Clay composite support activator and catalyst composition

Abstract

Disclosed is a support activator and a catalyst composition comprising a support activator for polymerizing an olefin, the support activator comprising a clay heteroaddition product, also referred to as a composite material, which is prepared from a colloidal phyllosilicate such as a colloidal smectite clay chemically modified with a surfactant. In one aspect, the clay composite material can comprise a contact product of a colloidal smectite clay and a surfactant in a liquid carrier but in the absence of any other reactant such as a cationic polymethalate, and their use as a support activator for a metallocene pre-catalyst is also described. The use of a surfactant having a cationic polymethalate in forming the clay composite material is also described.

Description

Technical Field

[0001] Cross - Reference to Related Applications This application claims the benefit of U.S. Provisional Application No. 63 / 366,077, filed Jun. 9, 2022, and U.S. Patent Application No. 18 / 323,212, filed May 24, 2023, each of which is incorporated herein by reference in its entirety.

[0002] The present disclosure relates to catalyst compositions containing support activators for producing polyethylene and processes for preparing and using them.

Background Art

[0003] Support activators are generally used with metallocene pre - catalysts in the industrial heterogeneous polymerization of olefins. Generally, support activators serve a dual role of activating the metallocene and functioning as a template on which growing polymer chains can deposit. Widely used support activators include inorganic metal oxide supports such as silica or alumina treated with a co - catalyst or activator. One such support activator is methylaluminoxane (MAO) on silica. However, MAO is expensive to procure or manufacture, and MAO / silica requires multiple subsequent processing steps such as washing before it can be used.

[0004] To reduce the costs and time required for the production and use of materials such as MAO / silica for metallocene activation, various clay support activators have been investigated. For example, U.S. Patent Nos. 6,531,552 (Japan Polychem Corporation), 6,825,371 (Mitsubishi Chemical Corporation), and 7,220,695 (ExxonMobil) describe the treatment of clay-based supports such as smectite with mineral acids and, in some cases, additional components such as surfactants. However, the reaction of an acid with an ion-exchange clay can cause replacement of the interlayer ions with protons, thereby potentially destroying its porous structure that provides its catalytic activity. See, for example, Nascimento et al., Materials Research, 2015, 18(2), 283-287, Tavani et al., Ceramica, 1999, 45(295), 133-136, Kooli et al., Langmuir 2005, 21(19), 8717-8723, and Tayano et al., Macromolecular Reaction Engineering, 2017, 11(2), 1600017. Other limitations to the acid treatment approach include the difficulty of isolating the modified clay. Other efforts for producing a support activator include treating clay or organic polymer particles in combination with other components such as organic amides with surfactants (U.S. Patent No. 9,200,093 by Sumitomo Chemical Company), but these processes and components are also complex and expensive. Further, in these approaches, simply using a clay starting material that exhibits the desired particle size and morphology does not result in a support activator having these properties.

[0005] Accordingly, there is still a need for a highly active support activator that is economical to prepare and isolate. This need is particularly evident in the manufacture of metallocene polyolefins such as high transparency film resins. Such a support activator would present significant cost advantages over the currently used aluminoxane-based activators. Also, it would be desirable to develop a method for producing support activator particles having a uniform spherical morphology that is highly advantageous for generating the desired polymer morphology, ensuring reactor operability, and maintaining the activity of the support activator. SUMMARY OF THE INVENTION

[0006] Aspects of the present disclosure provide novel clay-based support activators and processes for their preparation, catalyst compositions comprising the novel support activators, methods for manufacturing the catalyst compositions, and processes for polymerizing olefins. In one aspect, the chemically modified clay support activators can readily activate metallocene compounds for the polymerization of olefins, and they are surprisingly easy and cost-effective to prepare and recover in high yields. The support activators of the present disclosure can exhibit high polymerization activity and processability compared to acid-treated clay activators where clay structure decomposition and pore collapse (often resulting in leaching of the clay into solution) can occur during the activation process and prevent easy separation of the resulting activator and high polymerization activity. Further, the support activators of the present disclosure retain their desirable structural properties (e.g., high pore volume, shape, and size) under granulation / drying conditions that often result in a high degree of pore collapse with other support activators.

[0007] Applicant's International Patent Application Publication No. 2021 / 154204 (incorporated herein by reference in its entirety) discloses a novel clay-based support activator prepared by contacting colloidal smectite clay in a liquid carrier with a hetero-coagulation reagent comprising at least one cationic polymetallate, and a surfactant may be present if desired. The clay adducts described in this disclosure are efficient support activators for metallocenes in olefin polymerization. When the cationic polymetallate is used in an amount relative to the colloidal smectite clay within a specific range, the smectite adduct can be easily isolated from the slurry obtained by conventional filtration processes. This ease of filtration is in contrast to the difficult isolation of previous chemically modified clay support activators, which may require filtration over several days or multiple washing and centrifugation steps.

[0008] It has unexpectedly been found that clay-based support activators having the desired spherical shape, size and activity for metallocene activation in olefin polymerization can be prepared by contacting colloidal smectite clay in a liquid carrier with a surfactant reagent in the absence of a cationic polymetallate. These clay-based support activators are referred to as clay or smectite "adducts" or "composites", or more specifically "clay (or smectite)-surfactant adducts (or composites)". The isolation of these smectite-surfactant adducts can be achieved using conventional filtration without the need for centrifugation or high dilution of the reaction mixture and then extensive washing of the resulting solid. This process exhibits activity superior to that of the corresponding untreated clay, activity equivalent to that of more difficult-to-prepare pillared clay supports, and activity equivalent to that of hetero-coagulated clays prepared using cationic polymetallates, thereby providing a solid clay adduct that meets the need.

[0009] A wide range of reagents used to prepare clay-based support activators can be excluded from the fractionation method, and it has been further discovered that they still provide an active support activator and offer significant advantages in their manufacture. Further, these clay adducts can be spray dried from a suspension of the adducts in a dispersion medium consisting essentially of water to form the support activator, which offers economic and environmental advantages over conventional methods that require an organic liquid carrier.

[0010] Accordingly, the present disclosure provides a method for manufacturing a support activator comprising a smectite adduct, the method comprising, in a first liquid carrier, (a) a colloidal smectite clay, and (b) a surfactant, the surfactant comprising or selected from a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or any combination thereof to provide a slurry of the smectite adduct in the first liquid carrier, contacting, the contacting step being capable of occurring in the absence of certain reactants. In aspects of the present disclosure, the contacting step can be carried out in the absence of [i][A] cationic polymethalate, [B] non-layered silicate, soluble silicate (e.g., sodium silicate), charged inorganic component, metal oxide, organic amide, anionic surfactant, inorganic acid, organic acid, inorganic base, organic base, oxidizing agent, or any combination thereof, [C] any one or any two of a cationic surfactant, a nonionic surfactant, or an amphoteric surfactant, or [D] any combination thereof, [ii] in the absence of any other cationic reactant except when a cationic surfactant is present, or [iii] in the absence of any other reactant except the surfactant.

[0011] In a first liquid carrier, the method of contacting (a) a colloidal smectite clay and (b) a surfactant can further include the step of isolating a smectite adduct from a slurry in the first liquid carrier. In some embodiments, the colloidal smectite clay and the surfactant can be contacted at a ratio of 0.5 millimoles to 5 millimoles of surfactant per gram of colloidal smectite clay, which, for example, functions well in forming a smectite adduct having the disclosed preferred characteristics in providing an easily filterable colloidal smectite clay.

[0012] The present disclosure further provides a method of manufacturing a support activator comprising a smectite adduct, the method comprising, in a first liquid carrier, (a) a colloidal smectite clay, and (b) a surfactant, wherein the surfactant comprises, or is selected from, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or any combination thereof, for providing a slurry of the smectite adduct in the first liquid carrier, and contacting the surfactant with the colloidal smectite clay, or consisting essentially of contacting the surfactant with the colloidal smectite clay, The first liquid carrier consists essentially of water, an organic liquid, or a combination thereof. This method can also further include the step of isolating the smectite adduct from the slurry in the first liquid carrier.

[0013] Once the smectite adduct is isolated from the slurry in the first liquid carrier disclosed herein, the method of manufacturing a support activator can further include suspending (or resuspending) the smectite adduct in a dispersion medium to provide a suspension of the smectite adduct in the dispersion medium, and spray drying the smectite adduct from the suspension to provide the support activator in particulate form. In one aspect, the dispersion medium can comprise, or consist essentially of, water. This latter step of spray drying can be referred to herein as "granulating" the smectite adduct.

[0014] Also, it has been recognized that when colloidal smectite clay in a liquid carrier contacts a hetero-coagulation reagent containing both a cationic polymethalate and a surfactant reagent, the resulting clay-cationic polymethalate-surfactant hetero-adduct can exhibit unexpectedly improved polymerization activity when combined with a metallocene. Accordingly, the present disclosure also demonstrates a method for producing a support activator comprising a smectite hetero-adduct, the method comprising, in any order in a first liquid carrier, (a) colloidal smectite clay, and (b) a cationic polymethalate, and (c) contacting a surfactant comprising or selected from a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or any combination thereof, to provide a slurry of the smectite hetero-adduct in the first liquid carrier, or consisting essentially thereof. If desired, this contacting step can also occur in the absence of certain reactants. In embodiments, for example, the contacting step can be carried out in the absence of [i] non-layered silicates, soluble silicates (e.g., sodium silicate), charged inorganic components, metal oxides, organic amides, anionic surfactants, inorganic acids, organic acids, inorganic bases, organic bases, oxidizing agents, or any combination thereof, [B] any one or any two of cationic surfactants, nonionic surfactants, or amphoteric surfactants, or [C] any combination thereof, [ii] in the absence of any other cationic reactants except when cationic polymethalate and a cationic surfactant are present, or [iii] in the absence of any other reactants except cationic polymethalate and surfactants. This method of manufacturing a clay cationic polymethalate-surfactant adduct can further include the step of isolating the adduct from a slurry in a first liquid carrier. In one embodiment, the method can further include suspending (or resuspending) a smectite adduct in a dispersion medium to provide a suspension of the smectite adduct in the dispersion medium, and spray drying the smectite adduct from the suspension to provide a support activator in particulate form. In one embodiment, the dispersion medium can comprise or consist essentially of water.

[0015] Compared to the corresponding clay cationic polymethalate adducts disclosed in Applicant's U.S. Patent Application Publication No. 2021 / 0230318, which is hereby incorporated by reference in its entirety, the clay cationic polymethalate-surfactant adducts can exhibit improved polymerization activity. Further, these clay cationic polymethalate-surfactant adducts are convenient to manufacture, are readily filterable, and can be spray dried from an aqueous slurry in the absence of organic liquids to provide highly spherical support activators.

[0016] In another aspect, providing a clay cationic polymetallate-surfactant heteroaddition by spray drying can also be achieved by forming an aqueous spray drying slurry of a preformed or isolated clay cationic polymetallate heteroaddition, the aqueous spray drying slurry containing a surfactant. That is, the clay cationic polymetallate heteroaddition can be formed as disclosed in Applicant's U.S. Patent Application Publication No. 2021 / 0230318. The clay cationic polymetallate heteroaddition can then be isolated and resuspended in an aqueous dispersion medium containing a surfactant to form a spray drying suspension, which can be spray dried. Preparing the heteroaddition in this manner is advantageous in that it provides an easily filterable clay cationic polymetallate heteroaddition and can provide a highly spherical support activator by spray drying from an aqueous slurry in the absence of an organic liquid. Thus, the order of addition of the components can be varied, particularly with respect to when the surfactant is added in relation to the isolation of the heteroaddition, and an active and useful product can be produced in either order of addition.

[0017] The present disclosure also provides the smectite heteroaddition itself. For example, a smectite heteroaddition or a support activator comprising a smectite heteroaddition is provided, the smectite heteroaddition being in the absence of certain reactants in a first liquid carrier, (a) a colloidal smectite clay, and (b) a surfactant, wherein the surfactant can comprise, or be selected from, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or any combination thereof, and the contact product of the surfactant. According to aspects of the present disclosure, the contact product can occur or can be in the absence of [i] [A] cationic polymethalate, [B] non-layered silicate, soluble silicate (e.g., sodium silicate), charged inorganic component, metal oxide, organic amide, anionic surfactant, inorganic acid, organic acid, inorganic base, organic base, oxidizing agent, or any combination thereof, [C] any one or any two of cationic surfactant, nonionic surfactant, or amphoteric surfactant, or [D] any combination thereof, [ii] in the absence of any other cationic reactant, except when a cationic surfactant is present, or [iii] in the absence of any other reactant, except for surfactants.

[0018] According to a further aspect, a smectite heteroadduct or a support activator comprising a smectite heteroadduct is provided, the smectite heteroadduct being in a first liquid carrier, (a) a colloidal smectite clay and, (b) a contact product of a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or any combination thereof, or a surfactant selected therefrom, or consisting essentially thereof, The first liquid carrier consists essentially of water, an organic liquid, or a combination thereof.

[0019] Yet another aspect of the present disclosure provides a support activator comprising a smectite heteroadduct, the smectite heteroadduct being in a first liquid carrier, (a) a colloidal smectite clay and, (b) a cationic polymethalate, and (c) a contact product of a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or any combination thereof, or a surfactant selected therefrom, or consisting essentially thereof. In aspects of the present disclosure, optionally, the contacting product is prepared in the absence of [i] [A] non-layered silicates, soluble silicates (e.g., sodium silicate), charged inorganic components, metal oxides, organic amides, anionic surfactants, inorganic acids, organic acids, inorganic bases, organic bases, oxidizing agents, or any combination thereof, [B] any one or any two of cationic surfactants, nonionic surfactants, or amphoteric surfactants, or [C] any combination thereof, [ii] in the absence of any other cationic reactants, except when a cationic polymetallate and a cationic surfactant are present, or [iii] in the absence of any other reactants, except for the cationic polymetallate and the surfactant.

[0020] These surfactant-treated clays (smectite clay adducts) of the present disclosure, whether clay-surfactant adducts or clay-cationic polymetallate-surfactant adducts, when subjected to a drying process of granulation and spray drying, followed by firing, constitute particles having higher sphericity, porosity, and particle uniformity compared to clay activators dried by other methods. When granulated and dried as described herein, the clay adducts also retain high olefin polymerization activity when activating metallocene compounds. This desirable performance is in contrast to the performance of clay activators treated only with cationic polymetallate in the absence of surfactant, which can lose polymerization activity and / or particle porosity during spray drying. The disclosed spray drying process can be carried out with clay-surfactant adducts and clay-cationic polymetallate-surfactant adducts dispersed in an aqueous dispersion medium, as opposed to requiring an organic liquid or a mixture of an organic liquid and an aqueous dispersion medium. Thus, the economic viability, safety, and environmental sustainability of this process are substantially improved over processes requiring an organic liquid-containing dispersion medium.

[0021] The smectite adduct prepared by this means can be used very effectively in combination with a cocatalyst such as an alkylaluminum compound for a transition metal-based olefin polymerization process. This smectite adduct-cocatalyst combination can provide a very active support activator for metallocene olefin polymerization when compared to conventional MAO-SiO2 or borane-derived support activators. Further, the surfactant used in this process can also be very inexpensive and can be used with a cocatalyst that is relatively inexpensive compared to, in particular, aluminoxanes and borane-based activators such as alkylaluminum compounds.

[0022] Also disclosed herein is a catalyst system for olefin polymerization, the catalyst system comprising (a) at least one metallocene compound, and (b) at least one support activator according to any aspect of the present disclosure. This catalyst system can further comprise additional components, such as at least one cocatalyst such as an alkylaluminum compound, and / or at least one coactivator such as methylaluminoxane (MAO). The support activator of the catalyst system can also be free of any of the specific reactants not present in the contact product as described herein.

[0023] The present disclosure also provides a method of making a catalyst system, the method comprising contacting, in a second liquid carrier, (a) at least one metallocene compound, and (b) at least one support activator comprising a smectite adduct according to the present disclosure. At least one support activator can include a smectite adduct prepared according to any of the methods provided in this disclosure. In this method of making a catalyst system, the method can further include contacting at least one cocatalyst such as an alkylaluminum compound and / or at least one coactivator such as methylaluminoxane (MAO) in a second liquid carrier, and the contacting can occur in any order. The support activator can also be free of any specific reactants not present in the contact product as described herein.

[0024] In yet another aspect, the present disclosure provides a process for polymerizing an olefin, comprising contacting at least one olefin monomer and a catalyst system under polymerization conditions to form a polyolefin, wherein the catalyst system (a) comprises at least one metallocene compound, and (b) at least one support activator comprising a smectite adduct according to the present disclosure. As disclosed herein, at least one support activator can also include a smectite adduct prepared according to any of the methods provided in this disclosure, and the catalyst system can further include additional components, such as at least one cocatalyst such as an alkylaluminum compound and / or at least one coactivator such as methylaluminoxane (MAO). The support activator can also be free of any specific reactants not present in the contact product as described herein.

[0025] These and other aspects, features, and embodiments of the support activator, catalyst composition, method of making the composition, and polymerization process, as well as related compositions and methods, are fully described by the detailed description, drawings, examples, and claims provided herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0026]

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Modes for Carrying Out the Invention

[0027] To more clearly define the terms and phrases used in this specification, the following definitions are provided. The definitions or usage provided by any document incorporated herein by reference shall be governed by the definitions or usage provided herein, provided that the definitions or usage provided herein are not inconsistent with those provided by such document.

