Alkyl aluminoxane compositions prepared from trimethylaluminum and triethylaluminum, and their use in ethylene oligomerization processes.

Abstract

Alkylaluminoxane compositions are produced by a process comprising the steps of reacting trimethylaluminum, triethylaluminum, and water in a hydrocarbon solvent to form an alkylaluminoxane, and then removing the insoluble aluminum-containing material from the solvent to form an alkylaluminoxane composition containing 0.1 to 20% by weight of aluminum. Generally, the molar ratio of trimethylaluminum to triethylaluminum is 5:95 to 80:20, and the molar ratio of water to aluminum is 0.2:1 to 1:1. Alkylaluminoxane compositions can be used as activators in transition metal catalyst systems and ethylene oligomerization processes.

Description

[Technical Field]

[0001] Reference to related applications This application was filed on April 23, 2024, as a PCT international patent application, claiming the benefits and priority of U.S. Provisional Patent Application No. 63 / 498,537, filed on April 27, 2023, the disclosures of which are incorporated herein by reference in their entirety.

[0002] Field of Invention This disclosure relates, in general, to alkylaluminoxane compositions and processes for preparing alkylaluminoxane compositions utilizing a combination of trimethylaluminum (TMA) and triethylaluminum (TEA). [Background technology]

[0003] Aluminoxanes, such as methylaluminoxane (MAO), are widely used activators in transition metal catalyst systems. MAO is very expensive, partly because it requires the trimethylaluminum (TMA) reactant. Therefore, modified MAO (MMAO) materials, in which some of the TMA reactant is replaced with triisobutylaluminum (TIBA), are available. However, there is a continuing need for improved activators that offer an acceptable combination of catalytic activation ability, shelf life and catalyst stability, solubility in non-aromatic hydrocarbons, and cost-effectiveness. This invention generally aims to address these issues. [Overview of the project]

[0004] This summary is provided to introduce, in a simplified form, a selection of concepts further described herein. This summary is not intended to identify any necessary or essential features of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter.

[0005] Alkyl aluminoxane compositions and processes for preparing alkyl aluminoxane compositions are described herein. In one embodiment, for example, the aluminoxane composition may comprise (i) an alkyl aluminoxane having random repeating units of formulas (A) and (B), and (ii) a hydrocarbon solvent, wherein the amount of aluminum in the composition may be in the range of 0.1 to 20% by weight. In formulas (A) and (B), R is methyl, and R 1 It is ethyl, and the molar ratio of methyl:ethyl is 5:95 to 80:20. [ka]

[0006] Another alkylaluminoxane composition provided herein can be produced by a process comprising (a) reacting trimethylaluminum (TMA), triethylaluminum (TEA), and water in a hydrocarbon solvent to form an alkylaluminoxane, and (b) removing the insoluble aluminum-containing material from the solvent to form an alkylaluminoxane composition containing 0.1 to 20% by weight of aluminum. In step (a), the molar ratio of TMA:TEA is 5:95 to 80:20, and the molar ratio of water:Al is 0.2:1 to 1:1.

[0007] Processes for preparing alkylaluminoxane compositions are also described herein. Typical processes may include (a) reacting trimethylaluminum (TMA), triethylaluminum (TEA), and water in a hydrocarbon solvent to form an alkylaluminoxane, and (b) removing the insoluble aluminum-containing material from the solvent to form an alkylaluminoxane composition containing 0.1 to 20% by weight of aluminum. In step (a), the molar ratio of TMA:TEA is 5:95 to 80:20, and the molar ratio of water:Al is 0.2:1 to 1:1.

[0008] Alkyl aluminoxane compositions can be used as activators and combined with heteroatom ligand transition metal compound complexes (or heteroatom ligands and transition metal compounds) to prepare catalyst compositions, and are not limited to these. These catalyst compositions can then be used in ethylene oligomerization processes to produce ethylene oligomers such as 1-hexene and 1-octene.

[0009] Both the above summary and the following detailed description are illustrative and provide examples only. Therefore, the above summary and the following detailed description should not be considered limiting. Furthermore, additional features or variations may be provided beyond those described herein. For example, certain embodiments may involve combinations and partial combinations of the various features described in the embodiments for carrying out the invention. [Brief explanation of the drawing]

[0010] [Figure 1] The plots of aluminum loss against the molar ratio of water to aluminum in the experiments of Examples 1 to 12 are presented. [Figure 2] The plots of catalytic activity against catalyst storage time for the alkylaluminoxane composition and MMAO oligomerization experiment of Example 13 are presented. [Figure 3] The plots of catalytic activity against catalyst storage time for the alkylaluminoxane composition of Example 14, the alkylaluminoxane composition mixed with TIBA, and the MMAO oligomerization experiment are presented. [Figure 4] The plot of catalytic activity against catalyst storage time in the alkylaluminoxane composition oligomerization experiment of Example 15 is presented. [Modes for carrying out the invention]

[0011] definition To more clearly define the terms used herein, the following definitions are provided. Unless otherwise indicated, the following definitions apply to this disclosure. If a term is used herein but is not specifically defined herein, the definition in the IUPAC Compendium of Chemical Terminology, 2nd Ed (1997) may apply, provided that the applicable definition does not conflict with any other disclosure or definition applicable herein, or that it does not obscure or make impossible any patent claim to which the definition applies. To the extent that any definition or usage shown in any document incorporated herein by reference conflicts with any definition or usage shown herein, the definition or usage shown herein shall prevail.

[0012] In this specification, subject matter features may be described in such a way that different combinations of features may be envisioned within a particular embodiment. With respect to all embodiments and / or features disclosed herein, all combinations that do not adversely affect the designs, compositions, processes, and / or methods described herein, whether or not a particular combination is explicitly stated, are intended. In addition, unless expressly stated otherwise, any embodiments and / or features disclosed herein may be combined to illustrate inventive features consistent with this disclosure.

[0013] In this disclosure, compositions and processes / methods are described in terms of "including" various materials, components, and steps, but unless otherwise stated, such compositions and processes / methods may "essentially consist of" or "consist of" such various materials, components, and steps. Unless otherwise specified, the terms "a," "an," and "the" are intended to include multiple options, e.g., at least one.

[0014] Generally, a group of elements is represented using the numbering scheme shown in the version of the periodic table of the elements published in Chemical and Engineering News, 63(5), 27, 1985. In some cases, a group of elements may be represented using the common name assigned to the group, e.g., alkali metals for Group 1 elements, alkaline earth metals for Group 2 elements, transition metals for Groups 3 - 12 elements, and halogens or halides for Group 17 elements.

[0015] For any particular compound or group disclosed herein, any name or structure presented is intended to encompass all conformational isomers, positional isomers, stereoisomers, and mixtures thereof that can arise from a particular set of substituents, unless otherwise specified. The name or structure is also intended to encompass all enantiomeric forms, whether enantiomorphic or racemic, all enantiomers, diastereomers, and other optical isomers (if any), as well as mixtures of stereoisomers, as would be recognized by one of ordinary skill in the art, unless otherwise specified. For example, a general reference to hexene (or hexenes) includes all straight-chain or branched, acyclic or cyclic hydrocarbon compounds having six carbon atoms and one carbon-carbon double bond, a general reference to pentane includes n-pentane, 2-methylbutane, and 2,2-dimethylpropane, and a general reference to a butyl group includes an n-butyl group, a sec-butyl group, an isobutyl group, and a t-butyl group.

[0016] As used herein, the terms "contacting" and "combining" are used to describe compositions and processes / methods in which materials are contacted or combined together in any order, by any method, and for any length of time, unless otherwise specified. For example, substances may be blended, mixed, slurried, dissolved, reacted, treated, impregnated, formulated, or otherwise combined, or by any suitable method or technique.

[0017] As used in this specification and the claims, the term "hydrocarbon" always means a compound containing only carbon and hydrogen. Other identifiers can be used to indicate the presence of specific groups in the hydrocarbon (e.g., a halogenated hydrocarbon indicates the presence of one or more halogen atoms that replace an equal number of hydrogen atoms in the hydrocarbon).

[0018] The term "oligomer" refers to a compound containing 2 to 20 monomer units. The terms "oligomerization product" and "oligomer product" include all products made by an "oligomerization" process that includes "oligomers" and products that are not "oligomers" (e.g., products containing more than 20 monomer units or solid polymers), but exclude other non-oligomer components in the oligomerization reactor effluent stream, such as, among other components, unreacted ethylene, organic reaction medium, and hydrogen.

