Catalyst composition, olefin polymerization process and process for producing fluoridated silica-coated alumina.

Description

1 / 55 “CATALYST COMPOSITION, OLEFIN POLYMERIZATION PROCESS AND PROCESS FOR PRODUCING SILICA-COATED ALUMINA "FLUORIDATED" (Order split from BR 11 2024 024998 0, filed on 01 / 06 / 2023) REFERENCE TO RELATED REQUEST

[0001] This application is being filed on June 1, 2023, as a PCT International Patent Application and claims the benefit and priority of U.S. Provisional Patent Application No. 63 / 348,044, filed on June 2, 2022, disclosure of which is incorporated herein by reference in its entirety. FIELD OF THE INVENTION

[0002] This disclosure generally relates to fluorinated solid oxide activating supports, methods for making the activating supports, metallocene-based catalyst compositions containing the activating supports, methods for using the catalyst compositions to polymerize olefins, and the polymer resins produced using such catalyst compositions. More particularly, this disclosure relates to fluorinated silica-coated alumina activating supports with higher pore volume and porosity, and with average pore diameters greater than 10 nm. FUNDAMENTALS OF THE INVENTION

[0003] It would be beneficial to produce solid activator supports that increase catalytic activity in olefin polymerization processes, for example, using metallocene-based catalyst systems for the production of ethylene-based polymers. An increase in the catalytic activity of the solid activator support results in a reduction in the amount of metallocene component required in the catalyst system, which can translate into significant cost savings. Consequently, it is to these purposes that the present invention is generally directed. SUMMARY OF THE INVENTION

[0004] This summary is provided to present a selection of concepts in a simplified form which are further described below in the detailed description. This summary is not intended to identify necessary or essential features of the claimed subject matter. This summary should also not be used for Petition 870260050793, dated 05 / 27 / 2026, page 14 / 88 2 / 55 limit the scope of the matter claimed.

[0005] Aspects of this invention are directed to activating supports of alumina coated with fluorinated silica. For example, in one aspect, the alumina coated with fluorinated silica may have (or may be characterized by) an apparent density of 0.15 to 0.37 g / mL, a total pore volume of 0.85 to 2 mL / g, a BET surface area of ​​200 to 500 m2 / g and an average pore diameter of 10 to 25 nm. In another aspect, alumina coated with fluorinated silica may have (or may be characterized by) an apparent density of 0.15 to 0.37 g / mL, a total pore volume of 0.85 to 2 mL / g, a BET surface area of ​​200 to 500 m2 / g, and 80 to 99% of the pore volume of the alumina coated with fluorinated silica in pores with diameters greater than 6 nm.

[0006] Catalyst compositions are also provided in this document, and such catalyst compositions may comprise a metallocene compound, any of the fluorinated silica-coated alumina activating supports disclosed in this document, and an optional cocatalyst. Olefin polymerization processes are also covered, and such processes may comprise contacting any of the catalyst compositions provided in this document with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer.

[0007] Another aspect of the invention is a process for producing alumina coated with fluorinated silica, and in this aspect, the process may comprise contacting a fluorinating agent with silica-coated alumina to produce the fluorinated silica-coated alumina. The silica-coated alumina may have (or may be characterized by) an apparent density of 0.15 to 0.37 g / mL, a total pore volume of 1.1 to 2.5 mL / g, a BET surface area of ​​250 to 600 m2 / g and an average pore diameter of 10 to 25 nm.

[0008] In yet another aspect, supported metallocene catalysts are provided and such catalysts may comprise a metallocene compound and alumina coated with fluorinated silica. The amount of metallocene compound adsorbed per gram of fluorinated silica-coated alumina may be at least 55 pmol / g (such as 60 to 130 pmol / g) and / or the number of molecules of metallocene compound adsorbed per nm2 of the surface area of ​​alumina Petition 870260050793, dated 05 / 27 / 2026, p. 15 / 88 3 / 55 coated with fluorinated silica may have a density of at least 0.1 molecules per nm2 (such as 0.1 to 0.3 molecules per nm2).

[0009] Other aspects of this invention are directed to ethylene polymers (which are typically in the form of pellets or granules) characterized by a melt index (MI) in the range of 0.1 to 10 g / 10 min and a density in the range of 0.91 to 0.96 g / cm3. These ethylene polymers may contain from 70 to 270 ppm of solid oxide (e.g., silica-coated alumina) and from 2 to 18 ppm of fluorine. In addition, such ethylene polymers may also contain from 0.5 to 5 ppm of zirconium or hafnium.

[0010] Both the aforementioned summary and the following detailed description provide examples and are explanatory only. Consequently, the preceding summary and the detailed description below should not be considered restrictive. Furthermore, features or variations may be provided beyond those set forth in this document. For example, certain aspects may be directed to various combinations and subcombinations of features described in the detailed description. BRIEF DESCRIPTION OF THE FIGURES

[0011] FIG. 1 presents graphical representations of the pore volume distributions as a function of pore diameter (nm) for the silica-coated aluminas of Comparative Example 1 (CE-1) and Inventive Example 1 (IE-1).

[0012] FIG. 2 presents graphical representations of the surface area distributions as a function of pore diameter (nm) for aluminas coated with CE-1 and IE-1 silica.

[0013] FIG. 3 presents graphical representations of the pore volume distributions as a function of pore diameter (nm) for the fluorinated silica-coated aluminas of Comparative Example 2 (CE-2) and Inventive Example 2 (IE-2).

[0014] FIG. 4 presents graphical representations of the surface area distributions as a function of pore diameter (nm) for aluminas coated with CE-2 and IE-2 silica.

[0015] FIG. 5 presents a graphical representation of the particle size distributions of aluminas coated with fluorinated silica of CE-2 and IE-2. DEFINITIONS Petition 870260050793, dated 05 / 27 / 2026, page 16 / 88 4 / 55

[0016] To define more clearly the terms used in this document, the following definitions are provided. Unless otherwise indicated, the following definitions apply to this disclosure. If a term is used in this disclosure but is not specifically defined in this document, the definition from the IUPAC Compendium of Chemical Terminology, 2nd Ed. (1997), may be applied, provided that such definition does not conflict with any other disclosure or definition applied in this document, or render undefined or ineffective any claim to which such definition applies. To the extent that any definition or usage provided by any document incorporated herein by reference conflicts with the definition or usage provided in this document, the definition or usage provided in this document shall prevail.

[0017] In this document, features of the material are described in such a way that, within the particular aspects, a combination of different features can be predicted. For each and every aspect and each and every feature disclosed in this document, all combinations that do not negatively affect the compounds, compositions, processes, or methods described in this document are contemplated, with or without explicit description of the particular combination. Additionally, unless explicitly stated otherwise, any aspect or feature disclosed in this document may be combined to describe inventive compounds, compositions, processes, or methods consistent with this disclosure.

[0018] Generally, groups of elements are indicated using the numbering scheme indicated in the version of the periodic table of elements published in Chemical and Engineering News, 63(5), 27, 1985. In some cases, a group of elements may be indicated using a common name assigned to the group; for example, alkali metals for Group 1 elements, alkaline earth metals for Group 2 elements, transition metals for Group 3-12 elements, and halogens or halides for Group 17 elements.

[0019] Although compositions and methods / processes are described in this document in terms of “comprising” various components or steps, the compositions and methods / processes may also “consist essentially of” or “consist of” various components and steps, unless otherwise indicated. For example, a catalyst composition consistent with aspects of the present Petition 870260050793, dated 05 / 27 / 2026, page 17 / 88 5 / 55 The invention may comprise; alternatively, it may consist essentially of; or, alternatively, it may consist of; a metallocene compound, a fluorinated silica-coated alumina and a cocatalyst.

[0020] The terms “a”, “an”, “the”, “the”, etc., are intended to include plural alternatives, for example, at least one, unless otherwise specified. For example, the disclosure of a metallocene compound or a comonomer is intended to cover one, or mixtures or combinations of more than one, metallocene compound or comonomer, respectively, unless otherwise indicated.

[0021] For any particular compound disclosed in this document, the general structure or name presented is also intended to encompass all structural isomers, conformational isomers, and stereoisomers that may arise from a particular set of substituents, unless otherwise indicated. Thus, a general reference to a compound includes all structural isomers unless explicitly stated otherwise; for example, a general reference to pentane includes n-pentane, 2-methylbutane, and 2,2-dimethylpropane, while a general reference to a butyl group includes an n-butyl group, a sec-butyl group, an iso-butyl group, and a tert-butyl group. Additionally, the reference to a general structure or name encompasses all enantiomers, diastereomers, and other optical isomers, whether in enantiomeric or racemic forms, as well as mixtures of stereoisomers, as the context permits or requires.For any particular formula or name that is presented, any general formula or name presented also encompasses all conformational isomers, regioisomers, and stereoisomers that may arise from a particular set of substituents.

[0022] The term “substituted” when used to describe a group, for example, when referring to a substituted analogue of a particular group, is intended to describe any non-hydrogen moiety that formally replaces a hydrogen in that group, and is intended to be non-limiting. A group or groups may also be referred to in this document as non-substituted 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 within that group. Unless otherwise specified, substituted is intended to be non-limiting and includes inorganic substituents or organic substituents, as understood by a Petition 870260050793, dated 05 / 27 / 2026, page 18 / 88 6 / 55 versed in the technique.

[0023] The term polymer is used in this document generically to include homopolymers, copolymers, olefin terpolymers and the like, as well as alloys and blends thereof. The term polymer also includes impact, blocking, graft, random and alternative copolymers. A copolymer is derived from an olefin monomer and an olefin comonomer, while a terpolymer is derived from an olefin monomer and two olefin comonomers. Consequently, polymer encompasses copolymers and terpolymers derived from any olefin monomers and comonomers disclosed in this document. Similarly, the scope of the term polymerization includes homopolymerization, copolymerization and terpolymerization. Therefore, an ethylene polymer includes ethylene homopolymers, ethylene copolymers (e.g., ethylene / α-olefin copolymers), ethylene terpolymers and the like, as well as blends or mixtures thereof.Thus, an ethylene polymer encompasses polymers frequently referred to in the art as LLDPE (linear low-density polyethylene) and HDPE (high-density polyethylene). As an example, an olefin copolymer, such as an ethylene copolymer, 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 categorized as an ethylene / 1-hexene copolymer. The term polymer also includes all possible geometric configurations, unless otherwise indicated, and such configurations may include isotactic, syndiotactic, and random symmetries. Furthermore, unless otherwise indicated, the term "polymer" is also intended to include all polymers of molecular weight.

[0024] The term “cocatalyst” is used generally in this document to refer to compounds such as aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds, organoaluminum compounds, organozinc compounds, organomagnesium compounds, organolithium compounds and the like, which may constitute a component of a catalyst composition when used, for example, in addition to a fluorinated silica-coated alumina. The term cocatalyst is used regardless of the actual function of the compound or any chemical mechanism. Petition 870260050793, dated 05 / 27 / 2026, page 19 / 88 7 / 55 by which the compound can operate.

[0025] The term “metallocene,” as used in this document, describes compounds comprising at least one η3a n5-cycloalkadienyl type fraction, wherein the η3a n5-cycloalkadienyl fractions include cyclopentadienyl ligands, indenyl ligands, fluorenyl ligands, and the like, including partially saturated or substituted derivatives or analogues of any of these. Possible substituents for these ligands may include H, therefore this invention comprises ligands such as tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, partially saturated substituted indenyl, partially saturated substituted fluorenyl, and the like. In some contexts, the metallocene is referred to simply as the catalyst, in the same way that the term cocatalyst is used in this document to refer, for example, to an organoaluminum compound.

[0026] The terms catalyst composition, catalyst mixture, catalyst system and the like are independent of the actual product or composition resulting from the contact or reaction of the initial components of the disclosed or claimed catalyst composition / mixture / system, the nature of the active catalytic site or the fate of the cocatalyst, metallocene compound or fluorinated silica-coated alumina, after the combination of these components. Therefore, the terms catalyst composition, catalyst mixture, catalyst system and the like encompass the initial starting components of the composition as well as any products that may result from the contact of these initial starting components, and this includes both heterogeneous and homogeneous systems or compositions. The terms catalyst composition, catalyst mixture, catalyst system and the like may be used interchangeably throughout this disclosure.

[0027] The terms “contact” and “combination” are used in this document to describe compositions, processes, and methods in which materials or components are contacted or combined in any order, in any manner, and for any period of time, unless otherwise specified. For example, materials or components may be blended, mixed, suspended, dissolved, reacted, treated, compounded, or otherwise contacted or combined in any other way or by any method or technique. Petition 870260050793, dated 05 / 27 / 2026, page 20 / 88 8 / 55 adequate.

[0028] Various types of ranges are disclosed in the present invention. When a range of any type is disclosed or claimed, the intention is to disclose or claim individually every possible number that such range could reasonably encompass, including range outcomes, as well as any subranges and combinations of subranges covered therein. As a representative example, the total pore volume of a fluorinated silica-coated alumina may be in certain ranges in various aspects of this invention. By a disclosure that the pore volume may be in a range of 0.85 to 2 mL / g, the intention is to demonstrate that the pore volume may be any amount in the range and, for example, may include any range or combination of ranges from 0.85 to 2 mL / g, such as from 0.85 to 1.6 mL / g, from 0.9 to 1.8 mL / g, from 0.9 to 1.5 mL / g or from 1 to 1.7 mL / g and so forth.Similarly, all other tracks disclosed in this document should be interpreted in a manner similar to this example.

[0029] In general, a quantity, size, formulation, parameter, range, or other quantity or characteristic is about or approximate, whether or not expressly stated as such. Whether or not modified by the term about or approximate, the claims include equivalents to the quantities or characteristics.

[0030] Although any methods, devices and materials similar or equivalent to those described in this document may be used in the practice or testing of the invention, the typical methods, devices and materials are described in this document.

[0031] All publications and patents mentioned in this document are incorporated herein by reference in their entirety for the purpose of describing and disclosing, for example, the constructs and methodologies that are described in the publications and patents, which may be used in connection with the present invention described. DETAILED DESCRIPTION OF THE INVENTION

[0032] Processes for the preparation of fluorinated silica-coated aluminas and metallocene-based catalyst compositions containing fluorinated silica-coated aluminas are disclosed in this document. The processes of Petition 870260050793, dated 05 / 27 / 2026, p. 21 / 88 9 / 55 Polymerization using metallocene-based catalyst compositions to produce olefin polymers is also provided.