[0028] A. Definitions and Explanations of Terms Surfactant. The term "surfactant" and similar terms such as "surface-active agent", "surfactant compound", "surfactant component", or "surface-active agent" refer to chemical compounds or reagents that can reduce the surface tension between phases, e.g., two liquid phases, gas phase and liquid phase, or liquid phase and solid phase. Many surfactant compounds include a hydrophobic section or region and a hydrophilic section or region, e.g., a polar region and a non-polar region, respectively. The hydrophilic section may, but not necessarily, include a negatively charged portion, a positively charged portion, or a hydrogen-bonding portion (hydroxyl, other oxygen-containing groups, etc.), while the hydrophobic section may, but not necessarily, include an alkyl or aromatic group. Surfactants are often characterized by the terms anionic, cationic, or non-ionic, respectively, based on whether their hydrophilic sections include a negatively charged portion, a positively charged portion, or a hydrogen-bonding portion. Unless otherwise specified or excluded, references to "surfactant" in this disclosure can include cationic surfactants, non-ionic surfactants, and amphoteric surfactants, and, in some cases, anionic surfactants that can be used in combination with cationic surfactants, non-ionic surfactants, or amphoteric surfactants as described herein, all of which are further described.

[0029] An "amphoteric" surfactant refers to a surfactant that can contain a positively charged moiety (or a moiety that can readily become positively charged by accepting a proton) and a negatively charged moiety (or a moiety that can readily become negatively charged by donating a proton) within the same molecule. The term "zwitterionic" surfactant is used interchangeably with "amphoteric" surfactant based on the inclusion of both a cationic and an anionic moiety within the same molecule. In one aspect, an "amphoteric" surfactant includes a moiety that can react with an acid and a moiety that can react with a base. An "amphiprotic" surfactant is a type of amphoteric surfactant that donates or accepts a proton (H + +). Examples thereof are amino acids. Unless otherwise excluded, references to amphoteric or zwitterionic surfactants include amphiprotic surfactants. "Amphoteric" surfactants such as amino acids may be regarded as a type of nonionic surfactant, but in the present disclosure, the term "nonionic" surfactant is reserved for non-zwitterionic molecules such as poly(ethylene) glycol, poly(propylene) glycol, or cyclodextrin, and the term "amphoteric" surfactant is used for zwitterionic surfactants.

[0030] Heterocoagulation reagent. The terms "heterocoagulation reagent", "heterocoagulant", etc. are used herein to describe a compound or composition containing monomeric, oligomeric, or polymeric species that are present in solution or as a colloidal suspension and, when combined with a colloidal clay dispersion in an appropriate ratio, form a readily filterable solid (as defined herein). Thus, the term heterocoagulation reagent is used herein to refer to the cationic surfactants, nonionic surfactants, and amphoteric surfactants described in the present disclosure, as well as positively charged oligomeric or polymeric metal oxides containing species such as aluminum chlorohydrate (ACH) described in detail in the applicant's US Patent Application Publication No. 2021 / 0230318, which is hereby incorporated by reference in its entirety. These polymetallates are also referred to as "cationic polymetallates". "Heterocoagulation" is a term in the art and is described by Lagaly in Ullmann’s Encyclopedia of Chemistry 2012. Thus, a heterocoagulation reagent can include only surfactants, only cationic polymetallates, or a combination of surfactants and cationic polymetallates.

[0031] In the context of the present disclosure, "heterocoagulation" is defined, unless otherwise specified, as the process of combining negatively charged colloidal clay particles with a heterocoagulation reagent to form a readily filterable solid. Most, but not all, of the heterocoagulation reagents described in the present disclosure are positively charged species that bind to negatively charged colloidal clay particles to form a readily filterable solid heteroadduct. Heterocoagulation is also sometimes referred to in the art and herein as heteroaggregation, as described, for example, by Cerbelaud et al. in Advances in Physics:X, 2017, vol. 2, 35-53.

[0032] Hetero-adducts or hetero-coagulants. The terms "hetero-adduct", "hetero-coagulant", "coagulant", "hetero-composite", "composite", and similar terms such as "clay composite", "hetero-coagulated clay", or "smectite hetero-adduct" refer to contact products obtained by combining the hetero-coagulating reagents disclosed herein with colloidal clays such as colloidal smectite clay. That is, aggregates formed by the attraction of negatively charged colloidal clay particles by the hetero-coagulating reagents of the present disclosure, such as cationic polymethalate, surfactants disclosed herein, or both cationic polymethalate and surfactants, are referred to as "hetero-adducts" or "hetero-coagulants", or sometimes simply as "adducts" or "coagulants". Reference is made to U.S. Patent No. 8,642,499 to Wu Cheng et al. which uses the term "hetero-coagulation" and which is incorporated herein by reference. In one aspect, these terms refer to "readily filterable" contact products of the hetero-coagulating reagent and the colloidal clay as defined herein. These terms are used to distinguish readily filterable hetero-coagulants from contact products of hetero-coagulating reagents and colloidal clays combined in a ratio that provides products that are not readily filterable, such as products formed when following columnar viscosity synthesis.

[0033] The terms "hetero-adduct" and "hetero-coagulant" and similar terms are also used when explaining the formation of hetero-coagulated clay formed by contacting clay with cationic polymethalate, whether the contact occurs in the presence or absence of a surfactant. These hetero-adducts, including the contact product of clay and cationic polymethalate, are described in U.S. Patent Application Publication No. 2021 / 0230318. Other hetero-coagulants of the present disclosure can be prepared by contacting colloidal clay with a surfactant in the absence of cationic polymethalate.

[0034] Accordingly, unless otherwise specified and when the context permits or requires, "heteroadduct" or "heterocoagulate" can be a smectite clay-surfactant heteroadduct, a smectite clay-cationic polymetallate-surfactant heteroadduct, or simply a smectite clay-cationic polymetallate heteroadduct.

[0035] Polymetallate. The terms "polymetallate", "cationic polymetallate", and similar terms such as "polyoxometallate" are used interchangeably in this disclosure as they are in U.S. Patent Application Publication No. 2021 / 0230318 and refer to a water-soluble polyatomic cation containing two or more metal atoms (e.g., aluminum, silicon, titanium, zirconium, or other metals) together with at least one bridging ligand between the metals such as an oxo, hydroxy, and / or halide ligand. For clarity, the "polymetallate" of this disclosure is typically referred to herein as "cationic polymetallate". The specific ligands can depend on the precursors and other factors such as the process for generating the polymetallate, solution pH, etc. For example, the polymetallate of this disclosure can be a hydrated metal oxide, a hydrated metal oxyacid, etc., including these combinations. Bridging ligands such as oxo ligands bridging two or more metals can occur in these species, but the polymetallate can also include terminal oxo, hydroxyl, and / or halide ligands.

[0036] Many known polymetallate species are anionic, and the suffix "-ate" is often used to reflect anionic species, but the polymetallate (polyoxometallate) species used according to the present disclosure are cationic. These materials may be referred to as compounds, species, or compositions, but those skilled in the art will understand that, for example, depending on the solution pH, concentration, starting precursors from which the polymetallate is formed in an aqueous solution, etc., a plurality of species can be contained in a suitable carrier such as an aqueous solution. For clarity and convenience, these plurality of species are collectively referred to as "polymetallate" or "polyoxometallate", regardless of whether the composition contains species such as cationic polyoxometallates, polyhydroxymetallates, polyoxohydroxymetallates, or other ligands such as halides, or a mixture of compounds, or whether they are predominantly composed of them. Examples of polymetallates include, but are not limited to, polyaluminum oxyhydroxychloride, aluminum chlorohydrate (ACH), polyaluminum chloride (PAC), or aluminum sesquichlorohydrate compositions, and may include linear, cyclic, or cluster compounds. These compositions are collectively referred to as polymetallates, but the terms "polymetallate" or "polyoxometallate" are also used to describe compositions containing substantially a single species.

[0037] Both isopolymetallates containing a single type of metal and heteropolymetallates containing two or more types of metals (or electropositive atoms such as phosphorus) are included in the general term polymetallate or polyoxometallate. In a further aspect, the polymetallate according to the present disclosure can be non-alkylated with respect to transition metal compounds such as metallocene compounds. That is, it is possible that the polymetallate of interest does not have a direct metal-carbon bond as found in aluminoxanes or other organometallic species.

[0038] In another aspect, the polymetallate can be at least one aluminum polymetallate. As an example, the general formula is Al n Cl 3n-m (OH) mAluminum chlorohydrate (ACH), also known as aluminum chlorohydrate, which is usually considered to have a plurality of water-soluble aluminum species, including but not limited to these. These polymetallate species can be referred to as aluminum oxyhydroxy chloride compounds or compositions. Another polymetallate that can be used according to the present disclosure is polyaluminum chloride (PAC), which is an aggregate of a plurality of aluminum polymer species that can include linear, cyclic, or cluster compounds rather than a single species, and examples of these can contain from 2 to about 30 aluminum atoms, oxo, chloride, and hydroxyl groups. Other examples of aluminum polymetallates include compounds having the general formula [Al m O n (OH) x Cl y ·zH2O, and cluster-type species such as Keggin ions, for example, sometimes referred to as " 13 -mer" polycations [AlO4Al 12 (OH) 24 (H2O) 12 7+ ·7[Cl] - , including but not limited to these. For example, polyaluminum chloride (PAC) can be produced by combining an aqueous hydroxide and AlCl3, and the resulting mixture of aluminum species has various basicities. Aluminum chlorohydrate (ACH) is generally considered to be the most basic, and polyaluminum chloride (PAC) is considered to have a lower basicity.

[0039] ​Readily filterable. Terms such as "readily filterable," "readily filtered," "easily filterable," and "easily filtered or separated" are used herein to describe a composition according to the present disclosure in which solids in a mixture containing a liquid phase can be separated from the liquid phase by filtration without the use of centrifugation, ultracentrifugation, or dilution of the solution of less than about 2 wt% solids, long sedimentation times, followed by decanting the liquid from the solids, and other such techniques. The terms are generally used herein to describe clay heteroadditives that do not require separation by centrifugation, high dilution, and sedimentation or sedimentation tanks, or ultrafiltration. Thus, a readily filterable clay heteroadditive can be isolated or separated in good yield in a time period of less than a few minutes or less than about 1 hour from synthetic soluble salts and by-products by passing a slurry containing the heteroadditive through conventional filter materials such as sintered glass, metal or ceramic frits, paper, natural or synthetic mat fibers, etc. under gravity or vacuum filtration conditions.

[0040] The present disclosure provides some specific experimental and quantitative methods by which "readily filterable" can be evaluated. Colloids or suspensions as described by Lagaly in Ulmmann’s Encyclopedia of Chemistry 2012 that require long sedimentation times or ultrafiltration are not considered "filterable" in the context of the present disclosure. For example, a readily filterable suspension or slurry of the present disclosure can yield a clear filtrate upon filtration, while a "not readily filterable" suspension that requires a substantially long time for filtration can contain particulate matter observable as a visibly turbid or opaque filtrate indicative of a colloidal clay dispersion.

[0041] Colloid. The terms "colloid", "colloidal clay", "colloidal solution", "colloidal suspension", and similar terms are used as defined in the chapter entitled "Colloid" in Gerhard Lagaly in Ullmannn’s Encyclopedia of Industrial Chemistry, published on January 15, 2007. These terms are used synonymously.

[0042] Catalyst composition and catalyst system. The terms "catalyst composition", "catalyst mixture", "catalyst system", etc. are used to represent combinations of the listed components that are ultimately formed or used to form the active catalyst according to the present disclosure. The use of these terms does not depend on any particular contacting step, contact order, whether any reaction can occur between or within the components, or any product that can be formed from any contact of any or all of the listed components. The use of these terms also does not depend on the nature of the active catalyst sites, or the fate of any cocatalyst, metallocene compound(s), or support activator after contacting or combining any of these components in any order. Thus, these and similar terms include the initially listed components or starting components of the catalyst composition, whether the catalyst composition is heterogeneous or homogeneous, or contains soluble and insoluble components, and any combination of any product(s) that can result from contacting these initially listed starting components. The terms "catalyst" and "catalyst system" or "catalyst composition" can be used synonymously, and such use will be apparent to those skilled in the art from the context of the present disclosure.

[0043] Catalytic activity. Unless otherwise specified, terms such as "activity", "catalytic activity", and "catalytic composition activity" refer to the polymerization activity of a catalytic composition containing a dried or calcined clay heteroaddition as disclosed herein, and typically, per hour of polymerization, in the absence of any transition metal catalyst component such as a metallocene compound, any cocatalyst such as an organoaluminum compound, or any cocatalyst such as an aluminoxane, it is expressed as the weight of the polymerized polymer per weight of the catalyst clay support activator only. In other words, it is the weight of the produced polymer divided by the weight / hour of the calcined clay heteroaddition, expressed in units of g / g / hour (grams / gram / hour).

[0044] The activity of a reference or comparative catalytic composition refers to the polymerization activity of a catalytic composition containing the comparative catalytic composition and is based on the weight of the comparative ion exchange or columnar clay or other support activator used to prepare the clay heteroaddition, or the weight of the clay component itself. Terms such as "increase in activity" or "improvement in activity" describe the activity of the catalytic composition according to the present disclosure, which is generally greater than the activity of a comparative catalytic composition that uses the same catalyst components such as metallocene compounds and cocatalysts, except that the comparative catalytic composition uses a different support activator or activator such as columnar clay, or the clay component used in the catalytic reaction is not a hetero-coagulated clay. Standard settings for ethylene homopolymerization conditions that can be used to compare activities are described in the examples.

[0045] Contact product. The term "contact product" is used in this specification to describe a composition in which the components are combined or "contacted" in any order, except where a particular order is described, required, or implied by the context of the present disclosure in any manner and for any length. A "contact product" can include a reaction product, but the respective components do not have to react with each other, and this term is used regardless of whether it can occur when the listed components are contacted. For example, to form a contact product, the listed components can be contacted by blending or mixing, or the components can be contacted by adding or mixing the components in any order, or by adding them simultaneously to or with a liquid carrier.

[0046] Unless specifically stated or required, or implied by the context in which the term is used, the contact of any component can occur in the presence or absence of any other component of the compositions described herein. Examples of contact products that exclude specific components used to form the contact product include the following. In some embodiments, the present disclosure describes a smectite adduct that includes a contact product of (a) a colloidal smectite clay and (b) a surfactant in a first liquid carrier, specifically in the absence of various reagents, or in the absence of other specific reagents, or in the absence of any other reagents. In another example, the smectite adduct can include a contact product of (a) a colloidal smectite clay and (b) a surfactant in a first liquid carrier, and the first liquid carrier can consist essentially of water, an organic liquid, or a combination thereof. By describing the contact product in a first liquid carrier consisting essentially of water or an organic liquid or a combination thereof, once the smectite adduct is formed, additional reagents can be contacted with the smectite adduct, or additional reagents can be excluded from contact with the smectite adduct as specified.

[0047] Combining or contacting the listed ingredients or any additional materials can be carried out by any suitable method. Thus, the term "contact product" includes mixtures, blends, solutions, slurries, reaction products, etc., or combinations thereof. Similarly, the term "contacting" is used herein to refer to materials that can be contacted by blending, mixing, slurrying, dissolving, reacting, treating, or other means in any order and unless otherwise specified.

[0048] Pore diameter (pore size) and pore volume. Nitrogen adsorption / desorption measurements were used to determine the pore size and pore volume distribution using the BJH (Barrett, Joyner, and Halenda) pore volume analysis method. Based on the International Union of Pure and Applied Chemistry (IUPAC) system for classifying porous materials (see Pure & Appl. Chem., 1994, 66, 1739-1758) and Klobes et al., National Institute of Standards and Technology Special Publication 960-17, the pore size is defined as follows. "Micropores" and "microporous" as used herein refer to pores present in a catalyst or catalyst support produced according to the processes of the present disclosure having a diameter of less than 20 Å. "Mesopores" and "mesoporous" as used herein refer to pores present in a catalyst or catalyst support produced according to the processes of the present disclosure having a diameter in the range of 20 Å to less than 500 Å (i.e., 2 nm to <50 nm). "Macropores" and "macroporous" as used herein refer to pores present in a catalyst or catalyst support produced according to the processes of the present disclosure having a diameter of 500 Å (50 nm) or greater.

[0049] Each of the above definitions of micropores, mesopores, and macropores is considered distinct and non-overlapping so that pores are not double-counted when summing the percentages or values in the pore size distribution (pore diameter distribution) of any given sample.

[0050] The term "d50" or "D50" means the median pore diameter measured by pore size measurement. Thus, "d50" corresponds to the median pore diameter calculated based on the pore size distribution and is the pore diameter at which half of the pore size has a larger diameter. The d50 values reported herein are based on nitrogen desorption using the well-known calculation method described by E.P. Barrett, L.G. Joyner and P.P. Halenda ("BJH"), "The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms," J. Am. Chem. Soc., 1951, 73(1), pp 373-380.

[0051] The "median pore diameter" (MPD) can be calculated, for example, based on volume, surface area, or based on pore size distribution data. The median pore diameter calculated by volume means the pore diameter at which half of the total pore volume exists. The median pore diameter calculated by surface area means that there is a pore diameter that exceeds half of the total pore surface area. Similarly, the median pore diameter calculated based on the pore size distribution means, for example, through derivation from nitrogen adsorption / desorption isotherms, the pore diameter at which half of the pores have a larger diameter according to the determined pore size distribution described elsewhere herein.

[0052] Transition metal catalyst. A "transition metal catalyst" refers to a transition metal compound or composition that functions as, or can be converted to, an active olefin polymerization catalyst when contacted with the support activator of the present disclosure in its current form or when contacted with a cocatalyst that can transfer or impart a polymerization activating ligand to the transition metal catalyst. Thus, a "transition metal catalyst" includes a transition metal species that can function as a catalyst and a transition metal species that is a "pre-catalyst" or "pro-catalyst" that can be converted to a composition that can function as a catalyst.

[0053] The use of the term "catalyst" is not intended to reflect any particular mechanism, nor is the "transition metal catalyst" itself intended to represent an active site for catalytic polymerization when it is activated or when it is provided with a ligand capable of activating polymerization. The transition metal catalyst is described in terms of a transition metal compound or compounds used in a process for preparing a polymerization catalyst and can include metallocene compounds and related compounds as defined herein.

