Method for preparing metallocene compound

Abstract

Disclosed herein are synthetic methods for increasing the solubility of metallocenes, such as metallocenes containing perfluorobenzyl (indene) groups. These methods can include alkylating a perfluoroaromatic ring of a metallocene precursor using a lithium alkylate reagent in a one-pot reaction. In addition, these processes may be employed without changing reaction equipment or conditions, without separating new intermediates, and at the same time, generally retaining the desired catalyst characteristics.

Description

[0001] Reference to Related Applications

[0002] This application is being filed on June 24, 2024 as a PCT International Patent Application and claims priority to U.S. Provisional Patent Application No. 63 / 510,495 filed on June 27, 2023, the disclosure of which is incorporated by reference herein in its entirety. TECHNICAL FIELD

[0003] The present disclosure relates generally to methods for preparing metallocene compounds and the use of metallocene compounds in catalyst compositions for oligomerization and polymerization processes, and more specifically to preparing metallocene compounds having improved solubility. BACKGROUND

[0004] Metallocene compounds have been developed as effective catalysts for oligomerization and polymerization processes. The structural properties of metallocenes are finely tuned to produce desired oligomer and polymer properties. For example, metallocene compounds comprising at least one indenyl ligand containing at least one halo substituent can produce polyethylenes having low levels of short chain branching. There is a need for metallocene compounds having improved solubility without changing the properties of the oligomers and polymers produced by a given metallocene compound. Accordingly, the present invention is generally directed to this end. SUMMARY

[0005] This Summary is provided to introduce a selection of concepts in a simplified form that are further described below in the DETAILED DESCRIPTION. This Summary is not intended to identify key or essential features of the claimed subject matter. Nor is this Summary intended to be used to limit the scope of the claimed subject matter.

[0006] Disclosed herein are methods for preparing a metallocene compound comprising: (i) contacting a first compound having the formula Cp A –(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 having the formula Cp A –(CH2) n –Ar–R x ; and (iii) contacting the substituted compound with a second compound having the formula Cp B –M–X3 to form a metallocene compound having the formula (I):

[0007]

[0008] In certain aspects, M can be Zr, Ti, or Hf; each X can independently be a halogen or NRy 2; X 1 and X 2 each can be a monoanionic ligand; Cp A may be a cyclopentadienyl, indenyl, or fluorenyl group, optionally substituted with one or more other substituents; Cp B may be a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group; Ar can be an aryl group comprising a halogen substituent; R x may be a C1to C 18 hydrocarbyl substituent (e.g., selected from alkyl or alkenyl or aryl; phenyl, benzyl, C1to C8alkyl, or C3to C8alkenyl); and n can be an integer from 0 to 5.

[0009] Also disclosed herein are metallocene compounds, and they can have the formula (I) and substituents as generally mentioned above. Relative to metallocenes that do not have R x substituents, the metallocene compounds disclosed herein can have improved solubility. Also disclosed herein are catalyst compositions, and they can comprise a metallocene compound as described above, an activator, and optionally a co-catalyst. In certain aspects, the activation can comprise an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, a chemically-treated solid oxide, or any combination thereof.

[0010] Disclosed herein are oligomerization processes, and they can comprise contacting a catalyst composition with an alpha olefin monomer and optionally H2under oligomerization conditions to produce an oligomer product. Disclosed herein are polymerization processes, and they can comprise contacting a catalyst composition with an ethylene monomer and optionally an alpha olefin comonomer under polymerization conditions in a polymerization reactor system to produce an ethylene polymer.

[0011] The foregoing summary and the following detailed description both provide examples and are explanatory only of the application. Accordingly, the foregoing summary and the following detailed description should not be considered to be restrictive of such aspects, but merely illustrative. Further, features or variations can be provided in addition to those set forth herein. For example, certain aspects and embodiments can be directed to various feature combinations and sub-combinations described in the detailed description.

[0012] Definitions

[0013] To more clearly define the terms used herein, the following definitions are provided. The following definitions are applicable to the disclosure unless otherwise indicated. If a term is used in this disclosure but is not specifically defined herein, the definition from the IUPAC Compendium of Chemical Terminology, 2nd Ed (1997) is applicable, provided that the definition does not conflict with any other disclosure or definition applied to the term in this document. If any document incorporated by reference in this document conflicts with the definition of a term in this document, the definition of the term provided in this document controls.

[0014] Herein, features of the subject matter are described so that within a particular aspect, combinations of different features can be contemplated. For each aspect and / or feature disclosed herein, all combinations that do not detrimentally affect the compounds, compositions, and / or methods described herein are contemplated, with or without explicit description of the particular combination. Additionally, any aspect and / or feature disclosed herein can be combined to describe inventive features consistent with the disclosure, unless explicitly stated otherwise.

[0015] While compositions and methods are described herein in terms of "comprising" various components or steps, the compositions and methods can also "consist essentially of" or "consist of" the various components or steps, unless stated otherwise. For example, a catalyst composition consistent with aspects of the present invention can include, alternatively can consist essentially of, or alternatively can consist of a metallocene compound, a co-catalyst, and a chemically treated solid oxide.

[0016] The terms "a," "an," "the" and the like, unless specifically stated otherwise, are intended to include one or more alternatives, e.g., at least one. For example, the disclosure of "a co-catalyst" or "a metallocene compound" is intended to encompass a co-catalyst or metallocene compound or a mixture or combination of more than one co-catalyst or metallocene compound, unless otherwise specified.

[0017] Generally, element groups are indicated using the numbering scheme indicated in the version of the Periodic Table of the Elements published in Chemical and Engineering News, 63(5), 27, 1985. In some cases, a group of elements can be indicated using a common name assigned to the group; for example, alkali metals are indicated with Group 1 elements, alkaline earth metals are indicated with Group 2 elements, transition metals are indicated with Groups 3-12 elements, and halogens or halides are indicated with Group 17 elements.

[0018] For any particular compound disclosed herein, the general structure or name presented is also intended to encompass all structural isomers, conformational isomers, and stereoisomers that can result from a particular set of substituents, unless otherwise indicated. Thus, a general reference to a compound includes all structural isomers, unless explicitly indicated otherwise; for example, a general reference to pentane includes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane, while a general reference to a butyl group includes n-butyl, sec-butyl, iso-butyl, and t-butyl. Additionally, a general structure or name referred to encompasses all enantiomers, diastereomers, and other optical isomers (whether in enantiomeric or racemic forms), where the context allows or requires, as well as mixtures of stereoisomers.

[0019] For any particular formula or name provided, any general formula or name provided also encompasses all conformational isomers, regioisomers, and stereoisomers that can result from a particular set of substituents.

[0020] The term “metallocene” as used herein describes a compound comprising at least one η 3 to η 5 - a cycldienyl-type moiety, wherein η 3 to η 5 - the cycldienyl moiety includes cyclopentadienyl ligands, indenyl ligands, fluorenyl ligands, and the like (including partially saturated or substituted derivatives or analogs of any of these). Possible substituents on these ligands can include H, thus the present invention includes ligands such as tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, substituted partially saturated indenyl, substituted partially saturated fluorenyl, and the like. In some contexts, metallocenes are simply referred to as “catalysts,” in much the same way that the term “co-catalyst” is used herein to refer to, for example, organoaluminum compounds.

[0021] The term “hydrocarbon” refers to a compound containing only carbon and hydrogen. Other designators can be used to indicate the presence of particular groups in a hydrocarbon (e.g., halogenated hydrocarbon indicates the presence of one or more halogen atoms in place of the same number of hydrogen atoms in a hydrocarbon). The term “hydrocarbyl” is used herein according to the definition specified by IUPAC: a monovalent radical formed by the removal of one 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.

[0022] The term "co-catalyst" is used herein generally to refer to a compound, such as an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, an organoaluminum compound, an organozinc compound, an organomagnesium compound, an organolithium compound, and the like, which in use can constitute one component of a catalyst composition, in addition to a chemically treated solid oxide activator, for example. The use of the term "co-catalyst" is not related to the actual function of the compound or any chemical mechanism by which the compound can function.

[0023] The term "substituted" when used to describe a group, such as when referring to a substituted analog of a particular group, is intended to describe any non-hydrogen moiety formally replacing a hydrogen in the group, and is intended to be non-limiting. A group or groups can also be referred to herein as "unsubstituted," or by equivalent terms such as "non-substituted," which refers to the original group in which a non-hydrogen moiety does not replace a hydrogen in the group. Unless otherwise specified, "substituted" is intended to be non-limiting and to include inorganic substituents or organic substituents, as understood by one of ordinary skill in the art.

[0024] The term "olefin" refers to a hydrocarbon having at least one carbon-carbon double bond that is not part of an aromatic ring or aromatic ring system. Unless specifically provided otherwise, the term "olefin" includes aliphatic and aromatic, cyclic and acyclic, and / or straight-chain and branched hydrocarbons having at least one carbon-carbon double bond that is not part of an aromatic ring or ring system. Olefins having only one, only two, only three, etc. carbon-carbon double bonds can be identified by use of the terms "mono," "di," "tri," etc. in the name of the olefin. Olefins can be further identified by the position of the carbon-carbon double bond.

[0025] The term "alpha olefin" as used herein refers to any olefin having 1) a carbon-carbon double bond between the first and second carbon atoms of the longest chain of contiguous carbon atoms, and 2) at least one hydrogen atom bound to the second carbon atom of the chain. Unless explicitly stated otherwise, the term "alpha olefin" includes straight-chain and branched alpha olefins and alpha olefins that can have more than one non-aromatic carbon-carbon double bond. In the case of branched olefins, the branch can be in the 2 position relative to the 1-olefin (vinylidene) of the olefin double bond.

[0026] The term "polymer" is used herein generically to include olefin homopolymers, copolymers, terpolymers, and the like, as well as alloys and blends thereof. The term "polymer" also includes impact, block, graft, random, and alternating copolymers. Copolymers are derived from an olefin monomer and one olefin comonomer, while terpolymers are derived from an olefin monomer and two olefin comonomers. Thus, "polymer" encompasses copolymers and terpolymers derived from any of the olefin monomers and comonomers disclosed herein. Similarly, the scope of the term "polymerization" includes homopolymerization, copolymerization, and terpolymerization. Thus, an ethylene polymer includes ethylene homopolymers, ethylene copolymers (e.g., ethylene / alpha-olefin copolymers), ethylene terpolymers, and the like, as well as blends or mixtures thereof. Thus, ethylene polymers encompass polymers commonly 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 can 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 can be classified as an ethylene / 1-hexene copolymer. Unless otherwise indicated, the term "polymer" also includes all possible geometric configurations, and such configurations can include isotactic, syndiotactic, and atactic symmetries. Furthermore, unless otherwise indicated, the term "polymer" is also intended to include polymers of all molecular weights.

[0027] The terms "catalyst composition," "catalyst mixture," "catalyst system," and the like do not depend on 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 sites, or the fate of the cocatalyst, metallocene compound, or activator after combining these components. Thus, 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 can result from contacting these initial starting components, and this includes heterogeneous and homogeneous catalyst systems or compositions. The terms "catalyst composition," "catalyst mixture," "catalyst system," and the like can be used interchangeably throughout the present disclosure.

[0028] Unless otherwise indicated, the terms "contacting" and "combining" are used herein to describe compositions, processes, and methods in which materials or components are brought together in any order, in any manner, and for any length of time. For example, materials or components can be blended, mixed, slurried, dissolved, reacted, treated, compounded, or otherwise contacted or combined in some other manner or by any suitable method or technique.

[0029] Several types of ranges are disclosed herein. When any type of range is disclosed or claimed, it is intended to include every possible subset of the range, including the end points of the range and any combination of sub-ranges within the range. For example, the weight ratio of metallocene compound to chemically-treated solid oxide in a catalyst composition can be within various ranges. It is disclosed that the weight ratio of metallocene compound to chemically-treated solid oxide can be within the range of 1 : 10 to 1 : 10,000, it is intended to state that the weight ratio can be any ratio within the range and can include, for example, any range or combination of ranges of 1 : 10 to 1 : 10,000, such as 1 : 10 to 1 : 1,000, 1 : 10 to 500: 1, or 1 : 10 to 1 : 100, and the like. Likewise, all other ranges disclosed herein are to be interpreted in a similar manner as this example.

[0030] Generally, the amounts, sizes, formulations, parameters, ranges or other quantities or characteristics are "about" or "approximately" unless otherwise explicitly stated or indicated. The terms "about" and "approximately" are used interchangeably herein to mean that quantities, values, or other elements are within 10% of the stated value, unless otherwise explicitly stated or indicated.

[0031] Although any methods, devices, and materials similar or equivalent to those described herein can be used in the practice or testing of the present application, the typical methods, devices, and materials are described herein.

[0032] All publications and patents mentioned herein are incorporated herein by reference in their entirety for the purpose of describing and disclosing the constructs and methodologies which are described in the publications and patents, which might be used in connection with the presently described application. DETAILED DESCRIPTION

[0033] Disclosed herein are methods for preparing metallocene compounds having hydrophobic substituents to improve solubility. These methods can be performed using a one-pot approach, thus eliminating, in certain aspects, the isolation of air- and moisture-sensitive intermediates. Also disclosed herein are metallocene compounds prepared from these methods. Surprisingly, these metallocene compounds exhibit improved solubility while maintaining comparable catalytic performance in oligomerization and polymerization processes.

[0034] Methods of preparing metallocene compounds

[0035] Conventional metallocene preparation requires isolation of an intermediate containing a cyclopentadienyl group prior to coordination with a metal compound, thus a new pre-synthesis can be required for each new metallocene compound desired. The metallocene synthesis disclosed herein involves in situ modification of a known cyclopentadienyl-containing metallocene substrate and is performed within the reaction framework (e.g., reaction system, conditions) employed in conventional metallocene synthesis protocols. The disclosed method for preparing a metallocene compound is applicable to any metallocene compound suitable for use within a catalyst composition and where improved solubility can be beneficial.