[0019] Terms such as "catalyst composition", "catalyst mixture", "catalyst system", etc. do not depend on the actual product or composition obtained from the contact or reaction of the initial components of the disclosed or claimed catalyst composition / mixture / system, the nature of the active catalyst sites, or the fate of the alkylaluminoxane and heteroatom ligand transition metal compound complex (or alkylaluminoxane, and heteroatom ligand, and transition metal compound) after combining these components. Thus, the terms "catalyst composition", "catalyst mixture", "catalyst system", etc. encompass the initial starting components of the composition, as well as any product(s) that may result from contacting these initial starting components. The terms "catalyst composition", "catalyst mixture", "catalyst system", etc. may be used interchangeably throughout this disclosure.

[0020] In the present invention, several types of ranges are disclosed. Where any type of range is disclosed or claimed, the intent is to individually disclose or claim each number that can be reasonably considered to be included in such range, including the endpoint values ​​of that range, as well as any partial ranges and combinations of partial ranges that fall within that range. For example, the molar ratio of water to aluminum can be in a variety of ranges. The disclosure that the molar ratio of water to Al can be in the range of 0.2:1 to 1:1 is intended to indicate that the molar ratio can be any ratio within the range, and can be any range or combination such as 0.2:1 to 1:1, for example 0.2:1 to 0.8:1, 0.3:1 to 0.8:1, 0.3:1 to 0.7:1, 0.3:1 to 0.6:1, 0.4:1 to 0.8:1, 0.4:1 to 0.6:1, 0.4:1 to 0.5:1, or 0.5:1 to 0.6:1. Similarly, all other scopes disclosed herein should be interpreted in the same manner as this example.

[0021] In general, numbers, sizes, formulations, parameters, ranges, or other quantities or characteristics are "about" or "approximate," whether or not they are explicitly stated as such. Whether or not they are modified by the terms "about" or "approximate," the claims include equivalents of such quantities or characteristics.

[0022] Any method or material similar to or equivalent to the method and material described herein may be used in carrying out or testing the present invention, but this specification describes representative methods and materials.

[0023] All publications and patents referenced herein, for example, constructs and methodologies described in those publications and patents, are incorporated herein by reference in their entirety for the purpose of describing and disclosing constructs and methodologies that may be used in connection with the present invention as described herein.

[0024] Detailed description of the invention This specification discloses alkylaluminoxane compositions, processes for preparing alkylaluminoxane compositions, catalyst compositions containing alkylaluminoxane compositions, methods for producing catalyst compositions, and ethylene oligomerization processes utilizing the catalyst compositions. The alkylaluminoxane compositions are prepared from mixtures or combinations of trimethylaluminum (TMA) and triethylaluminum (TEA).

[0025] An object of the present invention is to produce alkylaluminoxane compositions that are more cost-effective than conventional MAO and MMAO activators. Another object is to produce alkylaluminoxane compositions that have solubility in non-aromatic hydrocarbons, excellent shelf life and stability in solution form, and the ability to perform acceptable activation of certain transition metal catalysts. Unexpectedly, alkylaluminoxane compositions prepared herein from mixtures or combinations of trimethylaluminum (TMA) and triethylaluminum (TEA) achieve these objectives.

[0026] Alkylaluminoxane composition In one embodiment, an alkylaluminoxane composition is disclosed herein. This aluminoxane composition may comprise (i) an alkylaluminoxane having random repeating units of formulas (A) and (B), and (ii) a hydrocarbon solvent, wherein the amount of aluminum in the composition may be in the range of 0.1 to 20% by weight. In formulas (A) and (B), R is methyl, and R 1 It is ethyl, and the molar ratio of methyl:ethyl is in the range of 5:95 to 80:20. [ka]

[0027] The total number of repeating units containing both (A) and (B) in alkylaluminoxanes is not particularly limited, but is often in the range of 2 to 20. Other typical ranges for the total number of repeating units include 3 to 18, 5 to 20, 5 to 18, 6 to 20, 6 to 15, 8 to 20, or 8 to 16.

[0028] Alkylaluminoxanes having random repeating units of formulas (A) and (B) also include structures that may have crosslinked or aggregated units resulting in non-linear 2D and 3D alkylaluminoxane structures, including cluster / cage structures, as described in Collins, Chem. Eur. J. 2021, 27, 15460-71 and the references in the same document.

[0029] In another embodiment, this specification discloses an alkylaluminoxane composition produced by a process comprising (a) reacting trimethylaluminum (TMA), triethylaluminum (TEA), and water in a hydrocarbon solvent to form an alkylaluminoxane, and (b) removing the insoluble aluminum-containing material from the solvent to form an alkylaluminoxane composition containing 0.1 to 20% by weight of aluminum. In step (a), the molar ratio of TMA:TEA is 5:95 to 80:20, and the molar ratio of water:Al is 0.2:1 to 1:1.

[0030] In yet another embodiment, a process for preparing an alkylaluminoxane composition is disclosed herein. This process may include (a) reacting trimethylaluminum (TMA), triethylaluminum (TEA), and water in a hydrocarbon solvent to form an alkylaluminoxane, and (b) removing the insoluble aluminum-containing material from the solvent to form an alkylaluminoxane composition containing 0.1 to 20% by weight of aluminum. In step (a), the molar ratio of TMA:TEA is 5:95 to 80:20, and the molar ratio of water:Al is 0.2:1 to 1:1.

[0031] In general, the characteristics of these compositions and processes (e.g., the relative amounts of TMA (or methyl to ethyl) to TEA, the hydrocarbon solvent, the amount of aluminum in the composition, and the relative amounts of water to aluminum) are described separately herein and can be combined in any combination without limiting these characteristics to further describe the disclosed compositions and processes. Furthermore, additional steps may be taken before, during, and / or after the process steps and can be used in any combination without limiting unless otherwise specified to further describe the process of preparing alkylaluminoxane compositions. Similarly, alkylaluminoxane compositions may contain other materials or components unless otherwise specified.

[0032] Alkylaluminoxane compositions (generally, solutions of alkylaluminoxanes in a hydrocarbon solvent) may contain 0.1 to 20% by weight of aluminum. For example, a composition may contain 1 to 20% by weight of aluminum in one embodiment, 2 to 15% by weight of aluminum in another embodiment, 3 to 12% by weight of aluminum in another embodiment, 3 to 7% by weight of aluminum in another embodiment, 4 to 12% by weight of aluminum in another embodiment, and 5 to 10% by weight of aluminum in yet another embodiment. These weight percentages are based on the weight of aluminum (in any form) in the composition compared to the total weight of the composition. The amount of aluminum in an alkylaluminoxane composition is determined by ICP analysis. Diluted alkylaluminoxane compositions are also contemplated herein, and such diluted compositions or solutions of alkylaluminoxanes in a hydrocarbon solvent may contain aluminum in amounts such as 0.1 to 2% by weight, more often 0.1 to 1.5% by weight, 0.1 to 1% by weight, or 0.2 to 0.8% by weight, the amount of aluminum which may depend on considerations of viscosity and pumping while using the alkylaluminoxane composition.

[0033] The relative amounts of TMA:TEA or methyl:ethyl in the process or in the alkylaluminoxane composition are not particularly limited. Nevertheless, exemplary and non-limiting ranges include the molar ratios of TMA:TEA (or methyl:ethyl) of 10:90 to 70:30, 15:85 to 60:40, 15:85 to 40:60, 15:85 to 30:70, 15:85 to 25:75, 20:80 to 70:30, 20:80 to 40:60, 20:80 to 30:70, or 20:80 to 25:75. In many cases, it is beneficial for the amount of TEA (or ethyl) to be greater than the amount of TMA (or methyl). In such circumstances, the molar ratio of TMA:TEA (or methyl:ethyl) may be, but is not limited to, 15:85-40:60, 15:85-30:70, 15:85-25:75, 20:80-40:60, 20:80-30:70, or 20:80-25:75.

[0034] Alkylaluminoxane compositions generally contain virtually no water (less than 1% by weight of water) due to water consumption in the process of producing the alkylaluminoxane composition. More often, these compositions contain less than 1000 ppm (by weight) of water, less than 500 ppm of water, or less than 100 ppm of water. Furthermore, alkylaluminoxane compositions may contain TEA, or TMA, or both TEA and TMA, which are unreacted or free TEA and / or TMA that were not consumed in the process of producing the alkylaluminoxane composition.

[0035] Various hydrocarbon solvents can be used in the alkylaluminoxane compositions and processes for preparing alkylaluminoxane compositions disclosed herein. For example, the hydrocarbon solvent may include any suitable saturated aliphatic hydrocarbon, any suitable aromatic hydrocarbon, any suitable linear α-olefin, or any combination thereof.