[0054] Co-catalyst. As used herein, "co-catalyst" refers to a chemical reagent, compound, or composition capable of attaching a ligand to a transition metal compound such as a metallocene that can initiate polymerization when the metallocene is activated by a support activator or other means. In other words, "co-catalyst" is used herein to refer to a chemical reagent, compound, or composition capable of providing a polymerization-activatable ligand to a metallocene compound. Polymerization-activatable ligands include, but are not limited to, alkyls such as methyl or ethyl, aryls and substituted aryls, substituted aryls such as phenyl or tolyl, substituted alkyls such as benzyl or trimethylsilylmethyl (-CH2SiMe3), hydrides, silyls, and hydrocarbyl substituents such as trimethylsilyl. Thus, in one aspect, the co-catalyst can be an alkylating agent, a hydriding agent, a silylating agent, etc. There is no limitation on the mechanism by which the co-catalyst provides a polymerization-activatable ligand to the metallocene compound. For example, the co-catalyst can participate in a metathesis reaction to exchange an exchangeable ligand such as a halide or alkoxide on the metallocene compound for a polymerization-activating / initiating ligand such as methyl or hydride. In one aspect, the co-catalyst is an optional component of the catalyst composition, for example, when the metallocene compound already contains a polymerization-activating / initiating ligand, such as methyl or hydride. In another aspect, as will be understood by those skilled in the art, even when the metallocene compound contains a polymerization-activatable ligand, the co-catalyst can be used for other purposes, such as removing moisture from the polymerization reactor or process. According to a further aspect, the term "co-catalyst" can refer to an "activator" that can be used synonymously with the "co-catalyst" described herein, as required or permitted by the context.

[0055] Activator. As used herein, the term "activator" generally refers to a substance that can convert a metallocene component into an active catalyst system capable of polymerizing olefins, and is intended to be independent of the mechanism by which such activation occurs. The "activator" can, for example, convert the contact product of a metallocene component and a component that provides an activatable ligand (such as an alkyl or hydride) to the metallocene, when the metallocene compound does not already contain such a ligand, into a catalyst system capable of polymerizing olefins. This term is used regardless of the actual activation mechanism. Exemplary activators can include, but are not limited to, supported activators, aluminoxanes, organoboron compounds or organoborate compounds, ionizing compounds such as ionizing ionic compounds. Aluminoxanes, organoboron compounds or organoborate compounds, and ionizing compounds can be referred to as "activators" or "co-activators" when used in a catalyst composition in which a supported activator is present, but the catalyst composition is supplemented with one or more aluminoxanes, organoboron, organoborate, ionizing compounds, or other co-activators.

[0056] Supported activator. As used herein, the term "supported activator" refers to an activator in solid form such as ion-exchanged clay, protonic acid-treated clay, or pillared clay, and similar insoluble activators that also function as a support. When a supported activator is combined with a metallocene and an activatable ligand, or optionally a co-catalyst that can provide a metallocene and an activatable ligand, it provides a catalyst system capable of polymerizing olefins. Thus, the smectite heteroadditive according to the present disclosure is a supported activator.

[0057] Ion-exchanged clay. As used in the specification and understood by those skilled in the art, the term "ion-exchanged clay" refers to a clay in which the exchangeable ions of a naturally occurring or synthetic clay have been replaced or exchanged with another selected ion(s). Ion exchange can occur by treatment of a natural or synthetic clay with a source of selected cations from a concentrated ion solution, such as a 2N aqueous solution of cations, usually involving multiple exchange steps, e.g., three exchange steps. Subsequently, the exchanged clay can be washed several times with deionized water to remove excess ions generated during the treatment process, as described, for example, in Sanchez, et al., Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2013, 423, 1-10, and Kawamura et al., Clay and Clay Minerals, 2009, 57(2), 150-160. Generally, centrifugation is used to isolate the clay from the solution between the ion treatment and washing.

[0058] Metallocene compound. As used herein, the term "metallocene" or "metallocene compound" refers to a transition metal or lanthanide metal compound containing at least one substituted or unsubstituted cycloalkadienyl-type ligand or alkadienyl-type ligand, including its heteroatom analogs, regardless of the specific binding mode, e.g., whether a cycloalkadienyl-type ligand or alkadienyl-type ligand is bonded to the metal in an η 5 -, η 3 -, or η 1 -binding mode, and regardless of whether one or more of these binding modes are accessible by the ligand. In the present disclosure, the term "metallocene" is also used to refer to a compound containing at least one π-bonded allyl-type ligand in which η 3 -allyl is not part of a cycloalkadienyl-type or alkadienyl-type ligand and can be used as the transition metal compound component of the catalyst composition described herein. Thus, "metallocene" refers to a substituted or unsubstituted η 3~η 5 -Cycloalkadienyl type and η 3 ~η 5 -Alkadienyl type ligands, including their heteroatom analogs, and including cyclopentadienyl ligands, indenyl ligands, fluorenyl ligands, η 3 -Allyl ligands, pentadienyl ligands, boratabenzenyl ligands, 1,2-azaborolyl ligands, 1,2-diaza-3,5-diborolyl ligands, their substituted analogs, and their partially saturated analogs, including but not limited to η 3 -Compounds having allyl type ligands. Partially saturated analogs are partially saturated η 5 -Compounds containing cycloalkadienyl type ligands are included, examples of which include tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, their substituted analogs, etc., but are not limited thereto. In some contexts, metallocenes are simply referred to as "catalysts", and similarly, the term "cocatalyst" is used herein, for example, to refer to organoaluminum compounds. Thus, metallocene ligands can be considered in the present disclosure to include at least one substituted or at least one unsubstituted cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, allyl, boratabenzenyl, 1,2-azaborolyl, or 1,2-diaza-3,5-diborolyl ligand, including their substituted analogs. For example, any substituent can be independently selected from halides, C1-C 20 hydrocarbyl, C1-C 20 heterohydrocarbyl, C1-C 20 organoheteryl, fused C4-C 12 carbocyclic moieties, or fused C4-C having at least one heteroatom independently selected from nitrogen, oxygen, sulfur, or phosphorus 11 heterocyclic moieties can be independently selected.

[0059] Organic aluminum compounds and organic boron compounds. As used herein, the terms "organic aluminum compounds" and "organic boron compounds" include neutral compounds such as AlMe3 and BEt3, and also include anionic complexes such as LiAlMe4, LiAlH4, NaBH4, and LiBEt4. Thus, unless otherwise specified, hydride compounds of aluminum and boron are included in the definitions of organic aluminum compounds and organic boron compounds, respectively, regardless of whether the compound is neutral or anionic.

[0060] Pillared clay. In the present disclosure, "pillared clay" is defined as a clay species having an ordered layer with a basal spacing substantially greater than 9 Å to 13 Å. When a powdered clay sample is analyzed using an X-ray diffractometer capable of scanning 2θ angles of 2° or more, species containing such pillar order are usually observed to have a substantial peak at 2θ values of 2° to 9°. These are typically prepared by the introduction of an oxygen-containing inorganic cation, such as a pillaring agent, for example, an oxygen-containing cation of lanthanum, aluminum, or iron. Aluminum pillared clay is often prepared by contacting the clay with the pillaring agent in an amount in the range of about 5 mmol Al / g clay or 6 mmol Al / g clay, up to about 30 mmol Al / g clay.

[0061] Intercalated. The terms "intercalated" or "intercalation" are terms in the art that indicate the insertion of a material into the interlayer of a clay substrate. These terms are used herein in a manner understood by those skilled in the art and as described in U.S. Patent No. 4,637,992, unless otherwise described.

[0062] Basal spacing. The terms "basal spacing", "basal d001 spacing", or "d001 spacing", when used in connection with smectite clays such as montmorillonite, typically refer to the distance, expressed in angstroms or nanometers, between similar faces of adjacent layers within the clay structure. Thus, for example, in the 2:1 family of smectite clays that includes montmorillonite, the basal distance is the distance from the top of the tetrahedral sheet to the top of the next tetrahedral sheet of the adjacent 2:1 layer, with the intervening octahedral sheet included, regardless of the presence or absence of modification or pillaring. Basal spacing values are measured using X-ray diffraction analysis (XRD) of the d001 plane. For example, natural montmorillonite as found in bentonite has a basal spacing range of about 12 Å to about 15 Å. (See, for example, Fifth National Conference on Clays and Clay Minerals, National Academy of Sciences, National Research Council, Publication 566, 1958: Proceedings of the Conference: “Heterogeneity In Montmorillonite”, J.L. McAtee, Jr., pp. 279 - 88 and Table 1 at p. 282.) The XRD test method for determining basal spacing is described in Pillared Clays and Pillared Layered Solids, R.A. Schoonheydt et al., Pure Appl. Chem., 71(12), 2367 - 2371, (1999), and in column 27, lines 22 - 43 of U.S. Patent No. 5,202,295 (McCauley).

[0063] Zeta potential. As used herein, the term "zeta potential" refers to the potential difference between the junction of the Stern layer (the layer of firmly attached counterions formed to neutralize the surface charge of the colloidal particles) and the diffuse layer (the cloud of loosely attached ions existing farther from the particle surface than the Stern layer) and the bulk solution or slurry. This property is expressed in units of voltage, such as millivolts (mV). The zeta potential can be obtained by quantifying the "electrokinetic sonic amplitude effect" (ESA), which is the generation of ultrasonic waves as a result of applying a potential across the entire colloidal suspension, as described in U.S. Patent No. 5,616,872, which is incorporated herein by reference.

[0064] Hydrocarbyl group. As used herein, the term "hydrocarbyl group" is used according to the IUPAC definition recognized in the art as a monovalent, straight-chain, branched, or cyclic group formed by removing a monovalent hydrogen atom from a parent hydrocarbon compound. Unless otherwise specified, a hydrocarbyl group can be aliphatic or aromatic, saturated or unsaturated, and can include straight-chain, cyclic, branched, and / or fused-ring structures, provided that none of these are specifically excluded. See IUPAC Compendium of Chemical Terminology, 2 nd Ed(1997) at 190. Examples of hydrocarbyl groups include, but are not limited to, aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, cycloalkadienyl, alkynyl, aralkyl, aralkenyl, and aralkynyl groups.

[0065] Heterohydrocarbyl group. The term "heterohydrocarbyl" is used in this disclosure to encompass monovalent, straight-chain, branched, or cyclic groups formed by removing a single hydrogen atom from a carbon atom of a parent "heterohydrocarbon" molecule in which at least one carbon atom is replaced by a heteroatom. The parent heterohydrocarbon can be aliphatic or aromatic. Examples of "heterohydrocarbyl" groups include halide substituents, nitrogen substituents, phosphorus substituents, silicon substituents, oxygen substituents, and sulfur-substituted hydrocarbyl groups in which a hydrogen has been removed to form a carbon atom and generate a free valence. Examples of heterohydrocarbyl groups include -CH2OCH3, -CH2SPh, -CH2NHCH3, -CH2CH3NMe2, -CH2SiMe3, -CMe2SiMe3, -CH2(C6H4-4-OMe), -CH2(C6H4-4-NHMe), -CH2(C6H4-4-PPh2), -CH2CH3PEt2, -CH2Cl, -CH2(2,6-C6H3Cl2), and the like, but are not limited thereto.

[0066] Heterohydrocarbyl encompasses both heteroaliphatic groups (including saturated and unsaturated groups) and heteroaromatic groups. Thus, heteroatom-substituted vinyl groups, heteroatom-substituted alkenyl groups, heteroatom-substituted dienyl groups, etc. are all encompassed by the heterohydrocarbyl group.

[0067] Organoheteryl group. The term "organoheteryl" group is also used as a monovalent group containing carbon in accordance with the IUPAC definition recognized in the art, and thus is organic but has its free valence on an atom other than carbon. IUPAC Compendium of Chemical Terminology, 2 ndSee Ed(1997) at 284. The organoheteryl group can be linear, branched, or cyclic and includes common groups such as alkoxy, aryloxy, organothio (or organilylthio), organogermanium (or organilylgermanium), acetamide, acetonylacetanato, alkylamide, dialkylamide, arylamide, diarylamide, trimethylsilyl, etc. Groups such as -OMe, -OPh, -S(tolyl), -NHMe, -NMe2, -N(aryl)2, -SiMe3, -PPh2, -O3S(C6H4)Me, -OCF2CF3, -O2C(alkyl), -O2C(aryl), -N(alkyl)CO(alkyl), -N(aryl)CO(aryl), -N(alkyl)C(O)N(alkyl)2, hexafluoroacetonylacetanato, etc.

[0068] Organilyl group. The organilyl group, as defined by IUPAC, is used in this disclosure to refer to any organic substituent, regardless of functional type, having one free valence on a carbon atom, such as CH3CH2-, ClCH2C-, CH3C(=O)-, 4-pyridylmethyl, etc. The organilyl group may be linear, branched, or cyclic, and the term "organilyl" may be used in combination with other terms, such as organilylthio- (e.g., MeS-) and organilyloxy.

[0069] Heterocyclyl group. The IUPAC Compendium compares the organilyl group with other groups such as heterocyclyl groups and organoheteryl groups. These terms are defined in the IUPAC Compendium of Chemical Terminology, 2 ndEd(1997) describes as follows, which shows the convention of associating the suffix “-yl” with a part of a molecule or group having a valence from a missing hydrogen. Thus, a heterocyclyl group is defined as a monovalent group formed by removing a hydrogen atom from any ring atom of a heterocyclic compound. For example, the piperidin-1-yl group and the piperidin-2-yl group shown below, where the lines drawn from the nitrogen atom or carbon atom represent free valences, and both the piperidin-1-yl group and the piperidin-2-yl group, which are not methyl groups, are heterocyclyl groups. [Chemical Structure] However, the piperidin-1-yl group is also regarded as an organoheteryl group, and the piperidin-2-yl group is also regarded as a hetero hydrocarbyl group. Thus, the valence of “heterocyclyl” can occur on any appropriate ring atom, while the valence of “organoheteryl” occurs on a heteroatom, and the valence of hetero hydrocarbyl occurs on a carbon atom.

[0070] Hydrocarbylene group and hydrocarbylidene group. The “hydrocarbylene” group is also, as described in the IUPAC Compendium of Chemical Terminology, 2 nd Ed(1997), a divalent group formed by removing two hydrogen atoms from a hydrocarbon, and is defined according to its general and customary meaning, where its free valence is not engaged in a double bond. Examples of hydrocarbylene groups include, for example, 1,2-phenylene, 1,3-phenylene, 1,3-propanediyl (-CH2CH2CH2-), cyclopentylidene (=CC4H8), or a methylene that does not form a double bond with a crosslink (-CH2-). A hydrocarbylene group whose free valence is not engaged in a double bond is distinguished from a hydrocarbylidene group such as an alkylidene group.

[0071] A "hydrocarbylidene" group is a divalent group formed from a hydrocarbon by removing two hydrogen atoms from the same carbon atom, and its free valence is part of a double bond. An alkylidene group is an exemplary hydrocarbylidene and is defined as a divalent group formed from an alkane by removing two hydrogen atoms from the same carbon atom, and its free valence is part of a double bond. Examples of alkylidene groups such as =CHMe, CHEt, =CMe2, =CHPh, or methylene where the methylene carbon forms a double bond (=CH2).

[0072] Heterohydrocarbylene groups and heterohydrocarbylidene groups. The term "heterohydrocarbylene" group is used to refer to a divalent group formed by removing two hydrogen atoms from a parent hetero-hydrocarbon molecule, similar to a hydrocarbylene group, and its free valence is not engaged in a double bond. The hydrogen atoms can be removed from two carbon atoms, two heteroatoms, or one carbon and one heteroatom so that the free valence is not engaged in a double bond. Examples of "heterohydrocarbylidene" groups include, but are not limited to, -CH2OCH2-, -CH2NPhCH2-, -SiMe2(1,2-C6H4)SiMe2-, -CMe2SiMe2-, -CH2NCMe3-, -CH2CH2PMe-, -CH2[1,2-C6H3(4-OMe)]CH2-, etc.

[0073] Similar to hydrocarbylidene, a "heterohydrocarbylidene" group is a divalent group formed from a hetero-hydrocarbon by removing two hydrogen atoms from the same carbon atom, and its free valence is part of a double bond. Examples of heterohydrocarbylidene groups include, but are not limited to, groups such as =CHNMe2, =CHOPh, =CMeNMeCH2Ph, =CHSiMe3, =CHCH2Cl, etc.

[0074] Halides and Halogens. The terms "halide" and "halogen" are used herein to refer to ions or atoms of fluorine, chlorine, bromine, or iodine, individually or in any combination, as the context and chemistry allow or dictate. These terms may be used synonymously regardless of the charge or bonding pattern of these atoms.

[0075] Polymers. The term "polymer" is generally used herein to include olefin homopolymers, copolymers, terpolymers, etc. Copolymers are derived from an olefin monomer and one olefin comonomer, while terpolymers are derived from an olefin monomer and two olefin comonomers. Thus, "polymer" encompasses copolymers, terpolymers, etc. derived from any olefin monomer and comonomer(s) disclosed herein. Similarly, ethylene polymers include ethylene homopolymers, ethylene copolymers, ethylene terpolymers, etc. Thus, olefin copolymers such as ethylene copolymers can be derived from comonomers such as ethylene and propylene, 1-butene, 1-hexene, or 1-octene. If the monomer and comonomer are ethylene and 1-hexene, respectively, the resulting polymer is classified as an ethylene / 1-hexene copolymer. Similarly, the term "polymerization" includes homopolymerization, copolymerization, terpolymerization, etc. For example, a copolymerization process involves contacting one olefin monomer such as ethylene with one olefin comonomer such as 1-hexene to produce a copolymer. Well-known abbreviations of polyolefin types such as "HDPE" for high-density polyethylene can be used herein. Further, unless otherwise expressly stated, the term polymer is not limited by molecular weight and thus encompasses both low molecular weight polymers, which may be referred to as oligomers, and high molecular weight polymers.

[0076] A procatalyst or a pre-catalyst. As used herein, the terms "procatalyst" or "pre-catalyst" mean a compound that can polymerize, oligomerize, or hydrogenate an olefin when activated by an aluminoxane, borane, borate, or other acidic activator, regardless of whether it is a Lewis acid or a Bronsted acid, or when activated by a support activator as disclosed herein.