[0036] In certain aspects, the method for preparing a metallocene compound can comprise: (i) contacting a first compound having the formula Cp A –(CH2) n –Ar–X with a Bronsted base to form a deprotonated compound having the formula Cp A(-) –(CH2) n –Ar–X; (ii) contacting the deprotonated compound with a substitution reagent to form a substituted compound having the formula Cp A –(CH2) n –Ar–R x ; and (iii) contacting the substituted compound with a second compound having the formula Cp B –M–X3 to form a metallocene compound having the formula (I):

[0037]

[0038] Generally, as shown in formula (I) and further defined below, each M can be Zr, Ti, or Hf; X can be a halogen or NR y 2; X 1 and X 2 each can independently be a monoanionic ligand; Cp A may be a cyclopentadienyl, indenyl, or fluorenyl group, optionally substituted with one or more other substituents; Cp B may be a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group; Ar can be an aryl group comprising a halogen substituent; R x may be a C1to C 18 alkyl substituent on Ar (e.g., selected from alkyl or alkenyl or aryl; phenyl, benzyl, C1to C8alkyl, or C3to C8alkenyl); and n can be an integer from 0 to 5. However, it will be appreciated that the method for preparing a metallocene compound disclosed herein is applicable to any metallocene as described below. Moreover, it follows that the first compound and the second compound can be any combination of the chemical formula components listed above suitable for preparing any metallocene compound.

[0039] The processes disclosed herein can include deprotonating a first compound comprising a cyclopentadienyl moiety as described above (Cp A ) by contacting the first compound with a Bronsted base. In the first compound, X can be a halogen or NR y ; alternatively, X can be CI; alternatively, X can be Br; alternatively, X can be F. In certain aspects, each R y may independently be a Ci to Cs hydrocarbyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl; alternatively, methyl, ethyl, butyl, hexyl, octyl; alternatively, methyl, ethyl, n-propyl, n-butyl, iso-butyl, n-hexyl, or n-octyl; alternatively, methyl, ethyl, n-butyl, or iso-butyl; alternatively, methyl; alternatively, ethyl; alternatively, n-propyl; alternatively, n-butyl; alternatively, iso-butyl; alternatively, n-hexyl; or alternatively, n-octyl.

[0040] In the first compound (Cp - (CH2) n -Ar - X), Ar can also be further substituted, such as with any additional number of halogen substituents. In certain aspects, the Ar group in Cp - (CH2) n -Ar - X as described above can have one or more additional substituents (e.g., one halogen substituent, or two halogen substituents, or three halogen substituents, or four halogen substituents) in addition to those present in the formula. In certain aspects, each halogen substituent can be F. Thus, the Ar group of the first compound can comprise one F, or two F, or three F, or four F, or 5 F, arranged at any position of Ar. In certain aspects, the first compound can comprise Ar as a 2,6-difluoroaryl group, a 2,4,6-trifluoroaryl group, a 2,3,4,5,6-pentafluoroaryl group, a 4-fluoroaryl group, and the like. Suitable Bronsted bases can generally be defined as and include any compound capable of accepting a proton from the first compound. Thus, in the context of the embodiments contemplated herein, the Bronsted base can be any species or compound capable of accepting or abstracting a proton from the cyclopentadienyl moiety (Cp A ) of the first compound. While not being bound by theory, it is contemplated that, given the pKa of cyclopentadiene is about 15, suitable Bronsted bases can generally include those having a conjugate acid with a pKa of about 15 or above. In certain aspects, the Bronsted base can be a metal carbonate, a metal acetylide, a tert-butoxide, an enolate, a metal hydride, a metal amide, an organolithium, or an organomagnesium halide, among others. Of these, organolithium and organomagnesium halides are most likely to be applied to the preparation of certain metallocene compounds due to their hydrophobicity and solubility in organic solvents.

[0041] In certain aspects, the Bronsted base can include an organolithium compound or an organomagnesium compound selected from the group consisting of methyllithium, ethyllithium, n-butyllithium, t-butyllithium, n-hexyllithium, benzyllithium, phenyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, isopropylmagnesium chloride, t- butylmagnesium chloride, vinylmagnesium bromide, allylmagnesium bromide, ethynylmagnesium chloride, phenylmagnesium chloride, benzylmagnesium chloride, and combinations thereof. In certain aspects, the Bronsted base can include methyllithium, n-butyllithium, t-butyllithium, n-hexyllithium, phenyllithium, and / or benzyllithium. In other aspects, the Bronsted base can include methyllithium, n-butyllithium, and / or n-hexyllithium.

[0042] The processes disclosed herein can also include contacting the deprotonated compound with a substitution reagent to form a substituted compound having the formula Cp A -(CH2) n -Ar-R x The substitution reagent can be any reagent that is sufficiently reactive (e.g., sufficiently nucleophilic) to replace X with an R x group as defined herein. In certain aspects, the substitution reagent can include an organolithium compound or an organomagnesium halide. Thus, for the Bronsted bases listed above, in certain aspects, the substitution reagent can include an organolithium compound or an organomagnesium halide selected from the group consisting of methyllithium, ethyllithium, n-butyllithium, t-butyllithium, n-hexyllithium, benzyllithium, phenyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, isopropylmagnesium chloride, t- butylmagnesium chloride, vinylmagnesium bromide, allylmagnesium bromide, ethynylmagnesium chloride, phenylmagnesium chloride, benzylmagnesium chloride, and the like, and combinations thereof.

[0043] In certain aspects, the substitution reagent can be the same as the Bronsted base. Additionally or alternatively, the Bronsted base and the substitution reagent each can include an organolithium reagent. In certain aspects, the Bronsted base and the substitution reagent each can include methyllithium, n-butyllithium, n-hexyllithium, or combinations thereof.

[0044] The deprotonation and substitution reactions can be performed in situ, without requiring isolation of the deprotonated compound as an intermediate prior to contacting with the substitution reagent. Thus, in certain aspects, the first compound can be contacted with the Bronsted base and the deprotonated compound can be contacted with the substitution reagent in a concerted manner by adding two equivalents of the organolithium and / or organomagnesium halide within a one-pot synthesis. In such aspects, it will be understood that the organolithium and / or organomagnesium halide constitutes both the Bronsted base and the substitution reagent.

[0045] In any event, the molar ratio of Bronsted base to first compound can range from 0.9: 1 to 1.3: 1. In aspects where single substitution of the first compound is desired, the molar ratio of substitution reagent to first compound can also range from 0.9: 1 to 1.3: 1. When multiple substitution of the first compound is desired, the ratio of substitution reagent to first compound can be in multiples as appropriate. For example, when di-substitution is desired, the molar ratio of substitution reagent to first compound can range from 1.7: 1 to 2.3: 1. Alternatively, when tri-substitution of the first compound is desired, the molar ratio of substitution reagent to first compound can range from 2.7: 1 to 3.3: 1. Of course, when the Bronsted base and substitution reagent are the same, the respective appropriate ratio of reagent to first compound can be obtained by adding the typical ratio of each compound. For example, an organolithium reagent can be used as both the Bronsted base and substitution reagent, such that the molar ratio of organolithium reagent to first compound can range from 1.9: 1 to 2.6: 1, in certain aspects, such as in aspects where single substitution of the first compound is desired.

[0046] Without being bound by theory, when the Bronsted base and substitution reagent are added simultaneously (e.g., when two equivalents of an organolithium reagent are added as both the Bronsted base and substitution reagent), the relative reaction rates of the deprotonation and substitution reactions as described can allow deprotonation to proceed before substitution, resulting in the particular substituted product in high yield. It will be appreciated, however, that the deprotonation and substitution steps can proceed in either order, or simultaneously.

[0047] The conditions of the substitution and deprotonation steps can be the same or different. In certain aspects, the deprotection temperature can range from -78 °C to 25 °C, -40 °C to 0 °C, or -30 °C to -10 °C. Similarly, in other aspects, the substitution temperature can also range from -78 °C to 25 °C, -40 °C to 0 °C, or -30 °C to -10 °C. The reaction temperature can be static or dynamic over the course of the reaction, within any of the ranges disclosed herein. For example, deprotonation can begin at -20 °C and warm to 25 °C over the course of the reaction.

[0048] The deprotonation and substitution steps can proceed for any amount of time necessary for the reaction to go to completion. In certain aspects, the reaction time for either or both of the deprotonation and substitution steps can range from 1 min to 1 day, or 12 to 24 hours.

[0049] Metallocene compounds

[0050] The metallocene compounds prepared according to the above-described methods can be any compound resulting from the organic substitution of an aryl leaving group (e.g., aryl halide). Generally, the metallocene compounds disclosed herein can be substitution products of known metallocene compounds having an established use in catalyst compositions. More specifically, in certain aspects, substitution can be observed on the aromatic ring of a cyclopentadienyl-containing ligand, such as an indenyl ligand containing at least one halo-substituted group, such that the leaving group is replaced with a hydrophobic organic substituent. In this manner, the metallocene compounds disclosed herein can generally have an increased solubility in hydrophobic solvents. Surprisingly, in certain aspects, this organic substitution of the metallocene compound in this region does not appreciably decrease the catalytic properties of the metallocene, generally resulting in similar catalytic activity, as well as similar product properties (e.g., oligomer distribution, polymer molecular weight distribution) in oligomerization and polymerization processes.

[0051] As described above, the metallocene compounds disclosed herein can have the formula (I):

[0052]

[0053] In formula (I), M, Cp A , Cp B , Ar, R x , X 1 , and X 2 are each independent elements of the non-bridged metallocene compound. Thus, the non-bridged metallocene compounds having formula (I) can be described using any combination of the M, Cp A , Cp B , Ar, R x , X 1 , and X 2 disclosed herein. Unless otherwise indicated, the above formula (I), any other structural formula disclosed herein, and any metallocene complex, compound, or species disclosed herein are not intended to show stereochemistry or isomeric positioning of different moieties (e.g., these formulas are not intended to show cis or trans isomers, or R or S diastereomers), although such compounds are contemplated and encompassed by these formulas and / or structures.

[0054] According to aspects of the present application, the metal M in formula (I) can be Zr, Ti, or Hf. Thus, in one aspect M can be Zr, in yet another aspect M can be Ti, and in still another aspect M can be Hf.

[0055] X 1 , and X 2 may each independently be a monoanionic ligand. In some aspects, suitable monoanionic ligands can include, but are not limited to, H (hydride), BH4, halide, C1 to C 36 alkyl, C1 to C36 hydrocarbyloxy, C1to C 36 hydrocarbylamino, C1to C 36 hydrocarbylsilyl, C1to C 36 hydrocarbylamidosilyl, -OBR 1 2or -OSO2R 1 wherein R 1 is C1to C 36 hydrocarbyl. X 1 and X 2 may be the same or different monanionic ligand. Suitable hydrocarbyl, hydrocarbyloxy, hydrocarbylamino, hydrocarbylsilyl, and hydrocarbylamidosilyl groups are disclosed, for example, in U.S. Patent No. 9,758,600.

[0056] In formula (I), Cp A may be a cyclopentadienyl, indenyl, or fluorenyl group; substituted as shown or further substituted, where each further substituent can be H, halide, C1to C 36 hydrocarbyl, C1to C 36 halohydrocarbyl, C1to C 36 hydrocarbyloxy, or C1to C 36 hydrocarbylsilyl. Importantly, each substituent on Cp A may be the same or different substituent. Further, each substituent can be located on the respective cyclopentadienyl, indenyl, or fluorenyl ring structure in any position consistent with the rules of chemical valency. In an aspect, the number of substituents on Cp A and / or the location of each substituent on Cp A are independent of one another. For example, two or more substituents on Cp A may be different, or alternatively, each substituent on Cp A may be the same. In these and other aspects, each substituent can be located on the respective cyclopentadienyl, indenyl, or fluorenyl ring structure in any position. Thus, Cp A may have one substituent, or two substituents, or three substituents, or four substituents, or five substituents, and so on. In certain aspects, Cp A may have C1-C 12 alkyl, C2-C 12 alkenyl, C6-C 10 aryl, or C7-C 12 aralkyl substituents (e.g., benzyl).

[0057] In formula (I), Cp B may be a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group. In an aspect, Cp A and Cp B may independently be an unsubstituted cyclopentadienyl or indenyl group. Alternatively, CpA and Cp B may independently be a substituted indenyl group or a cyclopentadienyl group, e.g., having up to 5 substituents. Cp A and Cp B may be the same or different. In certain aspects, Cp A may be an indenyl group, and Cp B may be a cyclopentadienyl group.

[0058] each substituent on Cp B may independently be H, halide, C1to C 36 alkyl, C1to C 36 haloalkyl, C1to C 36 alkoxy, or C1to C 36 haloalkoxy. As with the Cp A described above, each substituent on Cp B may be the same or different substituent. Further, each substituent can be located on the corresponding cyclopentadienyl, indenyl, or fluorenyl ring structure in any position consistent with the rules of chemical valency. In one aspect, the number of substituents on Cp B and / or the position of each substituent on Cp B are independent of one another. For example, two or more substituents on Cp B may be different, or alternatively, each substituent on Cp B may be the same. In another aspect, one or more substituents on Cp A may be different from one or more substituents on Cp B , or alternatively, all substituents on Cp A and / or Cp B may be the same. In these and other aspects, each substituent can be located on the corresponding cyclopentadienyl, indenyl, or fluorenyl ring structure in any position. If substituted, Cp B may independently have one substituent, or two substituents, or three substituents, or four substituents, or five substituents, and so on. As with the Cp A described above, in certain aspects, Cp B may have C1-C 12 alkyl, C2-C 12 alkenyl, C6-C 10 aryl, or C7-C 12 aralkyl substituents (e.g., benzyl). Cp B may also be similarly substituted as Cp A as shown in Formula (I). Thus, in certain aspects, Cp B may have substituents –(CH2) n ArR x . Alternatively, CpB may be unsubstituted.

[0059] In certain aspects, Ar can be a hydrocarbon aryl group. In one aspect, the aromatic ring of the metallocene compound can be a C5to C 30 aromatic group, or alternatively, can be a C5to C 20 aromatic group. In other aspects, Ar can be a heteroaryl group, such as pyrrolidinyl, pyrrolinyl, furanyl, thienyl, imidazolyl, oxazolyl, thiazolyl, indolyl, pyridyl, pyrazinyl, isoxazolyl, pyrazolyl, pyrrolyl, isothiazolyl, oxadiazolyl, triazolyl, indolyl, carbazolyl, benzofuranyl, or benzothienyl.