[0036] Saturated aliphatic hydrocarbons can be linear aliphatic hydrocarbons, branched aliphatic hydrocarbons, or cyclic aliphatic hydrocarbons, or combinations thereof. Therefore, hydrocarbon solvents may include linear alkanes, branched alkanes, cyclic alkanes, or combinations thereof. Specific examples of saturated aliphatic hydrocarbons that can be used as solvents, either alone or in combination, include propane, butane (e.g., n-butane or isobutane), pentane (e.g., n-pentane, neopentane, cyclopentane, or isopentane), hexane, heptane, octane, cyclohexane, methylcyclohexane, and combinations thereof. In certain embodiments of this disclosure, the hydrocarbon solvent may include (or consist essentially of, or consist of) cyclohexane.

[0037] Additionally or alternatively, the hydrocarbon solvent may include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, styrene, and mesitylene. A combination of two or more aromatic hydrocarbons may be used if desired.

[0038] Specific examples of linear α-olefins that can be used as hydrocarbon solvents, either alone or in combination, include 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, and combinations thereof.

[0039] Generally, the alkylaluminoxane compositions described herein may contain at least 40% by weight of a hydrocarbon solvent, and more often, at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, or at least 85% by weight of the composition is the hydrocarbon solvent. These weight percentages are based on the weight of the hydrocarbon solvent(s) compared to the total weight of the composition.

[0040] As disclosed herein, alkylaluminoxane compositions may be solutions at standard temperature and pressure (25°C and 1 atm), etc. This means that under standard conditions, there is no visible precipitate of alkylaluminoxane in the hydrocarbon solvent (or only minimal visible precipitate). Therefore, alkylaluminoxane compositions may be solutions in aromatic hydrocarbon solvents such as toluene, or in saturated aliphatic solvents such as cyclohexane, or in linear α-olefin solvents such as 1-hexene.

[0041] Beneficially, such alkylaluminoxane compositions are solutions that can be stable (without (or with minimal visible precipitation of) alkylaluminoxane in the hydrocarbon solvent) for at least 1 day, and in some embodiments, at least 3 days, at least 7 days, at least 10 days, or at least 14 days, at standard temperature and pressure (25°C, 1 atm).

[0042] Referring here to the process for preparing an alkylaluminoxane composition and the alkylaluminoxane composition produced by that process, step (a) involves reacting trimethylaluminum (TMA), triethylaluminum (TEA), and water in a hydrocarbon solvent to form an alkylaluminoxane. The options for the molar ratio of TMA:TEA in step (a) are as described above. The molar ratio of water:Al in step (a) may be in the range of 0.2:1 to 1:1. More often, the molar ratio of water:Al may be in the range of 0.2:1 to 0.8:1, e.g., 0.3:1 to 0.8:1, 0.3:1 to 0.7:1, 0.3:1 to 0.7:1, 0.3:1 to 0.6:1, 0.4:1 to 0.8:1, 0.4:1 to 0.6:1, 0.4:1 to 0.5:1, or 0.5:1 to 0.6:1. While not limited to these, molar ratios in the range of 0.3:1 to 0.8:1 or 0.3:1 to 0.6:1, for example around 0.5:1, provide a good balance between catalytic activity and aluminum loss.

[0043] The order in which the components are added in step (a) is not particularly limited, but in one embodiment, TMA, TEA, and hydrocarbon solvent may be added first, often followed by water. In another embodiment, TMA and solvent may be added first, followed by water, then TEA. In yet another embodiment, TEA and solvent may be added first, followed by water, then TMA.

[0044] Step (a) can be carried out at any suitable temperature, but typically below the standard boiling point of the hydrocarbon solvent, taking into consideration that the reaction in step (a) is exothermic. Typical temperature ranges include, but are not limited to, 10°C to 90°C, 20°C to 70°C, 15°C to 55°C, 20°C to 45°C, or 20°C to 30°C. In these and other embodiments, these temperature ranges are intended to also include situations in which step (a) is carried out at a series of different temperatures, rather than a single fixed temperature in which at least one temperature falls within each temperature range. The pressure at which step (a) is carried out is not particularly limited, but may be high pressure (e.g., 5 psig to 100 psig), atmospheric pressure, or any suitable near-atmospheric pressure. In some cases, step (a) is carried out at atmospheric pressure to eliminate the need for pressurized vessels and the associated costs and complexities. Step (a) can be carried out over any suitable period of time, and the addition of water in step (a) can be carried out over any suitable period of time. Exemplary and non-limiting periods (for example, for the complete or slow addition of water) include, but are not limited to, a wide range of periods, such as 1 minute to 10 hours, 1 minute to 6 hours, 5 minutes to 6 hours, 5 minutes to 2 hours, or 15 minutes to 3 hours. Other suitable ranges of temperature, pressure, and period are readily apparent from this disclosure.

[0045] It should be noted that no catalyst is required in step (a) for forming the alkylaluminoxane, and therefore the alkylaluminoxane is generally formed in the substantially absence of a catalyst (i.e., less than 1% by weight of catalyst based on the total weight of TMA, TEA, water, and hydrocarbon solvent in step (a)). For example, less than 1000 ppm (by weight) of catalyst, less than 100 ppm of catalyst, or less than 10 ppm of catalyst may be present, and more often, no catalyst is used, as shown by the following examples.

[0046] In step (b), the insoluble aluminum-containing material is removed from the solvent to form an alkylaluminoxane composition containing 0.1 to 20% by weight of aluminum. The step of removing the insoluble aluminum-containing material from the solvent may include any suitable technique, such as discharge, decantation, pressing, centrifugation, filtration, sedimentation, stripping, evaporation, drying, or any combination thereof, and each technique(s) may be performed once or multiple times. Often, the insoluble aluminum-containing material is removed from the solvent by filtration.

[0047] It is desirable to minimize the amount of aluminum removed in step (b), based on the total aluminum before step (b), for example, to 40% by weight or less, 30% by weight or less, 20% by weight or less, or 10% by weight or less. However, the loss of aluminum must often be balanced with the amount of water added, the molar ratio of TMA:TEA, and the resulting catalytic activity. In light of these considerations, the amount of aluminum removed in step (b) is generally within the range of 10–50% by weight, 15–45% by weight, 5–30% by weight, 5–20% by weight, or 20–40% by weight, based on the total aluminum before step (b).

[0048] In aspects of the present invention, the process for preparing an alkylaluminoxane composition does not require a step of removing insoluble aluminum-containing material from the solvent (e.g., by filtration) to form the alkylaluminoxane composition. In these aspects, the process for preparing an alkylaluminoxane composition may thus include reacting trimethylaluminum (TMA), triethylaluminum (TEA), and water in a hydrocarbon solvent (any hydrocarbon solvent disclosed herein) to form an alkylaluminoxane composition (including insoluble aluminum-containing material). The alkylaluminoxane composition contains 0.1 to 20% by weight of aluminum (or any amount of aluminum disclosed herein). The molar ratio of TMA:TEA is 5:95 to 80:20 (or any molar ratio disclosed herein), and the molar ratio of water:Al is 0.2:1 to 1:1 (or any molar ratio disclosed herein). Alkyl aluminoxane compositions may be prepared and then used directly (without removing insoluble aluminum-containing material) in any of the catalyst compositions and oligomerization processes disclosed herein.

[0049] Catalyst composition and oligomerization process Similarly, this specification includes catalyst compositions and processes for producing catalyst compositions. An exemplary catalyst composition may comprise (I) any of the alkylaluminoxane compositions disclosed herein and (II) a heteroatom ligand transition metal compound complex, or a heteroatom ligand and a transition metal compound. An exemplary process for producing a catalyst composition may comprise (A) performing any of the processes for producing an alkylaluminoxane composition disclosed herein and (B) contacting the alkylaluminoxane composition with a heteroatom ligand transition metal compound complex (or a heteroatom ligand and a transition metal compound) to form a catalyst composition.

[0050] The alkylaluminoxane compositions disclosed herein include a hydrocarbon solvent, and the resulting catalyst composition may therefore also contain a hydrocarbon solvent, such as any suitable saturated aliphatic hydrocarbon or aromatic hydrocarbon. Combinations of two or more hydrocarbon solvents may be present in the catalyst composition.

[0051] The components of the catalyst composition can be combined at any suitable temperature, such as 0°C to 90°C, 20°C to 70°C, 15°C to 55°C, 20°C to 45°C, or 20°C to 30°C (room temperature can be conveniently used), but are not limited thereto. The catalyst composition may be formed in or without the presence of an olefin (e.g., an oligomerizable olefin such as ethylene). If the catalyst composition is formed in the reactor at the time of contact with the olefin, the appropriate pressure and temperature are typical for the oligomerization process, which will be further discussed below.

