80°C to about 140°C); 2) at atmospheric pressure up to about 10 MPa (e.g., about 0.35 MPa to about 10 MPa, e.g., about 0.45 MPa to about 6 MPa, e.g., about 0.5 MPa to about 4 MPa); and 3) without the use of an aliphatic hydrocarbon diluent, e.g., in a gas-phase reactor, or with the monomer as a diluent. 4) The polymerization is carried out under conditions that allow it to function, for example, in a slurry reactor using propylene as a monomer and diluent, or in an aliphatic hydrocarbon diluent, for example isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof, in cyclic and alicyclic hydrocarbons, for example cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, in which case, for example, aromatics are present in the diluent at a concentration of less than 1% by mass, e.g., less than 0.5% by mass, e.g., 0% by mass, relative to the mass of the diluent for solution polymerization or slurry polymerization, 4) the catalyst system used for polymerization contains less than 0.5 mol%, for example, MAO is present in an aluminum to transition metal molar ratio of less than 500:1, e.g., less than 300:1, e.g., less than 100:1, e.g., less than 1:1, 5) polymerization occurs within at least one reaction zone, 6) optionally, scavengers (e.g., trialkylaluminum compounds) are absent (e.g., zero moles) 7) optionally hydrogen is present in the polymerization reactor at a partial pressure of about 0.001 psig to about 50 psig (0.007 kPa to 345 kPa) (e.g., about 0.01 psig to about 25 psig (0.07 kPa to 172 kPa), or about 0.1 psig to about 10 psig (0.7 kPa to 70 kPa)). In at least one embodiment, the catalyst system used for polymerization includes one or more pre-catalyst compounds. The “reaction zone” is also called the “polymerization zone,” which is the vessel in which polymerization takes place, e.g., a stirred tank reactor or a loop reactor.When multiple reactors are used in a continuous polymerization process, each reactor is considered a separate polymerization zone. In multi-step polymerization in a batch polymerization process, each polymerization step is considered a separate polymerization zone. In at least one embodiment, polymerization occurs in one or more reaction zones. Room temperature is 23°C unless otherwise specified.

[0154] If desired, other additives, such as one or more scavengers, hydrogen, aluminum alkyl, or chain transfer agents, such as higher alkyl-modified MAO, compounds represented by formulas AlR3 or ZnR2 (wherein each R is independently a C1-C8 aliphatic radical, such as methyl, ethyl, propyl, butyl, pentyl, hexyloctyl, or isomers thereof), or combinations thereof, such as diethylzinc, MAO, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or combinations thereof, may be used in polymerization. Other additives, such as reactor destaticizers or antifouling agents, such as EvonikS202 or Atmer® antistatic agents, may also be added during catalyst preparation, after catalytic treatment, or during or after polymerization.

[0155] Polyolefin products This disclosure also relates to compositions of substances produced by the methods described herein. The processes described herein can be used to produce polymers or mixtures of olefins. Polymers that can be prepared include polyethylene, polypropylene, C4-C 20 Olefin homopolymer, C4-C 20 Olefin copolymers, ethylene and C3-C 20 Olefin copolymers, propylene and C4-C 20 Olefin copolymer, C4-C 20 Olefin terpolymers, ethylene and propylene and C4-C 20Examples include olefin terpolymers, and terpolymers of ethylene and propylene with 5-ethylidene-2-norbornene. The processes described herein can be used to produce the following polymers: for example, HDPE, MDPE, LDPE, or LLDPE obtained by changing the polymer density using butene, hexene, or octene as comonomers; iPP, sPP, or aPP obtained by different stereoregularity or site regularity on a precatalyst; random copolymer plastomers obtained from ethylene copolymers rich in ethylene with an ethylene content of 30% or less, or ethylene-rich propylene copolymers with a propylene content of 30% or less; and ethylene having ethylene and propylene in a ratio close to 50:50, for example, 30:70, 40:60, 50:50, 60:40, or 70:30. Teylene propylene elastomers (rubbers), i.e., EP rubber; for example, ethylene-butadiene copolymers obtained from solution polymerization; for example, impact copolymers, for example, iPP-EPR, iPP-EBR (ethylene butylene rubber), iPP-EHR (ethylene hexene rubber) biphase copolymers produced in a reactor by supported catalytic polymerization, for example, EPDM (vulcanizable ethylene propylene dienterpolymer), EBDM (vulcanizable ethylene butylene dienterpolymer), EHDM (vulcanizable ethylene hexene dienterpolymer) obtained from solution polymerization, or for example, vulcanizable iPP-EPDM, iPP-EBDM, iPP-EHDM biphase copolymers produced in a reactor. Heterophase copolymers with more than two phases can be obtained from more reaction zones, and these are, for example, PE-RCP-EPR or iPP-RCP-EPR three-phase copolymers.

[0156] In some embodiments, the melt index (MI) for PE-based polymers is 0.01 to about 50 g / 10 min, e.g., 0.1 to 10 g / 10 min, e.g., 0.5 to 5 g / 10 min, e.g., 1 to 2 g / 10 min, or the melt flow rate or mass flow rate (MFR) for PP-based polymers is 0.01 to 2000 g / 10 min, e.g., 0.05 to 1000 g / 10 min, e.g., 0.1 to 500 g / 10 min, e.g., 0.5 to 100 g / 10 min, e.g., 2 to 50 g / 10 min, and the measurement methods are described in similar standards ASTM D1238 and ISO 1133.