[0033] Beneficially, alumina activating supports with fluorinated silica have high pore volume and increased porosity, as well as greater adsorption for metallocene compounds, allowing significant increases in catalytic activity. Fluoridated silica coated aluminum activating supports

[0034] A fluorinated silica-coated alumina activator support covered in this document may have (or may be characterized by) an apparent density of 0.15 to 0.37 g / mL, a total pore volume of 0.85 to 2 mL / g, a BET surface area of ​​200 to 500 m2 / g and an average pore diameter of 10 to 25 nm. Another fluorinated silica-coated alumina covered in this document may have (or may be characterized by) an apparent density of 0.15 to 0.37 g / mL, a total pore volume of 0.85 to 2 mL / g, a BET surface area of ​​200 to 500 m2 / g and 80 to 99% of the pore volume of the fluorinated silica-coated alumina in pores with diameters greater than 6 nm. These illustrative and non-limiting examples of fluorinated silica-coated alumina activating supports consistent with the present invention may also have any of the properties listed below and in any combination, unless otherwise indicated.

[0035] Generally, fluorinated silica-coated alumina can have an apparent density of 0.15 to 0.37 g / mL. Other representative and non-limiting ranges for apparent density include 0.15 to 0.32 g / mL, 0.17 to 0.3 g / mL, 0.18 to 0.28 g / mL, or 0.18 to 0.25 g / mL and similar ranges. The total pore volume of fluorinated silica-coated alumina can vary from 0.85 to 2 mL / g, while the BET surface area can vary from 200 to 500 m² / g. In some aspects, the total pore volume can vary from 0.85 to 1.6 mL / g; alternatively, from 0.9 to 1.8 mL / g; alternatively, from 0.9 to 1.5 mL / g; or alternatively, from 1 to 1.7 mL / g. Similarly, the surface area of ​​BET, in some respects, can vary from 250 to 450 m2 / g; alternatively, from 200 to 425 m2 / g; or alternatively, from 270 to 425 m2 / g.

[0036] Beneficially, the silica-coated alumina activator support Petition 870260050793, dated 05 / 27 / 2026, p. 22 / 88 Fluoridated 10 / 55 alumina has a significant amount of mesopores (pores with a pore size greater than or equal to 10 nm in diameter). A test to quantify the significant amount of larger pores is the average pore diameter in nanometers (4000*PV / SA, with PV in mL / g and SA in m² / g). For example, a fluoridated silica-coated alumina with a total pore volume of 0.96 mL / g and a total BET surface area of ​​330 m² / g translates to an average pore diameter of 11.6 nm. Although not limited to this, the fluoridated silica-coated alumina disclosed in this document may have an average pore diameter of 10 to 20 nm in one aspect, 10.5 to 22 nm in another aspect, 11 to 22 nm in yet another aspect, and 11 to 19 nm in yet another aspect.

[0037] Another indicator of the significant quantity of larger pores is the percentage of pore volume in pores with diameters greater than 6 nm. Fluoridated silica-coated alumina can have, for example, 80 to 97%, 82 to 99%, 82 to 97%, 83 to 98%, or 84 to 99% of the pore volume in pores with diameters greater than 6 nm.

[0038] Another indicator of the quantity of larger pores in fluorinated silica-coated alumina is a significant amount of pore volume in pores with diameters greater than 20 nm and / or greater than 40 nm. In one aspect, the amount of pore volume in pores with diameters greater than 20 nm may fall within a range of 9.5 to 30%, 10 to 30%, 10 to 27%, 10.5 to 28%, or 11 to 26%, although it is not limited to these. Additionally or alternatively, fluorinated silica-coated alumina may be characterized as having 3.5 to 15%, 3.5 to 13%, 4 to 15%, 4 to 13%, or 5 to 15% of pore volume in pores with diameters greater than 40 nm.

[0039] Another indicator of the significant quantity of larger pores is the amount of pore volume present in pores with diameters greater than 6 nm. Although not limited to this, fluorinated silica-coated alumina may have a pore volume with diameters greater than 6 nm of at least 0.7 mL / g, at least 0.8 mL / g, or at least 0.85 mL / g, with representative ranges including 0.7 to 1.6 mL / g, 0.7 to 1.4 mL / g, 0.75 to 1.5 mL / g, 0.8 to 1.6 mL / g, or 0.8 to 1.4 mL / g and similar ranges. Similarly, fluorinated silica-coated alumina may have a pore volume with diameters greater than 20 nm of at least 0.09 mL / g or at least 0.1 mL / g, with representative ranges including Petition 870260050793, dated 05 / 27 / 2026, p. 23 / 88 11 / 55 from 0.09 to 0.4 mL / g, from 0.09 to 0.34 mL / g, from 0.1 to 0.4 mL / g, from 0.1 to 0.36 mL / g or from 0.11 to 0.34 mL / g and similar.

[0040] With reference now to characterizations of fluorinated silica-coated alumina based on surface area, the vast majority of the surface area resides in pores with diameters greater than 6 nm. Although not limited to this, fluorinated silica-coated alumina may have 65 to 98%, 65 to 94%, 65 to 91%, 68 to 94%, 70 to 98%, or 70 to 91% of surface area in pores with diameters greater than 6 nm. Additionally or alternatively, fluorinated silica-coated alumina may be characterized as having 19.5 to 55%, 20 to 55%, 20 to 50%, 21 to 55%, or 21 to 50% of the surface area in pores with diameters greater than 10 nm, although not necessarily limited to these.

[0041] Another indicator of the greater amount of surface area residing in larger pores is the amount of surface area of ​​fluorinated silica-coated alumina in pores with diameters greater than 6 nm. While not limited to this, fluorinated silica-coated alumina may have a surface area of ​​pores with diameters greater than 6 nm of at least 250 m² / g or at least 275 m² / g, with representative ranges including 250 to 475 m² / g or 275 to 450 m² / g and similar. Similarly, fluorinated silica-coated alumina may have a surface area of ​​pores with diameters greater than 10 nm of at least 78 m² / g or at least 85 m² / g, with representative ranges including 78 to 200 m² / g or 85 to 180 m² / g and similar.

[0042] Fluoridated silica-coated alumina may have any suitable particle size, as would be recognized by those skilled in the art. Illustrative and non-limiting ranges for the average particle size (d50) of fluoridated silica-coated alumina may include 30 to 150 microns, 40 to 100 microns, or 45 to 85 microns and the like.

[0043] The silica content of fluorinated silica-coated alumina, while not necessarily limited to, often ranges from 10 to 80% by weight, based on the weight of the silica-coated alumina. Most frequently, fluorinated silica-coated alumina contains 20 to 60% by weight of silica in one aspect, 25 to 55% by weight of silica in another aspect, and 35 to 45% by weight of silica in yet another aspect. These percentages are based on the weight of the alumina coated with Petition 870260050793, dated 05 / 27 / 2026, p. 24 / 88 12 / 55 silica.

[0044] Similarly, though not limited to this, fluorinated silica-coated alumina may contain from 0.5 to 18% by weight of F, although any suitable amount case shall be used. In many cases, the fluorinated silica-coated alumina described in this document contains from 1 to 13% by weight of F, from 2 to 9% by weight of F, from 3 to 16% by weight of F, or from 3 to 10% by weight of F, and the like. These percentages are based on the weight of the silica-coated alumina. CATALYST COMPOSITIONS

[0045] The present invention encompasses catalyst compositions comprising a metallocene compound and a fluorinated silica-coated alumina activator support. These catalyst compositions can be used to produce polyolefins – homopolymers, copolymers and the like – for a variety of end-use applications. In aspects of the present invention, it is contemplated that the catalyst composition may contain a metallocene compound (or two or more metallocene compounds). Furthermore, more than one fluorinated silica-coated alumina may also be used.As one skilled in the art would readily recognize, the support of metallocene compounds on fluorinated silica-coated alumina would not affect the total pore volume and surface area, the pore volume distribution and the surface area distribution; thus, these characteristics of a supported metallocene catalyst would effectively be the same as those disclosed above for fluorinated silica-coated alumina (based on the amount of metallocene adsorbed, as illustrated in the following example section).

[0046] A metallocene catalyst supported in one aspect of this invention may comprise a metallocene compound and a fluorinated silica-coated alumina, and the amount of metallocene compound adsorbed per gram of fluorinated silica-coated alumina may be at least 55 pmol / g or at least 60 pmol / g, with representative ranges including 55 to 155 pmol / g, 60 to at least 130 pmol / g and similar ranges. A metallocene catalyst supported in another aspect of this invention may comprise a metallocene compound and a fluorinated silica-coated alumina, and the number of molecules of the metallocene compound adsorbed per nm² of the surface area of ​​the alumina Petition 870260050793, dated 05 / 27 / 2026, p. 25 / 88 13 / 55 coated with fluorinated silica may have a density of at least 0.1 molecules per nm2 or at least 0.12 molecules per nm2, with representative ranges including 0.1 to 0.3 molecules per nm2, 0.1 to 0.24 molecules per nm2 or 0.12 to 0.22 molecules per nm2 and similar ranges.

[0047] The catalyst compositions of the present invention comprise a metallocene compound and a fluorinated silica-coated alumina and, optionally, such catalyst compositions may further comprise one or more cocatalyst compounds (suitable cocatalysts, such as organoaluminum compounds, are discussed in this document). Thus, a catalyst composition of this invention may comprise a metallocene compound, a fluorinated silica-coated alumina and an organoaluminum compound. Consequently, a catalyst composition consistent with aspects of the invention may comprise (or essentially consist of or consist of) a metallocene compound, a fluorinated silica-coated alumina and an organoaluminum compound.

[0048] In another aspect of the present invention, a catalyst composition is provided comprising a metallocene compound, a fluorinated silica-coated alumina, and an organoaluminum compound, wherein this catalyst composition is substantially free of aluminoxane, organoboron, or organoborate compounds, ionizing ionic compounds, or combinations thereof; alternatively, substantially free of aluminoxanes; alternatively, substantially free of organoboron or organoborate compounds; or alternatively, substantially free of ionizing ionic compounds. For example, the catalyst composition may contain less than 500 ppm, less than 100 ppm, less than 10 ppm, or less than 1 ppm, independently, of aluminoxane, organoboron, or organoborate compounds and ionizing ionic compounds. In these aspects, the catalyst composition has catalyst activity, discussed below, in the absence of these additional materials.For example, a catalyst composition of the present invention may consist essentially of a metallocene compound, a fluorinated silica-coated alumina, and an organoaluminum compound, wherein no other materials are present in the catalyst composition that would increase / decrease the activity of the catalyst composition by more than 10% of the catalyst activity of the composition. Petition 870260050793, dated 05 / 27 / 2026, page 26 / 88 14 / 55 catalyst in the absence of the aforementioned materials.

[0049] However, in other aspects of this invention, these cocatalysts may be employed. For example, a catalyst composition comprising a metallocene complex and a fluorinated silica-coated alumina may further comprise a cocatalyst. Suitable cocatalysts in this respect may include, but are not limited to, aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds, organoaluminum compounds, organozinc compounds, organomagnesium compounds, organolithium compounds and the like, or any combination thereof; or alternatively, organoaluminum compounds, organozinc compounds, organomagnesium compounds, organolithium compounds or any combination thereof. More than one cocatalyst may be present in the catalyst composition.

[0050] In particular aspects relating to catalyst compositions containing a cocatalyst and polymerization processes using a cocatalyst, the cocatalyst may comprise an aluminoxane compound (for example, a supported aluminoxane), an organoboron or organoborate compound, an ionizing ionic compound, an organoaluminum compound, an organozinc compound, an organomagnesium compound or an organolithium compound, and this includes any combinations of these materials. In one aspect, the cocatalyst may comprise an organoaluminum compound. In another aspect, the cocatalyst may comprise an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, an organozinc compound, an organomagnesium compound, an organolithium compound or any combination thereof.In yet another aspect, the cocatalyst may comprise an aluminoxane compound; alternatively, an organoboron or organoborate compound; alternatively, an ionizing ionic compound; alternatively, an organozinc compound; alternatively, an organomagnesium compound; or alternatively, an organolithium compound.

[0051] 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-nhexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, ethoxide of Petition 870260050793, dated 05 / 27 / 2026, p. 27 / 88 15 / 55 diethylaluminum, diethylaluminum chloride and the like, or combinations thereof. Representative and non-limiting examples of aluminoxanes include methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, n-butylaluminoxane, t-butylaluminoxane, sec-butylaluminoxane, isobutylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane, neopentylaluminoxane and the like, or any combination thereof. Representative and non-limiting examples of organoboron / organoborate compounds include N,N-dimethylaniline tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)borate, N,N-dimethylaniline tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)phenyl]boron and the like, or mixtures thereof.

[0052] Examples of ionizing ionic compounds may include, but are not limited to, the following compounds: tri(n-butyl)ammonium tetrakis(p-tolyl)borate, tri(n-butyl)ammonium tetrakis(m-tolyl)borate, tri(n-butyl)ammonium tetrakis(2,4-dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylaniline tetrakis(p-tolyl)borate, N,N-dimethylaniline tetrakis(m-tolyl)borate, N,N-dimethylaniline tetrakis(2,4-dimethylphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-dimethylphenyl)borate, N,Ndimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylbenium tetrakis(p-tolyl)borate, triphenylcarbenium tetrakis(m-tolyl)borate, triphenylcarbenium tetrakis(2,4-dimethylphenyl)borate, triphenylcarbenium tetrakis(3,5-dimethylphenyl)borate, triphenylcarbenium tetrakis[3,5bis(trifluoromethyl)phenyl]borate,triphenylcarbenium tetrakis(pentafluorophenyl)borate, tropylium tetrakis(p-tolyl)borate, tropylium tetrakis(m-tolyl)borate, tropylium tetrakis(2,4-dimethylphenyl)borate, tropylium tetrakis(3,5-dimethylphenyl)borate, tropylium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tropylium tetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)borate, lithium tetraphenylborate, lithium tetraphenylborate, lithium tetraphenylborate, lithium tetrakis(p-tolyl)borate, lithium tetrakis(m-tolyl borate), lithium tetrakis(2,4-dimethylphenyl)borate, lithium tetrakis(3,5-dimethylphenyl)borate, lithium, Petition 870260050793, dated 05 / 27 / 2026, page 28 / 88 16 / 55 tetrafluoroborate, sodium (pentafluorophenyl)borate, sodium tetraborate, sodium tetrakis(ptolyl)borate, sodium tetrakis(m-tolyl)borate, sodium tetrakis(2,4-dimethylphenyl)borate, sodium tetrakis(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassium tetrakis(pentafluorophenyl)borate, potassium tetraphenylborate, potassium tetrakis(p-tolyl)borate, potassium tetrakis(m-tolyl)borate, potassium tetrakis(2,4-dimethylphenyl)borate, potassium tetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoroborate, lithium tetrakis(pentafluorophenyl)aluminate, lithium tetraphenylaluminate, lithium tetrakis(p-tolyl)aluminate, lithium tetrakis(m-tolyl)aluminate lithium, lithium tetrakis(2,4-dimethylphenyl)aluminate, lithium tetrakis(3,5-dimethylphenyl)aluminate, lithium tetrafluoroaluminate, sodium tetrakis(pentafluorophenyl)aluminate, sodium tetraphenylaluminate, sodium tetrakis(p-tolyl)aluminate, sodium tetrakis(m-tolyl)aluminate, tetrakis(2,4-dimethylphenyl)aluminate sodium, tetrakis(3,5-dimethylphenyl)aluminate sodium, tetrafluoroaluminate sodium, tetrafluorophenyl (pentafluorophenyl)aluminate potassium, tetrakis(p-tolyl)aluminate potassium, tetrakis(m-tolyl)aluminate potassium, tetrakis(m-tolyl)aluminate potassium, tetrakis(2,4-dimethylphenyl)aluminate potassium, tetrakis(3,5-dimethylphenyl)aluminate potassium and combinations thereof.

