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

Abstract

This disclosure relates to an almoxane composition substantially or completely free of uncoordinated hydrocarbyl aluminum contents, 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, the catalyst system includes at least one pre-catalyst compound. The catalyst system includes an unsupported or supported almoxane. The almoxane includes a monodentate siloxy ligand. In some embodiments, the method for producing an almoxane includes the step of forming an ionic alkylalmoxane by reacting a supported or unsupported alkylalmoxane with a polydentate chelating agent to form a silanealkylaluminum complex. The method includes the step of heating or aging the silanealkylaluminum complex to form a supported or unsupported alkylalmoxane containing a monodentate ligand.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims the benefit and priority of U.S. Provisional Patent Application No. 63 / 506541, filed on June 6, 2023, whose disclosure is incorporated herein by reference.

[0002] This disclosure relates to an almoxane composition substantially or completely free of hydrocarbyl aluminum contents, 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. [Background technology]

[0003] 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 methylalmoxanes (MAOs), obtained from partially hydrolyzed trimethylaluminum (TMA), are effective in activating catalysts of the type known as metallocenes for olefin polymerization. MAOs are generally preferred in the industry as aluminum co-catalysts (also called activators). MAOs are commercially available in the form of aromatic diluents, usually as a 10% to 30% by mass solution in toluene.

[0004] Considerable effort has been made to improve the effectiveness of catalytic systems for olefin polymerization based on the use of methylalmoxane or modified methylalmoxane. 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 “Ligand Exchange and Alkyl Abstraction Involving (Perfluoroaryl) boranes and -alanes with Aluminum and Gallium Alkyls,” Organometallics, 2000, v.19(23), pp.4684 - 4686. US9090720 describes that ethylenebisindenylzirconium dimethoxide (EtInd2Zr(OMe)2), a metallocene with a dimethoxy leaving group, 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 evidence strongly supporting the activation by AlMe2 from MAO. The fully activated [EtInd2Zr(μ - Me)2AlMe2] + species is similar to other MAO - activated metallocenes that form metallocene - dialkylaluminum cation species, such as, for example, [Cp2Zr(μ - Me)2AlMe2] + or [Cp2Ti(μ - Me)2AlMe2] + and is described, for example, by Babushkin, D. E. et al. (2002) “Activation of Dimethyl Zirconocene by Methylaluminoxane (MAO) - Size Estimate for Me - MAO + for the activation of zirconocene catalyst precursors by MAO -Examples include "Anions by Pulsed Field-Gradient NMR" J. Am. Chem. Soc., v.124, pp.12869-12873, and Sarzotti, DM et al. (2006) "A Kinetic Study of Metallocene-Catalyzed Ethylene Polymerization Using Different Aluminoxane Cocatalysts," J. Polymer Sci. A, v.45, pp.1677-1690. Also, see Bryliakov, KP et al. (2004) “Activation of titanocene catalyst precursors by MAO.” 1 H and 13 C NMR Spectroscopic Study of Titanium (IV) Species Formed by Activation of Cp2TiCl2and [(Me4C5)SiMe2N t See also “Bu]TiCl2 with Methylaluminoxane (MAO),” Organometallics, v.23, pp.149-152. Although the MAO structure remains unclear, the newly synthesized active MAO is based on the empirical formula (Al4O3Me6)4(TMA) described by Sinn and Kaminsky (Sinn, et al., “Formation, Structure, and Mechanism of Oligomeric Methylalumoxane”, in Kaminsky (ed.), Metalorg. Cat. for Synth. & Polym., Springer-Verlag, 1999, p.105). 1-2This provides evidence of coordination TMA in MAO, consistent with the above. Coordination TMA is in equilibrium with free TMA, and attempts to physically remove all free TMA result in the formation of a more stable but less active MAO gel due to the loss of coordination TMA (equation (1)), such MAO is difficult to find a solvent suitable for solution polymerization or to load onto a support for gas-phase or slurry-phase polymerization (i.e., to penetrate the pores of the support).

[0005] [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 is shown to function as an alkylating agent, as shown in equation (2). For clarity, circles are used in the equation to represent the main structure of MAO, e.g., (Al4O3Me6)4 units (Luo, Jain, and Harlan, INOR1169, 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)):

[0006] [ka]

[0007] Therefore, maintaining a substantial amount of free TMA in the active MAO solution is necessary to stabilize the active MAO composition, for example, by stabilizing the coordinated TMA-capped MAO molecular structure as shown in scheme or equation (1), thereby reducing the probability of dimerization / oligomerization that ultimately forms an MAO gel. Thus, physical removal of free TMA can lead to not only MAO gelation but also loss of coordinated TMA, resulting in a decrease in activation efficiency.

[0008] Nevertheless, post-metallocene catalysts, as well as geometrically constrained complex (CGC) catalysts (also called mono-cyclopentadienyl (mono-Cp) catalysts) containing polar ligands such as oxygen and / or nitrogen donors, present challenges to activation by standard MAO, for example, exhibiting low catalytic activity, short catalytic lifetimes, or both. 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 metal center of the pre-catalyst bonded to the heteroatom (an example at the Zr center is shown in Scheme 3 or equation (3)), which is analogous to the alkylation of metallocenes with dichloride leaving groups in equation (3):

[0009] [ka] Previous studies have shown that MAO can be precipitated as a clathrate using the chelating agent octamethyltrisiloxane (OMTS) (Sangokoya et al., WO2003 / 082879 (2003)). Free TMA can be separated from the clathrate, and in this case, most of the coordination TMA in MAO is [AlMe2(OMTS)] + By being converted to AlMe2, the equilibrium between free TMA and coordinated TMA is disrupted, leading to the precipitation of the clathrate phase in the original MAO solution, thereby allowing the free TMA to be removed from the solution. Unfortunately, however, due to the strong chelating action of the OMTS group, AlMe2 +The efficient release of is inhibited, and due to a significant positive activation enthalpy, it is prevented from functioning as an activator for the pre-catalyst.

[0010] Therefore, 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 CGCs. For example, a solution having sufficient coordination TMA or an MAO supported with sufficient coordination TMA is AlMe2 + It provides this AlMe2 + This allows for the absence of free TMA or a low content of free TMA, while maintaining efficiency as an activator. References cited in the Information Disclosure Statement (37C.FR1.97(h)): WO2003 / 082879; US2019 / 0127499; US2009 / 0124486; US6,667,272; US2019 / 0153135; US2013 / 0253155; US2018 / 0142046; US7,193,100. [Overview of the project]

[0011] This disclosure relates to an active cation-modified almoxane composition substantially or completely free of free (uncoordinated) aluminum hydrocarbyl contents, 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, the catalyst system comprises at least one precatalytic compound and an unsupported or supported almoxane containing a monodentate siloxy ligand.

[0012] In some embodiments, a method for producing an almoxane includes forming an ionic alkylalmoxane by (1) reacting a supported or unsupported alkylalmoxane with a polydentate chelating agent to form an ionic aluminoxane composition containing a siloxane-chelated alkylaluminum cation, and (2) heating or aging the ionic aluminoxane composition containing a siloxane-chelated alkylaluminum cation to form an ionic alkylalmoxane containing a supported or unsupported alkylalmoxane that contains at least one decomposition product of a siloxane-chelated cation in the siloxane-modified ionic aluminoxane composition.

[0013] In some embodiments, the method for preparing an almoxane composition includes the step of forming an alkylaluminoxane composition that does not contain uncoordinate alkylaluminum by reacting a supported or unsupported alkylaluminoxane with silanol to form an alkylaluminoxane composition containing a monodentate siloxy ligand, provided that the uncoordinate alkylaluminum content is 2% by mass or less of Al relative to the total Al. In some embodiments, the compound is of formula (I):

[0014] [ka] [In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 Each of these is independently represented as a hydrogen atom, a hydrocarbyl group, a silyl group, or a heteroatom-containing group.

[0015] In some embodiments, the method for preparing the almoxane composition is as follows: a) Supported or solid alkylalmoxane, formula (II): R3SiOAlR2(II) Contacting a dialkylaluminum siloxide represented by (wherein R is independently hydrogen, hydrocarbyl, or a non-coordinating or weakly coordinating heteroatom-containing group), and b) Separation of non-coordinating alkylaluminum from the siloxylated aluminoxane composition. The method includes the step of reacting a supported or solid alkylalmoxane with a dialkylaluminum siloxide to form an alkylaluminum alkylalmoxane composition. In some embodiments, supported or unsupported alkylaluminoxane compositions modified with anions and cationic compounds are provided. Anionic modification is achieved by treating the supported or unsupported alkylaluminoxane with a compound containing at least one electron-withdrawing compound. In either order, cationic modification is achieved by treating the supported or unsupported alkylaluminoxane with a chelate or monodentate siloxane compound, followed optionally by heating the anionic and cationic modified supported or unsupported alkylaluminoxane. [Brief explanation of the drawing]

[0016] [Figure 1] This shows a synthesis process for forming monodentate ligands according to some embodiments. [Figure 2] This shows a synthesis process for forming a monodentate ligand-coordinated AlMe2 composition according to some embodiments. [Figure 3] This graph shows the activity of gas-phase polyethylene polymerization of silica-MAO in some embodiments, compared to silica-supported ionic MAO. [Figure 4] This graph shows the productivity of TMA-free F-MAO in some embodiments compared to TMA-free ionic MAO. [Figure 5] This graph shows the catalyst productivity in some embodiments. [Figure 6]This is a 1H NMR spectrum of an ionic MAO having one of the decomposition products of [(OMTS)AlMe2]+ according to some embodiments, showing a peak consistent with the proposed structure with a Me-Al:SiMe ratio of 4:3. [Modes for carrying out the invention]

[0017] definition A new numbering system for the groups of elements in the periodic table is used, as described in Chemical and Engineering News, v. 63(5), pg.27 (1985). Therefore, "Group 4 metals" are elements of Group 4 of the periodic table, such as Hf, Ti, or Zr, and "Group 3 metals" are elements of Group 3 of the periodic table, such as Sc, Y, or Nd.

[0018] "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.

[0019] 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 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 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.

[0020] 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) 12This 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).

[0021] "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.

[0022] "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. Two types of TMA-free MAO compositions exist: 1) Cationic-modified MAO, which is an MAO composition modified with a chelating agent, which can form an ionic MAO composition containing a dimethylaluminum cation stabilized with the chelating agent or ligand, which can then be heated to decompose into a monodentate ligand-stabilized cation of the embodiments of this disclosure, and this cationic-modified MAO can also be called an ionic MAO; and 2) Anionic-modified MAO, i.e., an MAO composition modified with the compound AlMe2X (wherein X is an electron-withdrawing group (e.g., AlMe2F or AlMe2(OC6F5)) which is either pre-formed or formed in situ, which makes it possible to replace the coordination TMA to form the coordination AlMe2X. + When the pre-catalyst is activated in this MAO composition through complexation with (XMAO) - This results in an anion, which is described in a separate application filed separately. Non-coordinating alkylaluminum-free systems can also be obtained by cationically modified MAO and anionically modified MAO.

[0023] "Chelating agent or compound" means a compound having multiple donor groups for forming a chelate structure with a dialkylaluminum cation in an alkylaluminoxane system. Preferred chelating agents or chelating compounds contain multiple siloxy donor groups, for example, octamethyltrisiloxane (OMTS). Examples of chelating agents, but not limited to these, include linear or cyclic polysiloxanes, such as octamethyltrisiloxane (OMTS), octamethylcyclotetrasiloxane, decamethyltetrasiloxane, hexamethylcyclotrisiloxane, and hexaphenylcyclotrisiloxane.

[0024] "Monoceptive agent or compound" means a compound having a single donor group that forms a non-chelate structure with a dialkylaluminum cation in an alkylaluminoxane system. Examples of monocephalic agents include, but are not limited to, compounds having a single oxygen-containing siloxidizer group, such as hexamethyldisiloxane, hexaphenyldisiloxane, hexaethyldisiloxane, dimethylaluminum, trimethylsiloxide, and diethylaluminum triethylsiloxide. More preferred monocephalic agents are siloxidizer-modified alkylaluminum, such as dimethylaluminum trimethylsiloxide, diethylaluminum trimethylsiloxide, diisobutylaluminum trimethylsiloxide, dimethylaluminum triethylsiloxide, diethylaluminum triethylsiloxide, diisobutylaluminum triethylsiloxide, dimethylaluminum tripropylsiloxide, diethylaluminum tripropylsiloxide, diisobutylaluminum tripropylsiloxide, dimethylaluminum triphenylsiloxide, diethylaluminum triphenylylsiloxide, and diisobutylaluminum triphenylylsiloxide. The most preferred monocephalic agent is obtained by decomposing the MAO composition treated with a chelating agent, in These are produced situ, for example, by heating OMTS-treated MAO to produce dimethylaluminum trimethylsiloxide, as shown in Ib to Ia of Scheme 4.

[0025] In this specification, ionic aluminoxane or ionic MAO means a neutral-charged aluminoxane or MAO composition containing coordinating aluminum alkyl or TMA after treatment with an electron donor ligand or compound to form an ionic composition containing an aluminoxane anion or MAO anion and a dialkylaluminum cation or dimethylaluminum cation stabilized with an electron donor ligand or compound. Depending on the solubility of the ionic composition, phase separation of the ionic composition from the mother liquor may or may not occur. For example, ionic higher alkyl (e.g., C4-C8) modified MAO products (e.g., after ionization of MMAO from Nouryon) may have better solubility in a common concentration range such as 10-30% by mass, while on the other hand, ionic MAO at common concentrations may precipitate as a heavier liquid phase (or called the clathrate phase) and separate from the mother liquor. Depending on the elapsed time of the MAO, ionic MAO obtained from fresher MAO products may be more soluble than those that have been aged longer. Highly diluted solutions can dissolve all ionic MAOs.

[0026] 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.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] 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:

[0032] [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 , R19 , R 20 , and R 21 each of which is independently selected from hydrogen, C1-C 40 hydrocarbyl (e.g., C1-C 40 alkyl) or C1-C 40 substituted hydrocarbyl, heteroatom or heteroatom-containing group, or two or more of R 18 , R 19 , R 20 , and R 21 are joined together to form a C4-C 62 cyclic or polycyclic ring structure, or a combination thereof, and the wavy line indicates the position where the substituted phenolate group forms a bond with the remainder of the catalyst compound.] is represented by

[0033] "Alkyl-substituted phenolate" means that at least 1, 2, 3, 4 or 5 hydrogen atoms are replaced at the 2-, 3-, 4-, 5- and / or 6-positions by at least one alkyl group, e.g., C1-C 40 , alternatively C2-C 20 , alternatively C3-C 12 alkyl, e.g., methyl, ethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, adamantyl, etc., further including their substituted analogs, is a phenolate group that has been replaced.