[0157] In some embodiments, the mass-average molecular weight Mw of the polymer product, as measured by GPC, is in the range of 10k to 2000k, e.g., 50k to 1000k, e.g., 60k to 500k, e.g., 100k to 300k, and the molecular weight distribution (MWD) or polydispersity index (PDI) is 1.5 to 30, e.g., 2 to 10, e.g., 2.5 to 9, and may have a single-mode or multi-mode distribution, e.g., a bimodal distribution obtained from a two-step polymerization process in two different reaction zones, or a one-step polymerization process in one reaction zone using a catalyst system containing two different pre-catalyst compounds. In some embodiments, the comonomer distribution in the polymer product can be a conventional distribution, i.e., comonomer incorporation decreases with increasing Mw. The comonomer distribution can be a flat distribution, i.e., similar incorporation at compositions of different molecular weights, or a broad orthogonal comonomer distribution, i.e., a distribution in which comonomer incorporation increases with increasing Mw.

[0158] experiment In research aimed at improving prior art (e.g., US6,368,999), it was found that silica fluoride supports containing Si-F units react with free TMA in MAO to form more active supported MAO. Therefore, fluorinating agents used to fluorinate silica that also contain Si-F units, such as (NH4)2SiF6, were tested and found to react with free TMA in both supported and unsupported MAO systems (e.g., solution systems). It has been confirmed that standard supported or unsupported MAO systems requiring free TMA can be converted to active MAO systems with low or undetectable free TMA content without impairing MAO activation efficiency by treating them with Si-F-containing compounds, i.e., silica fluoride or fluorinating agents used to fluorinate silica. This is achieved by matching the total THF-extractable TMA content in the standard MAO system with the Si-F units.

[0159] Unless otherwise specified, all reactions were carried out in a CELSTIR reactor under a purified nitrogen atmosphere, using a standard glove box, high vacuum, or Schlenk technique. All solvents used were anhydrous and deoxygenated and purified according to known procedures. All starting materials were 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 Corporation (now Ecovyst). MAO was obtained from WRGrace as 30% by mass MAO in toluene solution (e.g., 13.6% by mass Al or 5.04 mmol Al / g). Deuterated solvents were obtained from Cambridge Isotope Laboratories (Andover, Mass.) and dried in 3A molecular sieves. 1 ¹H NMR data were collected at room temperature (RT) using a Broker AVANCE III 400MHz spectrometer with Topspin TM3.0 software enabled.

[0160] (Example 1) Quantification of THF-extractable total TMA content in commercially available MAO solutions. In supported or unsupported MAO compositions, the total TMA content, including coordination TMA and free TMA, is quantified via THF solvent treatment. Following the reaction in Scheme 8, both coordination TMA and free TMA are converted to AlMe3(THF) as the main product and AlMe2(THF)2 as a trace product. + It can be converted to AlMe3(THF) and AlMe2(THF)2. + This is the sum of (which is converted back to TMA in the calculation), and the following: 1 Quantitative analysis of MAO can be performed using 1H NMR, with toluene as the internal standard for solution-type MAO, or with an inert compound added as an internal standard for ether-based solution-type MAO, solid-type MAO, or supported-type MAO.

[0161] Chemical substances: WRGrace MAO 30% toluene solution (Al = 13.6% by mass (5.0 mmol / g), MAO = 26.6% by mass, total TMA (coordinate and free) = 4.76% by mass, Certificate of Analysis (COA) of the MAO product, and THF-d8 NMR solvent (Cambridge Isotope) treated with a 3Å molecular sieve). If the MAO used for the experiment has been stored at <-20°C for less than 3 months, the total TMA mass% of the MAO product COA can be used without significant error. For MAO solutions that have been stored for longer periods or have undergone frequent changes in storage temperature (e.g., if a portion of the MAO has been taken out of and returned to the freezer), the THF-extractable total TMA content may increase significantly due to the gelling process (Scheme 1) that releases TMA.

[0162] Procedure: Place an oven-dried 5mm NMR tube in a dry box, fill it with approximately 0.5 inches (12.7 mm) of MAO solution, followed by approximately 1.5 inches (38.1 mm) of THF-d8 solvent, shake well, then use D1=30 seconds, ns=4 to analyze the sample. 1Obtain a 1H NMR spectrum. A longer relaxation time D1 may yield greater accuracy, but a length of 30 seconds is sufficient to obtain an error of <2 mass% in the quantification of the CH3 and Al-CH3 signals of toluene. 1 The 1H NMR spectrum is shown in the lower spectrum of Figure 3 (Figure 3B).

[0163] Processing: CH3 peak of toluene, total area of ​​Al-CH3, AlMe2(THF)2 + Integrate the peaks of MAO, AlMe3(THF), and AlMe3(THF). Set the integral value of CH3 in toluene to 300 (set to 300 instead of the CH3 proton number 3, because decimal places may be truncated, so this is to ensure at least 3 digits of precision in the spectral output), MAO, AlMe3(THF), and AlMe2(THF)2 + Assuming the integral value for all Al-Me species, including AlMe, is 350.28, and the integral value for AlMe3(THF) is 78.96, 2 (THF)2 + The integral value is recorded as 7.98, and trace amounts of species, such as machining oils that are usually present in small amounts, for example, <1 mass%, are ignored. Based on COA, the MAO formula without coordination TMA is Al1O 0.78 Me 1.44 Therefore, Mw 61.1 is obtained. The integral value of MAO is 350.28 - 78.96 - 7.98 = 263.34. The number of protons in MAO is 1.44 * 3 = 4.32. AlMe2 + Since it is generated from the coordination TMA, it is counted as a TMA. The calculation results are listed in Table 1.