[0052] The heteroatom ligand transition metal compound complex or transition metal compound in the catalyst composition may include any suitable metal(s), such as chromium, iron, cobalt, vanadium, titanium, zirconium, hafnium, etc., or combinations thereof. In one embodiment, the transition metal catalyst system may include chromium, alternatively iron, alternatively cobalt, alternatively vanadium, alternatively titanium, alternatively zirconium, or alternatively hafnium. The molar ratio of Al to transition metal (e.g., Al:Cr or Al:Fe) in the catalyst composition may be in the range of 10:1 to 5,000:1, for example, 50:1 to 3,000:1, 75:1 to 3,000:1, 75:1 to 2,000:1, 100:1 to 2,000:1, or 100:1 to 1,000:1.

[0053] While not limited to use in any particular type of catalytic system, the alkylaluminoxane compositions disclosed herein are particularly suitable for use in combination with heteroatom ligand transition metal compound complexes, or catalysts comprising heteroatom ligands and transition metal compounds. Accordingly, the alkylaluminoxane compositions can be used in catalytic systems comprising (i) heteroatom ligand chromium (or iron) compound complexes, or (ii) heteroatom ligands and chromium (or iron) compounds. Examples of heteroatom ligand transition metal compound complexes (or heteroatom ligands and transition metal compounds) suitable for use with the disclosed alkylaluminoxane compositions include, for example, those described in U.S. Patents 8,680,003, 8,865,610, 9,962,689, 10,493,422, 10,464,862, 10,435,336, and 11,267,909. In many cases, the molar ratio of Al to heteroatomic ligands in catalyst compositions can range from 10:1 to 5,000:1, more often from 50:1 to 3,000:1, 75:1 to 3,000:1, 75:1 to 2,000:1, 100:1 to 2,000:1, or 100:1 to 1,000:1. When both heteroatomic ligands and transition metal compounds are present, the ligand-to-transition metal molar ratio is often in the range of 10:1 to 1:10, more often from 8:1 to 1:8, 5:1 to 1:5, 4:1 to 1:4, or 2:1 to 1:2. In some embodiments, the transition metal compound is present in molar excess relative to the heteroatomic ligand, but this is not essential.

[0054] Beneficially, such catalyst compositions are stable at standard temperatures and pressures (25°C and 1 atm). In this regard, the relationship between catalyst age and productivity is generally constant for at least one day, at least two days, at least three days, or at least five days. For example, the change in productivity over time (Δproductivity / Δtime) may be less than 20% per day, or less than 15% per day, or less than 10% per day. Δproductivity is the productivity at time zero minus the productivity at a specific time interval (e.g., one day). The stability of the catalyst composition is demonstrated in the following examples.

[0055] This specification also encompasses oligomerization processes. For example, an oligomerization process consistent with one aspect of the present invention may include: (1) performing any of the processes for producing a catalyst composition using an alkylaluminoxane composition disclosed herein; (2) contacting ethylene, the catalyst composition, an organic reaction medium, and optionally hydrogen in an oligomerization reactor; (3) forming an oligomer product in the oligomerization reactor, wherein the oligomer product comprises hexene and octene; and (4) discharging an effluent from the oligomerization reactor, wherein the effluent comprises unreacted ethylene and the oligomer product. An oligomerization process consistent with another aspect of the present invention may include (1) contacting ethylene, any catalyst composition comprising an alkylaluminoxane composition disclosed herein, an organic reaction medium, and optionally hydrogen in an oligomerization reactor; (2) forming an oligomer product in the oligomerization reactor, wherein the oligomer product comprises hexene and octene; and (3) discharging an effluent from the oligomerization reactor, wherein the effluent comprises unreacted ethylene and the oligomer product.

[0056] Along with other components, the effluent contains oligomeric products, including hexene, octene, and other C4 +Linear α-olefins may be included. The amount of octene in the oligomer product can typically be in the range of 20 to 99% by weight, based on the total amount of oligomers in the oligomer product. In one embodiment, the minimum amount of octene in the oligomer product may be 20, 30, or 40% by weight. In another embodiment, the maximum amount of octene in the oligomer product may be 99, 95, 92.5, 90, 87.5, or 85% by weight. Generally, the amount of octene in the oligomer product can range from any minimum to any maximum amount of octene in the oligomer product described herein. For example, the amount of octene in the oligomer product, based on the total weight of the oligomers, could be 30-95% by weight, 40-95% by weight, 40-90% by weight, 20-90% by weight, 30-87.5% by weight, 30-85% by weight, 40-87.5% by weight, 40-85% by weight, 20-60% by weight, 30-55% by weight, or 40-55% by weight.

[0057] Furthermore, or alternatively, the oligomer product may contain any suitable amount of hexene. In one embodiment, the minimum amount of hexene in the oligomer product may be 15, 20, 25, 30, or 35% by weight. In another embodiment, the maximum amount of hexene in the oligomer product may be 75, 65, 60, 55, or 50% by weight. Generally, the amount of hexene in the oligomer product may range from any minimum to any maximum amount of hexene in the oligomer product described herein. For example, the amount of hexene in the oligomer product based on the total weight of the oligomer may be 20-60% by weight, 25-55% by weight, or 30-50% by weight of hexene.

[0058] The amount of ethylene converted in the oligomerization reactor is not particularly limited, and generally, the minimum conversion rate of ethylene can be at least 20, 30, 35, 40, 45, or 50% by weight, and the maximum conversion rate of ethylene can be 99, 95, 90, 80, 75, 70, or 65% by weight. Generally, the ethylene conversion rate in the reactor can range from any minimum to any maximum conversion rate described herein. For example, the ethylene conversion rate can be in the range of 20–95% by weight, 30–90% by weight, 40–80% by weight, 50–70% by weight, or 55–65% by weight. The ethylene conversion rate is based on the amount of ethylene flowing into the reactor and the amount of (unreacted) ethylene in the effluent.

[0059] Here, we refer to the step of contacting ethylene, a catalyst composition, an organic reaction medium, and optionally hydrogen in an oligomerization reactor. Since the use of hydrogen is optional in this step, in one embodiment, hydrogen is not present in this step of the process, while in another embodiment, hydrogen is present in this step of the process.

[0060] Ethylene, the catalyst composition, the organic reaction medium, and hydrogen can be combined in any order or sequence and can be introduced into the oligomerization reactor separately or in any combination. For example, hydrogen and ethylene can be combined and supplied to the reactor separately from the catalyst composition. The present invention is not limited by the manner in which each feed stream is introduced into the reactor. In one embodiment, for example, the catalyst composition can be formed first and then introduced into the oligomerization reactor. In this embodiment, (I) the alkylaluminoxane composition is contacted with (II) the heteroatom ligand transition metal compound complex, or the heteroatom ligand and transition metal compound, before being introduced into the reactor. However, in another embodiment, the catalyst composition can be formed within the oligomerization reactor. In this embodiment, (I) the alkylaluminoxane composition and (II) the heteroatom ligand transition metal compound complex (or the heteroatom ligand and transition metal compound) are introduced into the reactor separately, and the catalyst composition is formed within the reactor.

[0061] Any suitable organic reaction medium (e.g., hydrocarbons) may be used in the disclosed oligomerization process. Exemplary hydrocarbons include, for example, saturated aliphatic hydrocarbons, aromatic hydrocarbons, linear α-olefins, and combinations thereof. The organic reaction medium can be selected from the same materials and associated processes for their preparation as those for the hydrocarbon solvent in the alkylaluminoxane composition. Thus, the organic reaction medium may include any alkane, aromatic, or α-olefin hydrocarbon disclosed herein, and any combination thereof. While not essential, the organic reaction medium may contain the same materials as the hydrocarbon solvent. Furthermore, in certain aspects of this disclosure, the organic reaction medium may include (or consist of, or essentially consist of) cyclohexane.

[0062] Formation of oligomer products in an oligomerization reactor can be carried out at any suitable oligomerization temperature and pressure. In many cases, oligomer products may be formed at the lowest temperatures of 0°C, 20°C, 30°C, 40°C, 45°C, or 50°C, and additionally or alternatively at the highest temperatures of 165°C, 160°C, 150°C, 140°C, 130°C, 115°C, 100°C, or 90°C. Generally, the oligomerization temperature at which oligomer products are formed may range from any lowest temperature disclosed herein to any highest temperature disclosed herein. Therefore, suitable non-limiting ranges include: 0-165, 20-160, 20-115, 40-160, 40-140, 50-150, 50-140, 50-130, 50-100, 60-115, 70-100, or 75-95°C. Other suitable oligomerization temperatures and temperature ranges are readily apparent from this disclosure.