[0060] In aspects disclosed herein, Ar can be substituted with at least one R x , which generally can represent an aryl organic substituent added in the above process by a substituent reagent. Thus, in certain aspects, R x may be any nucleophilic moiety in the substituent reagents disclosed above. For example, when the substituent reagent is methyl lithium, R x may be a methyl group. In aspects where the substituent reagent is phenylmagnesium chloride, R x may be a phenyl group. In other aspects, R x may be a Ci to C 18 hydrocarbon group substituent (e.g., selected from alkyl or alkenyl or aryl; phenyl, benzyl, Ci to C8alkyl, or C3to C8alkenyl). In yet further aspects, R x may be selected from the group consisting of methyl, ethyl, n-butyl, t-butyl, n-hexyl, benzyl, phenyl, ethenyl, allyl, and ethynyl. In other aspects, R x may be selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, sec-butyl, t-butyl, 3-butenyl, n-hexyl, and substituted or unsubstituted phenyl.

[0061] Ar can have one R x substituent, or two R x substituents, or three R x substituents, or four R x substituents, and so on, depending on the size of the Ar group as discussed above. For example, when Ar is phenyl, the metallocene compound can have up to five R x substituents. As noted above, R x may be substituted at any position on Ar, and thus in some non-limiting aspects, Ar-R x may be 2-R x -phenyl, 4-R x -phenyl, 2,6-di-R x -phenyl, or 2,4,6-tri-R x phenyl.

[0062] Ar can also be further substituted, for example, with any suitable number of halogen substituents. In certain aspects, Ar can be substituted with one or more R x substituents as described above, and can also include one or more substituents (e.g., one halogen substituent, or two halogen substituents, or three halogen substituents, or four halogen substituents). In such aspects, each halogen substituent can be F. Thus, Ar-R x may be further substituted with one F, or two F, or three F, or four F, and any position of Ar. In certain aspects, Ar-R x may be 2,6-difluoro-4-R x -aryl, 2,3,5,6-tetrafluoro-4-R x -aryl, 2-6-di-R x -4-fluoroaryl, and the like, including those shown below:

[0063]

[0064] The metallocene compounds can also include a hydrocarbon linker between Ar and Cp A as shown in Formula (I) -(CH2) n -. The length of the hydrocarbon linker is not limited to any particular length, and thus in certain aspects, n can be an integer ranging from 0 to 5 (e.g., 0, 1, 2, 3, 4, or 5). In certain aspects, n can be 0. In other aspects, n can be 1.

[0065] In certain aspects, illustrative and non-limiting examples of non-bridged metallocene compounds having Formula (I) and / or that can be prepared according to the methods described herein can include the following 4-substituted metallocene compounds:

[0066]

[0067] and the like, 2- and 6-monosubstituted analogs of MET-B through MET-F, disubstituted and trisubstituted analogs, and combinations thereof. It will be understood by one skilled in the art that additional metallocenes having alternating arrangements of R x and halide substituents as shown above are also contemplated herein.

[0068] As described above, the hydrophobic organic substituents (e.g., R xSubstituted aryl halogens (e.g., Ar substituents) surprisingly show improved solubility of the metallocene compound without causing significant changes in catalytic activity or properties of the oligomers and polymer products formed by the oligomerization and polymerization processes using catalyst compositions comprising the metallocene compound. In certain aspects, the solubility of the metallocene compound as described herein in 1-decene at 25 °C can be at least 0.01 wt%, at least 0.05 wt%, or at least 0.1 wt%, or at least 0.2 wt%. In other aspects, the solubility of the metallocene compounds disclosed herein in 1-decene at 25 °C can range from 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%.

[0069] The solubility of the metallocene compound can also be measured relative to a metallocene lacking the R x substituents and having F at this position. In certain aspects, the solubility of the metallocene compound in 1-decene at 25 °C can be at least 10% higher, at least 25% higher, at least 50% higher, at least 100% higher, or at least three times higher than the solubility of an otherwise identical metallocene compound wherein each R x is F. In other aspects, the solubility of the metallocene compound in 1-decene at 25 °C can be 50% to 500% higher, or 100% to 300% higher than the solubility of an otherwise identical metallocene compound wherein each R x is F.

[0070] Catalyst compositions

[0071] According to aspects of the present disclosure, the metallocene compounds disclosed herein can be used within catalyst compositions, for example, for oligomerization and polymerization processes as described below.

[0072] Generally, the catalyst compositions disclosed herein can comprise any of the metallocene compounds described above, an activator, and optionally a co-catalyst. In certain aspects, the activator can 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 the aluminoxane, organoboron or organoborate, and ionizing ionic material, if present, are referred to as co-catalysts. In certain aspects, one or more metallocene compounds, activators, or co-catalysts can be present in the catalyst composition. For example, the catalyst composition can also comprise a second metallocene compound (e.g., a bridged metallocene).

[0073] Aluminoxanes that can be used as activators (and co-catalysts) in the present disclosure generally have a formula such as (R 3 — Al— O) n , R3 (R 3 —Al—O) n Al(R 3 )2 etc. indicates that R 3 The functional group is typically a straight-chain or branched C1-C6 alkyl group, such as methyl, ethyl, propyl, butyl, pentyl, or hexyl, where n typically represents an integer from 1 to 50. In one aspect, the aluminum oxane compound used in the disclosed catalyst composition may include, but is not limited to, methylaluminoxane (MAO), ethylaluminoxane, modified methylaluminoxane (MMAO) (such as isobutyl-modified methylaluminoxane), n-propylaluminoxane, isopropylaluminoxane, n-butylaluminoxane, tert-butylaluminoxane, sec-butylaluminoxane, isobutylaluminoxane, tert-butylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane, neopentylaluminoxane, or combinations thereof.

[0074] Although this disclosure covers groups having different types of "R" groups (such as R... 3 The aluminum oxanes used are trimethylaluminum, triethylaluminum, or triisobutylaluminum, but methylaluminum oxane (MAO), ethylaluminum oxane, or isobutylaluminum oxane are typical aluminum oxane activators used in the catalyst compositions of this disclosure. These aluminum oxanes are prepared from trimethylaluminum, triethylaluminum, or triisobutylaluminum, and are sometimes referred to as poly(methylaluminum oxide), poly(ethylaluminum oxide), and poly(isobutylaluminum oxide), respectively. The use of aluminum oxanes and trialkylaluminum is also within the scope of this disclosure, such as that disclosed in U.S. Patent No. 4,794,096.

[0075] Similar variations exist for organoboron compounds that can be used in the catalyst compositions of this disclosure. In one aspect, the organoboron compound may comprise a neutral boron compound, a borate, or a combination thereof. For example, the organoboron compounds of this disclosure may comprise fluorinated organoboron compounds, fluorinated organoboronate compounds, or combinations thereof. Any fluorinated organoboron or fluorinated organoboronate compound known in the art may be utilized. The term fluorinated organoboron compound has its usual meaning as referring to a neutral compound in the form of BY3. The term fluorinated organoboronate compound also has its usual meaning as referring to a compound in the form of [cationic]+[BY4]. - These are monoanionic salts of organoboron fluorides, where Y represents a fluorinated organic group. For convenience, organoboron fluorides and organoboroates are generally referred to collectively as organoboron and organoboroate compounds, or as required by the context.

[0076] Examples of organoboron and organoborate compounds that can be used as activators in the present disclosure include, but are not limited to, fluorinated arylborate salts such as tetrakis(pentafluorophenyl)borate N,N-dimethylanilinium (DTPB), tetrakis(pentafluorophenyl)borate triphenylcarbenium, lithium tetrakis(pentafluorophenyl)borate, tetrakis[3,5-bis(trifluoromethyl)phenyl]borate N,N-dimethylanilinium, tetrakis[3,5-bis(trifluoromethyl)phenyl]borate triphenylcarbenium, and the like, including mixtures thereof; alternatively, tetrakis(pentafluorophenyl)borate N,N-dimethylanilinium (DTBP); alternatively, tetrakis(pentafluorophenyl)borate triphenylcarbenium; alternatively, lithium tetrakis(pentafluorophenyl)borate; alternatively, tetrakis[3,5-bis(trifluoromethyl)phenyl]borate N,N-dimethylanilinium; or alternatively, tetrakis[3,5-bis(trifluoromethyl)phenyl]borate triphenylcarbenium. Other suitable organoboron and organoborate activators include, but are not limited to, tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)phenyl]boron, and the like, including mixtures thereof.

[0077] While not wishing to be bound by the following theory, it is believed that these examples of organoboron and organoborate compounds and related compounds form "weakly coordinating" anions when combined with organometallic compounds, as disclosed in U.S. Patent No. 5,919,983.

[0078] Ionizing ionic compounds are ionic compounds that can be used to enhance the activity of the catalyst composition.Examples of ionizing ionic compounds that can be suitable as activators in the catalyst compositions disclosed herein 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-dimethylanilinium tetrakis(p-tolyl)borate, N,N-dimethylanilinium tetrakis(m-tolyl)borate, N,N-dimethylanilinium tetrakis(2,4-dimethylphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-dimethylphenyl)borate, N,N-dimethylanilinium 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, tetra(p-tolyl)borate, tetra(m-tolyl)borate, tetra(2,4-dimethylphenyl)borate, tetra(3,5-dimethylphenyl)borate, tetra[3,5-bis(trifluoromethyl)phenyl]borate, tetra(pentafluorophenyl)borate, lithium tetra(p-tolyl)borate, lithium tetraphenylborate, lithium tetra(m-tolyl)borate, lithium tetra(2,4-dimethylphenyl)borate, lithium tetra(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodium tetra(p-tolyl)borate, sodium tetraphenylborate, sodium tetra(m-tolyl)borate, sodium tetra(2,4-dimethylphenyl)borate, sodium tetra(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassium tetra(p-tolyl)borate, potassium tetraphenylborate, potassium tetra(m-tolyl)borate, potassium tetra(2,4-dimethylphenyl)borate, potassium tetra(3,5-dimethylphenyl)borate, potassium tetrafluoroborate, lithium tetra(pentafluorophenyl)aluminate, lithium tetraphenylaluminate, lithium tetra(p-tolyl)aluminate, lithium tetra(m-tolyl)aluminate, lithium tetra(2,4-dimethylphenyl)aluminate, lithium tetra(3,5-dimethylphenyl)aluminate, lithium tetrafluoroaluminate, sodium tetra(pentafluorophenyl)aluminate, sodium tetraphenylaluminate, sodium tetra(p-tolyl)aluminate, sodium tetra(m-tolyl)aluminate, sodium tetra(2,4-dimethylphenyl)aluminate, sodium tetra(3,5-dimethylphenyl)aluminate, sodium tetrafluoroaluminate, potassium tetra(pentafluorophenyl)aluminate, potassium tetraphenylaluminate, potassium tetra(p-tolyl)aluminate, potassium tetra(m-tolyl)aluminate, potassium tetra(2,4-dimethylphenyl)aluminate, potassium tetra(3,5-dimethylphenyl)aluminate, potassium tetrafluoroaluminate, and the like, or combinations thereof.Additional examples and descriptions of ionized ionic compounds are generally disclosed in U.S. Patent No. 11,186,665.

[0079] Chemically treated solid oxides are also suitable activators in the disclosed catalyst compositions. In certain aspects, the chemically treated solid oxides described herein can generally refer to those disclosed in, for example, U.S. Patent Nos. 8,536,391 and 10,919,996. In certain aspects, the chemically treated solid oxides can include a solid oxide comprising oxygen and at least one element selected from Groups 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 of the Periodic Table of the Elements, or comprising oxygen and at least one element selected from the lanthanide series or actinide series; alternatively, the solid oxide can comprise oxygen and at least one element selected from Groups 4, 5, 6, 12, 13, or 14 of the Periodic Table of the Elements, or comprising oxygen and at least one element selected from the lanthanide series. (See: Hawley's Condensed Chemical Dictionary, 11thEd., John Wiley & Sons; 1995; Cotton, F. A.; Wilkinson, G.; Murillo; C. A.; and Bochmann; M. Advanced Inorganic Chemistry, 6thEd., Wiley-Interscience, 1999) In some aspects, the inorganic oxide can 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 can comprise oxygen and at least one element selected from Al, B, Si, Ti, P, Zn, or Zr.

[0080] In certain aspects, the chemically treated solid oxides can include a solid oxide comprising AI2O3, 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 can comprise silica, alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination thereof. In other aspects, the solid oxide can comprise silica-coated alumina.

[0081] In certain aspects, the chemically treated solid oxide can comprise at least one solid oxide treated with at least one electron-withdrawing anion, wherein the solid oxide can comprise any oxide characterized by a high surface area, and the electron-withdrawing anion can comprise any anion that increases the acidity of the solid oxide compared to the solid oxide that has not been treated with at least one electron-withdrawing anion.

[0082] The solid oxide material can be treated with a halide ion, a sulfate ion, or a combination thereof, and optionally treated with a metal ion. In one aspect, the solid oxide material can be treated with a sulfate source (referred to as a sulfating agent), a phosphate source (referred to as a phosphating agent), an iodide ion source (referred to as an iodinating agent), a bromide ion source (referred to as a brominating agent), a chloride ion source (referred to as a chlorinating agent), a fluoride ion source (referred to as a fluorinating agent), or any combination thereof, and calcined to provide a chemically treated solid oxide.

[0083] In certain aspects, the chemically treated solid oxide can comprise a solid oxide treated with an electron-withdrawing anion, wherein the solid oxide is selected from the group consisting of silica, alumina, silica-alumina, aluminum phosphate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or mixtures thereof, and the electron-withdrawing anion is selected from the group consisting of fluoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate, fluorophosphate, fluorosulfate, or any combination thereof. Thus, in certain aspects, the chemically treated solid oxide can comprise fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, brominated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, chlorinated silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, fluorinated silica-coated alumina, fluorinated chlorinated silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, and the like, or any combination thereof. In certain aspects, the chemically treated solid oxide can comprise fluorinated alumina, sulfated alumina, fluorinated silica-alumina, sulfated silica-alumina, fluorinated silica-coated alumina, fluorinated chlorinated silica-coated alumina, sulfated silica-coated alumina, or any combination thereof. In other aspects, the chemically treated solid oxide can comprise sulfated alumina and / or fluorinated silica-coated alumina.

[0084] In some aspects, the chemically treated solid oxides disclosed herein may include calcined solid oxides. Therefore, in this respect, the solid oxide may be calcined or uncalcined; alternatively, calcined; or alternatively, uncalcined. In some aspects, the solid oxide may be calcined before, during, or after contact with an electron-withdrawing anion source to obtain the chemically treated solid oxide. Calcination of the treated solid oxide is typically carried out in an ambient atmosphere; alternatively, in a dry ambient atmosphere. The solid oxide may be calcined at a temperature of about 200°C to about 900°C; alternatively, about 300°C to about 800°C; alternatively, about 400°C to about 700°C; or alternatively, about 350°C to about 550°C. The solid oxide may be maintained at the calcination temperature for a period of time 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.