[0053] Exemplary organozinc compounds that can be used as cocatalysts may include, but are not limited to, dimethylzinc, diethylzinc, dipropylzinc, dibutylzinc, dineopentylzinc, di(trimethylsilyl)zinc, di(triethylsilyl)zinc, di(triisopropylsilyl)zinc, di(triphenylsilyl)zinc, di(allyldimethylsilyl)zinc, di(trimethylsilylmethyl)zinc and the like, or combinations thereof.

[0054] Similarly, exemplary organomagnesium compounds may include, but are not limited to, dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, dinepentylmagnesium, di(trimethylsilylmethyl)magnesium, methylmagnesium chloride, ethylmagnesium chloride, propylmagnesium chloride, butylmagnesium chloride, neopentylmagnesium chloride, trimethylsilylmethylmagnesium chloride, methylmagnesium bromide, ethylmagnesium bromide, propylmagnesium bromide, butylmagnesium bromide, neopentylmagnesium bromide, trimethylsilylmethylmagnesium bromide, methylmagnesium iodide, ethylmagnesium iodide, iodide of propylmagnesium, butylmagnesium iodide, neopentylmagnesium iodide, trimethylsilylmethylmagnesium iodide, methylmagnesium ethoxide, Petition 870260050793, dated 05 / 27 / 2026, page 29 / 88 17 / 55 ethylmagnesium ethoxide, propylmagnesium ethoxide, butylmagnesium ethoxide, neopentylmagnesium ethoxide, trimethylsilylmethylmagnesium ethoxide, methylmagnesium propoxide, ethylmagnesium propoxide, propylmagnesium propoxide, butylmagnesium propoxide, neopentylmagnesium propoxide, trimethylsilylmethylmagnesium propoxide, methylmagnesium phenoxide, ethylmagnesium phenoxide, propylmagnesium phenoxide, butylmagnesium phenoxide, neopentylmagnesium phenoxide, trimethylsilylmethylmagnesium phenoxide, and the like, or any combinations thereof.

[0055] Similarly, exemplary organolithium compounds may include, but are not limited to, methyllithium, ethyllithium, propyllithium, butyllithium (e.g., t-butyllithium), neopentyllithium, trimethylsilylmethyllithium, phenyllithium, tolyllithium, xyllithium, benzyllithium, (dimethylphenyl)methyllithium, allyllithium, and the like or combinations thereof.

[0056] Cocatalysts that can be used in the catalyst compositions and polymerization processes of this invention are not limited to the cocatalysts described above. Other suitable cocatalysts are well known to those skilled in the art, including, for example, those disclosed in U.S. Patents Nos. 3,242,099, 4,794,096, 4,808,561, 5,576,259, 5,807,938, 5,919,983, 7,294,599, 7,601,665, 7,884,163, 8,114,946 and 8,309,485.

[0057] Any suitable metallocene compound may be used in the catalyst composition. For example, the metallocene component of the catalyst systems provided in this document may, in some respects, comprise an unbridged metallocene; alternatively, an unbridged zirconium- or hafnium-based metallocene compound; alternatively, an unbridged zirconium- or hafnium-based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or one cyclopentadienyl group and one indenyl group; alternatively, an unbridged zirconium-based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or one cyclopentadienyl group and one indenyl group. These cyclopentadienyl groups and indenyl groups may independently be unsubstituted or may be substituted with any suitable substituent (one or more than one).Illustrative and non-limiting examples of unbridged metallocene compounds (e.g., with zirconium or hafnium) that can be employed in catalyst systems consistent with aspects of the present invention are: Petition 870260050793, dated 05 / 27 / 2026, page 30 / 88 18 / 55 described in U.S. Patents Nos. 7,199,073, 7,226,886, 7,312,283 and 7,619,047.

[0058] In other respects, the metallocene component of the catalyst compositions provided in this document may comprise a bridged metallocene compound, for example, with titanium, zirconium or hafnium, such as a zirconium- or hafnium-based metallocene compound bridged with a fluorenyl group; or alternatively, a zirconium- or hafnium-based metallocene compound bridged with a cyclopentadienyl group and a fluorenyl group. These cyclopentadienyl groups and fluorenyl groups may independently be unsubstituted or may be substituted with any suitable substituent (one or more). For example, such bridged metallocenes may contain an alkenyl substituent (e.g., a terminal alkenyl) on the bridged group, on a cyclopentadienyl-type group (e.g., a cyclopentadienyl group or a fluorenyl group), or on both the bridged group and the cyclopentadienyl-type group.In some respects, the metallocene catalyst component may comprise a zirconium- or hafnium-based metallocene compound bridged with a fluorenyl group and an aryl group in the linking group; alternatively, a zirconium- or hafnium-based metallocene compound bridged with a cyclopentadienyl group and a fluorenyl group and an aryl group in the linking group; alternatively, a zirconium-based metallocene compound bridged with a fluorenyl group and an aryl group in the linking group; or alternatively, a hafnium-based metallocene compound bridged with a fluorenyl group and an aryl group in the linking group. In these and other respects, the aryl group in the bridging group may be a phenyl group. Optionally, these bridging metallocenes may contain an alkenyl substituent (e.g., a terminal alkenyl) on the bridging group, on a cyclopentadienyl-type group, or on both the bridging group and the cyclopentadienyl group.Illustrative and non-limiting examples of bridged metallocene compounds (e.g., with zirconium or hafnium) that can be employed in catalyst systems consistent with aspects of the present invention are described in U.S. Patents Nos. 7,026,494, 7,041,617, 7,226,886, 7,312,283, 7,517,939 and 7,619,047.

[0059] The catalyst composition can be produced in any way, such as by contacting the metallocene compound, the fluorinated silica-coated alumina and the cocatalyst (if used) in any order or sequence.

[0060] Generally, the weight ratio of cocatalyst (e.g., Petition 870260050793, dated 05 / 27 / 2026, page 31 / 88 19 / 55 an organoaluminum compound) to fluorinated silica-coated alumina can be in the range of 10:1 to 1:1000. If more than one cocatalyst compound and / or more than one fluorinated silica-coated alumina are used, this ratio is based on the total weight of each respective component. Alternatively, the weight ratio of cocatalyst to fluorinated silica-coated alumina can be in the range of 3:1 to 1:500 or 1:10 to 1:350.

[0061] In some aspects of this invention, the weight ratio of the metallocene complex to the fluorinated silica-coated alumina may be in the range of 1:1 to 1:1,000,000. If more than one metallocene compound and / or more than one fluorinated silica-coated alumina are employed, this ratio is based on the total weights of the respective components. In another aspect, this weight ratio may be in the range of 1:5 to 1:100,000 or 1:10 to 1:10,000. Still, in another aspect, the weight ratio of the metallocene to the fluorinated silica-coated alumina may be in the range of 1:20 to 1:1000.

[0062] The catalyst compositions of the present invention generally have a catalyst activity greater than 2,000 grams, greater than 3,000 grams, greater than 4,000 grams, greater than 5,000 grams, etc., of ethylene polymer (homopolymer or copolymer, as the context requires) per gram of fluorinated silica-coated alumina per hour (abbreviated as g / g / h). In another aspect, the catalyst activity may vary from 3,000 to 20,000, from 4,000 to 15,000, or from 4,000 to 9,000 grams of polyethylene per gram of fluorinated silica-coated alumina per hour (g / g / h). These activities are measured under flow paste polymerization conditions, with a triisobutylaluminum cocatalyst, using isobutane as the diluent at a polymerization temperature of 75 to 100°C (e.g., 95°C) and a reactor pressure of 300 psig (2.07 MPa) to 500 psig (3.45 MPa) (e.g., 400 psig (2.76 MPa)).Additionally, an excess of the metallocene compound in the catalyst composition can be used (e.g., 1-(methyl)-1-(3-butenyl)-1-(cyclopentadienyl)-1-(2,7-di-tert-butylfluorenyl)methane zirconium dichloride).

[0063] Additionally or alternatively, the catalyst compositions of the present invention generally have a catalyst activity greater than 100,000 grams, greater than 150,000 grams, greater than 200,000 grams, etc., of ethylene polymer (homopolymer or copolymer, as the context requires) per gram of Petition 870260050793, dated 05 / 27 / 2026, p. 32 / 88 20 / 55 metallocene compound per hour (abbreviated as g / g / h). In another aspect, catalyst activity can vary from 100,000 to 1,000,000, from 150,000 to 600,000, or from 200,000 to 500,000 g / g / h. These activities are measured under flow paste polymerization conditions, with a triisobutylaluminum cocatalyst, using isobutane as the diluent at a polymerization temperature of 75 to 100°C (e.g., 95°C) and a reactor pressure of 300 (2.07 MPa) to 500 psig (3.45 MPa) (e.g., 400 psig (2.76 MPa)). POLYMERIZATION PROCESSES

[0064] Olefin polymers (e.g., ethylene polymers) can be produced from the disclosed catalyst compositions using any suitable polymerization process with the use of various types of polymerization reactors, polymerization reactor systems, and polymerization reaction conditions. A polymerization process may comprise contacting any catalyst composition disclosed in this document with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer. This invention also encompasses any olefin polymers (e.g., ethylene polymers) produced by the polymerization processes disclosed in this document.

[0065] As used in this document, a polymerization reactor includes any polymerization reactor capable of polymerizing olefin monomers and comonomers (one or more than one comonomer) to produce homopolymers, copolymers, terpolymers, and the like. The various types of polymerization reactors include those that may be referred to as a batch reactor, fluidized paste reactor, gas-phase reactor, solution reactor, high-pressure reactor, tubular reactor, autoclave reactor, and the like, or combinations thereof; or alternatively, the polymerization reactor system may comprise a fluidized paste reactor, a gas-phase reactor, a solution reactor, or a combination thereof. The polymerization conditions for the various types of reactors are well known to those skilled in the art. Gas-phase reactors may comprise fluidized bed reactors or stacked horizontal reactors.Fluid slurry reactors comprise vertical and / or horizontal loops. High-pressure reactors may comprise reactors of... Petition 870260050793, dated 05 / 27 / 2026, page 33 / 88 21 / 55 autoclave and / or tubular reactors. Reactor types may include batch or continuous processes. Continuous processes may use intermittent or continuous product discharge. Polymerization reactor systems and processes may also include partial or total direct recycling of unreacted monomer, unreacted comonomer, and / or diluent.

[0066] A polymerization reactor system may comprise a single reactor or multiple reactors (2 reactors, more than 2 reactors, etc.) of the same type or of different types. For example, the polymerization reactor system may comprise a fluid paste reactor, a gas-phase reactor, a solution reactor, or a combination of two or more of these reactors. Polymer production in multiple reactors may include several stages in at least two separate polymerization reactors interconnected by a transfer device that makes it possible to transfer the resulting polymer from the first polymerization reactor to the second reactor. The desired polymerization conditions in one of the reactors may be different from the operating conditions of the other reactors. Alternatively, polymerization in multiple reactors may include the manual transfer of the polymer from one reactor to subsequent reactors for continuous polymerization.Multiple reactor systems may include any combination including, but not limited to, multiple loop reactors, multiple gas-phase reactors, a combination of loop and gas-phase reactors, multiple high-pressure reactors, or a combination of high-pressure with loop and / or gas-phase reactors. The multiple reactors may operate in series, in parallel, or both. Consequently, the present invention encompasses polymerization reactor systems comprising a single reactor, comprising two reactors, and comprising more than two reactors. The polymerization reactor system may comprise a fluidized paste reactor, a gas-phase reactor, a solution reactor, in certain aspects of this invention, as well as combinations of multiple reactors thereof.

[0067] According to one aspect, the polymerization reactor system may comprise at least one loop-type fluidized paste reactor comprising vertical or horizontal loops. The monomer, diluent, catalyst, and comonomer may be continuously fed into a loop-type reactor where polymerization occurs. Generally, continuous processes may comprise the Petition 870260050793, dated 05 / 27 / 2026, page 34 / 88 22 / 55 Continuous introduction of monomer / comonomer, a catalyst, and a diluent into a polymerization reactor and continuous removal from this reactor of a suspension comprising polymer and diluent particles. The reactor effluent can be instantaneously evaporated to remove the solid polymer from the liquids comprising the diluent, monomer, and / or comonomer. Various technologies can be used for this separation step including, but not limited to, evaporation which may include any combination of heat addition and pressure reduction, cyclonic separation in a cyclone or hydrocyclone, or centrifugal separation.

[0068] A typical fluid paste polymerization process (also known as the particle-form process) is disclosed, for example, in U.S. Patents Nos. 3,248,179, 4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191, 6,833,415 and 8,822,608. Suitable diluents used in fluid paste polymerization include, but are not limited to, the monomer being polymerized and hydrocarbons that are liquid under reaction conditions. Examples of suitable diluents include, but are not limited to, hydrocarbons such as propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane and n-hexane. Some loop-type polymerization reactions can occur under bulk conditions where no diluent is used.

[0069] According to yet another aspect, the polymerization reactor system may comprise at least one gas-phase reactor (e.g., a fluidized bed reactor). Such reactor systems may employ a continuous recycle stream containing one or more monomers continuously cycled through a fluidized bed in the presence of the catalyst under polymerization conditions. A recycle stream may be withdrawn from the fluidized bed and recycled back into the reactor. Simultaneously, the polymer product may be withdrawn from the reactor and new or fresh monomer may be added to replace the polymerized monomer.Such gas-phase reactors may comprise a process for the multi-stage gas-phase polymerization of olefins, wherein the olefins are polymerized in the gas phase in at least two independent gas-phase zones of polymerization by feeding a catalyst-containing polymer formed in a first polymerization zone to a second polymerization zone. Representative gas-phase reactors are... Petition 870260050793, dated 05 / 27 / 2026, page 35 / 88 23 / 55 disclosed in U.S. Patent Nos. 5,352,749, 4,588,790, 5,436,304, 7,531,606 and 7,598,327.

