Methods for preparing metallocene compounds

Description

ΛΓ73 METHODS FOR PREPARING METALLOCENE COMPOUNDS REFERENCE TO RELATED REQUEST

[0001] This application is being filed on June 24, 2024, as a PCT International Patent Application and claims the benefit and priority of U.S. Provisional Patent Application No. 63 / 510,495, filed on June 27, 2023, the disclosure of which is incorporated herein by reference in its entirety. FIELD OF THE INVENTION

[0002] This disclosure relates generally to methods for the preparation of metallocene compounds and the use of metallocene compounds within catalyst compositions for oligomerization and polymerization processes and, more particularly, relates to the preparation of metallocene compounds with improved solubility. FUNDAMENTALS

[0003] Metallocene compounds have been developed as effective catalysts for oligomerization and polymerization processes. The structural properties of metallocenes have been finely tuned to produce the desired oligomer and polymer characteristics. For example, metallocene compounds comprising at least one indenyl linker containing at least one halogenated substituent can produce polyethylene with low levels of short-chain branching. There is a need for metallocene compounds with improved solubility without altering the properties of the oligomer and polymer produced from a given metallocene compound. Therefore, it is to this end that the present invention is generally directed. SUMMARY OF THE INVENTION

[0004] This summary is provided to present a selection of concepts in a simplified manner, which are better described below in the detailed description. This summary is not intended to identify necessary or essential features of the claimed subject matter. This summary is also not Petition 870250087486, dated 09 / 26 / 2025, p. 84 / 166 2 / 73 to be used to limit the scope of the claimed subject matter.

[0005] The methods for preparing a metallocene compound are disclosed in this document, comprising (i) contacting a first compound with formula CpA-(CH2)n-Ar-X with a Bronsted base to form a deprotonated compound; (ii) contacting the deprotonated compound with a substitution reagent to form a substituted compound with formula CpA-(CH2)n-Ar-Rx; and (iii) contacting the substituted compound with a second compound with formula CpB-M-X3 to form a metallocene compound with formula (I): Rx^Ar / χ| M CpBX* (I).

[0006] In certain respects, M may be Zr, Ti or Hf; each X independently may be a halogen or NRy2; X1 and X2 may each be a monoanionic ligand; CpA may be a cyclopentadienyl, indenyl or fluorenyl group, optionally substituted by one or more other substituents; CpB may be a substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl group; Ar may be an aryl group comprising a halogen substituent; Rx may be a C1 to C18 hydrocarbyl group substituent on Ar (e.g., selected from alkyl or alkenyl or aryl; a phenyl group, a benzyl group, a C1 to C8 alkyl group or a C3 to C8 alkenyl group); en may be an integer from 0 to 5.

[0007] Metallocene compounds are also disclosed in this document and may have formula (I) and substituents generally as referenced above. The metallocene compounds disclosed in this document may have improved solubility compared to metallocenes without an Rx substituent. Catalyst compositions are also disclosed in this document. Petition 870250087486, dated 09 / 26 / 2025, page 85 / 166 3 / 73 document and may comprise metallocene compounds as described above, an activator and an optional cocatalyst. In certain respects, the activator may comprise an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, a chemically treated solid oxide or any combination thereof.

[0008] Oligomerization processes are disclosed in this document and may comprise contacting a catalyst composition with an alpha-olefin monomer and optionally H2 under oligomerization conditions to produce an oligomer product. Polymerization processes are disclosed in this document and may comprise contacting a catalyst composition with an ethylene monomer and an optional α-olefin comonomer in a polymerization reactor system under polymerization conditions to produce an ethylene polymer.

[0009] Both the aforementioned summary and the detailed description below provide examples and are merely explanatory. Therefore, the summary above and the detailed description that follows should not be considered restrictive. Additionally, features or variations may be provided in addition to those set forth in this document. For example, certain aspects and modalities may be directed to various combinations and subcombinations of features described in the detailed description. DEFINITIONS

[0010] To define more clearly the terms used in this document, the following definitions are provided. Unless otherwise indicated, the following definitions apply to this disclosure. If a term is used in this disclosure but is not specifically defined in this document, the definition from the IUPAC Compendium of Chemical Terminology, 2nd Ed. (1997) may be applied, provided that such definition does not conflict with any other disclosure or definition applied in this document, or render undefined or ineffective any claim to which such definition is applied. To the extent that any definition or usage provided Petition 870250087486, dated 09 / 26 / 2025, page 86 / 166 4 / 73 If any document incorporated into this document by reference conflicts with the definition or use provided in this document, the definition or use provided in this document shall prevail.

[0011] In this document, features of the material are described in such a way that, within the particular aspects, a combination of different features can be predicted. For each aspect and / or feature disclosed in this document, all combinations that do not adversely affect the compounds, compositions and / or methods described in this document are contemplated with or without explicit description of the particular combination. Furthermore, unless explicitly stated otherwise, any aspect and / or feature disclosed in this document may be combined to describe inventive features consistent with this disclosure.

[0012] Although compositions and methods are described in terms of “comprising” various components or steps, the compositions and methods may also “essentially consist of” or “consist of” various components or steps, unless stated otherwise. For example, a catalyst composition consistent with aspects of the present invention may comprise; alternatively, it may essentially consist of; or alternatively, it may consist of; a metallocene compound, a cocatalyst, and a chemically treated solid oxide.

[0013] The terms “a”, “an”, “the”, “the”, etc., are intended to include plural alternatives, for example, at least one, unless otherwise specified. For example, the disclosure of a cocatalyst or a metallocene compound is intended to cover one, or mixtures or combinations of more than one, cocatalyst or metallocene compound, respectively, unless otherwise specified.

[0014] Generally, groups of elements are indicated using the numbering scheme shown in the version of the periodic table of elements published in Chemical and Engineering News, 63(5), 27, 1985. In some Petition 870250087486, dated 09 / 26 / 2025, page 87 / 166 In 5 / 73 cases, a group of elements can be indicated using a common name assigned to the group; for example, alkali metals for elements of Group 1, alkaline earth metals for elements of Group 2, transition metals for elements of Groups 3-12, and halogens or halides for elements of Group 17.

[0015] For any specific compound disclosed in this document, the general structure or name presented is also intended to encompass all structural isomers, conformational isomers, and stereoisomers that may emerge from a particular set of substituents, unless otherwise indicated. Thus, a general reference to a compound includes all structural isomers unless explicitly stated otherwise; for example, a general reference to pentane includes n-pentane, 2-methylbutane, and 2,2-dimethylpropane, while a general reference to a butyl group includes an n-butyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group. Furthermore, the reference to a general structure or name encompasses all enantiomers, diastereomers, and other optical isomers, whether in enantiomeric or racemic forms, as well as mixtures of stereoisomers, as the context permits or requires.

[0016] For any particular formula or name that is presented, any general formula or name presented also encompasses all conformational isomers, regioisomers, and stereoisomers that may emerge from a particular set of substituents.

[0017] The term “metallocene”, as used in this document, describes compounds comprising at least one η3a η5-cycloalkadienyl fraction, wherein the η3a η5-cycloalkadienyl fractions include cyclopentadienyl ligands, indenyl ligands, fluorenyl ligands and the like, including partially saturated or substituted derivatives or analogues of any of these. Possible substituents for these ligands may include H, therefore this invention comprises ligands such as tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, Petition 870250087486, dated 09 / 26 / 2025, p. 88 / 166 6 / 73 partially saturated substituted indenyl, partially saturated substituted fluorenyl and the like. In some contexts, the metallocene is referred to simply as the catalyst, in the same way that the term cocatalyst is used in this document to refer, for example, to an organoaluminum compound.

[0018] The term hydrocarbon refers to a compound containing only carbon and hydrogen. Other identifiers may be used to indicate the presence of particular groups in the hydrocarbon (for example, halogenated hydrocarbon indicates the presence of one or more halogen atoms replacing an equivalent number of hydrogen atoms in the hydrocarbon). The term hydrocarbyl group is used in this document according to the definition specified by IUPAC: a univalent group formed by the removal of a hydrogen atom from a hydrocarbon (i.e., a group containing only carbon and hydrogen). Non-limiting examples of hydrocarbyl groups include alkyl, alkenyl, aryl, and aralkyl groups, among others.

[0019] The term “cocatalyst” is used generally in this document to refer to compounds such as aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds, organoaluminum compounds, organozinc compounds, organomagnesium compounds, organolithium compounds and the like, which may constitute a component of a catalyst composition when used, for example, in addition to a chemically treated solid oxide activator. The term cocatalyst is used independently of the actual function of the compound or of any chemical mechanism by which the compound may operate.

[0020] The term “substituted,” when used to describe a group, for example, when referring to a substituted analogue of a particular group, is intended to describe any non-hydrogen moiety that formally replaces a hydrogen in that group and is intended to be non-limiting. A group or groups may also be referred to in this document. Petition 870250087486, dated 09 / 26 / 2025, p. 89 / 166 7 / 73 as non-substituted or by equivalent terms as non-substituted, which refers to the original group in which a non-hydrogen moiety does not replace a hydrogen within that group. Unless otherwise specified, substituted is intended to be non-limiting and includes inorganic substituents or organic substituents, as understood by one skilled in the art.

[0021] The term olefin refers to hydrocarbons that have at least one carbon-carbon double bond that is not part of an aromatic ring or aromatic ring system. The term olefin includes aliphatic and aromatic, cyclic and acyclic, and / or linear and branched hydrocarbons with at least one carbon-carbon double bond that is not part of an aromatic ring or ring system, unless specifically indicated otherwise. Olefins with only one, only two, only three, etc., carbon-carbon double bonds can be identified by using the terms mono, di, tri, etc., within the olefin name. Olefins can also be identified by the position of the carbon-carbon double bonds.

[0022] The term alpha olefin, as used in this document, refers to any olefin having 1) a carbon-carbon double bond between the first and second carbon atoms of the longest contiguous chain of carbon atoms and 2) at least one hydrogen atom bonded to the second carbon of the chain. The term alpha olefin includes linear and branched alpha olefins and alpha olefins that may have more than one non-aromatic carbon-carbon double bond, unless expressly stated otherwise. In the case of branched olefins, a branch may be at position 2 of a 1-alkene (a vinylidene) relative to the olefin double bond.

[0023] The term polymer is used in this document generically to include homopolymers, copolymers, olefin terpolymers and the like, as well as alloys and blends thereof. The term polymer also includes impact, interlocking, graft, random and alternating copolymers. A copolymer is derived from an olefin monomer and an olefin comonomer, while a terpolymer is derived from a monomer Petition 870250087486, dated 09 / 26 / 2025, pp. 90 / 166 8 / 73 of olefin and two olefin comonomers. Accordingly, polymer encompasses copolymers and terpolymers derived from any olefin monomers and comonomers disclosed in this document. Similarly, the scope of the term polymerization includes homopolymerization, copolymerization, and terpolymerization. Therefore, an ethylene polymer includes ethylene homopolymers, ethylene copolymers (e.g., ethylene / α-olefin copolymers), ethylene terpolymers and the like, as well as blends or mixtures thereof. Thus, an ethylene polymer encompasses polymers frequently referred to in the art as LLDPE (linear low-density polyethylene) and HDPE (high-density polyethylene). As an example, an olefin copolymer, such as an ethylene copolymer, may be derived from ethylene and a comonomer, such as 1-butene, 1-hexene, or 1-octene.If the monomer and comonomer are ethylene and 1-hexene, respectively, the resulting polymer may be categorized as an ethylene / 1-hexene copolymer. The term polymer also includes all possible geometric configurations, unless otherwise stated, and such configurations may include isotactic, syndiotactic, and random symmetries. Furthermore, unless otherwise indicated, the term polymer is also intended to include all polymers of molecular weight.

[0024] The terms catalyst composition, catalyst mixture, catalyst system and the like are independent of the actual product or composition resulting from the contact or reaction of the initial components of the disclosed or claimed catalyst composition / mixture / system, the nature of the active catalytic site or the fate of the cocatalyst, metallocene compound or activator, after the combination of these components. Therefore, the terms “catalyst composition, catalyst mixture, catalyst system and the like” encompass the initial starting components of the composition as well as any products that may result from the contact of these initial starting components, and this includes both heterogeneous and homogeneous catalyst systems or compositions. The terms catalyst composition, catalyst mixture, catalyst system and the like Petition 870250087486, dated 09 / 26 / 2025, page 91 / 166 9 / 73 can be used interchangeably throughout this publication.

[0025] The terms “contact” and “combination” are used in this document to describe compositions, processes and methods in which materials or components are brought into contact or combined in any order, in any manner and for any period of time, unless otherwise specified. For example, materials or components may be blended, mixed, suspended, dissolved, reacted, treated, compounded or otherwise brought into contact or combined in any other way or by any suitable method or technique.

[0026] Various types of ranges are disclosed in this document. When a range of any type is disclosed or claimed, the intent is to disclose or claim individually every possible number that such range could reasonably encompass, including the endpoints of the ranges as well as any subranges and combinations of subranges covered by them. For example, the weight ratio of the metallocene compound to the chemically treated solid oxide in the catalyst composition may be in various ranges. By a disclosure that the weight ratio of the metallocene compound to the chemically treated solid oxide may range from 1:10 to 1:10,000, the intent is to demonstrate that the weight ratio may be any ratio within the range and, for example, may include any range or combination of ranges from 1:10 to 1:10,000, such as from 1:10 to 1:1,000, from 1:10 to 500:1 or from 1:10 to 1:100 and so forth.Similarly, all other tracks disclosed in this document should be interpreted in a manner similar to this example.

[0027] In general, a quantity, size, formulation, parameter, range, or other quantity or characteristic is about or approximate, whether or not expressly stated as such. Whether or not modified by the term about or approximate, claims include equivalents to quantities or characteristics.

[0028] Although any methods, devices and materials similar or equivalent to those described in this document may be used Petition 870250087486, dated 09 / 26 / 2025, page 92 / 166 10 / 73 In practice or testing of the invention, the typical methods, devices and materials are described in this document.

[0029] All publications and patents mentioned in this document are incorporated herein by reference in their entirety for the purpose of describing and disclosing, for example, the constructions and methodologies that are described in the publications and patents, which may be used in connection with the present invention described. DETAILED DESCRIPTION

[0030] Methods for the preparation of metallocene compounds with hydrophobic substituents for improved solubility are disclosed in this document. These methods can be carried out using a one-pot procedure and therefore, in certain respects, can exclude the isolation of air- and moisture-sensitive intermediates. Metallocene compounds prepared from these methods are also disclosed in this document. Surprisingly, these metallocene compounds demonstrate improved solubility while maintaining comparable catalytic performance in both oligomerization and polymerization processes. METHODS FOR PREPARING METALLOCENE COMPOUNDS

[0031] Conventional metallocene preparations require the isolation of a cyclopentadienyl-containing intermediate prior to coordination with a metal compound, and therefore novel preparative syntheses may be required for each new metallocene compound desired. The metallocene syntheses disclosed in this document involve the modification of known cyclopentadienyl-containing metallocene substrates in situ and within the reaction framework (e.g., reaction systems, conditions) employed by conventional metallocene synthesis schemes. The disclosed methods for the preparation of metallocene compounds can be applied to any metallocene compounds suitable for use within a catalyst composition and where improved solubility may be beneficial. Petition 870250087486, dated 09 / 26 / 2025, page 93 / 166 11 / 73

[0032] In certain respects, methods for the preparation of a metallocene compound may comprise (i) contacting a first compound with formula CpA-(CH2)n-Ar-X with a Bronsted base to form a deprotonated compound with formula CpA(')-(CH2)n-Ar-X; (ii) contacting the deprotonated compound with a substitution reagent to form a substituted compound with formula CpA-(CH2)n-Ar-Rx; and (iii) contacting the substituted compound with a second compound with formula CpB-M-X3 to form a metallocene compound with formula (I): Rx^Ar ^χ1 M Cpb / \2(I).

[0033] Generally, as represented in formula (I) and defined below, each M can be Zr, Ti or Hf; X can be a halogen or NRy2; X1 and X2 can each independently be a monoanionic ligand; CpA can be a cyclopentadienyl, indenyl or fluorenyl group, optionally substituted by one or more other substituents; CpB can be a substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl group; Ar can be an aryl group comprising a halogen substituent; Rx can be a C1 to C18 hydrocarbyl group substituent on Ar (for example, selected from alkyl or alkenyl or aryl; a phenyl group, a benzyl group, a C1 to C8 alkyl group or a C3 to C8 alkenyl group); en can be an integer from 0 to 5. However, it will be understood that the methods for the preparation of metallocene compounds disclosed in this document can be applied to any metallocene as described below in this document.Furthermore, it follows that the first compound and the second compound may be any combination of the formula components listed above suitable for the preparation of any metallocene compound. Petition 870250087486, dated 09 / 26 / 2025, page 94 / 166 12 / 73

[0034] The processes disclosed in this document may comprise the deprotonation of a first compound comprising a cyclopentadienyl moiety (CpA as described above) by contact of the first compound with a Bronsted base. In the first compound, X may be a halogen or NRy; alternatively, X may be Cl; alternatively, X may be Br; alternatively, X may be F.In certain respects, each Ry may independently be a C1 to C8 hydrocarbyl group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group; alternatively, a methyl group, an ethyl group, a butyl group, a hexyl group, an octyl group; alternatively, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an iso-butyl group, an n-hexyl group or an n-octyl group; alternatively, a methyl group, an ethyl group, an n-butyl group or an iso-butyl group; alternatively, a methyl group; alternatively, an ethyl group; alternatively, an n-propyl group. Alternatively, an n-butyl group; alternatively, an isobutyl group; Alternatively, an n-hexyl group; or alternatively, an n-octyl group.