[0085] In some aspects disclosed herein, the catalyst composition may also include a co-catalyst. In some aspects, the co-catalyst may include an organoaluminum compound, an aluminum oxane compound, an organoboron or organoborate compound, an ionized compound, or a combination thereof; alternatively, the co-catalyst may include an organoaluminum compound. In one aspect, a suitable organoaluminum compound may have the formula (R... Z )3Al, where each R Z It can be an aliphatic group having 1 to 10 carbon atoms independently. For example, each R Z It can be methyl, ethyl, propyl, butyl, hexyl, or isobutyl. On the other hand, examples of organoaluminum compounds suitable for use according to the invention include, but are not limited to, trialkylaluminum compounds, dialkylaluminum halide compounds, dialkylaluminum hydride compounds, and combinations thereof. Specific, non-limiting examples of suitable organoaluminum compounds may include trimethylaluminum (TMA), triethylaluminum (TEA), tri-n-propylaluminum (TNPA), tri-n-butylaluminum (TNBA), triisobutylaluminum (TIBA), tri-n-hexylaluminum, tri-n-octylaluminum (TNOA), and combinations thereof.

[0086] Typically, organoaluminum compounds (or other co-catalysts) can be used in any suitable amount relative to the metallocene compound. In some aspects, the molar ratio of the co-catalyst to the metallocene compound in the catalyst composition can range from 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 herein can also be characterized according to the weight ratio of the metallocene compound to the activator, which in some aspects can range from 1:10 to 1:10,000, 1:10 to 1:1,000, 1:10 to 500:1, or 1:10 to 1:100.

[0087] In another aspect of the application, the catalyst composition can be substantially free of aluminoxane, organoboron or organoborate compounds, ionizing ionic compounds, and / or other similar materials; alternatively, substantially free of aluminoxane; alternatively, substantially free of organoboron or organoborate compounds; or alternatively, substantially free of ionizing ionic compounds. In these aspects, the catalyst composition has the catalyst activity discussed herein in the absence of these additional materials. For example, the catalyst composition of the application can consist essentially of the metallocene, activator, and organoaluminum compound, wherein no other materials are present in the catalyst composition that increase / decrease the catalyst activity of the catalyst composition by more than about 10% compared to the catalyst activity of the catalyst composition in the absence of the materials.

[0088] The catalyst compositions of the application generally have a catalyst activity of greater than 250 grams of ethylene polymer (homopolymer and / or copolymer, as needed depending on the context) per hour per gram of activator-support (abbreviated as g / (g*h)). In another aspect, the catalyst activity can be greater than 350 g / (g*h), greater than 450 g / (g*h), or greater than 550 g / (g*h). However, in another aspect, the catalyst activity can be greater than 700 g / (g*h), greater than 1000 g / (g*h), or greater than 2000 g / (g*h), and generally up to 5000-10,000 g / (g*h). Exemplary and non-limiting ranges of catalyst activity include 500 to 5000, 750 to 4000, or 1000 to 3500 g / (g*h), etc. In certain aspects, the above activities can be obtained under slurry polymerization conditions using triisobutylaluminum cocatalyst, using isobutane as diluent, a polymerization temperature of 80°C, and a reactor pressure of 320 psig. Further, in some aspects, the activator-support can comprise a sulfated alumina, a fluorided silica-alumina, or a fluorided silica-coated alumina, but is not limited thereto.

[0089] Oligomerization process

[0090] The processes disclosed herein can include contacting any of the catalyst compositions disclosed herein with alpha olefin monomers and optionally H2 under oligomerization conditions to produce an oligomer product.

[0091] A variety of alpha olefin monomers can be reacted in the processes provided herein. For example, the alpha olefins can include, consist essentially of, or consist of C4 to C 30 alpha olefins; alternatively, C4 to C 18 alpha olefins; alternatively, C4 to C 14 alpha olefins; alternatively, C5 to C 18 alpha olefins; alternatively, C6 to C 16 alpha olefins; or alternatively, C8 to C 12α-olefins. In one respect, oligomer products can be produced from α-olefins that include, are substantially composed of, or consist of: C6 α-olefins, C8 α-olefins, C... 10 α-olefins, C 12 α-olefins, C 14 α-olefins, C 16 α-olefins or any combination thereof; alternatively, C8 α-olefins, C 10 α-olefins, C 12 α-olefins or any combination thereof; alternatively, C6 α-olefins; alternatively, C8 α-olefins; alternatively, C 10 α-olefins; alternatively, C 12 α-olefins; alternatively, C 14 α-olefins; alternatively, C 16 α-olefins; or alternatively, C 18 α-olefins. In another aspect, α-olefins may include, consist essentially of, or be composed of: 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, or any combination thereof. For example, α-olefins may include, consist essentially of, or be composed of: 1-octene; alternatively, 1-decene; or alternatively, 1-dodecene.

[0092] The alpha olefin monomers can be derived from ethylene, which is produced from fossil-based feedstocks, bio-based feedstocks, or recycled, circular feedstocks that are either fossil-based or bio-based. For example, the alpha olefins can be derived from ethylene produced from natural gas feedstocks. Alternatively, the alpha olefins can be derived from ethylene produced from naphtha obtained from crude oil. Alternatively, the alpha olefins can be derived from ethylene produced from ethanol, where the ethanol is derived from cellulosic or lignocellulosic feedstocks (i.e., sugar cane, corn, etc.). Alternatively, the alpha olefins can be derived from ethylene produced from recycled plastic materials that are pyrolyzed to form a circular pyrolysis gas or pyrolysis oil feedstock. When renewable or circular feedstocks are used, the resulting products can be certified as circular or renewable products. Any suitable amount of the alpha olefin feed can be normal alpha olefins. Typically, the alpha olefins contain at least 50 wt% normal alpha olefins, and more often at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 85 wt%, at least 90 wt%, at least 92.5 wt%, or at least 95 wt% normal alpha olefins, and in some aspects less than or equal to 99.9 wt%, less than or equal to 99.5 wt%, less than or equal to 97 wt%, or less than or equal to 95 wt% normal alpha olefins, and in other aspects normal alpha olefins ranging from any minimum amount disclosed herein to any maximum amount disclosed herein, for example, the alpha olefins contain 85 wt% to 95 wt% or 90 wt% to 99 wt% 1-hexene, 1-octene, 1-decene, 1-dodecene, or 1-tetradecene. Thus, mixtures of various alpha olefins (or normal alpha olefins) having different carbon atom numbers can be used, or alpha olefins (or normal alpha olefins) having primarily a single carbon atom number can be used. While mixtures of different carbon number olefins can be used, the processes disclosed herein are particularly suitable for use with alpha olefins (or normal alpha olefins) having a single carbon number.

[0093] In an aspect, the alpha olefin monomers can be C 10 mono-olefin mixture. In an aspect, the alpha olefin monomers can also contain C 14 mono-olefin. In another aspect, alpha olefin feedstocks suitable for use in the processes described herein are described in U.S. Patent No. 10,435,336.

[0094] The ratio of certain components can be used to control the oligomerization process. For example, increasing the weight ratio of metallocene compound to alpha olefin monomer in the catalyst composition can result in higher conversion, but can also result in a heavier oligomer product mixture (e.g., less desired dimer and trimer products). Nonetheless, the catalyst composition and alpha olefin monomer can be contacted at a weight ratio of metallocene compound to alpha olefin monomer in the range of 1 : 100 to 1 : 1,000,000, 1 : 1,000 to 1 : 1,000,000, 1 : 1,000 to 1 : 500,000, or 1 : 10,000 to 1 : 250,000, without limitation.

[0095] The catalyst composition has relatively high activity. For example, the activity can be at least 50,000 g oligomer / g metallocene compound per hour (g / (g*h)), or 20,000 g / (g*h) to 180,000 g / (g*h), 40,000 g / (g*h) to 160,000 g / (g*h), or 60,000 to 120,000 g / (g*h), for example in aspects where the oligomerization conditions include an oligomerization temperature of 110 °C, and where the catalyst composition includes a TIBA cocatalyst.

[0096] As described herein, the catalyst activity of the catalyst composition can be unexpectedly comparable or higher than a catalyst system comprising an otherwise identical catalyst composition of a metallocene compound where each R x The catalyst activity of the catalyst composition can be unexpectedly comparable or higher than a catalyst system comprising an otherwise identical catalyst composition of a metallocene compound where each R x The catalyst activity of the catalyst composition can be unexpectedly comparable or higher than a catalyst system comprising an otherwise identical catalyst composition of a metallocene compound where each R

[0097] The oligomerization conditions utilized in the oligomerization process can include 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 can be in the range of 70 °C to 90 °C, alternatively, 90 °C to 120 °C; or alternatively, 110 °C to 140 °C.

[0098] In another non-limiting aspect, the oligomerization conditions utilized in the disclosed oligomerization processes herein can include conducting the oligomerization reaction in the presence of hydrogen. The hydrogen partial pressure in the oligomerization reaction can be any hydrogen pressure that does not adversely affect the oligomerization reaction. In some non-limiting aspects, the oligomerization conditions can include a hydrogen partial pressure of at least 0.1 psig, and typically up to and including 50 psig. Typical ranges for the hydrogen partial pressure can 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.

[0099] In certain aspects, the oligomerization process can further include a step of separating at least a portion of the catalyst composition from the oligomer product using any suitable technique, such as by filtration. Likewise, the oligomerization process can further include a step of separating unreacted alpha olefin monomer from the oligomer product using any suitable technique, such as, for example, wiped film evaporation, distillation, short path distillation, or any combination thereof. Optionally, the oligomerization process can further include recycling either or both of the recovered catalyst composition and the recovered unreacted alpha olefin monomer, for example, for reuse in the oligomerization process.

[0100] Further, in certain aspects, the oligomerization process can further include a step of fractionating the oligomer product into alpha olefin dimers, alpha olefin trimers, and alpha olefin heavies (including alpha olefin tetramers and higher oligomers) using any suitable technique, such as, for example, wiped film evaporation, distillation, short path distillation, or any combination thereof. Similarly, the oligomerization process can further include a step of hydrogenating at least a portion of the oligomer product (e.g., alpha olefin trimers) to form polyalphaolefins. The process of fractionating the oligomer product into several oligomer fractions is well known, and one skilled in the art will understand the techniques and conditions for fractionation, and subsequent separation, purification, and / or hydrogenation steps to convert the oligomer fractions into polyalphaolefins.

[0101] The oligomer product typically contains dimers of the alpha olefin monomer, trimers of the alpha olefin monomer, and higher molecular weight oligomers of the alpha olefin monomer (e.g., tetramers and heavies). Advantageously, the disclosed oligomerization processes can produce an oligomer product having a relatively high amount of dimers and trimers, which can be used in subsequent reactions and the production of polyalphaolefins.

[0102] Thus, the oligomer product formed by the oligomerization process can be characterized by the relative amounts of particular oligomers. For example, it is beneficial to maximize the amount of dimers and trimers, while minimizing the amount of heavier oligomers in the oligomer product. Surprisingly, the oligomerization process is able to proceed at high conversion of the alpha olefin monomer without resulting in a shift of the resulting oligomer product to heavier oligomers. In certain aspects, the oligomer product can 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 tetramers. Additionally or alternatively, the oligomer product can 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 dimers and trimers (total). Unreacted alpha olefin monomer is not included in the compositional breakdown of the oligomer product.

[0103] In certain aspects, and advantageously, the dimers can be the predominant component of the oligomer product, and the oligomer product can 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 dimers (based on total oligomers in the oligomer product, and not including unreacted alpha olefin monomer).

[0104] Generally, vinylidene is desirable because of its high reactivity relative to internal and branched dimers of the alpha olefin monomer. In certain aspects, the dimers in the oligomer product comprise 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. Thus, the amount of internal olefins 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%.

[0105] For the above catalyst composition activities, the product properties of the oligomerization process disclosed herein can be comparable to oligomerization processes relying on similar metallocene compounds without the R x substituents. Thus, in certain aspects, under the same catalyst preparation and oligomerization conditions, the oligomer product can have a dimer content and properties (e.g., the amount of internal, tri-substituted dimers, and / or vinylidene dimers in the dimer product) comparable (e.g., within 20%, 15%, 10%, or 5%) to the dimer content and properties of a catalyst system having other aspects of the metallocene compound where each R x

[0106] ​Polyalphaolefins can have certain desirable properties. For example, one desirable property that can be achieved through the use of one or more separation steps is a 100°C kinematic viscosity. A second desirable property that can be achieved through the use of one or more separation steps is to achieve a desired flash point. A third desirable property that can be achieved through the use of one or more separation steps is to achieve a desired fire point. A fourth desirable property that can be achieved through the use of one or more separation steps is to achieve a desired Noack volatility. A fifth desirable property that can be achieved through the use of one or more separation steps is to achieve a desired pour point. In an embodiment, the separation steps can be used to remove lower and / or higher molecular weight oligomers to produce an alpha olefin oligomer product having a desired 100°C kinematic viscosity, flash point, fire point, Noack volatility, and / or pour point, or to produce an alpha olefin oligomer product that will produce a polyalphaolefin.

[0107] Polymerization process

[0108] Olefin polymers (e.g., ethylene polymers) can be produced using any suitable olefin polymerization process, using various types of polymerization reactors, polymerization reactor systems, and polymerization reaction conditions, using the catalyst compositions disclosed herein. One such olefin polymerization process for polymerizing olefins in the presence of the catalyst compositions of the present application can include contacting the catalyst composition with olefin monomers and optional olefin comonomer(s) in a polymerization reactor system under polymerization conditions to produce an olefin polymer (e.g., an ethylene polymer). The present application also includes any olefin polymers (e.g., ethylene polymers) produced by any of the polymerization processes disclosed herein.

[0109] Olefin monomers that can be used in the catalyst compositions and polymerization processes of the present application can generally include olefin compounds having 2 to 30 carbon atoms per molecule and having at least one olefinic double bond, such as ethylene or propylene. In an aspect, the olefin monomers can comprise C2-C 20 olefin; alternatively, the C2-C 20 alpha-olefin; alternatively, the C2-C 10 olefin; alternatively, the C2-C 10 alpha-olefin; alternatively, the olefin monomers can comprise ethylene; or alternatively, the olefin monomers can comprise propylene (e.g., to produce a polypropylene homopolymer or a propylene-based copolymer).