[0070] According to yet another aspect, the polymerization reactor system may comprise a high-pressure polymerization reactor, for example, it may comprise a tubular reactor or an autoclave reactor. Tubular reactors may have several zones where fresh monomer, initiators or catalysts are added. The monomer may be entrained in an inert gas stream and introduced into one zone of the reactor. Initiators, catalysts and / or catalyst components may be entrained in a gas stream and introduced into another zone of the reactor. The gas streams may be intermixed for polymerization. Heat and pressure may be appropriately employed to obtain ideal polymerization reaction conditions.

[0071] According to yet another aspect, the polymerization reactor system may comprise a solution polymerization reactor, in which the monomer / comonomer is brought into contact with the catalyst composition by means of agitation or other suitable means. A carrier comprising an inert organic diluent or excess monomer may be employed. If desired, the monomer / comonomer may be brought into contact with the catalytic reaction product in the presence or absence of liquid material in the vapor phase. The polymerization zone may be maintained at temperatures and pressures that will result in the formation of a polymer solution in a reaction medium. Agitation may be employed to obtain better temperature control and to maintain uniform polymerization mixtures throughout the polymerization zone. Suitable means are used to dissipate the exothermic heat of polymerization.

[0072] The polymerization reactor system may further comprise any combination of at least one raw material feed system, at least one feed system for the catalyst or catalyst components, and / or at least one polymer recovery system. Suitable reactor systems may further comprise systems for raw material purification, catalyst storage and preparation, extrusion, reactor cooling, polymer recovery, fractionation, recycling, storage, unloading, laboratory analysis, and process control. Depending on the Petition 870260050793, dated 05 / 27 / 2026, page 36 / 88 24 / 55 desired properties of the olefin polymer, hydrogen can be added to the polymerization reactor as needed (e.g., continuously or pulsed).

[0073] Polymerization conditions that can be controlled for efficiency and to provide desired polymer properties may include temperature, pressure, and the concentrations of various reagents. The polymerization temperature can affect catalyst productivity, polymer molecular weight, and molecular weight distribution. Several polymerization conditions can be kept substantially constant (such as within + / - 20%, + / - 10%, or + / - 5%), for example, for the production of a particular grade of olefin polymer (or ethylene polymer). A suitable polymerization temperature can be any temperature below the depolymerization temperature according to the Gibbs free energy equation. Typically, this includes 60°C to 280°C, for example, or 60°C to 120°C, depending on the type of polymerization reactors. In some reactor systems, the polymerization temperature can generally be within a range of 70°C to 105°C or 75°C to 100°C.

[0074] The appropriate pressures will also vary depending on the reactor and the type of polymerization. The pressure for liquid-phase polymerizations in a loop reactor is typically less than 1000 psig (6.9 MPa). The pressure for gas-phase polymerization is typically 200 to 500 psig (1.4 MPa to 3.4 MPa). High-pressure polymerization in tubular or autoclave reactors is generally performed at 20,000 to 75,000 psig (138 to 517 MPa). Polymerization reactors can also be operated in a supercritical region, generally occurring at higher temperatures and pressures. Operation above the critical point of a pressure / temperature diagram (supercritical phase) can offer advantages to the polymerization reaction process.

[0075] Olefin monomers that can be employed with the catalyst compositions and in the polymerization processes of this invention may typically include olefin compounds having from 2 to 30 carbon atoms per molecule and having at least one olefinic double bond, such as ethylene or propylene. In one aspect, the olefin monomer may comprise a C2-C20 olefin; alternatively, a C2-C20 alpha-olefin; alternatively, a C2-C10 olefin; alternatively, a C2-C10 alpha-olefin; alternatively, the monomer of Petition 870260050793, dated 05 / 27 / 2026, page 37 / 88 25 / 55 olefin may comprise ethylene; or alternatively, the olefin monomer may comprise propylene (for example, to produce a polypropylene homopolymer or a propylene-based copolymer).

[0076] When a copolymer (or alternatively, a terpolymer) is desired, the olefin monomer and the olefin comonomer may independently comprise, for example, a C2-C20 alpha-olefin. In some aspects, the olefin monomer may comprise ethylene or propylene, which is copolymerized with at least one comonomer (for example, a C2-C20 alpha-olefin or a C3C20 alpha-olefin). According to one aspect of this invention, the olefin monomer used in the polymerization process may comprise ethylene.In this respect, the comonomer may comprise a C3-C10 alpha-olefin; alternatively, the comonomer may comprise 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, styrene, or any combination thereof; alternatively, the comonomer may comprise 1-butene, 1-hexene, 1-octene, or any combination thereof; alternatively, the comonomer may comprise 1-butene; alternatively, the comonomer may comprise 1-hexene; or alternatively, the comonomer may comprise 1-octene. POLYMERS AND ARTICLES

[0077] The olefin polymers covered in this document may include any polymer produced from any olefin monomer and optional comonomers described in this document. For example, the olefin polymer may comprise an ethylene homopolymer, an ethylene copolymer (e.g., ethylene / α-olefin, ethylene / 1-butene, ethylene / 1-hexene, ethylene / 1-octene, etc.), a propylene homopolymer, a propylene copolymer, an ethylene terpolymer, a propylene terpolymer, and the like, including any combinations thereof. In one aspect, the olefin polymer may be (or may comprise) an ethylene / 1-butene copolymer, an ethylene / 1-hexene copolymer, or an ethylene / 1-octene copolymer, while in another aspect, the olefin polymer may be (or may comprise) an ethylene / 1-hexene copolymer.

[0078] If the resulting polymer produced according to the present invention is, for example, an ethylene polymer, its properties can be characterized by various analytical techniques known and used in the polyolefin industry. The Petition 870260050793, dated 05 / 27 / 2026, page 38 / 88 26 / 55 articles of manufacture may be formed from, and / or may comprise, the olefin polymers (e.g., ethylene polymers) of this invention, whose typical properties are given below.

[0079] The densities of ethylene-based polymers disclosed in this document are frequently greater than or equal to 0.90 g / cm3 and less than or equal to 0.97 g / cm3. However, in particular aspects, the density may vary from 0.91 to 0.965 g / cm3, from 0.91 to 0.93 g / cm3, from 0.92 to 0.96 g / cm3, from 0.93 to 0.955 g / cm3 or from 0.94 to 0.955 g / cm3. Although not limited to this, the ethylene polymer may have a high-charge melt index (HLMI) in a range of 0 to 100 g / 10 min; alternatively, from 1 to 80 g / 10 min; alternatively, from 2 to 40 g / 10 min; alternatively, from 2 to 30 g / 10 min; Alternatively, from 1 to 20 g / 10 min; or alternatively, from 50 to 100 g / 10 min. In one aspect, the ethylene polymers described in this document may have an Mw / Mn ratio, or polydispersity index, in a range of 2 to 40, 5 to 40, 7 to 25, 8 to 15, 2 to 10, 2 to 6, or 2 to 4.Additionally or alternatively, the ethylene polymer may have a weight-average molecular weight (Mw) in the range of 75,000 to 700,000, 75,000 to 200,000, 100,000 to 500,000, 150,000 to 350,000, or 200,000 to 320,000 g / mol. Furthermore, olefin polymers may be produced with a single or double metallocene catalyst system containing zirconium and / or hafnium. In such cases, the olefin polymer or ethylene polymer must not contain any measurable amount of Mg, V, Ti, and Cr, i.e., less than 0.1 ppm by weight. In additional aspects, the olefin polymer or ethylene polymer may independently contain less than 0.08 ppm, less than 0.05 ppm, or less than 0.03 ppm of Mg, V, Ti, and Cr.

[0080] An illustrative and non-limiting example of a particular ethylene polymer (e.g., an ethylene / α-olefin copolymer) covered in this document – ​​produced using the fluorinated silica-coated aluminas supported with the porosity and other attributes disclosed in this document – ​​may have a melt index (MI) in the range of 0.1 to 10 g / 10 min and a density in the range of 0.91 to 0.96 g / cm3, and the ethylene polymer may contain 70 to 270 ppm of solid oxide and 2 to 18 ppm of fluorine. The fluorine content is based on the elemental weight of F and generally the fluorine is from an inorganic source used in the preparation of the fluorinated silica-coated alumina. Due to catalytic activity Petition 870260050793, dated 05 / 27 / 2026, page 39 / 88 27 / 55 unexpectedly high and to the catalyst productivity of the fluorinated silica-coated aluminas disclosed, the resulting ethylene polymer has beneficially low amounts of catalyst residue.

[0081] The melting index of ethylene polymer varies from 0.1 to 10 g / 10 min, but more frequently, the melting index falls within a range of 0.3 to 8, 0.5 to 5, 0.8 to 3, or 0.5 to 2 g / 10 min and similar values. The density of ethylene-based polymer can often vary from 0.91 to 0.96 or from 0.915 to 0.958 g / cm3. In one aspect, the density can vary from 0.916 to 0.956, from 0.917 to 0.954 in another aspect, and from 0.915 to 0.952 g / cm3 in yet another aspect.

[0082] In one aspect, the ethylene polymer may have an Mw in the range of 25,000 to 400,000, 40,000 to 300,000, 50,000 to 250,000 or 80,000 to 200,000 g / mol. Additionally or alternatively, ethylene polymers may have an Mw / Mn ratio in the range of 2 to 25, 2.1 to 20, 2.3 to 20, 2 to 5 or 8 to 25 and the like. The ethylene polymer may have a unimodal molecular weight distribution, such as it may be produced using a single metallocene catalyst and thus would generally have a narrow MWD. Alternatively, the ethylene polymer can have a bimodal molecular weight distribution, as it can be produced using two metallocene catalysts and therefore would generally have a wide MWD.

[0083] As discussed in this document, the ethylene polymer can be produced with a metallocene catalyst, therefore chromium and Ziegler-Natta catalyst systems are not required. Therefore, the ethylene polymer cannot contain any measurable quantity of magnesium, vanadium, titanium, or chromium (catalyst residue), i.e., less than 0.1 ppm by weight. In some respects, the ethylene polymer may independently contain less than 0.08 ppm, less than 0.05 ppm, or less than 0.03 ppm of magnesium (or vanadium, or titanium, or chromium). The quantities of these elements can be determined by ICP analysis on a PerkinElmer Optima 8300 instrument. Polymer or article samples can be burned in a Thermolyne furnace with sulfuric acid overnight, followed by acid digestion in a HotBlock with HCl and HNO3 (3:1 v:v).

[0084] Instead, ethylene polymer typically contains 70 to 270 ppm of solid oxide (such as silica-coated alumina) and 2 to 18 ppm of fluorine (by weight). Other illustrative ranges for the fluorine content of ethylene polymer. Petition 870260050793, dated 05 / 27 / 2026, page 40 / 88 28 / 55 includes, but is not limited to, 2 to 16 ppm, 2 to 14 ppm, 2 to 12 ppm, 2 to 10 ppm, 3 to 16 ppm, 3 to 12 ppm, 4 to 12 ppm, or 4 to 10 ppm of fluorine. Other illustrative ranges for the solid oxide content of the ethylene polymer include, but are not limited to, 70 to 250 ppm, 100 to 250 ppm, 100 to 200 ppm, 100 to 150 ppm, 120 to 250 ppm, 120 to 200 ppm, or 120 to 170 ppm of solid oxide. The solid oxide content of the polymer is quantified by an ash test, discussed below. Although not required, the solid oxide may contain silica and alumina in any suitable relative amount, and illustrative weight ratios of silica:alumina may include 20:80 to 80:20, 20:80 to 60:40, 25:75 to 55:45, or 35:65 to 45:55, and so forth. The ethylene polymer also contains residual metal from the metallocene compound, such as zirconium and / or hafnium (or titanium, if used).Generally, ethylene polymer can contain 0.5 to 5 ppm, 0.5 to 4 ppm, 0.5 to 3 ppm, 0.6 to 5 ppm, 0.6 to 4 ppm, 0.6 to 3 ppm, 0.7 to 4 ppm, or 0.7 to 2.5 ppm of zirconium (or hafnium or titanium).

[0085] Ethylene polymers, whether homopolymers, copolymers, and so forth, can be formed into various manufactured articles. Articles that may comprise the polymers of this invention include, but are not limited to, an agricultural film, an automobile part, a bottle, a drum, a fiber or fabric, a food packaging film or container, a food service article, a fuel tank, a geomembrane, a household container, a lining, a molded product, a medical device or material, a tube, a sheet or tape, a toy, and the like. Various processes can be employed to form these articles. Non-limiting examples of such processes include injection molding, blow molding, spin molding, film extrusion, sheet extrusion, profile extrusion, thermoforming, and the like.Additionally, additives and modifiers are frequently added to these polymers in order to provide beneficial polymer processing or end-use product attributes. Such processes and materials are described in Modern Plastics Encyclopedia, Mid-November 1995 Edition, Vol. 72, No. 12; and Film Extrusion Manual - Process, Materials, Properties, TAPPI Press, 1992. In some aspects of this invention, a manufactured article may comprise any of the olefin polymers (or ethylene polymers) described in this document, and the manufactured article may be or may comprise a film (e.g., a blown film), a tube, or a... Petition 870260050793, dated 05 / 27 / 2026, page 41 / 88 29 / 55 molded product (e.g., a blow-molded product). Preparation of aluminas coated with fluoridated silica.

[0086] A process for producing a fluorinated silica-coated alumina activating support is described in this document. This process may comprise (or essentially consist of or consist of) contacting a fluorinating agent with silica-coated alumina to produce fluorinated silica-coated alumina. The silica-coated alumina, before being combined with the fluorinating agent, has (or is characterized by) the following properties: an apparent density of 0.15 to 0.37 g / mL, a total pore volume of 1.1 to 2.5 mL / g, a BET surface area of ​​250 to 600 m2 / g and an average pore diameter of 10 to 25 nm.Generally, the characteristics of this process (e.g., the fluorinating agent, silica-coated alumina and its characteristics, and fluorinated silica-coated alumina and its characteristics, among others) are independently described in this document, and these characteristics may be combined in any combination to further describe the disclosed process. Furthermore, other process steps may be conducted before, during, and / or after any of the steps listed in the disclosed processes, unless otherwise indicated. Additionally, fluorinated silica-coated alumina activating supports produced according to the disclosed process are within the scope of this disclosure and are covered in this document.