[0034] "Aryl-substituted phenolate" means that at least 1, 2, 3, 4 or 5 hydrogen atoms are replaced at the 2-, 3-, 4-, 5- and / or 6-positions by at least one aryl group, e.g., C1-C 40 , alternatively C2-C 20 , alternatively C3-C 12These are phenolate groups that have been replaced with aryl groups, such as phenyl, 4-fluorophenyl, 2-methylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, mesityl, 2-ethylphenyl, naphthalenyl, and their substituted analogs. The term "ring atom" refers to an atom that is part of the ring structure of a cyclic compound. By this definition, the benzyl group has six ring atoms, and tetrahydrofuran has five ring atoms. A heterocycle, also called a heteroring, is a ring that contains a heteroatom within its ring structure, in contrast to a heteroatom-substituted ring where a hydrogen atom on a ring atom is replaced by a heteroatom. For example, tetrahydrofuran is a heterocycle, and 4-N,N-dimethylaminophenyl is a heteroatom-substituted ring. A substituted heterocycle refers to a heterocycle in which one or more hydrogen groups are replaced by a hydrocarbyl, a substituted hydrocarbyl, a heteroatom, or a heteroatom-containing group.

[0035] 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 this disclosure, in relation to catalyst compounds (e.g., substituted bis(phenolate) catalyst compounds), the term “substituted” means that the hydrogen group is a hydrocarbyl group, a heteroatom or heteroatom-containing group, e.g., a halogen (e.g., Br, Cl, F or I) or at least one functional group, e.g., -NR * 2, -OR * -SeR * ,-TeR * ,-PR * 2, -AsR * 2, -SbR * 2, -SR * ,-BR * 2, -SiR * 3, -GeR * 3, -SnR * 3, -PbR * 3 etc (in the formula, each R * These are independently hydrogen, hydrocarbyl, or halocarbyl radicals, and two or more R *This means that the atoms are bonded together and replaced by (which may form a substituted or unsubstituted, fully saturated, partially unsaturated, aromatic cyclic or polycyclic ring structure), or that at least one heteroatom is inserted into the hydrocarbyl ring.

[0036] A tertiary hydrocarbyl group has a carbon atom bonded to three other carbon atoms. When the hydrocarbyl group is an alkyl group, it is also called a tertiary alkyl group. Examples of tertiary hydrocarbyl groups include tert-butyl, 2-methylbutan-2-yl, 2-methylhexane-2-yl, 2-phenylpropane-2-yl, 2-cyclohexylpropane-2-yl, 1-methylcyclohexyl, 1-adamantyl, and bicyclo[2.2.1]heptan-1-yl. The formula for a tertiary hydrocarbyl group is:

[0037] [ka] [In the formula, R A , R B and R C These are independently hydrocarbyl groups or substituted hydrocarbyl groups that may be bonded to each other, and the wavy lines indicate the positions where tertiary hydrocarbyl groups form bonds to other groups. This can be shown as follows.

[0038] A cyclic tertiary hydrocarbyl group is defined as a tertiary hydrocarbyl group that forms at least one alicyclic (non-aromatic) ring. A cyclic tertiary hydrocarbyl group is also called an alicyclic tertiary hydrocarbyl group. When the hydrocarbyl group is an alkyl group, a cyclic tertiary hydrocarbyl group is also called a cyclic tertiary alkyl group or an alicyclic tertiary alkyl group. Examples of cyclic tertiary hydrocarbyl groups include 1-adamantyl, 1-methylcyclohexyl, 1-methylcyclopentyl, 1-methylcyclooctyl, 1-methylcyclodecyl, 1-methylcyclododecyl, bicyclic[3.3.1]nonane-1-yl, bicyclo[2.2.1]heptan-1-yl, bicyclo[2.3.3]hexane-1-yl, bicyclic[1.1.1]pentan-1-yl, and bicyclic[2.2.2]octane-1-yl. A cyclic tertiary hydrocarbyl group is represented by formula B:

[0039] [ka] [In the formula, R A is a hydrocarbyl group or a substituted hydrocarbyl group, and each R D R is independently a hydrogen atom, a hydrocarbyl group, or a substituted hydrocarbyl group, w is an integer from 1 to about 30, and R A and one or more R D and / or two or more R D They may be joined to each other to form an additional ring. This can be shown by: If a cyclic tertiary hydrocarbyl group contains one or more alicyclic rings, 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.

[0040] 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. 100Alkyl 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, or aromatic cyclic or polycyclic ring structure), or in which at least one heteroatom is inserted into the hydrocarbyl ring.

[0041] 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 )

[0042] The following abbreviations may be used herein: Me is methyl, MAO is methylaluminoxane (or methylaluminoxane), OMTS is octamethyltrisiloxane, TMS is trimethylsilyl or tetramethylsilane, depending on whether it is a group (the former) or a compound (the latter), Bn is benzyl (i.e., CH2Ph), THF (also called thf) is tetrahydrofuran, RT is room temperature (and 23°C unless otherwise noted), tol is toluene, Cp is cyclopentadienyl, NMR is nuclear magnetic resonance, and TMA is trimethylaluminum.

[0043] 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.

[0044] In this specification, catalysts may also be referred to as catalysts, catalyst precursors, pre-catalyst compounds, catalyst compounds, or 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.

[0045] 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. Lanthanide metals (La-Lu) include La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.

[0046] Detailed explanation This disclosure relates to an active ionic almoxane that does not contain or contains in small amounts of non-coordinating aluminum alkyl, a method for forming an active ionic almoxane that does not contain or contains in small amounts of non-coordinating aluminum alkyl, a catalyst system having the active ionic almoxane, and a method for polymerizing olefins using a catalyst system derived from the active ionic almoxane. In some embodiments, a method for producing an ionic aluminoxane that does not contain or contains a small amount of non-coordinating aluminum alkyl includes the step of introducing an aluminoxane together with a chelating compound to form an ionic aluminoxane, and the subsequent steps include separating the non-coordinating aluminum alkyl and heating the ionic aluminoxane. In some embodiments, a method for producing an ionic aluminoxane that does not contain or contains a small amount of non-coordinating aluminum alkyl includes the step of introducing an aluminoxane together with a chelating agent to form an ionic aluminoxane, and the subsequent steps include separating the non-coordinating aluminum alkyl and heating the ionic aluminoxane. This method includes the step of introducing a hydrocarbyl aluminum compound together with an oxygen source at a temperature of about -60°C to about 100°C to form an aluminoxane.

[0047] In some embodiments, the catalyst system comprises a pre-catalyst compound and an ionic aluminoxane or heated ionic aluminoxane derivative that does not contain or contains in small amounts of non-coordinating aluminum alkyl.

[0048] In some embodiments, the method for polymerizing an olefin includes the step of using a catalyst system having a pre-catalyst compound and an ionic alumoxane or heated ionic aluminoxane derivative that does not contain or contains low amounts of non-coordinating aluminum alkyl. The method may further include a step of forming an alkylalmoxane for subsequent treatment with a silanol or polydentate silane. For example, the method may include a step of introducing trimethylaluminum with an oxygen source, optionally in a carrier, at a temperature of about -60°C to about 100°C, before ionic treatment, to form a standard MAO composition.

[0049] In some embodiments, a method for producing an alkylaluminum-free alkylaluminoxane (e.g., TMA-free MAO), which is an "ionic alkylaluminoxane," involves using a dialkylaluminum cation (e.g., [AlMe2(μ-O(SiMe3))AlMe2]) stabilized with at least a portion of a monodentate ligand from all alkylaluminum (e.g., free and coordinated TMA). +The process includes the step of treating an unsupported or supported alkylalumoxane with a monodentate compound (e.g., Me3SiOH) that can be converted into a composition containing ). Dialkylaluminum cations stabilized with monodentate ligands can also be formed by treating an alumoxane (e.g., MAO) with a silanol that reacts with free alkylaluminum (e.g., TMA) to form an ionic alumoxane (e.g., B in Figure 2) (for example, as shown in Figure 2). Without being constrained by theory, compounds derived from silanols and free alkylaluminum are thought to extract dialkylaluminum cations from alkylaluminum coordinated on an aluminoxane, forming monodentate ligand-stabilized dialkylaluminum cations, while the MAO main structure acts as a counteranion. An ionic aluminoxane composition derived from a monodentate compound, which contains little to no non-coordinating alkylaluminum, can be activated by treating it with a polymerization pre-catalyst containing at least one non-leaving polar group (e.g., a metallocene, half-metallocene, or post-metallocene pre-catalyst).

[0050] Alternatively, an ionic aluminoxane composition containing a monodentate ligand can be formed by treating an alkylalmoxane having free alkylaluminum with a polydentate (e.g., bidentate) siloxane to form a dialkylaluminum cation having an aluminoxane-aion stabilized with a chelated siloxane, a so-called chelated ionic aluminoxane composition. The chelated ionic aluminoxane composition can be formed by heating for a certain period of time to form a composition containing a monodentate ligand derived from the decomposed chelated ligand. The ionic aluminoxane composition containing a monodentate ligand can be activated by treating it with a polymerization pre-catalyst (e.g., a metallocene catalyst).

[0051] Alternatively, an ionic aluminoxane composition containing a monodentate ligand can be formed by treating an alkylaluminoxane (e.g., MAO) having free alkylaluminum (e.g., TMA) with a polydentate (e.g., bidentate) siloxane to form a dialkylaluminum cation having an aluminoxane-versus-anion stabilized by the chelated siloxane, a so-called chelated ionic aluminoxane composition, which can then be precipitated as a clathrate phase. A separation process can then be carried out to isolate the free aluminum alkyl from the ionic aluminoxane composition. The chelated ionic aluminoxane composition can be heated for a certain period of time to form a composition containing a monodentate ligand derived from the decomposed chelated ligand. The ionic aluminoxane composition containing a monodentate ligand can be more efficiently activated by treating it with a polymerization pre-catalyst (e.g., a half-metallocene or post-metallocene pre-catalyst).

[0052] MAO can be treated with a polydentate siloxane to form an ionic complex containing a dimethyl cation and an aluminoxane counteranion stabilized with a chelated siloxane, such as [AlMe2(OMTS)]. + (MeMAO) - It was discovered that this complex can form a dialkylaluminoxane or dimethylaluminoxane, which is normally less active than untreated aluminoxane or MAO, but becomes more active after heating. This is probably due to the decomposition of the chelate ligand, which forms an ionic alkylaluminoxane or MAO derived from a less stable monodentate ligand, such as a dialkylaluminum cation or dimethylaluminum cation, e.g., [AlMe2(μ-O(SiMe3))AlMe2] + (MeMAO) -This facilitates the release of the precatalyst, resulting in more efficient precatalyst activation. Without being constrained by theory, the reason why an ionic aluminoxane composition containing a dialkylaluminum cation stabilized with a chelated siloxane exhibits lower precatalyst activation activity than a heated composition without heat treatment is due to the energy difference between the following bond cleavage and bond formation reactions. Scheme (1) shows the reaction with a chelated ligand, and scheme (2) shows the reaction with a monodentate ligand:

[0053] [ka]

[0054] [ka]

[0055] It was also discovered that by using silanol to react with free TMA in MAO, a monodentate-stabilized dialkylaluminum cation can be directly formed, eliminating the need for phase separation and heating to remove free TMA. However, the resulting composition is a monodentate complex derived from the chelated complex by heating, such as [AlMe2(OMTS)]. + (MeMAO) - [AlMe2(μ-O(SiMe3))AlMe2] is induced by heating. + (MeMAO) - It is not very active, which is probably because the active OH group reacts not only with the free TMA but also with the coordinating TMA (active site) to form a strong cross-linked O (structure a), which is AlMe2 + This is to block the elimination of (trimethylsilanol is shown as an example in scheme (3)).

[0056] [ka] A slightly better approach to overcome the silanol toxicity of the MAO active site is to pre-form and use a product obtained from the reaction of free alkylaluminum with silanol, for example, free TMA with trimethylsilanol: Me3SiOH + AlMe3 = Me3SiOAlMe2 + CH4. However, this route is only applicable to supported or solid aluminoxanes to obtain a system free of coordinating alkylaluminum. This is because coordinating alkylaluminum is converted to free alkylaluminum, making separation from the solution system difficult. Using supported or solid alkylaluminoxane systems, such as silica-supported MAO or solid MAO, more practical separation processes can be applied, such as filtration or decantation, or, for low-boiling free alkylaluminum, such as free TMA, a vacuum drying (which may also be heated) process.

[0057] The most efficient route is a chelating agent treatment route, which can be OMTS treatment of supported or unsupported MAO, followed by a phase separation process for the solution aluminoxane system, or a filtration / decantation process (or a vacuum / heating process for low-boiling alkylaluminum removal) for the supported or solid aluminoxane system. Similarly, TMA-free ionic almoxane compositions reduce or eliminate side reactions with non-leaving heteroatom coordination pre-catalyst compounds such as oxygen donors and nitrogen donors in half-metallocenes (e.g., geometrically constrained catalysts (CGCs)) and post-metallocenes, thereby promoting improved catalytic activity and lifetime.

[0058] In addition, the almoxane may be formed such that free TMA in the solution remains in the upper solution phase and can be removed from the ionic MAO by phase separation between the clathrate phase and the solution phase. In some embodiments, free TMA may remain in the supernatant phase of the supported ionic MAO composition and can be removed by washing, filtration, or decantation. Thus, after removal, the resulting solution or supported ionic activator can be used to activate single-site catalyst precursors containing TMA reactive groups, such as post-metallocene catalysts and single-site catalyst precursors containing O donors and / or N donors on the CGC half-metallocene family.

[0059] Dimethylaluminum cations stabilized with monodentate ligands, derived from MAO treated with chelate ligands after heat treatment, provide more dimethylaluminum cations for pre-catalyst activation, and these dimethylaluminum cations can be detected by nuclear magnetic resonance spectroscopy. In addition, by using silanol compounds, when the ratio of siloxy group to hydrocarbylaluminum compound is approximately 1:1, the amount of free trihydrocarbylaluminum compound (e.g., trimethylaluminum) present in the catalyst system can be reduced or eliminated, and thus the decomposition reactions of oxygen-containing and / or nitrogen-containing catalyst compounds by oxygen-reactive or nitrogen-reactive trihydrocarbylaluminum in the catalyst system are reduced. For example, the presence of monodentate ligands allows the most reactive primary trihydrocarbylaluminum (e.g., dimerized AlMe3 or TMA) to be decomposed by less reactive secondary dihydrocarbylaluminum (e.g., [Al2Me4(OSiMe3)]). + Alternatively, it can be converted to SiMe3(OAlMe2)2.

[0060] In addition, without being constrained by theory, the presence of monodentate ligands in treated MAO similarly reduces or eliminates the probability of forming free TMA, as shown in the standard MAO free TMA and coordination TMA equilibrium scheme (4), thereby reducing or eliminating side reactions associated with free TMA of oxygen-containing catalytic compounds and / or nitrogen-containing catalytic compounds, thereby promoting improved catalytic activity and lifetime.

[0061] [ka]

[0062] In some embodiments, uncoordinated TMA-free ionic MAO can be formed as a reaction product by heating an ionic MAO composition stabilized with a chelating agent to produce a compound derived from the decomposed chelating agent containing at least one monodentate ligand species. Uncoordinated TMA-free ionic MAO exhibits superior performance to standard MAO activators or N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (D4) / diisobutylaluminum hydride (DIBAH) activators against bis(phenolate)-containing Group 3 and lanthanide metal catalyst precursors. Furthermore, TMA-free ionic MAO may be more efficient at activating some of the post-metallocene catalyst precursors that exhibit lower activation efficiencies than TMA-free anion-modified activators, such as electron-withdrawing MAOs (e.g., TMA-free fluorinated MAO or F-MAO). Generally, non-coordinating TMA-free ionic MAO (or cation-modified MAO) can broaden the activation range of O and / or N-containing post-metallocene precatalysts and CGC half-metallocene precatalysts, which exhibit limited activation compared to non-coordinating TMA-free anionic-modified MAO. Therefore, a greater number of polyolefin products with desired plastic properties can be produced at lower costs and at desired production rates based on half-metallocene or post-metallocene precatalysts.