[0063] Oligomer products may be formed at minimum pressures (or ethylene partial pressures) of 50 psig (344 kPa), 100 psig (689 kPa), 200 psig (1.4 MPa), or 250 psig (1.5 MPa), and additionally or alternatively, at maximum pressures (or ethylene partial pressures) of 4,000 psig (27.6 MPa), 3,000 psig (20.9 MPa), 2,000 psig (13.8 MPa), or 1,500 psig (10.3 MPa). Generally, the oligomerization pressure (or ethylene partial pressure) at which oligomer products are formed may range from any minimum pressure to any maximum pressure disclosed herein. Therefore, suitable non-limiting ranges may include 50 psig (344 kPa) to 4,000 psig (27.6 MPa), 100 psig (689 kPa) to 3,000 psig (20.9 MPa), 100 psig (689 kPa) to 2,000 psig (13.8 MPa), 200 psig (1.4 MPa) to 2,000 psig (13.8 MPa), 200 psig (1.4 MPa) to 1,500 psig (10.3 MPa), or 250 psig (1.5 MPa) to 1,500 psig (10.3 MPa). Other suitable oligomerization pressures (or ethylene partial pressures) are readily apparent from this disclosure.

[0064] When used, hydrogen can be supplied directly to the reactor or combined with the ethylene feed before the reactor. In the reactor, the hydrogen partial pressure can be at least 1 psig (6.9 kPa), 5 psig (34 kPa), 10 psig (69 kPa), 25 psig (172 kPa), or 50 psig (345 kPa), and additionally or alternatively, 2000 psig (13.8 MPa), 1750 psig (12.1 MPa), 1500 psig (10.3 MPa), 1250 psig (8.6 MPa), 1000 psig (6.9 MPa), 750 psig (5.2 MPa), 500 psig (3.4 MPa), or 400 psig (2.8 MPa). Generally, the hydrogen partial pressure can range from any minimum hydrogen partial pressure disclosed herein to any maximum hydrogen partial pressure disclosed herein. Therefore, suitable non-limiting ranges for hydrogen partial pressure are as follows: 1 psig (6.9 kPa) to 2000 psig (13.8 MPa), 1 psig (6.9 kPa) to 1750 psig (12.1 MPa), 5 psig (34 kPa) to 1500 psig (10.3 MPa), 5 psig (34 kPa) to 1250 psig (8.6 MPa), 10 psig (69 kPa) to 1000 psig (6.9 MPa), and 1 Possible ranges include 0 psig (69 kPa) to 750 psig (5.2 MPa), 10 psig (69 kPa) to 500 psig (3.5 MPa), 25 psig (172 kPa) to 750 psig (5.2 MPa), 25 psig (172 kPa) to 500 psig (3.4 MPa), 25 psig (172 kPa) to 400 psig (2.8 MPa), or 50 psig (345 kPa) to 500 psig (3.4 MPa). Other suitable hydrogen partial pressures in the reactor for oligomer product formation are readily apparent from this disclosure.

[0065] The oligomerization reactor in which the oligomer product is formed may include any suitable reactor. Non-limiting examples of reactor types include stirred-tank reactors, plug-flow reactors, or any combination thereof; alternatively, fixed-bed reactors, continuous stirred-tank reactors, loop slurry reactors, solution reactors, tubular reactors, recirculation reactors, or any combination thereof. In some embodiments, multiple reactors may be present in series or in parallel, including any combination of reactor type and arrangement. Furthermore, the oligomerization process used to form the oligomer product may be a continuous or batch process, or any reactor or tank used in the process may be operated continuously or in batches. [Examples]

[0066] The present invention will be further illustrated by the following embodiments, which should not be construed as limiting the scope of the invention. After reading this description, various other embodiments, modifications, and equivalents thereof can be suggested to those skilled in the art without departing from the spirit of the invention or the appended claims.

[0067] The general procedure for producing alkylaluminoxane compositions was as follows: In a dry box, a stirring bar was added to a 1-liter three-necked flask. A thermocouple was attached to one opening of the flask, a vent line to another opening, and the third opening was used for adding reagents. At room temperature (approximately 23°C), trimethylaluminum (TMA) and triethylaluminum (TEA) were added to the flask either directly or in an aliphatic or aromatic diluent, followed by the addition of the diluent targeting the final weight percentage of aluminum in the final product. Stirring was started, ensuring the tip of the thermocouple was immersed in the liquid, and the septum was attached to the third neck of the flask. Next, an appropriate amount of water, targeting the desired ratio of water to aluminum, was slowly added through the septum using a syringe. This addition immediately generated heat, which was then released through the vent line. In a typical reaction, the addition of water took approximately one hour, but this time depended on the batch size, the water:aluminum ratio, and the resulting heat. The reaction temperature reached a high of 65°C, but no preferred maximum or minimum exothermic reaction was targeted. Following the addition of water, the reactants were continued to stir until the temperature reached approximately 30°C, and the reaction mixture was filtered to remove precipitate species. The filtrate was then analyzed by ICP to determine the weight percentage of aluminum in the final product. By determining the percentage of aluminum in the final product and the mass of the aluminoxane solution, it was possible to calculate the percentage of "lost" aluminum (insoluble matter) isolated as precipitate.

[0068] The ICP method involved carefully weighing aliquots from the final product, quenching the alkyl with a carefully weighed amount of heavy-chain alcohol, and weighing this combination (some loss occurs during quenching). The weight percentage of aluminum in the aluminoxane was then calculated using the weight percentage of aluminum in the quenched mixture. Performing ICP experiments with toluene solution is not recommended due to the presence of nitric acid in the digestion step. ICP analysis of the amount of aluminum (weight %) and aluminum loss (weight %) in the composition was performed using a PerkinElmer Optima 8300 instrument.

[0069] Examples 1-12 Examples 1-12 were conducted to determine the amount of aluminum lost due to the formation of insoluble material as a function of the water:aluminum ratio. Table 1 summarizes the experiments in Examples 1-12. Unless otherwise stated, the reactions were started at room temperature, and the reaction conditions shown in Table 1 include the relative molar amounts of TEA:TMA and the hydrocarbon solvent used.

[0070] As the data in Figure 1 and Table 1 show, aluminum loss generally increased with increasing water:aluminum molar ratio. While the aluminum loss may suggest that lower water:aluminum ratios are preferable, this must be balanced with the overall activity of the resulting alkylaluminoxane composition. It should also be noted that any reduction in the amount of TMA (i.e., more TEA used to produce the alkylaluminoxane) also represents cost savings. The alkylaluminoxane compositions of Examples 10-12 offer a beneficial combination of properties, while Examples 11-12 result in less aluminum loss. [Table 1]

[0071] Example 13 Example 13 demonstrates that a catalyst composition containing the alkylaluminoxane composition described herein is more stable and has a longer shelf life (constant oligomerization activity) compared to a similar catalyst composition containing MMAO. The results are summarized in Figure 2.

[0072] The following chromium catalyst compositions were prepared and subjected to ethylene oligomerization. In a dry box, equal amounts of representative heteroatom ligand chromium compound complexes (N) were added to two glass scintillation vials. 2- Phosfinylguanidine chromium(III) trichloride tetrahydrofuran complex, 10.0 g of ethylbenzene, and 10.0 g of n-nonane (internal standard) were added. After stirring for 30 minutes, MMAO with an Al:Cr ratio of 400:1 was added to one of these vials (control), and the alkylaluminoxane composition of the present invention from Example 4 (molar ratio of water:Al 0.6:1, molar ratio of TEA:TMA 75:25) was added to the second vial, also with an Al:Cr ratio of 400:1. Both vials were continued to stir for a further 1 hour, and the contents of each vial were further diluted with cyclohexane to a solution concentration of 2.0 × 10⁻⁶. -4 M[Cr] was obtained. The solution was stored in separate 500 mL bottles in an air- and moisture-free environment.

[0073] To test the stored catalyst solutions, 23.4 mL of each solution was taken at different time intervals and diluted with cyclohexane to a total volume of 200 mL. The resulting solutions were then placed in a vented 0.5 L stainless steel reactor heated to 70°C. Hydrogen (50 psig), followed by ethylene (875 psig), was added to the reactor. The reaction proceeded exothermically to the target temperature of 85°C, with ethylene supplied as needed to maintain the desired reactor pressure. After 30 minutes, the oligomerized product was rapidly cooled to 30°C, and then unreacted ethylene and hydrogen gases were discharged.