[0087] Typically, silica-coated alumina starting material has an apparent density of 0.15 to 0.37 g / mL. Other representative and non-limiting ranges for apparent density include 0.15 to 0.32 g / mL, 0.17 to 0.3 g / mL, 0.18 to 0.28 g / mL, or 0.18 to 0.25 g / mL and similar ranges. The total pore volume of silica-coated alumina can range from 1.1 to 2.5 mL / g, while the BET surface area can range from 250 to 600 m² / g. In some respects, the total pore volume can range from 1.2 to 2.2 mL / g; alternatively, from 1.3 to 2.4 mL / g; alternatively, from 1.4 to 2 mL / g; or alternatively, from 1.3 to 1.8 mL / g. Similarly, the surface area of ​​BET, in some aspects, can vary from 300 to 550 m2 / g; alternatively, from 300 to 500 m2 / g; or alternatively, from 325 to 475 m2 / g.

[0088] Silica-coated alumina has a significant number of larger pores, and a particular measurable parameter is the average pore diameter in nanometers (4000*PV / SA, with PV in mL / g and SA in m² / g). For example, a Petition 870260050793, dated 05 / 27 / 2026, p. 42 / 88 30 / 55 alumina coated with fluorinated silica with a total pore volume of 1.6 mL / g and a total BET surface area of ​​410 m² / g translates to an average pore diameter of 15.6 nm. Although not limited to this, the silica-coated alumina starting material may have an average pore diameter of 10 to 20 nm in one aspect, 11 to 19 nm in another aspect, 12 to 20 nm in yet another aspect, and 12 to 18 nm in yet another aspect.

[0089] Silica-coated alumina may contain any suitable amount of silica, based on the weight of the silica-coated alumina. Representative ranges include 10 to 80% by weight silica, 20 to 60% by weight silica, 25 to 55% by weight silica, or 35 to 45% by weight silica, and the like.

[0090] Although not limited to this, the process for producing the fluorinated silica-coated alumina activator support can be carried out by contacting the fluorinating agent and the silica-coated alumina in water to form an aqueous mixture containing the fluorinated silica-coated alumina. The order in which the components are combined to produce the aqueous mixture is not particularly limited. In one aspect, for example, the fluorinating agent may first come into contact with water and then the silica-coated alumina may be introduced, while in another aspect, the silica-coated alumina may first come into contact with water and then the fluorinating agent may be introduced.Furthermore, in another aspect, these components can be contacted in a substantially concomitant manner, which, in this context, means that the fluoridating agent, the silica-coated alumina, and the water are contacted together as soon as commercially practicable, such as within 15 minutes, within 5 minutes, or within 1 minute of two of the components being contacted (for example, water and the fluoridating agent or the silica-coated alumina).

[0091] Any suitable fluorinating agent or fluorine-containing compound may be used to produce fluorinated silica-coated alumina. Illustrative and non-limiting examples of fluorinating agents include hydrogen fluoride (HF), ammonium bifluoride (NH4HF2), triphilic acid (CF3SO3H), tetrafluoroboric acid (HBF4), hexafluorosilicic acid (H2SiF6), hexafluorophosphoric acid (HPF6), zinc tetrafluoroborate (Zn(BF4)2), and the like. Combinations of two or more fluorinating agents may be used if desired. In one aspect, the agent Petition 870260050793, dated 05 / 27 / 2026, page 43 / 88 31 / 55 Fluoridating agent may comprise (or consist essentially of, or consist of) hydrogen fluoride (HF); alternatively, ammonium bifluoride (NH4HF2); alternatively, triphilic acid (CF3SO3H); alternatively, tetrafluoroboric acid (HBF4); alternatively, hexafluorosilicic acid (H2SiF6); alternatively, hexafluorophosphoric acid (HPF6); or alternatively, zinc tetrafluoroborate (Zn(BF4)2).

[0092] The fluorinating agent and silica-coated alumina can be contacted or combined at any suitable pH and over a variety of temperatures and time periods. Ambient temperatures are generally conveniently used, and high temperatures are typically avoided in order to prevent the release of gaseous fluorine compounds.

[0093] The process for producing the fluorinated silica-coated alumina activator support may further comprise a drying step of the fluorinated silica-coated alumina, and any suitable technique may be used. For example, excess liquid may be removed from the fluorinated silica-coated alumina (e.g., drainage, filtration, decantation, pressing, centrifugation, etc.) and the wet fluorinated silica-coated alumina may be subjected to a wide range of drying times, drying temperatures, and drying pressures. For example, the drying time may vary from 15 min to 48 h, from 30 min to 24 h, or from 1 to 12 h, and the drying temperature may vary from 50°C to 300°C, from 95°C to 300°C, or from 100°C to 275°C.The drying pressure can be equal to or around atmospheric pressure, but in many cases, the drying step can be conducted under vacuum conditions at any suitable subatmospheric pressure, such as less than 100 torr (13.3 kPa), less than 50 torr (6.67 kPa), or less than 10 torr (1.33 kPa).

[0094] Various types of drying devices can be used for the drying step, such as tray dryers, rotary dryers, fluidized bed dryers, and spray dryers, although not limited to these. In a particular aspect of this invention, the drying step comprises spray drying the (wet) fluoridated silica-coated alumina (for example, a fluid paste or suspension of fluoridated silica-coated alumina in water) to a dry particulate or powder form. For spray drying, the drying times are different from those described above for drying times. Petition 870260050793, dated 05 / 27 / 2026, p. 44 / 88 32 / 55 of less than 30 minutes, less than 20 minutes, less than 10 minutes, less than 5 minutes, or even less than 1 minute.

[0095] Optionally, after drying, the alumina coated with fluorinated silica can be calcined, which can be conducted at a variety of temperatures and time periods. Typical peak calcination temperatures generally fall within a range of 400°C to 1000°C, such as 400°C to 900°C, 500°C to 800°C, or 550°C to 700°C. In these and other respects, these temperature ranges are also intended to cover circumstances where the calcination step is conducted at a series of different temperatures (e.g., an initial calcination temperature, a peak calcination temperature), rather than at a single fixed temperature, falling within the respective ranges, where at least one temperature is within the respective ranges.

[0096] The duration of the calcination step is not limited to any particular time period. Thus, the calcination step can be carried out, for example, over a period of time ranging from 30-45 minutes to 36-48 hours or more. The appropriate calcination time may depend, for example, on the initial / peak calcination temperature, among other variables. Generally, however, the calcination step can be conducted over a period of time that can be in a range of 30 minutes to 48 hours, such as, for example, 1 hour to 24 hours, 1 hour to 12 hours, 2 hours to 12 hours or 2 hours to 8 hours.

[0097] The calcination step may be carried out in a calcination gas stream comprising (or essentially consisting of, or consisting of) an inert gas (e.g., nitrogen), oxygen, air, or any mixture or combination thereof. In some respects, the calcination gas stream may comprise air, while in other respects, the calcination gas stream may comprise a mixture of air and nitrogen. However, in certain respects, the calcination gas stream may be an inert gas, such as nitrogen and / or argon.

[0098] The calcination step can be carried out using any suitable technique and equipment, whether in batch or continuous. For example, the calcination step can be carried out in a belt calciner or, alternatively, a rotary calciner. In some respects, the calcination step can be carried out in a continuous or batch calcination vessel comprising a bed. Petition 870260050793, dated 05 / 27 / 2026, page 45 / 88 33 / 55 fluidized. As those skilled in the art would recognize, other suitable techniques and equipment may be employed for the calcination step, and such techniques and equipment are covered in this document.

[0099] Fluoridated silica-coated alumina produced by the disclosed process may have any of the properties or characteristics disclosed above, for example, an apparent density of 0.15 to 0.37 g / mL, a total pore volume of 0.85 to 2 mL / g, a BET surface area of ​​200 to 500 m2 / g, an average pore diameter of 10 to 25 nm, 80 to 99% of the pore volume in pores with diameters greater than 6 nm, and the like. Furthermore, fluorinated silica-coated alumina can be produced with any target amount of fluorine, such as from 0.5 to 18% by weight of F, from 1 to 13% by weight of F, from 2 to 9% by weight of F, from 3 to 16% by weight of F, or from 3 to 10% by weight of F, based on a weight of fluorinated silica-coated alumina. EXAMPLES

[0100] This invention is further illustrated by the following examples, which should not be interpreted in such a way as to impose limitations on the scope of the invention in any way. Various other aspects, modifications, and equivalents thereof, which, after reading the description in this document, may of themselves be suggested to one skilled in the art without departing from the spirit of the present invention or the scope of the appended claims.

[0101] For characterization of silica-coated alumina and fluorinated silica-coated alumina, approximately 0.2 grams of sample were degassed in a physisorption tube using a Quantachrome Instruments NOVATOUCH® surface area and pore volume analyzer. To prevent portions of the fine particles from boiling into a region of the test tube that is not in the heated zone, the pressure was gradually reduced and the temperature was increased in stages. The pressure was initially reduced from ambient to 1 mm Hg at a controlled rate of 5 mm Hg / s, maintaining the samples at 30°C. After reaching sufficient vacuum (~0.1 mm Hg), the temperature was increased to 80°C and maintained for 30 minutes, then to 150°C and maintained for 30 minutes, then to 250°C and maintained for 720 minutes, with the final vacuum reaching a pressure of approximately 1 Millitorr.After cooling to room temperature, the samples were filled with nitrogen and analyzed in the same physisorption instrument. Petition 870260050793, dated 05 / 27 / 2026, page 46 / 88 34 / 55 Approximately 39 adsorption points were collected to construct an isotherm, and software packages included with the instrument were used to determine surface areas, pore volumes, and to generate pore size distribution curves. Surface areas were determined using the BET method (Brunauer, J. Am Chem. Soc., 1938, 60, 309), from isothermal adsorption points with P / Po values ​​from 0.0 to 0.2. Pore volume values ​​were calculated from the isothermal point with a P / Po value closest to 0.982. Pore ​​size distributions were generated from desorption isotherm data using the BJH method (J. Am. Chem. Soc., 1951, 73, 373), with thickness curves generated using the Halsey equation (J. Chem. Phys., 1948, 16, 931). Total pore volumes were determined according to Halsey (J. Chem. Phys., 1948, 16, 931).

[0102] Apparent density measurements were determined in accordance with ASTM D6683-19. The d50 particle size, or average or median particle size, refers to the particle size for which 50% of the sample has a smaller size and 50% of the sample has a larger size. Particle size distributions (including d10, d50, and d90) were determined using laser diffraction in accordance with ISO 13320.

[0103] The rheological characterizations of the melt were performed as follows. Small deformation (less than 10%) oscillatory shear measurements were performed on an ANTON PAAR® MCR rheometer using parallel plate geometry. All rheological tests were performed at 190°C. The complex viscosity (η*) versus frequency (ω) data were then curve-fitted using the modified three-parameter Carreau-Yasuda (CY) empirical model to obtain the zero shear viscosity - ηο, viscous relaxation time characteristics - τη, and the amplitude parameter - a (CYa parameter). The simplified Carreau-Yasuda (CY) empirical model is as follows. | η * (ω) | =-------ηο [1 + (τηω)α](1-Ν) / α' where: \ η*(ω) \ = magnitude of the complex shear viscosity; ηο = zero shear viscosity; τη = viscous relaxation time (Tau(n)); Petition 870260050793, dated 05 / 27 / 2026, page 47 / 88 35 / 55 a = “amplitude” parameter (CY-a parameter); n = sets the final slope of the force law, fixed at 2 / 11; and ω = angular frequency of oscillatory shear deformation.

[0104] Details of the meaning and interpretation of the CY model and derived parameters can be found in: CA Hieber and HH Chiang, Rheol. Acta, 28, 321 (1989); CA Hieber and HH Chiang, Polym. Eng. Sci., 32, 931 (1992); and RB Bird, RC Armstrong and O. Hasseger, Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics, 2nd Edition, John Wiley & Sons (1987).

[0105] The melting index (MI, g / 10 min) was determined in accordance with ASTM D1238 at 190°C, with a weight of 2,160 grams. Density can be determined in grams per cubic centimeter (g / cm3) in a compression-molded sample, cooled at 15°C per minute and conditioned for 40 hours at room temperature in accordance with ASTM D1505 and ASTM D4703.

[0106] Molecular weights and molecular weight distributions were obtained using a PL-GPC 220 system (Polymer Labs, an Agilent company) equipped with an IR4 detector (Polymer Char, Spain) and three Styragel HMW-6E GPC columns (Waters, MA) run at 145°C. The mobile phase flow rate of 1,2,4-trichlorobenzene (TCB) containing 0.5 g / L 2,6-di-t-butyl-4-methylphenol (BHT) is fixed at 1 mL / min, and the polymer solution concentrations are in the range of 1.0-1.5 mg / mL, depending on the molecular weight. Sample preparation was conducted at 150°C for approximately 4 hours with occasional gentle agitation before the solutions were transferred to sample vials for injection. An injection volume of approximately 400 µL is used. The integral calibration method is used to deduce molecular weights and molecular weight distributions using a Chevron Phillips Chemical Company HDPE polyethylene resin, MARLEX® BHB5003, as the broad standard.A comprehensive table of the broad standard is predetermined in a separate experiment with SEC-MALS. Mn is the number-average molecular weight, Mw is the weight-average molecular weight, Mz is the z-average molecular weight, Mv is the viscosity-average molecular weight, and Mp is the peak molecular weight (location, in molecular weight, of the highest point on the molecular weight distribution curve).

[0107] In this document, the ASTM ash content of the polymer (measured per ASTM D5630-13, procedure B) covers the amount of solid oxide (per Petition 870260050793, dated 05 / 27 / 2026, page 48 / 88 36 / 55 example, silica-coated alumina), metallocene transition metal and fluorine. Since metallocene transition metal and fluorine are minor portions of the ash content, the ash content is very close to the solid oxide content, but the solid oxide content in this document is equal to the ash content minus the metallocene transition metal content and minus the fluorine content.

[0108] The metal content, such as that of the transition metal of the metallocene compound, can be determined by ICP analysis on a PerkinElmer Optima 8300 instrument. Polymer samples or articles can be burned in a Thermolyne furnace with sulfuric acid overnight, followed by acid digestion in a HotBlock with HCl and HNO3 (3:1 v:v).

[0109] The fluoride content was determined by direct weight of the added fluoride compound. Additionally, the fluoride content can be determined by X-ray fluorescence, using calibrated samples of known fluoride content. In all cases, the added fluoride remained on the support after calcination, indicating that there was no loss due to evaporation. Comparative and Inventive Examples 1-2

[0110] Two silica-coated alumina supports were obtained from Sasol Olefins & Surfactants GmbH under the designations Siral® 40 (Comparative Example 1, CE-1) and Siral® 40 HPV (Inventive Example 1, IE-1), each containing 40% by weight silica and 60% by weight alumina, based on dry weight composition. Both supports were then treated with an aqueous solution of hydrofluoric acid to yield approximately 5% by weight of fluorine based on the dry weight of the support. The particles were dried, yielding a white powder. A 10 g sample of each powder product was then calcined in dry air in a fluidized bed at 600°C for three hours, cooled to room temperature, and washed with dry nitrogen for 30 minutes. The fluorinated silica-coated alumina powder product (Comparative Example 2 (CE-2) and Inventive Example 2 (IE-2)) was stored under nitrogen for later use.