[0164] [Table 2] Here, we can see that the total TMA content has increased from 4.76 mass% (COA) to 5.33 mass%, which indicates a low degree of gelation.

[0165] (Example 2) Quantification of coordination TMA in commercially available MAO solutions The quantification of coordination TMA is based on the following reaction (Scheme 11): [ka]

[0166] In the above reaction product, KF can form an ionic MAO composition by precipitating MAO as a clathrate phase and separating it from the solution phase containing free TMA via substitution of coordinating TMA. A large excess of known amounts of KF(W1 KF ) is applied to the MAO solution, and the remaining KF (W2) after the reaction is applied. KF By isolating ), the consumption of KF is reduced to W1 KF -W2 KF This can be calculated as follows, and this is an indirect method of quantifying the coordination TMA content. Chemical substance: KF (Aldrich), 10g placed in a 50mL round-bottom flask and dried in an oil bath at 110°C under vacuum for 4 hours. The same MAO solution and THF-d8 as in Example 1 were used.

[0167] Procedure: In a dry box, 10.0 g of MAO solution (51.1 mmol of Al, calculated based on the results in Table 1) was added to each of four oven-dried vials (20 mL). Then, 59.6 mg (2 mol%) of KF (58.1 g / mol) (2 mol%), 118.9 mg (4 mol%) (4 mol%), 207.6 mg (7 mol%) (7 mol%), and 298 mg (10 mol%) of KF (58.1 g / mol) were added, respectively. The vials were placed on a shaker and shaken overnight. The vials were removed from the shaker and the clathrate phase was allowed to settle for 10 hours. All KF in the vials treated with 2 mol%, 4 mol%, and 7 mol% disappeared, but the vial treated with 10 mol% showed that KF remained. All upper phase solutions from the four vials were NMRed in THF-d8 solvent. 1Figure 4A, which compares the Al-Me region spectra analyzed using 1H nuclear magnetic resonance spectroscopy, shows a decrease in MAO concentration. Similarly, the clathrate phase obtained from a sample (10 mmol% KF treated vial) in which the standard MAO was completely converted to ionic MAO was also analyzed in THF-d8 NMR solvent. 1 The spectrum was analyzed by 1H nuclear magnetic resonance spectroscopy, and the Al-Me region spectrum is shown in Figure 4B along with a comparative parent MAO solution. This spectrum is AlMe2 in relation to ionic MAO. + This indicates the absence of species, which means that all coordination TMAs have been removed by KF, and that coordination TMAs are AlMe2 + This confirms that it is the source of the substance. The KF remaining in the vial after 10 mol% treatment was collected using a pre-mass-measured frit filter, washed with 3 × 10 mL of dry toluene and 30 mL of dry isohexane, and then gravimetrically measured, revealing 75.3 mg of unreacted KF (2.54 mol% relative to total Al), and a coordinated TMA of 10 - 2.5 = 7.5 mol% in the MAO solution was obtained. The total Al% was 13.8 mass%, and the total TMA (free + coordinated) was 5.33 mass% based on Table 1. The total TMA can be converted to 2.00 mass% Al to obtain 14.5 mol%.

[0168] (Example 3) (NH) of commercially available MAO solution 4 ) 2 SiF 6 process This example uses (NH4)2SiF6 as the electron-withdrawing compound to convert most of the total TMA into AlMe2F. NMR stoichiometric studies suggest that 1 equivalent of (NH4)2SiF6 can consume 8 equivalents of TMA to form a species containing 6 equivalents of AlMe2F, 2 equivalents of NH, and 2 equivalents of Al-M. This species likely has two 6-membered rings to satisfy 3-coordination of H and 4-coordination of Al as a stable product, although whether it is exactly that structure does not affect the stoichiometry of the reaction (Scheme 12). Scheme 12 (NH4)2SiF6 + 8AlMe3 (or 4(AlMe3)2) = 6AlMe2F + 2 / 6[(NHAlMe)3]2 + 6CH4 + SiMe4.

[0169] Therefore, the solution-type MAO after quantification of total TMA was treated with 1 / 8 equivalent (NH4)2SiF6 relative to the total TMA content. Chemical substance: The same commercially available MAO solution as above; (NH4)2SiF6 (Aldrich, vacuum-dried overnight at ambient temperature, Mw=178.17). Procedure: 40 g MAO solution (204 mmol of Al) was placed in a 6 ounce (approximately 0.18 L) bottle along with a stirring rod. 0.66 g (NH4)2SiF6 (3.70 mmol) was slowly added to the MAO solution while vigorously stirring. After stirring for 1 hour, all solids disappeared. Using THF-d8 as the NMR solvent, the solution was analyzed. 1 Samples were taken for 1H NMR. Figure 3 shows the treated MAO spectrum in the Al-Me region (Figure 3A) compared with the spectrum of the original MAO solution (Figure 3B).

[0170] From the NMR spectra in Figures 3A and 3B, after treatment with an electron-withdrawing compound, the integral value of TMA (AlMe3(THF)) that can be extracted with THF decreased from 78.96 (3B) to 37.94 (3A), and AlMe2(THF)2 + The integral value of the species can be seen to increase from 7.98 (3B) to 15.23 (3A). The THF-extractable TMA is thought to originate from AlMe2F coordinated according to the following reaction (Scheme 13), which indicates that, due to the strong electron-withdrawing group F, Al bound to F is less likely to become coordinately unsaturated when no donor is present (reaction on the left), and that AlMe2F is a poor source of free TMA.