[0035] In the first compound (Cp-(CH2)n-Ar-X), Ar can also be additionally substituted, for example, by any additional number of halogen substituents. In certain respects, the Ar group of Cp-(CH2)n-Ar-X as described above may have one or more additional substituents besides those present in the formula (for example, one halogen substituent or two halogen substituents or three halogen substituents or four halogen substituents). In certain respects, each halogen substituent may be F. Thus, the Ar group of the first compound may comprise one F, or two F, or three F, or four F, or 5 F, arranged in any position of Ar. In certain respects, the first compound may comprise Ar as a 2,6-difluoroaryl group, a 2,4,6-trifluoroaryl group, a 2,3,4,5,6-pentafluoroyl group, a 4-fluoroaryl group, and so forth.Suitable Brønsted bases can generally be defined as, and include, any compound that is capable of accepting a proton from the first compound. Thus, in the context of... Petition 870250087486, dated 09 / 26 / 2025, p. 95 / 166 13 / 73 modalities contemplated in this document, the Bronsted base can be any species or compound capable of accepting or abstracting a proton from the cyclopentadienyl moiety of the first compound (CpA). Although not limited by theory, given that cyclopentadiene has a pKa of about 15, in certain respects, suitable Bronsted bases can generally include those that have a conjugate acid with a pKa of about 15 or above. In certain respects, the Bronsted base can be a metal carbonate, a metal acetylide, a t-butoxide salt, an enolate, a metal hydride, a metal amide, an organolithium or organomagnesium halide, and the like. Of these, organolithium and organomagnesium halides can be more practically applied in the preparation of certain metallocene compounds, given their hydrophobicity and solubility in organic solvents.

[0036] In certain respects, the Bronsted base may comprise an organolithium compound or organomagnesium compound selected from ethyl lithium, n-butyl lithium, t-butyl lithium, n-hexyl lithium, benzyl lithium, phenyl lithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, isopropylmagnesium chloride, t-butyl magnesium chloride, vinylmagnesium bromide, allylmagnesium bromide, ethinylmagnesium chloride, phenylmagnesium chloride, benzylmagnesium chloride and combinations thereof. In certain respects, the Bronsted base may comprise methyl lithium, n-butyl lithium, t-butyl lithium, n-hexyllithium, phenyllithium and / or benzyl lithium. In other respects, the Bronsted base may comprise methyllithium, n-butyllithium, and / or n-hexyllithium.

[0037] The processes disclosed in this document may also involve contacting the deprotonated compound with a substitution reagent to form a substituted compound with the formula CpA-(CH2)nAr-RxO. The substitution reagent may be any reagent sufficiently reactive (e.g., sufficiently nucleophilic) to displace X with an Rx group as defined in this document. In certain respects, the substitution reagent may comprise an organolithium compound or an organomagnesium halide. Thus, with regard to the Bronsted bases listed above, in certain Petition 870250087486, dated 09 / 26 / 2025, page 96 / 166 14 / 73 aspects, the replacement reagent may comprise methyl-lithium, ethyl-lithium, n-butyl-lithium, t-butyl-lithium, n-hexyl-lithium, benzyl-lithium, phenyl-lithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, isopropylmagnesium chloride, t-butylmagnesium chloride, vinylmagnesium bromide, allylmagnesium bromide, ethinylmagnesium chloride, phenylmagnesium chloride, benzylmagnesium chloride and the like, as well as combinations thereof.

[0038] In certain respects, the replacement reagent may be the same as the Bronsted base. Additionally, or alternatively, the Bronsted base and the replacement reagent may each comprise an organolithium reagent. In certain respects, each Bronsted base and replacement reagent may comprise methyllithium, n-butyllithium, n-hexyllithium, or combinations thereof.

[0039] Deprotonation and substitution reactions can be carried out in situ, without requiring the deprotonated compound to be isolated as an intermediate before contact with a substitution reagent. Thus, in certain respects, the contact of the first compound with a Bronsted base and the contact of the deprotonated compound with a substitution reagent can occur in a concerted manner, by the addition of two equivalents of an organolithium and / or organomagnesium halide within a one-pot synthesis. In such respects, it will be understood that the organolithium and / or organomagnesium halide constitutes both the Bronsted base and the substitution reagent.

[0040] In any given matter, the molar ratio of the Bronsted base to the first compound may be in the range of 0.9:1 to 1.3:1. The molar ratio of the replacement reagent to the first compound may also be in the range of 0.9:1 to 1.3:1, in aspects where mono-substitution of the first compound is desired. When multiple substitutions of the first compound are desired, the ratio of the replacement reagent to the first compound may approach the appropriate multiple. For example, when a di-substitution is desired, the molar ratio of the replacement reagent to the first compound may be in the range of 1.7:1 to 2.3:1. Alternatively, Petition 870250087486, dated 09 / 26 / 2025, page 97 / 166 15 / 73 When a tri-substitution of the first compound is desired, the molar ratio of the replacement reagent to the first compound can be in the range of 2.7:1 to 3.3:1. Of course, when the Bronsted base and the replacement reagent are the same, the respective appropriate ratios of the reagent to the first compound can be obtained by summing the typical ratios for each compound. For example, an organolithium reagent can be used as both the Bronsted base and the replacement reagent, so that a molar ratio of organolithium reagent to the first compound can be in the range of 1.9:1 to 2.6:1, in certain respects, such as when monosubstitution of the first compound is desired.

[0041] Without being limited by theory, where the Bronsted base and the replacement reagent are added simultaneously (for example, when the Bronsted base and the replacement reagent are added as two equivalents of an organolithium reagent), the relative reaction rate of the deprotonation and substitution reactions, as described, may allow deprotonation to proceed before substitution, generating a particular substituted product in high yield. Still, it will be understood that the deprotonation and substitution steps may be conducted in any order, or simultaneously.

[0042] The conditions of the substitution and deprotonation steps may be the same or different. In certain respects, a deprotection temperature may be in the range of -78 °C to 25 °C, -40 °C to 0 °C, or -30 °C to -10 °C. Similarly, in other respects, the substitution temperature may also be in the range of -78 °C to 25 °C, -40 °C to 0 °C, or -30 °C to -10 °C. The reaction temperature may be static or dynamic throughout the reaction, within any range disclosed in this document. For example, deprotonation may start at -20 °C and be allowed to heat up to 25 °C throughout the reaction.

[0043] The deprotonation and substitution steps can proceed for any amount of time required for the reaction. Petition 870250087486, dated 09 / 26 / 2025, p. 98 / 166 16 / 73 is sufficiently complete. In certain respects, the reaction time for one or both of the deprotonation and replacement steps may be in the range of 1 minute to 1 day, or 12 to 24 hours. metallocene compounds

[0044] Metallocene compounds prepared according to the above methods can be any that can be produced by organosubstitution of a labile aryl group (e.g., an aryl halide). Generally, the metallocene compounds disclosed in this document can be substitution products of known metallocene compounds with an established utility in catalyst compositions. More specifically, in certain aspects, the substituent can be observed on an aryl ring of the cyclopentadienyl-containing ligand, for example, an indenyl ligand containing at least one halogenated substituent, such that a labile group is substituted by a hydrophobic organic substituent. In this way, the metallocene compounds disclosed in this document can generally have improved solubility in hydrophobic solvents.Surprisingly, in certain respects, organo-substitution in this region of the metallocene compound does not appreciably diminish the catalytic properties of the metallocene, generally resulting in similar catalytic activity and similar product characteristics in oligomerization and polymerization processes (e.g., oligomer distribution, polymer molecular weight distribution).

[0045] As stated generally above, the metallocene compounds disclosed in this document may have Formula (I): Rx^Ar χΐ M cX \2(I).

[0046] Within formula (I), M, CpA, CpB, Ar, Rx, X1 and X2 are, each Petition 870250087486, dated 09 / 26 / 2025, page 99 / 166 17 / 73 one, independent elements of the unbridged metallocene compound. Therefore, the unbridged metallocene compound with formula (I) can be described using any combination of M, CpA, CpB, Ar, Rx, X1 and X2 disclosed in this document. Unless otherwise specified, formula (I) above, any other structural formulas disclosed in this document and any metallocene complex, compound or species disclosed in this document are not designed to show the stereochemistry or isomeric positioning of the different fractions (e.g., these formulas are not intended to exhibit cis or trans isomers or R or S diastereomers), although such compounds are contemplated and encompassed by these formulas and / or structures.

[0047] According to aspects of this invention, the metal in formula (I), M, can be Zr, Ti or Hf. Thus, M can be Zr in one aspect, M can be Ti in another aspect and M can be Hf in yet another aspect.

[0048] X1 and X2, each independently, may be a monoanionic ligand. In some respects, suitable monoanionic ligands may include, among others, H (hydride), BH4, a halide, a C1 to C36 hydrocarbyl group, a C1 to C36 hydrocarboxy group, a C1 to C36 hydrocarbylaminyl group, a C1 to C36 hydrocarbysilyl group, a C1 to C36 hydrocarbylaminylsilyl group, -OBR12 or -OSO2R1, wherein R1 is a C1 to C36 hydrocarbyl group. It is contemplated that X1 and X2 may be the same or a different monoanionic ligand. Suitable hydrocarbyl groups, hydrocarboxy groups, hydrocarbylaminyl groups, hydrocarbysilyl groups and hydrocarbylaminylsilyl groups are disclosed, for example, in U.S. Patent No. 9,758,600.

[0049] In formula (I), CpA may be a cyclopentadienyl, indenyl, or fluorenyl group; either substituted, as shown, or additionally substituted, where each additional substituent may be H, a halide, a C1 to C36 hydrocarbyl group, a halogenated C1 to C36 hydrocarbyl group, a C1 to C36 hydrocarboxy group, or a C1 to C36 hydrocarbysilyl group. Importantly, each substituent in CpA may be the same substituent group or a different one. Petition 870250087486, dated 09 / 26 / 2025, pp. 100 / 166 Λ8Γ73 Furthermore, each substituent can be in any position in the respective cyclopentadienyl, indenyl, or fluorenyl ring structure that conforms to the rules of chemical valence. In one aspect, the number of substituents in CpA and / or the positions of each substituent in CpA are independent of each other. For example, two or more substituents in CpA may be different, or alternatively, each substituent in CpA may be the same. In these and other aspects, each substituent can be in any position in the respective cyclopentadienyl, indenyl, or fluorenyl ring structure. Therefore, CpA can have one substituent, or two substituents, or three substituents, or four substituents, or five substituents, and so on. In certain aspects, CpA can have a C1-C12 alkyl, C2-C12 alkenyl, C6-C10 aryl, or C7-C12 aralkyl (e.g., benzyl) substituent.

[0050] In formula (I), CpB can be a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group. In one aspect, CpA and CpB independently can be an unsubstituted cyclopentadienyl or indenyl group. Alternatively, CpA and CpB independently can be a substituted indenyl or cyclopentadienyl group, for example, with up to 5 substituents. CpA and CpB can be the same or different. In certain aspects, CpA can be an indenyl group and CpB can be a cyclopentadienyl group.

[0051] If present, each substituent in CpB can independently be H, a halide, a C1 to C36 hydrocarbyl group, a C1 to C36 halogenated hydrocarbyl group, a C1 to C36 hydrocarboxy group, or a C1 to C36 hydrocarbysilyl group. As above for CpA, each substituent in CpB can be the same substituent group or a different substituent group. Furthermore, each substituent can be in any position in the respective cyclopentadienyl, indenyl, or fluorenyl ring structure that conforms to the rules of chemical valence. In one respect, the number of substituents in CpBe / or the positions of each substituent in CpB are independent of each other. For example, two or more substituents in CpB can be different or, alternatively, all substituents in CpB can be the same. In another Petition 870250087486, dated 09 / 26 / 2025, pp. 101 / 166 19 / 73 aspect, one or more substituents on CpA may be different from one or more substituents on CpB or, alternatively, all substituents on CpA and / or CpB may be the same. In these and other aspects, each substituent may be in any position in the respective cyclopentadienyl, indenyl or fluorenyl ring structure. If substituted, CpB may independently have one substituent or two substituents or three substituents or four substituents or five substituents and so forth. As above for CpA, in certain aspects, CpB may have a C1-C12 alkyl, C2-C12 alkenyl, C6-C10 aryl or C7-C12 aralkyl (e.g., benzyl) substituent. CpB may also be substituted similarly to CpA as represented in Formula (I). Thus, in certain respects, CpB may have the substituent -(CH2)nArRx. Alternatively, CpB may be unsubstituted.

[0052] In certain aspects, Ar may be an aryl hydrocarbon group. In one aspect, the aromatic ring, Ar, of the metallocene compound may be a C5 to C30 aromatic group or, alternatively, a C5 to C20 aromatic group. In other aspects, Ar may be a heteroaryl group, for example, pyrrolidinyl, pyrrolinyl, furanyl, thiopheneyl, imidazoleyl, oxazolyl, thiazoleyl, indoyl, pyridinayl, pyrazinyl, isoxazolyl, pyrazoleyl, pyrroleyl, isothiazolyl, oxadiazoleyl, triazolyl, indoyl, carbazolyl, benzofuranyl or benzothiopheneyl.

[0053] In aspects disclosed in this document, Ar can be replaced at least by Rx, which can generally represent the aryl organosubstituent added by the replacement reagent in processes disclosed above. Thus, in certain aspects, Rx can be any nucleophilic moiety within the replacement reagents disclosed above. For example, when the replacement reagent is methyllithium, Rx can be a methyl group. In aspects where the replacement reagent is phenylmagnesium chloride, Rx can be a phenyl group. In other aspects, Rx can be a C1 to C18 hydrocarbyl group substituent (for example, selected from alkyl or alkenyl or aryl; a phenyl group, a benzyl group, a C1 to C8 alkyl group or a C3 to C8 alkenyl group). In still other aspects, Rx can be selected Petition 870250087486, dated 09 / 26 / 2025, pp. 102 / 166 20 / 73 from among methyl, ethyl, n-butyl, t-butyl, n-hexyl, benzyl, phenyl, vinyl, allyl and ethinyl. In other respects, Rx can be selected from among substituted or unsubstituted methyl, ethyl, n-propyl, n-butyl, sec-butyl, t-butyl, 3-butenyl, n-hexyl and phenyl.

[0054] Ar can have one Rx substituent, or two Rx substituents, or three Rx substituents, or four Rx substituents, and so on, as appropriate according to the size of the Ar group as discussed above. For example, where Ar is phenyl, the metallocene compound can have up to five Rx substituents. As stated above, Rx can be substituted at any position of Ar and therefore, in some non-limiting respects, Ar-Rx can be a 2-Rx-phenyl group, a 4-Rx-phenyl group, a 2,6-di-Rx-phenyl group, or a 2,4,6-tri-Rx-phenyl group.

[0055] Ar may also be further substituted, for example, by any appropriate number of halogen substituents. In certain aspects, Ar may be substituted by one or more Rx as described above and may further comprise one or more substituents (for example, one halogen substituent or two halogen substituents or three halogen substituents or four halogen substituents). In such aspects, each halogen substituent may be F. Thus, Ar-Rx may be further substituted by one F, or two F, or three F, or four F and any position of Ar. In certain aspects, Ar-Rx may be a 2,6-difluoro-4-Rx-aryl group, a 2,3,5,6-tetrafluoro-4-Rx-aryl group, a 2-6-di-Rx-4-fluoroaryl group and so forth, including those represented as below: Petition 870250087486, dated 09 / 26 / 2025, pp. 103 / 166 21 / 73

[0056] Metallocene compounds may also comprise a hydrocarbon ligand between the Ar and CpA groups as represented in Formula (I) as -(CH2)n- The length of the hydrocarbon ligand is not limited to any particular length and thus, in certain respects, n may be an integer in a range from 0 to 5 (e.g., 0, 1, 2, 3, 4, or 5). In certain respects, n may be 0. In other respects, n may be 1.

[0057] Illustrative and non-limiting examples of unbridged metallocene compounds with formula (I) and / or that can be prepared according to methods described in this document may, in certain respects, include the following substituted 4-metallocene compounds: MET-E Similar MET-F, 2- and 6-monosubstituted analogs of MET-B via MET-F, disubstituted and trisubstituted analogs, and combinations thereof. Additional metallocenes with alternative arrangements of Rx and halide substituents, as represented above, are also contemplated in this document, as would be understood by those skilled in the art.