[0111] FIGS. 1-2 illustrate the pore volume distributions and surface area distributions, respectively, as a function of pore diameter (nm) for aluminas coated with CE-1 and IE-1 silica, while FIGS. 3-4 illustrate the pore volume distributions and surface area distributions as a function of pore diameter (nm) for aluminas coated with Petition 870260050793, dated 05 / 27 / 2026, p. 49 / 88 37 / 55 fluorinated silica of CE-2 and IE-2. Some of the data expressed graphically in FIGS. 1-4 are tabulated in Table I. Table I shows the result of the sum of pore volume and surface area in various pore size categories, using the raw data obtained from the nitrogen desorption curves. The data are expressed as percentages, as well as in absolute terms: mL / g for pore volume and m² / g for surface area. The particle size test of the aluminas coated with fluorinated silica of CE-2 and IE-2, presented in FIGS. 3-4 and Table I, was performed after drying and calcination of the respective aluminas coated with fluorinated silica.

[0112] Referring first to the silica-coated aluminas CE-1 and IE-1 in the figures and data table, the total pore volume of IE-1 was significantly increased compared to CE-1, but, in addition, there were also large increases in the average pore diameter, the peak pore diameter, and the respective amounts of pore volume and surface area present in larger pores.

[0113] After fluoridation, drying, and calcination, the figures and data table also demonstrate the same beneficial improvements for IE-2 fluorinated silica-coated alumina compared to CE-2. Although the total pore volume did not increase as dramatically as for the silica-coated alumina base material, there were large increases in the average pore diameter and peak pore diameter (more than 20%) and significant increases in the respective amounts of pore volume and surface area present in larger pores for IE-2 compared to CE-2. Advantageously, IE-2 fluorinated silica-coated alumina, compared to CE-2, had a much larger amount of mesopores (generally, pores with a pore diameter greater than or equal to 10 nm), with a significant reduction in the amount of small pores (e.g., less than 6 nm in diameter).

[0114] FIG. 5 illustrates the particle size distributions of IE-2 and CE2, and the main particle size distribution metrics for IE-2 are summarized in Table II. Very small particles, often referred to as fines, can be problematic in polymerization reactor systems. Beneficially, although the particle size distribution of IE-2 was slightly wider than CE-2, only a very small fraction of IE-2 Petition 870260050793, dated 05 / 27 / 2026, page 50 / 88 38 / 55 had a particle size smaller than 10 μm (the d10 particle size was 24.6 μm). The fluorinated silica-coated alumina of IE-2 had an average d50 particle size of 63 μm, a d90 / d10 ratio of 5.4, a d90 / d50 ratio of 2.1, and a gap of 1.7.

[0115] The ability of IE2 fluorinated silica-coated alumina (FSCA) to adsorb a metallocene compound was also compared with CE-2. The metallocene compound (MET) was 1-(methyl)-1-(3-butenyl)-1-(cyclopentadienyl)-1-(2,7-di-tert-butylfluorenyl)methane zirconium dichloride (a bridged cyclopentadienyl-fluorenyl metallocene compound with a carbon bridge substituted by a methyl and a terminal butenyl). First, a stock solution of the metallocene compound (MET) was prepared by dissolving 80 mg of MET in a solvent mixture containing 8 mL of toluene and 80 mL of heptane. The concentration of MET in the stock solution was 0.91 mg / mL or 1.56 μmol / mL.

[0116] The adsorption experiments were performed by mixing 8 mL of the MET stock solution with IE-2 and CE-2, respectively, at room temperature, then stirring the mixture for 1 minute, then allowing the mixture to settle for 15 minutes. The supernatant liquid of the mixture was measured by UV-Vis at a wavelength of 582 nm to determine the amount of MET in the supernatant liquid. The amount of MET adsorbed on IE-2 or CE-2 was calculated by subtracting the amount of MET left in the supernatant liquid from the amount of MET in the stock solution used in the experiment.

[0117] Table III summarizes the adsorption experiments with IE-2 and CE-2. CE-2 adsorbed only 51 micromoles of the metallocene compound MET per gram of CE-2, while IE-2 unexpectedly adsorbed 98 micromoles of MET per gram of IE-2 (a 92% increase). In other words, CE-2 adsorbed only 0.087 molecules of the metallocene compound MET per nm² of the surface area of ​​CE-2, while IE-2 unexpectedly adsorbed 0.178 molecules of MET per nm² of the surface area of ​​IE-2 (a 104% increase). The MET molecules adsorbed per nm² of the surface area of ​​the respective FSCA were determined using the BET surface area from Table I, the adsorption in μπα^ from Table III, and Avogadro's number.

[0118] Although not wishing to be limited by the following theory, it is believed that IE-2 has better contact (or dispersion) between silica and alumina, which generates more Petition 870260050793, dated 05 / 27 / 2026, page 51 / 88 39 / 55 acidic sites, which increases absorptivity (and catalytic activity, discussed below). Thus, IE-2 effectively has a greater number of acidic sites or a greater number of ionizing sites than CE-2, and each site can adsorb a base molecule (the metallocene compound MET is a weak base) and subsequently ionize the metallocene base. Examples of Polymerization 3-12

[0119] The general procedure for polymerization experiments was as follows. The polymerization experiments are summarized in Table IV and were conducted in a 1-gallon autoclave reactor, with isobutane diluent (~2 L) used in all experiments. Fluoridated silica-coated alumina (~50 mg), 1 mmol of TIBA (1 M solution in hexanes), and 0.5–1.0 mg of a metallocene compound (which was 1-(methyl)-1-(3-butenyl)-1-(cyclopentadienyl)-1-(2,7-di-tert-butylfluorenyl)methane zirconium dichloride; 1 mg / mL toluene solution) were loaded into the reactor, followed by the addition of isobutane. The excess metallocene was used so that the activity of the fluoridated silica-coated alumina could be evaluated. The contents of the reactor were stirred and heated to the desired polymerization temperature of 90°C.Ethylene was then introduced into the reactor (no hydrogen or comonomer was added) and ethylene was fed on demand to maintain the target pressure of 390 psig (2.69 MPa) for the desired reaction time of 30 minutes. The reactor was maintained at 90°C throughout the run by an automated heating and cooling system. After reactor venting, purging, and cooling, the resulting polymer product was dried under reduced pressure.

[0120] Table IV summarizes the results of the polymerization experiments, where Examples 3-8 used fluorinated silica-coated alumina CE-2, Examples 9-12 used fluorinated silica-coated alumina IE-2, catalyst activity is in units of grams of polymer per gram of fluorinated silica-coated alumina per hour (g / g / h), and the CY-a parameter of the resulting polymer was measured. Unexpectedly, the catalytic activity using IE-2 fluorinated silica-coated alumina was improved, on average, by over 100% versus CE-2.

[0121] The Carreau-Yasuda parameter “a” (CY-a parameter) is particularly sensitive to small changes in the polymer, such as the long-chain branching (LCB) content. Surprisingly, given the differences Petition 870260050793, dated 05 / 27 / 2026, p. 52 / 88 40 / 55 significant in catalytic activity between Examples 3-8 and Examples 9-12, there was no difference in the CY-a parameter, thus indicating that the basic properties of the polymer were not significantly altered. INVENTIVE EXAMPLES 13-16

[0122] Inventive Examples 14A-15A, similar to IE-1, each contained 40% by weight silica and 60% by weight alumina, while Inventive Example 13A contained 28% by weight silica and 72% by weight alumina. Using the same fluoridation and calcination procedures described above, IE-13A was treated with an aqueous solution of HBF4 to yield 12.5% ​​by weight F (IE13B), and IE-14A was treated with an aqueous solution of HBF4 to yield 5% by weight F (IE-14B). IE-15A was first calcined at 600°C for three hours and then treated with an aqueous solution of HBF4 to yield 7% by weight F (IE-15B). The apparent densities for these examples were in the range of 0.18 to 0.32 g / mL.

[0123] As in Table I, Table V shows the result of summing pore volume and surface area in various pore size categories, using raw data obtained from nitrogen desorption curves. Data are expressed as percentages as well as in absolute terms: mL / g for pore volume and m² / g for surface area. After fluoridation, drying, and calcination, Table V demonstrates the same beneficial improvements as for IE-2 fluorinated silica-coated alumina compared to CE-2 in Table I. Compared to CE-2, IE-13B, IE-14B, and IE-15B fluorinated silica-coated alumina materials had higher pore volumes and much larger average pore diameters.Beneficially, the fluorinated silica-coated aluminas IE-13B, IE-14B, and IE-15B, compared to CE-2, had a much greater number of mesopores (generally, pores with a pore diameter greater than or equal to 10 nm), with a significant reduction in the number of small pores (e.g., less than 6 nm in diameter).

[0124] As in Table III, Table VI summarizes the adsorption experiments with IE-13B, IE-14B, IE-15B, and IE-16B (IE-16B was prepared similarly to IE-15B, except with 14 wt% F). Unexpectedly, these inventive fluorinated silica-coated alumina support materials adsorbed from 60 to over 120 micromoles of MET per gram of the respective support. While CE-2 adsorbed only 0.087 molecules of the metallocene compound MET per nm² of area. Petition 870260050793, dated 05 / 27 / 2026, page 53 / 88 41 / 55 of the surface area of ​​CE-2, the fluorinated silica-coated alumina support materials of the invention in Table VI unexpectedly adsorbed 0.13 to 0.21 MET molecules per nm2 of the respective support surface area. Table I Fluoridated Silica Coated Alumina Silica Coated Alumina Increase in (IE versus CE) Example CE-2 IE-2 CE-1 IE-1 After F Before F BET surface area, m2 / g 352 331 464 407 -6% -12% Total PV, mL / g 0.840 0.963 0.961 1.643 15% 71% Average pore diameter, nm 9.54 11.65 8.28 16.15 22% 95% Peak pore diameter, nm 7.73 9.45 6.51 7.71 22% 18% Apparent density, g / mL 0.32 0.21 -34% PV>diameter 6 nm, mL / g 0.664 0.863 0.702 1.611 30% 129% PV>diameter 10 nm mL / g 0.313 0.390 0.471 1.000 24% 112% PV>diameter 16 nm, mL / g 0.110 0.153 0.124 0.521 39% 319% PV>diameter 20 nm, mL / g 0.078 0.112 0.089 0.234 43% 162% PV>diameter 40 nm, mL / g 0.027 0.045 0.034 0.164 65% 378% BJH Desorption PV, mL / g 0.848 0.993 0.924 1,703 PV>diameter 6 nm,% 78.3% 86.9% 76.0% 94.6% 11% 25% PV>diameter 10 nm,% 36.9% 39.3% 51.0% 58.7% 6% 15% PV>diameter 16 nm,% 13.0% 15.4% 13.4% 30.6% 19% 127% PV>diameter 20 nm,% 9.2% 11.3% 9.7% 13.7% 22% 42% PV>diameter 40 nm% 3.2% 4.5% 3.7% 9,6% 41% 159% SA>diameter 6 nm, m2 / g 239 307 251 479 28% 91% SA>diameter 10 nm, m2 / g 72 88 75.4 198 21% 162% SA>diameter 16 nm, m2 / g 13 18 11.8 59 32% 397% SA>diameter 20 nm, m2 / g 7.4 11 8.6 11 44% 22% SA>diameter 40 nm, m2 / g 1.3 2.1 1.6 7.6 57% 382% BJH Desorption SA, m2 / g 392 411 435 545 SA>diameter 6 nm,% 60.9% 74.6% 57.8% 88.0% 23% 52% SA > diameter 10 nm,% 18.5% 21.4% 17.3% 36.3% 16% 109% SA > diameter 16 nm,% 3.4% 4.3% 2.7% 10.7% 26% 297%, Petition 870260050793, dated 05 / 27 / 2026, page 54 / 88 42 / 55 SA > diameter 20 nm,% 1.90% 2.61% 1.98% 1.93% 38% -2% SA > diameter 40 nm% 0.33% 0.50% 0.36% 1.39% 50% 285% Table II Example IE-2 Mv, mean, μm 73.3 Mn, mean number, μm 19.3 MA, area mean, μm 48.0 CS, surface area 0.125 Standard Deviation, μm 40.5 Mz, graphic mean 68.9 σ1, standard deviation Graph pattern 42.3 Ski, asymmetry 0.29 Kg, peak 1.12 D10, μm 24.66 D20, μm 35.15 D30, μm 44.89 D40, μm 54.12 D50, μm 63.44 D60, μm 73.71 D70, μm 85.97 D80, μm 102.8 D90, μm 132.2 D95, μm 164.1 D90 / D10 5.36 D90 / D50 2.08 Interval 1.69 Table II Fluoridated Silica Coated Alumina FSCA CE-2 IE-2 Weight FSCA mg 105 103 MET Stock Solution mL 8 8 mg / mL 0.91 0.91 MET in stock solution μmol / mL mg 1.56 7.27 1.56 7.27 μmol / mL 12.45 12.45 mg / mL 0.52 0.18 MET in supernatant after adsorption μmol / mL 0.89 0.30 mg 4.16 1.40 μmol / mL 7.13 2.40 Petition 870260050793, dated 05 / 27 / 2026, page 55 / 88 43 / 55 mg pmol 3.11 5.32 5.87 10.05 MET adsorbed by FSCA mg / g 29.6 57.0 pmol / g molecule 50.7 97.6 s / nm2 0.087 0.178 Table IV Example: Fluoridated Silica Coated Alumina Supporting Activity (g / g / h) CY-a Parameter 3 CE-2 3.042 4 CE-2 3.524 5 CE-2 3.532 0.4698 6 CE-2 3.340 0.4150 7 CE-2 3.246 0.4570 8 CE-2 3.324 0.4676 9 IE-2 7.244 0.4352 10 IE-2 7.192 0.4037 11 IE-2 7.376 0.4554 12 IE-2 7.728 0.4714 Table V Fluorinated Silica Coated Alumina Silica Coated Alumina Example IE-13B IE-14B IE-15B IE-13A IE-14A IE-15A BET surface area, m² / g 270 424 381 326 440 468 Total PV, mL / g 1.219 1.388 1.458 1.396 1.618 1.352 Average pore diameter, nm 18.07 13.11 15.30 17.15 14.69 11.55 PV > diameter 6 nm, mL / g 1.214 1.287 1.396 1.374 1.508 1.172 Petition 870260050793, dated 05 / 27 / 2026, page 56 / 88 44 / 55 PV>diameter 10 nm mL / g 0.874 0.746 0.830 1.062 0.844 0.563 PV>diameter 16 nm, mL / g 0.420 0.322 0.409 0.468 0.463 0.281 PV>diameter 20 nm, mL / g 0.324 0.242 0.312 0.336 0.368 0.216 PV>diameter 40 nm, mL / g 0.158 0.101 0.123 0.139 0.167 0.087 BJH desorption PV, mL / g 1.256 1.426 1.519 1,420 1,673 1,376 PV>diameter 6 nm,% 96.7% 90.3% 91.9% 96.8% 90.1% 85.2% PV>diameter 10 nm,% 69.6% 52.3% 54.7% 74.8% 50.5% 40.9% PV>diameter 16 nm,% 33.4% 22.6% 26.9% 33.0% 27.7% 20.4% PV>diameter 20 nm,% 25.8% 17.0% 20.6% 23.7% 22.0% 15.7% PV>diameter 40 nm% 12.6% 7.1% 8.1% 9.8% 10.0% 6.3% SA>diameter 6 nm, m2 / g 324 407 427 358 471 401 SA>diameter 10 nm, m2 / g 174 161 169 222 159 114 SA>diameter 16 nm, m2 / g 45 37 47 57 49 32 SA>diameter 20 nm, m2 / g 27 22 29 31 32 20 SA>diameter 40 nm, m2 / g 7 5 6 7 8 4 BJH desorption SA, m2 / g 356 519 519 391 596 562 SA>diameter 6 nm, % 91.0% 78.4 % 82.3% 91.6% 79.1% 71.2% SA > diameter 10 nm,% 49.0% 31.1% 32.5% 56.9% 26.7% 20.2% SA > diameter 16 nm,% 12.6% 7.1% 9,0% 14.5% 8.2% 5.6% SA > diameter 20 nm,% 7.6% 4.2% 5.7% 7.9% 5.4% 3.6% SA > diameter 40 nm% 2.0% 0.9% 1.1% 1.7% 1.3% 0.7%, Table VI Example IE-13B IE-14B IE-15B IE-16B Petition 870260050793, dated 05 / 27 / 2026, page 57 / 88 45 / 55 Silica, weight% 28 40 40 40 Total PV, mL / g 1.22 1.39 1.46 1.40 Pre-calcined No No Yes Yes Fluorine, weight% 12.5 5 7 14 Adsorbed MET, pmol / g 59.6 122.1 117.7 107.3 BET surface area, m2 / g 270 424 381 310 Adsorbed MET, molecules / nm2 0.133 0.173 0.186 0.208