[0171] Scheme 13 [ka]

[0172] Scheme 13 also helps in understanding the observed chemical properties of EWC-treated MAO, namely, monodentate donors such as THF can replace the AlMe2 in the AlMe2F configuration with the AlMe3 configuration, using the adjacent Me directly bonded to the Al in the AlMe2F configuration to form THF-coordinated TMA (AlMe3(THF) in Figure 3A), which is shown as pathway I. Alternatively, from AlMe2F to AlMe2 + Pull it out, (AlMe2 in Figure 3A) + (THF)2) is formed, which is shown as pathway II. On the other hand, the catalytic precursor that has two leaving donor groups and acts as a chelating agent is AlMe2F from AlMe2 + It could only extract the catalyst precursor-AlMe2 + It forms a complex, which is an ion pair containing a bimetallic cation. This is shown as pathway III.

[0173] (Examples 4-1, 4-2, 4-3) Small-scale solution propylene polymerization Polymerization reagents: Pre-catalyst solutions were prepared using a given transition metal complex dissolved in toluene (ExxonMobil Chemical, anhydrous, stored under N2) (98%) at a concentration of typically 0.5 mmol / L. The complexes were activated using various commercially available methylaluminoxes (MAOs), including cMAO (10% by mass in toluene, Albemarle Corp., control) and F-MAO. Complex 6 can be prepared as described in US11,254,763. All MAO was typically used as a 0.2 mass% toluene solution. The micromoles of MAO reported below are based on the micromoles of aluminum in the MAO, which has a formula weight of 58.0 g / mol.

[0174] Polymer-grade toluene and / or isohexane, used as solvents, were supplied by ExxonMobil Chemical Co. and purified by passing the solution through a series of columns: two 500cc OXYCLEAR cylinders in series, manufactured by Labclear (Oakland, Calif.), followed by two 500cc columns in series packed with dry 3Å molecular sieves (8-12 mesh; Aldrich Chemical Company), and then two 500cc columns in series packed with dry 5Å molecular sieves (8-12 mesh; Aldrich Chemical Company).

[0175] Polymerized propylene was purified by passing it through a series of columns: a 2,250cc OXICLEAR cylinder (manufactured by Labclear), followed by a 2,250cc column packed with 3Å molecular sieves (8-12 mesh; Aldrich Chemical Company), then two 500cc columns in series packed with 5Å molecular sieves (8-12 mesh; Aldrich Chemical Company), then a 500cc column packed with SELEXSORB CD (BASF), and finally a 500cc column packed with SELEXSORB COS (BASF).

[0176] Reactor Description and Preparation: Polymerization was carried out in an autoclave equipped with an external heater for temperature control, a glass insert (internal reactor volume approximately 22.5 mL), a septum inlet, controlled supply of nitrogen, ethylene, and propylene, and a disposable PEEK mechanical agitator (800 RPM) in a dry box under an inert atmosphere (N2). The autoclave was prepared by purging with dry nitrogen at 110°C or 115°C for 5 hours, followed by purging at 25°C for 5 hours.

[0177] Propylene polymerization (PP): The reactor was prepared as described above, heated to 40°C, and then purged with propylene gas at atmospheric pressure. For the MAO activation trial, toluene, MAO, propylene (1.0 ml unless otherwise specified in the table), and comonomer (if used) were added via syringe. The reactor was then heated to process temperature (usually 70°C or 100°C unless otherwise specified) with stirring at 800 RPM. While the reactor was under process conditions, the pre-catalyst solution was added via syringe. The reactor temperature was monitored and maintained within + / - 1°C, usually. Polymerization was stopped by adding an air-gas mixture of approximately 50 psi or CO2 gas to the autoclave for approximately 30 seconds. Polymerization was quenched based on a predetermined pressure drop of approximately 8 psi unless otherwise specified (maximum quench value (in psi)), or the polymerization time was up to 30 minutes unless otherwise specified. The reactor was then cooled and vented. After removing the solvent under vacuum, the polymer was isolated. The actual quench time is reported. If the quench time is shorter than the maximum reaction time, it indicates that the reaction was quenched by incorporation. The reported yield includes the total mass of polymer and residual catalyst. Catalytic activity is reported as grams of polymer per mmol of complex per hour of reaction time (gP / mmolcat·hour). Examples of propylene homopolymerization, including characterization, are summarized in Table 1 below.

[0178] Characterization of small-scale polymers. 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%) and treating the solution in a shaking oven at 165°C for approximately 3 hours. Typical polymer concentrations in the solution were 0.1–0.9 mg / ml, and the BHT concentration was 1.25 mg BHT / TCB (ml). For testing, the samples were cooled to 135°C.