[0058] As discussed above, substitutions of aryl halogens (e.g., Ar substituents) with a hydrophobic organic substituent (e.g., Rx) are surprisingly shown to improve the Petition 870250087486, dated 09 / 26 / 2025, pp. 104 / 166 22 / 73 solubility of the metallocene compound without causing significant variation in the catalytic activity or in the properties of oligomer and polymer products formed by the respective oligomerization and polymerization processes employing catalyst compositions comprising the metallocene compounds. In certain aspects, the metallocene compounds, as described in this document, may have a solubility at 25°C in 1-decene of at least 0.01% by weight, at least 0.05% by weight, or at least 0.1% by weight, or at least 0.2% by weight. In other respects, the metallocene compounds disclosed in this document may have a solubility at 25 °C in 1-decene in a range of 0.01 wt% to 2 wt%, 0.1 wt% to 1 wt%, 0.1 wt% to 0.5 wt%, 0.2 wt% to 1 wt%, or 0.2 wt% to 0.5 wt%.

[0059] The solubility of metallocene compounds can also be measured relative to metallocenes without the substitution of Rx₀ with an F in their place. In certain respects, metallocene compounds may have a solubility at 25 °C in 1-decene at least 10% greater than, at least 25% greater than, at least 50% greater than, at least 100% greater than, or at least three times greater than that of an otherwise identical metallocene compound in which each Rx₀ is F. In other respects, metallocene compounds may have a solubility at 25 °C in 1-decene in a range of 50% to 500% greater or 100% to 300% greater than that of an otherwise identical metallocene compound in which each Rx₀ is F. CATALYST COMPOSITIONS

[0060] According to aspects of the present invention, the metallocene compounds disclosed in this document can be employed within catalyst compositions, for example, for oligomerization and polymerization processes as described below.

[0061] Generally, the catalyst compositions disclosed in this document may comprise any of the above metallocene compounds, an activator and, optionally, a cocatalyst. In certain Petition 870250087486, dated 09 / 26 / 2025, pp. 105 / 166 23 / 73 aspects, the activator may comprise an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, a chemically treated solid oxide, or a combination thereof. When the activator in the catalyst composition is a chemically treated solid oxide (activator), then aluminoxane, organoboron or organoborate, and ionizing ionic materials, if present, are referred to as cocatalysts. In certain aspects, one or more of a metallocene compound, activator, or cocatalyst may be present in the catalyst composition. For example, catalyst compositions may further comprise a second metallocene compound (e.g., a bridging metallocene).

[0062] Aluminoxanes that may serve as activators (and cocatalysts) in this disclosure are generally represented by formulas such as (R3—Al—O)n, R3(R3—Al—O)nAl(R3)2 and the like, wherein the R3 group is typically a linear or branched C1-C6 alkyl, such as methyl, ethyl, propyl, butyl, pentyl or hexyl, wherein n typically represents an integer from 1 to 50. In one aspect, the aluminoxane compound used in the disclosed catalyst composition may include, among others, methylaluminoxane (MAO), ethylaluminoxane, modified methylaluminoxane (MMAO), such as an isobutyl-modified methylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, n-butylaluminoxane, t-butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane, t-butylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, iso-pentylaluminoxane, neopentylaluminoxane, or combinations thereof.

[0063] While aluminoxanes with different types of R groups, such as R3, are covered by this disclosure, methyl aluminoxane (MAO), ethyl aluminoxane, or isobutyl aluminoxane are typical aluminoxane activators used in the catalyst compositions of this disclosure. These aluminoxanes are prepared from trimethylaluminum, triethylaluminum, or triisobutylaluminum, respectively, and are sometimes referred to as poly(methylaluminum oxide), poly(ethylaluminum oxide), and poly(isobutylaluminum oxide), respectively. Petition 870250087486, dated 09 / 26 / 2025, pp. 106 / 166 24 / 73 It is also within the scope of the disclosure to use an aluminoxane in combination with a trialkylaluminum, as disclosed in U.S. Patent No. 4,794,096.

[0064] The organoboron compounds that can be used in the catalyst composition of this disclosure are similarly varied. In one aspect, the organoboron compound may comprise neutral boron compounds, borate salts, or combinations thereof. For example, the organoboron compounds of this disclosure may comprise a fluoroorganoboron compound, a fluoroorganoborate compound, or a combination thereof. Any fluoroorganoboron or fluoroorganoborate compound known in the art may be used. The term fluoroorganoboron compound has its usual meaning to refer to neutral compounds of the form BY3. The term fluoroorganoborate compound also has its usual meaning to refer to monoanionic salts of a fluoroorganoboron compound of the form [cation]+[BY4]-, where Y represents a fluorinated organic group.For convenience, fluoroorganoboric compounds and fluoroorganoborate compounds are typically referred to collectively as organoboron and organoborate compounds, or by any name as the context requires.

[0065] Examples of organoboron or organoborate compounds that can be used as activators in the present disclosure include, among others, fluorinated aryl borates, such as N,N-dimethylaniline tetrakis(pentafluorophenyl)borate (DTPB), triphenylcarbenium tetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)borate, N,N-dimethylaniline tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate and the like, including mixtures thereof; alternatively, N,N-dimethylaniline tetrakis-(pentafluorophenyl)borate (DTBP); alternatively, triphenylcarbenium tetrakis(pentafluorophenyl)borate; alternatively, lithium tetrakis(pentafluorophenyl)borate; Alternatively, N,N-dimethylaniline tetrakis[3,5-bis(trifluoromethyl)phenyl]borate; or alternatively, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate. Other activators of Petition 870250087486, dated 09 / 26 / 2025, pp. 107 / 166 25 / 73 Suitable organoboron or organoborate compounds include, among others, tris(pentafluorophenyl)-boron, tris[3,5-bis(trifluoromethyl)phenyl]boron and the like, including mixtures thereof.

[0066] Although not intended to be limited by the following theory, it is believed that these examples of organoboron and organoborate compounds and related compounds form weak coordination anions when combined with organometallic compounds, as disclosed in U.S. Pat. No. 5,919,983.

[0067] An ionizing ionic compound is an ionic compound that can function to enhance the activity of the catalyst composition. Examples of ionizing ionic compounds that may be suitable as activators in catalyst compositions disclosed in this document include, but are not limited to, the following compounds: tri(n-butyl)ammonium tetrakis(p-tolyl)borate, tri(n-butyl)ammonium tetrakis(m-tolyl)borate, tri(n-butyl)ammonium tetrakis(2,4-dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylaniline tetrakis(p-tolyl)borate, N,N-dimethylaniline tetrakis(m-tolyl)borate, N,N-dimethylaniline tetrakis(2,4-dimethylphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-dimethylphenyl)borate, N,Ndimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,triphenylcarbenium tetrakis(p-tolyl)borate, triphenylcarbenium tetrakis(m-tolyl)borate, triphenylcarbenium tetrakis(2,4-dimethylphenyl)borate, triphenylcarbenium tetrakis(3,5-dimethylphenyl)borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, tropylium tetrakis(p-tolyl)borate, tropylium tetrakis(m-tolyl)borate, tropylium tetrakis(2,4-dimethylphenyl)borate, tropylium tetrakis(3,5-dimethylphenyl)borate, tropylium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tropylium tetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)borate, lithium tetraphenylborate, lithium tetrakis(p-tolyl)borate, lithium tetrakis(m-tolyl)borate, lithium tetrakis(2,4-dimethylphenyl)borate, lithium, Petition 870250087486, dated 09 / 26 / 2025, pp. 108 / 166 26 / 73 tetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodium tetrakis(pentafluorophenyl)borate, sodium tetraphenylborate, sodium tetrakis(ptolyl)borate, sodium tetrakis(m-tolyl)borate, sodium tetrakis(2,4-dimethylphenyl)borate, sodium tetrakis(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassium tetrakis(pentafluorophenyl)borate, potassium tetraphenylborate, potassium tetrakis(ptolyl)borate, potassium tetrakis(m-tolyl)borate, potassium tetrakis(2,4-dimethylphenyl)borate, potassium tetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoroborate, lithium tetrakis(pentafluorophenyl)aluminate, lithium tetraphenylaluminate, lithium tetrakis(p-tolyl)aluminate, lithium tetrakis(m-tolyl)aluminate, lithium tetrakis(2,4-dimethylphenyl)aluminate, lithium tetrakis(3,5-dimethylphenyl)aluminate, lithium tetrafluoroaluminate, sodium tetrakis(pentafluorophenyl)aluminate, sodium tetraphenylaluminate, sodium tetrakis(ptolyl)aluminate, sodium tetrakis(m-tolyl)aluminate, sodium tetrakis(2,4-dimethylphenyl)aluminate,Sodium tetrakis(3,5-dimethylphenyl)aluminate, sodium tetrafluoroaluminate, potassium tetrakis(pentafluorophenyl)aluminate, potassium tetraphenylaluminate, potassium tetrakis(p-tolyl)aluminate, potassium tetrakis(mtolyl)aluminate, potassium tetrakis(2,4-dimethylphenyl)aluminate, potassium tetrakis(3,5-dimethylphenyl)aluminate, potassium tetrafluoroaluminate and the like or combinations thereof. Additional examples and descriptions of ionizing ionic compounds are generally disclosed throughout U.S. Patent 11,186,665.

[0068] Chemically treated solid oxides are also suitable activators in the disclosed catalyst compositions. In certain respects, the chemically treated solid oxides described in this document may generally refer to those disclosed, for example, in U.S. Patent Nos. 8,536,391 and 10,919,996. In certain respects, the chemically treated solid oxide may comprise a solid oxide comprising oxygen and at least one element selected from Group 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 of the periodic table, or comprise oxygen and at least one element selected from the lanthanide or actinide elements; Petition 870250087486, dated 09 / 26 / 2025, pp. 109 / 166 27 / 73 Alternatively, the solid oxide may comprise oxygen and at least one element selected from Group 4, 5, 6, 12, 13, or 14 of the periodic table, or it may comprise oxygen and at least one element selected from the lanthanide elements. (See: Hawley's Condensed Chemical Dictionary, 11th Ed., John Wiley & Sons; 1995; Cotton, FA; Wilkinson, G.; Murillo; CA; and Bochmann; M. Advanced Inorganic Chemistry, 6th Ed., Wiley-Interscience, 1999.) In some respects, the inorganic oxide may comprise oxygen and at least one element selected from Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn, or Zr; Alternatively, the inorganic oxide may comprise oxygen and at least one element selected from Al, B, Si, Ti, P, Zn, or Zr.

[0069] In certain aspects, the chemically treated solid oxide may comprise a solid oxide comprising Al2O3, B2O3, BeO, Bi2O3, CdO, CO3O4, Cr2O3, CuO, Fe2O3, Ga2O3, La2O3, Mn2O3, MoO3, NiO, P2O5, Sb2O5, SiO2, SnO2, SrO, ThO2, TiO2, V2O5, WO3, Y2O3, ZnO, ZrO2, mixed oxides thereof and combinations thereof. In certain aspects, the solid oxide may comprise silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, zirconia, magnesia, boron, zinc oxide, a mixed oxide thereof or any combination thereof. In other respects, solid oxides may comprise alumina coated with silica.

[0070] In certain respects, the chemically treated solid oxide may comprise a solid oxide treated with at least one electron-withdrawing anion, wherein the solid oxide may comprise any oxide that is characterized by a high surface area and the electron-withdrawing anion may comprise any anion that increases the acidity of the solid oxide compared with the solid oxide that is not treated with at least one electron-withdrawing anion.

[0071] The solid oxide material can be treated with a halide ion source, sulfate ion source, or a combination thereof and, optionally, Petition 870250087486, dated 09 / 26 / 2025, pp. 110 / 166 28 / 73 treated with a metallic ion. In one aspect, the solid oxide material may be treated with a sulfate source (called a sulfate-sparing agent), a phosphate source (called a phosphating agent), an iodide ion source (called an iodizing agent), a bromide ion source (called a brominating agent), a chloride ion source (called a chlorinating agent), a fluoride ion source (called a fluorinating agent), or any combination thereof, and calcined to provide the chemically treated solid oxide.

[0072] In certain respects, the chemically treated solid oxide may comprise a solid oxide treated with an electron-removing anion, wherein the solid oxide is selected from silica, alumina, silica-alumina, aluminum phosphate, heteropolytungstates, titania, zirconia, magnesia, boron, zinc oxide, mixed oxides thereof or mixtures thereof and the electron-removing anion is selected from fluoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate, fluorophosphate, fluorosulfate or any combination thereof.Thus, in certain respects, the chemically treated solid oxide may comprise fluorinated alumina, chloride alumina, brominated alumina, sulfated alumina, fluorinated silica-alumina, chloride silica-alumina, brominated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, chloride silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, alumina coated with fluorinated silica, alumina coated with fluorinated-chlorinated silica, alumina coated with sulfated silica, alumina coated with phosphated silica, or any combination thereof. In certain respects, the chemically treated solid oxide may comprise fluorinated alumina, sulfated alumina, fluorinated silica-alumina, sulfated silica-alumina, alumina coated with fluorinated silica, alumina coated with fluorinated-chlorinated silica, alumina coated with sulfated silica, or any combination thereof.In other respects, the chemically treated solid oxide may comprise sulfated alumina and / or alumina coated with fluorinated silica. Petition 870250087486, dated 09 / 26 / 2025, pp. 111 / 166 29 / 73

[0073] In certain aspects, the chemically treated solid oxides disclosed in this document may comprise a calcined solid oxide. Thus, in this aspect, the solid oxide may be calcined or uncalcined; alternatively, calcined; or alternatively, uncalcined. In certain aspects, the solid oxide may be calcined before, during, or after the solid oxide compound is brought into contact with the electron-removing anion source, resulting in the chemically treated solid oxide. The calcination of the treated solid oxide is generally conducted in an ambient atmosphere; alternatively, in a dry ambient atmosphere. The solid oxide may be calcined at a temperature of 200 °C to 900 °C; alternatively, from 300 °C to 800 °C; alternatively, from 400 °C to 700 °C; or alternatively, from 350 °C to 550 °C.The time period during which the solid oxide is held at the calcination temperature can be from 1 minute to 100 hours; alternatively, from 1 hour to 50 hours; alternatively, from 3 hours to 20 hours; or alternatively, from 1 to 10 hours.

[0074] In certain aspects disclosed in this document, the catalyst composition may further comprise a cocatalyst. In certain aspects, the cocatalyst may comprise an organoaluminum compound, an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or a combination thereof; alternatively, the cocatalyst may comprise an organoaluminum compound. In one aspect, suitable organoaluminum compounds may have the formula (RZ)3Al, wherein each RZ may independently be an aliphatic group with 1 to 10 carbon atoms. For example, each RZ may independently be methyl, ethyl, propyl, butyl, hexyl, or isobutyl. In another aspect, examples of suitable organoaluminum compounds for use according to the present invention may include, among others, trialkylaluminum compounds, dialkylaluminum halide compounds, dialkylaluminum hydride compounds, as well as combinations thereof.Specific, but not limiting, examples of suitable organoaluminum compounds may be provided. Petition 870250087486, dated 09 / 26 / 2025, pp. 112 / 166 30 / 73 include trimethylaluminum (TMA), triethylaluminum (TEA), tri-n-propylaluminum (TNPA), tri-n-butylaluminum (TNBA), tri-isobutylaluminum (TIBA), tri-n-hexylaluminum, tri-noctylaluminum, (TNOA) and the like, or combinations thereof.

[0075] Generally, the organoaluminum compound (or other cocatalyst) may be used in any suitable amount relative to the metallocene compound. In certain respects, a molar ratio of cocatalyst to metallocene compound in the catalyst composition may be in a range of 0.1:1 to 100,000:1, 1:1 to 10,000:1, 10:1 to 1,000:1, or 50:1 to 500:1. The catalyst compositions disclosed in this document may also be characterized according to the weight ratio of the metallocene compound to the activator, which in certain respects may be in a range of 1:10 to 1:10,000, 1:10 to 1:1,000, 1:10 to 500:1, or 1:10 to 1:100.

[0076] In another aspect of the present invention, a catalyst composition may be substantially free of aluminoxane, organoboron or organoborate compounds, ionizing ionic compounds and / or other similar materials; alternatively, substantially free of aluminoxanes; alternatively, substantially free of organoboron or organoborate compounds; or alternatively, substantially free of ionizing ionic compounds. In these aspects, the catalyst composition has catalyst activity, discussed in this document, in the absence of these additional materials. For example, a catalyst composition of the present invention may consist essentially of a metallocene, an activator and an organoaluminum compound, wherein no other materials are present in the catalyst composition that would increase / decrease the activity of the catalyst composition by more than 10% of the catalyst activity of the catalyst composition in the absence of said materials.