[0110] When a copolymer (or alternatively, a terpolymer) is desired, the olefin monomers and the olefin comonomers can independently include, for example, C2-C 20 alpha-olefin. In some aspects, the olefin monomers can include ethylene or propylene, with at least one comonomer (e.g., C2-C 20 alpha-olefin or C3-C 20alpha-olefins) copolymerization. According to one aspect of the application, the olefin monomer used in the polymerization process can include ethylene. In this aspect, the comonomer can include C3-C 10 alpha-olefins; alternatively, the comonomer can include 1-butene, 1-pentene, 1- hexene, 1-octene, 1-decene, styrene, or any combination thereof; alternatively, the comonomer can include 1-butene, 1-hexene, 1-octene, or any combination thereof; alternatively, the comonomer can include 1-butene; alternatively, the comonomer can include 1-hexene; or alternatively, the comonomer can include 1-octene.

[0111] In certain aspects, the polymerization process can include contacting the catalyst composition, the olefin monomer, and the optional comonomer with a diluent. Suitable diluents for use in slurry polymerization include, but are not limited to, the monomers being polymerized and hydrocarbons that are liquid at the 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, heptane, octane, petroleum ether, light naphtha, heavy naphtha, or any combination thereof. Some loop polymerization reactions can occur under bulk conditions in which no diluent is used.

[0112] As used herein, a “polymerization reactor” includes any polymerization reactor capable of polymerizing (including oligomerizing) olefin monomers and comonomers (one or more than one comonomer) to produce homopolymers, copolymers, terpolymers, etc. Various types of polymerization reactors include those that can be referred to as batch reactors, slurry reactors, gas phase reactors, solution reactors, etc., or combinations thereof; or alternatively, the polymerization reactor system can include a slurry reactor, a gas phase reactor, a solution reactor, or combinations thereof. Polymerization conditions for various reactor types are well known to those skilled in the art. Gas phase reactors can include fluidized bed reactors or staged horizontal reactors. Slurry reactors can include vertical and / or horizontal loops. Reactor types can include batch or continuous processes. Continuous processes can use batch and / or continuous product withdrawal. The polymerization reactor system and process can also include partial or total direct recycle of unreacted monomer, unreacted comonomer, and / or diluent.

[0113] The polymerization reactor system can include a single reactor or multiple reactors of the same or different types (2 reactors, more than 2 reactors). For example, the polymerization reactor system can include a slurry reactor, a gas phase reactor, a solution reactor, or a combination of two or more of these reactors. Polymerization in multiple reactors can include several stages in at least two separate polymerization reactors interconnected by transfer means, making it possible to transfer the polymer from a first polymerization reactor to a second reactor. The polymerization conditions required in one of the reactors can differ from the operating conditions of the other reactors. Alternatively, polymerization in multiple reactors can include manual transfer of the polymer from one reactor to a subsequent reactor to continue polymerization. The multiple reactor system can include any combination, including but not limited to multiple loop reactors, multiple gas phase reactors, or a combination of loop reactors and gas phase reactors. The multiple reactors can be operated in series, in parallel, or in series and in parallel. Accordingly, the present invention encompasses polymerization reactor systems including a single reactor, including two reactors, and including more than two reactors. In certain aspects of the invention, the polymerization reactor system can include a slurry reactor, a gas phase reactor, a solution reactor, and multiple reactor combinations thereof.

[0114] According to one aspect, the polymerization reactor system can include at least one loop slurry reactor including a vertical or horizontal loop. Monomer, diluent, catalyst, and comonomer can be continuously fed to the loop reactor where polymerization occurs. Generally, a continuous process can include continuous introduction of monomer / comonomer, catalyst, and diluent into the polymerization reactor, and continuous removal from this reactor of a suspension comprising polymer particles and diluent. The reactor effluent can be flashed to remove the solid polymer from the liquid comprising diluent, monomer, and / or comonomer. Various techniques can be used for this separation step, including but not limited to flashing, which can include any combination of heating and reduced pressure, separation by cyclonic action in a cyclone or hydrocyclone, or by centrifugation.

[0115] A typical slurry polymerization process (also referred to as a particle formation process) is disclosed, for example, in U.S. Patent 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.

[0116] According to yet another aspect, the polymerization reactor system can include at least one gas phase reactor (e.g., a fluidized bed reactor). Such reactor systems can employ a continuous recycle stream containing one or more monomers that is continuously circulated through a fluidized bed under polymerization conditions in the presence of a catalyst. The recycle stream can be withdrawn from the fluidized bed and recycled back into the reactor. At the same time, polymer product can be withdrawn from the reactor and new or fresh monomer can be added to replace polymerized monomer. Such gas phase reactors can include processes for multistep gas phase polymerization of olefins, in which the olefins are polymerized in gas phase in at least two separate gas phase polymerization zones, while feeding the catalyst-containing polymer formed in a first polymerization zone to a second polymerization zone. Representative gas phase reactors are disclosed in U.S. Patent Nos. 5,352,749; 4,588,790; 5,436,304; 7,531,606; and 7,598,327, each of which is incorporated by reference herein in its entirety.

[0117] According to yet another aspect, the polymerization reactor system can include a solution polymerization reactor, in which monomer / co-monomer is contacted with a catalyst composition by suitable agitation or other means. A carrier comprising an inert organic diluent or excess monomer can be employed. If desired, the monomer / co-monomer can be contacted with the catalytic reaction product in the gas phase in the presence or absence of liquid material. The polymerization zone can be maintained at a temperature and pressure that will cause a polymer solution to form in the reaction medium. Agitation can be employed to obtain better temperature control and to maintain a homogeneous polymerization mixture throughout the polymerization zone. Suitable means are used to dissipate the heat of polymerization.

[0118] The polymerization reactor system can also include any combination of at least one feedstock feed system, at least one feed system for catalyst or catalyst components, and / or at least one polymer recovery system. Suitable reactor systems can also include systems for feedstock purification, catalyst storage and preparation, extrusion, reactor cooling, polymer recovery, fractionation, recycle, storage, loading, laboratory analysis, and process control. Hydrogen can be added to the polymerization reactor as desired (e.g., continuously or pulsed) depending on the desired properties of the olefin polymer.

[0119] Polymerization conditions, which can be controlled to improve efficiency and provide desired polymer properties, can include temperature, pressure, and concentration of various reactants. Polymerization temperature can affect catalyst production rate, polymer molecular weight, and molecular weight distribution. For example, to produce an olefin polymer (or ethylene polymer) of a particular grade, various polymerization conditions can be held substantially constant. Suitable polymerization temperatures can be any temperature below the depolymerization temperature, according to the Gibbs Free energy equation. Generally, this includes, for example, 60 °C to 280 °C or 60 °C to 120 °C depending on the type of polymerization reactor. In some reactor systems, the polymerization temperature can generally range from about 70 °C to about 105 °C or from about 75 °C to about 100 °C.

[0120] Suitable pressures will also vary depending on the reactor and type of polymerization. The pressure for liquid phase polymerization in a loop reactor is generally less than 1000 psig (6.9 MPa). The pressure for gas phase polymerization is generally at about 200 to 500 psig (1.4 MPa to 3.4 MPa). In certain aspects, the polymerization conditions can include a reaction pressure in the range of 200 to 1000 psig. Polymerization reactors can also operate in the supercritical region, which generally occurs at higher temperatures and pressures. Operation above the critical point of the pressure / temperature chart (supercritical phase) can provide advantages to the polymerization reaction process.

[0121] The olefin polymers encompassed herein can include any polymer produced from any of the olefin monomers (and optional comonomers) described herein. For example, the olefin polymers can include ethylene homopolymers, propylene homopolymers, ethylene copolymers (e.g., ethylene / alpha-olefin, ethylene / 1-butene, ethylene / 1-hexene, or ethylene / 1-octene), propylene copolymers, ethylene terpolymers, propylene terpolymers, etc., including combinations thereof. In one aspect, the olefin polymers can be (can include) ethylene homopolymers, ethylene / 1-butene copolymers, ethylene / 1-hexene copolymers, or ethylene / 1-octene copolymers, or combinations thereof; or, alternatively, ethylene / 1-hexene copolymers. In another aspect, the olefin polymers can be (or can include) polypropylene homopolymers and / or propylene-based copolymers. In some aspects, the olefin polymers can have a bimodal molecular weight distribution, while in other aspects, the olefin polymers can have a multimodal molecular weight distribution. However, in still other aspects, the olefin polymers can have a unimodal molecular weight distribution.

[0122] The polymerization processes disclosed herein can produce ethylene polymers having substantially similar properties to ethylene polymers produced by analogous unsubstituted fluorinated metallocene compounds.

[0123] The ethylene polymers can have a density greater than or equal to 0.94 g / cm 3 , for example, greater than or equal to 0.942 g / cm3 or greater than or equal to 0.945 g / cm 3 However, in particular aspects, the density can be in the range of 0.92 to 0.96, 0.93 to 0.95, 0.925 to 0.94, or 0.93 to 0.94 g / cm 3 In an aspect, the ethylene polymer can have a number average molecular weight (Mn) in the range of 5,000 g / mol to 250,000 g / mol, 10,000 g / mol to 200,000 g, or 20,000 g / mol to 150,000 g / mol. In other aspects, the ethylene polymer can have a Mw in the range of 50,000 to 700,000, 75,000 to 500,000, or 100,000 to 400,000 g / mol. In other aspects, the ethylene polymer can have a Mw / Mn ratio in the range of 2 to 15, or 2 to 10. In other aspects, the ethylene polymer can 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 can have a 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.

[0124] In certain aspects, the ethylene polymers of the present application can have (or can be characterized by) a density in the range of 0.92 to 0.96 g / cm 3 a weight average molecular weight (Mw) in the range of 50,000 to 700,000, a molecular weight (Mn) in the range of 5,000 to 250,000 g / mol, a Mw / Mn ratio in the range of 1 to 40, a high load melt index (HLMI) in the range of 0 to 100 g / 10 min. In certain aspects, the HLMI of the ethylene polymer can 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.

[0125] As described herein, the catalyst activity of these catalyst compositions can be unexpectedly comparable to or higher than the catalyst activity of other aspects of catalyst compositions comprising metallocene compounds in which each R x is F when tested and compared under the same polymerization conditions. Thus, the disclosed polymerization process (or catalyst composition) is characterized by the activity of the catalyst composition being comparable (e.g., within 20%, 15%, 10%, or 5%) to the activity of other aspects of catalyst systems comprising metallocene compounds in which each R x is F under the same catalyst preparation and polymerization conditions.

[0126] Articles and Products

[0127] Articles can be formed from and / or can include the olefin polymers (e.g., ethylene polymers, ethylene / 1-hexene polymers) and olefin oligomers (e.g., 1-decene oligomers) and products thereof (e.g., polyalphaolefins derived from 1-decene oligomers) of the present application, and are therefore contemplated herein.

[0128] For example, articles that can include the polymers of the present application can include, but are not limited to, agricultural films, automotive parts, bottles, chemical containers, buckets, fibers or fabrics, food packaging films or containers, food service articles, fuel tanks, geomembranes, household containers, liners, molded products, medical devices or materials, outdoor storage products (e.g., panels for outdoor shed walls), outdoor play equipment (e.g., bases for basketball hoops), pipes, sheets or tapes, toys or traffic barriers, and the like. Various processes can be employed to form these articles. Non-limiting examples of these processes include injection molding, blow molding, rotational molding, film extrusion, sheet extrusion, profile extrusion, thermoforming, and the like. In addition, 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, Volume 72, Number 12; and Film Extrusion Manual - Process, Materials, Properties, TAPPI Press, 1992.

[0129] In some aspects of the present application, the article can include any of the olefin polymers (or ethylene polymers) described herein, and the article can be or can include a film, such as a blown film; alternatively, a pipe product; or alternatively, a blow molded product, such as a blow molded bottle.

[0130] Examples

[0131] The present application is further exemplified by the following examples, which should not be construed as in any way limiting the scope of the present application. Various other aspects, embodiments, modifications, and equivalents thereof, become apparent to those skilled in the art once the description has been read and understood.

[0132] Disclosed are methods for preparing metallocene compounds, and in particular, methods for preparing metallocene compounds by in situ substitution of a metallocene precursor as part of a one-pot reaction. Advantageously, metallocenes prepared by the disclosed methods maintain their catalytic properties and functionality while improving solubility in 1-decene relative to otherwise identical unsubstituted metallocene compounds.

[0133] Preparation of metallocene compounds

[0134] Prior art example 1 - synthesis of fluorinated metallocene (MET-A)

[0135] A fluorinated metallocene (denoted MET-A) was prepared for comparison with substituted metallocenes according to the following Reaction Scheme 1 and subsequent experimental procedures. Typically, a single equivalent of n-butyllithium was used as the organic base for deprotonation of the substituted indenyl precursor in the first step deprotonation step. The deprotonated indenyl precursor was then contacted with a metal cyclopentadienyl trichloride complex, which was prepared as disclosed previously in U.S. Patent No. 11,186,655 (“IE2”), and typically as shown in the following reaction.

[0136]

[0137] 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 hexanes, 2.4 mL, 3.8 mmol) was added slowly. The resulting solution was allowed to warm to ambient temperature and stirred for 30 minutes. The solution was again cooled to -78 °C and a slurry of cyclopentadienyl zirconium(IV) trichloride (1.0 g, 3.8 mmol) in diethyl ether (30 mL) was added. The resulting slurry was allowed to warm to ambient temperature with stirring overnight. The mixture was stripped under high vacuum to a bright yellow solid. The solid was dissolved in 30 mL of toluene and centrifuged. The supernatant was transferred to a clean flask and concentrated to approximately 5 mL. The solution was partitioned with approximately 10 mL of pentane and placed in a freezer at -35 °C. MET-A was isolated as yellow needles in 0.659 g yield. 1 H NMR (300 MHz, C6D6) 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, -CH2C6F5). 19 F NMR (282.4 MHz, C6D6, 25 °C) δ = -144.75 (m), -158.70 (t), -164.01 (m).

[0138] Example 2-6 - One-pot alkylation of metallocene precursors

[0139] Surprisingly, it was found that hydrophobic substituents could be incorporated into Cp Ain the metallocene precursor, as shown in the following reaction equation. The reaction can be carried out under the same conditions as deprotonation with an organic base and thus allows for the incorporation of the hydrophobic R x fluorinated Cp in situ A in the precursor as part of the one-pot synthesis of the metallocene compound.