[0074] The liquid samples were collected, filtered, and analyzed by gas chromatography, typically using n-nonane as an internal standard, to determine the amount of oligomers produced and therefore the catalytic activity in grams of oligomer product per gram of chromium. Both the control and experimental catalyst solutions were tested at 1, 24, 48, and 72 hours, as well as at 1, 1.5, 2, and 3 weeks. Figure 2 shows that productivity was not reduced in the alkylaluminoxane composition catalyst solution, but significantly reduced in the control catalyst solution.

[0075] The upper (flat) line in Figure 2 represents the results of a series of oligomerization experiments using the alkylaluminoxane composition, and the lower (declining) line represents the results of a series of oligomerization experiments using a comparative MMAO activator. Unexpectedly, the catalyst composition containing the alkylaluminoxane composition disclosed herein exhibited stable catalytic activity for three weeks. This catalyst maintained essentially the same activity throughout the three-week test period. This is particularly beneficial in manufacturing operations where large batches of the mixture can be prepared and stored for extended periods. In contrast, the catalyst composition containing the MMAO activator showed a significant decrease in activity after only 24 hours, and its activity was halved after approximately one week.

[0076] Example 14 Example 14 demonstrates that the catalyst composition containing the alkylaluminoxane composition described herein is more stable and has a longer shelf life (constant oligomerization activity) compared to similar catalyst compositions containing MMAO or alkylaluminoxane compositions mixed with TIBA. The results are summarized in Figure 3.

[0077] The experiment in Example 14 was carried out in the same manner as in Example 13, except that the catalyst sample of the present invention was prepared using the alkylaluminoxane from Example 6 (molar ratio of water:Al 0.6:1, molar ratio of TEA:TMA 75:25). Furthermore, an excess of TIBA was added to the solution containing the chromium complex and alkylaluminoxane from Example 6 to prepare a third catalyst solution. In the experiment using TIBA, TIBA was added to the chromium complex and alkylaluminoxane composition in a molar ratio of TIBA:Cr of 25:1. Similar to Figure 2, Figure 3 also shows that the catalyst composition containing the alkylaluminoxane composition exhibits unexpectedly superior stability and catalytic activity compared to the catalyst composition containing the comparative MMAO activator. However, the catalyst composition containing the alkylaluminoxane composition mixed with TIBA behaved worse than that of the catalyst system of the present invention and was similar to the control MMAO catalyst system. Although we do not wish to be bound by theory, it is thought that the presence of TIBA resulted in poor stability and catalytic activity of the catalyst composition containing the alkylaluminoxane composition mixed with TIBA.

[0078] Example 15 A third shelf-life study was conducted, but only the catalyst of the present invention was prepared. The Cr complex was activated by stirring in the same manner as in Example 13, except that the stirred suspension of the Cr complex was activated using the alkylaluminoxane composition of Example 7 (molar ratio of water:Al 0.68:1, molar ratio of TEA:TMA 75:25). This activated catalyst solution was stored at this concentration. No control catalyst solution was prepared, and the solution was stored at 2.0 × 10⁻⁶. -4 No additional cyclohexane was added to further dilute it to M[Cr]. The concentration of the resulting solution was approximately 2.0 × 10⁻⁶. -3 The solution was M[Cr]. Aliquots of the solution were tested for catalyst productivity at 1, 24, 48, and 168 hours. As shown in Figure 4, the triple run data showed no loss of productivity after one week. This indicates that even the concentrated activated catalyst solution has high stability over a long period.

[0079] Examples 16-23 The heteroatom ligand shown in Table 2 and the soluble iron source (transition metal compound) were combined in a small amount of aromatic or aliphatic hydrocarbon solvent such as toluene, xylene, or cyclohexane, added to a sealed NMR tube, and then attached to the impeller shaft of a high-pressure autoclave according to the procedure described in Organometallics 2003, 22, 3178 (Small). Cyclohexane solvent (200 ml) and a cocatalyst were added to the sealed evacuated autoclave, the reactor was pressurized with ethylene (in the range of 400 - 800 psig), stirring was started, and the reaction was initiated by breaking the glass. The initial reaction temperature (T initial ) and the maximum temperature (T max ) are shown in Table 3. Ethylene was supplied as necessary, and the reaction was terminated by degassing after 15 minutes. The product was analyzed by gas chromatography using an internal standard.

[0080] The ethylene oligomerization experiments of Examples 16 - 23 are summarized in Table 3. The yield of the volatile product (i.e., C4) was extrapolated using the Schultz - Flory constant K, and the total yield and productivity were based on the C4 - C 26 product. In some cases, the Schultz - Flory constant is known to typically drift upward with an increase in the number of carbon atoms. Therefore, the extrapolation for calculating the K value of C6 / C4 was based on the rate of change of the previous three fraction measurement values. For example, if the K values of C 12 / C 10 , C 10 / C8, and C8 / C6 are 0.52, 0.50, and 0.48, respectively, the extrapolated K value for calculating the amount of 1 - butene formed will be 0.46. As shown in Table 3, the alkylaluminoxane compositions of Examples 11 - 12 were excellent activators for the Fe - based catalyst systems of Examples 16 - 23.

Table 2

Table 3

[0081] Examples 24-25 Polymerization of 1-hexene using metallocene catalysts and different activators was evaluated in Examples 24-25. A solution of bis(ethylcyclopentadienyl)zirconium(IV) dichloride (CAS number 1291-32-3) was prepared from a metallocene complex at a concentration of 2.0 mg per 1 ml of m-xylene. Two test reaction solutions were prepared using 0.5 mL of standard metallocene solution (1.0 mg of metallocene) and 20 g of 1-hexene in each reaction vessel.

[0082] In Example 24, used as a control, 0.45 g of commercially available MMAO was added to activate the catalyst, initiating polymerization, which was confirmed by the exothermic reaction that raised the reaction temperature from room temperature to 57°C. The molar ratio of Al:Zr in this reaction was 400:1. The reaction was quenched after 2 hours, and the conversion rate was determined to be 61% by GC using m-xylene as an internal standard.

[0083] For Example 25, the same procedure was used except that the alkylaluminoxane composition from Example 7 (water:Al molar ratio 0.68:1, TEA:TMA molar ratio 75:25) was used instead of MMAO. In Example 25, no exothermic reaction was observed after activation. The Al:Zr molar ratio in this reaction was 400:1. The reaction was quenched after 2 hours, and no essential transformation was observed by GC. This surprising result indicates that the alkylaluminoxanes of the present invention are not effective in activating metallocenes, and therefore, their high effectiveness in activating Cr and Fe catalytic systems was unexpected.

[0084] Examples 26-29 Examples 26-29 were carried out in substantially the same manner as Examples 1-12. Table 4 summarizes the experiments of Examples 26-29. The reactions were initiated at room temperature, and the reaction conditions shown in Table 4 include the molar ratio of TEA:TMA, the molar ratio of water:aluminum, and the hydrocarbon solvent used. Table 4 summarizes the final amount of aluminum in the composition and the amount of aluminum lost due to the formation of insoluble material. In summary, each of Examples 26-29 produced excellent alkylaluminoxane compositions, with Examples 26-28 exhibiting less aluminum loss. [Table 4]

[0085] Examples 30-32 Examples 30-32 were carried out in substantially the same manner as Examples 16-23. Table 5 summarizes the ethylene oligomerization experiments of Examples 30-32 and the initial reaction temperature (T initial ) and the highest (T max The temperatures are shown in Table 5. The structure of ligand 11 is shown below. [ka]

[0086] As shown in Table 5, the alkylaluminoxane compositions of Examples 27-29 were excellent activators for the Fe-based catalyst systems of Examples 30-32. [Table 5]

[0087] The present invention is described herein with reference to numerous embodiments and specific examples. In view of the detailed description, many variations are suggested to those skilled in the art. Any such obvious variations fall within the entire intended scope of the appended claims. Other embodiments of the present invention may include, but are not limited to, the following (aspects are described as "comprising," but can instead be described as "consist essentially of" or "consist of").

[0088] Appearance 1. (i) an alkylaluminoxane having random repeating units of formulas (A) and (B): [ka] In the formula, R is methyl, and R 1 It is ethyl, and the molar ratio of methyl:ethyl is 5:95 to 80:20; (ii) an alkylaluminoxane composition comprising a hydrocarbon solvent, The alkylaluminoxane composition wherein the amount of aluminum in the composition is 0.1 to 20% by weight.

[0089] Appearance 2. (a) Reacting trimethylaluminum (TMA), triethylaluminum (TEA), and water in a hydrocarbon solvent to form an alkylaluminoxane, The molar ratio of TMA:TEA is 5:95 to 80:20. The formation is such that the molar ratio of water to Al is 0.2:1 to 1:1. (b) The alkylaluminoxane composition produced by a process comprising removing an insoluble aluminum-containing material from the solvent to form an alkylaluminoxane composition containing 0.1 to 20% by weight of aluminum.