[0125] The invention has been described above with reference to numerous specific aspects and examples. Many variations will be suggested to those skilled in the art in light of the detailed description above. All such obvious variations are within the intended scope of the appended claims. Other aspects of the invention may include, but are not limited to, the following (the aspects are described as comprising, but alternatively may consist essentially of or consist of): Aspect 1. A fluorinated silica-coated alumina having (or characterized by) an apparent density of 0.15 to 0.37 g / mL, a total pore volume of 0.85 to 2 mL / g, a BET surface area of ​​200 to 500 m2 / g and an average pore diameter of 10 to 25 nm.

[0126] Aspect 2. A fluorinated silica-coated alumina having (or characterized by) an apparent density of 0.15 to 0.37 g / mL, a total pore volume of 0.85 to 2 mL / g, a BET surface area of ​​200 to 500 m2 / g and 80 to 99% of the pore volume in pores with diameters greater than 6 nm.

[0127] Aspect 3. Fluoridated silica-coated alumina defined aspect 1 or 2, wherein fluoridated silica-coated alumina contains any suitable amount of silica or an amount of silica in any range disclosed in this document, for example, 10 to 80% by weight of silica, 20 to 60% by weight of silica, 25 to 55% by weight of silica or 35 to 45% by weight of silica, based on the weight of silica-coated alumina.

[0128] Aspect 4. Fluoridated silica-coated alumina defined in any of the preceding aspects, wherein the fluoridated silica-coated alumina contains any suitable amount of fluorine or an amount of fluorine in any range disclosed in this document, for example, from 0.5 to 18% by weight of F, from 1 to 13% by weight of F, from 2 to 9% by weight of F, from 3 to 16% by weight Petition 870260050793, dated 05 / 27 / 2026, p. 58 / 88 46 / 55 of F, or 3 to 10% by weight of F, based on a weight of alumina coated with fluorinated silica.

[0129] Aspect 5. Fluoridated silica-coated alumina defined in any of the preceding aspects, wherein the fluoridated silica-coated alumina has any suitable average particle size (d50) or an average particle size in any range disclosed in this document, for example, 30 to 150 microns, 40 to 100 microns or 45 to 85 microns.

[0130] Aspect 6. Fluoridated silica-coated alumina defined in any of the preceding aspects, wherein the apparent density is in any suitable range or in any range disclosed in this document, for example, 0.15 to 0.32 g / mL, 0.17 to 0.3 g / mL, 0.18 to 0.28 g / mL or 0.18 to 0.25 g / mL.

[0131] Aspect 7. Fluoridated silica-coated alumina defined in any of the preceding aspects, wherein the total pore volume is in any suitable range or in any range disclosed in this document, for example, 0.85 to 1.6 mL / g, 0.9 to 1.8 mL / g, 0.9 to 1.5 mL / g or 1 to 1.7 mL / g.

[0132] Aspect 8. Fluoridated silica-coated alumina defined in any of the preceding aspects, wherein the BET surface area is in any suitable range or in any range disclosed in this document, for example, 250 to 450 m2 / g, 200 to 425 m2 / g or 270 to 425 m2 / g.

[0133] Aspect 9. Fluoridated silica-coated alumina defined in any of the preceding aspects, wherein the fluoridated silica-coated alumina has an average pore diameter in any suitable range or in any range disclosed in this document, for example, 10 to 20 nm, 10.5 to 22 nm, 11 to 22 nm or 11 to 19 nm.

[0134] Aspect 10. Fluoridated silica-coated alumina defined in any of the preceding aspects, wherein the fluoridated silica-coated alumina has any suitable percentage of the pore volume in pores with diameters greater than 6 nm or an amount in any range disclosed in this document, for example, 80 to 97%, 82 to 99%, 82 to 97%, 83 to 98% or 84 to 99%.

[0135] Aspect 11. Fluoridated silica-coated alumina defined in Petition 870260050793, dated 05 / 27 / 2026, p. 59 / 88 47 / 55 any of the foregoing aspects, wherein the alumina coated with fluorinated silica has any suitable percentage of the pore volume in pores with diameters greater than 20 nm or an amount in any range disclosed in this document, for example, 9.5 to 30%, 10 to 30%, 10 to 27%, 10.5 to 28% or 11 to 26%.

[0136] Aspect 12. Fluoridated silica-coated alumina defined in any of the preceding aspects, wherein the fluoridated silica-coated alumina has any suitable percentage of the pore volume in pores with diameters greater than 40 nm or an amount in any range disclosed in this document, for example, 3.5 to 15%, 3.5 to 13%, 4 to 15%, 4 to 13% or 5 to 15%.

[0137] Aspect 13. Fluoridated silica-coated alumina defined in any of the preceding aspects, wherein the fluoridated silica-coated alumina has any suitable pore volume with diameters greater than 6 nm or an amount in any range disclosed in this document, for example, at least 0.7 mL / g, at least 0.8 mL / g, at least 0.85 mL / g, from 0.7 to 1.6 mL / g, from 0.7 to 1.4 mL / g, from 0.75 to 1.5 mL / g, from 0.8 to 1.6 mL / g or from 0.8 to 1.4 mL / g.

[0138] Aspect 14. Fluoridated silica-coated alumina defined in any of the preceding aspects, wherein the fluoridated silica-coated alumina has any suitable pore volume with diameters greater than 20 nm or an amount in any range disclosed in this document, for example, at least 0.09 mL / g, at least 0.1 mL / g, from 0.09 to 0.4 mL / g, from 0.09 to 0.34 mL / g, from 0.1 to 0.4 mL / g, from 0.1 to 0.36 mL / g or from 0.11 to 0.34 mL / g.

[0139] Aspect 15. Fluoridated silica-coated alumina defined in any of the preceding aspects, wherein the fluoridated silica-coated alumina has any suitable percentage of surface area in pores with diameters greater than 6 nm or an amount in any range disclosed in this document, for example, 65 to 98%, 65 to 94%, 65 to 91%, 68 to 94%, 70 to 98% or 70 to 91%.

[0140] Aspect 16. Fluoridated silica-coated alumina defined in any of the preceding aspects, wherein the fluoridated silica-coated alumina has any suitable percentage of surface area in pores with diameters greater than 10 nm or an amount in any range disclosed in this Petition 870260050793, dated 05 / 27 / 2026, pp. 60 / 88 48 / 55 document, for example, from 19.5 to 55%, from 20 to 55%, from 20 to 50%, from 21 to 55% or from 21 to 50%.

[0141] Aspect 17. Fluoridated silica-coated alumina defined in any of the preceding aspects, wherein the fluoridated silica-coated alumina has any suitable surface area of ​​pores with diameters greater than 6 nm or an amount in any range disclosed in this document, for example, at least 250 m2 / g, at least 275 m2 / g, from 250 to 475 m2 / g or from 275 to 450 m2 / g.

[0142] Aspect 18. Fluoridated silica-coated alumina defined in any of the preceding aspects, wherein the fluoridated silica-coated alumina has any suitable surface area of ​​pores with diameters greater than 10 nm or an amount in any range disclosed in this document, for example, at least 78 m2 / g, at least 85 m2 / g, from 78 to 200 m2 / g or from 85 to 180 m2 / g.

[0143] Aspect 19. A catalyst composition comprising a metallocene compound, fluorinated silica-coated alumina defined in any of the preceding aspects and an optional cocatalyst.

[0144] Aspect 20. The composition defined in aspect 19, wherein the metallocene compound comprises any suitable metallocene compound or any metallocene compound disclosed in this document.

[0145] Aspect 21. The composition defined in aspect 19 or 20, wherein the metallocene compound comprises a zirconium- or hafnium-based unbridged metallocene compound containing two cyclopentadienyl groups, two indenyl groups or one cyclopentadienyl group and one indenyl group.

[0146] Aspect 22. The composition defined in any of the aspects 1921, wherein the metallocene compound comprises a zirconium- or hafnium-based metallocene compound bridged with a fluorenyl group.

[0147] Aspect 23. The composition defined in any of the aspects 1921, wherein the metallocene compound comprises a zirconium- or hafnium-based metallocene compound bridged with a cyclopentadienyl group and a fluorenyl group.

[0148] Aspect 24. The composition defined in any of the aspects 1923, wherein the catalyst composition comprises only one compound of Petition 870260050793, dated 05 / 27 / 2026, p. 61 / 88 49 / 55 metallocene.

[0149] Aspect 25. The composition defined in any of the aspects 1923, wherein the catalyst composition comprises two or more metallocene compounds.

[0150] Aspect 26. The composition defined in any of the aspects 1925, wherein the catalyst composition comprises the cocatalyst, for example, any cocatalyst disclosed in this document.

[0151] Aspect 27. The composition defined in aspect 26, wherein the cocatalyst comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, an organoaluminum compound, an organozinc compound, an organomagnesium compound, an organolithium compound or any combination thereof.

[0152] Aspect 28. The composition defined in aspect 26, wherein the cocatalyst comprises any suitable organoaluminum compound or any organoaluminum compound disclosed in this document.

[0153] Aspect 29. The composition defined in any of the aspects 1926, wherein the catalyst composition is substantially free of aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds or combinations thereof.

[0154] Aspect 30. The composition defined in any of the aspects of 1929, wherein a catalyst activity of the catalyst composition is in any range disclosed in this document, for example, from 3,000 to 20,000, from 4,000 to 15,000 or from 4,000 to 9,000 grams of ethylene polymer per gram of fluorinated silica-coated alumina per hour (additionally or alternatively, from 100,000 to 1,000,000, from 150,000 to 600,000 or from 200,000 to 500,000 grams of ethylene polymer per gram of metallocene compound per hour) under flow paste polymerization conditions, with a triisobutylaluminum cocatalyst, using isobutane as the diluent, at a polymerization temperature of 75 to 100°C (e.g., 95°C) and a reactor pressure of 300 psig (2.07 MPa) to 500 psig (3.45 MPa) (e.g., 400 psig (2.76 MPa)).

[0155] Aspect 31. An olefin polymerization process, the process comprising placing the catalyst composition defined in any of aspects 19-30 in contact with an olefin monomer and a comonomer of Petition 870260050793, dated 05 / 27 / 2026, pp. 62 / 88 50 / 55 optional olefin in a polymerization reactor system under polymerization conditions to produce an olefin polymer.

[0156] Aspect 32. The olefin polymerization process defined in aspect 31, wherein the olefin monomer comprises any olefin monomer disclosed in this document, for example, any C2-C20 olefin.

[0157] Aspect 33. The olefin polymerization process defined in aspect 31, wherein the olefin monomer and the optional olefin comonomer independently comprise a C2-C20 alpha-olefin.

[0158] Aspect 34. The olefin polymerization process defined in any one of aspects 31-33, wherein the olefin monomer comprises ethylene.

[0159] Aspect 35. The olefin polymerization process defined in any one of aspects 31-34, wherein the catalyst composition is contacted with ethylene and an olefin comonomer comprising a C3-C10 alpha-olefin.

[0160] Aspect 36. The olefin polymerization process defined in any one of aspects 31-35, wherein the catalyst composition is brought into contact with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene or a mixture thereof.

[0161] Aspect 37. The olefin polymerization process defined in any one of aspects 31-36, wherein the polymerization reactor system comprises a batch reactor, a flow slurry reactor, a gas phase reactor, a solution reactor, a high pressure reactor, a tubular reactor, an autoclave reactor or a combination thereof.

[0162] Aspect 38. The olefin polymerization process defined in any one of aspects 31-37, wherein the polymerization reactor system comprises a fluid paste reactor, a gas phase reactor, a solution reactor or a combination thereof.

[0163] Aspect 39. The olefin polymerization process defined in any one of aspects 31-38, wherein the polymerization reactor system comprises a loop-type fluidized paste reactor.

[0164] Aspect 40. The olefin polymerization process defined in any one of aspects 31-39, wherein the polymerization reactor system comprises a single reactor. Petition 870260050793, dated 05 / 27 / 2026, pp. 63 / 88 51 / 55

[0165] Aspect 41. The olefin polymerization process defined in any one of aspects 31-39, wherein the polymerization reactor system comprises 2 reactors.