[0077] The catalyst compositions of the present invention generally have a catalyst activity greater than about 250 grams of ethylene polymer (homopolymer and / or copolymer, as the context requires) per gram of activator support per hour (abbreviated as g / (g*h)). In another Petition 870250087486, dated 09 / 26 / 2025, pp. 113 / 166 31 / 73 aspect, catalyst activity can be greater than 350, greater than 450, or greater than 550 g / (g*h). However, in another aspect, catalyst activity can be greater than 700 g / (g*h), greater than 1000 g / (g*h), or greater than 2000 g / (g*h), and often as high as 5000-10,000 g / (g*h). Illustrative and non-limiting ranges for catalyst activity include 500 to 5000, 750 to 4000, or 1000 to 3500 g / (g*h) and similar ranges. In certain aspects, the activities mentioned above can be obtained under flow paste polymerization conditions, with a tri-isobutylaluminum cocatalyst, using isobutane as the diluent at a polymerization temperature of 80°C and a reactor pressure of 320 psig. Furthermore, in some aspects, the activator support may comprise sulfated alumina, fluorinated silica-alumina, or silica-coated fluorinated alumina, although not limited to these. OLIGOMERIZATION PROCESSES

[0078] The processes disclosed in this document may involve contacting any catalyst composition disclosed in this document with an alpha olefin monomer and, optionally, H2 under oligomerization conditions to produce an oligomer product.

[0079] A wide range of alpha-olefin monomers can be reacted in the processes provided in this document. For example, the alpha olefin may comprise, consist essentially of, or consist of a C4 to C30 alpha olefin; alternatively, a C4 to C18 alpha olefin; alternatively, a C4 to C14 alpha olefin; alternatively, a C5 to C18 alpha olefin; alternatively, a C6 to C16 alpha olefin; or alternatively, a C8 to C12 alpha olefin. In one aspect, the oligomer product may be produced from an alpha olefin comprising, consisting essentially of, or consisting of, a C6 alpha olefin, a C8 alpha olefin, a C10 alpha olefin, a C12 alpha olefin, a C14 alpha olefin, a C16 alpha olefin, or any combination thereof; Alternatively, a C8 alpha olefin, a C10 alpha olefin, a C12 alpha olefin, or any combination thereof; alternatively, a C6 alpha olefin; alternatively, a C8 alpha olefin; Petition 870250087486, dated 09 / 26 / 2025, pp. 114 / 166 32 / 73 alternatively, a C10 alpha olefin; alternatively, a C12 alpha olefin; alternatively, a C16 alpha olefin; or alternatively, a C18 alpha olefin. In a further aspect, the alpha olefin may comprise, consist essentially of, or consist of 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, or any combination thereof. For example, the alpha olefin may comprise, consist essentially of, or consist of 1-octene; alternatively, 1-decene; or alternatively, 1-dodecene.

[0080] Alpha-olefin monomers can be derived from ethylene produced from fossil-based feedstocks, bio-based feedstocks, or recycled circular feedstocks that are either fossil-based or bio-based. For example, alpha-olefin can be derived from ethylene produced from natural gas feedstocks. Alternatively, alpha-olefin can be derived from ethylene produced from naphtha obtained from crude oil. Alternatively, alpha-olefin can be derived from ethylene produced from ethanol, wherein the ethanol is derived from cellulosic or lignocellulosic feedstocks (i.e., sugarcane, corn, etc.). Alternatively, alpha-olefin can be derived from ethylene produced from recycled plastic materials that have been pyrolyzed to form a circular pyrolysis gas or pyrolysis oil feedstock.When a renewable or circular feedstock is used, the resulting products can be certified as circular or renewable products. Any adequate amount of alpha-olefin feed can be normal alpha-olefin. Generally, alpha-olefin contains at least 50% by weight of normal alpha-olefins and, more frequently, contains at least 60% by weight, at least 70% by weight, at least 80% by weight, at least 85% by weight, at least 90% by weight, at least 92.5% by weight or at least 95% by weight of normal alpha-olefins and, in some respects, less than or equal to 99.9% by weight, less than or equal to 99.5% by weight, less than or equal to 97% by weight or less than or equal to 95% by weight of normal alpha-olefins and, in other respects, a range of. Petition 870250087486, dated 09 / 26 / 2025, pp. 115 / 166 33 / 73 any minimum quantity disclosed in this document to any maximum quantity disclosed in this document of normal alpha olefins, for example, the alpha olefin containing 85% by weight to 95% by weight or 90% by weight to 99% by weight of 1-hexene, 1-octene, 1-decene, 1-dodecene or 1-tetradecene. Thus, mixtures of various alpha-olefins (or normal alpha-olefins) with different numbers of carbon atoms, or alpha-olefins (or normal alpha-olefins) with predominantly a single number of carbon atoms, may be used. Although a mixture of different carbon number olefins may be used, the processes disclosed in this document are particularly suitable for use with alpha olefins (or normal alpha olefins) with a single number of carbon atoms.

[0081] In one aspect, the alpha olefin monomer may be a mixture of C10 mono-olefins comprising 2-butyl-1-hexene, 3-propyl-1-heptene, 4-ethyl-1-octene, 5-methyl-1-nonene, or any combination thereof. In one aspect, the alpha olefin monomer may also contain C14 mono-olefins. In a further aspect, an alpha-olefin feedstock suitable for use in the processes described in this document is described in U.S. Patent No. 10,435,336.

[0082] Certain component ratios can be used to control the oligomerization process. For example, increasing the weight ratio of the metallocene compound in the catalyst composition to the alpha olefin monomer can lead to higher conversion, but can also lead to a heavier mixture of oligomer products (e.g., less of the desirable dimer and trimer products). However, the catalyst composition and the alpha olefin monomer can be brought into contact at a weight ratio of the metallocene compound to the alpha olefin monomer ranging from 1:100 to 1:1,000,000, from 1:1,000 to 1:1,000,000, from 1:1,000 to 1:500,000, or from 1:10,000 to 1:250,000, although not limited to these.

[0083] The catalyst composition activity is relatively high. For example, the activity can be at least 50,000 g oligomer / g Petition 870250087486, dated 09 / 26 / 2025, pp. 116 / 166 34 / 73 of metallocene compound per hour (g / (g*h)) or from 20,000 g / (g*h) to 180,000 g / (g*h), from 40,000 g / (g*h) to 160,000 g / (g*h) or from 60,000 to 120,000 g / (g*h), for example, in aspects where the oligomerization conditions comprise an oligomerization temperature of 110 °C and where the catalyst composition comprises a TIBA cocatalyst.

[0084] As described in this document, the catalyst activities of catalyst compositions may unexpectedly be comparable to or greater than those of identical catalyst compositions comprising a metallocene compound in which each Rx is F, when tested and compared under the same oligomerization conditions. Thus, the disclosed oligomerization processes (or catalyst compositions) may be characterized by a catalyst composition activity that is comparable (e.g., within 20%, 15%, 10% or 5% more or less) to that of an otherwise identical catalyst system comprising a metallocene compound in which each Rx is F, under the same catalyst preparation and oligomerization conditions.

[0085] The oligomerization conditions used in the oligomerization processes may comprise an oligomerization temperature of 10°C to 250°C, 20°C to 180°C, 50°C to 160°C; alternatively, 55°C to 160°C; alternatively, 60°C to 155°C; alternatively, 65°C to 150°C; alternatively, 70°C to 140°C; or alternatively, 75°C to 140°C. In another non-limiting aspect, the oligomerization temperature may vary from 70°C to 90°C; alternatively, 90°C to 120°C; or alternatively, 110°C to 140°C.

[0086] In another non-limiting aspect, the oligomerization conditions used in the oligomerization processes disclosed in this document may include carrying out the oligomerization reaction in the presence of hydrogen. The partial pressure of hydrogen in the oligomerization reaction may be any hydrogen pressure that does not negatively affect the oligomerization reaction. In some non-limiting aspects, Petition 870250087486, dated 09 / 26 / 2025, pp. 117 / 166 35 / 73 Oligomerization conditions may include a partial pressure of hydrogen of at least 0.1 psig and often up to and including a partial pressure of 50 psig. Typical ranges for the partial pressure of hydrogen may include 0.1 psig to 50 psig, 0.1 psig to 20 psig, 0.1 psig to 10 psig, 1 psig to 20 psig, 1 psig to 10 psig, 2 psig to 20 psig, or 2 psig to 10 psig.

[0087] Oligomerization processes may, in certain aspects, further comprise a step of separating at least a portion of the catalyst composition from the oligomer product using any suitable technique, for example, by filtration. Similarly, oligomerization processes may further comprise a step of separating the unreacted alpha-olefin monomer from the oligomer product using any suitable technique, for example, clean film evaporation, distillation, short path distillation, or any combination thereof. Optionally, oligomerization processes may further comprise recycling one or both of the recovered catalyst compositions and the recovered unreacted alpha-olefin monomer, for example, for reuse in oligomerization processes.

[0088] Furthermore, oligomerization processes, in certain aspects, may comprise a step of fractionating the oligomer product into alpha olefin dimer, alpha olefin trimer and alpha olefin heavys (including alpha olefin tetramer and higher oligomers), using any suitable technique, for example, clean film evaporation, distillation, short path distillation or any combination thereof. Similarly, oligomerization processes may further comprise a step of hydrogenating at least a portion of the oligomer product (e.g., alpha olefin trimer) to form a polyalphaolefin. The process of fractionating an oligomer product into various oligomer fractions is generally known and the techniques and conditions for carrying out the fractionation and the subsequent separation, purification and / or hydrogenation steps to transform the oligomer fractions into a polyalphaolefin will be understood Petition 870250087486, dated 09 / 26 / 2025, pp. 118 / 166 36 / 73 by those versed in the technique.

[0089] The oligomer product often contains a dimer of the alpha olefin monomer, a trimer of the alpha olefin monomer, and higher molecular weight oligomers of the alpha olefin monomer (e.g., tetramers and heavy ones). Advantageously, the disclosed oligomerization processes can produce oligomer products with a relatively high number of dimers and trimers that can be useful in subsequent reactions and in the production of polyalphaolefins.

[0090] The oligomer product formed by oligomerization processes can therefore be characterized by the relative amount of specific oligomers. For example, it may be beneficial to maximize the amount of dimer and trimer while minimizing the heavier oligomers in the oligomer product. Surprisingly, oligomerization processes are capable of operating at high conversions of the alpha olefin monomer without causing a shift in the resulting oligomer product towards heavier oligomers. In certain respects, the oligomer product may comprise less than or equal to 20 mol%, less than or equal to 15 mol%, less than or equal to 10 mol%, or less than or equal to 5 mol% of tetramer. Additionally, or alternatively, the oligomer product may comprise at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 85 mol%, at least 90 mol%, or at least 95 mol% of dimer and trimer (total).The unreacted alpha-olefin monomer is excluded from the oligomer product decomposition.

[0091] In certain respects, and beneficially, the dimer may be the major component of the oligomer product and the oligomer product may contain at least 30 mol%, at least 40 mol%, at least 50 mol%, at least 55 mol%, at least 60 mol%, at least 65 mol%, at least 70 mol% or at least 75 mol% of alpha olefin dimer, based on the total oligomers in the oligomer product and excluding unreacted alpha olefin monomer. Petition 870250087486, dated 09 / 26 / 2025, pp. 119 / 166 37 / 73

[0092] Vinylidene is often desirable because of its high reactivity with respect to internal and branched dimers of the alpha-olefin monomer. In certain respects, the dimer in the oligomer product comprises at least 50 mol%, at least 60 mol%, at least 70 mol%, at least 75 mol%, at least 80 mol%, at least 85 mol%, at least 90 mol%, or at least 95 mol% vinylidene. It follows, then, that the amount of internal olefin within the dimer portion of the oligomer product can generally be less than or equal to 15 mol%, less than or equal to 12 mol%, or less than or equal to 10 mol%.

[0093] Regarding the activity of the catalyst composition described above, the product characteristics of the oligomerization processes disclosed in this document can be compared to oligomerization processes that rely on analogous metallocene compounds without the Rx substituent. Thus, in certain respects, the oligomer product may have a dimer content and character (e.g., an amount of internal dimer, trisubstituted dimer and / or vinylidene dimer in the dimer product) that is comparable (e.g., within 20%, 15%, 10% or 5% more or less) to that of an otherwise identical catalyst system comprising a metallocene compound in which each Rx is F, under the same catalyst preparation and oligomerization conditions.

[0094] Polyalphaolefins can have certain desirable properties. For example, a desirable property that can be achieved using a separation step or steps is a kinematic viscosity of 100 °C. A second desirable property that can be achieved using a separation step or steps is achieving a desired flash point. A third desirable property that can be achieved using a separation step or steps is achieving a desired ignition point. A fourth desirable property that can be achieved using a separation step or steps is achieving a desired noack volatility. A fifth desirable property that can be achieved using a separation step or steps is achieving a Petition 870250087486, dated 09 / 26 / 2025, pp. 120 / 166 38 / 73 desired pour point. In one embodiment, the separation steps can be used to remove lower and / or higher molecular weight oligomers to produce an alpha olefin oligomer product or an alpha olefin oligomer product that will produce a polyalphaolefin, with a desired kinematic viscosity at 100 °C, flash point, ignition point, Noack volatility and / or pour point. POLYMERIZATION PROCESSES

[0095] Olefin polymers (e.g., ethylene polymers) can be produced from the catalyst compositions disclosed in this document using any suitable olefin polymerization process using various types of polymerization reactors, polymerization reactor systems, and polymerization reaction conditions. One such olefin polymerization process for polymerizing olefins in the presence of a catalyst composition of the present invention may comprise contacting the catalyst composition with an olefin monomer and optionally an olefin comonomer (one or more) in a polymerization reactor system under polymerization conditions to produce an olefin polymer (e.g., an ethylene polymer). This invention also encompasses any olefin polymers (e.g., ethylene polymers) produced by any of the polymerization processes disclosed in this document.

[0096] Olefin monomers that can be employed with catalyst compositions and polymerization processes of this invention typically include olefin compounds with 2 to 30 carbon atoms per molecule and with at least one olefinic double bond, such as ethylene or propylene. In one aspect, the olefin monomer may comprise a C2C20 olefin; alternatively, a C2-C20 alpha-olefin; alternatively, a C2C10 olefin; alternatively, a C2-C10 alpha-olefin; alternatively, the olefin monomer may comprise ethylene; or alternatively, the olefin monomer may comprise propylene (for example, to produce Petition 870250087486, dated 09 / 26 / 2025, pp. 121 / 166 39 / 73 a polypropylene homopolymer or a propylene-based copolymer).

[0097] When a copolymer (or alternatively, a terpolymer) is desired, the olefin monomer and the olefin comonomer may independently comprise, for example, a C2-C20 alpha-olefin. In some aspects, the olefin monomer may comprise ethylene or propylene, which is copolymerized with at least one comonomer (for example, a C2-C20 alpha-olefin or a C3-C20 alpha-olefin). According to one aspect of this invention, the olefin monomer used in the polymerization process may comprise ethylene.In this respect, the comonomer may comprise a C3-C10 alpha-olefin; alternatively, the comonomer may comprise 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, styrene, or any combination thereof; alternatively, the comonomer may comprise 1-butene, 1-hexene, 1-octene, or any combination thereof; alternatively, the comonomer may comprise 1-butene; alternatively, the comonomer may comprise 1-hexene; or alternatively, the comonomer may comprise 1-octene.

[0098] In certain aspects, polymerization processes may involve contacting the catalyst composition, olefin monomer, and optional comonomer with a diluent. Suitable diluents used in flow paste polymerization include, but are not limited to, the monomer being polymerized and hydrocarbons that are liquid under reaction conditions. Examples of suitable diluents include, but are not limited to, hydrocarbons such as propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, and n-hexane, heptanes, octanes, petroleum ether, light naphtha, heavy naphtha, or any combination thereof. Some closed-loop polymerization reactions may occur under bulk conditions where no diluent is used.

[0099] As used in this document, a “polymerization reactor” includes any polymerization reactor capable of polymerizing (including oligomerizing) olefin monomers and comonomers (one or more Petition 870250087486, dated 09 / 26 / 2025, pp. 122 / 166 40 / 73 of a comonomer) to produce homopolymers, copolymers, terpolymers and the like. The various types of polymerization reactors include those that may be referred to as batch reactors, fluidized paste reactors, gas-phase reactors, solution reactors and the like, or combinations thereof; or, alternatively, the polymerization reactor system may comprise a fluidized paste reactor, a gas-phase reactor, a solution reactor or a combination thereof. The polymerization conditions for the various types of reactors are well known to those skilled in the art. Gas-phase reactors may comprise fluidized bed reactors or stacked horizontal reactors. Fluidized paste reactors comprise vertical or horizontal closed circuits. Reactor types may include batch or continuous processes. Continuous processes may use intermittent or continuous product discharge.Polymerization reactor systems and processes may also include partial or total direct recycling of unreacted monomer, unreacted comonomer, and / or diluent.