[0077] Additional Explanation of Terms. The following additional explanations of terms are provided in the fully disclosed embodiments and claims of the present disclosure.

[0078] Several types of numerical ranges are disclosed herein, including but not limited to numerical ranges such as the number of atoms, basal spacing, weight ratio, molar ratio, percentage, temperature, etc. When disclosing or claiming any type of range, the applicant's intention is that each number that such a range may reasonably encompass be individually disclosed or claimed, consistent with the written description and context, to include the endpoints of the range, and any sub-ranges and combinations of sub-ranges subsumed therein. For example, if the applicant discloses or claims a chemical moiety having a specific number of carbon atoms, such as a C1-C12 (or C1-C 12 ) alkyl group, or alternative language having 1 to 12 carbon atoms, the applicant's intention is that an alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms can be independently selected, and also refers to moieties including any combination of ranges between these two numbers (e.g., a C1-C6 alkyl group), and any combination of ranges between these two numbers (e.g., C2-C4, and C6-C8 alkyl groups). The applicant reserves the right to exclude or except any individual members of any such range or group, including any sub-ranges or combinations of sub-ranges within the group, that can be claimed in a range or similar manner if, for any reason, the applicant chooses to claim less than the full measure of the disclosure, for example, in consideration of references not recognized by the applicant at the time of filing.

[0079] In another aspect, any numerical range described in this specification or the claims that represents a particular set of characteristics, units of measurement, conditions, physical states, or percentages is intended to expressly incorporate by reference, or otherwise, any number falling within that range that includes any subset of the numbers within the range so described. For example, when a numerical range having a lower limit, RL, and an upper limit, RU, is disclosed, any numerical value R falling within that range is specifically disclosed. In particular, the following numbers R within the range are specifically disclosed: R = RL + k(RU - RL), where k is a variable in the range of 1% to 100% with 1% increments, for example, k is 1%, 2%, 3%, 4%, 5%....50%, 51%, 52%....95%, 96%, 97%, 98%, 99% or 100%. Further, any numerical range represented by any two values of R calculated as above is also specifically disclosed.

[0080] For any particular compound disclosed herein, any general or specific structure presented, unless otherwise indicated, includes all stereoisomers, positional isomers, and tautomers that can result from a particular set of substituents. Similarly, unless otherwise specified, the general or specific structure also includes enantiomers, diastereomers, and other optical isomers (in any form of enantiomers or racemates), as well as mixtures of stereoisomers, as recognized by those skilled in the art.

[0081] Unless otherwise indicated, values or ranges may be expressed in the present disclosure using the term "about", e.g., the recited value of "about", greater than or less than the recited value of "about", or a range from one value of "about" to another value of "about". When such values or ranges are expressed, other disclosed embodiments include the specific recited values, the ranges between the specific recited values, and other values close to the specific recited values. In one aspect, the use of the term "about" means ±15%, ±10%, ±5%, or ±3% of the recited value. For example, when the term "about" is used as a modifier for or in relation to a variable, property, or condition, the numerical values, ranges, properties, and conditions disclosed herein may deviate somewhat from the recited ranges or be different from a single recited value, such as properties like temperature, speed, time, concentration, amount, content, base interval, etc., and sizes including pore size, pore volume, surface area, etc., and the practice of the present disclosure by those skilled in the art using such properties is intended to convey that it is flexible enough to achieve the desired results described in the present application, such as the preparation of porous catalyst support particles having defined properties and their use in the preparation of active olefin polymerization catalysts and olefin polymerization processes using such catalysts.

[0082] Terms such as "a", "an", "the", etc. (e.g., "this") are intended to include plural alternatives such as at least one unless otherwise specified. For example, the disclosure of "a support activator", "an organoaluminum compound", or "a metallocene compound" each means to include one or more ( "at least one") of a support activator, an organoaluminum compound, or a metallocene compound, or a mixture or combination thereof.

[0083] The term "comprising" and its variants such as "comprise", "comprised of", "having", "including", etc., are inclusive and open-ended as listed in the transitional phrase or specification, and do not exclude additional, unlisted elements or method steps. The transitional phrase "consisting of" and its variants exclude any element, step, or component not specified in the claims. The transitional phrase "consists essentially of" limits the scope of the claims to the specified components or steps, and components or steps that do not substantially affect the basic and novel features of the claimed invention. Unless otherwise indicated, describing a compound or composition as "consisting essentially of" is not intended to be construed as "comprising", since this phrase is intended to describe the recited components including materials that do not significantly modify the composition or the manner in which the term applies. For example, a precursor or catalyst component can consist essentially of a material that can contain impurities commonly present in a commercially produced sample of the material when prepared by a particular procedure.

[0084] When a composition or process is described in terms of "comprising" various components or steps, the composition and process can also "consist essentially of" or "consist of" the various components or process steps.

[0085] Where the claims include different features and / or feature classes (e.g., among other possibilities, method steps, feedstock features, and / or product features), the transitional terms can include, consist essentially of, and consist of only the feature classes being utilized and can have different transitional terms or phrases utilized with the different features within the claims. For example, a method can include some recited steps (and other unrecited steps), but utilize a catalyst system preparation that consists of particular or alternatively consists essentially of particular steps, and utilize a catalyst system that includes the recited components and other unrecited components.

[0086] Unless otherwise defined with respect to a particular property, characteristic, or variable, the terms "substantially" and "substantially" as applied to any criterion such as a property, characteristic, or variable mean meeting the criterion described in a measure sufficient for one of ordinary skill in the relevant art to understand that the benefit being achieved, or the desired condition or characteristic value, is met. For example, the term "substantially" can be used when describing a metallocene catalyst or catalyst system that substantially does not contain or is substantially free of aluminoxane, borate activator, protonic acid-treated clay, or pillared clay. In other words, the terms "substantially" and "substantially" serve to reasonably describe the subject matter so that its scope is understood by one of ordinary skill in the relevant art and to distinguish the claimed subject matter from any prior art. In one aspect, "substantially free of" can be used to describe a composition in which, of the recited components, only those that the composition is substantially free of are added, and only an impurity amount, e.g., an amount resulting from purity limitations of other components, or an amount produced as a byproduct, is present. In a further aspect, when a composition is said to be "substantially free of" a particular component, the composition can have less than 10 wt%, less than 5 wt%, less than 3 wt%, less than 2 wt%, less than 1 wt%, less than 0.5 wt%, or less than 0.1 wt% of the component.

[0087] Regarding the elements of the claims, terms such as "optionally", "optional", etc. are intended to mean that the subject element is required, or alternatively, is not required, and both alternatives are intended to be within the scope of the claims, and it is assumed that the claims can encompass either or both alternatives.

[0088] References to the periodic table or groups of elements within the periodic table refer to the periodic table of the elements published by the International Union of Pure and Applied Chemistry (IUPAC) and made publicly available online at http: / / old.iupac.org / reports / periodic_table / (version of February 19, 2010). The "group" or "groups" of the periodic table as reflected in the periodic table of the elements are referred to using the IUPAC system for the numbering of the groups of elements as groups 1 - 18. To avoid confusion, any group is further identified by one or more of its elements, to the extent that the group is identified by Roman numerals according to the periodic table of the elements published in, for example, "Hawley’s Condensed Chemical Dictionary" (2001) (the "CAS" system), and a cross-reference to the numerical IUPAC identifier is provided.

[0089] In this specification, various patents, publications, and documents are disclosed and referenced. Each reference cited in this disclosure is incorporated herein by reference in its entirety, whether a patent, publication, or other document, unless otherwise specifically noted.

[0090] Examples of reference documents that may provide some background information related to the present disclosure include, for example, U.S. Patent Nos. 4,169,926, 5,135,756, 5,308,811, 6,034,187, 6,531,552, 6,825,371, 6,838,507, 6,927,261, 7,220,695, 7,732,542, 8,642,499, and 9,200,093, each of which is hereby incorporated by reference in its entirety. Additional publications that may provide some background information related to the present disclosure include Materials Research 2015, 18(2), 283 - 287, Ceramica, 1999, 45(295), 133 - 136, Langmuir 2005, 21(19), 8717 - 8723, Macromolecular Reaction Engineering 2017, 11(2), 1600017, and Clay Minerals 2003, 38(1), 127 - 138, each of which is hereby incorporated by reference in its entirety.

[0091] B. Summary The support activators of the present disclosure can be formed by contacting a swelling clay such as smectite or dioctahedral smectite clay, or a preformed smectite-clay cationic polymethalate adduct, with a surfactant in a liquid carrier, and there are several embodiments or aspects for the method and the resulting adduct. For example, a method for producing a support activator comprising a smectite adduct is provided, the method comprising, in a first liquid carrier, (a) a colloidal smectite clay and (b) a surfactant, wherein the surfactant provides a slurry of the smectite adduct in the first liquid carrier by comprising or being selected from a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or any combination thereof. The process can optionally involve the further addition of other reagents such as cationic polymethalate or metal oxide, but the contacting step can also occur in the absence of the specific reactants as described above. For example, the contacting step may be carried out in the absence of cationic polymethalate and other reactants, or the contacting step can be carried out in the absence of any other reactant except the surfactant. An unexpected advantage of the method of the present disclosure for producing a support activator is the observation that it provides the smectite adduct in the form of highly spherical particles, which are desirable for forming highly spherical catalyst particles.

[0092] In another aspect, the present disclosure provides a method for manufacturing a support activator comprising a smectite adduct, the method comprising, in a first liquid carrier, in any order, (a) a colloidal smectite clay, (b) a cationic polymethalate, and (c) a surfactant comprising, or selected from, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or any combination thereof, contacting to provide a slurry of the smectite adduct in the first liquid carrier, or consisting essentially of providing. This process can optionally involve further addition of other reagents as needed, but this contacting step can also occur in the absence of the specific reactants described herein, or in the absence of any other reactants as needed.

[0093] According to a further aspect, the present disclosure provides for pre-forming a clay-cationic polymethalate adduct and preparing an aqueous spray-dried slurry of the pre-formed or isolated clay cationic polymethalate adduct, the aqueous spray-dried slurry comprising a surfactant. The resulting adduct can be spray-dried from the aqueous slurry in the absence of an organic dispersion medium or in the absence of an organic liquid (excluding the surfactant) to provide a highly spherical support activator. This process can also optionally involve further addition of other reagents as needed, but this contacting step can also occur in the absence of the specific reactants described herein, or in the absence of any other reactants as needed.

[0094] Heterocoagulants produced according to the process of the present disclosure can be conveniently isolated by simple filtration and then dried and calcined to provide a support activator useful for supporting and activating metallocene catalysts for olefin polymerization. It has been unexpectedly discovered that the calcined surfactant supports described herein have improved porosity compared to calcined clays and calcined clay-polymethalate mixtures, even when dried from an aqueous slurry by spray drying. When attempting to maintain the porosity of the isolated contact product of clay and polymethalate during the drying process, methods such as using an organic liquid to azeotropically remove water are often required to maintain porosity. However, in the clay-surfactant adducts of the present invention, substantial BJH porosity remains when spray dried in the absence of an organic dispersion liquid.

[0095] Conventional processes for activating the aforementioned clay to provide a clay-based support activator involve contacting the clay with an inorganic acid such as hydrochloric acid or sulfuric acid and may include a surfactant treatment (see, for example, U.S. Patent No. 7,220,695). However, these treatments may reduce the structural integrity of the clay, perhaps because the clay structure itself is disrupted by peptidization during the process of acidifying the clay, as described in Clay Minerals, 2003, 38(1), 127-138. However, acid is generally considered necessary to activate the clay, and thus previous approaches to addressing the stability of the resulting support activator have not completely removed the acid treatment. The applicant has discovered that the acid is unnecessary and even unexpectedly undesirable because the clay in question can be fully activated in the absence of an acid such as hydrochloric acid or sulfuric acid to provide a highly active support activator with higher structural integrity.

[0096] In the applicant's previous patent applications, published as US Patent Application Publication No. 2021 / 0230318 and International Application Publication No. 2021 / 154204, the smectite clay, upon contact with a cationic polymetallate and including in the presence of a surfactant, forms heteroadditives that function as highly active support activators for metallocenes when fired. In one aspect, the applicant has unexpectedly discovered that the target clay can be activated in the presence of a surfactant but in the absence of a cationic polymetallate such as aluminum chlorohydrate (ACH), polyaluminum chloride (PAC), or an aluminum sesquichlorohydrate composition, and still provide a highly active support activator with desirable structural properties. The resulting support activator has high porosity, particle uniformity, and high particle sphericity.

[0097] To provide means of consistency and uniformity to the catalyst prepared from the support activator and any resulting polymer, and also due to the sensitivity of the supported metallocene catalyst to moisture, the support activator can be fired or otherwise dried to control any residual moisture present in the support. However, firing of previous support activators is known to result in a significant reduction in the porosity of the support activator. Without intending to be bound by theory, it is believed that under the support activator preparation conditions, the clay layers become swollen by the liquid carrier molecules, but they then tend to collapse when the liquid molecules are removed at high temperature.

[0098] In the present disclosure, the introduction of the bulky ionic or non-ionic surfactant molecules described herein imparts improved thermal stability to these clay-based support activators. Without intending to be bound by any theory of the mechanism by which this occurs, it is believed that the surfactant molecules or surfactant cations can act as pillars to support the layered structure and intercalate between the clay layers, even in the absence of other existing activating components such as acids or polymetallates.

[0099] The surfactant-clay supports described herein have been unexpectedly discovered to have improved olefin polymerization activity compared to their calcined clays or calcined clay-polymetallate analogs. Although not wishing to be bound by theory, it is believed that the enhanced porosity obtained by the combination of surfactant and clay allows the metallocene to access and form more catalytically active sites. These improved activities and properties of the surfactant-clay support activators are economically desirable and provide substantial advantages for their use in olefin catalyst processes.

[0100] Accordingly, in one aspect, the present disclosure provides a support activator comprising a smectite heteroaddition product that can be calcined, the smectite heteroaddition product being in a first liquid carrier and comprising, (a) a colloidal smectite clay, and (b) a surfactant reagent comprising [i] a cationic surfactant, [ii] a nonionic surfactant, or [iii] an amphoteric surfactant, or any combination thereof, or being selected from them.

[0101] C. Colloidal smectite clay In addition to the definition section, the following disclosure provides additional information related to smectite clay.

[0102] Expansive clays, such as smectites or 2:1 dioctahedral smectite clays, or combinations of expansive clays can be used in the preparation of the support activators described herein. Since these expansive clays can use specific members of the phyllosilicate clay mineral group, they can be described as phyllosilicates or phyllosilicate clays. Suitable starting clays can include layered, naturally occurring, or synthetic smectites. The starting clays can also include dioctahedral smectite clays. Further, suitable starting clays can also include clays such as montmorillonite, sauconite, nontronite, hectorite, beidellite, saponite, bentonite, or any combination thereof. Smectites are 2:1 layered clay minerals that carry a lattice charge and can expand when solvated with water and alcohol. Thus, suitable starting clays include, for example, dioctahedral smectites such as monoion-exchanged, lithium-exchanged clay, sodium-exchanged clay, or potassium-exchanged clay, or combinations thereof.

[0103] Water can also coordinate to the layered clay structural units either associated with the clay structure itself or coordinated to cations as a hydration shell. When dehydrated, the 2:1 layer clay has a repeat distance or d001 basal spacing of about 9 Å (angstroms) to about 12 Å (angstroms) in powder X-ray diffraction (XRD), or alternatively, has a range of about 10 Å (angstroms) to about 12 Å (angstroms) in powder X-ray diffraction (XRD).

[0104] Because their structure is a "sandwich" structure that includes two outer sheets of tetrahedral silicate and an inner sheet of octahedral alumina sandwiched between the silica sheets, layered smectite clays are also referred to as 2:1 clays. Thus, these structures are also referred to as "TOT" (tetrahedral-octahedral-tetrahedral) structures. These sandwich structures are stacked one on top of the other to form clay particles. This configuration provides a repeating structure every approximately 9 angstroms and a half angstrom (Å), compared to pillared or intercalated clays produced by inserting "pillars" of inorganic oxide materials between these layers, and can provide a larger space between the natural clay layers.

[0105] In one aspect, the clay used to prepare the clay-heterocoagulate and the support activator can be colloidal smectite clay. For example, the colloidal smectite clay can have an average particle size of 10 μm (microns) or more, 5 μm or more, 3 μm or more, 2 μm or more, or 1 μm or more, and the average particle size can also be 15 μm or less, 25 μm or less, 50 μm or less, 75 μm or less, 100 μm or less, 125 μm or less, 150 μm or less, 175 μm or less, 200 μm or less, 225 μm or less, or 250 μm or less. That is, any range of clay particle sizes between these listed numbers is disclosed. Unless otherwise specified, any particle size cited herein for smectite clay itself is the particle size specified by the clay supplier. Clays that do not allow the formation of a colloidal suspension can be used, but the use of these non-colloidal clays presents additional processing and separation problems that are avoided by the use of colloidal clays. These upper and lower limits of the average particle size of colloidal smectic clay are also applicable to clay-surfactant adducts (dried or calcined) and support metallocene catalysts (dried) as described herein.

[0106] In another aspect, the colloidal smectite clay can have, for example, an average particle size of 1 μm (micron) to 250 μm. For example, the colloidal smectite clay can have an average particle size of about 1 μm (micron), about 2 μm, about 3 μm, about 5 μm, about 7 μm, about 10 μm, about 12 μm, about 15 μm, about 18 μm, about 20 μm, about 25 μm, about 30 μm, about 35 μm, about 40 μm, about 45 μm, about 50 μm, about 55 μm, about 60 μm, about 65 μm, about 70 μm, about 75 μm, about 80 μm, about 85 μm, about 90 μm, about 95 μm, about 100 μm, about 110 μm, about 120 μm, about 125 μm, about 130 μm, about 140 μm, about 150 μm, about 160 μm, about 170 μm, about 175 μm, about 185 μm, about 200 μm, about 225 μm, or about 250 μm, or an average particle size within any range between these recited values. For example, the colloidal smectite clay can have an average particle size of 1 μm to 250 μm, 2 μm to 125 μm, 3 μm to 100 μm, 5 μm to 150 μm, 5 μm to 80 μm, 7 μm to 70 μm, 10 μm to 100 μm, 10 μm to 60 μm, 15 μm to 80 μm, 15 μm to 50 μm, or 20 μm to 75 μm.