[0179] High-temperature size exclusion chromatography was performed using automated “Rapid GPC” systems described in U.S. documents 6,491,816; 6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632; 6,175,409; 6,454,947; 6,260,407; and 6,294,388, each of which is incorporated herein by reference. Molecular weight (mass-average molecular weight (Mw), number-average molecular weight (Mn), z-average molecular weight (Mz)) and molecular weight distribution (PDI=MWD=Mw / Mn) (sometimes also called polymer polydispersity (PDI)) were measured by gel permeation chromatography using a Symyx Technology GPC equipped with an evaporative light scattering detector (ELSD) and calibrated with polystyrene standards (Polymer Laboratories: Polystyrene Calibration Kit SM-10: Mp (peak Mw) 5,000~3,390,000). Alternatively, samples were measured by gel permeation chromatography using a Symyx Technology GPC equipped with a dual-wavelength infrared detector and calibrated with polystyrene standards (Polymer Laboratories: Polystyrene Calibration Kit SM-10: Mp (peak Mw) 580~3,039,000). The sample (250 μL of polymer solution in TCB injected into the system) was measured using three Polymer Laboratories PLgel 10 μm Mixed-B 300 × 7.5 mm columns in series at an eluent flow rate of 2.0 ml / min (sample temperature 135°C, oven / column 165°C). Column spreading correction was not used. Numerical analysis was performed using Epoch® software available from Symyx Technologies or Automation Studio software available from Freeslate. The obtained molecular weights are relative to linear polystyrene standards. Molecular weight data are reported in the table below under the headings Mn, Mw, Mz, and PDI as defined above.

[0180] To determine the melting point of the polymer, differential scanning calorimetry (DSC) measurements were performed using a TA-Q100 instrument. The sample was pre-annealed at 220°C for 15 minutes (first melting), and then cooled 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. The melting point was collected during the heating period. The reported value is the peak melting temperature, referred to as the second melting for the purposes of this disclosure. The results are shown in the table under heading T. m It is reported below.

[0181] Table 2. Propylene polymerization trials. Standard conditions included 0.015 micromoles of pre-catalyst complex 6 (see above) and the type and amount of activator shown in the table. 1 ml of propylene and a total of 4.1 ml of solvent were used. The reaction mixture was heated to either 70°C or 100°C, stirred at 800 rpm, and quenched after a pressure reduction of 8 psi, or for up to 30 minutes if the quench pressure was not met.

[0182] [Table 3]

[0183] The data in Table 2 shows that even with very short contact times between the precatalyst and MAO (see catalyst solution and polymerization procedure above) and very short polymerization times (quench times) to match high-throughput polymerization designs, the activity for TMA-free MAO (TF-MAO) is significantly higher than that for standard MAO. The longer the contact time between the precatalyst and MAO, the greater the difference in activity, for example, in the case of the supported catalysts listed below. The significantly higher Mw for TF-MAO than for MAO is probably because TF-MAO does not contain free TMA capable of chain transfer, indicating that manipulating the free TMA concentration in MAO-based systems provides yet another control mechanism for obtaining the desired polymer molecular weight.

[0184] (Examples 5-7 and Comparative Examples 2-7) Solution ethylene-butadiene copolymerization Polymerization vessel: Symyx Discovery Tools TI-6AL-4V High Pressure Parallel Reactor Chemical substances: Complexes 34, 35, and 36 were prepared as described in US11,254,763; iBu2AlH(DIBAL)(solvent-free, Noryon); [HNMe2Ph] + B(C6F5)4 - (Boulder Scientifics); MAO (WR Grace 30% MAO, Al=13.5%); TF-MAO (obtained in Example 3); Toluene (Aldrich, stored overnight with 3A molecular sieves); Ethylene (purified on the factory line by a standard drying / purification column); Butadiene (BD) (Aldrich, cooled in a dry box freezer set to -20°C, poured into chilled toluene to produce a 10% by mass solution, and stored overnight with activated alumina).

[0185] Procedure: iBu2AlH (DIBAL, 20 equivalents relative to the pre-catalyst metal) and [HNMe2Ph] + B(C6F5)4 - Each pre-catalyst was activated by adding either (1.2 equivalents relative to the pre-catalyst metal), MAO (100 equivalents relative to the pre-catalyst metal), or TF-MAO (100 equivalents relative to the pre-catalyst). After stirring the pre-catalyst and activator for about 10 minutes, a 10% by mass solution of butadiene in toluene was added (approximately 2500 equivalents of butadiene / catalyst), and the reactor, containing six 20 mL vials, was then sealed. The reactor was heated to 100°C and stirred at 225 rpm, and then pressurized with ethylene (250 psi, Sigma, 99.5%). If the pressure dropped below 240 psi in the first hour, the reactor was repressurized. After 4 hours, the reactor was cooled and then reduced in pressure. The polymer products were isolated from each vial by precipitation and washing with acetone and methanol. The solid was then filtered off and washed with a large amount of acetone and methanol. The polymer samples were then dried in a vacuum oven at 50°C for 18 hours.

[0186] iBu2AlH-[HNMe2Ph] + B(C6F5)4 - Even when the copolymer reaction mixture was activated with an activator system, no product was formed (Table 3, Comparative Examples 1, 4, and 7). Compared to the standard MAO-activated reaction mixture, the yield of the ethylene-rich copolymer was low (43.5 kg). 生成物 / mol RE It was observed that the catalyst was formed up to (trials 2, 5, and 8). When TMA-free MAO (TF-MAO) was used, the activity of the three precatalysts was 239.4 kg. 生成物 / mol M This can be significantly increased (trials 3, 6, and 9). This is shown graphically in Figure 5.

[0187] [Table 4]

[0188] (Comparative Example 8 and Examples 8-12) In this example, a post-metallocene (complex 6) is used to perform tests on TMA-free supported MAO (TF-sMAO) and compared with standard supported MAO (sMAO). Catalyst preparation: Chemicals: Silica ES70 (Ecovyst (formerly PQ), calcined at 400°C); MAO (WRGrace, 30% MAO in toluene, Al=13.5% by mass); (NH4)2SiF6 (Aldrich, vacuum-dried overnight at ambient temperature, Mw=178.17); Solvents: Toluene (Aldrich, anhydrous, stored overnight with 3A molecular sieve before use) and isohexane (ExxonMobil factory solvent, stored overnight with 3A molecular sieve before use); Post-metallocene complex 6 (ExxonMobil lab, Mw=945 g / mol).