[0100] A polymerization reactor system may comprise a single reactor or multiple reactors (2 reactors, more than 2 reactors, etc.) of the same type or of different types. For example, the polymerization reactor system may comprise a fluidized paste reactor, a gas-phase reactor, a solution reactor, or a combination of two or more of these reactors. Polymer production in multiple reactors may include several stages in at least two separate polymerization reactors interconnected by a transfer device that makes it possible to transfer the resulting polymers from the first polymerization reactor to the second reactor. The desired polymerization conditions in one of the reactors may be different from the operating conditions of the other reactors. Alternatively, polymerization in multiple reactors may include the manual transfer of the polymer from one reactor to subsequent reactors for continuous polymerization.Multiple reactor systems can include any combination, including but not limited to multiple reactors in a loop. Petition 870250087486, dated 09 / 26 / 2025, pp. 123 / 166 41 / 73 closed, multiple gas-phase reactors or a combination of closed-circuit and gas-phase reactors. The multiple reactors may operate in series, in parallel or both. Therefore, the present invention encompasses polymerization reactor systems comprising a single reactor, comprising two reactors and comprising more than two reactors. The polymerization reactor system may comprise a fluid paste reactor, a gas-phase reactor, a solution reactor, in certain aspects of this invention, as well as combinations of multiple reactors thereof.

[0101] According to one aspect, the polymerization reactor system may comprise at least one circuit-flowing slurry reactor comprising closed vertical or horizontal circuits. The monomer, diluent, catalyst, and comonomer may be continuously fed into a closed-circuit reactor where polymerization occurs. Generally, continuous processes may comprise the continuous introduction of the monomer / comonomer, a catalyst, and a diluent into a polymerization reactor and the continuous removal from this reactor of a suspension comprising polymer and diluent particles. The reactor effluent may be flash-separated to remove the solid polymer from the liquids comprising the diluent, monomer, and / or comonomer.Several technologies can be used for this separation step, including, but not limited to, flash separation, which can involve any combination of heat addition and pressure reduction, cyclonic separation in a cyclone or hydrocyclone, or centrifugal separation.

[0102] A typical process for polymerizing fluid paste (also known as the particle form process) is described, for example, in U.S. Patents Nos. 3,248,179, 4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191, 6,833,415 and 8,822,608, each of which is incorporated herein by reference in its entirety.

[0103] According to yet another aspect, the polymerization reactor system may comprise at least one gas-phase reactor (by Petition 870250087486, dated 09 / 26 / 2025, pp. 124 / 166 42 / 73 example, a fluidized bed reactor). Such reactor systems may employ a continuous recycle stream containing one or more monomers continuously cycled through a fluidized bed in the presence of catalyst under polymerization conditions. A recycle stream may be removed from the fluidized bed and recycled back into the reactor. Simultaneously, the polymer product may be removed from the reactor and new or fresh monomer may be added to replace the polymerized monomer. Such gas-phase reactors may comprise a process for a multi-stage gas-phase polymerization of olefins, in which olefins are polymerized in the gas phase in at least two independent gas-phase polymerization zones while feeding a catalyst-containing polymer formed in a first polymerization zone to a second polymerization zone. Representative gas-phase reactors are disclosed in U.S. Patents Nos.° 5,352,749, 4,588,790, 5,436,304, 7,531,606 and 7,598,327, each of which is incorporated by reference in its entirety in this document.

[0104] According to yet another aspect of the invention, the polymerization reactor system may comprise a solution polymerization reactor, in which the monomer / comonomer is brought into contact with the catalyst composition by means of agitation or other suitable means. A carrier comprising an inert organic diluent or excess monomer may be employed. If desired, the monomer / comonomer may be brought into contact with the catalytic reaction product in the presence or absence of liquid material in the vapor phase. The polymerization zone may be maintained at temperatures and pressures that will result in the formation of a polymer solution in a reaction medium. Agitation may be employed to obtain better temperature control and to maintain uniform polymerization mixtures throughout the polymerization zone. Suitable means are used to dissipate the exothermic heat of polymerization.

[0105] The polymerization reactor system may also comprise any combination of at least one feed system of Petition 870250087486, dated 09 / 26 / 2025, pp. 125 / 166 43 / 73 raw material, at least one feeding system for the catalyst or catalyst components and / or at least one polymer recovery system. Suitable reactor systems may further comprise systems for raw material purification, catalyst storage and preparation, extrusion, reactor cooling, polymer recovery, fractionation, recycling, storage, unloading, laboratory analysis and process control. Depending on the desired properties of the olefin polymer, hydrogen may be added to the polymerization reactor as needed (e.g., continuously or pulsed).

[0106] Polymerization conditions that can be controlled for efficiency and to provide desired polymer properties may include temperature, pressure, and the concentrations of various reagents. The polymerization temperature can affect catalyst productivity, polymer molecular weight, and molecular weight distribution. Several polymerization conditions can be kept substantially constant, for example, for the production of a particular grade of olefin polymer (or ethylene polymer). A suitable polymerization temperature can be any temperature below the depolymerization temperature according to the Gibbs free energy equation. Typically, this includes 60 °C to 280 °C, for example, or 60 °C to 120 °C, depending on the type of polymerization reactors. In some reactor systems, the polymerization temperature may generally be within a range of 70 °C to 105 °C or 75 °C to 100 °C.

[0107] The appropriate pressures will also vary depending on the reactor and the type of polymerization. The pressure for liquid-phase polymerizations in a closed-loop reactor is typically less than 1000 psig (6.9 MPa). The pressure for gas-phase polymerization is typically 200 to 500 psig (1.4 MPa to 3.4 MPa). In certain respects, polymerization conditions may comprise a reaction pressure in the range of 200 to 1000 psig. Polymerization reactors may also be operated in a supercritical region, generally occurring at higher temperatures and pressures. Petition 870250087486, dated 09 / 26 / 2025, pages 126 / 166 44 / 73 high. Operation above the critical point of a pressure / temperature diagram (supercritical phase) can offer advantages for the polymerization reaction process.

[0108] The olefin polymers covered in this document may include any polymer produced from any olefin monomer (and optional comonomers) described in this document. For example, the olefin polymer may comprise an ethylene homopolymer, a propylene homopolymer, an ethylene copolymer (e.g., ethylene / α-olefin, ethylene / 1-butene, ethylene / 1-hexene or ethylene / 1-octene), a propylene copolymer, an ethylene terpolymer, a propylene terpolymer and the like, including combinations thereof. In one aspect, the olefin polymer may be (or may comprise) an ethylene homopolymer, an ethylene / 1-butene copolymer, an ethylene / 1-hexene copolymer or an ethylene / 1-octene copolymer or a combination thereof; or alternatively, an ethylene / 1-hexene copolymer. In another aspect, the olefin polymer may be (or may comprise) a polypropylene homopolymer and / or a propylene-based copolymer.In some respects, the olefin polymer may have a bimodal molecular weight distribution, while in other respects, the olefin polymer may have a multimodal molecular weight distribution. However, in still other respects, the olefin polymer may have a unimodal molecular weight distribution.

[0109] Polymerization processes disclosed in this document can produce ethylene polymers with characteristics generally similar to those produced by analogous unsubstituted fluorinated metallocene compounds.

[0110] The densities of ethylene polymers can be greater than or equal to 0.94 g / cm3, for example, greater than or equal to 0.942 g / cm3, or greater than or equal to 0.945 g / cm3. However, in particular aspects, the density can be in a range of 0.92 to 0.96, 0.93 to 0.95, 0.925 to 0.94, or 0.93 to 0.94 g / cm3. In one aspect, ethylene polymers can have a weight Petition 870250087486, dated 09 / 26 / 2025, pp. 127 / 166 45 / 73 average molecular weight (Mn) in a range of 5,000 g / mol to 250,000 g / mol, 10,000 g / mol to 200,000 g / mol, or 20,000 g / mol to 150,000 g / mol. In other respects, the ethylene polymer may have a Mw in a range of 50,000 to 700,000, 75,000 to 500,000, or 100,000 to 400,000 g / mol. In other respects, the ethylene polymer may have an Mw / Mn ratio in the range of 2 to 15 or 2 to 10. In other respects, the ethylene polymer may have a melt index in the range of 0 to 20 g / 10 min, 0.01 to 10 g / 10 min, or 0.1 to 5 g / 10 min. Alternatively, or additionally, the ethylene polymer may have an HLMI in the range of 0 to 100 g / 10 min, less than or equal to 25 g / 10 min, less than or equal to 20 g / 10 min, or less than or equal to 15 g / 10 min.

[0111] In certain aspects, the ethylene polymers of the present invention may have (or may be characterized by) a density in the range of 0.92 to 0.96 g / cm3, a Mw in the range of 50,000 to 700,000, a Mn in the range of 5,000 to 250,000 g / mol, an Mw / Mn ratio in the range of 1 to 40, a high-charge melt index (HLMI) in the range of 0 to 100 g / 10 min. In certain aspects, the HLMI of the ethylene polymer may be less than or equal to 25 g / 10 min, less than or equal to 20 g / 10 min, or less than or equal to 15 g / 10 min.

[0112] As described in this document, the catalyst activities of these catalyst compositions may unexpectedly be comparable to or greater than those of identical catalyst compositions comprising a metallocene compound in which each Rx is F, when tested and compared under the same polymerization conditions. Thus, the disclosed polymerization processes (or catalyst compositions) may be characterized by a catalyst composition activity that is comparable (e.g., within 20%, 15%, 10% or 5% more or less) to that of an otherwise identical catalyst system comprising a metallocene compound in which each Rx is F, under the same catalyst preparation and polymerization conditions. ARTICLES AND PRODUCTS Petition 870250087486, dated 09 / 26 / 2025, pp. 128 / 166 46 / 73

[0113] The manufactured articles may be formed from, and / or may comprise, the olefin polymers (e.g., ethylene polymers, ethylene / 1-hexene polymers) and olefin oligomers (e.g., 1-decene oligomers) of this invention and products thereof (e.g., polyalphaolefins derived from 1-decene oligomers) and, consequently, are covered in this document.

[0114] For example, articles that may comprise the polymers of this invention may include, among others, an agricultural film, an automobile part, a bottle, a container for chemicals, a drum, a fiber or fabric, a film or container for food packaging, a food service article, a fuel tank, a geomembrane, a household container, a coating, a molded product, a medical device or material, an outdoor storage product (e.g., panels for the walls of an outdoor shed), outdoor recreational equipment (e.g., kayaks, bases for basketball hoops), a pipe, a plate or tape, a toy or a traffic barrier, and the like. Various processes may be employed to form these articles.Non-limiting examples of these processes include injection molding, blow molding, spin molding, film extrusion, sheet extrusion, profile extrusion, thermoforming, and the like. Additionally, additives and modifiers are often added to these polymers to provide beneficial polymer processing or end-use product attributes. Such processes and materials are described in Modern Plastics Encyclopedia, Mid-November 1995 Edition, Vol. 72, No. 12; and Film Extrusion Manual - Process, Materials, Properties, TAPPI Press, 1992.

[0115] In some aspects of this invention, a manufactured article may comprise any of the olefin polymers (or ethylene polymers) described in this document and the manufactured article may be or may comprise a film, such as a blown film; alternatively, a tube product; or alternatively, a molded product. Petition 870250087486, dated 09 / 26 / 2025, pp. 129 / 166 47 / 73 by blowing, like a bottle molded by blowing. EXAMPLES

[0116] The invention is further illustrated by the following examples, which should in no way be construed as imposing limitations on the scope of this invention. Various other aspects, embodiments, modifications and equivalents thereof, after reading the description in this document, may be suggested by themselves to one skilled in the art without departing from the spirit of the present invention or the scope of the appended claims.

[0117] Methods for preparing metallocene compounds are disclosed, and specifically, methods for preparing metallocene compounds by in situ substitution of metallocene precursors as part of a one-pot reaction. Advantageously, the metallocenes prepared by the disclosed methods retain their characteristic catalytic function while improving solubility in 1-decene compared to otherwise identical unsubstituted metallocene compounds. PREPARATION OF METALLOCENE COMPOUNDS Example 1 of the State of the Art - Synthesis of Fluorinated Metallocenes (MET-A)

[0118] A fluorinated metallocene (denoted MET-A) was prepared for comparison with substituted metallocenes, according to Reaction Equation 1 below and the experimental procedure that follows. Generally, a substituted indenyl precursor was deprotonated in a first deprotonation step using a single equivalent of n-butyllithium as an organic base. The deprotonated indenyl precursor was then contacted with the metal cyclopentadienyl trichloride complex, prepared as described previously in U.S. Pat. No. 11,186,655 (IE2) and generally as shown in the reaction below. Petition 870250087486, dated 09 / 26 / 2025, pp. 130 / 166 48 / 73 GOAL

[0119] Example 1 (MET-A): A 250 mL flask was charged with 1-((perfluorophenyl)methyl)-1H-indene (1.1 g, 3.8 mol) and 100 mL of diethyl ether. The solution was cooled to -78 °C and nBuLi (1.6 M hexane, 2.4 mL, 3.8 mmol) was added slowly. The resulting solution was allowed to warm to room temperature and stirred for 30 minutes. The solution was cooled again to -78 °C and a fluid paste of cyclopentadienylzirconium(IV) trichloride (1.0 g, 3.8 mmol) in diethyl ether (30 mL) was added. The resulting fluid paste was allowed to warm to room temperature with stirring overnight. The mixture was reduced under high vacuum to a bright yellow solid. The solid was absorbed in 30 mL of toluene and centrifuged. The supernatant was transferred to a clean flask and brought up to approximately 5 mL. The solution was layered with approximately 10 mL of pentane and placed in a freezer at 35 °C. MET-A was isolated as yellow needles with a yield of 0.659 g.1H NMR (300 MHz, CgDg) δ= 7.74 (d, 1H, indene), 7.02 (m, 1H, indene), 6.92 (m, 1H, indene), 6.77 (m, 1H, indene), 6.59 (d, 1H, indene), 5.71 (s, 5H, cyclopentadiene), 4.15 (dd, 2H, -CH 2C6F5).19F NMR (282.4 MHz, C6D6, 25 °C) δ = -144.75 (m), -158.70 (t), -164.01 (m). Examples 2-6 - Alkylation of a pot of metallocene precursors

[0120] Surprisingly, it has been found that a hydrophobic substituent can be incorporated within the CpA metallocene precursor using an additional equivalent of the Bronsted base as a replacement reagent, as shown in the reaction equation below. The reaction can proceed under identical conditions to deprotonation using the organic base and, Petition 870250087486, dated 09 / 26 / 2025, pp. 131 / 166 49 / 73 therefore allows the incorporation of the hydrophobic Rx group into the fluorinated CpA precursor, in situ, as part of a one-pot synthesis of the metallocene compound. F R = Me (MET-B), Et (MET-C), nBu (MET-D), nHex (MET-E), Ph (MET-F)

[0121] Example 2 (MET-B): A 200 mL flask was charged with 1-((perfluorophenyl)methyl)-1H-indene (850 mg, 2.87 mmol) and 100 mL of diethyl ether. The mixture was cooled to -20 °C and MeLi (4.1 mL, 6.6 mmol) was added. The mixture was heated to room temperature with stirring overnight. After 14 hours, a separate flask was filled with CpZrCl3 (75 mg, 2.87 mmol) and 50 mL of diethyl ether. The resulting fluid paste was cooled to 78 °C and the first reaction mixture was rapidly added. The mixture was slowly heated to room temperature with stirring overnight. After 16 hours, the diethyl ether was removed from the mixture by evaporation at room temperature to produce a yellow solid. The solid was absorbed in 50 mL of toluene, centrifuged, and the supernatant was decanted.The resulting solution was concentrated to 20 mL, layered with 10 mL of hexane, and placed in a freezer at -30 °C to produce the product as a yellow solid. Yield: 5.75 (s, 5H, Cp), 5.74 (m, 1H, Indene), 4.51 (d, 1H, Benzyl), 4.22 (d, 1H, Benzyl), 1.65 (t, 3H, Me).19F NMR (282.4 MHz, C6D6, 25 °C) δ = -145.76 (m), 146.34 (m).

[0122] Example 3 (MET-C): A 200 mL flask was filled with 1-((perfluorophenyl)methyl)-1H-indene (1.0 g, 3.38 mmol). The solids were Petition 870250087486, dated 09 / 26 / 2025, pp. 132 / 166 50 / 73 dissolved in 50 mL of toluene and 10 mL of diethyl ether. The solution was cooled to -20 °C and ethyl lithium (15.5 mL, 0.5 M solution, 7.76 mmol) was added slowly. The mixture was allowed to warm to room temperature and stirred overnight. A separate flask was filled with CpZrCl3 (0.88 g, 3.4 mmol) and 20 mL of toluene. The mixture was cooled to -78 °C and the first reaction mixture was added. The resulting fluid paste was allowed to warm to room temperature with stirring overnight. The mixture was then concentrated to 40 mL under high vacuum and centrifuged. The orange supernatant was isolated and stripped of the solvent by rotary evaporation at room temperature to produce an oily paste. The paste was absorbed in 15 mL of toluene and filtered to produce an orange filtrate. The solution was layered with 6 mL of pentane was added and placed in a freezer at -20 °C to crystallize. Several cultures of yellow solids yielded 0.319 g.1H RMN (300 MHz, CD2CU 25°C) δ = 7.78 (d, 1H, Indeno), 7.63 (m, 1H, Indeno), 7.30 (m, 2H, Indeno), 6.77 (m, 1H, Indeno), 6.49 (m, 1H, Indeno), 6.22 (s, 5H, Cp), 4.45 (d, 1H, Benzil), 4.20 (d, 1H, Benzil), 2.69 (m, 2H, Etil), 1.17 (t, 3H, Etil).19F RMN (282.4 MHz, C6D6, 25°C) δ = -145.76 (m), -147.62 (m).