[0107] In another aspect, the particle size of commercially available Volclay® HPM-20 bentonite provides a suitable particle size for use according to the present disclosure. For example, the colloidal smectite clay used according to the present disclosure can be characterized by a particle size that is at least 99.00% finer than 200 mesh (74 microns). In another aspect, the colloidal smectite clay used according to the present disclosure can be characterized by a particle size that is at least 99.75% finer than 200 mesh (74 microns) and at least 99.00% finer than 325 mesh (44 microns).

[0108] In one aspect, the clay used to prepare the support activator may lack the divalent or trivalent ion-exchanged smectites described in U.S. Patent No. 6,531,552, such as Mg-exchanged montmorillonite or Al ion-exchanged montmorillonite. In another aspect, the clay used to prepare the support activator may lack mica or synthetic hectorite as described in U.S. Patent Nos. 6,531,552 and 5,973,084. In a further aspect, the clay used to prepare the support activator may lack trioctahedral smectite or may lack vermiculite.

[0109] In one aspect, the smectite clay also has the following formula: (M A IV)8(M B VI) p O 20 (OH)4, where a) M A IV is 4-coordinate Si 4+ and Si 4+ is optionally partially substituted by a 4-coordinate cation other than Si 4+ (e.g., a cation other than Si 4+ can be independently selected from Al 3+ , Fe 3+ , P 5+ , B 3+ , Ge 4+ , Be 2+ , Sn 4+ etc.), b) M B VI is 6-coordinate Al 3+ or Mg 2+ and Al 3+ or Mg 2+ is optionally partially substituted by a 6-coordinate cation other than Al 3+ or Mg 2+ (e.g., a cation other than Al 3+ or Mg 2+ can be Fe 3+ , Fe 2+ , Ni 2+ , Co 2+ , Li +, Zn 2+ , Mn 2+ , Ca 2+ , Be 2+ etc. can be independently selected), c) p is 4 for a cation with a +3 formal charge, or p is 6 for a cation with a +2 formal charge, d) M A IV substitution of Si 4+ Any charge deficiency caused by partial substitution of cations that are not, and / or M B VI substitution of Al 3+ or Mg 2+ Any charge deficiency caused by partial substitution of cations that are not is balanced by cations intercalated between structural units (e.g., the cations intercalated between structural units can be selected from monocations, dications, trications, other multocations, or any combination thereof), and the structural unit can include this feature.

[0110] In another aspect, the smectite clay can be a monocation exchanged with at least one of lithium, sodium, or potassium. The examples, data, and aspects in the disclosure section provide additional detailed information on various aspects and embodiments of the smectite clay.

[0111] D. Surfactant The step of contacting the clay with the surfactant can be carried out using any suitable surfactant, which can include cationic surfactants, nonionic surfactants, amphoteric surfactants (including ampholytic surfactants), and combinations thereof. In one aspect, the contact product and the method for manufacturing the support activator may be absent any one or any two of cationic surfactants, nonionic surfactants, or amphoteric surfactants.

[0112] According to one aspect, the colloidal smectite clay and the surfactant can be contacted at a ratio of 0.5 mmol to 5 mmol of surfactant per gram of colloidal smectite clay. For example, the colloidal smectite clay and the surfactant can be provided or contacted at a ratio of 0.75 mmol to 4 mmol, 1 mmol to 3.5 mmol, 1.25 mmol to 3 mmol, or 1.5 mmol to 2.75 mmol of surfactant per gram of colloidal smectite clay.

[0113] Cationic surfactant. In one aspect, the cationic surfactant can include, or can be selected from, primary, secondary, tertiary, or quaternary ammonium compounds or phosphonium compounds. When describing the cationic surfactant, the present disclosure can refer to a cationic surfactant that includes a cationic component and a counterion or anion. In one aspect, the cationic surfactant can include, or can be selected from, ammonium compounds (salts) having the following general formula: [R 1 R 2 R 3 R 4 N] + X - , wherein, each R 1 , R 2 , R 3 , and R 4 is independently selected from hydrogen, a substituted or unsubstituted C1-C 25 hydrocarbyl group, or a substituted or unsubstituted C1-C 25 heterohydrocarbyl group, and any two or more of R 1 , R 2 , R 3 , and R 4 can be part of a ring structure, and at least one of R 1 , R 2 , R 3 , and R 4 is a non-hydrogen moiety, X - is selected from an organic or inorganic monoanion, dianion, or trianion.

[0114] In a further aspect, the ammonium compound can have the general formula [R 1 R 2 R 3 R 4 N] + X - wherein R 1 , R 2 , R 3 , and R 4 are independently selected from hydrogen, a substituted or unsubstituted C1-C 25 aliphatic group, a substituted or unsubstituted C1-C 25 heteroaliphatic group, a substituted or unsubstituted C6-C 25 aromatic group, or a substituted or unsubstituted C4-C 25 heteroaromatic group, and any two or more of R 1 , R 2 , R 3 , and R 4 can be part of a ring structure, and at least one of R 1 , R 2 , R 3 , and R 4 is a non-hydrogen moiety, and X - is selected from any suitable anion such as fluoride, chloride, bromide, iodide, formate, acetate, oxalate, nitrate, sulfate, sulfite, perchlorate, carbonate, bromate, chlorate, chlorite, hypochlorite, or phosphate.

[0115] According to another aspect, the cationic surfactant can include, or can be selected from, phosphonium compounds (salts) having the following general formula: [R 1 R 2 R 3 R 4 P] + X - wherein each R 1 , R 2 , R 3 , and R 4 are independently hydrogen, a substituted or unsubstituted C1-C 25Selected from a hydrocarbyl group, or a substituted or unsubstituted C1-C 25 heterohydrocarbyl group, R 1 , R 2 , R 3 , and R 4 Any two or more of can be part of a ring structure, R 1 , R 2 , R 3 , and R 4 At least one of is a non-hydrogen moiety, X - is selected from an organic or inorganic monoanion, dianion, or trianion.

[0116] In a further aspect, the phosphonium compound has the general formula R 1 R 2 R 3 R 4 P] + X - wherein R 1 , R 2 , R 3 , and R 4 are independently selected from hydrogen, a substituted or unsubstituted C1-C 25 aliphatic group, a substituted or unsubstituted C1-C 25 heteroaliphatic group, a substituted or unsubstituted C6-C 25 aromatic group, or a substituted or unsubstituted C4-C 25 heteroaromatic group, and any two or more of R 1 , R 2 , R 3 , and R 4 can be part of a ring structure, and at least one of R 1 , R 2 , R 3 , and R 4 is a non-hydrogen moiety, and the counterion X - is selected from any suitable anion such as fluoride, chloride, iodide, carboxylates such as formate, acetate, oxalate, nitrate, sulfate, sulfite, perchlorate, carbonate, bromate, chlorate, chlorite, hypochlorite, or phosphate.

[0117] In an embodiment, the cationic surfactant can include a cation selected from lauryltrimethylammonium, stearyltrimethylammonium, trioctylammonium, distearyldimethylammonium, distearyldibenzylammonium, cetyltrimethylammonium, benzylhexadecyldimethylammonium, dimethyld(hydrogenated tallow)ammonium, dimethylbenzyl(hydrogenated tallow)ammonium, or any combination thereof.

[0118] According to some embodiments, the cation of the cationic surfactant is tetramethylammonium, tetraethylammonium, tetrabutylammonium, tetrapentylammonium, tetrahexylammonium, tetraoctylammonium, tetrabenzylammonium, cetylammonium, decylammonium, dodecylammonium, methyloctadecylammonium, ethyloctadecylammonium, butyloctadecylammonium, dimethyloctadecylammonium, diethyloctadecylammonium, dibutyloctadecylammonium, trimethyloctadecylammonium, triethyloctadecylammonium, tributyloctadecylammonium, methyltridecylammonium, ethyltridecylammonium, butyltridecylammonium, N,N-dimethylanilinium, N,N-diethylanilinium, N,N-2,4,5-pentamethylanilinium, N,N-dimethyloctadecylammonium, N,N-dimethyl-N,N-dipropylammonium, N,N-dimethyl-N,N-dihexylammonium, N,N-dipropyl-N,N-dihexylammonium, trimethylphosphonium, triethylphosphonium, tributylphosphonium, trihexylphosphonium, tetramethylphosphonium, tetraethylphosphonium, tetrapropylphosphonium, tetrabutylphosphonium, tetrahexylphosphonium, tetrabenzylphosphonium, trihexyltetradecylphosphonium, diallyldimethylammonium, triethylmethylammonium, tributylethylammonium, trimethylsulfoniumammonium, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium, glycidyltrimethylammonium, N,N-dimethyl-N-ethyl-N-propylammonium, N,N-dimethyl-N-ethyl-N-butylammonium, N,N-dimethyl-N-ethyl-N-amylammonium, N,N-dimethyl-N-ethyl-N-hexylammonium, N,N-dimethyl-N-ethyl-N-heptylammonium, N,N-dimethyl-N-ethyl-N-decylammonium, N,N-dimethyl-N-propyl-N-butylammonium, N,N-dimethyl-N-propyl-N-amylammonium, N,N-dimethyl-N-propyl-N-hexylammonium, N,N-dimethyl-N-propyl-N-heptylammonium, N,N-dimethyl-N-butyl-N-hexylammonium, N,N-dimethyl-N-butyl-N-heptylammonium, N,N-dimethyl-N-pentyl-N-hexylammonium, trimethylheptylammonium, N,N-diethyl-N-methyl-N-propylammonium, N,N-diethyl-N-methyl-N-amylammonium, N,N-diethyl-N-methyl-N-heptylammonium, N,N-diethyl-N-propyl-N-amylammonium, triethylmethylammonium, triethylpropylammonium, triethylammonium ammonium, triethylheptylammonium, N,N-dipropyl-N-methyl-N-ethylammonium, N,N-dipropyl-N-methyl-N-amylammonium, N,N-dipropyl-N-butyl-N-hexylammonium, N,N-dibutyl-N-methyl-N-amylammonium, N,N-dibutyl-N-methyl-N-hexylammonium, trioctylmethylammonium, N-methyl-N-ethyl-N-propyl-N-amylammonium, diethyldimethylphosphonium, dibutyldiethylphosphonium, or any combination thereof, or can be selected from them.,

[0119] In various embodiments, the counterion X to the cationic component of the cationic surfactant -It can contain or can be selected from inorganic anions such as organic anions or halides. Exemplary organic anions include, but are not limited to, carboxylates such as formate, acetate, and oxalate. Exemplary inorganic anions include, but are not limited to, nitrate, sulfate, perchlorate, carbonate, chlorate, chlorite, hypochlorite, and phosphate. Exemplary halide anions include fluoride, chloride, and bromide. Embodiments of the cationic surfactant include, but are not limited to, the cationic components as exemplified above in combination with an anion containing or selected from halide ions or anions of inorganic Bronsted acids.

[0120] In one aspect, examples of cationic surfactants include, but are not limited to, the chlorides or bromides of benzalkonium, benzetonium, methylbenzetonium, cetylpyridinium, alkyl-dimethyldichlorobenzeneammonium, decalinium, phenamilinium, cetrimonium, or cetexonium.

[0121] In another aspect, examples of cationic surfactants that can be used in accordance with the present disclosure include tetrabutylammonium bromide, dioctadecyldimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecylammonium chloride, trimethylstearylammonium, cetyltrimethylammonium bromide, octenidine dihydrochloride, cetyltrimethylammonium bromide (CTAB), cetyltrimethyltrimethylammonium chloride (CTAC), cetylpyridinium chloride (CPC), benzalkonium chloride (BAC), benzetonium chloride (BZT), dimethyldioctadecylammonium chloride, dioctadecyldimethylammonium (DODAB) bromide, or combinations thereof.

[0122] In some embodiments, the cationic surfactant can include or can be selected from aliphatic dialkylbenzylammonium compounds (also referred to as aliphatic alkylbenzylammonium compounds), which describe a class of quaternary ammonium compounds including alkyldimethylbenzylammonium chloride (ADBAC), where the alkyl can be, for example, C 12 ~C 16 or C 12 ~C 14 alkyl. The term "aliphatic dialkylbenzylammonium" compound can be used to describe a family of quaternary ammonium compounds that can be prepared or are commercially available in the form of compound mixtures. For example, commercially available "ADBAC" products or safety data sheets state that the commercially available products contain a mixture of alkyldimethylbenzylammonium chloride and alkyl (C 12 ~C 14 ) dimethyl(ethylbenzyl)ammonium chloride. Such common commercially available ammonium compounds can be used in accordance with the present disclosure.

[0123] Nonionic surfactants. In another aspect, the surfactant can include, consist essentially of, or be selected from nonionic surfactants. In the present disclosure, amphoteric surfactants (including ampholytic surfactants) are described together with non-bipolar nonionic surfactants for convenience.

[0124] In one aspect, examples of nonionic surfactants include, but are not limited to, polyhydric alcohols, monoalkyl ethers and dialkyl ethers of polyhydric alcohols, or their polyalkylene glycols, and any combination of two or more such nonionic surfactants can be used. Suitable polyhydric alcohols can contain two, three, or more hydroxyl groups. In one aspect, the polyhydric alcohol has the formula CH2OH(CHOH) nIt can have CH2OH, where n is an integer from 2 to 5. Exemplary polyhydric alcohols, also referred to as sugar alcohols, include glycerol, 1,2,4 - butanetriol, erythritol, pentaerythritol, maltitol, xylitol, and sorbitol. Exemplary ethers of polyhydric alcohols include, but are not limited to, mono - and di - methyl and mono - and di - ethyl ethers of ethylene glycol, propylene glycol, and diethylene glycol. Exemplary polyalkylene glycols include poly(ethylene) glycol and poly(propylene) glycol. These compounds and their preparation means are disclosed in Kirk - Othmer, Encyclopedia of Chemical Technology, Second Edition, Vol. 10, pages 638 - 674, which is hereby incorporated by reference. Polyolamines are also suitable non - ionic surfactants according to the present disclosure. For example, the non - ionic surfactant can include polyethoxylated tallow amine (also polyoxyethylene amine or POEA).

[0125] In another aspect, the non - ionic surfactant reagent can contain or can be selected from sugars such as monosaccharides, disaccharides, oligosaccharides, or mixtures thereof, such as those found in a corn syrup solid mixture derived from the hydrolysis of corn starch. Exemplary sugars include glucose, fructose, mannose, maltose, lactose, sucrose, etc. Exemplary oligosaccharides include, but are not limited to, cyclodextrin and maltodextrin. The non - ionic surfactants used according to the present disclosure can also include amino - modified sugars such as glucosamine, and oxidized sugar acids such as glucuronic acid.

[0126] In a further aspect, the nonionic surfactant can include a single fatty acid or a mixture of several fatty acids. These species typically include carbon chains 6 to 21 carbons in length, optionally containing internal unsaturations where the carbon chain is terminated with a carboxylic acid. Exemplary fatty acids include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, ricinoleic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolenic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid, or any combination thereof. In another aspect, the nonionic surfactant can include a fatty acid, examples of which are listed immediately above, condensed with an alcohol having one or more hydroxyl groups such as methanol, ethanol, butanol, hexanol, or glycerol, for example, monoglyceride, diglyceride, or triglyceride.

[0127] In embodiments, the nonionic surfactant can include an ethoxylate, glycol ether, fatty alcohol polyglycol ether, or combinations thereof, examples of which include, but are not limited to, octylphenol ethoxylate, polyethylene glycol tert-octylphenyl ether, ethylenediaminetetrakis(ethoxylate-block-propoxylate) tetrol, or ethylenediaminetetrakis(propoxylate-block-ethoxylate) tetrol.

[0128] In embodiments, the nonionic surfactant can include or be selected from hydrocarbyl (hydrocarbon) sulfonates having the formula R 1 SO2OR 2 wherein R 1 and R 2 are substituted or unsubstituted C1-C 25 alkyl, C6-C 25 aryl, C7-C 25 aralkyl, or C7-C25 It is selected independently of the alkali.

[0129] According to other embodiments, the nonionic surfactant can contain, or can be selected from, (a) a monosaccharide, disaccharide, oligosaccharide, or any combination thereof, or (b) an amino-modified sugar such as glucose, fructose, mannose, maltose, lactose, sucrose, cyclodextrin, maltodextrin, glucosamine, an oxidized sugar acid such as glucuronic acid, or any combination thereof.

[0130] In one aspect, the nonionic surfactant according to the present disclosure has the formula R 1 SiX3, R 1 R 2 SiX2, or R 1 R 2 R 3 SiX, and can contain, or can be selected from, silanes having the formula, wherein R 1 , R 2 , and R 3 are independently selected from a substituted or unsubstituted C1-C 25 hydrocarbyl group, a C1-C 25 heterohydrocarbyl group, or any other group that is hydrolytically stable when bonded to silicon in the nonionic surfactant, X is independently selected from hydrolyzable groups that are converted to a hydroxyl group (-OH) upon hydrolysis, thereby forming a silanol. In this aspect, the substituents R 1 , R 2 , and R 3 can independently be hydrogen, a substituted or unsubstituted C1-C 25 aliphatic group, a substituted or unsubstituted C1-C 25 heteroaliphatic group, a substituted or unsubstituted C6-C 25 aromatic group, or a substituted or unsubstituted C4-C 25 heteroaromatic group. This aspect further includes that the X group is a C1-C 25 alkoxy, a C1-C 25Acryloxy, halogen, or C1-C 25 It can be selected from amines. Without intending to be bound by theory, this type of silane is thought to be able to interact with clay hydroxyl groups, thereby repelling water from adhering to the internal clay pore surfaces.