[0140]

[0141] Example 2 (MET-B): A 200 mL flask was charged with l-((perfluorophenyl)methyl)-lH-indene (850 mg, 2.87 mmol) and 100 mL diethyl ether. The mixture was cooled to -20 °C and MeLi (4.1 mL, 6.6 mmol) was added. The mixture was allowed to warm to ambient temperature with stirring overnight. After 14 hours, a separate flask was charged with CpZrCl3(75 mg, 2.87 mmol) and 50 mL diethyl ether. The resulting slurry was cooled to -78 °C and the first reaction mixture was added quickly. The mixture was allowed to warm slowly to ambient temperature with stirring overnight. After 16 hours, the diethyl ether was removed from the mixture by evaporation at room temperature to give a yellow solid. The solid was dissolved in 50 mL toluene, centrifuged, and the supernatant was decanted. The resulting solution was concentrated to 20 mL, partitioned with 10 mL hexanes, and placed in a freezer at -30 °C to give the product as a yellow solid. Yield = 0.156 g. 1 HNMR (300 MHz, C6D6, 25 °C) δ = 7.85 (d, 1H, indene), 6.98 (d, 1H, indene), 6.91 (t, 1H, indene), 6.78 (t, 1H, indene), 6.67 (m, 1H, indene), 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). 19 F NMR (282.4 MHz, C6D6, 25 °C) δ = -145.76 (m), -146.34 (m).

[0142] Example 3 (MET-C): A 200 mL flask was charged with 1-((perfluorophenyl)methyl)-1H-indene (1.0 g, 3.38 mmol). The solid was dissolved in 50 mL of toluene and 10 mL of diethyl ether. The solution was cooled to -20 °C and ethyllithium (15.5 mL, 0.5 M solution, 7.76 mmol) was added slowly. The mixture was warmed to ambient temperature and stirred overnight. A separate flask was charged 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 slurry was allowed to warm to ambient temperature with stirring overnight. The mixture was then concentrated under high vacuum to 40 mL and centrifuged. The orange supernatant was separated and stripped of solvent by rotary evaporation at room temperature to give an oily paste. The paste was dissolved in 15 mL of toluene and filtered to give an orange filtrate. The solution was layered with 6 mL of pentane and placed in a freezer at -20 °C to crystallize. Several batches of yellow solid were obtained, 0.319 g. 1 H NMR (300 MHz, CD2Cl2, 25 °C) δ = 7.78 (d, 1H, indene), 7.63 (m, 1H, indene), 7.30 (m, 2H, indene), 6.77 (m, 1H, indene), 6.49 (m, 1H, indene), 6.22 (s, 5H, Cp), 4.45 (d, 1H, benzyl), 4.20 (d, 1H, benzyl), 2.69 (m, 2H, ethyl), 1.17 (t, 3H, ethyl). 19 F NMR (282.4 MHz, C6D6, 25 °C) δ = -145.76 (m), -147.62 (m).

[0143] Example 4 (MET-D): A 200 mL flask was charged with 100 mL of diethyl ether and 1.13 g (3.81 mmol) of 1-((perfluorophenyl)methyl)-1H-indene. 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 ambient temperature. After 2 hours, the dark solution was added to a second flask containing CpZrCl3(1.0 g, 3.8 mmol) suspended in 50 mL of diethyl ether at -78 °C. The resulting slurry was allowed to warm to ambient temperature with stirring. After 16 hours, the mixture was stripped to a paste and 50 mL of toluene was added. The yellow slurry was filtered through diatomaceous earth and stripped under high vacuum to a tan oil. The resulting oil was dissolved in 40 mL of hexanes to form a yellow slurry. The slurry was filtered and the filtrate was placed in a freezer at -30 °C. Several batches of light yellow solid were collected. Yield = 0.576. 1H NMR (300 MHz, C6D6, 25 °C) δ = 7.84 (d, 1H, indenyl), 6.96 (d, 1H, indenyl), 6.89 (t, 1H, indenyl), 6.76 (t, 1H, indenyl), 6.66 (m, 1H, indenyl), 5.74 (s, 5H, Cp), 5.70 (m, 1H, indenyl), 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). 19 F NMR (282.4 MHz, C6D6, 25 °C) δ = -145.76 (m), -146.78 (m).

[0144] 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 diethyl ether. The compound was cooled to -20 °C and n-hexyllithium (3.38 mL, 7.76 mmol) was added. The cooling bath was removed and the reaction mixture was allowed to warm to ambient temperature with stirring. After 1.5 hours, a separate flask was charged with CpZrCl3(0.88 g, 3.4 mmol) and 30 mL of diethyl ether. The slurry was cooled to -78 °C and the first reaction mixture was added over 5 minutes. The resulting dark brown slurry was allowed to warm slowly to ambient temperature with stirring. After 13 hours of stirring, the pale yellow slurry was stripped under vacuum to a brown oily solid. Hexane (80 mL) was added and the resulting slurry was stirred for 1.5 hours. Toluene (20 mL) was added and the slurry was stirred for an additional 2 hours. The mixture was then centrifuged and the supernatant was decanted. The resulting solution was stripped to a solid and the solid was then dissolved in 10 mL of toluene. The toluene solution was partitioned with 5 mL of hexane and placed in a freezer at -30 °C. Several fractions of yellow-orange solid were obtained, 0.261 g. 1 H NMR (300 MHz, C6D6, 25 °C) δ = 7.85 (d, 1H, indenyl), 6.96 (d, 1H, indenyl), 6.88 (t, 1H, indenyl), 6.76 (t, 1H, indenyl), 6.67 (m, 1H, indenyl), 5.74 (s, 5H, Cp), 5.70 (m, 1H, indenyl), 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). 19 F NMR (282.4 MHz, C6D6, 25 °C) δ = -145.70 (m), -146.83 (m).

[0145] Example 6 (MET-F): A 200 mL flask was charged 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 allowed to slowly warm to ambient temperature. 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 slurry was allowed to warm to ambient temperature. After 16 hours, the mixture was concentrated under high vacuum to 50 mL and centrifuged. The orange supernatant was collected and stripped to a viscous solid. The solid was re-dissolved in 15 mL of toluene, filtered, partitioned with 6 mL of pentane, and placed in a freezer at -30 °C to crystallize. Several batches of yellow solid were isolated. Yield = 0.336 g. 1 H NMR (300 MHz, CD2Cl2, 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). 19 F NMR (282.4 MHz, C6D6, 25 °C) δ = -144.93 (m), -145.87 (m).

[0146] Example 7 - Alkylation of metallocene precursors (MET-G)

[0147] Another potential synthetic route to incorporate hydrophobic substituents to improve solubility is to prepare metallocenes with substituents on the Cp B novel metallocene precursors with substituents on the Cp ring to maintain catalytic activity of the fluorinated metallocenes. However, this route can require isolation of new intermediates for each metallocene derivative, which introduces additional steps and reduces yield. For example, the following reaction requires isolation of n-butylcyclopentadienylzirconium trichloride as an intermediate for metallocene preparation in the first step, as described above for MET-A.

[0148]

[0149] Example 7 (MET-G): A 200 mL flask was charged with l-((perfluorophenyl)methyl)-lH-indene (1.09 g, 3.68 mmol) and diethyl 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 to room temperature slowly. After 2 hours, the mixture was added to a separate flask containing 30 mL diethyl ether and butylcyclopentadienyl zirconium (IV) chloride (1.17 g, 3.68 mmol) at -78 °C. The resulting slurry was allowed to warm to room temperature overnight with vigorous stirring. The solvent was removed under high vacuum and toluene (40 mL) was added. The slurry was centrifuged and the supernatant was concentrated to approximately 20 mL, partitioned with hexanes, and placed in a freezer at -20 °C. Several batches of yellow solid yielded 0.357 g of the desired metallocene. 1 HNMR (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).

[0150] Solubility of metallocene compounds

[0151] It is advantageous to increase the solubility of metallocene compounds in common oligomerization and polymerization solvents, such as 1-decene. Surprisingly, metallocene compounds prepared as described above exhibit increased solubility. The solubility of metallocenes prepared in Examples 1-7 above in 1-decene was tested according to the following procedure: A 20 mL vial sealed with a crimp cap was charged with 7.40 g (10.0 mL) of 1-decene, 7.5 mg of the desired metallocene, and a small magnetic stir bar. Additional portions of the desired metallocene were then added in increments of 3-4 mg and the mixture was stirred at ambient temperature (21 °C) for 30 minutes after each addition. The resulting mixture was visually inspected for the presence of solids or a noticeable haze. If no noticeable haze or solids were observed, the metallocene was considered soluble.

[0152] Table I. Solubility of metallocenes

[0153] Example MET Solubility (wt%) 0.1 0.1 0.1 0.1 0. 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

[0154] Surprisingly, in certain cases, Cp A -Rx 2The solubility of the substituted metallocenes was unexpectedly increased up to 4 times or more relative to their unsubstituted equivalents, as shown in Table I (e.g., MET-C, D, and E). Thus, the solubility of the metallocene compounds of Examples 2-7 can be increased by additional in situ substitution without the need to isolate and handle new reactive metallocene intermediates.

[0155] Oligomerization

[0156] Metallocene catalyzed oligomerization was performed using MET-A and MET-D as follows. Typically, 1-decene was oligomerized in the presence of MET-A or MET-D to oligomer products of dimers, trimers, and tetramers, as shown in Table II below. For Examples 8-9, a 1 gallon batch reactor was charged with 675 g of 1-decene. A syringe was charged with CTSO (0.750 g), TIBA (1.3 mL of a 1.0 M hexane solution), and metallocene (5 mg). The chemically treated solid oxide (CTSO) was a fluorided silica-coated alumina (alumina: silica weight ratio of 60:40) containing 4 wt% F and having a d50 average 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 shaken to mix, and then charged to the reactor under a nitrogen purge. The reactor was heated to 110 °C while stirring at 600-900 rpm. Once the reactor temperature reached the set point, 633 mg of hydrogen gas was charged to the reactor. After 1 hour, the reactor was cooled to 35 °C. A solution of 10% HC1 in isopropyl alcohol was added (10 mL total), and the reactor contents were removed. 2

[0157] The reaction mixture was then filtered and analyzed by gas chromatography to determine the yield of oligomer products formed in the reaction mixture, and to determine the relative amounts of certain oligomers within the oligomer products (e.g., weight ratio of trimers: tetramers).

[0158] Gas chromatography (GC) analysis was performed using split injection on a Bruker 430-GC gas chromatograph equipped with a flame ionization detector (FID). The initial column oven temperature was 70 °C for 2 minutes, and ramped to 290 °C at 5 °C / min and held for 7 minutes. The column was a Universal Capillary column (Agilent J&W VF-5ms, 30 m x 0.25 mm x 0.25 pm). Data analysis was performed using Compass CDS software.

[0159] The distribution of olefin end groups was determined using 1 H NMR. The spectra were recorded in CDC13 and reported relative to SiMe4 as per residual 1 ​H solvent peak determination. Integration of the following chemical shift ranges was used to determine the relative amount of olefin end groups: vinylidene: 4.55-4.75 ppm, tri-substituted: 4.95-5.15 ppm, internal: 5.20-5.45 ppm.

[0160] The oligomerization results for Examples 8-9 are shown in Table II.

[0161] Surprisingly, as shown in Table II, the use of MET-D, which has a higher solubility than MET-A, resulted in even higher activity than MET-A for the oligomerization reaction. x The observed activity for the oligomerization reaction using MET-D was even higher than that observed for the unmodified fluorinated metallocene (MET-A). More surprisingly, despite the increase in activity, the distribution of oligomers in the product mixture using MET-D was essentially unchanged, with only a 0.3% difference in the amount of dimer product, and a slight increase in the heavy ends including tetramer. Advantageously, the dimer distribution in the oligomer product is acceptable, with 71% of the desired vinylidene being produced. While MET-A produced more dimer and more vinylidene overall, the increase in activity and solubility observed for MET-D gives MET-D oligomerization an unexpected practical advantage.

[0162] Table II. Comparison of oligomer properties.

[0163]

[0164]

[0165] Polymerization reaction

[0166] Polymerization experiments with catalyst compositions comprising MET-A, MET-B, MET-C, MET-D, MET-E, and MET-F were performed as follows. Unless otherwise indicated, the polymerization experiments used in the following examples were performed in a one-gallon (3.8 L) stainless steel autoclave reactor containing isobutane as diluent for 30 min. A 250 mg solid activator support, 2 mL hexanes, 0.5 mL 1 M TIBA in hexanes, and 2.0 mg metallocene (MET-A, MET-B, MET-C, MET-D, MET-E, or MET-F, as shown in Tables III and IV) were sequentially loaded into a syringe. The slurry was loaded into the reactor under isobutane purge. The reactor was sealed, charged with 2 L isobutane and heated to 80 °C. Ethylene was charged to the reactor and fed as needed to maintain a target pressure of 320 psig (2.2 MPa). 1 -hexene was added at a feed ratio of 12 wt% relative to ethylene, with the total amount of 1 -hexene fed as shown in Tables III and IV. The reactor was maintained at the target temperature throughout the experiment by an automatic heating-cooling system. After the reactor was vented, purged, and cooled, 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 ethylene, with a 1 -hexene feed ratio of 20 wt% relative to ethylene.

[0167] Melt index (MI, g / 10 min) was determined according to ASTM D1238 at 190 °C using a 2,160 gram weight, and high load melt index (HLMI, g / 10 min) was determined according to ASTM D1238 at 190 °C using a 21,600 gram weight. Density was determined in units of grams per cubic centimeter (g / cm3) according to ASTM D1505 and ASTM D4703 on compression molded samples that were cooled at 15 °C per minute, and conditioned at room temperature for 40 hours. 3 ) as units of grams per cubic centimeter (g / cm

[0168] Molecular weights and molecular weight distributions were obtained using a PL-GPC 220 (Polymer Labs, Agilent Company) system equipped with an IR4 detector (Polymer Char, Spain) and three Styragel HMW-6E GPC columns (Waters, MA) operating at 145 °C. The flow rate of mobile phase 1,2,4-trichlorobenzene (TCB) containing 0.5 g / L 2,6-di-tert-butyl-4-methylphenol (BHT) was set 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 performed at 150 °C, typically for 4 hours, with occasional gentle agitation, before transferring the solution to a sample vial for injection. An injection volume of about 200 μL was used. HDPE polyethylene resins BHB5003 as a broad standard, molecular weights and molecular weight distributions were derived using an integral calibration method. The integral table for the broad standard was pre-determined in a separate SEC-MALS experiment. Mn is the number average molecular weight, Mw is the weight average molecular weight, Mz is the z average molecular weight, and MWD is the ratio of Mw / Mn.