[0123] Example 4 (MET-D): A 200 mL flask was filled with 100 mL of diethyl ether and 1.13 g (3.81 mmol) of 1-((perfluorophenyl)methyl)-1Hindene. The solution was cooled to -10 °C and nBuLi (5.4 mL, 8.6 mmol, 2.3 eq) was added. The resulting mixture was allowed to warm to room temperature. After 2 hours, the dark solution was added to a second flask containing CpZrCla (1.0 g, 3.8 mmol) suspended in 50 mL of diethyl ether at -78 °C. The resulting fluid paste was allowed to warm to room temperature with stirring. After 16 hours, the mixture was reduced to a paste and 50 mL of toluene were added. The yellow fluid paste was filtered through celite and reduced to a brown oil under high vacuum. The resulting oil was absorbed in 40 mL of hexane, forming a yellow, fluid paste. The fluid paste was filtered, and the filtrate was placed in a freezer at -30 °C. Several pale yellow solid cultures were collected. Yield = 0.576.1H NMR (300 MHz, C6D6, 25°C) δ = 7.84. Petition 870250087486, 09 / 26 / 2025, p. 133 / 1 51 / 73 (d, 1H, Indeno), 6.96 (d, 1H, Indeno), 6.89 (t, 1H, Indeno), 6.76 (t, 1H, Indeno), 6.66 (m, 1H, Indeno), 5.74 (s, 5H, Cp), 5.70 (m, 1H, Indeno), 4.52 (d, 1H, Benzyl), 4.25 (d, 1H, Benzyl), 2.34 (t, 2H, Butyl), 1.26 (m, 2H, Butyl), 1.06 (m, 2H, Butyl), 0.70 (t, 3H, Butyl).19F NMR (282.4 MHz, C6D6, 25 °C) δ = -145.76 (m), -146.78 (m).

[0124] Example 5 (MET-E): A 200 mL flask was charged with 1.00 g (3.38 mmol) of 1-((perfluorophenyl)methyl)-1H-indene and 100 mL of ether. The solution was cooled to -20°C and n-hexyllithium (3.38 mL, 7.76 mmol) was added. The cold bath was removed and the reaction mixture was allowed to warm to room temperature with stirring. After 1.5 hours, a separate flask was charged with CpZrClA (0.88 g, 3.4 mmol) and 30 mL of diethyl ether. The fluid paste was cooled to -78°C and the first reaction mixture was added over 5 minutes. The resulting dark brown fluid paste was allowed to warm slowly to room temperature with stirring. After stirring for 13 hours, the pale yellow fluid paste was reduced under vacuum to a brown oily solid. Hexanes (80 mL) were added and the resulting fluid paste was stirred for 1.5 hours. Toluene (20 mL) was added and the fluid paste was stirred for a further 2 hours. The mixture was then centrifuged and the supernatant was decanted.The resulting solution was reduced to solids, and the solids were then absorbed in 10 mL of toluene. The toluene solution was layered with 5 mL of hexane and placed in a freezer at -30 °C. Various fractions of yellow-orange solid gave 0.261 g.1H NMR (300 MHz, C6D6.25°C) δ = 7.85 (d, 1H, Indene), 6.96 (d, 1H, Indene), 6.88 (t, 1H, Indene), 6.76 (t, 1H, Indene), 6.67 (m, 1H, Indene), 5.74 (s, 5H, Cp), 5.70 (m, 1H, Indene), 4.51 (d, 1H, Benzyl), 4.25 (d, 1H, Benzyl), 2.37 (t, 2H, Hexyl), 1.49-1.03 (br m, 8H, Hexyl), 0.81 (t, 3H, Hexyl).19F NMR (282.4 MHz, C6D6, 25 °C) δ = -145.70 (m), 146.83 (m).

[0125] Example 6 (MET-F): A 200 mL flask was filled with 1-((perfluorophenyl)methyl)-1H-indene (0.924 g, 2.61 mmol) and toluene (100 mL). Diethyl ether (10 mL) was added and the solution was cooled to -20 °C. nBuLi (1.6 mL, 2.6 mmol) was added and the mixture was slowly heated to temperature Petition 870250087486, dated 09 / 26 / 2025, pp. 134 / 166 52 / 73 ambient. After 1.5 hours, the mixture was added to a flask containing CpZrCl3 (0.682 g, 2.61 mmol) and 25 mL of toluene at -78 °C. The resulting fluid paste was allowed to warm to room temperature. After 16 hours, the mixture was concentrated under high vacuum to 50 mL and centrifuged. The orange supernatant was collected and reduced to sticky solids. The solids were redissolved in 15 mL of toluene, filtered, layered with 6 mL of pentane, and placed in a freezer at -30 °C to crystallize. Several cultures of yellow solid were isolated. Yield = 0.336 g.1H NMR (300 MHz, CD2CU 25°C) δ = 7.82 (m, 1H, Indene), 7.65 (m, 1H, Indene), 7.46 (m, 2H, Indene), 7.42 (m, 3H, Phenyl), 7.32 (m, 2H, Phenyl), 6.83 (m, 1H, Indene), 6.54 (m, 1H, Indene), 6.23 (s, 5H, Cp), 4.55 (d, 1H, Benzyl), 4.29 (d, 1H, Benzyl).19F NMR (282.4 MHz, C6D6, 25 °C) δ = -144.93 (m), -145.87 (m). Example 7 - Alkylation of Metallocene Precursors (MET-G)

[0126] Another potential synthetic route to incorporate hydrophobic substituents to improve solubility is to prepare new metal coordinate precursors with substituents on the CpBa ring in order to preserve the catalytic activity of the fluorinated metallocene. However, this route may require the isolation of new intermediates for each metallocene derivative, which introduces an additional step and reduced yield. For example, the reaction below requires a first step of isolating n-butylcyclopentadienyl zirconium trichloride as an intermediate for the preparation of metallocene as described above for MET-A. Petition 870250087486, dated 09 / 26 / 2025, pages 135 / 166 53 / 73 Bu MET-G

[0127] Example 7 (MET-G): A 200 mL flask was charged with 1-((perfluorophenyl)methyl)-1H-indene (1.09 g, 3.68 mmol) and ether (100 mL). NBuLi (2.3 mL, 1.6 M, 3.68 mmol) was added slowly at -20 °C and the mixture was allowed to warm slowly to room temperature. After 2 hours, the mixture was added to a separate flask containing butylcyclopentadienyl zirconium(IV) trichloride (1.17 g, 3.68 mmol) in 30 mL of diethyl ether at -78 °C. The resulting fluid paste was allowed to warm to room temperature with vigorous stirring overnight. The solvent was removed under high vacuum and toluene (40 mL) was added. The fluid paste was centrifuged and the supernatant was concentrated to approximately 20 mL, layered with hexane, and placed in a freezer at -20 °C. Several yellow solid cultures yielded 0.357 g of the desired metallocene.1H NMR (300 MHz, C6D6, 25 °C) δ = 7.80 (d, 1H, Indene), 7.03 (d, 1H, Indene), 6.91 (m, 1H, Indene), 6.85 (m, 1H, Indene), 6.70 (m, 1H, Indene), 5.87 (m, 1H, Indene), 5.80 (m, 1H, Cp), 5.61 (m, 1H, Cp), 5.52 (m, 1H, Cp), 5.39 (m, 1H, Cp), 4.39 (d, 1H, Benzyl), 4.12 (d, 1H, Benzyl), 2.52 (m, 2H, Butyl), 1.34 (m, 2H, Butyl), 1.18 (m, 2H, Butyl), 0.80 (t, 3H, Butyl). SOLUBILITY OF METALLOCENE COMPOUNDS

[0128] The increased solubility of metallocene compounds in common oligomerization and polymerization solvents (e.g., 1-decene) is Petition 870250087486, dated 09 / 26 / 2025, pages 136 / 166 54 / 73 advantageous. Surprisingly, the metallocene compounds prepared as above demonstrated improved solubility. The solubility of the metallocenes prepared in Examples 1-7 above in 1-decene was examined according to the following procedure: 20 mL flasks sealed with crimp stoppers were loaded with 7.40 g (10.0 mL) of 1-decene, 7.5 mg of the desired metallocenes, and a small magnetic stirring bar. Additional portions of the desired metallocenes were then added in increments of 3-4 mg, and the mixture was left to stir for 30 minutes after each addition at room temperature (21 °C). The resulting mixtures were visually inspected for significant solids or haze. The metallocenes were considered soluble if no significant haze or solids were observed. Table I. Solubility of Metallocenes Ex. MET Solubility (% by weight) %) 1 A <0.1 2 B 0.1 3 C 0.4 4 D 0.4 5 E 0.5 6 F 0.1 7 G 0.4

[0129] Surprisingly, the solubility of CpA-Rx substituted metallocenes was unexpectedly improved by up to more than 4 times compared to their unsubstituted equivalents in certain cases, as shown in Table I (e.g., MET-C, D, and E). Thus, the solubility of the metallocene compounds of Examples 2-7 was able to be improved by an additional in situ substitution that did not require isolation and handling of new reactive metallocene intermediates. OLIGOMERIZATION REACTIONS Petition 870250087486, dated 09 / 26 / 2025, pp. 137 / 166 55 / 73

[0130] Metallocene-catalyzed oligomerizations were performed using MET-A and MET-D as follows. Generally, 1-decene was oligomerized into an oligomer product of dimers, trimers, and tetramers in the presence of MET-A or MET-D, as observed in Table II below. For Examples 8-9, a 1-gallon batch reactor was charged with 675 g of 1-decene. A syringe was loaded with CTSO (0.750 g), TIBA (1.3 mL of 1.0 M hexane solution), and metallocene (5 mg). The chemically treated solid oxide (CTSO) was a fluorinated silica-coated alumina (60:40 alumina:silica by weight) containing 4 wt% F and with an average d50 particle size of 35 microns, a BET surface area of ​​450 m² / g and a pore volume of 1.1 mL / g. The catalyst mixture was stirred to mix and then loaded into the reactor under a nitrogen purge. The reactor was heated to 110 °C while being stirred at 600–900 rpm.Once the reactor temperature reached the set point, 633 mg of hydrogen were loaded into the reactor. After 1 hour, the reactor was cooled to 35 °C. A 10% HCl solution in isopropyl alcohol (10 mL total charge) was added, and the reactor contents were removed.

[0131] The reaction mixture was then filtered and analyzed by gas chromatography to determine the yield of the oligomer product formed in the reaction mixture and to determine the relative amount of certain oligomers within the oligomer product (e.g., the trimer:tetramer weight ratio).

[0132] Gas chromatographic (GC) analyses were performed using a split injection method on a Bruker 430GC gas chromatograph with a flame ionization detector (FID). The initial oven temperature was 70 °C for 2 minutes and increased 5 °C / min to 290 °C and maintained for 7 minutes. The column was an all-purpose capillary column (Agilent J&W VF5ms, 30 m x 0.25 mm x 0.25 μm). Data analysis was performed using CompassCDS software.

[0133] The distribution of olefin terminal groups was determined Petition 870250087486, dated 09 / 26 / 2025, pp. 138 / 166 56 / 73 using 1H NMR on a Bruker 300 MHz NMR. Spectra were recorded on CDCl3 and are reported relative to SiMe4 as determined by reference to the residual 1H solvent peak. Integration of the following chemical shift bands was used to determine the relative amounts of the terminal olefin group: Vinylidene: 4.55-4.75 ppm, Trisubstituted: 4.95-5.15 ppm, Internal: 5.20-5.45 ppm.

[0134] The results of the oligomerizations of Examples 8-9 are presented in Table II.

[0135] Surprisingly, as shown in Table II, the activity observed from oligomerization using the more soluble Rx-substituted metallocene (MET-D) was even greater than that observed for the unmodified fluorinated metallocene (MET-A). More unexpectedly, despite the improved activity, the oligomer distribution in the product mixture was essentially unchanged with MET-D, with only a 0.3% difference in the amount of dimer product and slight increases in the heavy fraction including tetramer. Beneficially, the dimer distribution in the oligomer product was acceptable with 71% of the desired vinylidene produced. While MET-A produced more dimer and more vinylidene in total, the increase in activity and solubility observed by MET-D allows MET-D oligomerization to have unexpected practical advantages. Table II. Comparison of Oligomer Properties Ex. MET Metallocene Activity (g / (g*h)) Dimer (% by mol) Trimer (% by mol) Tetramer (% by mol) Total % internal % trisubstituted % vinylidene 8 A 75,060 62.3 6.3 20.7 73.0 25.8 11.8 9 D 108,000 62.0 9.7 19.3 71.0 25.7 12.5 POLYMERIZATION REACTIONS

[0136] Polymerization experiments using compositions Petition 870250087486, dated 09 / 26 / 2025, pp. 139 / 166 57 / 73 catalyst comprising MET-A, MET-B, MET-C, MET-D, MET-E, and MET-F were conducted as follows. Unless otherwise indicated, the polymerization experiments used in the following examples were conducted for 30 min in a one-gallon (3.8 L) stainless steel autoclave reactor containing isobutane as diluent. A syringe was loaded with 250 mg of solid activator support, 2 mL of hexane, 0.5 mL of 1M TIBA (in hexane), and 2.0 mg of metallocene (MET-A, MET-B, MET-C, MET-D, MET-E, or MET-F, as noted in Tables III and IV) in that order. The flowable paste was loaded into the reactor under an isobutane purge. The reactor was sealed, loaded with 2 L of isobutane, and heated to 80 °C. Ethylene was loaded into the reactor and fed on demand to maintain the target pressure of 320 psig (2.2 MPa). 1-Hexene was added as a feed ratio of 12% by weight versus ethylene with total feed mass of 1-hexene as shown in Tables III and IV.The reactor was maintained at the target temperature throughout the experiment by an automated heating and cooling system. After reactor venting, purging, and cooling, the resulting polymer product was dried under reduced pressure. For Examples 40-41, the polymerization temperature was 90 °C, and the ethylene pressure was maintained at 390 psig of ethylene, with a 1-hexene feed ratio of 20% by weight vs. ethylene.

[0137] Melting index (MI, g / 10 min) was determined according to ASTM D1238 at 190 °C with a weight of 2,160 grams and high load melt index (HLMI, g / 10 min) was determined according to ASTM D1238 at 190 °C with a weight of 21,600 grams. Density was determined in grams per cubic centimeter (g / cm3) in a compression-molded sample, cooled at 15 °C per minute and conditioned for 40 hours at room temperature according to ASTM D1505 and ASTM D4703.

[0138] Molecular weights and molecular weight distributions, when measured, were obtained using a PL-GPC 220 system (Polymer Labs, an Agilent company) equipped with an IR4 detector (Polymer Char, Spain) Petition 870250087486, dated 09 / 26 / 2025, pp. 140 / 166 58 / 73 and three Styragel HMW-6E GPC columns (Waters, MA) were run at 145 °C. The mobile phase flow rate of 1,2,4-trichlorobenzene (TCB) containing 0.5 g / L of 2,6-di-t-butyl-4-methylphenol (BHT) was fixed at 1 mL / min, and the polymer solution concentrations were in the range of 1.0–1.5 mg / mL, depending on the molecular weight. Sample preparation was conducted at 150 °C for approximately 4 h with occasional gentle stirring before the solutions were transferred to sample vials for injection. An injection volume of approximately 200 μL was used. The integral calibration method was used to deduce the molecular weights and molecular weight distributions using a Chevron Phillips Chemical Company HDPE polyethylene resin, MARLEX® BHB5003, as the broad standard. The comprehensive table of the broad pattern was pre-determined in a separate experiment with SEC-MALS.Mn is the number-average molecular weight, Mw is the weight-average molecular weight, Mz is the weight-average molecular weight, and MWD is the ratio of Mw / Mn.