[0131] According to one aspect, the non-ionic surfactant according to the present disclosure can contain or can be selected from silyl alcohols having the formula R 4-n Si(OH) n wherein n is 1 or 2, and R is selected from C1-C 20 alkyl group or C6-C 20 aryl group. Examples of silanols include, but are not limited to, triphenylsilanol, dimethylphenylsilanol, diphenylsilanediol, triisopropylsilanol, or any combination thereof.

[0132] Without intending to be bound by theory, high-temperature drying such as that which occurs during firing can result in the loss of hydrogen-bonded water strongly adhering to the clay pore surface hydroxyls, leading to the collapse of these pores, thereby reducing the BJH porosity. When a clay heteroadditive contacts a silanol or a silane containing a hydrolyzable group that is converted to a hydroxyl upon hydrolysis, thereby forming a silanol, some substitution of this water can occur with these hydroxyl-containing silanol compounds. By this means, these silanol compounds are thought to reduce the potential collapse of the porosity induced by the high-temperature treatment of the clay support.

[0133] Amphoteric surfactants. In one aspect, “amphoteric” surfactants are those surfactants that contain a positively charged moiety (or a moiety that can readily become positively charged by accepting a proton) and a negatively charged moiety (or a moiety that can readily become negatively charged by donating a proton) within the same molecule. The term “zwitterionic” surfactant is used interchangeably with “amphoteric” surfactants based on the inclusion of both a cationic and an anionic moiety within the same molecule. Unless otherwise excluded, “amphoteric” surfactants that donate or accept a proton (H + ) are included within the scope of “amphoteric” surfactants. Also, unless otherwise excluded, references to amphoteric or zwitterionic surfactants include amphoteric surfactants.

[0134] In one aspect, examples of amphoteric surfactants include amino acids or combinations of amino acids, polypeptides, or proteins. When the surfactant includes an amino acid, the step of contacting the clay with the surfactant can be performed under conditions including a pH of about 2.5 to 9.5 where the amino acid or combination of amino acids is zwitterionic. Without intending to be bound by theory, it is believed that the cationic terminus of a zwitterionic amino acid can intercalate clay layers similar to the aforementioned cationic surfactants. In embodiments, the amphoteric surfactant can include an amino acid selected from alanine, arginine, asparagine, aspartic acid (aspartate), cysteine, cystine, glutamic acid (glutamate), glutamine, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, or any combination thereof.

[0135] In a further aspect, the zwitterionic surfactant of the present disclosure has both a cationic moiety and an anionic moiety, or a center bonded to the same molecule. Examples of the cationic center of the zwitterionic surfactant include, or are selected from moieties including, primary amines, secondary amines, tertiary amines, or quaternary ammonium cations. Examples of the anionic center of the zwitterionic surfactant include, but are not limited to, sulfates, phosphonates, phosphates, or carboxylates.

[0136] In one aspect, the zwitterionic surfactant can include, or can be selected from, sultaines such as hydroxy sultaine compounds. Examples of sultaines include, but are not limited to, lauramidopropyl hydroxy sultaine (ISOTAINE LAPHS), cocoamidopropyl hydroxy sultaine (ISOTAINE CAPHS), oleamidopropyl hydroxy sultaine (ISOTAINE OAPHS), tallowamidopropyl hydroxy sultaine (ISOTAINE TAPHS), erucamidopropyl hydroxy sultaine (ISOTAINE EAPHS), and lauryl hydroxy sultaine (ISOTAINE LHS).

[0137] In another aspect, the zwitterionic surfactant can include, or can be selected from, betaines including the simple betaine N,N,N-trimethylglycine. Other examples of betaines that can be used in accordance with the present disclosure include cocoamidopropyl betaine.

[0138] A further aspect provides zwitterionic surfactants that can include, or can be selected from, biological zwitterionic surfactants such as compounds having a phosphate anion having an amine moiety or ammonium moiety within the same molecule, examples of which include phospholipids, phosphatidylserine, phosphatidylethanolamine, phosphatidylcholine, and sphingomyelin.

[0139] In an embodiment, it can contain or can be selected from amino - N - oxides such as quaternary amine N - oxide. Examples include lauryldimethylamine oxide, myristamine oxide, pyridine - N - oxide, and N - methylmorpholine - N - oxide. The amphoteric surfactant of the present disclosure can contain or can be selected from hydrocarbylamine - N - oxides such as alkylamine - N - oxide or arylamine - N - oxide.

[0140] In a further aspect, the amphoteric surfactant can contain or can be selected from CHAPS, which is 3 - [(3 - colamidopropyl)dimethylammonio]-1 - propane sulfonate, also known as 3 - {dimethyl[3 - (3α,7α,12α - trihydroxy - 5β - cholan - 24 - amide)propyl]azaniumyl}propane - 1 - sulfonate.

[0141] An anionic surfactant. In a further aspect, the smectite adducts described herein are prepared by contacting, in a first liquid carrier, (a) a colloidal smectite clay with (b) a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or any combination thereof, to provide a slurry of the smectite adduct in the first liquid carrier, and the contacting step further comprises contacting the colloidal smectite clay or the smectite adduct with an anionic surfactant before, during, or after contacting the colloidal smectite clay with the cationic surfactant, nonionic surfactant, amphoteric surfactant, or a combination thereof. In one aspect, a smectite adduct formed from a smectite clay and a cationic surfactant, nonionic surfactant, and / or amphoteric surfactant can subsequently be contacted with an anionic surfactant. For example, the contact product of a colloidal smectite clay and a cationic surfactant can be further contacted with an anionic surfactant before optionally isolating the adduct or before spray drying the slurry of the adduct. In another aspect, the anionic surfactant can be used to contact the clay simultaneously with the cationic surfactant when forming the adduct. Without intending to be bound by theory, it is believed that the use of the anionic surfactant can enhance the ease of drying of the smectite adduct.

[0142] In this aspect, the anionic surfactants used in accordance with the present disclosure can include, or can be selected from, sulfate surfactants, sulfonate surfactants, phosphate surfactants, carboxylate surfactants, or other anionic surfactants. Examples of these include, but are not limited to, dialkyl sulfocarboxylic acid esters, alkyl sulfonates, aralkyl sulfonates, alkyl sulfonates, aryl sulfonates, sulfosuccinates, fatty acid alkali salts, polycarboxylates, polyoxyethylene alkyl ether phosphate ester salts, alkyl naphthalene sulfonates, and the salts can be selected from alkali metals such as lithium, sodium, or potassium, alkaline earth metals such as calcium or magnesium, or salts of ammonium or hydrocarbyl ammonium.

[0143] Further aspects and embodiments of the anionic surfactant include, but are not limited to, alkyl ether sulfate compounds or alkenyl ether sulfate compounds having the formula [RO(C2H4O) x SO3]M, wherein R is a C8 - C 20 alkyl group or a C8 - C 20It is an alkenyl group, x is an integer from 1 to 30 (including both ends), and M is a cation that imparts water solubility to alkyl ether sulfate or alkenyl ether sulfate. Embodiments of alkyl ether sulfate useful in the present disclosure include condensation products of ethylene oxide and a monohydric alcohol having 8 to 20 carbon atoms, for example, about 14 to about 18 carbon atoms. The monohydric alcohol can be derived from natural sources (e.g., fats, coconut oil, or tallow), or they can be synthetic. Lauryl alcohol (dodecanol) and linear alcohols derived from tallow are examples of useful alcohols. When such an alcohol is reacted with ethylene oxide using a proportion of ethylene oxide of about 1 to about 30 moles, for example, about 6 moles of ethylene oxide, the resulting mixture of molecular species can have an average of about 6 moles of ethylene oxide per mole of alcohol, can be sulfated and neutralized, and can be used as an alkyl ether sulfate.

[0144] In other embodiments, the anionic surfactant can include or be selected from carboxylate compounds having the formula [RCOO]M, wherein R is a C8-C 21 alkyl group and M is a cation selected from sodium, potassium, or ammonium.

[0145] According to another embodiment, the anionic surfactant (a) a sulfonate compound having the formula R'SO3Na, wherein R' is a C8-C 21 alkyl group, a C8-C 21 aralkyl group, or a C8-C 21 alkaryl group, the sulfonate compound, or (b) an alkyl sulfate having the formula R"OSO3M, wherein R" is a C8-C 21 alkyl group and M is NH4 + , Na + , K + , 1 / 2Mg 2+An alkyl sulfate, which is a cation selected from diethanolammonium or triethanolammonium, can be included or can be selected therefrom.

[0146] In another aspect, the anionic surfactant according to the present disclosure can include or can be selected from a sulfated polyoxyethylene alkylphenol having the formula R”C6H4(OCH2CH2) n OSO3M, wherein R” is a C1-C9 alkyl group, M is NH4 + Na + or triethanolamine, and n is an integer from 1 to 50 (inclusive).

[0147] Embodiments of the anionic surfactant of the present disclosure are (a) an alkyl sulfate having the formula [(R 1 O)SO2O]M, (b) an alkyl sulfonate having the formula [R 1 SO2O]M, (c) an alkyl sulfinate having the formula [R 1 S(O)O]M, (d) a sulfated polyoxyalkylene having the formula [R 1 (OCH2CH2) n OSO2O]M or [R 1 (OCH2C(CH3)CH2) n OSO2O]M, or (e) a sulfonated polyoxyalkylene having the formula [R 1 (OCH2CH2) n SO2O]M or [R 1 (OCH2C(CH3)CH2) n SO2O]M, can be included or can be selected therefrom, wherein R 1 is independently selected from substituted or unsubstituted C1-C 25 alkyl-, C6-C 25 aryl-, C7-C 25 aralkyl-, or C7-C 25 alkaryl. M is NH4 + , Na + , K + , 1 / 2Mg 2+ , a cation such as diethanolammonium or triethanolammonium, and n is an integer from 1 to 50.

[0148] In another aspect, the anionic surfactant can include, or can be selected from, alkali metal salts of fatty acids having from about 8 to about 30 carbon atoms. In embodiments, the anionic surfactant can include, or can be selected from, alkali metal salts of fatty acids selected from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, ricinoleic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolenic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid, or any combination thereof.

[0149] According to other embodiments, the anionic surfactant can include, or can be selected from, potassium oleate, dodecylbenzenesulfonic acid, dioctylsulfonic acid, sodium laurylsulfonate, sodium stearate, sodium lauryl sulfate, sodium myristyl sulfate, potassium lauryl sulfate, ammonium lauryl sulfate, triethanolamine lauryl sulfate, sodium cetyl sulfate, sodium stearyl sulfate, sodium polyoxyethylene (POE) lauryl ether sulfate, POE lauryl ether triethanolamine sulfate, POE lauryl ether ammonium sulfate, sodium POE stearyl ether sulfate, sodium stearoyl methyl taurate, triethanolamine dodecylbenzenesulfonic acid, sodium tetradecenesulfonate, sodium lauryl phosphate, or any combination thereof.

[0150] In a further aspect, the anionic surfactant is (a) a substituted or unsubstituted alkyl sulfonate selected from methanesulfonate, ethanesulfonate, 1-propanesulfonate, 2-propanesulfonate, 3-methylbutanesulfonate, trifluoromethanesulfonate, trichloromethanesulfonate, chloromethanesulfonate, 1-hydroxyethanesulfonate, 2-hydroxy-2-propanesulfonate, 1-methoxy-2-propanesulfonate, or any combination thereof, (b) a substituted or unsubstituted alkyl sulfate selected from methyl sulfate, ethyl sulfate, 1-propyl sulfate, 2-propyl sulfate, 3-methylbutyl sulfate, trifluoromethanesulfate, trichloromethyl sulfate, chloromethyl sulfate, 1-hydroxyethyl sulfate, 2-hydroxy-2-propyl sulfate, 1-methoxy-2-propyl sulfate, or any combination thereof, (c) a substituted or unsubstituted aryl sulfonate selected from benzenesulfonate, naphthalenesulfonate, p-toluenesulfonate, m-toluenesulfonate, 3,5-xylenesulfonate, trifluoromethoxybenzenesulfonate, trichloro-methoxybenzenesulfonate, trifluoromethylbenzenesulfonate, trichloromethylbenzenesulfonate, fluorobenzenesulfonate, chlorobenzenesulfonate, 1-hydroxyethane-benzenesulfonate, 3-fluoro-4-methoxybenzenesulfonate, or any combination thereof, or (d) any combination thereof, or can include or be selected from them.

[0151] Examples of anionic surfactants that can be used in accordance with the present disclosure include sulfates, sulfonates, phosphates, carboxylates, or other anionic surfactants, and examples thereof include, but are not limited to, dialkylsulfocarboxylic acid esters, alkylaryl sulfonates, alkyl sulfonates, sulfosuccinic acid esters, fatty acid alkali salts, polycarboxylates, polyoxyethylene alkyl ether phosphate ester salts, alkylnaphthalene sulfonates, and the salts can be selected from alkali metals such as lithium, sodium or potassium, alkaline earth metals such as calcium or magnesium, or salts of ammonium or hydrocarbylammonium.

[0152] In an embodiment, the anionic surfactant includes sulfates, phosphonates, phosphates, or carboxylates, and other anionic functional moieties as described herein. In one embodiment, the anionic surfactant further includes a counterion, examples of which include NH4 + 、Na + 、K + 、1 / 2Mg 2+ 、diethanolammonium, or triethanolammonium, but are not limited thereto.

[0153] E. Cationic polymethalate In addition to the "Definition" section and the embodiments of the present disclosure, the following additional information further describes the cationic polymethalate.

[0154] As described in the Definitions section, the term "polymetallate" and similar terms such as "polyoxometallate" refer to polyatomic cations containing two or more metals (e.g., aluminum, silicon, titanium, zirconium, or other metals) together with at least one bridging ligand between the metals such as oxo, hydroxy and / or halide ligands. For example, a polymetallate can be a hydrated metal oxide, a hydrated metal oxoacid, etc., and can include bridging ligands such as oxo ligands capable of bridging two or more metals in these species, and can also include terminal oxo, hydroxyl, and / or halide ligands. Many polymetallate species are anionic, and the suffix "-ate" is often used to reflect the anionic species, but the polymetallate (polyoxometallate) compounds used according to the present disclosure are cationic.

[0155] The hetero-coagulating reagents of the present disclosure can be positively charged species that, when combined with a colloidal suspension of clay in an appropriate ratio, readily form a coagulum that is easily filtered and easily washed. Examples of positively charged species include soluble polyoxometallates, polyhydroxylmetallates, and polyoxohydroxymetallate cations, and related cations that are partially halide-substituted, such as polyaluminum oxyhydroxychloride or aluminum chlorohydrate or polyaluminum chloride species that are linear, cyclic, or cluster compounds. These compounds are collectively referred to as polymetallates. The latter aluminum compounds can contain from about 2 to about 30 aluminum atoms.

[0156] Useful hetero - coagulation reagents can also include any colloidal species characterized by a positive zeta potential when dispersed in an aqueous solvent or in a mixed aqueous and organic solvent (e.g., alcohol). For example, a useful dispersion of a hetero - coagulation reagent can exhibit a zeta potential greater than (>)+20 mV (greater than positive 20 mV), greater than +25 mV, or greater than +30 mV. The starting colloidal clay can contain monovalent ions or species such as protons, lithium ions, sodium ions, or potassium ions, but at least a portion of these ions can be replaced by the hetero - coagulation reagent during the formation of an easily filterable clay adduct.

[0157] In one aspect, the cationic polymetallate hetero - coagulation reagent can include a colloidal suspension of boehmite (aluminum hydroxide oxide) that gives a positive zeta potential (e.g., fumed alumina), or a metal oxide such as a fumed metal oxide. In another aspect, the hetero - coagulation reagent can include a chemically modified or treated metal oxide, e.g., fumed silica treated with aluminum chlorohydrate, such that when in suspension, the chemically treated metal oxide gives a positive zeta potential as described below. In a further aspect, the hetero - coagulation reagent is produced by treating a metal oxide or metal oxide hydroxide, etc. with a reagent in a fluidized bed, resulting in a positive zeta potential when the reagent is dispersed in a suspension. The hetero - coagulant can exhibit a positive value exceeding +20 mV prior to combination with the phyllosilicate clay component.

[0158] In one aspect, the cationic polymetallate is present in an amount sufficient to provide a colloidal suspension of a chemically treated first metal oxide having a positive zeta potential, e.g., a zeta potential greater than +20 mV (millivolts), and can include a first metal oxide chemically treated with a second metal oxide, a metal halide, a metal oxyhalide, or a combination thereof. That is, the chemically treated first metal oxide is a contact product of the first metal oxide with [1] a second metal oxide, i.e., another different metal oxide, [2] a metal halide, [3] a metal oxyhalide, or [4] a combination thereof. For example, the first metal oxide to be chemically treated can include fumed silica, fumed alumina, fumed silica-alumina, fumed magnesia, fumed zinc oxide, fumed titania, fumed zirconia, fumed ceria, etc., or any combination thereof. The second metal oxide, metal halide, or metal oxyhalide can be obtained from an aqueous solution or suspension of a metal oxide, hydroxide, oxyhalide, or halide such as ZrOCl2, ZnO, NbOCl3, B(OH)3, AlCl3, or a combination thereof. For example, the treatment can consist of dispersing the fumed oxide in a solution of aluminum chlorohydrate. In the case of fumed silica, which can exhibit a negative zeta potential in suspension, after treatment with aluminum chlorohydrate, the suspension of the chemically treated fumed silica exhibits a positive zeta potential greater than about +20 mV.