[0189] Preparation procedure for catalysts in Examples 8-12: 2.04 g of silica and 12 g of toluene were added slowly to a 20 mL vial of MAO solution (14 mmol of Al, relative to 7.0 mmol / g silica); heated at 100°C for 4 hours. The supernatant was sampled for NMR (no Al-Me species were detected); 29.1 mg of (NH4)2SiF6 based on 7 mol F% relative to Al (14 mmol of Al x 7% / 6 x 178.12 = 29.1 mg) was added, shaken for 30 minutes, heated at 70°C for 20 minutes, filtered and washed with 10 x 2 toluene and 1 x 20 g of iC6, and dried under vacuum for 30 minutes. The yield was 3.0 g (this step removed most of the free TMA). 1.0 g of sMAO was re-slurried in 4 g of toluene, 31 mg of complex 6 was added, the mixture was shaken on a shaker for 1 hour, filtered, washed with 2 × 5 g of toluene and 1 × 10 g of iC6, and dried under vacuum for 1 hour. Yield: 1.0 g. Preparation procedure for the catalyst of Comparative Example 8: The same chemicals and similar procedure as above, except that the (NH4)2SiF6 treatment is omitted.

[0190] Salt bed gas-phase PE polymerization Chemicals: NaCl (Fisher S271-10, dehydrated at 180°C, subjected to several pump / purge cycles, and finally screened through a 16-mesh screen before use); ES-70 silica (calcined at 875°C), Al i Carrying Bu3. Procedure: Heat the A2 L autoclave to 110°C and purge with N2 for at least 30 minutes. Add 350g of dry NaCl and silica-supported Al to it. i36 g of Bu was added at 105°C and stirred for 30 minutes. The temperature was adjusted to 85°C. Dry, degassed 1-hexene (2.0 mL) was added to the reactor by syringe at an N2 pressure of 2 psig, and then N2 was added to the reactor to a pressure of 20 psig. A mixture of H2 and N2 was flowed into the reactor while stirring the bed (120 SCCM; 10% H2 in N2). The catalysts shown in Table 3 were injected into the reactor together with ethylene at a pressure of 220 psig. To maintain a constant pressure in the reactor, an ethylene stream was supplied during operation. 1-hexene was supplied to the reactor in a ratio to the ethylene stream (0.1 g / g). Hydrogen was supplied to the reactor in a ratio to the ethylene stream (0.5 mg / g). The hydrogen and ethylene ratios were measured by online GC analysis. After 1 hour, polymerization was stopped by venting the reactor, cooling to room temperature, and then exposing it to air. The salts were removed by washing twice with water, the polymer was isolated by filtration, briefly washed with acetone, and dried in the air for at least two days. The yields and calculated activities based on the yields in the trials of Comparative Example 8, which used the final catalyst derived from Complex 6 obtained from standard supported MAO, and in the trials of Examples 8-12, which used the final catalyst derived from Complex 6 obtained from the supported MAO (TF-sMAO) of the present invention, are listed in Table 3.

[0191] [Table 5]

[0192] The data in Table 3 shows that the TF-sMAO-complex 6 catalyst system is more active, and its activity can be enhanced by including hexane. Its H2 response is not as sensitive as that of metallocene, but its activity increases with increasing H2 input. Overall, the MAO and catalyst systems of this disclosure provide improvements in catalytic activity and catalyst lifetime compared to post-metallocene and CGC catalysts. In addition, hydrocarbyl aluminum compounds having strongly electron-withdrawing atoms or groups can be formed in situ during MAO formation.

[0193] Unless otherwise specified, the phrases "consists essentially of" and "consisting essentially of" do not preclude the presence of other steps, elements, or materials, whether or not they are specifically described herein, unless such steps, elements, or materials affect the fundamental and novel features of the disclosure, nor do these phrases preclude impurities and errors that are typically associated with the elements and materials used.

[0194] For the sake of brevity, only certain ranges are explicitly disclosed herein. However, any range from any lower limit can be combined with any upper limit to detail ranges not explicitly enumerated, and any range from any lower limit can be combined with any other lower limit to detail ranges not explicitly enumerated, and similarly, any range from any upper limit can be combined with any other upper limit to detail ranges not explicitly enumerated. Furthermore, any range includes all points or individual values ​​between its endpoints, even if they are not explicitly enumerated. Thus, every point or individual value can function as a lower or upper limit itself, and can be combined with any other point or individual value or any other lower or upper limit to detail ranges not explicitly enumerated.

[0195] All documents referenced herein, including any priority documents and / or test procedures, are incorporated herein by reference only to the extent that they do not contradict the text. As is evident from the above general description and specific embodiments, while the forms of this disclosure are illustrative and described, various modifications can be made without departing from the spirit and scope of this disclosure. Therefore, this disclosure is not intended to be limited thereto. Similarly, the term “comprising” is to be considered to have the same meaning as the term “including.” Similarly, when a composition, element, or group of elements is preceded by the transitional phrase “comprising,” it is also understood that the composition, element, or enumeration of elements may be preceded by a transitional phrase such as “consisting essentially of,” “consisting of,” “selected from the group consisting of,” or “is,” and vice versa.

[0196] While this disclosure describes several embodiments and examples, those skilled in the art who are interested in this disclosure will recognize that other embodiments can be devised without departing from the scope and spirit of this disclosure.