[0063] 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). 12 An oligomeric compound containing an alkyl group, for example, the inert MAO gel shown in scheme (1). An example of a useful almoxane is a soluble, active methylaluminoxane (MAO) with a Me:Al ratio in the range of 1.4 to 1.5, where this Me:Al ratio corresponds to an O:Al ratio in the range of 0.8 to 0.75 based on the valence balance of the elements (according to Imhoff, DW et al. (1998) “Characterization of Methylaluminoxanes and Determination of Trimethylaluminum Using Proton NMR,” Organometallics, v.17(10), p.1941-1945), for example, the fresh MAO formula (Al4O3Me6)4(TMA) of Sinn / Kaminsky, where O:Al=0.75. 1-2 Therefore, as the method of Organometallics shows, excluding coordination TMA, as well as other modified MAOs, e.g., C1-C 10These include MAO modified with alkyl-containing higher alkylaluminum, carbocation agents, dialkylaluminum cation precursors, and contain elements / groups other than Al, Me, and O, such as F, Cl, bulky aryloxy, and fully fluorinated aryloxy (e.g., -OC6F5). Therefore, fresh, soluble, active MAO obtained from the reaction of a significantly excess amount of TMA with water at a sufficiently low temperature may have an Al:O ratio of 1:0.75, and oxygen may increase during preparation if the oxygen supply is of a high concentration or if the reaction is carried out at a higher temperature (e.g., -10°C instead of -20°C), or if the MAO has a longer storage time (maturation time) after MAO formation, or if the storage temperature is higher (e.g., -5°C instead of -20°C), or if the free TMA in equilibrium with the coordinated TMA in scheme (1) is physically removed. For example, in Grace's 30% MAO solution, after removing a significantly excess amount of TMA, the ratio becomes approximately 1:0.78, forming a product containing approximately 85 mol% MAO and approximately 15 mol% total TMA (Imhoff, et al., Organometallics, 1998, v.17(10), p1941). The gelation process can be initiated even under cooling after the solution-like MAO has been prepared. Therefore, the composition of the solution MAO may change over time, as can be seen from observations such as the increase in oxygen content within the major MAO structure with increasing free TMA and decreasing coordination TMA. In some embodiments, solution MAO can be used under similar storage conditions and with similar maturation. In some embodiments, solution MAO can be used under low-temperature storage, for example, below -10°C, more preferably below -20°C, and most preferably below -30°C, with a maturation of less than 6 months. In some embodiments, solution MAO can be used under cooling, for example, below -10°C, more preferably below -20°C, and most preferably below -30°C, with a maturation of less than 1 week.

[0064] Various methods exist for preparing MAO and modified MAO, such as those described in U.S. Patent No. 4,542,199 and Chen, E. et al. (2000) “Cocatalysts for Metal-Catalyzed Olefin Polymerization: Activators, Activation Processes, and Structure-Activity Relationships,” Chem. Rev., v100(4), pp.1391-1434. For example, MAO can be modified for different purposes, such as increasing its activity or solubility. Examples of useful MAOs include TMA-derived MAOs with oxygen donors (e.g., WRGrace MAO from TMA containing water, or PMAO from Nouryon or solid MAO from Tosoh from TMA containing an organic element source), higher alkyl-modified MAOs (e.g., MMAO from Nouryon), MAOs modified with carbocation agents (US9090720), MAOs modified with dialkylaluminum cation precursors (US8575284), and MAOs modified with halogens (US7355058).

[0065] Activated MAO can be formed by contacting a significantly excess 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.

[0066] The active unsupported MAOs of this disclosure can be commercially available or synthesized. Examples of unsupported active MAOs include solution MAOs (e.g., a 30% MAO solution of WRGrace, Lanxess, or Nouryon in toluene) and solid MAOs (solid MAO products obtained by removing the solvent from solution MAO, e.g., solid MAOs sold by Tosoh FineChem Corporation). The active solution MAOs or solid 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, e.g., -10°C to -50°C, e.g., -15°C to -30°C).

[0067] 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 or reverse-added to a solid support or support slurry, followed optionally by heating, 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. The operation is usually carried out in a suitable inert liquid phase, for example, in a liquid hydrocarbon diluent such as a liquid aromatic hydrocarbon or aliphatic hydrocarbon. For example, following the heating process described in US11,161,922 and WO2022 / 108974A1, water pre-supported on a support 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 support (e.g., silica), followed by the heating process.

[0068] For a solution-type MAO support, a diluent suitable 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. In some embodiments, the supported catalyst can be prepared, for example, by contacting or mixing a supported ionic aluminoxanate with a metal catalyst compound or complex. For in situ-supported MAO, a suitable diluent is a liquid material in which the reactants, such as hydrocarbyl aluminum, 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 diluent of a non-limiting example is 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.

[0069] Various ratios of the supported ionic aluminoxane to the metal catalyst compound can be used. For example, ratios such as approximately 10:1 to 300:1, or approximately 100:1 to 150:1, can be used, where the molar ratio of aluminum to the catalyst metal is in the range of approximately 1:1 to 2000:1. When contacting the supported aluminoxane and the pre-catalyst, temperatures in the range of approximately 0°C to 80°C can be used.

[0070] Hydrocarbyl aluminum compounds for alkylalmoxanes and modified alkylalmoxanes Active almoxane compositions (e.g., MAOs) can be formed exclusively with trimethylaluminum (TMA), but other aluminum alkyl compounds (also called alkylaluminum compounds) can 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).

[0071] 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.

[0072] Oxygen source for forming alkylalmoxanes The method may further include a step of forming an alkylalmoxane for subsequent treatment with a silanol or polydentate silane. For example, the method may include a step of introducing a hydrocarbyl aluminum compound (e.g., trimethylaluminum) with an oxygen source, optionally in a support at a temperature of about -60°C to about 100°C, before ionic treatment, to form a standard MAO composition. Preferred oxygen sources are water containing ice, or water absorbed or dispersed in an inorganic or organic substance. However, suitable oxygen sources may also include 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. 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.

[0073] 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).

[0074] 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.

[0075] 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, the hydrocarbyl aluminum compound can be removed, for example, by filtration, then washed with an aliphatic diluent, and / or treated with a chelating agent of the present disclosure. It should be understood that the above Al:O ratios are the ratios of the starting materials (or at the end of the preparation). The reaction between TMA and certain oxygen sources, such as water, is extremely rapid and exothermic; therefore, the order of addition can significantly alter the true reagent ratio by determining the "ratio at the end of preparation." For example, if water is added slowly, as required to avoid overheating or explosive reactions, the ratio of TMA to the initial water (e.g., the first drop) in the reactor approaches infinity when the reaction is complete. Furthermore, in a continuous process, unreacted TMA can be recovered and reused in the reaction, allowing for the use of Al:O ratios greater than 1000:1. Thus, Al:O ratios >1000:1 can still be practical.

[0076] In some embodiments, the oxygen source is any form of water, including accretionaries. 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 R2 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 this disclosure, the oxygen source is hydrocarbylboroxine, as described in Welborn's U.S. Patent No. 5,001,244, which is incorporated herein by reference.

[0077] Cationic (or ionic) aluminumoxanes Stable chelating or monodentate ligands (e.g., silanols and dialkylaluminum siloxides or polydentate siloxanes derived therefrom) can be used as starting materials in the production of ionic almoxanes. A wide variety of organic, inorganic, or organometallic compounds may be suitable for use in the formation of ionic almoxanes. In some embodiments, various almoxanes can be used to form stable alkyl almoxanes, such as methyl almoxanes. When forming stable ionic almoxanes, the denser lower liquid phase (or clathrate phase) can be readily separated from the upper solution phase by conventional separation techniques, such as phase separation, decantation, or discharge.

[0078] Ionic MAO derived from chelating agentsIn some embodiments, the starting material may be a chelating agent dissolved in a hydrocarbon solvent such as an aromatic solvent. For example, the starting material may include a hydrocarbyl-aluminoxane, e.g., an alkyl-aluminoxane, and a chelating agent which is a hydrocarbyl-polysiloxane, e.g., a hydrocarbyl-trisiloxane. In some embodiments, the chelated hydrocarbyl-polysiloxane compound may have at least three silicon atoms in the molecule, which are separated from each other by oxygen atoms so that there is a linear, branched, or cyclic skeleton with alternating Si and oxygen atoms, and the remaining four valence bonds of each of these silicon atoms are individually filled by monovalent hydrocarbyl groups. The hydrocarbyl-polysiloxane may have as many as 18 or more silicon atoms in the molecule. Each monovalent hydrocarbyl group of the polysiloxane may independently contain up to about 18 carbon atoms and can be alkyl, cycloalkyl, aryl, aralkyl, or other groups.

[0079] In some embodiments, the chelating agent is of the formula R(SiR2O) n The formula may include a polydentate siloxane having SiR3 (wherein each R is independently hydrogen, alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl), alkenyl, aryl, or heteroatom-substituted hydrocarbyl group, n=2 to 8). In some embodiments, each R is methyl. In some embodiments, the chelating agent is of the formula (SiR2O) n (wherein R is independently a hydrogen, an alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl), an alkenyl, an aryl, or a heteroatom-substituted hydrocarbyl group, and n=3 to 6) cyclic polydentate siloxane may also be included.

[0080] Non-limiting examples of such polysiloxanes include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, octamethyltrisiloxane (OMTS), decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane (as an example of an alkenyl substituent on a polydentate compound), and 1,3,5,7-tetrakis(3,3,3-trifluoropropyl)1,3,5,7-tetramethylcyclosiloxane (as an example of a heteroatom-containing substituent on a polydentate compound).

[0081] In some embodiments, the ionic alkylaluminoxane, for example, the ionic MAO, contains a dialkylaluminum cation stabilized with a chelate ligand, for example, [AlMe2(OMTS)] + It can be heated to become more active, which is probably because after heating, dialkylaluminum cations, such as AlMe2, are formed. + This is due to the formation of an unstable monodentate complex that readily releases the substance. 1 Structure Ia is shown by H-NMR:

[0082] [ka] Ionic MAO derived from monocephalic agentsAlternatively, ionic alumoxanes may be formed by using silanol SiR3OH to convert free alkylaluminum in an aluminoxane composition, e.g., MAO composition, e.g., TMA, thereby forming a monodentate coordination compound AlR2OSiR3 in situ (e.g., as shown in Figure 2, where R=Me), which functions as a dialkylaluminum cation stabilizer and can eliminate or reduce free alkylaluminum, which is desirable for solution aluminoxane systems because the process for removing free alkylaluminum in solution systems is difficult. Each R is independently a hydrogen, alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl), alkenyl, aryl, or heteroatom-containing group of the silanol having the formula HO-SiR3. In some embodiments, each R is methyl.

[0083] In some embodiments, a monodentate coordination compound, AlR2OSiR3 (Formula II), can be pre-formed and applied to a solid or supported aluminoxane system after a free alkylaluminum separation process, for example by filtration or decantation, to reduce or eliminate free alkylaluminum in the system. Low-boiling free alkylaluminum, for example, free TMA, can also be optionally applied to the supported or solid aluminoxane system, including any vacuum drying process.

[0084] In some embodiments, the non-coordinating alkylaluminum-free ionic almoxane is formed in an aromatic hydrocarbon, such as benzene, toluene, xylene, ethylbenzene, cumene, etc., and the reactants are the alkyl almoxane and at least one chelating agent or monocephalic agent, most preferably methyl almoxane and octamethyltrisiloxane.

[0085] In some embodiments in which polydentate siloxanes are used, the almoxane having a siloxane alkylaluminum complex (e.g., A in Figure 1) is a siloxane alkylaluminum complex. 12 The mixture can also be thoroughly washed with saturated hydrocarbon solvents, such as isobutene, isohexane, isopentane, isohexane, heptane, or octane (before heating). If a low-boiling point solvent, such as isobutene, is used, a cooling and / or sealed environment may be required to limit solvent desorption. Alternatively, the formed ionic almoxane (e.g., B in Figure 1 or B in Figure 2) can be washed with an aromatic or aliphatic solvent, such as benzene, toluene, xylene, ethylbenzene, or other aromatic solvents, such as a mixture of two or more liquid aromatic hydrocarbons, or C3-C 12 The mixture can also be thoroughly washed with saturated hydrocarbon solvents, such as isobutene, isohexane, isopentane, isohexane, heptane, octane, or a solvent mixture of an aromatic solvent and an aliphatic solvent, or two or more aliphatic solvents. The amount of solvent used can be varied compared to the initial almoxane, as long as a stirable solution is produced. After each wash, a two-phase liquid system may be formed, and the less dense upper layer can be separated from the denser lower liquid phase, for example, by decantation (this removes any remaining free alkylaluminum). Such washing can be carried out at ambient temperature or a appropriately lowered or raised temperature, for example, in the range of about 10°C to about 100°C, although higher or lower temperatures may also be used. In some embodiments, washing is carried out at one or more temperatures in the range of about 20°C to about 80°C. In some embodiments, washing is carried out at room temperature. In some embodiments, stirring can be used to agitate the mixture formed after washing. Washing may result in the formation of a relatively high-density or oily washed liquid almoxane composition. Next, an inert liquid non-solvent can be added to the almoxane to form a precipitated solid, which may have a lower content of neutral almoxane.

[0086] In some embodiments, the non-solvent causes precipitation by forcing the solvent contained in the almoxane out of the almoxane, thereby generating a novel composition as a solid. Various inert non-solvents, e.g., C3-C 12 Aliphatic hydrocarbon solvents, such as one or more isobutene, isopentane, isohexane, heptane, octane, nonane, or decane isomers, cyclopentane, one or more liquid alkylcyclopentanes, cyclohexane, one or more liquid alkylcyclohexanes, and mixtures of any two or more of these hydrocarbons can be used. Non-solvents can be added at ambient room temperature, or at appropriately lowered or raised temperatures, for example, about 20°C to about 100°C.

[0087] The precipitate solid generated by washing an ionic alumoxane having a dialkylaluminum cation stabilized with a chelated polysiloxane (e.g., A in Figure 1) or a dialkylaluminum cation stabilized with a monodentat dialkylaluminum siloxide (e.g., B in Figure 1 or B in Figure 2) can be recovered in solid form by techniques such as filtration, centrifugation, or decantation. In some embodiments, the recovered solid is washed with a fresh non-solvent.