[0169] The results of Examples 10-39 are summarized in Table III below. Comparing the MI and density of the polymers formed in the presence of MET-A through MET-F and varying amounts of 1-hexene comonomer, it was surprisingly found that the polymers formed using MET-A through MET-F generally had similar physical properties (e.g., melt index and density) and similar responses to 1-hexene. Thus, it was surprising that R x Substituted metallocenes can be used in similar polymerization processes to produce generally similar polymer products. Thus, for example, the advantageous catalytic properties of fluorinated metallocenes can be used in R x are retained in the substituted metallocenes.

[0170] Table III. Comparison of polymer properties using alkylated / non-alkylated metallocenes.

[0171]

[0172]

[0173] In addition, Table IV shows that similar principles apply to metallocenes having R x Substituted Cp B groups, as shown in Example 40 (MET-G). As shown above, while the preparation of MET-G required the preparation of a new intermediate, it was shown that the Cp BSubstitution can also yield highly soluble metallocenes. Surprisingly, Cp B Substituted metallocenes also exhibit excellent catalytic properties, although with greater impact on product resin properties (e.g., in terms of MI and density) than MET-A through MET-F. Given the preparation of Cp B Substituted metallocenes also require MET-G, and require isolation of a new intermediate, Cp A Substituted metallocenes can provide a surprising beneficial pathway to metallocenes with improved solubility.

[0174] Table IV. Polymer properties.

[0175]

[0176] The present application is described above by reference to many aspects and specific embodiments. Many variations will occur to those skilled in the art upon consideration of the above description. All such variations are contemplated by the appended claims to be within the full intended scope of the application. Other aspects of the application can include, but are not limited to, the following aspects (aspects are described as “comprising,” but can alternatively “consist essentially of” or “consist of”):

[0177] Aspect 1. A method for preparing a metallocene compound, the method comprising: (i) contacting a compound having the formula Cp A –(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 having the formula Cp A –(CH2) n –Ar–R x ; and (iii) contacting the substituted compound with a second compound having the formula Cp B –M–X3 to form a metallocene compound having the formula (I):

[0178]

[0179] wherein: M is Zr, Ti, or Hf; each X is independently a halogen or NR y 2; X 1 and X 2 are each independently a monanionic ligand; Cp A is a cyclopentadienyl, indenyl, or fluorenyl group, optionally substituted with one or more additional substituents; Cp B is a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group; Ar is an aryl group comprising a halogen substituent; R x is a C1to C 18hydrocarbyl substituent (e.g., selected from alkyl or alkenyl or aryl; phenyl, benzyl, Ci to Cs alkyl, or C3 to Cs alkenyl); n is an integer from 0 to 5; and R y is a Ci to Cs hydrocarbyl.

[0180] Aspect 2. The method of aspect 1, wherein the Bronsted base is selected from an organolithium reagent (e.g., methyllithium, ethyllithium, n-butyllithium, t-butyllithium, n-hexyllithium, benzyl lithium, phenyllithium) and an organomagnesium halide (e.g., methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, isopropylmagnesium chloride, t-butyimagnesium chloride, vinylmagnesium bromide, allylmagnesium bromide, ethynylmagnesium chloride, phenylmagnesium chloride, benzylmagnesium chloride).

[0181] Aspect 3. The method of aspect 1 or 2, wherein the substitution reagent is selected from an organolithium reagent (e.g., methyllithium, ethyllithium, n-butyllithium, t-butyllithium, n-hexyllithium, benzyl lithium, phenyllithium) and an organomagnesium halide (e.g., methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, isopropylmagnesium chloride, t-butyimagnesium chloride, vinylmagnesium bromide, allylmagnesium bromide, ethynylmagnesium chloride, phenylmagnesium chloride, benzylmagnesium chloride).

[0182] Aspect 4. The method of any one of aspects 1-3, wherein the Bronsted base and the substitution reagent are each an organolithium reagent (e.g., methyllithium, n-butyllithium, n-hexyllithium).

[0183] Aspect 5. The method of any one of aspects 1-4, wherein the Bronsted base and the substitution reagent are the same.

[0184] Aspect 6. The method of any one of aspects 1-5, wherein steps (i) and (ii) are performed in a one-pot synthesis.

[0185] Aspect 7. The method of any one of aspects 1-6, wherein each of steps (i)-(iii) are performed in a one-pot synthesis.

[0186] Aspect 8. A metallocene compound having formula (I):

[0187]

[0188] wherein: M is Zr, Ti, or Hf; X 1 and X 2 are independently a monoanionic ligand (e.g., selected from H, halide, Ci to C 36 hydrocarbyl, or Ci to C 36 hydrocarbyloxy (or Ci to C 36 hydrocarbyl amino, Ci to C 36 hydrocarbylsilyl, Ci to C 36Hydrocarbon-based aminosilyl groups, -OBR 1 2 or —OSO2R 1 , where R 1 It is C1 to C 36 (Hydrocarbon group); Cp A It is cyclopentadienyl, indenyl, or fluorenyl, with a substituent –(CH2). n ArR x And optionally substituted by one or more other substituents; Cp B It is a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group; Ar is an aryl group containing a halogen substituent; R x It is C1 to C on Ar 18 Hydrocarbon substituents (e.g., selected from alkyl, alkenyl or aryl; phenyl, benzyl, C1 to C8 alkyl or C3 to C8 alkenyl); and n is an integer from 0 to 5.

[0189] Aspect 9. The metallocene compound as described in aspect 8, wherein X 1 and X 2 Independently, they are H, F, Cl, Br, Cl to C 12 Hydrocarbon group, C1 to C 12 Hydroxyl groups, C1 to C 12 Hydroxyl amino, C1 to C 12 Hydrocarbon silyl group, C1 to C 12 Hydrocarbon aminosilyl, –OBR 1 2 or –OSO2R 1 , where R 1 It is C1 to C 12 Hydrocarbon group.

[0190] Aspect 10. The metallocene compound as described in aspect 8 or 9, wherein Ar is a phenyl having two, three, or four halogen substituents.

[0191] Aspect 11. The metallocene compound as described in any one of Aspects 8-10, wherein each halogen substituent is F.

[0192] Aspect 12. The metallocene compound as described in any one of Aspects 8-11, wherein Ar is selected from:

[0193]

[0194] Aspect 13. The metallocene compound as described in any one of Aspects 8-12, wherein R x It is selected from methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, 3-butenyl, n-hexyl, phenyl and substituted phenyl.

[0195] Aspect 14. The metallocene compound as described in any one of Aspects 8-13, wherein n is 0.

[0196] Aspect 15. The metallocene compound of any one of aspects 8-13, wherein n is 1.

[0197] Aspect 16. The metallocene compound of any one of aspects 8-15, wherein Cp A is substituted with at least one additional substituent selected from C1-C 12 alkyl, C2-C 12 alkenyl, C6-C 10 aryl, or C7-C 12 aralkyl substituents.

[0198] Aspect 17. The metallocene compound of any one of aspects 8-16, wherein Cp A is an indenyl group, and Cp B is a cyclopentadienyl group.

[0199] Aspect 18. The metallocene compound of any one of aspects 8-17, wherein Cp B comprises C1-C 12 alkyl, C2-C 12 alkenyl, C6-C 10 aryl, or C7-C 12 aralkyl substituents.

[0200] Aspect 19. The metallocene compound of any one of aspects 8-18, wherein Cp B comprises the substituent –(CH2) n ArR x .

[0201] Aspect 20. The metallocene compound of any one of aspects 8-17, wherein Cp B is unsubstituted.

[0202] Aspect 21. The metallocene compound of any one of aspects 8-20, wherein the metallocene compound is selected from:

[0203]

[0204] Aspect 22. The metallocene compound of any one of aspects 8-21, having a solubility in 1-decene at 25 °C of at least 0.1 wt% (e.g., 0.2 wt% to 2 wt%, 0.2 wt% to 1.0 wt%, 0.2 wt% to 0.5 wt%).

[0205] Aspect 23. The metallocene compound of any one of aspects 8-22, having a solubility in 1-decene at 25 °C that is greater than that of the otherwise identical metallocene compound of any one of aspects 8-22 wherein each R xis a metallocene compound of F has a high solubility (e.g., 50% to 500% higher, 100% to 300% higher).

[0206] Aspect 24. A catalyst composition comprising: the metallocene compound of any one of aspects 8-23; 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 co-catalyst.

[0207] Aspect 25. The catalyst composition of aspect 24, wherein the activator comprises an aluminoxane compound (e.g., methylaluminoxane (MAO), ethylaluminoxane, modified methylaluminoxane (MMAO), such as isobutyl-modified methylaluminoxane, n-propylaluminoxane, i-propylaluminoxane, n-butylaluminoxane, t-butylaluminoxane, s-butylaluminoxane, i-butylaluminoxane, t-butylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, i-pentylaluminoxane, neopentylaluminoxane, and combinations thereof).

[0208] Aspect 26. The catalyst composition of aspect 24 or 25, wherein the activator comprises an organoboron or organoborate compound (e.g., N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, and combinations thereof).

[0209] Aspect 27. The catalyst composition of any one of aspects 24-26, wherein the activator comprises the ionizing ionic compound (e.g., 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-dimethylanilinium tetrakis(p-tolyl)borate, N,N-dimethylanilinium tetrakis(m-tolyl)borate, N,N-dimethylanilinium 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, lithium tetrakis(p-tolyl)aluminate, lithium tetrakis(m-tolyl)aluminate, lithium tetrakis(2,4-dimethylphenyl)aluminate, lithium tetrakis(3,5-dimethylphenyl)aluminate, or combinations thereof).

[0210] Aspect 28. The catalyst composition of any of aspects 24-27, wherein the activator comprises the chemically-treated solid oxide.

[0211] Aspect 29. The catalyst composition of any of aspects 24-28, wherein the chemically-treated solid oxide comprises a fluorided alumina, a chlorided alumina, a bromided alumina, a sulfated alumina, a fluorided silica-alumina, a chlorided silica-alumina, a bromided silica-alumina, a sulfated silica-alumina, a fluorided silica-zirconia, a chlorided silica-zirconia, a bromided silica-zirconia, a sulfated silica-zirconia, a fluorided silica-titania, a fluorided chlorided silica-coated alumina, a fluorided silica-coated alumina, a sulfated silica-coated alumina, a phosphated silica-coated alumina, or any combination thereof.

[0212] Aspect 30. The catalyst composition of any of aspects 24-29, wherein the chemically-treated solid oxide comprises a fluorided solid oxide and / or a sulfated solid oxide.

[0213] Aspect 31. The catalyst composition of any of aspects 24-30, wherein the weight ratio of the metallocene compound to the activator is within any range disclosed herein, for example, 1:1 to 1:10,000, 1:10 to 1:1,000, 1:10 to 500:1, or 1:10 to 1:100.

[0214] Aspect 32. The catalyst composition of any of claims 24-31, wherein the co-catalyst comprises an organoaluminum compound, an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or a combination thereof.

[0215] Aspect 33. The catalyst composition of any of aspects 24-32, wherein the co-catalyst comprises an organoaluminum compound.

[0216] Aspect 34. The catalyst composition of aspect 32 or 33, wherein the organoaluminum compound comprises trimethylaluminum (TMA), triethylaluminum (TEA), tri-n-propylaluminum (TNPA), tri-n-butylaluminum (TNBA), triisobutylaluminum (TIBA), tri-n-hexylaluminum, tri-n-octylaluminum (TNOA), or a combination thereof.

[0217] Aspect 35. The catalyst composition of any of aspects 24-34, wherein the molar ratio of the co-catalyst to the metallocene compound in the catalyst composition is within any range disclosed herein, for example, 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.

[0218] Aspect 36. The catalyst composition of any one of aspects 28-35, wherein the catalyst composition is substantially free of an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or a combination thereof.

[0219] Aspect 37. The catalyst composition of any one of aspects 24-36, wherein the catalyst composition further comprises a second metallocene compound.

[0220] Aspect 38. An oligomerization process comprising contacting the catalyst composition of any one of aspects 24-37 with an alpha olefin monomer and optionally H2 under oligomerization conditions to produce an oligomer product.

[0221] Aspect 39. The process of aspect 38, wherein the alpha olefin monomer comprises any C4 to C 14 alpha olefin or a mixture of C8 to C 12 alpha olefins, for example 1-octene and / or 1-decene.

[0222] Aspect 40. The process of aspect 38 or 39, wherein the alpha olefin monomer comprises a branched alpha olefin.

[0223] Aspect 41. The process of any one of aspects 38-40, wherein the alpha olefin monomer comprises a mixture of alpha olefins (e.g., a mixture of C8 to C 12 alpha olefins, or a mixture of C 10 alpha olefins).

[0224] Aspect 42. The process of any one of aspects 38-41, wherein the weight ratio of the metallocene compound to the alpha olefin monomer is within any range disclosed herein, for example 1:100 to 1:1,000,000, 1:1,000 to 1:1,000,000, 1:1,000 to 1:500,000, or 1:10,000 to 1:250,000.

[0225] Aspect 43. The process of any one of aspects 38-42, wherein the oligomerization conditions comprise an oligomerization temperature within any range disclosed herein, for example -10 °C to 250 °C, 20 °C to 180 °C, 50 °C to 160 °C, or 70 °C to 140 °C.

[0226] Aspect 44. The process of any one of aspects 38-43, wherein the catalyst composition is contacted with the alpha olefin monomer and H2 at any suitable hydrogen partial pressure (e.g., 0.1 to 10 psig of H2).

[0227] Aspect 45. The process of any of aspects 38-44, wherein the activity of the catalyst composition is at least 50,000 g oligomer per g metallocene compound per hour (g / (g*h)), 20,000 g / (g*h) to 180,000 g / (g*h), 40,000 g / (g*h) to 160,000 g / (g*h), or 60,000 to 120,000 g / (g*h) at oligomerization conditions including an oligomerization temperature of 90 °C, and wherein the catalyst composition is TIBA.