[0139] The results of Examples 10-39 are summarized in Table III below. Comparing the MI and density of polymers formed in the presence of MET-A to MET-F and various amounts of 1-hexene comonomer, it was surprisingly found that the polymers formed using MET-A to MET-F generally had similar physical properties (e.g., melting indices and density) and a similar response to 1-hexene. Thus, it is surprisingly shown that Rx-substituted metallocenes can be employed within similar polymerization processes to produce generally similar polymeric products. As a result, the advantageous catalytic properties of fluorinated metallocenes, for example, can be preserved in Rx-substituted metallocenes which demonstrate improved solubility as shown in Table I above. Petition 870250087486, dated 09 / 26 / 2025, pp. 141 / 166 59 / 73 Table III. Comparison of polymer properties using alkylated / non-alkylated metallocenes Input MET 1-Hexene (g) Supporting Activity (g / (g*h)) MI (g / 10 min) Density (g / mL) 10 A 7.5 1.920 0.1 0.943 11 12 1.776 0.2 0.94 12 17.5 1.872 0.3 0.938 13 30 2.144 0.3 0.937 14 B 0 1.840 0 0.943 15 7 960 0.3 0.941 16 17 968 ​​0.2 0.937 17 35 1.536 0.5 0.934 18 47 1.256 0.4 0.934 19 C 0 1336 0.0 0.947 25 6.5 560 0.1 0.943 26 13 576 0.3 0.939 28 21 648 0.3 0.938 29 37 712 0.7 0.936 30 E 0 1.144 0 0.944 31 8 1,056 0.2 0.94 32 17 1,248 0.4 0.937 33 30 1,232 0.8 0.934 34 64 1,880 0.5 0.936 35 F 0 822 0 0.945 36 6 696 0 0.944 37 13.5 792 0.4 0.938 38 26 976 0.5 0.936 39 34 832 0.8 0.935 Petition 870250087486, dated 09 / 26 / 2025, pp. 142 / 166 60 / 73

[0140] Furthermore, Table IV shows that a similar principle applies to metallocenes with Rx-substituted CpB groups, as presented in Example 40 (MET-G). As shown above, although the preparation of MET-G requires the preparation of new intermediates, it is shown that CpB substitutions can also produce highly soluble metallocenes. Surprisingly, CpB-substituted metallocenes also exhibit excellent catalytic properties, despite having a greater impact on the resin properties of the product than observed for MET-A to MET-F (e.g., with respect to MI and density). Given that the preparation of CpB-substituted metallocenes also requires MET-G, it also requires the isolation of a new intermediate, CpA-substituted metallocenes may offer a surprisingly beneficial pathway to metallocenes with improved solubility. Table IV. Polymer Properties Ex. MET 1-Hexene (g) Supporting Activity (g / g / h) MI (g / 10 min) d (g / mL) Mn (x 10-3) Mw (x 10-3) Mz (x 10-3) Mw / Mn 39 A 49 2937 0.65 0.935 66.0 139 232 2.12 40 G 51 1392 1.5 0.941 49.8 112 194 2.25

[0141] The invention is described above with reference to numerous specific aspects and examples. Many variations will suggest themselves to those skilled in the art in light of the above detailed description. All such obvious variations are within the intended full scope of the appended claims. Other aspects of the invention may include, but are not limited to, the following (the aspects are described as comprising, but alternatively may consist essentially of or consist of):

[0142] Aspect 1. A method for the preparation of a metallocene compound, the method comprising: (i) contacting a compound of formula CpA-(CH2)n-Ar-X with a Bronsted base to form a deprotonated compound; (ii) contacting the deprotonated compound with a Petition 870250087486, dated 09 / 26 / 2025, pp. 143 / 166 61 / 73 replacement reagent to form a substituted compound with the formula CpA-(CH2)n-Ar-Rx; and (iii) contact of the substituted compound with a second compound with the formula CpB-M-X3 to form a metallocene compound with the formula (I): Rx .x1 M q / \2(I); where: M is Zr, Ti or Hf; each X independently is a halogen or NRy2; X1 and X2 are each independently a monoanionic ligand; CpA is a cyclopentadienyl, indenyl or fluorenyl group, optionally substituted by one or more other substituents; CpB is a substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl group; Ar is an aryl group comprising a halogen substituent; Rx is a C1 to C18 hydrocarbyl group substituent on Ar (for example, selected from alkyl or alkenyl or aryl; a phenyl group, a benzyl group, a C1 to C8 alkyl group or a C3 to C8 alkenyl group); n is an integer from 0 to 5; and Ry is a C1 to C8 hydrocarbyl group.

[0143] Aspect 2. The method of aspect 1, wherein the Bronsted base is selected from an organolithium reagent (for example, methyllithium, ethyllithium, n-butyllithium, t-butyllithium, n-hexyllithium, benzyllithium, phenyllithium) and an organomagnesium halide (for example, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, isopropylmagnesium chloride, t-butylmagnesium chloride, vinylmagnesium bromide, allylmagnesium bromide, ethinylmagnesium chloride, phenylmagnesium chloride, benzylmagnesium chloride).

[0144] Aspect 3. The method of aspect 1 or 2, wherein the replacement reagent is selected from an organolithium reagent (for example, methyllithium, ethyllithium, n-butyllithium, t-butyllithium, n-hexyllithium, benzyllithium, phenyllithium) and an organomagnesium halide (for example, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, isopropylmagnesium chloride, chloride Petition 870250087486, dated 09 / 26 / 2025, pp. 144 / 166 62 / 73 tert-butyl magnesium, vinylmagnesium bromide, allylmagnesium bromide, ethinylmagnesium chloride, phenylmagnesium chloride, benzylmagnesium chloride).

[0145] Aspect 4. The method of any of the aspects from 1 to 3, wherein the Bronsted base and the replacement reagent are each an organolithium reagent (for example, methyllithium, n-butyllithium, n-hexyllithium).

[0146] Aspect 5. The method of any of the aspects from 1 to 4, wherein the Bronsted base and the replacement reagent are the same.

[0147] Aspect 6. The method of any of aspects 1 to 5, in which steps (i) and (ii) are conducted in a one-pot synthesis.

[0148] Aspect 7. The method of any of aspects 1 to 6, in which each of the steps from (i) to (iii) is carried out in a one-pot synthesis.

[0149] Aspect 8. A metallocene compound with formula (I): Rx X1 M cX \2(I); where: M is Zr, Ti or Hf; X1 and X2 are independently a monoanionic ligand (for example, selected from H, a halide, a C1 to C36 hydrocarbyl group or a C1 to C36 hydrocarboxyl group, (or a C1 to C36 hydrocarbylaminyl group, a C1 to C36 hydrocarbysilyl group, a C1 to C36 hydrocarbylaminylsilyl group, -OBR12 or -OSO2R1, wherein R1 is a C1 to C36 hydrocarbyl group); CpA is a cyclopentadienyl, indenyl or fluorenyl group with a -(CH2)nArRxe substituent optionally substituted by one or more other substituents; CpB is a substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl group; an alkenyl or aryl group; a phenyl group, a benzyl group, a C1 to C8 alkyl group or a C3 to C8 alkenyl group); Petition 870250087486, dated 09 / 26 / 2025, pp. 145 / 166 63 / 73

[0150] Aspect 9. The metallocene compound of aspect 8, wherein X1 and X2 are independently H, F, Cl, Br, a C1 to C12 hydrocarbyl group, a C1 to C12 hydrocarboxy group, a C1 to C12 hydrocarbylaminyl group, a C1 to C12 hydrocarbysilyl group, a C1 to C12 hydrocarbylaminylsilyl group, -OBR12 or OSO2R1, wherein R1 is a C1 to C12 hydrocarbyl group.

[0151] Aspect 10. The metallocene compound of aspect 8 or 9, where Ar is a phenyl group with two, three or four halogen substituents.

[0152] Aspect 11. The metallocene compound of any of aspects 8 to 10, where each halogen substituent is F.

[0153] Aspect 12. The metallocene compound of any of the aspects from 8 to 11, in which Ar is selected from: FF

[0154] Aspect 13. The metallocene compound of any one of aspects 8 to 12, wherein Rx is selected from methyl, ethyl, n-propyl, n-butyl, sec-butyl, t-butyl, 3-butenyl, n-hexyl, phenyl and substituted phenyl.

[0155] Aspect 14. The metallocene compound of any of the aspects from 8 to 13, where n is 0.

[0156] Aspect 15. The metallocene compound of any of the aspects from 8 to 13, where n is 1.

[0157] Aspect 16. The metallocene compound of any of aspects 8 to 15, wherein CpA is substituted with at least one other substituent selected from a C1-C12 alkyl, C2-C12 alkenyl, C6C10 aryl or C7-C12 aralkyl substituent. Petition 870250087486, dated 09 / 26 / 2025, pp. 146 / 166 64 / 73

[0158] Aspect 17. The metallocene compound of any of the aspects from 8 to 16, where CpA is an indenyl group and CpB is a cyclopentadienyl group.

[0159] Aspect 18. The metallocene compound of any one of aspects 8 to 17, wherein CpB comprises a C1-C12 alkyl, C2C12 alkenyl, C6-C10 aryl or C7-C12 aralkyl substituent.

[0160] Aspect 19. The metallocene compound of any of aspects 8 to 18, where CpB comprises the substituent -(CH2)nArRx.

[0161] Aspect 20. The metallocene compound of any of the aspects from 8 to 17, where CpBé is unsubstituted.

[0162] Aspect 21. The metallocene compound of any of the aspects from 8 to 20, wherein the metallocene compound is selected from: JJJ

[0163] Aspect 22. The metallocene compound of any of the aspects from 8 to 21, with solubility at 25 °C in 1-decene at least 0.1% by weight (for example, from 0.2% by weight to 2% by weight, from 0.2% by weight to 1.0% by weight, from 0.2% by weight to 0.5% by weight).

[0164] Aspect 23. The metallocene compound of any of the aspects from 8 to 22, having a solubility at 25 °C in 1-decene greater than (for example, 50% to 500% greater, 100% to 300% greater) that of a compound of Petition 870250087486, dated 09 / 26 / 2025, pp. 147 / 166 65 / 73 metallocene otherwise identical in that each Rxé F.

[0165] Aspect 24. A catalyst composition comprising: the metallocene compound of any of aspects 8 to 23; an activator comprising an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, a chemically treated solid oxide or any combination thereof; and optionally, a cocatalyst.

[0166] Aspect 25. The catalyst composition of aspect 24, wherein the activator comprises the aluminoxane compound (for example, methylaluminoxane (MAO), ethylaluminoxane, modified methylaluminoxane (MMAO), such as isobutyl-modified methylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, n-butylaluminoxane, t-butylaluminoxane, sec-butylaluminoxane, isobutylaluminoxane, t-butyl aluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane, neopentylaluminoxane and combinations thereof).

[0167] Aspect 26. The catalyst composition of aspect 24 or 25, wherein the activator comprises the organoboron or organoborate compound (for example, N,N-dimethylaniline tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)borate, N,N-dimethylaniline tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate and combinations thereof).

[0168] Aspect 27. The catalyst composition of any of the aspects from 24 to 26, wherein the activator comprises the ionizing ionic compound (for example, tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylaniline tetrakis(p-tolyl)borate, N,N-dimethylaniline tetrakis(m-tolyl)borate, N,N-dimethylaniline tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, N,N-dimethylaniline tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(p-tolyl)borate, Petition 870250087486, dated 09 / 26 / 2025, pp. 148 / 166 66 / 73 triphenylcarbenium tetrakis(m-tolyl)borate, triphenylcarbenium tetrakis(2,4-dimethylphenyl)borate, triphenylcarbenium tetrakis(3,5-dimethylphenyl)borate, or triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, lithium tetrakis(ptolyl)aluminate, lithium tetrakis(m-tolyl)aluminate, lithium tetrakis(2,4-dimethylphenyl)aluminate, lithium tetrakis(3,5-dimethylphenyl)aluminate) or combinations thereof).

[0169] Aspect 28. The catalyst composition of any of the aspects from 24 to 27, wherein the activator comprises the chemically treated solid oxide.

[0170] Aspect 29. The catalyst compound of any of aspects 24 to 28, wherein chemically treated solid oxide comprises fluorinated alumina, chloride alumina, brominated alumina, sulfated alumina, fluorinated silica-alumina, chloride silica-alumina, brominated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, chloride silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, alumina coated with fluorinated-chlorinated silica, alumina coated with fluorinated silica, alumina coated with sulfated silica, alumina coated with phosphated silica or any combination thereof.

[0171] Aspect 30. The catalyst composition of any of aspects 24 to 29, wherein the chemically treated solid oxide comprises a fluorinated solid oxide and / or a sulfated solid oxide.

[0172] Aspect 31. The catalyst composition of any of aspects 24 to 30, wherein a weight ratio of the metallocene compound to the activator is in any range disclosed in this document, for example, 1:10 to 1:10,000, 1:10 to 1:1,000, 1:10 to 500:1 or 1:10 to 1:100.

[0173] Aspect 32. The catalyst composition of any of the aspects from 24 to 31, wherein the cocatalyst comprises an organoaluminum compound, an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound or a combination thereof. Petition 870250087486, dated 09 / 26 / 2025, pp. 149 / 166 67 / 73

[0174] Aspect 33. The catalyst composition of any of the aspects from 24 to 32, wherein the cocatalyst comprises an organoaluminum compound.

[0175] Aspect 34. The catalyst composition of aspects 32 or 33, wherein the organoaluminum compound comprises trimethylaluminum (TMA), triethylaluminum (TEA), tri-n-propylaluminum (TNPA), tri-n-butylaluminum (TNBA), tri-isobutylaluminum (TIBA), tri-n-hexylaluminum, tri-n-octylaluminum (TNOA) or combinations thereof.

[0176] Aspect 35. The catalyst composition of any of aspects 24 to 34, wherein a molar ratio of the cocatalyst to the metallocene compound in the catalyst composition is in any range disclosed in this document, for example, from 0.1:1 to 100,000:1, from 1:1 to 10,000:1, from 10:1 to 1,000:1, or from 50:1 to 500:1.

[0177] Aspect 36. The catalyst composition of any of the aspects from 28 to 35, wherein the catalyst composition is substantially free of aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds or combinations thereof.

[0178] Aspect 37. The catalyst composition of any of the aspects from 24 to 36, wherein the catalyst composition further comprises a second metallocene compound.

[0179] Aspect 38. An oligomerization process comprising placing the catalyst composition of any of aspects 24 to 37 in contact with an alpha olefin monomer and optionally H2 under oligomerization conditions to produce an oligomer product.

[0180] Aspect 39. The process of aspect 38, wherein the alpha olefin monomer comprises any C4 to C14 alpha olefin or Cs to C12 alpha olefin disclosed in this document, for example, 1-octene and / or 1-decene.

[0181] Aspect 40. The process of aspect 38 or 39, wherein the alpha olefin monomer comprises a branched alpha olefin. Petition 870250087486, dated 09 / 26 / 2025, pp. 150 / 166 68 / 73

[0182] Aspect 41. The process of any of the aspects from 38 to 40, wherein the alpha olefin monomer comprises a mixture of alpha olefins (for example, a mixture of C8 to C12 alpha olefins or a mixture of C10 alpha olefins).

[0183] Aspect 42. The process of any of the aspects from 38 to 41, wherein a weight ratio of the metallocene compound to the alpha olefin monomer is in any range disclosed in this document, for example, from 1:100 to 1:1,000,000, from 1:1,000 to 1:1,000,000, from 1:1,000 to 1:500,000, or from 1:10,000 to 1:250,000.

[0184] Aspect 43. The process of any of the aspects from 38 to 42, wherein the oligomerization conditions comprise an oligomerization temperature in any range disclosed in this document, for example, from -10 °C to 250 °C, from 20 °C to 180 °C, from 50 °C to 160 °C or from 70 °C to 140 °C.

[0185] Aspect 44. The process of any of the aspects 3843, in which the catalyst composition is brought into contact with the alpha olefin monomer and H2 at any suitable partial pressure of hydrogen (e.g., from 0.1 to 10 psig of H2).

[0186] Aspect 45. The process of any of the aspects from 38 to 44, wherein an activity of the catalyst composition is in any range disclosed in this document, for example, at least 50,000 g of oligomer / g of metallocene compound per hour (g / (g*h)), from 20,000 g / (g*h) to 180,000 g / (g*h), from 40,000 g / (g*h) to 160,000 g / (g*h) or from 60,000 to 120,000 g / (g*h) under oligomerization conditions comprising an oligomerization temperature of 90 °C and wherein the cocatalyst is TIBA.

[0187] Aspect 46. The process of any of the aspects from 38 to 45, in which the activity of the catalyst composition is comparable (for example, within 20%, 15%, 10% or 5% more or less) to that of an otherwise identical process employing a catalyst composition comprising a metallocene compound in which each Rx is F.

[0188] Aspect 47. The process of any of the aspects of 38 Petition 870250087486, dated 09 / 26 / 2025, pp. 151 / 166 69 / 73 to 46 further comprising a step of separating at least a portion of the catalyst composition from the oligomer product using any technique disclosed in this document, for example, filtration.

[0189] Aspect 48. The process of any of the aspects from 38 to 47 further comprising recycling the separated catalyst composition.

[0190] Aspect 49. The process of any of aspects 38 to 48 further comprising a step of separating the unreacted alpha olefin monomer from the oligomer product using any technique disclosed in this document, for example, clean film evaporation, distillation, short path distillation or any combination thereof.

[0191] Aspect 50. The process of any of aspects 38 to 49 further comprising recycling unreacted alpha-olefin monomer.

[0192] Aspect 51. The process of any of aspects 38 to 50 further comprising a step of fractionating the oligomer product into alpha olefin dimer, alpha olefin trimer and heavy alpha olefin including alpha olefin tetramer and higher oligomers, using any technique disclosed in this document, for example, clean film evaporation, distillation, short path distillation or any combination thereof.