Claims

1. A method for preparing an almoxane composition, The process includes the step of introducing an unsupported or supported almoxane composition together with an electron-withdrawing compound to form an almoxane composition, wherein the almoxane composition is determined by titration of the almoxane composition using tetrahydrofuran, and the almoxane composition contains 0% to about 2% by mass of free and / or dimerized Al derived from the trihydrocarbyl aluminum compound relative to the total aluminum content of the almoxane composition, and the electron-withdrawing compound is Equation (I): A m B (u) X ｎ (I) A method for an inorganic compound having [wherein A is an ammonium cation, m = 0, 1, or 2, provided that when m = 0, B is H or an element from Group 3, Group 4, Group 5, Group 6, Group 7, Group 13, Group 14, Group 15, Group 16, or Group 17; when m is not zero, B is an element from Group 3, Group 4, Group 5, Group 13, Group 14, or Group 15; u is the valence state of element B, which can be 1, 2, 3, or 4; X is a halogen or pseudohalogen atom or an aryl or aryloxy halide, where n = m + u].

2. The inorganic compound of formula (I) is NH 4 BF 4 ,(NH 4 ) 2 SiF 6 ,NH 4 PF 6 ,NH 4 F,(NH 4 ) 2 TaF 7 ,NH 4 NbF 4 ,(NH 4 ) 2 GeF 6 ,(NH 4 ) 2 SmF 6 ,(NH 4 )<00​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​

3. A method for preparing unsupported or supported almoxane compositions, The process includes the step of introducing an unsupported or supported almoxane composition together with an electron-withdrawing compound to form an almoxane composition, wherein the almoxane composition is determined by titration of the unsupported or supported almoxane composition with tetrahydrofuran, and the almoxane composition contains 0% to about 2% by mass of free and / or dimerized Al derived from the trihydrocarbyl aluminum compound relative to the total aluminum content of the almoxane composition, and the electron-withdrawing compound is Formula (II): ( o * (u) ︸ (u-o) (=) [In the formula, R is C 1 -C 10 Organic compounds having a hydrocarbyl group, where M is a group 13 or group 14 element, o=1 for group 13 elements, o=2 for group 13 elements other than Al, and o=1, 2, or 3 for group 14 elements, X is an electron-withdrawing atom or group, u is the valence state of element M3 or 4, and X is a halogen, pseudohalogen, or aryl or aryloxy halide. The method.

4. The organic compound of formula (II) is Me 3 SiF, Me 2 SiF 2 MeSiF 3 Et 3 SiF, Et 2 SiF 2 EtSiF 3 Ph 3 SiF, Ph 2 SiF 2 PhSiF 3 Me 3 CF, Me 2 CF 2 MeCF 3 Et 3 CF, Et 2 CF 2 EtCF 3 Ph 3 CF, Ph 2 CF 2 PhCF 3 Me 2 BF, MeBF 2 MeAlF 2 Et 2 BF, EtBF 2 EtAlF 2 Ph 2 BF, PhBF 2 Me 3 Si(OC 6 F 5 ), Me 2 Si(OC 6 F 5 ) 2 MeSi(OC 6 F 5 ) 3 Me 3 C(OC 6 F 5 ), Ph 3 C(OC 6 F 5 ), Me 2 B(OC 6 F 5 )MeB(OC 6 F<00.00109>) 2 MeAl(OC 6 F 5 ) 2 The method according to claim 3, selected from the group consisting of the following, and combinations thereof.

5. Trihydrocarbyl aluminum compounds, AlMe 3 AlEt 3 Al i Bu 3 AlOct 3 The method according to any one of claims 1 to 4, selected from the group consisting of the following and combinations thereof.

6. The method according to claims 1 to 5, further comprising the step of introducing a trihydrocarbyl aluminum compound together with an oxygen source at a temperature of approximately -60°C to approximately 0°C to form an almoxane.

7. The method according to any one of claims 1 to 6, further comprising the step of introducing a carrier slurry together with an oxygen source into a trihydrocarbyl aluminum compound solution to form an aluminoxane on the carrier in situ as a supported aluminoxane.

8. The method according to claim 6 or 7, wherein the trihydrocarbyl aluminum compound is trimethylaluminum.

9. The method according to claims 6 to 8, wherein the oxygen source is water.

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

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

12. The method according to claim 11, wherein the number of moles of the trihydrocarbyl aluminum compound is the trihydrocarbyl aluminum compound present in the aluminoxane after aluminoxane formation.

13. The method according to any one of claims 1 to 12, wherein the almoxane is a solution methylalmoxane (MAO), and the introduction of the solution MAO together with an electron-withdrawing compound is carried out at a temperature of about 10°C to about 100°C.

14. The method according to claims 1 to 12, wherein the almoxane is a supported methylalmoxane (MAO), and the introduction of the supported MAO together with an electron-withdrawing compound is carried out in the presence of a diluent at a temperature of about 10°C to about 100°C.

15. The method according to any one of claims 1 to 14, further comprising the step of introducing a supported or unsupported almoxane composition together with at least one pre-catalyst compound.

16. 1) A solid or supported almoxane composition, 2) Equation AlR 2 X (where R is C) 1 -C 8 A blocking agent represented by a hydrocarbyl group, where X is a halogen atom, a pseudohalogen group, or an aryl or aryloxy halide, 3) When determined by titration of the composition using tetrahydrofuran, the composition contains 0% to about 2% by mass of Al derived from trihydrocarbyl aluminum compounds in the form of free and / or dimers, relative to the total aluminum content of the composition. A composition containing the following:

17. R is methyl, ethyl, isobutyl, or octyl, and X is an F atom or C 6 F 5 The composition according to claim 16, wherein the group is O-.