[0088] In some embodiments where a polydentate siloxane is used as a chelating agent, the solid is then dissolved in any suitable liquid so that dissolution occurs, and heated at a high temperature to convert the polysiloxane alkylaluminum complex in the ionic aluminoxane composition into at least one decomposed chelating ligand fragment to form a more active ionic MAO composition, which has a dialkylaluminum cation (e.g., B in Figure 1) stabilized with a monodentate ligand, and in the presence of a precatalyst, it becomes less stable and readily releases the cation. The heating process can be carried out for a certain period of time, for example, about 0.1 to about 5 hours, or for example, about 1 hour, in a specific temperature range, e.g., about 70°C to about 110°C, e.g. Alternatively, the solid can be converted from a polydentate aluminoxane to a monodentate ligand aluminoxane (forming a less stable cation) by being aged at room temperature for a period of time, for example, about 1 to 12 months, or for example, about 5 months. The resulting clathrate with monodentate or chelate ligands can have higher conductivity than the nonionic aluminoxane of the mother liquor, demonstrating a stronger ionic nature.

[0089] The monodentate ligand or chelated ligand formed by the method of this disclosure may be a hydrocarbyl monosiloxy group having at least one oxygen atom in the molecule, the remaining three valence bonds of the silicon atom being individually filled by monovalent hydrocarbyl groups. Each monovalent hydrocarbyl group of the hydrocarbyl monosiloxy group may independently contain up to about 18 carbon atoms and may be an alkyl, cycloalkyl, aryl, or heteroatom-containing group. A non-limiting example of such a monodentate ligand is [Me2Al(μ-OSiMe3)SiMe2] + (For example, A in Figure 1) or [Me2Al(μ-OSiMe3)AlMe2] + (For example, Figure 1B) is one such example. In some embodiments, the single-seat ligand is given by formula (I):

[0090] [ka] [In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 Each of these is independently represented as a hydrogen atom, a hydrocarbyl group, a silyl group, or a heteroatom-containing group.

[0091] In some embodiments, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 Each of these is independently an alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl), alkenyl, or aryl. In some embodiments, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 Each of them is methyl.

[0092] As discussed above, there are at least three main methods for obtaining unsupported or supported aluminoxane systems that do not contain non-coordinating alkylaluminum: 1) Free or uncoordinated hydrocarbyl aluminum compounds (or their dimers) as essential components in standard unsupported or supported alkylaluminoxane compositions, such as commercially available MAO toluene solutions, solid MAO, supported standard MAO, or MAO supported in situ, can be removed after separation from the unsupported or supported aluminoxane is possible by treating the unsupported or supported aluminoxane composition with a chelating agent to form an ionic alkylaluminoxane composition. This makes it possible to obtain an unsupported or supported aluminoxane system free of coordinated alkylaluminoxanes, either as a lighter phase in the case of solution-type MAO, or as a supernatant phase in the case of solid MAO or supported MAO. 2) Aluminoxane systems free of non-coordinating alkylaluminum can be obtained by silanol treatment, in which case non-coordinating alkylaluminum can be quantified in advance and matched with the silanol used. The main advantage of this method is that it does not require a separation process for free alkylaluminum. The disadvantage is that the activation of the derived system is not as efficient as in method 1), probably because silanol reacts not only with free alkylaluminum but also with coordinating alkylaluminum, for example, as shown in scheme (4), it reacts not only with free TMA but also with coordinating TMA (active site), and AlMe2 from coordinating TMA + This is because it blocks the release of [the substance]. 3) Non-coordinating alkylaluminum-free aluminoxane systems can also be obtained by treatment with a pre-formed silanol-derived compound R3SiOAlR2 (formula (II), where R is independently hydrogen, hydrocarbyl, non-coordinating, or weakly coordinating heteroatom-containing group) to avoid the toxic effects of silanols from coordinating alkylaluminum, as shown in 2). However, this method may be more suitable for solid or supported MAOs because the resulting ionic MAO has higher solubility, which weakens phase separation in solution and makes the removal of free alkylaluminum more difficult. This method has better activation efficiency, but is not as good as method 1), and is not constrained by theory, for example, by replacing the inactivated species, e.g., the species obtained from coordinating alkylaluminum, with R3SiOAlR2, thus enabling AlR2 from coordinating R3SiOAlR2. + Detachment becomes more difficult.

[0093] In some embodiments, monodentate ligands are formed in situ by treating a solution, solid, or supported almoxane (e.g., MAO) composition with a chelating agent or a monodentate agent (i.e., a polydentate siloxane or silanol or a dialkylaluminum compound derived from a silanol).

[0094] In some embodiments, the amount of chelating agent (e.g., OMTS) applied to the alkylaluminoxane composition can be determined by chelating the target alkylaluminoxane, for example, by a known excess amount of OMTS (W i ) was placed in an alkylaluminoxane solution, and proton NMR was used to distinguish between uncoordinated (neutral) OMTS and [AlMe2(OMTS)] + The ratio can be determined, and therefore the percentage of reactive OMTS can be calculated; for example, as follows: Reactive OMTS% = ([AlMe2(OMTS)] + / ([AlMe2(OMTS)] + +Neutral OMTS)) × 100. Therefore, the total amount of reactive OMTS is W i×Calculated as reactivity OMTS%. See the Experimental Examples section for details. The amount of chelating agent is most preferably W i × Reactive OMTS (%) is equal to, but higher or lower input amounts are still acceptable, for example, more than or less than 20% W i ×Reactive OMTS (%), W greater than or less than 10% i × Reactive OMTS (%), or more than 5% or less of W i ×Reactive OMTS (%) is also acceptable.

[0095] In some embodiments, silanol SiR3OH can be added based on the amount of free alkylaluminum in the aluminoxane composition, for example, free TMA in the MAO composition. A method for determining the amount of free alkylaluminum, for example, free TMA, is described in the Experimental Examples section below. The amount of silanol is most preferably equal to the amount of free alkylaluminum (moles:moles) in the alkylaluminoxane composition, but amounts greater or less than this are still acceptable, for example, amounts greater than or less than 20 mol% of free alkylaluminum, greater than or less than 10% of free alkylaluminum, or greater than or less than 5% of free alkylaluminum.

[0096] In some embodiments, SiR3OAlR2 derived from pre-formed silanol (SiR3OH) can be added based on a coordinating alkylaluminum in the aluminoxane composition, for example, coordinating TMA in the MAO composition. The method for determining the coordinating alkylaluminum, for example, coordinating TMA, is described in the Experimental Examples section. The amount of SiR3OAlR2 is most preferably equal to the amount (moles:moles) of coordinating alkylaluminum in the alkylaluminoxane composition, but amounts greater or less than this are still acceptable, for example, amounts greater than or less than 20 mol% of the coordinating alkylaluminum, greater than or less than 10% of the coordinating alkylaluminum, or greater than or less than 5% of the coordinating alkylaluminum.

[0097] The reaction for the formation of dialkylaluminum cations stabilized with chelating ligands or monodentate ligands 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 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 cycloalkane (wherein n=5 to 30) having the formula, for example, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and mixtures thereof. The aromatic diluent may include benzene, toluene, or xylene. The ionic alkylaluminoxane composition derived from the chelate ligand can also be subjected to a heating process to increase the pre-catalyst activation efficiency. The heating temperature can be 60°C to 120°C, more preferably 80°C to 110°C, and most preferably 90°C to 100°C. Heating can be carried out in an open system under 1 atmosphere, or in a closed system with a corresponding safe pressure rating under reduced or high pressure, for example, 0.1 atm to 15 atm, 0.5 atm to 10 atm, or 0.9 atm to 5 atm.

[0098] After treatment with monocementary or chelating agents, using any free alkylaluminum separation process, alkylaluminoxanes, such as MAO (unsupported or supported), can have amounts of free hydrocarbyl aluminum compounds of about 2% by mass or less, e.g., about 1.5% by mass or less, e.g., about 1% by mass or less, e.g., about 0.5% by mass or less, e.g., about 0.25% by mass or less, e.g., about 0.1% to about 2% by mass, e.g., about 0.1% to about 1.5% by mass, e.g., about 0.2% to about 1% by mass, e.g., about 0.3% to about 0.7% by mass, or instead about 0.1% to about 0.5% by mass, relative to the total aluminum content of the MAO. The method for determining free alkylaluminum is described in the Experimental Examples section below.

[0099] Any carrier material 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.

[0100] 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.

[0101] 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 400m 2 It can be / g, and the pore volume is approximately 0.8 cm³. 3 / g~approx.3.0cm 3The 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 (for example, a surface area of ​​approximately 300 m²). 2 The pore volume is approximately 1.65 cm³ / gm. 3 (is / gm). For example, suitable silica may 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.

[0102] The support material should be dried for the pre-formed MAO support, i.e., free from or substantially free from absorbed water, although it does not need to be calcined for in situ MAO support if water is used as an oxygen source. The amount of hydroxyl groups on the pore surface of the support material can be controlled by heating or calcining at different temperatures, e.g., about 100°C to about 1000°C, e.g., at least about 600°C. If the support material is silica, heating is performed at at least about 150°C, e.g., about 200°C to about 850°C, e.g., about 400°C to 600°C for a period of time 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 this disclosure.

[0103] Formation of non-coordinating alkylaluminum-free supported ionic almoxanes and the final catalyst derived therefrom In embodiments of this specification, the catalyst system may include a carrier material as described above. For example, the carrier material is contacted with a pre-formed solution almoxane, such as a commercially available solution MAO, to form a supported MAO, following a process to remove free alkylaluminum, such as free TMA, by a separation process for free alkylaluminum, such as a filtration process, a decantation process, or, in the case of low-boiling free alkylaluminum (e.g., free TMA), a vacuum evacuation process, and thereafter the supported MAO is contacted with a monodentate agent (e.g., silanol SiR3OH or a silanol-derived SiR3OAlR2 compound) and optionally AlR3 or a chelating agent (e.g., polysiloxane, e.g., OMTS) to form a monodentate ligand or a chelating ligand-stabilized dialkylaluminum cation in situ, or contacted with a pre-formed monodentate agent of this disclosure (e.g., a dialkylaluminum siloxide) (e.g., Figure 1A, Figures 1 and 2B). To increase the activation efficiency of chelate species A in Figure 1 derived from the chelating agent, a heating process can also be applied to convert at least a portion of chelate species A in Figure 1 into monodentate species B in Figure 1. For example, 20 mol% of species A, 40 mol% of species A, or >70 mol% of species A may be converted, or until species A becomes undetectable.

[0104] Alternatively, the support material may be contacted with a non-coordinating alkylaluminum-free almoxane of the present disclosure (e.g., a non-coordinating TMA-free ionic MAO) to form a supported activator, which may then be contacted with a pre-catalyst compound. Alternatively, the pre-catalyst compound can be brought into contact with a non-coordinating TMA-free MAO to form a solution catalyst system, and this solution catalyst system can then be brought into contact with a support material to form a supported catalyst system.

[0105] Alternatively, the support material can be made by supporting an oxygen source, such as water, and then adding the support with the oxygen source in solid or slurry form to a cooled solution of TMA, with or without cooling, and optionally heating to form a supported MAO composition. Subsequently, treatment with a chelating agent is optionally carried out together with AlR3, and a separation process for free alkylaluminum is performed, for example, by filtration, decantation, or, in the case of free TMA, by a vacuum evacuation process to remove the free TMA and form an alkylaluminoxane system supporting coordinating alkylaluminum, which is then brought into contact with a pre-catalyst to form the final catalyst.

[0106] Alternatively, a supported MAO composition can be formed by supporting an oxygen source, such as water, in the support material, and then adding the oxygen-supported support to a cooled TMA solution in solid or slurry form, with or without cooling, and optionally heating it. Subsequently, the supported MAO can be treated with a monodentate SiR3OAlR2 compound formed in situ by contacting it with silanol SiR3OH and optionally AlR3, and optionally performing a filtration / washing process, or by treating it with a pre-formed monodentate SiR3OAlR2 compound along with the necessary filtration / washing process, to form a non-coordinating TMA-free supported MAO, which can then be contacted with a pre-catalyst to form the final catalyst.

[0107] The carrier material has reactive surface groups such as hydroxyl groups and, depending on the specific process, is contacted with at least one pre-catalyst compound and an MAO-based activator in solid or solution form, either as a nonpolar solvent slurry or as a solid, in any order including the order described above; however, if the pre-catalyst has a non-leaving heteroatom donor (e.g., O and / or N), the pre-catalyst should be contacted with the MAO-based activator after the MAO has been converted to a non-coordinating TMA-free ionic MAO. In at least one embodiment, the carrier material is first contacted with a pre-formed activator solution (e.g., standard MAO or non-coordinating TMA-free ionic MAO) for a period such as about 0.5 hours to about 24 hours, about 2 hours to about 16 hours, or about 4 hours to about 8 hours. In the case of standard MAO support, the supported standard MAO is then converted to a non-coordinating TMA-free supported ionic MAO in the manner described above. The pre-catalyst compound in solution or solid form is then brought into contact with a non-coordinating TMA-free supported activator. In at least one embodiment, the supported MAO for the catalyst system is produced in situ. In an alternative embodiment, a slurry of non-coordinating TMA-free supported MAO is brought into contact with the pre-catalyst compound for a period 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. In a further alternative embodiment, a pre-formed non-coordinating TMA-free ionic MAO solution is first mixed with at least one pre-catalyst and then brought into contact with a support material using either a slurry preparation process or an initial wetting preparation process.

[0108] The mixture of catalyst, activator, and support is stirred at approximately 0°C to approximately 100°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. The ratio of insoluble components (insoluble silica, supported MAO, activated pre-catalyst, and additives) to solvent can be any practical ratio, for example, 3:97, 10:90, 30:70, or 50:50 (mass:mass), depending on the specific process used. For example, for a continuous process, a lower insoluble component:solvent ratio, for example, 3:97 or 1:99 or less, can be used. For an initial wetting process, a high insoluble component:solvent ratio, for example, 60:40 or more, can be used.

[0109] A suitable nonpolar diluent is a material that is liquid at the reaction temperature and to which all reactants used herein, such as 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.

[0110] In at least one embodiment, the supported activator is a supported non-coordinating TMA-free ionic MAO, which is a silica-supported MAO (e.g., ES70 silica calcined at 400°C) from which free TMA has been removed physically, for example by phase separation, filtration / decantation, or vacuum evacuation, or chemically, for example by reaction with silanol, and which is free of or contains low amounts of free TMA. Embodiments of the present disclosure include a method for preparing a final catalyst system, comprising contacting a non-coordinating TMA-free solid MAO or supported MAO with at least one pre-catalyst compound having a group 3 to 12 metal atom or a lanthanide metal atom in an organic diluent. In at least one embodiment, the uncoordinated TMA-free solid MAO or supported MAO is heated before being brought into contact with the precatalyst compound. In at least one embodiment, the solid MAO or supported MAO is heated after being brought into contact with the precatalyst compound.

[0111] Formation of solution catalyst Embodiments of the present disclosure include a method for preparing a solution or homogeneous catalyst system, comprising the step of contacting a non-coordinating TMA-free ionic liquid MAO (TF-iMAO) with at least one pre-catalyst compound having a group 3 to group 12 metal atom or a lanthanide metal atom in an organic diluent. In at least one embodiment, the TF-iMAO is heated, for example, at 50°C to 120°C, 80°C to 110°C, or 90°C to 100°C for 0.5 to 24 hours, 1 to 10 hours, or 2 to 5 hours before being brought into contact with the pre-catalyst compound. TF-iMAO can be solvated in an organic diluent, and the resulting mixture is brought into contact with a solution of at least one pre-catalyst compound. The pre-catalyst compound can also be added as a solid to the mixture of organic diluent and TF-iMAO. In at least one embodiment, the TF-iMAO mixture is brought into contact with the pre-catalyst compound for a period of about 0.02 hours to about 24 hours, for example, about 0.1 hours to about 1 hour, about 0.2 hours to about 0.6 hours, about 2 hours to about 16 hours, or about 4 hours to about 8 hours, and then brought into contact with an olefin monomer for polymerization.