[0193] Aspect 52. The process of any of the aspects from 38 to 51, wherein the oligomer product comprises less than or equal to 20 mol%, less than or equal to 15 mol%, less than or equal to 10 mol%, or less than or equal to 5 mol% of tetramer.

[0194] Aspect 53. The process of any of the aspects from 38 to 52, wherein the oligomer product comprises at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 85 mol%, at least 90 mol% or at least 95 mol% of dimer and trimer (total).

[0195] Aspect 54. The process of any of the aspects from 38 to 53, wherein the oligomer product comprises at least 30 mol%, at least 40 mol%, at least 50 mol%, at least 55 mol%, at least 60 mol%, at least 65 mol%, at least 70 mol% or at least 30 mol%. Petition 870250087486, dated 09 / 26 / 2025, pp. 152 / 166 70 / 73 minus 75 mol% alpha olefin dimer.

[0196] Aspect 55. The process of any of the aspects from 38 to 54, wherein the oligomer product comprises at least 50 mol%, at least 60 mol%, at least 70 mol%, at least 75 mol%, at least 80 mol%, at least 85 mol%, at least 90 mol% or at least 95 mol% of vinylidene dimer, relative to the amount of dimer in the oligomer product.

[0197] Aspect 56. The process of any of the aspects from 38 to 55, in which the amount of internal olefin within the dimer portion of the oligomer product is less than or equal to 15 mol%, less than or equal to 12 mol%, or less than or equal to 10 mol%.

[0198] Aspect 57. The process of any of the aspects from 38 to 56, wherein the oligomer product has a dimer content and character (for example, the amount of internal dimer, trisubstituted and / or vinylidene dimer in the dimer product) that is comparable (for example, within 20%, 15%, 10% or 5% more or less) to that of an otherwise identical process employing a catalyst composition comprising a metallocene compound wherein each Rx is F.

[0199] Aspect 58. The process of any of the aspects from 38 to 57 further comprising a hydrogenation step of at least a portion of the oligomer product (e.g., alpha olefin trimer) to form a polyalphaolefin.

[0200] Aspect 59. The process of aspect 58, wherein the polyalphaolefin has a kinematic viscosity at 100 °C less than or equal to 20 cSt, 10 cSt, 5 cSt, 4 cSt or 3 cSt (for example, in a range of 1 to 10 cSt).

[0201] Aspect 60. A polymerization process, the process comprising placing the catalyst composition of any of aspects 24 to 37 in contact with an ethylene monomer and an optional α-olefin comonomer in a polymerization reactor system under polymerization conditions to produce an ethylene polymer. Petition 870250087486, dated 09 / 26 / 2025, pages 153 / 166 71 / 73

[0202] Aspect 61. The process of aspect 60, in which the α-olefin comonomer comprises a C3-C20 α-olefin or, alternatively, a C3-C10 α-olefin.

[0203] Aspect 62. The process of aspect 60 or 61, wherein the α-olefin comonomer comprises 1-butene, 1-hexene, 1-octene or a mixture thereof.

[0204] Aspect 63. The process of any of the aspects from 60 to 62, wherein the polymerization reactor system comprises a bulk reactor, a fluid paste reactor, a gas phase reactor, a solution reactor or a combination thereof.

[0205] Aspect 64. The process of any of the aspects from 60 to 63, wherein the polymerization reactor system comprises a fluid paste reactor, a gas phase reactor, a solution reactor or a combination thereof.

[0206] Aspect 65. The process of any of the aspects from 60 to 64, wherein the polymerization reactor system comprises a closed-circuit fluid paste reactor.

[0207] Aspect 66. The process of any of the aspects from 60 to 65, in which the polymerization reactor system comprises a single reactor.

[0208] Aspect 67. The process of any of the aspects from 60 to 65, in which the polymerization reactor system comprises 2 reactors.

[0209] Aspect 68. The process of any of the aspects from 60 to 65, in which the polymerization reactor system comprises more than 2 reactors.

[0210] Aspect 69. The process of any of the aspects from 60 to 68, wherein the polymerization conditions comprise a polymerization reaction temperature in a range of 60 °C to 120 °C (e.g., 80 °C) and a reaction pressure in a range of 200 to 1000 psig (1.4 to 6.9 MPa).

[0211] Aspect 70. The process of any of the aspects from 60 to 69, in which the polymerization conditions are substantially constant, Petition 870250087486, dated 09 / 26 / 2025, pp. 154 / 166 72 / 73 for example, for a particular polymer grade.

[0212] Aspect 71. The process of any of the aspects from 60 to 70, in which no hydrogen is added to the polymerization reactor system.

[0213] Aspect 72. The process of any of the aspects from 60 to 70, in which hydrogen is added to the polymerization reactor system.

[0214] Aspect 73. The process of any of aspects 60 to 72 further comprising the contact of the catalyst composition, ethylene monomer, an optional α-olefin comonomer with a diluent, for example, propane, butanes (e.g., n-butane, iso-butane), pentanes (e.g., n-pentane, iso-pentane), hexanes, heptanes, octanes, petroleum ether, light naphtha, heavy naphtha or any combination thereof.

[0215] Aspect 74. The process of any of the aspects from 60 to 73, wherein the ethylene polymer comprises an ethylene homopolymer, an ethylene / 1-butene copolymer, an ethylene / 1-hexene copolymer and / or an ethylene / 1-octene copolymer.

[0216] Aspect 75. The process of any of the aspects from 60 to 74, wherein the ethylene polymer comprises an ethylene / 1-hexene copolymer.

[0217] Aspect 76. The process of any of the aspects from 60 to 75, in which the catalyst composition is characterized by a total metallocene activity in a range of 30,000 g / (g*h) (grams of polyethylene per gram of metallocene per hour) to 800,000 g / (g*h).

[0218] Aspect 77. The process of any of the aspects from 60 to 76, in which the activity of the catalyst composition is comparable (for example, within 20%, 15%, 10% or 5% more or less) to that of an otherwise identical process employing a catalyst composition comprising a metallocene compound in which each Rx is F.

[0219] Aspect 78. The process of any of the aspects from 60 to 77, in which the ethylene polymer has an average molecular weight (Mn) in a Petition 870250087486, dated 09 / 26 / 2025, pp. 155 / 166 73 / 73 range from 5,000 g / mol to 250,000 g / mol, from 10,000 g / mol to 200,000 g or from 20,000 g / mol to 150,000 g / mol.

[0220] Aspect 79. The process, according to any one of aspects 60 to 78, wherein the ethylene polymer has an Mw in any range disclosed in this document, for example, from 50,000 to 700,000, from 75,000 to 500,000 or from 100,000 to 400,000 g / mol.

[0221] Aspect 80. The process of any of the aspects from 60 to 79, in which the ethylene polymer has an Mw / Mn ratio in a range of 2 to 15 or 2 to 10.

[0222] Aspect 81. The process, according to any of aspects 60 to 80, in which the ethylene polymer has a density in any range disclosed in this document, for example, 0.92 to 0.96, 0.93 to 0.95, 0.925 to 0.94 or 0.93 to 0.94 g / cm3.

[0223] Aspect 82. The process, according to any of aspects 60 to 81, in which the ethylene polymer has a melting index in any range disclosed in this document, for example, 0 to 20 g / 10 min, 0.01 to 10 g / 10 min or 0.1 to 5 g / 10 min.

[0224] Aspect 83. The polymer of any of the aspects from 60 to 82, wherein the ethylene polymer has an HLMI in any range disclosed in this document, for example, from 0 to 100 g / 10 min, less than or equal to 25 g / 10 min, less than or equal to 20 g / 10 min, or less than or equal to 15 g / 10 min. Petition 870250087486, dated 09 / 26 / 2025, pp. 156 / 166

Claims

1 / 9 CLAIMS 1. Metallocene compound characterized by having formula (I): Rx Y4ícpí / χ1 M CX \2 (I); where: M is Zr, Ti or Hf; X1 and X2 are independently a monoanionic ligand; CpA is a cyclopentadienyl, indenyl or fluorenyl group with the substituent -(CH2)nArRx and optionally substituted by one or more other substituents; CpB is a substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl group; Ar is an aryl group comprising a halogen substituent; Rx is a C18 hydrocarbyl group substituent on Ar; en is an integer from 0 to 5.

2. Catalyst composition characterized by comprising: (a) metallocene compound with formula (I): Rx \r V)hCpA X1 M CPb / \2 (I); where: M is Zr, Ti or Hf; X1 and X2 are independently a monoanionic ligand; CpA is a cyclopentadienyl, indenyl or fluorenyl group with the substituent -(CH2)nArRx and optionally substituted by one or more other substituents; CpB is a substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl group; Ar is an aryl group comprising a halogen substituent; Rx is a C18 hydrocarbyl group substituent on Ar; en is an integer from 0 to 5; (b) an activator comprising an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, a chemically treated solid oxide or any combination thereof; and (c) optionally, a cocatalyst.

3. Metallocene compound or catalyst composition according to claim 1 or 2, characterized in that X1 and X2 are independently H, F, Cl, Br or a C1 to C12 hydrocarbyl group.

4. Metallocene compound or catalyst composition, according to any one of claims 1 to 3, characterized in that Ar is a phenyl group with two, three or four halogen substituents.

5. Metallocene compound or catalyst composition, according to any one of claims 1 to 4, characterized in that each halogen substituent is F.

6. Metallocene compound or catalyst composition, according to any one of claims 1 to 5, characterized in that Ar is selected from: Rx; F; Rx; F · J ! !JFF FF rxxA^rx ​​​​rvAx^Rx R'lX / F rxxA^f Jn II Ijl Ijl Vy^F ' / γ F χγ F Rx is selected from methyl, ethyl, n-propyl, n-butyl, sec-butyl, t-butyl, 3-butenyl, n-hexyl, phenyl and substituted phenyl. Petition 870250087486, dated 09 / 26 / 2025, pp. 158 / 166 3 / 9 7. Metallocene compound or catalyst composition according to claim 1 or 2, characterized in that the metallocene compound is selected from:

8. Metallocene compound or catalyst composition according to claim 1 or 2, characterized in that the metallocene compound is:

9. Metallocene compound or catalyst composition, according to any one of claims 1 to 8, characterized in that the metallocene compound has a solubility at 25 °C in 1-decene in a range of 0.1% by weight to 1.0% by weight.

10. Metallocene compound or catalyst composition, according to any one of claims 1 to 8, characterized in that the metallocene compound has a solubility at 25 °C in 1-decene in a range of 0.2% by weight to 0.5% by weight.

11. Catalyst composition, according to any of claims 2 to 10, characterized in that the activator comprises the aluminoxane compound.

12. Catalyst composition, according to any one of claims 2 to 10, characterized in that the activator comprises the chemically treated solid oxide.

13. Catalyst composition according to claim 12, characterized in that the chemically treated solid oxide comprises a fluorinated solid oxide and / or a sulfated solid oxide.

14. Catalyst compound, according to claim 12, characterized in that the chemically treated solid oxide comprises fluorinated alumina, chloride alumina, brominated alumina, sulfated alumina, fluorinated silica-alumina, chloride silica-alumina, brominated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, chloride silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, alumina coated with fluorinated-chlorinated silica, alumina coated with fluorinated silica, alumina coated with sulfated silica, alumina coated with phosphated silica or any combination thereof.

15. Catalyst composition, according to any one of claims 2 to 14, characterized in that the catalyst composition comprises a cocatalyst.

16. Catalyst composition according to claim 15, characterized in that the cocatalyst comprises trimethylaluminum (TMA), triethylaluminum (TEA), tri-n-propylaluminum (TNPA), tri-n-butylaluminum (TNBA), triisobutylaluminum (TIBA), tri-n-hexylaluminum, tri-n-octylaluminum (TNOA) or any combination thereof.

17. Catalyst composition, according to any one of claims 2 to 16, characterized in that the catalyst composition further comprises a second metallocene compound.

18. Oligomerization process characterized by comprising placing the catalyst composition as defined in any of claims 2 to 17 in contact with an alpha olefin monomer and, optionally, H2 under oligomerization conditions to produce an oligomer product.

19. Oligomerization process according to claim 18, characterized in that: the alpha olefin monomer comprises a C4 to C14 alpha olefin or a C5 to C12 alpha olefin; the oligomerization process further comprises a step of separating at least a portion of the catalyst composition from the oligomer product; the oligomerization process further comprises a step of separating the unreacted alpha olefin monomer from the oligomer product; the oligomerization process further comprises a step of fractionating the oligomer product into an alpha olefin dimer product, an alpha olefin trimer product, an alpha olefin tetramer, and a higher oligomer product; the oligomerization process further comprises a step of hydrogenating at least a portion of the oligomer product to form a polyalphaolefin; or any combination thereof.

20. Oligomerization process, according to claim 18 or 19, characterized in that the activity of the catalyst composition in the oligomerization process is within 20%, within 15%, within 10% or within 5% of an otherwise identical catalyst composition comprising a metallocene compound wherein each Rx is F.

21. Polymerization process, the process characterized by comprising placing the catalyst composition as defined in any one of claims 2 to 17 in contact with an ethylene monomer and an optional α-olefin comonomer in a polymerization reactor system under polymerization conditions to produce an ethylene polymer.

22. Polymerization process according to claim 21, characterized in that: the α-olefin comonomer comprises 1-butene, 1-hexene, 1-octene or a mixture thereof; the ethylene polymer comprises an ethylene homopolymer, ethylene / 1-butene copolymer, an ethylene / 1-hexene copolymer and / or an ethylene / 1-octene copolymer; the polymerization reactor system comprises a fluidized paste reactor, a gas-phase reactor, a solution reactor or a combination thereof; the polymerization reactor system comprises a single reactor or the polymerization reactor system comprises two reactors; or any combination thereof.

23. Polymerization process, according to claim 21 or 22, characterized in that the activity of the catalyst composition in the polymerization process is within 20%, within 15%, within 10% or within 5% of an otherwise identical catalyst composition comprising a metallocene compound wherein each Rx is F.

24. Method for the preparation of a metallocene compound, the method characterized by comprising: (i) placing a first compound with the formula CpA'(CH2)n-Ar-X in contact with a Bronsted base to form a deprotonated compound; (ii) placing the deprotonated compound in contact with a substitution reagent to form a substituted compound with the formula CpA-(CH2)nAr-Rx; and (iii) placing the substituted compound in contact with a second compound with the formula CpB-M-X3 to form a metallocene compound with the formula (I): Petition 870250087486, dated 26 / 09 / 2025, p.162 / 166 7 / 9 Rx \r / χ1 M q / \2 (I); where: M is Zr, Ti or Hf; each X is independently a halogen or NRy2; X1 and X2 are independently a monoanionic ligand; CpA is a cyclopentadienyl, indenyl or fluorenyl group, optionally substituted by one or more other substituents; CpB is a substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl group; Ar is an aryl group comprising a halogen substituent; Rx is a C1 to C18 hydrocarbyl group substituent on Ar; n is an integer from 0 to 5; and Ry is a C1 to C8 hydrocarbyl group.

25. Method according to claim 24, characterized by the Bronsted base comprising an organolithium reagent and / or an organomagnesium halide.

26. Method according to claim 25, characterized by the Bronsted base comprising the organolithium reagent and the organolithium reagent comprising methyl-lithium, ethyl-lithium, n-butyllithium, n-hexyllithium, phenyl-lithium or a combination thereof.

27. Method according to any one of claims 24 to 26, characterized in that the replacement reagent comprises an organolithium reagent and / or an organomagnesium halide.

28. Method according to claim 27, characterized by the substitution reagent comprising the organolithium reagent and the organolithium reagent comprising methyl-lithium, ethyl-lithium, n-butyllithium, n-hexyl-lithium, phenyl-lithium or a combination thereof.

29. Method according to any one of claims 24 to 28, characterized in that the Bronsted base and the replacement reagent are the same.

30. Method according to any one of claims 24 to 29, characterized in that steps (i) and (ii) are carried out in a one-pot synthesis.

31. Method, according to any one of claims 24 to 29, characterized in that each of the steps from (i) to (iii) is carried out in a one-pot synthesis.

32. Method according to any one of claims 24 to 31, characterized in that X1 and X2 are independently H, F, Cl, Br or a C12 to C12 hydrocarbyl group.

33. A method according to any one of claims 24 to 32, characterized in that Ar is a phenyl group with two, three, or four halogen substituents.

34. Method according to any one of claims 24 to 33, characterized in that each halogen substituent is F.

35. Method, according to any one of claims 24 to 34, characterized in that Ar is selected from: F Rx ; F ; Rx ; FJ ! ! JF ; RX ; F ; and RX ; and ; ; ; and Rx is selected from methyl, ethyl, n-propyl, n-butyl, sec-butyl, t-butyl, 3-butenyl, n-hexyl, phenyl and substituted phenyl. Petition 870250087486, dated 09 / 26 / 2025, p. 164 / 166 9 / 9 36. Method according to any one of claims 24 to 31, characterized in that the metallocene compound is selected from:

37. Method, according to any one of claims 24 to 31, characterized by the metallocene compound being: Petition 870250087486, dated 09 / 26 / 2025, pp. 165 / 166