18. 1) A solid or supported almoxane composition, 2) Equation AlR 2 X (where R is C) 1 -C 8 A blocking agent represented by a hydrocarbyl group, where X is a halogen atom, a pseudohalogen group, or an aryl or aryloxy halide, 3) Trihydrocarbyl aluminum compounds in free and / or dimer form A step of providing a first composition comprising, The step of separating the supernatant liquid from the first composition to form a second composition, wherein the second composition is 1) A solid or supported almoxane composition, 2) Blocking agent and 3) When determined by titration of the second composition using tetrahydrofuran, the amount of Al derived from free and / or dimerized trihydrocarbyl aluminum compounds is 0% to about 2% by mass relative to the total aluminum content of the second composition. Steps and Methods that include...

19. A method for preparing an almoxane composition, 1) A supported or solid methylalmoxane (MAO) composition, 2) Formula (III): AlR 2 X (III) [In the formula, R is C 1 -C 8 It is a hydrocarbyl group, and X is F or OC. 6 F 5 And, However, equation (III) is: a) Formula AlR 2 Y (where R is C) 1 -C 8 Compounds having a hydrocarbyl group (where Y is a non-fluorine halide or pseudohalide), formula (IV): MX u (IV) (In the formula, M is a Group 1 or Group 2 metal, u is the valence state of metal M1 or 2, and X is F or OC) 6 F 5 It is formed in advance by contacting an electron-withdrawing salt represented as (which is), or b) Trihydrocarbyl aluminum compound AlR that is not present in the MAO composition 3 (In the formula, R is C) 1 -C 8 A hydrocarbyl group is formed either beforehand or in situ by contacting it with either the inorganic compound of formula (I) described in claim 1 or the organic compound of formula (II) described in claim 2. A blocking agent represented by [one of the following] 3) A step of removing free trihydrocarbyl aluminum to obtain an almoxane composition, wherein the almoxane composition is determined by titration of the almoxane composition using tetrahydrofuran, and the almoxane composition contains 0% to about 2% by mass of Al derived from the trihydrocarbyl aluminum compound in the form of free and / or dimers, relative to the total aluminum content of the almoxane composition. Methods that include...

20. AlR 2 Y is AlMe 2 Cl, AlMe 2 Br, AlMe 2 I, AlEt 2 Cl, AlEt 2 Br, AlEt 2 I, Al i Bu 2 Cl, Al i Bu 2 Br, Al i Bu 2 I, AlOct 2 Cl, AlOct 2 Br, AlOct 2 I, AlMe 2 CN, AlEt 2 CN, Al i Bu 2 CN, AlOct 2 A compound of formula (IV) is selected from the group consisting of CN and combinations thereof, and LiF, NaF, KF, MgF 2 CaF 2 BaF 2 LiOC 6 F 5 NaOC 6 F 5 KOC 6 F 5 Mg(OC 6 F 5 ) 2 Ca(OC) 6 F 5 ) 2 , Ba(OC 6 F 5 ) 2 The method according to claim 19, selected from the group consisting of the following, and combinations thereof.

21. The method according to claim 19, wherein the supported or solid MAO composition contains a trihydrocarbyl aluminum compound in the form of free and / or dimers at a concentration of about 0.1% to about 1% by mass, relative to the total aluminum content of the supported almoxane composition.

22. At least one pre-catalyst compound, The supported or unsupported almoxane composition according to claim 16 and A catalyst system including the following.

23. The pre-catalyst compound is given by formula: T y Cp m MG n X q [In the formula, Cp is independently a substituted or unsubstituted cyclopentadienyl ligand, or an isoloval substituted or unsubstituted ligand to cyclopentadienyl. M is a group 4 transition metal, G is formula JR * z (In the formula, J is N, P, O or S, and R * C is a linear, branched, or cyclic C 1 -C 20 It is a heteroatom group represented as hydrocarbyl, z is either 1 or 2, T is a crosslinking group, y is either 0 or 1, X is a leaving group, m = 1, n = 1, 2, or 3, q = 0, 1, 2, or 3, The catalyst system according to claim 22, wherein the sum of m + n + q is equal to the oxidation state of the transition metal.

24. The catalyst system according to claim 22, wherein the pre-catalyst compound is a bis(arylphenolate)pyridine complex.

25. Bis(arylphenolate)pyridine complexes 【Chemistry 1】 【change】 【change】 【change】 The catalyst system according to claim 24, selected from the group consisting of and combinations thereof.

26. The catalyst system according to claim 22, wherein the pre-catalyst compound is selected from the group consisting of the following. Table 1-1 Table 1-2

27. A method for polymerizing olefins to produce a polyolefin composition, comprising the steps of: contacting at least one olefin with a catalyst system according to any one of claims 22 to 26; and obtaining the polyolefin composition from a polymerization configuration of one or more reactors using batch, continuous, or sequential solution polymerization, slurry polymerization, or gas-phase polymerization.

28. The catalyst system contains approximately 2,000 g Pgcat relative to the supported catalyst. -1 time -1 ~Approximately 30,000g Pgcat -1 time -1 , and approximately 10,000 g Pgcat relative to the solution catalyst -1 time -1 ~Approximately 1,000,000 g Pgcat -1 time -1 The method according to claim 27, having catalytic activity.

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