[0090] Embodiment 3. A process for preparing an alkylaluminoxane composition, (a) Reacting trimethylaluminum (TMA), triethylaluminum (TEA), and water in a hydrocarbon solvent to form an alkylaluminoxane, The molar ratio of TMA:TEA is 5:95 to 80:20. The formation is such that the molar ratio of water to Al is 0.2:1 to 1:1. (b) The process comprising removing the insoluble aluminum-containing material from the solvent to form the alkylaluminoxane composition containing 0.1 to 20% by weight of aluminum.

[0091] Embodiment 4. A composition or process as defined in any one of Embodiments 1 to 3, wherein the alkylaluminoxane composition (e.g., a solution) contains 0.1 to 2% by weight, 0.1 to 1% by weight, 1 to 20% by weight, 2 to 15% by weight, 3 to 12% by weight, 3 to 7% by weight, 4 to 12% by weight, or 5 to 10% by weight of aluminum.

[0092] Embodiment 5. A composition or process as defined in any one of Embodiments 1 to 4, wherein the molar ratio of methyl:ethyl (or the molar ratio of TMA:TEA) is 10:90 to 70:30, 15:85 to 60:40, 15:85 to 40:60, 15:85 to 30:70, 15:85 to 25:75, 20:80 to 70:30, 20:80 to 40:60, 20:80 to 30:70, or 20:80 to 25:75.

[0093] Embodiment 6. A composition or process as defined in any one of Embodiments 2 to 5, wherein the molar ratio of water to Al is 0.2:1 to 0.8:1, 0.3:1 to 0.8:1, 0.3:1 to 0.7:1, 0.3:1 to 0.6:1, 0.4:1 to 0.8:1, 0.4:1 to 0.6:1, 0.4:1 to 0.5:1, or 0.5:1 to 0.6:1.

[0094] Embodiment 7. A composition or process as defined in any one of Embodiments 1 to 6, wherein the composition is substantially free of water (less than 1 wt% water), or the composition contains less than 1000 ppm (by weight) of water, less than 500 ppm of water, or less than 100 ppm of water, and / or at least 40% by weight, at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, or at least 85% by weight of the composition is the hydrocarbon solvent.

[0095] Embodiment 8. A composition or process as defined in any one of Embodiments 1 to 7, wherein the composition further comprises TEA, TMA, or both TEA and TMA (e.g., unreacted or free TEA and / or TMA).

[0096] Embodiment 9. A composition or process defined in any one of Embodiments 2 to 8, wherein the TMA, TEA, and the hydrocarbon solvent are first combined, followed by the addition of water (and the water may be added over any suitable period of time).

[0097] Embodiment 10. A composition or process as defined in any one of Embodiments 2 to 9, wherein, based on the total amount of aluminum prior to step (b), the amount of aluminum removed in step (b) is 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 10 to 50% by weight, 15 to 45% by weight, 5 to 30% by weight, 5 to 20% by weight, or 20 to 40% by weight.

[0098] Embodiment 11. A composition or process as defined in any one of Embodiments 2 to 10, wherein the removal of the insoluble aluminum-containing material from the solvent is performed one or more times using any suitable technique, e.g., discharge, decantation, pressing, centrifugation, filtration, sedimentation, stripping, evaporation, drying, or any combination thereof.

[0099] Embodiment 12. A composition or process as defined in any one of Embodiments 1 to 11, wherein the hydrocarbon solvent comprises a saturated aliphatic hydrocarbon, an aromatic hydrocarbon, a linear α-olefin, or any combination thereof.

[0100] Embodiment 13. A composition or process as defined in any one of Embodiments 1 to 11, wherein the hydrocarbon solvent comprises saturated aliphatic hydrocarbons, such as propane, butane, pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, or a combination thereof, or alternatively, the hydrocarbon solvent comprises cyclohexane.

[0101] Embodiment 14. A composition or process as defined in any one of Embodiments 1 to 11, wherein the hydrocarbon solvent comprises an aromatic hydrocarbon, such as benzene, toluene, xylene, cumene, ethylbenzene, or a combination thereof.

[0102] Embodiment 15. A composition or process as defined in any one of Embodiments 1 to 11, wherein the hydrocarbon solvent comprises a linear α-olefin, such as 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, or a combination thereof.

[0103] Embodiment 16. A composition or process as defined in any one of Embodiments 1 to 15, wherein the composition is a solution at standard temperature and pressure (25°C and 1 atm).

[0104] Embodiment 17. A composition or process as defined in Embodiment 16, wherein the solution is stable at standard temperature and pressure (25°C and 1 atm) for at least 1 day, at least 3 days, at least 7 days, at least 10 days, or at least 14 days.

[0105] Embodiment 18. A composition or process as defined in any one of Embodiments 2 to 17, wherein the alkylaluminoxane is formed in the substantial absence of a catalyst.

[0106] Embodiment 19. A process for producing a catalyst composition, (A) Executing a process defined in any one of aspects 3 to 18, (B) The process comprising contacting the alkylaluminoxane composition with a heteroatomic ligand transition metal compound complex (or a heteroatomic ligand and a transition metal compound) to produce the catalyst composition.

[0107] Appearance 20. (I) an alkylaluminoxane composition defined in any one of embodiments 1 to 18, (II) A catalyst composition comprising a heteroatomic ligand transition metal compound complex (or a heteroatomic ligand and a transition metal compound).

[0108] Embodiment 21. The heteroatom ligand transition metal compound complex and the alkylaluminoxane are present in the catalyst composition in the following molar ratios of Al:transition metal (for example, if the transition metal is chromium or iron, Al:Cr or Al:Fe) A process or composition as defined in embodiment 19 or 20, wherein the heteroatomic ligand and the alkylaluminoxane are present in the catalyst composition in a molar ratio of Al:heteroatomic ligand of 10:1 to 5,000:1, 50:1 to 3,000:1, 75:1 to 3,000:1, 75:1 to 2,000:1, 100:1 to 2,000:1, or 100:1 to 1,000:1.

[0109] Embodiment 22. A process or composition as defined in any one of Embodiments 19 to 21, wherein the catalyst composition comprises a heteroatomic ligand chromium (or iron) compound complex, or a heteroatomic ligand and a chromium (or iron) compound.

[0110] Embodiment 23. A process or composition as defined in any one of Embodiments 19 to 22, wherein the catalyst composition is stable at standard temperature and pressure (25°C and 1 atm).

[0111] Appearance 24. (1) Performing a process for producing a catalyst composition defined in any one of embodiments 19 to 23, (2) Contacting ethylene, the catalyst composition, an organic reaction medium, and optionally hydrogen in an oligomerization reactor, (3) Forming an oligomer product in the oligomerization reactor, wherein the oligomer product comprises hexene and octene, (4) An oligomerization process comprising discharging an effluent from the oligomerization reactor, wherein the effluent contains unreacted ethylene and the oligomer product.

[0112] Appearance 25. (1) Contacting ethylene, a catalyst composition defined in any one of embodiments 20 to 23, an organic reaction medium, and optionally hydrogen in an oligomerization reactor, (2) Forming an oligomer product in the oligomerization reactor, wherein the oligomer product comprises hexene and octene, (3) An oligomerization process comprising discharging an effluent from the oligomerization reactor, wherein the effluent contains unreacted ethylene and the oligomer product.

[0113] Embodiment 26. An oligomerization process as defined in Embodiment 24 or 25, wherein the oligomer product contains any amount of octene disclosed herein, for example, at least 20, 30, or 40% by weight, and up to 99, 95, 92.5, 90, 87.5, or 85% by weight, or 20-99% by weight, 30-95% by weight, 40-95% by weight, 40-90% by weight, 20-90% by weight, 30-87.5% by weight, 30-85% by weight, 40-87.5% by weight, 40-85% by weight, 20-60% by weight, 30-55% by weight, or 40-55% by weight of octene.

[0114] Embodiment 27. An oligomerization process as defined in any one of Embodiments 24 to 26, wherein the oligomer product comprises any amount of hexene disclosed herein, for example, at least 15, 20, 25, 30, or 35% by weight, and up to 75, 65, 60, 55, or 50% by weight, or 20-60% by weight, 25-55% by weight, or 30-50% by weight, based on the total amount of oligomers in the oligomer product.

[0115] Embodiment 28. An oligomerization process as defined in any one of Embodiments 24 to 27, wherein the oligomerization reactor has any ethylene conversion rate disclosed herein, for example, at least 20, 30, 35, 40, 45, or 50% by weight, and up to 99, 95, 90, 80, 75, 70, or 65% by weight, or 20-95% by weight, 30-90% by weight, 40-80% by weight, 50-70% by weight, or 55-65% by weight, based on the amount of ethylene flowing into the reactor and the amount of ethylene in the effluent.