[0159] In another aspect, the cationic polymetallate composition can include, or can be selected from, [1] fumed silica, fumed alumina, fumed silica alumina, fumed magnesia, fumed zinc oxide, fumed titania, fumed zirconia, fumed ceria, or any combination thereof, and [2] is chemically treated with polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichlorohydrate, polyaluminum oxyhydroxy chloride, or any combination thereof. For example, the cationic polymetallate composition can include, or can be selected from, aluminum chlorohydrate-treated fumed silica, aluminum chlorohydrate-treated fumed alumina, aluminum chlorohydrate-treated fumed silica alumina, or any combination thereof. Some fumed metal oxides, such as fumed alumina, may already exhibit a positive zeta potential prior to chemical treatment. Nevertheless, fumed metal oxides that do not have a zeta potential, or that have a positive zeta potential of less than about +20 mV, may be chemically treated with a species such as aluminum chlorohydrate, and after treatment, a colloidal suspension having a zeta potential of greater than about +20 mV can be obtained.

[0160] In another aspect, the hetero-coagulation reagent can include a fuming process, or a mixture of metal oxides formed after a fuming process, that exhibits a positive zeta potential due to its composition. An example of this type of fumed oxide is fumed silica alumina.

[0161] In another embodiment, the hetero-coagulation reagent may include any colloidal inorganic oxide particles as described by U.S. Patent No. 4,637,992 to Lewis, et al., which is incorporated herein by reference, such as colloidal ceria or colloidal zirconia, or any positively charged colloidal metal oxide disclosed therein. In another aspect, the hetero-coagulation reagent may include magnetite or ferrihydrite. For example, cationic polymetallate can include, or be selected from, boehmite, fumed silica alumina, colloidal ceria, colloidal zirconia, magnetite, ferrihydrite, any positively charged colloidal metal oxide, or any combination thereof.

[0162] In another aspect, the hetero-coagulation reagent can include cationic oligomers or polymeric aluminum species in solution, such as aluminum chlorohydrate, also known as aluminum chlorohydrate (ACH), polyaluminum chloride (PAC), aluminum sesquichlorohydrate, or any combination or mixture thereof. For example, the cationic polymetallate hetero-coagulation reagent can include, or be selected from, the following empirical formula: Al2(OH) n Cl m (H2O) x 、 (where n + m = 6 and x is a number from 0 to about 4), or be selected from them. In one aspect, the cationic polymetallate can include, or be selected from, aluminum species having the formula [AlO4(Al 12 (OH) 24 (H2O) 20 7+ which is a so-called "Al 13 -mer" polycation and is considered a precursor of Al 13 pillared clay.

[0163] ​When using aluminum chlorohydrate as a hetero - coagulation reagent or chemical treatment reagent for treating other metal oxides, commercially available aluminum chlorohydrate (ACH) solutions or solid powders can be utilized. Aluminum chlorohydrate solutions are referred to as polymeric cationic hydroxyaluminum complexes or aluminum chlorohydrate hydroxides and refer to polymers formed from monomeric precursors having the general empirical formula 0.5[Al2(OH)5Cl(H2O)2]. The preparation of aluminum chlorohydrate solutions is described in U.S. Patent Nos. 2,196,016 and 4,176,090, which are incorporated herein by reference, and can include treating aluminum metal in an amount to produce a composition having the above formula with hydrochloric acid.

[0164] Alternatively, aluminum chlorohydrate solutions can be obtained using various aluminum sources such as alumina (Al2O3), aluminum nitrate, aluminum chloride or other aluminum salts, and treatment with acids or bases. A number of species that can be present in such solutions, for example, the tridecameric [AlO4(Al 12 (OH) 24 (H2O) 20 7+ (Al 13 -mer) polycations are described in Perry and Shafran, Journal of Inorganic Biochemistry, 2001, 87, 115 - 124, which is incorporated herein by reference. The species disclosed in this study can be used, either individually or in combination, as cationic polymetallates for the hetero - coagulation of smectite clays for the species present in such solutions.

[0165] ​In one aspect, the aqueous aluminum chlorohydrate solution used in accordance with the present disclosure can have an aluminum content calculated or expressed as weight percent of Al2O3 in the range of about 15 wt% to about 55 wt%, although more diluted concentrations can be used. The use of a more dilute solution can be accompanied by adjustments of other reaction conditions such as time and temperature, as will be understood by those skilled in the art. The alternative aluminum concentration in an aqueous aluminum polymetallate solution, such as an aqueous aluminum chlorohydrate solution, expressed as weight percent of Al2O3 can be about 0.1 wt% to about 55 wt% Al2O3, about 0.5 wt% to about 50 wt% Al2O3, about 1 wt% to about 45 wt% Al2O3, about 2 wt% to about 40 wt% Al2O3, about 3 wt% to about 37 wt% Al2O3, about 4 wt% to about 35 wt% Al2O3, about 5 wt% to about 30 wt% Al2O3, or about 8 wt% to about 25 wt% Al2O3, and each range includes all individual concentrations expressed in tenths (0.1) of the weight percent included therein, including any subranges therein. For example, the recitation of about 0.1 wt% to about 30 wt% Al2O3 includes the recitation of 10.1 wt% to 26.5 wt% Al2O3. Conveniently, solid polymetallate as solid aluminum chlorohydrate can be used and added to a slurry of colloidal clay when preparing the heteroagglomerate. Accordingly, the concentrations disclosed above are not limiting but rather exemplary.

[0166] In one aspect, the cationic polymetallate can include or can be selected from oligomers prepared by copolymerizing (co-oligomerizing) a soluble rare earth salt with a cationic metal complex of at least one additional metal selected from aluminum, zirconium, chromium, iron, or combinations thereof, in accordance with U.S. Patent No. 5,059,568, which is incorporated herein by reference. For example, at least one rare earth metal can be cerium, lanthanum, or combinations thereof. In one aspect, the heteroagglomeration reagent is a lanthanide and Al as described by McCauley in U.S. Patent No. 5,059,568 13It can contain an aqueous solution of Keggin ions. However, the fired clay heteroadditives of the present disclosure prepared using McCaulay-type polymetallates do not provide a uniform intercalation structure with an interlayer spacing exceeding 13 Å (angstrom). Without wishing to be bound by theory, this observation is thought to result from a much smaller amount of the Ce-Al hetero-coagulating reagent to colloidal clay ratio used in accordance with the present disclosure. This smaller amount results from conditions that bring the smectite clay into contact with the hetero-coagulating reagent in an amount sufficient to provide a slurry of the smectite heteroadditive having a zeta potential in the range of about +25 mV (millivolt) to about -25 mV.

[0167] In a further aspect, an exemplary polymetallate of the present disclosure can include [1] an ε-Keggin cation [ε-PMo 12 O 36 (OH)4{Ln(H2O)4}4] 5+ (wherein Ln can be La, Ce, Nd, or Sm), and [2] a lanthanide-containing cationic heteropolytungstovanadium cluster having the general formula [Ln2V 12 O 32 (H2O)8{Cl}]Cl (wherein Ln can be Eu, Gd, Dy, Tb, Ho, or Er).

[0168] In another aspect, the hetero-coagulant can be a layered double hydroxide, such as aluminum magnesium hydroxide nitrate as described by Abend et al., Colloid Polym. Sci. 1998, 276, 730 - 731, or synthetic hematite, hydrotalcite, or other positively charged layered double hydroxides including but not limited to those described in U.S. Patent No. 9,616,412 incorporated herein by reference. Thus, the cationic polymetallate used as the hetero-coagulant can be a layered double hydroxide or a mixed metal layered hydroxide. For example, the mixed metal layer hydroxide can be selected from Ni - Al, Mg - Al, or Zn - Cr - Al types having a positive layer charge. In another aspect, the layered double hydroxide or mixed metal layered hydroxide is aluminum magnesium hydroxide nitrate, aluminum magnesium hydroxide sulfate, aluminum magnesium hydroxide chloride, Mg x (Mg,Fe)3(Si,Al)4O 10 (OH)2(H2O)4 (where x is a number from 0 to 1, for example, about 0.33 for ferrosaponite), (Al,Mg)2Si4O 10 (OH)2(H2O)8, synthetic hematite, zinc white (basic zinc carbonate) Zn5(OH)6(CO3)2, hydrotalcite [Mg6Al2(OH) 16 CO3·4H2O, takovite [Ni6Al2(OH)6]CO3·4H2O, hydrocalumite [Ca2Al(OH)6]OH·6H2O, magaldrate [Mg 10 Al5(OH) 31 (SO4)2·mH2O, pyroaurite [Mg6Fe2(OH) 16 CO3·4.5H2O, ettringite [Ca6Al2(OH) 12 (SO4)3·26H2O, or any combination thereof, or can be selected from them.

[0169] In a further aspect, the hetero-coagulation reagent can contain an aqueous solution of Fe polycations as described by Oades, Clay and Clay Minerals, 1984, 32(1), 49 - 57 or as described by Cornell and Schwertmann in "The Iron Oxides: Structure, Properties, Reactions, Occurrences and Uses", 2003, Second Edition, Wiley VCH. The thionic polymetallate has the empirical formula FeO x (OH) y (H2O) z n+ (where 2× + y is (<) 3, z is a number from 0 to about 4, and n is a number from 1 to 3) can contain or can be selected from iron polycations having. The use of cations such as protons, lithium ions, sodium ions, or potassium ions does not result in clay hetero-adducts as provided by the cationic polymetallates of the present disclosure. For example, proton (acid) treated clays are generally not easily filterable.

[0170] In another aspect, the colloidal smectite clay can contain or can be selected from colloidal montmorillonites such as Volclay® HPM - 20 bentonite. The hetero - coagulation reagent can contain or can be selected from aluminum chlorohydrate, polyaluminum chloride, or aluminum sesquichlorohydrate.

[0171] According to one aspect, the cationic polymetallate can contain or can be selected from complexes of Formula I or Formula II according to the following formula, or any combination of complexes of Formula I or Formula II: [M(II) 1-x M(III) x (OH)2]A x / n ·mL (I) [LiAl2(OH)6]A​1 / n ·mL (II) wherein M(II) is at least one divalent metal ion, M(III) is at least one trivalent metal ion, A is at least one inorganic anion, L is an organic solvent or water, n is the valence of the inorganic anion A, or in the case of a plurality of anions A, their average valence, x is a number from 0.1 to 1, m is a number from 0 to 10. In this embodiment, M(II) can be zinc, calcium, strontium, barium, iron, cobalt, nickel, cadmium, manganese, copper, or magnesium, and independently, M(III) can be iron, chromium, manganese, bismuth, cerium, or aluminum, A can be, for example, bicarbonate, sulfate, nitrate, nitrite, phosphate, chloride, bromide, fluoride, hydroxide, or carbonate, n can be, for example, a number from 1 to 3, and L can be, for example, methanol, ethanol, or isopropanol, or water. In addition to this embodiment, the cationic polymetallate is selected from the complexes of formula I, wherein M(II) is magnesium, M(III) is aluminum, and A can be carbonate.

[0172] In one aspect, the cationic polymetallate can include polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichlorohydrate, or polyaluminum oxyhydroxychloride, or combinations thereof. In a further aspect, the cationic polymetallate can include, for example, linear, cyclic, or cluster aluminum compounds containing from 2 to 30 aluminum atoms. In a recipe for preparing a smectite adduct, the ratio of millimoles (mmol) of aluminum (Al) in polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichlorohydrate, or polyaluminum oxyhydroxychloride to grams (g) of colloidal smectite clay can be in the range of, for example, about 0.75 mmol Al / g clay to about 2.0 mmol Al / g clay, about 0.8 mmol Al / g clay to about 1.9 mmol Al / g clay, about 1.0 mmol Al / g clay to about 1.8 mmol Al / g clay, about 1.1 mmol Al / g clay to about 1.8 mmol Al / g clay, or about 1.1 mmol Al / g clay to about 1.7 mmol Al / g clay. Alternatively, per gram (g) of colloidal smectite clay in a recipe for preparing a smectite adduct, the millimoles (mmol) of aluminum (Al) in polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichlorohydrate, or polyaluminum oxyhydroxychloride can be, for example, about 0.75 mmol Al / g clay, about 0.8 mmol Al / g clay, about 0.9 mmol Al / g clay, about 1.0 mmol Al / g clay, about 1.1 mmol Al / g clay, about 1.2 mmol Al / g clay, about 1.3 mmol Al / g clay, about 1.4 mmol Al / g clay, about 1.5 mmol Al / g clay, about 1.6 mmol Al / g clay, about 1.7 mmol Al / g clay, about 1.8 mmol Al / g clay, about 1.9 mmol Al / g clay or about 2.0 mmol Al / g clay, including combinations of these ratios or any sub-ranges within that range.

[0173] In a further aspect, the ratio of millimoles (mmol) of aluminum (Al) in polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichlorohydrate, or polyaluminum hydroxy chloride to grams (g) of colloidal smectite clay or fired smectite adduct may be about 90% or less, about 80% or less, about 70% or less, about 60% or less, about 50% or less, about 45% or less, about 40% or less, or about 35% or less of the comparative ratio of millimoles of aluminum to grams of colloidal clay used in the preparation of pillared clay using the same colloidal smectite clay and hetero-coagulating reagent.

[0174] In this aspect, the ratio of aluminum uptake to clay in the pillaring recipe is expressed as mmol Al / g clay, which indicates the number of millimoles of Al in the aluminum chlorohydrate reagent and the number of grams of clay in the recipe. Specifically, this ratio reflects the ratio used in the synthetic recipe, not the ratio of the final pillared clay product. As an example, Al described in Ocelli, Clay and Clay Minerals, 2000, 48(2), 304 - 308 13 Considering the Al-type Keggin ions, the amount of Al used in the preparation of pillared clay far exceeds the amount of Al that is ultimately intercalated between the layers in the pillared clay solid. The use of excess aluminum reagent provides the maximum pillar content in the final product and is used to obtain the desired porosity and surface area of the final fired material. Kooli in Microporous and Mesoporous Materials; 2013, 167, 228 - 236 discloses that generally about 6 mmol Al / gram of clay is required in the recipe to optimize the pillar rings. Al 13 Recent scale-up studies and optimizations of the Al-Keggin ion pillar viscosities, Pergher and Bertella in Materials, 2017, 10, 712 disclose that 15 mmol Al / g clay and about 1 wt% dilution dispersion are required to obtain pillars with the desired basal spacing and surface area.

[0175] F. Preparation, Isolation, and Filtration of Clay-Heterocoagulants According to one aspect of the present disclosure, the surfactant reagent can be contacted with the clay by any means in a first liquid carrier. It has been found that adding the clay to the first liquid carrier, applying shear force to disperse the clay, and subsequently adding the surfactant to this dispersion functions well. The first liquid carrier can contain water or can be water, to which the clay is added, dispersed, and subsequently the surfactant is added. The surfactant reagent can be brought into contact with the clay dispersion by direct addition of the surfactant reagent in solid form or as a liquid directly to the slurry / dispersion of the clay, or by contacting a liquid mixture in which the reagent is dissolved or slurried in a suitable solvent with the clay slurry / dispersion. Solid clay can be added to a liquid surfactant or a liquid or solid surfactant dissolved or dispersed in a liquid carrier under high shear conditions, but more consistent results have been achieved by forming a well-dispersed clay suspension in the liquid carrier before adding the surfactant to the carrier.

[0176] The step of contacting the colloidal smectite clay with the heterocoagulant reagent can be carried out using high shear conditions obtained from high rpm (revolutions per minute), regardless of whether it is a surfactant, a cationic polymethalate, or a combination thereof, resulting in a dispersion without aggregation. On a laboratory scale, this can be achieved using a Waring® blender, and on an industrial scale, a Cowles-type mixer or other high-speed dispersion mixer can be used with a suitable mixing speed and, if necessary, a high shear impeller.

[0177] The smectite adduct can be prepared by contacting colloidal smectite clay and a surfactant in a "first" liquid carrier. Unless otherwise specified, the term "first" liquid carrier refers to the medium in which the smectite adduct is prepared, while the "second" liquid carrier refers to the medium in which the catalyst system is prepared by contacting the smectite adduct with a transition metal or a metallocene compound. An organic compound that can function as the first liquid carrier can also function as the second liquid carrier.

[0178] In one aspect, the first liquid carrier can comprise, consist essentially of, or be selected from water, an organic liquid, or a combination thereof. For example, the first liquid carrier can comprise, or consist essentially of, water, an alcohol, an ether, a ketone, an ester, or any combination thereof. In embodiments, the first liquid carrier can comprise, or consist essentially of, water, methanol, ethanol, n-propanol, isopropanol, n-butanol, diethyl ether, di-n-butyl ether, acetone, methyl acetate, ethyl acetate, or any combination thereof. For example, the first liquid carrier can be water in the absence of any organic liquid such that the colloidal smectite clay and the surfactant contact only in water.

[0179] In a further aspect, the step of contacting the colloidal smectite clay and the surfactant can include adding the surfactant in solid form or as a liquid directly to the mixture of colloidal smectite clay in the first liquid carrier, or adding a solution or slurry of the surfactant to the mixture of colloidal smectite clay in the first liquid carrier. When the smectite adduct is prepared by a process of contacting colloidal smectite clay, cationic polymethalate, and a surfactant, the contacting step is (a) Adding a surfactant and a cationic polymethacrylate to a colloidal smectite clay mixture in a first liquid carrier, either simultaneously or in any order, or (b) (1) Adding a cationic polymethacrylate to a colloidal smectite clay mixture in a first liquid carrier to form a smectite-cationic polymethacrylate heteroaddition product; (2) isolating the smectite-cationic polymethacrylate heteroaddition product; and (3) resuspending the smectite-cationic polymethacrylate heteroaddition product in a dispersion medium, wherein the surfactant is added to the dispersion medium before, during, or after the resuspending step.

[0180] In embodiments, the step of contacting the colloidal smectite clay with the surfactant and / or the cationic polymethacrylate can occur within a temperature range, for example, (i) from about 5°C to about 90°C, from about 10°C to about 50°C, or from about 15°C to about 30°C, or (ii) at about 5°C, about 10°C, about 15°C, about 20°C, about 25°C, about 30°C, about 35°C, about 40°C, about 45°C, about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, or any range between any of these temperatures.