[0112] The mixture of the precatalyst compound and TF-iMAO can be heated to a temperature of approximately 0°C to approximately 70°C, for example, approximately 23°C to approximately 60°C, for example, room temperature, and then contacted with the olefin monomer for polymerization.

[0113] A suitable organic diluent is preferably a material that is at least partially soluble in some or all of the reactants used herein, such as TF-iMAO and the pre-catalyst compound, and is liquid at the reaction temperature. 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), for example 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.

[0114] The diluent can be added to the reactor, followed by TF-iMAO. 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 diluent 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 this out under a vacuum, purging 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 100°C or less, for example, about 90°C or less. 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.

[0115] Precatalytic compounds The terms "catalyst," "catalytic compound," "catalytic complex," "metal complex," "metal compound," "precatalytic compound," and "precatalytic complex" are used interchangeably to describe transition metal complexes or lanthanide metal complexes that form olefin polymerization catalysts when combined with appropriate activators.

[0116] 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, e.g., +1, +2, +3, +4, or +5, e.g., +2, +3, or +4. The catalyst compounds of this disclosure can be rhenium or rhenium-based catalysts, scandium or scandium-based catalysts, or chromium or chromium-based catalysts.

[0117] 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-phase 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.

[0118] 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).

[0119] 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.

[0120] 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.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] The monoCp precatalyst compound is also preferably C s or pseudo-C s Equation (MC-II) exhibits symmetry:

[0125] [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].

[0126] In equation (MC-II), L 1Fluorenyl 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.

[0127] Examples of mono-Cp catalyst compounds with polar donors include, but are not limited to, the following:

[0128] [Table 1] JPEG2026521464000016.jpg178156

[0129] Monometallocene precatalytic compounds are also, Dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamide)titaniumdimethyl; Dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamide)titanium dichloride; Dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamide)titaniumdimethyl; Dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamide)titanium dichloride; The following may be selected, where M is selected from Ti, Zr, and Hf, and R is selected from halogens or C1-C5 alkyl groups.

[0130] 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.

[0131] 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.

[0132] 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).

[0133] 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.

[0134] 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 double rotation axis, thus conferring C2 symmetry to the complex. The C2 shape and eight-membered metallocycle rings are characteristic features of these complexes, and these features make them effective catalytic components for the production of polyolefins, particularly isotactic poly(alphaolefins). s When coordinated to the metal in a manner that exhibits symmetry, the catalyst is expected to produce only atactic poly(alphaolefins). These symmetry-reactivity concepts are summarized in Golisz, SR et al. (2009) “Synthesis of Early Transition Metal Bisphenolate Complexes and Their Use as Olefin Polymerization Catalysts,” Macromolecules, v. 42(22), pp.8751-8762. The pair of 8-membered metallocycle rings in the catalytic compound is also a notable feature advantageous for temperature stability and isoselectivity of the monomer chain. Related Group IV 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).

[0135] The oxygen donor group-containing (i.e., E=E'=oxygen in formula (PM-I)) bis(phenolate) ligand can be substituted with alkyl, substituted alkyl, aryl, or other groups. It may be advantageous for each phenolate group to be substituted at a ring position adjacent to the 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.

[0136] 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.

[0137] 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, Group 6, or Group 7 (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 these is independently 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 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.]

[0138] The metal, M, is selected from elements of Group 3, Group 4, Group 5, Group 6, or Group 7, 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.

[0139] A of heterocyclic Lewis bases 1 and A1 Each of the following (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 the ' is carbon. If Q is carbon, then A 1 and A 1 Each of these is nitrogen and C(R 22 ) can be selected from. If Q is nitrogen, then A 1 and A 1 Each of the ' 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 It is not necessary to have any hydrogen atoms bonded to the atom, and in some cases, it is preferable not to have any hydrogen atoms. This is because hydrogen at these positions is thought to be capable of causing undesirable decomposition reactions that reduce certain stability of catalytic activity. A 1 and A 1 Together with the curve that connects '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.

[0140] [ka]

[0141] In some embodiments, A 1 and A 1 Together with the curve that connects 'A1 QA 1 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 curve that connects '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.

[0142] 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 these is independently 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 the ' is a carbon atom. In some embodiments of formula (PM-I), A of formula (PM-I) 1 QA 1 ' is part of a heterocyclic Lewis base, such as pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, or their substituted variations.

[0143] In some embodiments of formula (PM-I), A 1 QA 1 ' 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 linked to '. In some embodiments, each A 1 and A 1 ' is a carbon atom, A 1 QA 1The fragments form pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan, or substituted forms thereof, or part of substituted forms 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.

[0144] 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.

[0145] [ka] It is a divalent group containing 2 to 20 nonhydrogen atoms, and A is formed via a two-atom bridge. 1 The ' 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.

[0146] In some embodiments of formula (PM-I), M is Zr or Hf, Q is nitrogen, and A 1 and A 1 ' is carbon, E and E' are both oxygen, R 1 and R 1 Both are C4-C 20 It is a cyclic tertiary alkyl group.

[0147] In some embodiments of formula (PM-I), M is Zr or Hf, Q is nitrogen, and A 1 and A 1 ' is carbon, E and E' are both oxygen, R 1 and R 1 Both are adamantane-1-yl or substituted adamantane-1-yl.

[0148] In some embodiments of formula (PM-I), M is Zr or Hf, Q is nitrogen, and A 1 and A 1 ' is carbon, E and E' are both oxygen, R 1 and R 1 Both are C6-C 20 It is Ariel.

[0149] In some embodiments, the catalyst compound is of formula (PM-II): [ka] [In the formula, M is a transition metal or lanthanide from Group 3, Group 4, Group 5, Group 6, or Group 7 (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 these is independently 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 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 ';R8 ', R 10 , 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.

[0150] 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.

[0151] In some embodiments, [ka] These are independently divalent hydrocarbyl groups, for example, C1-C 12 It is a hydrocarbyl group.

[0152] 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 Substitution is possible in '). 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 the elements is independently a non-aromatic cyclic alkyl group having one or more five-membered or six-membered rings (e.g., cyclohexyl, cyclooctyl, adamantyl, or 1-methylcyclohexyl, or substituted adamantyl), for example, a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, adamantyl, or substituted adamantyl).

[0153] In some embodiments of the catalyst compound of formula (PM-I) or (PM-II), R 1 and R 1 Each of the ' is independently a tertiary hydrocarbyl group. In other embodiments of formula (PM-I) or (PM-II), R 1 and R 1 Each of the ' is independently a cyclic tertiary hydrocarbyl group. In other embodiments of the catalytic compound of formula (PM-I) or (PM-II), R 1 and R 1Each 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 the ' is independently a tertiary hydrocarbyl group. In other embodiments of the catalytic compound of formula (PM-I) or (PM-II), R 1 and R 1 Each of the ' is independently a cyclic tertiary hydrocarbyl group. In other embodiments of the catalytic compound of formula (PM-I) or (PM-II), R 1 and R 1 Each of these is independently a polycyclic tertiary hydrocarbyl group. 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 of ' 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 of ' 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 groups.

[0154] 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 these is independently hydrogen, C1-C 40 Hydrocarbyl, C1-C 40 A substituted hydrocarbyl, a heteroatom, or a 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.

[0155] 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 4Each of the following 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.

[0156] 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.

[0157] 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.

[0158] 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.

[0159] In some embodiments of formulas (PM-I) and (PM-II), R 1 and R 1 Each of these 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. 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 Each of these is not 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 these is independently hydrogen, C1-C 20 Hydrocarbyl, substituted C1-C 20 Hydrocarbyl, heteroatom, or heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 1 'and R 2 ', R 2 'and R 3 ', R 3 'and R 4 One or more of the ' 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, 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 (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 (two or more L' may form a fused ring or part of a ring system).

[0160] In some embodiments of formula (PM-II), R 5 , R 6 , R 7 , R 8 , R 5 ', R6 ', 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.

[0161] 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.

[0162] 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.

[0163] 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 these is independently hydrogen, C1-C 20 Hydrocarbyl, substituted C1-C 20 Hydrocarbyl, heteroatom, or heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 1 'and R 2 ', R 2 'and R 3 ', R 3 'and R 4One or more of these may bond to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, and 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 11and R 12 Each of these is independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, 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.

[0164] 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.

[0165] In some embodiments of formula (PM-II), M is Zr or Hf, and both E and E' are oxygen, and R 1 and R 1 Both are adamantane-1-yl or substituted adamantane-1-yl.

[0166] In some embodiments of formula (PM-II), M is Zr or Hf, and both E and E' are oxygen, and R 1 , R 1 ', R 3 and R 3 Each of these is adamantane-1-yl or adamantane-1-yl substitute.

[0167] In some embodiments of formula (PM-II), M is Zr or Hf, and both E and E' 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.

[0168] 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. In some embodiments, the catalyst compound is of formula (PM-III), formula (PM-IV), or formula (PM-V): [ka] [In the formula, In formulas (PM-III), (PM-IV), or (PM-V), M represents Sc, Y, or La-Lu lanthanide metal. Q' in formula (PM-III), formula (PM-IV), or formula (PM-V) is a group 15 heteroatom, preferably N and P, most preferably N. In formulas (PM-III), (PM-IV), or (PM-V), X is an anionic ligand. In formulas (PM-III), (PM-IV), or (PM-V), each L is independently a Lewis base. Two or more L groups from formula (PM-III), formula (PM-IV), or formula (PM-V) may be bonded together to form a polydentate (e.g., a bidentate) Lewis base. The X group of formula (PM-III), formula (PM-IV), or formula (PM-V) may be bonded to the L group to form a monoanionic bidentate group. In formulas (PM-III), (PM-IV), or (PM-V), n is 1. In formulas (PM-III), (PM-IV), or (PM-V), m is 0, 1, or 2. In equations (PM-III), (PM-IV), or (PM-V), n+m does not exceed 3. R in formula (PM-III), formula (PM-IV), or formula (PM-V) 1 , R 2 , R 3 , R 4 , R 1 ', R 2 ', R 3 ', and R 4 Each of these is independently hydrogen, C1-C 40 Hydrocarbyl, substituted C1-C 40 Hydrocarbyl, heteroatom, or heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 1 'and R 2 ', R 2 'and R 3 ', R 3 'and R 4One or more of these may bond to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, and substitutions on the rings can bond to form additional rings. R in formula (PM-III), formula (PM-IV), or formula (PM-V) 5 , R 6 , R 7 , R 8 , R 5 ', R 6 ', R 7 ';R 8 ', R 10 , R 11 , and R 12 Each of them independently produces hydrogen, C1-C 40 Hydrocarbyl, substituted C1-C 40 Hydrocarbyl, heteroatom, or heteroatom-containing group, or R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 5 'and R 6 ', R 6 'and R 7 ', R 7 'and R 8 ', R 10 and R 11 , or R 11 and R 12 One or more of these may bond to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, and the substitutions on the rings can bond to form additional rings. In formulas (PM-III), (PM-IV), or (PM-V), each G is a heteroatom or heteroatomic group of Group 15 or Group 16, for example, S, O, NR', PR', where R' is a hydrogen atom and C1-C 40 This is represented as [selected from hydrocarbyl or substituted hydrocarbyl groups].

[0169] In some embodiments of the catalytic compounds of formula (PM-I to PM-II), when E and E' are oxygen, each phenolate group is located at the position adjacent to the oxygen atom (i.e., R in formula (PM-I to PM-II)). 1 and R 1 Substitution is possible in '). Therefore, if E and E' are oxygen, R 1 and R 1 Each of these is independently C1-C 40 Hydrocarbyl, substituted C1-C 40 Hydrocarbyl, heteroatom, or heteroatom-containing group, for example, R 1 and R 1 Each of the elements is independently a non-aromatic cyclic alkyl group having one or more five-membered or six-membered rings (e.g., cyclohexyl, cyclooctyl, adamantanyl, or 1-methylcyclohexyl, or substituted adamantanyl), for example, a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, adamantanyl, or substituted adamantanyl).

[0170] In some embodiments of the catalytic compounds of formula (PM-III~PM-V), each phenolate group is located at a position adjacent to the oxygen atom (i.e., R of formula (PM-III~PM-V)). 1 and R 1 It is possible that substitution occurs in '). Therefore, R 1 and R 1 Each of these is independently C1-C 40 Hydrocarbyl, substituted C1-C 40 A hydrocarbyl, heteroatom, or heteroatom-containing group, for example, R 1 and R 1 Each of the elements is independently a non-aromatic cyclic alkyl group having one or more five-membered or six-membered rings (e.g., cyclohexyl, cyclooctyl, adamantanyl, or 1-methylcyclohexyl, or substituted adamantanyl), for example, a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, adamantanyl, or substituted adamantanyl).

[0171] In some embodiments of the catalyst compounds of formula (PM-I~PM-V), R 1 and R 1 Each of the ' is independently a tertiary hydrocarbyl group. In other embodiments of formula (PM-I~PM-V), R 1 and R 1 Each of ' is independently a (substituted or unsubstituted) cyclic tertiary hydrocarbyl group. In other embodiments of the catalytic compounds of formula (PM-I~PM-V), R 1 and R 1 Each of these is independently (substituted or unsubstituted) a polycyclic tertiary hydrocarbyl group.

[0172] In some embodiments of the catalytic compounds of formula (PM-I to PM-II), when E and E' are oxygen, each phenolate group is in the para position relative to the oxygen atom (i.e., R of formula (PM-I to PM-II)). 3 and R 3 Substitution is possible in '). Therefore, if E and E' are oxygen, R 3 and R 3 Each of these is independently C1-C 40 Hydrocarbyl, substituted C1-C 40 A hydrocarbyl, heteroatom, or heteroatom-containing group, for example, R 3 and R 3 Each of these is independently C1-C 20 Alkyl, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or isomers thereof. Alternatively, R 3 and R 3 Each of the elements is independently a non-aromatic cyclic alkyl group having one or more five-membered or six-membered rings (e.g., cyclohexyl, cyclooctyl, adamantanyl, or 1-methylcyclohexyl, or substituted adamantanyl), for example, a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, adamantanyl, or substituted adamantanyl).

[0173] In some embodiments of the catalytic compounds of formula (PM-III~PM-V), each phenolate group is in the para position relative to the oxygen atom (i.e., R in formula (PM-III~PM-V)). 3 and R 3 It is possible that substitution occurs in '). Therefore, R 3 and R 3 Each of these is independently C1-C 40 Hydrocarbyl, substituted C1-C 40 A hydrocarbyl, heteroatom, or heteroatom-containing group, for example, R 3 and R 3 Each of these is independently C1-C 20 Alkyl, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or isomers thereof. Alternatively, R 3 and R 3 Each of these is independently a non-aromatic cyclic alkyl group having one or more five-membered or six-membered rings (e.g., cyclohexyl, cyclooctyl, adamantanyl, or 1-methylcyclohexyl, or substituted adamantanyl), for example, a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, adamantanyl, or substituted adamantanyl).