[0116] Embodiment 29. An oligomerization process as defined in any one of Embodiments 24 to 28, wherein hydrogen is contacted within the oligomerization reactor.

Claims

1. (i) an alkylaluminoxane having random repeating units of formula (A) and formula (B): 【Chemistry 1】 In the formula, R is methyl, １ It is ethyl, and the molar ratio of methyl:ethyl is 5:95 to 80:20; (ii) A hydrocarbon solvent and an alkylaluminoxane composition comprising The alkylaluminoxane composition wherein the amount of aluminum in the composition is 0.1 to 20% by weight.

2. (a) Reacting trimethylaluminum (TMA), triethylaluminum (TEA), and water in a hydrocarbon solvent to form an alkylaluminoxane, The molar ratio of TMA:TEA is 5:95 to 80:

20. The formation is such that the molar ratio of water to Al is 0.2:1 to 1:

1. (b) The alkylaluminoxane composition produced by a process comprising removing an insoluble aluminum-containing material from the solvent to form an alkylaluminoxane composition containing 0.1 to 20% by weight of aluminum.

3. A process for preparing an alkylaluminoxane composition, (a) Reacting trimethylaluminum (TMA), triethylaluminum (TEA), and water in a hydrocarbon solvent to form an alkylaluminoxane, The molar ratio of TMA:TEA is 5:95 to 80:

20. The formation is such that the molar ratio of water to Al is 0.2:1 to 1:

1. (b) The process comprising removing the insoluble aluminum-containing material from the solvent to form the alkylaluminoxane composition containing 0.1 to 20% by weight of aluminum.

4. The composition or process according to any one of the prior claims, wherein the alkylaluminoxane composition contains 0.1 to 2% by weight, 0.1 to 1% by weight, 1 to 20% by weight, 2 to 15% by weight, 3 to 12% by weight, 3 to 7% by weight, 4 to 12% by weight, or 5 to 10% by weight of aluminum.

5. The composition or process according to any one of the prior claims, wherein the molar ratio of methyl:ethyl and / or the molar ratio of TMA:TEA is 10:90 to 70:30, 15:85 to 60:40, 15:85 to 40:60, 15:85 to 30:70, 15:85 to 25:75, 20:80 to 70:30, 20:80 to 40:60, 20:80 to 30:70, or 20:80 to 25:

75.

6. The composition or process according to any one of claims 2 to 5, wherein the molar ratio of water to Al is 0.2:1 to 0.8:1, 0.3:1 to 0.8:1, 0.3:1 to 0.7:1, 0.3:1 to 0.6:1, 0.4:1 to 0.8:1, 0.4:1 to 0.6:1, 0.4:1 to 0.5:1, or 0.5:1 to 0.6:

1.

7. The composition is substantially water-free, or contains less than 1000 ppm (by weight) of water, less than 500 ppm of water, or less than 100 ppm of water, and / or The composition or process according to any one of claims 1 to 6, wherein the composition comprises at least 40% by weight, at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 80% by weight, or at least 85% by weight of a hydrocarbon solvent.

8. The composition or process according to any one of claims 1 to 7, wherein the composition further comprises TEA, TMA, or both TEA and TMA.

9. The composition or process according to any one of claims 2 to 8, comprising first combining the TMA, TEA, and the hydrocarbon solvent, and then adding the water.

10. The composition or process according to any one of claims 2 to 9, wherein, based on the total amount of aluminum before step (b), the amount of aluminum removed in step (b) is 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 10 to 50% by weight, 15 to 45% by weight, 5 to 30% by weight, 5 to 20% by weight, or 20 to 40% by weight.

11. The composition or process according to any one of claims 2 to 10, wherein the removal of the insoluble aluminum-containing material from the solvent comprises draining, decantation, pressing, centrifugation, filtration, sedimentation, stripping, evaporation, drying, or any combination thereof, and is performed once or more times.

12. The composition or process according to any one of claims 1 to 11, wherein the hydrocarbon solvent comprises a saturated aliphatic hydrocarbon, an aromatic hydrocarbon, a linear α-olefin, or any combination thereof.

13. The composition or process according to any one of claims 1 to 11, wherein the hydrocarbon solvent comprises propane, butane, pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, or a combination thereof.

14. The composition or process according to any one of claims 1 to 11, wherein the hydrocarbon solvent comprises benzene, toluene, xylene, cumene, ethylbenzene, or a combination thereof.

15. The composition or process according to any one of claims 1 to 11, wherein the hydrocarbon solvent comprises 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, or a combination thereof.

16. The composition or process according to any one of claims 1 to 15, wherein the composition is a solution at standard temperature and pressure (25°C and 1 atm).

17. The composition or process according to claim 16, wherein the solution is stable at standard temperature and pressure for at least 1 day, at least 3 days, at least 7 days, at least 10 days, or at least 14 days.

18. The composition or process according to any one of claims 2 to 17, wherein the alkylaluminoxane is formed in the substantial absence of a catalyst.

19. A process for producing a catalyst composition, (A) Performing the process described in any one of claims 3 to 18, (B) The process comprising contacting the alkylaluminoxane composition with a heteroatom ligand transition metal compound complex, or a heteroatom ligand and a transition metal compound, to produce the catalyst composition.

20. (I) an alkylaluminoxane composition according to any one of claims 1 to 18, (II) A catalyst composition comprising a heteroatomic ligand transition metal compound complex, or a heteroatomic ligand and a transition metal compound.

21. The process or composition according to claim 19 or 20, wherein the molar ratio of Al to transition metal in the heteroatomic ligand transition metal compound complex, or the molar ratio of Al to ligand in the heteroatomic ligand, is in the range of 10:1 to 5,000:1, 50:1 to 3,000:1, 75:1 to 3,000:1, 75:1 to 2,000:1, 100:1 to 2,000:1, or 100:1 to 1,000:

1.

22. The catalyst composition is Heteroatomic ligand-chromium compound complex, or heteroatomic ligand and chromium compound, A process or composition according to any one of claims 19 to 21, comprising a heteroatom ligand-iron compound complex, or a heteroatom ligand and an iron compound.

23. The process or composition according to any one of claims 19 to 22, wherein the catalyst composition is stable at standard temperature and pressure for at least 1 day, at least 3 days, at least 7 days, at least 10 days, or at least 14 days.

24. (1) Performing a process for producing the catalyst composition according to any one of claims 19 to 23, (2) Contacting ethylene, the catalyst composition, an organic reaction medium, and optionally hydrogen in an oligomerization reactor, (3) Forming an oligomer product in the oligomerization reactor, wherein the oligomer product comprises hexene and octene, (4) An oligomerization process comprising discharging an effluent from the oligomerization reactor, wherein the effluent contains unreacted ethylene and the oligomer product.

25. (1) Contacting ethylene, the catalyst composition according to any one of claims 20 to 23, an organic reaction medium, and optionally hydrogen in an oligomerization reactor, (2) Forming an oligomer product in the oligomerization reactor, wherein the oligomer product comprises hexene and octene, (3) An oligomerization process comprising discharging an effluent from the oligomerization reactor, wherein the effluent contains unreacted ethylene and the oligomer product.

26. The oligomerization process according to claim 24 or 25, wherein the catalyst composition is first formed and then introduced into the oligomerization reactor.

27. The oligomerization process according to claim 24 or 25, wherein the catalyst composition is formed in the oligomerization reactor.

28. The oligomerization process according to any one of claims 24 to 27, wherein the oligomer product contains 20-99% by weight, 30-95% by weight, 40-95% by weight, 40-90% by weight, 20-90% by weight, 30-87.5% by weight, 30-85% by weight, 40-87.5% by weight, 40-85% by weight, 20-60% by weight, 30-55% by weight, or 40-55% by weight of octene, based on the total amount of oligomers in the oligomer product.

29. The oligomerization process according to any one of claims 24 to 28, wherein the oligomer product contains 20 to 60% by weight, 25 to 55% by weight, or 30 to 50% by weight of hexene, based on the total amount of oligomers in the oligomer product.

30. The oligomerization process according to any one of claims 24 to 29, wherein the oligomerization reactor has an arbitrary ethylene conversion rate of 20 to 95% by weight, 30 to 90% by weight, 40 to 80% by weight, 50 to 70% by weight, or 55 to 65% by weight, based on the amount of ethylene flowing into the reactor and the amount of ethylene in the outflow logistics.

31. The oligomerization process according to any one of claims 24 to 30, wherein hydrogen is brought into contact within the oligomerization reactor.

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