[0228] Aspect 46. The process of any of aspects 38-45, wherein the activity of the catalyst composition is comparable (e.g., within 20%, 15%, 10%, or 5%) to the activity of a process that is otherwise identical except that the catalyst composition comprises a metallocene compound wherein each R x is F.

[0229] Aspect 47. The process of any of aspects 38-46, further comprising the step of separating at least a portion of the catalyst composition from the oligomer product using any of the techniques disclosed herein, for example, filtration.

[0230] Aspect 48. The process of any of aspects 38-47, further comprising recycling the separated catalyst composition.

[0231] Aspect 49. The process of any of aspects 38-48, further comprising the step of separating unreacted alpha olefin monomer from the oligomer product using any of the techniques disclosed herein, for example, wiped film evaporation, distillation, short path distillation, or any combination thereof.

[0232] Aspect 50. The process of any of aspects 38-49, further comprising recycling unreacted alpha olefin monomer.

[0233] Aspect 51. The process of any of aspects 38-50, further comprising the step of fractionating the oligomer product into alpha olefin dimers, alpha olefin trimers, and alpha olefin heavies, including alpha olefin tetramers and higher oligomers, using any of the techniques disclosed herein, for example, wiped film evaporation, distillation, short path distillation, or any combination thereof.

[0234] Aspect 52. The process of any of aspects 38-51, 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% tetramers.

[0235] Aspect 53. The process of any of Aspects 38-52, 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 dimers and trimers (total).

[0236] Aspect 54. The process of any of Aspects 38-53, 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 75 mol% of alpha olefin dimers.

[0237] Aspect 55. The process of any of Aspects 38-54, 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 products relative to the amount of dimers in the oligomer product.

[0238] Aspect 56. The process of any of Aspects 38-55, wherein the amount of internal olefins 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%.

[0239] Aspect 57. The process of any of Aspects 38-56, wherein the oligomer product has a dimer content and properties (e.g., the amount of internal, tri-substituted dimers, and / or vinylidene dimers in the dimer product) comparable (e.g., within 20%, 15%, 10%, or 5%) to the dimer content and properties of a process employing a catalyst composition comprising a metallocene compound wherein each R x is F.

[0240] Aspect 58. The process of any of Aspects 38-57, further comprising a step of hydrogenating at least a portion of the oligomer product (e.g., alpha olefin trimers) to form a polyalphaolefin.

[0241] Aspect 59. The process of Aspect 58, wherein the polyalphaolefin has a kinematic viscosity at 100°C of less than or equal to 20 cSt, 10 cSt, 5 cSt, 4 cSt, or 3 cSt (e.g., in the range of 1 to 10 cSt).

[0242] Aspect 60. A polymerization process comprising contacting the catalyst composition of any one of aspects 24-37 with ethylene monomer and optionally an a-olefin comonomer in a polymerization reactor system under polymerization conditions to produce an ethylene polymer.

[0243] Aspect 61. The process of aspect 60, wherein the a-olefin comonomer comprises C3-C 20 a-olefin, or alternatively, C3-C 10 a-olefin.

[0244] Aspect 62. The process of aspect 60 or 61, wherein the a-olefin comonomer comprises 1-butene, 1-hexene, 1-octene, or mixtures thereof.

[0245] Aspect 63. The process of any one of aspects 60-62, wherein the polymerization reactor system comprises a batch reactor, a slurry reactor, a gas phase reactor, a solution reactor, or a combination thereof.

[0246] Aspect 64. The process of any one of aspects 60-63, wherein the polymerization reactor system comprises a slurry reactor, a gas phase reactor, a solution reactor, or a combination thereof.

[0247] Aspect 65. The process of any one of aspects 60-64, wherein the polymerization reactor system comprises a loop slurry reactor.

[0248] Aspect 66. The process of any one of aspects 60-65, wherein the polymerization reactor system comprises a single reactor.

[0249] Aspect 67. The process of any one of aspects 60-65, wherein the polymerization reactor system comprises 2 reactors.

[0250] Aspect 68. The process of any one of aspects 60-65, wherein the polymerization reactor system comprises more than 2 reactors.

[0251] Aspect 69. The process of any one of aspects 60-68, wherein the polymerization conditions comprise a polymerization reaction temperature ranging from 60 °C to 120 °C (e.g., 80 °C) and a reaction pressure ranging from 200 to 1000 psig (1.4 to 6.9 MPa).

[0252] Aspect 70. The process of any one of aspects 60-69, wherein the polymerization conditions are substantially constant, e.g., for a particular polymer grade.

[0253] Aspect 71. The process of any one of aspects 60-70, wherein no hydrogen is added to the polymerization reactor system.

[0254] Aspect 72. The process of any of Aspects 60-70, wherein hydrogen is added to the polymerization reactor system.

[0255] Aspect 73. The process of any of Aspects 60-72, further comprising contacting the catalyst composition, ethylene monomer, optional alpha-olefin comonomer, and diluent, such as propane, butane (e.g., n-butane, isobutane), pentane (e.g., n-pentane, isopentane), hexane, heptane, octane, petroleum ether, light petroleum naphtha, heavy petroleum naphtha, or any combination thereof.

[0256] Aspect 74. The process of any of Aspects 60-73, 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.

[0257] Aspect 75. The process of any of Aspects 60-74, wherein the ethylene polymer comprises an ethylene / 1-hexene copolymer.

[0258] Aspect 76. The process of any of Aspects 60-75, wherein the catalyst composition is characterized by a total metallocene activity in the range of 30,000 g / (g*h) (grams of polyethylene per grams of metallocene per hour) to 800,000 g / (g*h).

[0259] Aspect 77. The process of any of Aspects 60-76, wherein the activity of the catalyst composition is comparable (e.g., within 20%, 15%, 10%, or 5%) to the activity of a process that is otherwise identical to the process of any of Aspects 60-76, employing a catalyst composition comprising a metallocene compound wherein each R x is F.

[0260] Aspect 78. The process of any of Aspects 60-77, wherein the ethylene polymer has a number average molecular weight (Mn) in the 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.

[0261] Aspect 79. The process of any of Aspects 60-78, wherein the ethylene polymer has a Mw within any range disclosed herein, for example, 50,000 to 700,000, 75,000 to 500,000, or 100,000 to 400,000 g / mol.

[0262] Aspect 80. The process of any of Aspects 60-79, wherein the ethylene polymer has a Mw / Mn ratio in the range of 2 to 15, or 2 to 10.

[0263] Aspect 81. The process of any of Aspects 60-80, wherein the ethylene polymer has a density within any range disclosed herein, 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. 3

[0264] Aspect 82. The process of any of Aspects 60-81, wherein the ethylene polymer has a melt index within any range disclosed herein, for example, 0 to 20 g / 10 min, 0.01 to 10 g / 10 min, or 0.1 to 5 g / 10 min.

[0265] Aspect 83. The process of any of Aspects 60-82, wherein the ethylene polymer has a HLMI within any range disclosed herein, for example, 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.​

Claims

1. A metallocene compound having the formula (I): wherein: M is Zr, Ti, or Hf; Ar is an aryl group comprising a halogen substituent; and n is an integer from 0 to 5.

2. A catalyst composition comprising: (a) a metallocene compound having the formula (I): wherein: M is Zr, Ti, or Hf; Ar is an aryl group comprising a halogen substituent; and n 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) an optional co-catalyst.

4. The metallocene compound or catalyst composition of any one of claims 1-3, wherein Ar is a phenyl group having two, three, or four halogen substituents. X 1 and X 2 are independently monanionic ligands; Cp A is a cyclopentadienyl, indenyl or fluorenyl group, having substituents -(CH2) n ArR x and is optionally substituted by one or more other substituents; Cp B is a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group; 5. The metallocene compound or catalyst composition of any one of claims 1-4, wherein each halogen substituent is F. R x is a C1to C 18 hydrocarbyl substituent; and 6. The metallocene compound or catalyst composition of any one of claims 1-5, wherein Ar is selected from the group consisting of:

7. The metallocene compound or catalyst composition of claim 1 or 2, wherein the metallocene compound is selected from the group consisting of:

8. The metallocene compound or catalyst composition of claim 1 or 2, wherein the metallocene compound is:

9. The metallocene compound or catalyst composition of any one of claims 1-8, wherein the metallocene compound has a solubility in 1-decene at 25 °C of 0.1 wt% to 1.0 wt%.

10. The metallocene compound or catalyst composition of any one of claims 1-8, wherein the metallocene compound has a solubility in 1-decene at 25 °C of 0.2 wt% to 0.5 wt%. X 1 and X 2 are independently monanionic ligands; Cp A is a cyclopentadienyl, indenyl or fluorenyl group, having a substituent - (CH2) n ArR x , and optionally substituted by one or more other substituents; Cp B is a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group; 11. The catalyst composition of any one of claims 2-10, wherein the activator comprises the aluminoxane compound. R x is a C1to C 18 hydrocarbyl substituent; and 12. The catalyst composition of any one of claims 2-10, wherein the activator comprises the chemically-treated solid oxide.

13. The catalyst composition of claim 12, wherein the chemically-treated solid oxide comprises a fluorided solid oxide and / or a sulfated solid oxide.

14. The catalyst composition of claim 12, wherein the chemically-treated solid oxide comprises a fluorided alumina, a chlorided alumina, a bromided alumina, a sulfated alumina, a fluorided silica-alumina, a chlorided silica-alumina, a bromided silica-alumina, a sulfated silica-alumina, a fluorided silica-zirconia, a chlorided silica-zirconia, a bromided silica-zirconia, a sulfated silica-zirconia, a fluorided silica-titania, a fluorided chlorided silica-coated alumina, a fluorided silica-coated alumina, a sulfated silica-coated alumina, a phosphated silica-coated alumina, or any combination thereof.

3. The metallocene compound or catalyst composition of claim 1 or 2, wherein X 1 and X 2 are independently H, F, Cl, Br, or a Ci to C 12 hydrocarbyl group.

15. The catalyst composition of any one of claims 2-14, wherein the catalyst composition comprises the co-catalyst. ​ ​ and R x is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, sec-butyl, t-butyl, 3-butenyl, n-hexyl, phenyl, and substituted phenyl. ​ ​ ​ ​ ​ ​ ​ ​ ​ 16. The catalyst composition of claim 15, wherein the co-catalyst 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. The catalyst composition of any one of claims 2-16, wherein the catalyst composition further comprises a second metallocene compound.

18. An oligomerization process comprising contacting the catalyst composition of any one of claims 2-17 with an alpha olefin monomer and optionally H2 under oligomerization conditions to produce an oligomer product.

19. The oligomerization process of claim 18, wherein: said alpha olefin monomers include C4 to C 14 alpha olefin or C8 to C 12 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 unreacted alpha olefin monomer from the oligomer product; the oligomerization process further comprises a step of fractionating the oligomer product into alpha olefin dimer product, alpha olefin trimer product, and alpha olefin tetramer and higher oligomer product; the oligomerization process further comprises a step of hydrogenating at least a portion of the oligomer product to form polyalphaolefin; or any combination thereof.

20. The oligomerization process of claim 18 or 19, wherein the activity of the catalyst composition in the oligomerization process is within 20%, within 15%, within 10%, or within 5% of the activity of the catalyst composition that is otherwise identical except that the metallocene compound comprises each R x is F.

21. A polymerization process comprising contacting the catalyst composition of any one of claims 2-17 with ethylene monomer and optionally alpha-olefin comonomer in a polymerization reactor system under polymerization conditions to produce an ethylene polymer.

22. The polymerization process of claim 21, wherein: the alpha-olefin comonomer comprises 1-butene, 1-hexene, 1-octene, or a mixture thereof; the ethylene polymer comprises an ethylene homopolymer, an ethylene / 1-butene copolymer, an ethylene / 1-hexene copolymer, and / or an ethylene / 1-octene copolymer; the polymerization reactor system comprises a slurry 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. The polymerization process of claim 21 or 22, wherein the activity of the catalyst composition in the polymerization process is within 20%, within 15%, within 10%, or within 5% of the activity of the catalyst composition that is otherwise identical except that the metallocene compound comprises a compound wherein each R x is F.

24. A method for preparing a metallocene compound, the method comprising: (i) contacting a first compound having the formula Cp A - (CH2) n the first compound of the formula -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 having the formula Cp A –(CH2) n –Ar–R x of the formula Ar–R and (iii) contacting the substituted compound with a second compound having the formula M— X3 B to form a metallocene compound having the formula (I): wherein: M is Zr, Ti, or Hf; each X is independently halogen or NR y 2; X 1 and X 2 are independently monanionic ligands; Cp A is cyclopentadienyl, indenyl or fluorenyl, optionally substituted by one or more other substituents; Cp B is a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group; Ar is an aryl group comprising a halogen substituent; R x is C1to C 18 hydrocarbyl substituents; n is an integer from 0 to 5; and R y is a Ci to C8alkyl group.

25. The method of claim 24, wherein the Bronsted base comprises an organolithium reagent and / or an organomagnesium halide.

26. The method of claim 25, wherein the Bronsted base comprises an organolithium reagent, and the organolithium reagent comprises methyllithium, ethyllithium, n-butyllithium, n- hexyllithium, phenyllithium, or a combination thereof.

27. The method of any one of claims 24-26, wherein the substitution reagent comprises an organolithium reagent and / or an organomagnesium halide.

28. The method of claim 27, wherein the substitution reagent comprises the organolithium reagent, and the organolithium reagent comprises methyllithium, ethyllithium, n-butyllithium, n- hexyllithium, phenyllithium, or a combination thereof.

29. The method of any one of claims 24-28, wherein the Bronsted base and the substitution reagent are the same.

30. The method of any one of claims 24-29, wherein steps (i) and (ii) are performed in a one-pot synthesis.

31. The method of any one of claims 24-29, wherein each of steps (i)-(iii) is performed in a one-pot synthesis.

32. The method of any one of claims 24-31, wherein X 1 and X 2 are independently H, F, Cl, Br, or a Ci to C 12 alkyl group.

33. The method of any one of claims 24-32, wherein Ar is phenyl having two, three, or four halogen substituents.

34. The method of any one of claims 24-33, wherein each halogen substituent is F.

35. The method of any one of claims 24-34, wherein Ar is selected from the group consisting of: and R x is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, sec-butyl, t-butyl, 3-butenyl, n-hexyl, phenyl, and substituted phenyl.

36. The method of any one of claims 24-31, wherein the metallocene compound is selected from the group consisting of:

37. The method of any one of claims 24-31, wherein the metallocene compound is:

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