[0174] In some embodiments of the catalyst compounds of formula (PM-I~PM-V), R 3 and R 3 Each of these is independently (substitutive or non-substitutive) C1-C 20 Alkyl, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or their isomers. In some embodiments of the catalyst compounds of formula (PM-I to PM-V), R 3 and R 3 Each of ' is independently an acyclic tertiary hydrocarbyl group (substituted or unsubstituted). In other embodiments of formula (PM-I to PM-V), R 3 and R 3 Each of these is independently tert-butyl. In some embodiments, R in formula (PM-II to PM-V) 1, R 2 , R 3 , R 4 , R 1 ', R 2 ', R 3 ', R 4 ', R 5 , R 6 , R 7 , R 8 , R 5 ', R 6 ', R 7 ';R 8 ', R 10 , R 11 , or R 12 One or more of these are independently hydrogen or C1-C 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.

[0175] In some embodiments of formula (PM-I to PM-V), M is a group 3 metal, such as Sc, Y, La, Lu, or Nd. In some embodiments of formulas (PM-I) and (PM-II), E and E' are each O.

[0176] In some embodiments of formula (PM-I~PM-V), R 1 , R 2 , R 3 , R 4 , R 1 ', R 2 ', R 3 ', and R 4Each of the following is independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthalenyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, adamantanyl, and their isomers. In embodiments of formula (PM-I to PM-V), X is selected from hydrocarbyl radicals (e.g., alkyl or aryl) having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, and alkyl sulfonates. For example, X is selected from halides, aryls, and C1-C5 alkyl groups. For example, X is a hydride, dimethylamide, diethylamide, bis(dimethylsilyl)amide, bis(trimethylsilyl)amide, methylenetrimethylsilyl, neopentyl, phenyl, benzyl, methyl, ethyl, propyl, butyl, pentyl, fluoro, iodine, bromo, or chloro group. In some embodiments, X is selected from bis(dimethylsilyl)amide, bis(trimethylsilyl)amide, and methylenetrimethylsilyl. Alternatively, X may be a halide, hydride, alkyl group, or alkenyl group.

[0177] In some embodiments of formula (PM-I to PM-V), each L is independently selected from ethers, thioethers, amines, nitriles, imines, pyridines, halocarbons, and phosphines, for example, ethers, thioethers, or combinations thereof, and optionally two or more L may form part of a fused ring or ring system, for example, each L is independently selected from ether or thioether groups, for example, each L is ethyl ether, tetrahydrofuran, dibutyl ether, or dimethyl sulfide group. In some embodiments of formula (PM-I~PM-V), R 1 and R 1 Each of these is independently a cyclic tertiary alkyl group. In some embodiments of formulas (PM-I to PM-V), m is 0, 1, or 2, for example, 0. In some embodiments of formula (PM-I~PM-V), R 1 and R 1 Each of these is not hydrogen.

[0178] In some embodiments of formula (PM-I~PM-V), R 3 and R 3 Each of these is not hydrogen. In some embodiments of formulas (PM-I) and (PM-II), M is Sc, Y, La, Lu, or Nd, and E and E' are each O, and R 1 and R 1 Each of these is independently C1-C 40 Hydrocarbyl, substituted C1-C 40 Hydrocarbyl, heteroatom, or heteroatom-containing group, R 2 , R 3 , R 4 , R 2 ', R 3 ', and R 4 Each of these is independently hydrogen, C1-C 20 Hydrocarbyl, or substituted C1-C 20 It is hydrocarbil. In some embodiments of formulas (PM-III to PM-V), M is Sc, Y, La, Lu, or Nd, and R 1 and R1 Each of these is independently C1-C 40 Hydrocarbyl, substituted C1-C 40 Hydrocarbyl, heteroatom, or heteroatom-containing group, R 2 , R 3 , R 4 , R 2 ', R 3 ', and R 4 Each of these is independently hydrogen, C1-C 20 Hydrocarbyl, or substituted C1-C 20 It is hydrocarbil.

[0179] In some embodiments of formulas (PM-II to PM-V), R 5 , R 6 , R 7 , R 8 , R 5 ', R 6 ', R 7 ', R 8 ', R 10 , R 11 and R 12 Each of these is independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof.

[0180] In some embodiments of formulas (PM-II to PM-V), R 5 , R 6 , R 7 , R 8 , R 5 ', R 6 ', R 7 ', R 8 ', R 10 , R 11 and R 12Each of these is independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthalenyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, or their isomers.

[0181] In some embodiments of formula (PM-II), M is Sc, Y, La, Lu, or Nd, and E and E' are each O, and R 1 and R 1 Each of these is independently C1-C 40 Hydrocarbyl, substituted C1-C 40 Hydrocarbyl, heteroatom, or heteroatom-containing group, R 3 and R 3 Each of these is independently C1-C 40 Hydrocarbyl, substituted C1-C 40 Hydrocarbyl, heteroatom, or heteroatom-containing group, R 1 , R 2 , R 4 , R 1 ', R 2 ', and R 4 Each of these is independently hydrogen, C1-C 20 Hydrocarbyl, substituted C1-C 20 Hydrocarbyl, heteroatom, or heteroatom-containing group, or R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 1 'and R 2 ', R 2 'and R 3 ', R 3 'and R 4One or more of the ' 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, where X is selected from the group consisting of substituted or unsubstituted substituted hydrocarbyl radicals (e.g., alkyl or aryl) having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, and ethers, where n is 1, m is 1, and R 5 , R 6 , R 7 , R 8 , R 5 ', R 6 ', R 7 ', R 8 ', R 10 , R 11 and R 12 Each of them independently produces hydrogen, C1-C 20 Hydrocarbyl, substituted C1-C 20 The group may be a hydrocarbyl, heteroatom, or 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 ring may bond to form additional rings, for example, R 5 , R 6 , R 7 , R 8 , R 5 ', R 6 ', R 7 ', R 8 ', R 10 , R 11 and R 12Each of them is independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, 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 isomers thereof.

[0182] In some embodiments of formula (PM-IV to PM-V), Q' is N.

[0183] In some embodiments of formula (PM-III to PM-V), M is Sc, Y, La, Lu, or Nd, and R 1 and R 1 ' each is independently a C1-C 40 hydrocarbyl, substituted C1-C 40 hydrocarbyl, heteroatom or heteroatom-containing group, and R 3 and R 3 ' each is independently a C1-C 40 hydrocarbyl, substituted C1-C 40 hydrocarbyl, heteroatom or heteroatom-containing group, and R 1 , R 2 , R 4 , R 1 ', R 2 ', and R 4 ' each is independently hydrogen, a 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 the ' 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 substitutions on the rings may bond to form additional rings, where X is selected from the group consisting of substituted or unsubstituted: hydrocarbyl radicals (e.g., alkyl or aryl) having 1 to 20 carbon atoms (e.g., alkyl or aryl), hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, and ethers, where n is 1, m is 1, and R 5 , R 6 , R 7 , R 8 , R 5 ', R 6 ', R 7 ', R 8 ', R 10 , R 11 and R 12 Each of them independently produces hydrogen, C1-C 20 Hydrocarbyl, substituted C1-C 20 The group may be a hydrocarbyl, heteroatom, or 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 ring may bond to form additional rings, for example, R 5 , R 6 , R 7 , R 8 , R 5 ', R 6 ', R 7 ', R 8 ', R 10 , R 11 and R 12Each of these is independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and their isomers.

[0184] In some embodiments of formula (PM-II), M is Sc, Y, La, Lu, or Nd, and both E and E' are oxygen, and R 1 and R 1’ Both are, independently, C4-C 20 It is a cyclic tertiary alkyl, R 3 and R 3 'Both are independently, C1-C 10 It is alkyl. In some embodiments of formulas (PM-III to PM-V), M is Sc, Y, La, Lu, or Nd, and R 1 and R 1 'Both are independently, C4-C 20 It is a cyclic tertiary alkyl, R 3 and R 3 'Both are independently, C1-C 10 It is alkyl.

[0185] In some embodiments of formula (PM-II), M is Sc, Y, La, Lu, or Nd, and E and E' are both oxygen, and R 1 and R 1 ' is either adamantane-1-yl or substituted adamantane-1-yl, R 3 and R 3 'Both are independently, C1-C 10 It is alkyl. In some embodiments of formulas (PM-III to PM-V), M is Sc, Y, La, Lu, or Nd, and R 1 and R 1 ' are both adamantan-1-yl or substituted adamantan-1-yl, and R 3 and R 3 ' are both, independently, C1-C 10 alkyl.

[0186] In some embodiments of formula (PM-II), M is Sc, Y, La, Lu, or Nd, E and E' are both oxygen, and each of R 1 , R 1 ' is, independently, adamantan-1-yl or substituted adamantan-1-yl, and R 3 and R 3 ' are both, independently, methyl or tert-butyl.

[0187] In some embodiments of formulas (PM-III to PM-V), M is Sc, Y, La, Lu, or Nd, and each of R 1 , R 1 ' is, independently, adamantan-1-yl or substituted adamantan-1-yl, and R 3 and R 3 ' are both, independently, methyl or tert-butyl.

[0188] In some embodiments of formulas (PM-IV to PM-V), G is S, O, NR', PR', where R' is selected from hydrogen and hydrocarbyl or substituted hydrocarbyl groups. In some embodiments of formulas (PM-IV to PM-V), G is S or O, more preferably S. In some embodiments of formulas (PM-IV to PM-V), G is NR', PR', where R' is selected from a hydrogen atom and C1-C 20 hydrocarbyl and substituted hydrocarbyl. In some embodiments of formulas (PM-IV to PM-V), G is NR', PR', where R' is selected from hydrogen or methyl.

[0189] In some embodiments of formula (PM-III), M is Sc, Y, La, Lu, or Nd, and R 1 , R 1 Each of ' is adamantane-1-yl or substituted adamantane-1-yl, R 3 and R 3 ' is either tert-butyl or methyl, R 2 , R 2 ', R 4 , R 4 ', R 5 , R 5 ', R 6 , R 6 ', R 7 , R 7 ', R 8 , R 8 ', R 10 , R 11 and R 12 It is hydrogen. In some embodiments of formula (PM-III), M is Sc, Y, La, Lu, or Nd, and R 1 , R 1 Each of ' is tert-butyl, R 3 and R 3 ' is either tert-butyl or methyl, R 2 , R 2 ', R 4 , R 4 ', R 5 , R 5 ', R 6 , R 6 ', R 7 , R 7 ', R 8 , R 8 ', R 10 , R 11 and R 12 It is hydrogen. In some embodiments of formula (PM-V), M is Sc, Y, La, Lu, or Nd, G is S, and R 1 , R 1 ' is both tert-butyl, R 3 and R 3 ' is methyl, R 2 , R 2 ', R 4 , R 4', R 5 , R 5 ', R 6 , R 6 ', R 7 , R 7 ', R 8 , R 8 ', R 10 , R 11 and R 12 It is hydrogen.

[0190] In some embodiments of formula (PM-V), M is Sc, Y, La, Lu, or Nd, G is S, and R 1 , R 1 ' is either adamantane-1-yl or substituted adamantane-1-yl, R 3 and R 3 ' is either methyl or tert-butyl, R 2 , R 2 ', R 4 , R 4 ', R 5 , R 5 ', R 6 , R 6 ', R 7 , R 7 ', R 8 , R 8 ', R 10 , R 11 and R 12 It is hydrogen. In some embodiments, the catalyst compound is one or more of the following:

[0191] [ka] JPEG2026521464000032.jpg204157 JPEG2026521464000033.jpg234157 JPEG2026521464000034.jpg90168

[0192] 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.

[0193] 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.

[0194] 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.

[0195] 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.

[0196] In some embodiments, two or more different pre-catalyst compounds are present in the catalyst system used herein. In some embodiments, two or more different pre-catalyst 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 catalyst compound, two different activators, such as the 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 catalyst compounds contain an X group that is not a hydride, hydrocarbyl, or substituted hydrocarbyl, the MAO may be brought into contact with the catalyst compound before the addition of the non-coordinating anionic activator.

[0197] Two catalyst compounds (pre-catalysts) can be used in any ratio. In some embodiments, the molar ratio of catalyst compound (A) to catalyst compound (B) falls within the range of (A:B) 1:1000-1000:1, instead within the range of 1:100-500:1, instead within the range of 1:10-200:1, instead within the range of 1:1-100:1, instead within the range of 1:1-75:1, or instead within the range of 5:1-50:1. The specific ratio to be selected depends on the specific pre-catalyst selected, the method of activation, 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 A 25%-99% vs B 0.5%-50%, instead A 50%-99% vs B 1%-25%, or instead A 75%-99% vs B 1%-10%.

[0198] 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.

[0199] 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.

[0200] 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.

[0201] 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.

[0202] 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).

[0203] 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.

[0204] 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.

[0205] 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.

[0206] In at least one embodiment, MAO may be present in zero mol%, or alternatively, MAO may be present in an aluminum-to-catalyst 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].

[0207] 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).

[0208] 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.

[0209] 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 catalyst 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 there are no scavengers (e.g., trialkylaluminum compounds) (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 fewer pre-catalyst compounds. The “reaction zone” is also called the “polymerization zone,” which is the vessel in which polymerization takes place, for example, 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.

[0210] 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.

[0211] 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.

[0212] 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.

[0213] 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.

[0214] Experimental example General considerations 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.

[0215] (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 by treatment with THF solvent, and both coordination TMA and free TMA are converted to AlMe3(THF) as the main product and AlMe2(THF)2 as a trace product according to the reaction in scheme (8). + It can be converted to AlMe3(THF) and AlMe2(THF)2. Therefore, all TMA 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.

[0216] 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% in 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 portions of the MAO are frequently taken out of and returned to the freezer), the THF-extractable total TMA content may increase significantly due to the gelation process that releases TMA.

[0217] 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. 1 Obtain a 1H NMR spectrum. A longer relaxation time D1 may yield greater accuracy, but a length of 30 seconds is sufficient to obtain an error of <2 mass% in the quantification of the CH3 and Al-CH3 signals of toluene. 1 The 1H NMR spectrum is shown in the lower spectrum (B) of Figure 3.

[0218] 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 g / mol 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.

[0219] [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.

[0220] (Example 2) Quantification of coordination TMA in commercially available MAO solutions The quantification of coordination TMA is based on the following reaction scheme (5):

[0221] [ka]

[0222] 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 amount 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 KFThis 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.

[0223] 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 1 hour. All KF in the vials treated with 2 mol%, 4 mol%, and 7 mol% disappeared, but the vial treated with 10 mol% showed that KF remained. All upper phase solutions from the four vials were NMRed in THF-d8 solvent. 1 Figure 5A, 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 5B 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 mass-measured. The amount of unreacted KF was 75.3 mg (2.54 mol% relative to total Al), and coordinated TMA in MAO solution was obtained as 10 - 2.5 = 7.5 mol%. Total Al% was 13.8 mass%, and total TMA (free + coordinated) was 5.33 mass%. Total TMA can be converted to 2.00 mass% Al to obtain 14.5 mol%.