[0166] Aspect 42. The olefin polymerization process defined in any one of aspects 31-39, wherein the polymerization reactor system comprises more than 2 reactors.

[0167] Aspect 43. The olefin polymerization process defined in any of aspects 31-42, wherein the olefin polymer comprises any olefin polymer disclosed in this document.

[0168] Aspect 44. The olefin polymerization process defined in any one of aspects 31-43, wherein the olefin polymer comprises an ethylene homopolymer, an ethylene / 1-butene copolymer, an ethylene / 1-hexene copolymer and / or an ethylene / 1-octene copolymer.

[0169] Aspect 45. The olefin polymerization process defined in any one of aspects 31-44, wherein the polymerization conditions comprise a polymerization reaction temperature in a range of 60°C to 120°C and a reaction pressure in a range of 200 to 1,000 psig (1.4 to 6.9 MPa).

[0170] Aspect 46. The olefin polymerization process defined in any one of aspects 31-45, wherein the polymerization conditions are substantially constant, for example, for a particular polymer grade, such as within + / - 20%, + / - 10% or + / - 5%.

[0171] Aspect 47. The olefin polymerization process defined in any of aspects 31-46, wherein no hydrogen is added to the polymerization reactor system.

[0172] Aspect 48. The process defined in any one of aspects 31-46, in which hydrogen is added to the polymerization reactor system.

[0173] Aspect 49. An olefin polymer produced by the olefin polymerization process defined in either of aspects 31-48.

[0174] Aspect 50. A process for producing a fluorinated silica-coated alumina, the process comprising contacting a fluorinating agent with a silica-coated alumina to produce the fluorinated silica-coated alumina, wherein the silica-coated alumina has (or is characterized by) a Petition 870260050793, dated 05 / 27 / 2026, pp. 64 / 88 52 / 55 apparent density of 0.15 to 0.37 g / mL, a total pore volume of 1.1 to 2.5 mL / g, a BET surface area of ​​250 to 600 m2 / g and an average pore diameter of 10 to 25 nm.

[0175] Aspect 51. The process defined in aspect 50, in which the fluorinating agent and silica-coated alumina are brought into contact in water to form an aqueous mixture of fluorinated silica-coated alumina.

[0176] Aspect 52. The process defined in aspect 50 or 51, further comprising a drying step of the alumina coated with fluorinated silica, a calcination step of the alumina coated with fluorinated silica or both.

[0177] Aspect 53. The process defined in any one of aspects 50-52, wherein the fluorinating agent comprises hydrogen fluoride (HF), ammonium bifluoride (NH4HF2), triphilic acid (CF3SO3H), tetrafluoroboric acid (HBF4), hexafluorosilicic acid (H2SiF6), hexafluorophosphoric acid (HPF6), zinc tetrafluoroborate (Zn(BF4)2), or any combination thereof.

[0178] Aspect 54. The process defined in any one of aspects 50-52, wherein the fluorinating agent comprises hydrogen fluoride (HF).

[0179] Aspect 55. The process defined in any one of aspects 50-54, wherein fluorinated silica-coated alumina is defined by any one of aspects 1-18.

[0180] Aspect 56. A supported metallocene catalyst comprising a metallocene compound and a fluorinated silica-coated alumina, wherein an amount of the metallocene compound adsorbed per gram of fluorinated silica-coated alumina is in any suitable range or in any range disclosed in this document, for example, at least 55 pmol / g, at least 60 pmol / g, from 55 to 155 pmol / g or from 60 to at least 130 pmol / g.

[0181] Aspect 57. A supported metallocene catalyst comprising a metallocene compound and a fluorinated silica-coated alumina, wherein the number of molecules of the metallocene compound adsorbed per nm2 of the surface area of ​​the fluorinated silica-coated alumina is in any suitable range or in any range disclosed in this document, for example, at least 0.1 molecules per nm2, at least 0.12 molecules per nm2, from 0.1 to 0.3 molecules per nm2, from 0.1 to 0.24 molecules per nm2 or from 0.12 to 0.22 molecules per nm2. Petition 870260050793, dated 05 / 27 / 2026, pp. 65 / 88 53 / 55

[0182] Aspect 58. The catalyst defined in aspect 56 or 57, wherein the supported metallocene catalyst (or fluorinated silica-coated alumina) is defined by either aspect 1-18.

[0183] Aspect 59. An ethylene polymer having (or characterized by) a melt index (MI) in a range of 0.1 to 10 g / 10 min and a density in a range of 0.91 to 0.96 g / cm3, wherein the ethylene polymer contains 70 to 270 ppm of solid oxide and 2 to 18 ppm of fluorine.

[0184] Aspect 60. The polymer defined in aspect 59, wherein the MI is in any range disclosed in this document, for example, 0.3 to 8, 0.5 to 5, 0.8 to 3 or 0.5 to 2 g / 10 min.

[0185] Aspect 61. The polymer defined in aspect 59 or 60, wherein the density is in any range disclosed in this document, for example, from 0.915 to 0.958, from 0.916 to 0.956, from 0.917 to 0.954 or from 0.915 to 0.952 g / cm3.

[0186] Aspect 62. The polymer defined in any of aspects 59-61, wherein the ethylene polymer contains 70 to 250 ppm, 100 to 250 ppm, 100 to 200 ppm, 100 to 150 ppm, 120 to 250 ppm, 120 to 200 ppm or 120 to 170 ppm of solid oxide.

[0187] Aspect 63. The polymer defined in any one of aspects 59-62, wherein the ethylene polymer contains 2 to 16 ppm, 2 to 14 ppm, 2 to 12 ppm, 2 to 10 ppm, 3 to 16 ppm, 3 to 12 ppm, 4 to 12 ppm or 4 to 10 ppm of fluorine.

[0188] Aspect 64. The polymer defined in any of aspects 59-63, wherein the solid oxide contains silica and alumina in any suitable relative amount or a silica:alumina ratio in any range disclosed in this document, for example, 20:80 to 80:20, 20:80 to 60:40, 25:75 to 55:45 or 35:65 to 45:55.

[0189] Aspect 65. The polymer defined in any of aspects 59-64, wherein the ethylene polymer contains 0.5 to 5 ppm, 0.5 to 4 ppm, 0.5 to 3 ppm, 0.6 to 5 ppm, 0.6 to 4 ppm, 0.6 to 3 ppm, 0.7 to 4 ppm or 0.7 to 2.5 ppm of zirconium (or hafnium or titanium).

[0190] Aspect 66. The polymer defined in any one of aspects 59-65, wherein the ethylene polymer independently contains less than 0.1 ppm (by weight), less than 0.08 ppm, less than 0.05 ppm or less than 0.03 ppm of Mg, V, Ti Petition 870260050793, dated 05 / 27 / 2026, pp. 66 / 88 54 / 55 or Cr.

[0191] Aspect 67. The polymer defined in any of aspects 59-66, wherein the ethylene polymer has a Mw in any range disclosed in this document, for example, 25 to 400, 40 to 300, 50 to 250 or 80 to 200 kg / mol.

[0192] Aspect 68. The polymer defined in any of aspects 59-67, wherein the ethylene polymer has an Mw / Mn ratio in any range disclosed in this document, for example, 2 to 25, 2.1 to 20, 2.3 to 20, 2 to 5 or 8 to 25.

[0193] Aspect 69. The polymer defined in any one of aspects 59-68, wherein the ethylene polymer has a unimodal molecular weight distribution.

[0194] Aspect 70. The polymer defined in either of aspects 59-68, wherein the ethylene polymer has a bimodal molecular weight distribution.

[0195] Aspect 71. The polymer defined in any one of aspects 59-70, wherein the ethylene polymer comprises an ethylene homopolymer and / or an ethylene / α-olefin copolymer.

[0196] Aspect 72. The polymer defined in any of aspects 59-71, 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.

[0197] Aspect 73. The polymer defined in any one of aspects 59-72, wherein the ethylene polymer comprises an ethylene / 1-hexene copolymer.

[0198] Aspect 74. The polymer defined in any one of aspects 59-73, wherein the polymer is produced by the olefin polymerization process defined in any one of aspects 31-48.

[0199] Aspect 75. An article (for example, a film, tube or molded product) comprising the ethylene polymer defined in any of aspects 59-74.

[0200] Aspect 76. An article comprising the ethylene polymer defined in any one of aspects 59-74, wherein the article is an agricultural film, an automobile part, a bottle, a container for chemicals, a drum, a fiber or fabric, a food packaging film or container, a food service article, a fuel tank, a geomembrane, a container Petition 870260050793, dated 05 / 27 / 2026, pp. 67 / 88 55 / 55 domestic, a lining, a molded product, a medical device or material, an outdoor storage product, outdoor recreational equipment, a tube, a sheet or tape, a toy or a traffic barrier. Petition 870260050793, dated 05 / 27 / 2026, pages 68 / 88

Claims

1 / 5 CLAIMS 1. Catalyst composition characterized by comprising: a metallocene compound, a fluorinated silica-coated alumina having: an apparent density of 0.15 to 0.37 g / mL; a total pore volume of 0.85 to 2 mL / g; a BET surface area of ​​200 to 500 m2 / g; and an average pore diameter of 10 to 25 nm and / or 80 to 99% of the pore volume in pores with diameters greater than 6 nm; and an optional cocatalyst.

2. Catalyst composition according to claim 1, characterized in that the catalyst composition comprises a metallocene compound.

3. Catalyst composition according to claim 1, characterized in that the catalyst composition comprises two or more metallocene compounds.

4. Olefin polymerization process characterized by comprising placing the catalyst composition, as defined in claim 1, in contact with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer.

5. Process according to claim 4, characterized in that: the catalyst composition is brought into contact with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene or a mixture thereof; and the polymerization reactor system comprises a loop-type fluidized paste reactor, a fluidized bed reactor, a solution reactor or a combination thereof.

6. Catalyst composition according to claim 1, characterized in that the alumina coated with fluorinated silica contains: from 10 to 80% by weight of silica, based on a weight of alumina coated with silica; and from 0.5 to 18% by weight of F, based on a weight of alumina coated with fluorinated silica.

7. Catalyst composition according to claim 1, characterized in that the alumina coated with fluorinated silica has an average particle size (d50) of 30 to 150 microns.

8. Catalyst composition according to claim 1, characterized in that: the apparent density is from 0.17 to 0.3 g / mL; the total pore volume is from 0.9 to 1.5 mL / g; the BET surface area is from 250 to 450 m2 / g; the average pore diameter is from 10 to 20 nm; and 83 to 98% of the pore volume is in pores with diameters greater than 6 nm.

9. Catalyst composition according to claim 1, characterized in that: 9.5 to 30% of the pore volume is in pores with diameters greater than 20 nm; 3.5 to 15% of the pore volume is in pores with diameters greater than 40 nm; fluorinated silica-coated alumina has a pore volume of 0.7 to 1.6 mL / g in pores with diameters greater than 6 nm; and fluorinated silica-coated alumina has a pore volume of 0.09 to 0.4 mL / g in pores with diameters greater than 20 nm.

10. Catalyst composition according to claim 1, characterized in that: 65 to 98% of the surface area is in pores with diameters greater than 6 nm; 19.5 to 55% of the surface area is in pores with diameters greater than 10 nm; the alumina coated with fluorinated silica has a surface area of ​​250 to 475 m² / g in pores with diameters greater than 6 nm; and the alumina coated with fluorinated silica has a surface area of ​​78 to 200 m² / g in pores with diameters greater than 10 nm.

11. Catalyst composition, according to claim 1, Petition 870260050793, dated 05 / 27 / 2026, p. 70 / 88 3 / 5 characterized in that the catalyst composition comprises the co-catalyst; and 80 to 99% of the pore volume is in pores with diameters greater than 6 nm.

12. Catalyst composition according to claim 11, characterized in that 83 to 98% of the pore volume is in pores with diameters greater than 6 nm.

13. Catalyst composition according to claim 12, characterized in that the catalyst composition comprises two or more metallocene compounds.

14. Catalyst composition according to claim 1, characterized in that the catalyst composition comprises a co-catalyst; and the average pore diameter of the fluorinated silica-coated alumina is 10 to 25 nm.

15. Catalyst composition according to claim 14, characterized in that the co-catalyst comprises an organoaluminum compound; and the metallocene compound comprises a non-alloyed metallocene compound based on zirconium or hafnium containing two cyclopentadienyl groups, two indenyl groups, or one cyclopentadienyl group and one indenyl group.

16. Catalyst composition according to claim 14, characterized in that the co-catalyst comprises an organoaluminum compound; and the metallocene compound comprises a zirconium- or hafnium-based metallocene compound with a bridge containing a cyclopentadienyl group and a fluorenyl group.

17. Catalyst composition according to claim 14, characterized in that the fluorinated silica-coated alumina contains: from 10 to 80% by weight of silica, based on a weight of silica-coated alumina; and from 0.5 to 18% by weight of F, based on a weight of fluorinated silica-coated alumina.

18. Catalyst composition, according to claim 14, characterized in that the alumina coated with fluorinated silica has an average particle size (d50) of 30 to 150 microns.

19. Catalyst composition according to claim 14, characterized in that: the apparent density is from 0.17 to 0.3 g / mL; the total pore volume is from 0.9 to 1.5 mL / g; the BET surface area is from 250 to 450 m2 / g; and 83 to 98% of the pore volume is in pores with diameters greater than 6 nm.

20. Catalyst composition according to claim 14, characterized in that: 9.5 to 30% of the pore volume is in pores with diameters greater than 20 nm; 3.5 to 15% of the pore volume is in pores with diameters greater than 40 nm; fluorinated silica-coated alumina has a pore volume of 0.7 to 1.6 mL / g in pores with diameters greater than 6 nm; and fluorinated silica-coated alumina has a pore volume of 0.09 to 0.4 mL / g in pores with diameters greater than 20 nm.

21. Catalyst composition according to claim 14, characterized in that: 65 to 98% of the surface area is in pores with diameters greater than 6 nm; 19.5 to 55% of the surface area is in pores with diameters greater than 10 nm; the alumina coated with fluorinated silica has a surface area of ​​250 to 475 m² / g in pores with diameters greater than 6 nm; and the alumina coated with fluorinated silica has a surface area of ​​78 to 200 m² / g in pores with diameters greater than 10 nm.

22. Process for producing fluorinated silica-coated alumina, characterized by comprising contacting a fluorinating agent with silica-coated alumina to produce fluorinated silica-coated alumina, wherein the silica-coated alumina has: an apparent density of 0.15 to 0.37 g / mL; a total pore volume of 1.1 to 2.5 mL / g; a BET surface area of ​​250 to 600 m² / g; and an average pore diameter of 10 to 25 nm.

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