[0224] (Example 3) Evaluation of free TMA In Example 1, the total mass percentage (Wt 全TMA Quantification method for %, coordination TMA and free TMA, and mass percentage (Wt) of coordination TMA in Example 2 配位TMA Based on a quantitative method for %), the free TMA content (Wt) 遊離TMA % is Wt 遊離TMA %=Wt 全TMA %-Wt 配位TMA It can be predicted in percentages.

[0225] (Example 4) OMTS titration It reacts with OMTS, AlMe2(OMTS) + The quantification of MAO active sites capable of forming cationic complexes is based on the reaction of the following scheme (6), using the Kaminsky active MAO formula with two coordination TMA molecules as an example.

[0226] Chemicals: Octamethyltrisiloxane (OMTS, obtained from Aldrich, stored overnight with a 3Å molecular sieve before use); the same MAO solution used in Example 1.

[0227] Procedure: In a dry box, 1.0 g (5.0 mmol Al) of 30% MAO solution and 0.236 g of OMTS (1.0 mmol, based on 20 mol% on Al) were placed in a 20 mL vial and thoroughly mixed. The mixture was shaken on a shaker at ambient temperature for 120 minutes. Then, 10 g of dry CDCl3 was slowly mixed into the mixture and shaken on a shaker for 10 minutes to obtain a homogeneous solution. The sample was then prepared. 1 Collected for 1H nuclear magnetic resonance spectroscopy. Free OMTS: -OSiMe3: 0.20 ppm, 18H; =SiMe2: 0.14 ppm, 6H. [AlMe2(OMTS)] + :AlMe2:-0.26ppm, 6H;-OSiMe3:0.61ppm18H;=SiMe2:0.94ppm, 6H. [AlMe2(OMTS)] + Details of the quantification are summarized in Table 2, where toluene is used as an internal standard based on the results of Example 1 (mother liquor MAO, Table 1): [Table 3]

[0228] Table 2 shows that OMTS controls only one of the two coordination TMA molecules on the MAO molecule. + While it can be converted to , KF can replace two molecules, as shown in the comparison in Example 2, where twice the amount of KF is consumed in the KF titration compared to the amount of OMTS in the OMTS titration. The reason for this difference is that the strong electron-withdrawing group F can actually draw a negative charge from the MAO molecule and impart a -2 charge to the MAO anion, whereas AlMe2 + In the formation of the OMTS complex, it is thought that the Al anion is placed in a state with two electron-donating Me groups and two electron-donating O atoms as shown in scheme (7), or in a state with three electron-donating Me groups and one electron-donating O atom (another possibility for the coordination TMA structure), making it difficult for it to acquire a second negative charge on the MAO anion.

[0229] [ka]

[0230] [ka] (Example 5) Solution-type ionic MAO (ionic MAO-1 and ionic MAO-2) obtained from OMTS treatment Chemicals: WRGrace in a 30% MAO-toluene solution (13.6% by mass of Al, according to the WRGrace analysis certificate; 7.5 mol% of coordination TMA, relative to total Al quantified according to the method of Example 4); OMTS (236.5 g / mol, Aldrich, 3 Å molecular sieve overnight).

[0231] Procedure: 41.5 g of MAO (207.5 mmol of Al) was placed in a 100 mL round-bottom flask equipped with a stirring rod. According to the OMTS titration results in Table 2 of Example 4, 1.84 g of OMTS (7.8 mmol), based on 3.7 mol% OMTS relative to total Al, was slowly added to the MAO solution. The mixture was stirred for 45 minutes. The mixture was transferred to a separation funnel and allowed to settle overnight. Two liquid phases formed. The bottom phase (product) was collected and weighed. 21 g of oily material was produced. The two-phase boundary was discarded. Mass of the top layer: 19.5 g (as a normal solution). Ionic MAO of the bottom phase in CDCl3 1 H NMR:[AlMe2(μ-OSiMe3)2SiMe2] + -MAO region: SiMe2: δ0.92(6H); SiMe3: δ0.92(18H); AlMe2: δ0.92(6H); Free TMA: δ-6.6(9H). Free TMA content, [AlMe2(μ-OSiMe3)2SiMe2] + Using this as an internal standard (3.7 mol% relative to total Al, AlMe2 integral value 59.70), the calculation yields free TMA (integral 9.70) = (9.70 / 9) * 3.7 mol% / (59.70 / 6) = 0.40 mol% (or 0.40 mass%) based on total Al. This ionic MAO is labeled as I-MAO-1.

[0232] Next, this oily ionic MAO is heated in an oil bath at 90°C for 60 minutes. 1 1H NMR was performed, as shown in Figure 6. A novel species containing Al-Me units appeared at -0.23 ppm, which increased along with the Si-Me unit-containing species at 0.56 ppm. The Si-Me:Al-Me ratio of 3:4 was maintained, and this is attributed to species Ia, which is described as the most likely structure in the cationically modified (ionic) MAO section. 1 The 1H NMR spectrum shows the Si-Me and Al-Me areas as follows. This ionic MAO is labeled as I-MAO-2.

[0233] [ka] Experimental evidence shows that all MAO molecules have two coordination TMAs, but OMTS chelated cations [AlMe2(OMTS)] + It was shown that only one molecule could form a single anionic charge. This was because it was difficult to create two anionic charges on a single molecule. Therefore, with approximately 3.7 mol% Al-based OMTS, it was possible to precipitate almost all MAO molecules as ionic MAO and separate them from the free TMA remaining in the upper solution phase. The free TMA was removed by phase separation. OMTS can be added without a solvent or as a solution.

[0234] (Examples (Ex) 6, 7 and 8 and Comparative Examples (cEx) 1, 2, 3 and 4) Small-scale 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 methylaluminoxes (MAOs), including commercially available methylaluminoxane (rMAO, 10% by mass in toluene, WRGrace, for reference), TMA-free F-MAO (described in another patent application), or TMA-free I-MAO-2 (Example 5). Catalyst A 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 grams / mol.

[0235] 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).

[0236] 1-Octene (C8; 98%, Aldrich Chemical Company) was dried by stirring overnight on NaK, followed by filtration through basic alumina (Aldrich Chemical Company, Brockman Basic 1). Polymerized ethylene (C2) was used, and the solution was further purified by passing it through a series of columns: a 500cc Oxyclear cylinder, manufactured by Labclear (Oakland, Calif.), followed by a 500cc column packed with dry 3Å mol sieves (8-12 mesh; Aldrich Chemical Company), and then a 500cc column packed with dry 5Å mol sieves (8-12 mesh; Aldrich Chemical Company).

[0237] 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).

[0238] 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 = 23.5 mL for C2 / C8; 22.5 mL for C3), 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.

[0239] 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 3 below.

[0240] Ethylene / 1-octene copolymerization (EO): As described above, the reactor was prepared and then purged with ethylene. For the MAO activation trial, toluene, 1-octene (100 μL), and activator (MAO) were added via syringe at room temperature and atmospheric pressure. The reactor was then heated to process temperature (100°C) with stirring at 800 RPM, and ethylene was added to process pressure (200 psig = 1480.3 kPa). The pre-catalyst solution was then added to the reactor via syringe under process conditions. During polymerization, ethylene was introduced into the autoclave (via a computer-controlled solenoid valve) to maintain the reactor gauge pressure (+ / - 2 psig). The reactor temperature was monitored and maintained within + / - 1°C. Polymerization was stopped by adding approximately 50 psi compressed air to the autoclave for approximately 30 seconds. Polymerization was quenched after adding a predetermined cumulative amount of ethylene (maximum quench value 15 psid) or after polymerization for up to 30 minutes. The reactor was then cooled and vented. After removing the solvent under vacuum, the polymer was isolated. The reported yield includes the total mass of the polymer and residual catalyst. Catalytic activity is reported as grams of polymer per mmol of transition metal compound per hour of reaction time (g / mmol·hr). Examples of ethylene-octene copolymerization are summarized in Table 4.

[0241] 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.

[0242] 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.

[0243] 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.

[0244] Samples for infrared analysis were prepared by depositing an FTIR-stabilized polymer solution onto a silane-treated wafer. This method resulted in the deposition of approximately 0.12 mg to 0.24 mg of polymer onto the wafer cell. The samples were then analyzed using a Brucker Equinox 55 FTIR spectrometer equipped with a Pikes MappIR specular reflection sample accessory. The spectra were obtained at 5000 cm⁻¹. -1 ~500cm -1 The spectral range is 2 cm -1 At this resolution, data was collected in 32 scans. For ethylene-1-octen copolymer, approximately 1375 cm³ was obtained. -1 The mass percentage of octene in the copolymer was determined by measuring the methyl angle-bending band. The peak height of this band was approximately 4321 cm². -1 The combined tone and harmonic bands were normalized. This corrects for the optical path length difference. The normalized peak height is 1 By correlating with individual standard curves obtained from 1H NMR data, the mass percentage of octene content is predicted within a concentration range of approximately 2–35 mass% relative to octene. Typically, R is 0.98 or higher. 2 The following correlations are achieved. These values ​​are reported in Table 2, under the heading C8 (mass%).

[0245] Two pre-catalysts, post-metallocene A and hafnocene B, having the following structures, were used in propylene and ethylene polymerization tests, respectively: [ka]

[0246] Table 3 lists examples of propylene polymerization. Standard conditions included 0.015 micromoles of catalyst A and the type and amount of activator (Act) shown in Table 3. 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.

[0247] [Table 4-1] [Table 4-2]

[0248] Table 3 compares a series of examples of cEx1-1 to cEx1-3 and Ex6-1 to Ex6-2 at 70°C, and a series of examples of cEx1-4 and Ex6-3 to Ex6-5 at 100°C, showing that non-coordinating TMA-free ionic MAOs are not as good as non-coordinating TMA-free F-MAOs as activators for zirconium-centered post-metallocene precatalysts. F-MAOs also perform better than standard MAOs when comparing cEx2-1 to cEx2-3 and cEx1-7 to cEx1-9. However, for ethylene polymerization (typically using a small amount of a higher alkylolefin such as butane, hexane, or octane as a comonomer to obtain a lower polymer density, e.g., LLDPE; octane is used in this specification), ionic MAO significantly outperforms F-MAO using catalyst A, the same precatalyst as used for propylene polymerization. Examples of this are listed in Table 4 below, along with catalyst B, a hafnocene precatalyst that is usually difficult to activate using standard MAO as an activator. When comparing cEx3-1 to cEx3-3 with Ex7-1 to Ex7-3 and cEx4-1 to cEx4-3 with Ex8-1 to Ex8-3, F-MAO actually shows almost no reactivity in ethylene-octane copolymerization using both precatalysts, catalyst A and catalyst B. Therefore, it has been shown that both anionically modified MAOs (e.g., F-MAO) and cationically modified MAOs (e.g., OMTS-treated MAO), which do not contain non-coordinating alkylaluminum, are required to activate precatalysts containing non-leaving heteroatoms in order to enable polymerization or copolymerization of various monomers and copolymers.

[0249] Table 4 lists examples of ethylene-octene copolymerization. Standard conditions include 0.015 micromoles of catalyst A or 0.025 micromoles of catalyst B, and the type and amount of activator (Act) indicated in the table. Octene (0.100 ml) and 4.9 ml of toluene were used. The reaction mixture was heated to 100°C and pressurized with a semi-continuous supply of 200 psi ethylene, and stirred at 800 rpm. After incorporating 15 psi of ethylene, or if the quench pressure was not met, the reaction was allowed to proceed for up to 30 minutes before quenching. * indicates that the octene content is outside the FTIR calibration range.

[0250] [Table 5]

[0251] (Example 9 and Comparative Examples 5, 6, and 7) Silica-supported MAO (sMAO), cation-modified (OMTS-treated) sMAO, OMTS-treated sMAO using heating, and anionic-modified ((NH 4 ) 2 SiF 6 Processing) sMAO Chemicals: Silica, ES70 (calcined at 600°C); WRGrace 30% MAO toluene solution (13.6 mass% Al(COA) or 5.0 mmol Al / g); OMTS (236.5 g / mol, Aldrich, overnight on 3A molecular sieves); (NH4)2SiF6 (178.2 g / mol, Aldrich, vacuum dried at 110°C); Catalyst A (945 g / mol, prepared as described above).

[0252] procedure: 1) sMAO and the derived supported catalyst A(cEx5): In a 100 mL CelSir reaction vessel, 10.0 g of ES70 silica was mixed with 50 g of dry toluene to form a 17% by mass slurry, and the mixture was stirred. Based on 6.5 (mmol Al / g silica), 13 g of MAO solution was slowly added to the silica slurry. The mixture was stirred at ambient temperature for 30 minutes, and then the temperature was increased to 100°C for 4 hours. After cooling to ambient temperature, the supernatant was filtered and washed with dry isohexane. The wet solid was then dried under vacuum to a certain mass. Yield: 13.8 g of sMAO (approximately 4.7 mmol Al / g). 1.0 g of sMAO was mixed with 4 g of toluene in a 20 mL vial. 38 mg of catalyst A (40 μmol / g) was added to the vial. The mixture was then shaken on a shaker for 2 hours. The solids were isolated by filtration, washed with isohexane, and dried under vacuum to a certain mass. Yield: 1.0 g. 2) TMA-free ionic sMAO obtained from OMTS treatment without heating (cEx6) In a 20 mL vial, 2.0 g of sMAO obtained from 1) above was mixed with 8 g of toluene. 223 mg of OMTS (0.94 mmol, 10 mol% relative to Al, intentionally added in excess) was added to the vial. Note that the main difference between obtaining a solution-type ionic MAO without uncoordinated TMA and a supported ionic MAO is that in the solution type, most of the excess OMTS remains in the upper solution phase and can be removed by phase separation, whereas in the supported type, it remains in the supernatant and can be removed by filtration or decantation. The mixture was shaken in a shaker for 1 hour, then filtered, washed with isohexane, and dried under vacuum to a certain mass. Yield: 2.1 g. 1.0 g of OMTS-treated sMAO was a slurry in a 20 mL vial containing 4 g of toluene and 38 mg of catalyst A (40 μmol / g). The vial was placed in a shaker and shaken for 1 hour. The mixture was filtered, washed with isohexane, and dried under vacuum to a constant mass. Yield: 1.0 g. 3) TMA-free ionic sMAO obtained from OMTS treatment with heating. (Ex9) 1.0 g of OMTS-treated sMAO obtained from step 2) above was mixed with 4 g of toluene in a 20 mL vial. The vial was lightly capped and placed in an oil bath, where it was heated at 100°C for 3 hours. The mixture was allowed to cool to ambient temperature, 38 mg of catalyst A (40 μmol / g) was added, and the mixture was shaken on a shaker for 1 hour. The mixture was filtered, washed with isohexane, and dried under vacuum to a certain mass. Yield: 1.0 g. 4) Heating (NH 4 ) 2 SiF 6 TMA-free anion-modified sMAO obtained from the process (cEx7) 2.0 g of sMAO was mixed with 8 g of toluene in a 20 mL vial. 20 mg of (NH4)2SiF6 (0.11 mmol based on 7 mol% of F relative to Al in sMAO) and 47 mg of solvent-free TMA (to aid in the dissolution of (NH4)2SiF6) were added to the vial, stirred on a shaker for 30 minutes, and heated at 70°C for 20 minutes. The mixture was then filtered, washed with toluene (this process removes most of the free TMA), and re-slurred with 3 g of toluene. 38 mg of catalyst A (40 μmol / g) was added to the mixture. The mixture was then shaken on a shaker for 2 hours. The solids were isolated by filtration, washed with isohexane, and dried under vacuum to a constant mass. Yield: 2.0 g.

[0253] 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), supporting TMA as a scavenger.

[0254] 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 using the final catalyst derived from Complex 6 obtained from standard supported MAO, and in the trials of Examples 8-12 using the final catalyst derived from Complex 6 obtained from the supported MAO (TF-sMAO) of the present invention are listed in Table 5.

[0255] [Table 6]

[0256] Table 5 shows that OMTS-treated sMAO without heating is not as good as standard MAO, which is due to the chelating effect of OMTS, making AlMe2 very stable. +This is consistent with the assumption that detachment from chelation becomes difficult, making it difficult to form a precatalyst with the dinuclear complex (Scheme 1). After heating, the activity increases, which is probably because the chelating ligand decomposes to form a monodentate ligand. Conversely, the anionically modified supported MAO (cEx7) also shows significantly higher activity than the ionic sMAO version when compared with the solution polymerization results shown in Table 4, which indicates that the anionically modified MAO shows almost no activity (cEx3-1~cEx3-3 vs. Ex7-1~Ex7-3, using the same precatalyst and catalyst A). The difficulty in separating active soluble byproducts in solution-treated MAO may be a factor affecting precatalyst activation. For example, in anion-modified MAO in solution, all TMA molecules, including coordinating TMA and free TMA, are converted to AlMe2F, resulting in an excess of AlMe2F in the system (for example, if the total TMA is about 14.5 mol% and the coordinating TMA is about 7.5 mol% (Table 2), it means that about half of the AlMe2F molecules do not replace the coordinating TMA but become free AlMe2F, which is toxic to certain activated precatalysts). Gas-phase PE polymerization using a post-metallocene Zr pre-catalyst (catalyst A) activated with silica-supported ionic MAO (siMAO-1) (2L salt bed reactor, 85°C, 1 hour (H2 input 120mL, H2:C2=0.5 supply; hexene (C6) = ) Input amount 2.5mL, C6 = Figure 3 shows the catalyst (C2 = 0.1; 12 mg).

[0257] (Examples 10-16 and Comparative Examples 8-21) Table 6 shows the results of solution polymerization of ethylene-butadiene copolymerization using complex 34-40 precatalysts activated with heated clathrate ionic MAO (ionic MAO-2).

[0258] Polymerization vessel: Symyx Discovery Tools TI-6AL-4V High Pressure Parallel Reactor.

[0259] Chemical substances: Complexes 34-40 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%); Ionic MAO-2 (obtained from Example 5); Toluene (Aldrich, stored overnight with 3A molecular sieves); Ethylene (purified on a factory line using 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, stored overnight with activated alumina).

[0260] Procedure: iBu2AlH (DIBAL, 20 equivalents relative to the pre-catalyst metal) and [HNMe2Ph] + B(C6F5)4 - The pre-catalysts were activated by adding either D4 (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 metal). After stirring the pre-catalysts and activators 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.

[0261] [Table 7-1] [Table 7-2]

[0262] In some embodiments, as shown in Table 6, the post-metallocene Group 3 pre-catalyst is a standard MAO and a conventional solution activator perfluoroaromatic borate (e.g., i [HNMe2Ph] combined with Bu2AlH(DIBAH) + B(C6F5)4 - Compared to (D4), activation can be performed more efficiently by using solution-type ionic MAO (ionic MAO-2). Post-metallocemule catalysts containing group 3 metal centers have also been compared with standard MAO, conventional borate systems, and TMA-free fluorinated MAO (F-MAO), and results from another application example for TMA-free anion-modified MAO are shown in Figure 4.

[0263] (Examples 17-18 and Comparative Example 22) SiMe 3 (OH) treated MAO and catalyst A (Ex17) Chemicals: SiMe3(OH) (90.2 g / mol, solvent-free, Aldrich, stored overnight with 3A molecular sieves before use); 30% MAO toluene solution (13.5% by mass of Al, WRGrace). Procedure: 5.0 g of solution-type MAO (25 mmol of Al) was placed in a 20 mL vial with a stirring bar and placed on a stirrer. While vigorously stirring, 0.169 g of SiMe3OH (1.857 mmol, relative to 7.5 mmol% free TMA in the MAO, according to Table 2) was slowly added as a solution (dissolved in 2.0 g of toluene). Bubbling was observed. This reaction may require cooling to minimize side reactions. The mixture was shaken on a shaker for 15 minutes. The solution mass was 7.14 g (3.50 mmol Al / g solution, assuming zero Al loss). The resulting solution was used for polymerization of the 1-hexene polymerization pre-catalyst described below. The results are summarized in Table 7.

[0264] SiMe 3 OAlMe 2 Treatment and solution-type MAO using catalyst A (Ex18) Chemicals: SiMe3(OH) (90.2 g / mol, solvent-free, Aldrich, stored overnight with 3A molecular sieves before use); TMA (72.1 g / mol, solvent-free, Aldrich, use as is); 30% MAO toluene solution (13.5% by mass Al, WRGrace). Procedure: In a 20 mL vial, 1.0 g of toluene was added to 0.169 g of SiMe3OH (1.87 mmol). In another 20 mL vial, 1.0 g of toluene and a stirring bar were added to 133.9 mg of TMA (1.86 mmol) and placed in a -30°C freezer for 30 minutes. Then, the silanol solution was slowly added to the cooled TMA solution while stirring vigorously. The mixture was placed on a shaker and shaken for 15 minutes. In another 20 mL vial, the formed SiMe3OAlMe2 was mixed with 5.0 g of MAO solution (25 mmol of Al) and stirred on a shaker for 60 minutes. The mass of the solution was 7.28 g (3.69 mmol of Al / g solution). The resulting solution was used for the polymerization of the 1-hexene polymerization pre-catalyst described below, and the results are summarized in Table 7.

[0265] 1-Hexene polymerization Rapid screening of 1-hexene polymerization at ambient temperature requires rapid activation of a precatalyst and rapid polymerization of 1-hexene; therefore, ethylene (bis(indenyl)) zirconium dimethyl is used here. Apparatus: A 50 mL round-bottom flask with a double jacket, designed to minimize heat loss and expose the thermocouple to the reaction solution, was filled with equal volumes of Al derived from MAO, equal volumes of toluene solvent, equal volumes of 1-hexene, and equal volumes of ethylene (bis(indenyl))zirconium dimethyl (Table 7). A thermocouple was used to measure the temperature increase during 1-hexene polymerization as a measure of activity.

[0266] Chemicals: Treated MAO solutions obtained in Ex.17 and Ex.18, untreated MAO solution as a reference (5 mmol Al / g) (cEx22). 1-Hexene (factory grade, stored overnight with 3A molecular sieves before use). Pre-catalyst ethylene (bis(indenyl)) zirconium dimethyl (377.6 g / mol). Procedure: MAO, toluene, and 1-hexene in the amounts shown in Table 7, along with a stirring bar, were placed in a 50 mL jacketed flask. The mixture was stirred at 600 rpm. The starting ambient temperature was recorded. Then, while counting time with a stopwatch, the amounts of ethylene (bis(indenyl)) zirconium dimethyl solution (10.0 mg in 1.0 g toluene, resulting in a concentration of 10.6 μmol Zr / g solution) shown in Table 7 were poured into the mixture in the flask. The final temperature at the 5-minute mark was recorded. After the polymerization test, the flask was emptied and washed three times with toluene before use in the next test. The results are summarized in Table 7.

[0267] [Table 8]

[0268] Table 7 only shows that the treated MAO can still activate metallocenes. From the perspective of post-metallocene activation, the performance of this pre-catalyst needs to be compared under conditions including differences in the metal center and ligand structure used, the monomers and comonomers used in polymerization, as well as differences in residence time, polymerization temperature, and whether it is supported polymerization or solution polymerization.

[0269] Overall, the MAO and catalyst systems of this disclosure provide improved catalytic activity and catalyst lifetime for certain post-metallocene and CGC pre-catalysts. In addition, monodentate ligands can be formed in situ during MAO formation, resulting in more highly active activators compared to those provided by polydentate chelated ligands (as siloxane alkylaluminum complexes). Ionization of MAO by chelating agents, such as OMTS of this disclosure, can remain gel-free for longer periods than standard aluminoxanes, or even monodentate siloxane-modified alkylaluminoxanes, thus ensuring stability during storage or transport. Furthermore, since siloxane alkylaluminum complexes can be stable, end-users can heat the siloxane alkylaluminum complex to obtain active monodentate ligands and increase efficiency, resulting in improved atomic economy / efficiency as active monodentate ligands can be formed immediately before use as a catalyst activator. The current cationically modified alkylalmoxanes of this disclosure enable more efficient activation of certain post-metallocenes or CGC half-metallocenes, primarily containing O and / or N, offering numerous advantages, particularly compared to anionically modified MAOs, standard MAOs, or boron / borate-based solution activators that exhibit low activation efficiency, while reducing the amount of activator (alkylalmoxane) required for catalyst activation through increased efficiency / atomic economics. The presence of monodentate or chelated ligands in the treated almoxane allows for the similar reduction or elimination of side reactions of O and / or N-containing post-metallocenes or CGC half-metallocenes, thereby promoting improved catalytic activity and lifetime, and resulting in better catalyst and polymer quality control. It should be understood that standard MAO can also be modified by both anionic and cationic modifications. For example, MAO can be treated with an electron-withdrawing agent, e.g., (NH4)2SiF6, followed by a chelating agent, e.g., OMTS, and then subjected to any heating process to form a double-modified alkylaluminoxane composition that does not contain or has a low content of uncoordinated alkylaluminum.

[0270] 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.

[0271] 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.

[0272] 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.

[0273] 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. At least one pre-catalyst compound, Unsupported or supported almoxanes containing a monodentate siloxy ligand A catalyst system including this.

2. The catalyst system according to claim 1, wherein the pre-catalyst compound comprises at least one non-leaving group heteroatom donor chemically bonded to the pre-catalyst metal catalyst center.

3. The catalyst system according to claim 2, wherein the unsupported or supported aluminoxane substantially does not contain uncoordinate alkylaluminum, or has 2% by mass or less of Al as uncoordinate alkylaluminum with respect to the total Al in the unsupported or supported aluminoxane composition.

4. A single-seat ligand is given by equation (I): 【Chemistry 1】 [In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 The catalyst system according to any one of claims 1 to 3, wherein each of the is independently represented as hydrogen, hydrocarbyl, silyl group, or heteroatom-containing group.

5. R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、and R 7 each of which is independently hydrogen, alkyl, or alkenyl, the catalyst system according to claim 4.

6. R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 The catalyst system according to claim 5, wherein each of them is methyl.

7. The catalyst system according to claim 1, wherein the almoxane is a supported almoxane.

8. The catalyst system according to claim 7, wherein the support for the supported aluminoxane contains silica, and the aluminoxane contains methylaluminoxane.

9. 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, such as indenyl, fluorenyl, and indacenyl. 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 any one of claims 1 to 8, wherein the sum of m + n + q is equal to the oxidation state of the transition metal.

10. The catalyst system according to claim 9, wherein the pre-catalyst compound is a bis(arylphenolate)pyridine complex.

11. Bis(arylphenolate)pyridine complexes 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]thiophen-3,2-diyl))bis(2-adamantan-1-yl)-4-methylphenolate)], Dimethylhafnium [6,6'-(pyridine-2,6-diylbis(benzo[b]thiophen-3,2-diyl))bis(2-adamantan-1-yl)-4-methylphenolate)], Dimethylzirconium [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)] and combinations thereof A catalyst system according to claim 10, selected from the group consisting of the following.

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

13. The catalyst system according to claim 1, wherein the pre-catalyst compound is selected from the group consisting of the following. 【Chemistry 2】 【change】 【change】 【change】

14. A method for producing almoxane, A supported or unsupported alkylaluminoxane is reacted with a polydentate chelating agent to form an ionic aluminoxane composition containing a siloxane-chelated alkylaluminum cation. By heating or aging an ionic aluminoxane composition containing a siloxane-chelated alkylaluminoxane cation, an ionic alkylaluminoxane is formed containing a supported or unsupported alkylaluminoxane that includes at least one decomposition product of the siloxane-chelated cation in the siloxane-modified ionic aluminoxane composition. A method comprising the step of forming an ionic alkylalmoxane.

15. The method according to claim 14, wherein the polydentate chelating agent is a bidentate siloxane.

16. The method according to claim 15, wherein the bidentate siloxane is octamethyltrisiloxane.

17. A method for preparing an almoxane composition, Reacting a supported or unsupported alkylalmoxane with silanol to form an alkylalmoxane composition containing a supported or unsupported alkylalmoxane with a monodentate siloxy ligand. A method comprising the step of forming an alkylalmoxane composition that does not contain non-coordinating alkylaluminum, wherein the non-coordinating alkylaluminum content is 2% by mass or less of Al relative to the total Al.

18. Silanol is, formula HO-SiR 3 The method according to claim 17, represented by the formula (wherein each R is independently a hydrogen, alkyl, alkenyl, aryl, or heteroatom-containing group).

19. The method according to claim 18, wherein each R is methyl.

20. Equation (I): 【Transformation 3】 (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 A compound represented by (each of which is independently a hydrogen atom, a hydrocarbyl group, a silyl group, or a heteroatom-containing group).

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

22. R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 The catalyst system according to claim 21, wherein each of them is methyl.

23. A method for preparing an almoxane composition, a) Supported or solid alkylalmoxane, formula (II): R 3 SiOAlR 2 (II) Contacting with a dialkylaluminum siloxide represented by the formula (wherein R is independently hydrogen, hydrocarbyl, or a non-coordinating or weakly coordinating heteroatom-containing group), and b) Separating uncoordinated alkylaluminum from the siloxylated aluminoxane composition. The step involves reacting a supported or solid alkylalmoxane with a dialkylaluminum siloxide to form an alkylaluminum alkylalmoxane composition. Methods that include...

24. The composition according to claim 23, wherein each R is methyl.

25. A supported or unsupported alkylaluminoxane composition modified with anions and cationic compounds, wherein, in either order, anionic modification is achieved by treating the supported or unsupported alkylaluminoxane with a compound containing at least one electron-withdrawing compound, cationic modification is achieved by chelation or treatment of the supported or unsupported alkylaluminoxane with a monodentate siloxane compound, and thereafter the supported or unsupported alkylaluminoxane modified with anions and cationic compounds is optionally heated.

26. Active electron-withdrawing compounds (NH 4 ) 2 SiF 6 The chelated siloxane compound used is octamethyltrisiloxane, and the monodentate siloxane compound is SiMe 3 OH or SiMe 3 OAlMe 2 The composition according to claim 25, wherein the heating temperature is any of the above, and the heating temperature is approximately 60°C to approximately 110°C.

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