[0181] Thus, the result of contacting the clay with the hetero-coagulation reagent in the first liquid carrier is the formation of a clay-heteroaddition product (or "hetero-coagulate"), regardless of whether a surfactant, a cationic polymethacrylate, or a combination thereof is used. Depending on the hetero-coagulation reagent, the clay-heteroaddition product can be referred to as a clay-surfactant heteroaddition product, a clay-cationic polymethacrylate-surfactant heteroaddition product, or a clay-cationic polymethacrylate hetero-coagulate when no surfactant is present. Once the clay heteroaddition product is formed, removal of salts and other soluble by-products of the hetero-coagulation preparation is easily achieved by isolating the hetero-coagulation product, washing the hetero-coagulate with water, and subsequently simple filtration to isolate the hetero-coagulate.

[0182] A method for producing a support activator comprising a smectite adduct can further include the step of (i) isolating the smectite adduct from a slurry in a first liquid carrier. Once isolated, the process can further include (ii) washing the smectite adduct with water, an organic liquid, or a combination thereof, and the process can further include (iii) drying or calcining the smectite adduct. Isolating the smectite adduct can include gravity filtering the slurry, vacuum filtering the slurry, subjecting the slurry to reduced pressure, heating the slurry, subjecting the slurry to rotary evaporation, sparging the slurry with a gas, or any combination thereof. The ease of isolating the smectite adduct by filtering the slurry from the contacting step provides advantages in their preparation and use as a support activator. Isolating the smectite adduct can include evaporating the first liquid carrier from the slurry to which an organic liquid azeotropic reagent has been added, or can include isolating the smectite adduct being performed in the absence of an azeotropic agent. In any case, the step of isolating the smectite adduct can be carried out without using ultrafiltration, centrifugation, or sedimentation tanks.

[0183] Once isolated, the smectite adduct can be washed, resuspended in a liquid carrier and filtered again, and resuspended in a dispersion medium before spray drying or the like. For example, a method of manufacturing a support activator can further include the steps of resuspending a smectite adduct in water, an organic liquid, or a combination thereof to form a suspension, and evaporating water from the suspension to isolate the smectite adduct or filtering the suspension to isolate the smectite adduct. The obtained smectite adduct can be washed with water, an organic liquid, or a combination thereof and re-isolated. In one aspect, the method can further include the step of measuring the conductivity of a suspension of the smectite adduct in water, and if the conductivity exceeds 300 μS / cm, washing the smectite adduct and filtering the suspension to provide a washed smectite adduct is repeated.

[0184] The isolated smectite adduct can then be dried or calcined. For example, drying the smectite adduct can be carried out by an azeotropic process or by a spray drying process. Drying or calcining the smectite adduct can also occur by heating the smectite adduct in air, an inert atmosphere, under vacuum, or a combination of these methods.

[0185] In one aspect, the heteroagglomerate solid can be dried with an azeotropic agent as needed. Suitable azeotropic agents can include, but are not limited to, ethanol, 1-propanol, 1-butanol, 2-butanol, benzene, or acetonitrile. In one aspect, the azeotropic agent can be combined with water by any means, such as before or after addition to the heteroagglomerate solid.

[0186] In another aspect, the product can be directly achieved up to a subsequent calcination / drying step without the addition of an azeotropic agent. This method enables the drying step to be carried out in the absence of an organic solvent and constitutes an advantageous embodiment as it provides substantial economic and safety benefits.

[0187] In one aspect, the shaping of the clay-surfactant heteroagglomerate, i.e., changing or fixing / setting the shape of the heteroagglomerate, can be carried out by granulating, pulverizing, or classifying before firing. That is, an ion-exchange layered clay (aluminosilicate) having a pre-treated shape can be subjected to a chemical treatment. Alternatively, the clay-surfactant heteroagglomerate can be subjected to shape treatment after firing. The treatment can occur before or after chemical treatment with an optional co-catalyst such as an organoaluminum compound and / or treatment with a polymerization catalyst.

[0188] In one aspect, the shape of the clay-surfactant heteroagglomerate can be changed or fixed / set by a method referred to as the "granulation" method. Examples of granulation methods that can be used include, but are not limited to, a stirring granulation process, a spray (spray drying) granulation process, a rolling granulation process, a pulverization granulation process, a briquetting granulation process, a compression granulation process, an extrusion granulation process, a fluidized bed granulation process, an emulsification granulation process, a suspension granulation process, a press molding granulation process, etc. In another aspect, granulation methods that function well according to the present disclosure include a stirring granulation process, a spray granulation process, a rolling granulation process, and a fluidized granulation process, but the granulation method is not limited to these specific processes.

[0189] The clay-surfactant heteroaddition prepared in slurry form according to the present disclosure, for example, prepared using the same smectite clay and a cationic polymethalate heteroagglomeration reagent, unexpectedly showed improved ease of isolation compared to columnar clay in different amounts. Specifically, the clay heteroaddition, unlike columnar clay, can be easily isolated by filtration.

[0190] One way to evaluate the filterability of the heteroagglomerated clay-surfactant slurry is to determine whether the heteroagglomerate is "easily filterable" by comparing the filtrate collected from the slurry of the heteroaddition with the aqueous carrier in the initial slurry. In one aspect, the slurry of the clay-surfactant heteroaddition has the following filtration behavior: (a) When the filtration of a 2.0 wt% aqueous slurry of the smectite adduct starts 0 to 2 hours after the colloidal smectite clay and the surfactant form a contact product, the proportion of the filtrate obtained with a filtration time of 2 to 12 hours using either vacuum filtration or gravity filtration is, based on the weight of the first liquid carrier in the slurry of the smectite adduct, (i) about 30 wt% to about 100 wt% of the first liquid carrier in the slurry before filtration, i.e., the initial slurry water weight, (ii) about 40 wt% to about 100 wt% of the first liquid carrier in the slurry, (iii) about 50 wt% to about 100 wt% of the first liquid carrier in the slurry, or (iv) within the range of about 60 wt% to about 100 wt% of the first liquid carrier in the slurry before filtration, and (b) when the filtrate from the adduct slurry, upon evaporation, gives a solid containing less than 20%, less than 15%, or less than 10% of the initial total weight of the smectite clay and the surfactant, it is characterized by being easily and smoothly filterable. A small amount of water can be added to the slurry for additional washing and recovery of the excess slurry. Although it is specified that filtration is carried out 0 to 2 hours after initial formation, this is because some non - adduct slurries, including some columnar clay slurries, can be filtered more easily after the slurry has been given an initial settling period of several days, and this filterability is not considered "easily filterable" according to these criteria.

[0191] In the present disclosure, the clay - surfactant adduct slurry could be filtered using a 20 - micron filter within minutes after the step of contacting the colloidal clay and the surfactant. In most cases, essentially all of the water from the adduct slurry was filtered at a 10 - minute level after starting vacuum filtration. In contrast, essentially none of the water from a similar columnar clay slurry could be filtered at 10 minutes after starting vacuum filtration.

[0192] By evaluating "easily filterable" using the combination of the two features listed above, it is not necessary to specify either the filter interval (e.g., 20 μm) or whether the filtration was performed by gravity filtration or vacuum filtration. That is, a filter with a specified aperture size can be easily identified by one of ordinary skill in the art. For example, a 20 μm filter used in the examples allows clay heteroadditives to meet both of these criteria, while any filter size does not allow columnar clay to meet both of these criteria.

[0193] As an example of applying this "easily filterable" test, when using a filter with an opening between the filter media that is too large such that the columnar clay filtration meets the requirements of part (a) of the above criteria, it fails part (b) and is not considered easily filterable. When using such a large filter size, the clay heteroadditive also fails part [b], but by reducing the filter size (e.g., to about 20 μm), the clay heteroadditive can meet both criteria (a) and (b), while the pillar-shaped clay fails part (a) when the filter size is reduced. This is because the filter becomes clogged and little or no liquid carrier is filtered.

[0194] Similarly, either gravity filtration or vacuum filtration can be used in the "easily filterable" test. Because at the specified time point of the filtrate measurement (10 minutes after the start of filtration), the appropriate filter size can be easily identified by one of ordinary skill in the art that allows the clay heteroadditive to meet both criteria (a) and (b), while the columnar clay fails at least one of criteria (a) and (b).

[0195] G. Spray drying and firing of smectite clay heteroadditives Once the smectite heteroadditive has been isolated, the method for producing the support activator is Suspending a smectite adduct in a dispersion medium to provide a suspension of the smectite adduct in the dispersion medium; It can further include spray drying the smectite adduct from the suspension to provide the support activator in particulate form. Examples of dispersion media used in the starting slurry to be sprayed include water, organic liquids, or combinations thereof. For example, water alone can be used as the dispersion medium for spray drying, which can be advantageous from a cost and environmental perspective. Examples of organic liquids (sometimes referred to herein as organic solvents even if the clay adduct is not soluble therein) that can be used alone or in combination with water include, but are not limited to, methanol, ethanol, i-propanol, n-propanol, n-butanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, xylene, etc., and mixtures thereof are included. In one aspect, water is used as the dispersion medium in the absence of an organic liquid. In one aspect, the dispersion medium can include or can consist essentially of water, an organic liquid, or a combination thereof, but one substantial advantage of this process is the ability to spray dry the smectite heteroagglomerate from an aqueous slurry in the absence of an organic liquid to obtain highly spherical particles of the smectite heteroagglomerate. In embodiments, suspending the smectite adduct in the dispersion medium can occur under high shear conditions.

[0196] In one aspect, when the isolated smectite adduct is suspended in a dispersion medium to obtain a spray-dried dispersion (since the smectite adduct itself is isolated from the suspension, sometimes referred to herein as the "resuspending" step), the smectite adduct can be maintained in the dispersion medium suspension during the period prior to spray drying. Without intending to be bound by theory, it has been found that improved processing of the smectite adduct can be achieved if it is maintained in the dispersion medium suspension for some time. For example, prior to spray drying, the smectite adduct is in the dispersion medium, (i) from 0.1 hour to 72 hours, from 0.25 hour to 72 hours, from 1 hour to 72 hours, from 12 hours to 72 hours, from 18 hours to 72 hours, or from 24 hours to 72 hours, (ii) from 0.1 hour to 48 hours, from 0.25 hour to 48 hours, from 1 hour to 48 hours, from 12 hours to 48 hours, from 18 hours to 48 hours, or from 24 hours to 48 hours, or (iii) can be suspended for a period of about 1 hour, about 2 hours, about 4 hours, about 6 hours, about 9 hours, about 12 hours, about 15 hours, about 18 hours, about 21 hours, about 24 hours, about 27 hours, or about 30 hours.

[0197] When using a spray or spray-drying granulation method, the concentration of the clay adduct in the starting slurry to be sprayed can be any concentration that provides a slurry that can be pumped. In one embodiment, the concentration of the clay adduct in the slurry to be sprayed is energy-efficient and high enough to provide a viable yield, but should not be so high that the slurry cannot be pumped using a spray-drying apparatus. For example, the concentration of the clay adduct in the starting slurry for spray granulation to produce spherical particles can be from 0.1 wt% to 70 wt%, from 1 wt% to 50 wt%, from 5 wt% to 30 wt%, or from 8 wt% to 25 wt%. For example, the concentration of the clay adduct in the starting slurry for spray granulation can be about 0.1 wt%, about 0.5 wt%, about 1 wt%, about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, about 12 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 35 wt%, about 40 wt%, about 45 wt%, about 50 wt%, about 55 wt%, about 60 wt%, about 65 wt%, or about 70 wt%, or any range between any of these concentrations. In one embodiment, the upper limit of the clay adduct concentration in the spray-dried slurry can be affected by the specific spray-drying apparatus and the mechanical limits of spray drying. In another embodiment, the lower limit of the clay adduct concentration in the spray-dried slurry can be affected by concentrations that are so low that insufficient evaporation occurs, leading to wet particles adhering to the spray-dryer surface, or that do not produce a desired form such as a spherical shape.

[0198] In another aspect, the inlet temperature of the hot air used in the spray granulation method to produce spherical particles can vary depending on the dispersion medium used. In one aspect, when spray drying a clay heteroaddition from a dispersion medium of only water, the inlet temperature of the hot air used for spray granulation can be 80°C to 260°C, 90°C to 250°C, or 100°C to 220°C. For example, when spray drying a clay heteroaddition from a dispersion medium of only water, the inlet temperature of the hot air can be about 80°C, about 90°C, about 100°C, about 110°C, about 120°C, about 130°C, about 140°C, about 150°C, about 160°C, about 170°C, about 180°C, about 190°C, about 200°C, about 210°C, about 220°C, about 230°C, about 240°C, about 250°C, about 260°C, or any range between any of these temperatures.

[0199] When the smectite heteroaddition is isolated or dried by any means, it can then be subjected to calcination to provide a calcined support activator that imparts activity to the polymerization catalyst. By calcining the smectite heterocoagulated solid by heating, it is further dried and prepared for further treatment with a metallocene pre-catalyst and optionally a co-catalyst and optionally a co-activator. This calcination heat treatment also sufficiently dries the clay heterocoagulate to impart high activity to the final catalyst. The calcination treatment can be carried out in an ambient atmosphere (ambient pressure air) or under various conditions that promote the removal of water.

[0200] In one aspect, the smectite adduct can be heated or calcined (a) under a non-dry ambient atmosphere (air) or (b) under a dry ambient atmosphere, where the dry ambient atmosphere includes air passing through a drying column or air having a relative humidity of from about 0% to about 60%. In another aspect, the smectite adduct can be heated or calcined under an inert atmosphere such as nitrogen or under vacuum. In a further aspect, the calcination can be carried out in a carbon monoxide atmosphere. Calcination in an atmosphere such as carbon monoxide can efficiently remove surface hydroxyls, enabling calcination to be achieved at a lower temperature than required in the ambient atmosphere, typically at least 100 °C, and helping to maintain pore volume and surface area during the surface dehydration period.

[0201] Calcination of the smectite adduct can be carried out, for example, by heating the smectite adduct in air, in an inert atmosphere, or under vacuum. In one aspect, the calcination can be carried out in a fluidized bed. In another aspect, the hetero-coagulated solid can be calcined by heating at a temperature from (i) 100 °C to 900 °C, 200 °C to 800 °C, 200 °C to 750 °C, 225 °C to 700 °C, 225 °C to 650 °C, 250 °C to 650 °C, 250 °C to 600 °C, 250 °C to 500 °C, 225 °C to 450 °C, or 200 °C to 400 °C, or (ii) about 100 °C, about 125 °C, about 150 °C, about 175 °C, about 200 °C, about 225 °C, about 250 °C, about 275 °C, about 300 °C, about 325 °C, about 350 °C, about 375 °C, about 400 °C, about 425 °C, about 450 °C, about 475 °C, about 500 °C, about 525 °C, about 550 °C, about 575 °C, about 600 °C, about 625 °C, about 650 °C, about 675 °C, about 700 °C, about 725 °C, about 750 °C, about 775 °C, about 800 °C, about 825 °C, about 850 °C, about 875 °C, about 900 °C, or any range between any of these temperatures.

[0202] In another aspect, the firing temperature can be selected from any single temperature, or the firing can typically be carried out over a range of at least two temperatures separated by at least 10°C, in the range of 110°C to 800°C. As described, when firing in an atmosphere such as carbon monoxide, the temperature used may be lower than the temperature used in ambient air, and / or the firing time may be shorter than when firing in ambient air.

[0203] In a further aspect, the firing can be carried out in an ambient atmosphere (air) or a dry ambient atmosphere (dry air) at a temperature of 110°C to, for example, about 200°C to 800°C, over a period of about 1 minute to about 100 hours. In embodiments, the clay adduct can be fired in ambient air or dry air at a temperature of about 225°C to about 700°C for a period of about 1 hour to about 10 hours, or at a temperature of about 250°C to about 500°C for a period of about 1 hour to about 10 hours.

[0204] In a further aspect, the smectite adduct can be fired using any one of the following conditions: (a) a temperature in the range of about 110°C to about 600°C and a period in the range of about 1 hour to about 10 hours, (b) a temperature in the range of about 150°C to about 500°C and a period in the range of about 1.5 hours to about 8 hours, or (c) a temperature in the range of about 200°C to about 450°C and a period in the range of about 2 hours to about 7 hours.

[0205] Without intending to be bound by theory, after firing, the fired hetero-coagulation product can be described as a continuous amorphous combination of clay and inorganic oxide particles and is very effective for activating metallocenes for olefin polymerization and can thus be considered to function as a support activator, also called an activator-support.

[0206] H. Characteristics of Clay Hetero-Coagulants Porosity and Particle Size. The hetero-coagulation of clay by the surfactant reagents described herein can provide a support activator having substantial porosity and enhance their activity as support activators for metallocenes. In one aspect, the calcined clay-surfactant adduct can exhibit a nitrogen adsorption / desorption BJH porosity of (i) 0.1 cc / g to 3.0 cc / g, 0.15 cc / g to 2.5 cc / g, 0.25 cc / g to 2.0 cc / g, or 0.5 cc / g to 1.8 cc / g, or (ii) about 0.10 cc / g, about 0.20 cc / g, about 0.30 cc / g, about 0.50 cc / g, about 0.75 cc / g, about 1.00 cc / g, about 1.25 cc / g, about 1.50 cc / g, about 1.75 cc / g, about 2.00 cc / g, about 2.25 cc / g, about 2.50 cc / g, about 2.75 cc / g, about 3.00 cc / g, about 3.25 cc / g, or about 3.50 cc / g. When combined with a metallocene such as bis(1-butyl-3-methylcyclopentadienyl)zirconium dichloride under polymerization reaction conditions, a clay hetero-adduct having a BJH porosity of <0.1 cc / g typically exhibits low polymerization activity, e.g., <200 gPE / g support activator / hour. Thus, a calcined clay-surfactant adduct having a low porosity of about 0.12 cc / g can be used in the polymerization process. In the present disclosure, the polymerization activity is measured using the term "g support activator" and refers to the grams of the calcined clay-surfactant adduct (or clay-surfactant-cationic polymethalate) used to produce the catalyst.

[0207] The preparation of fired hetero-coagulants that maintain substantial BJH porosity (≥0.1 cc / g) where the hetero-coagulant is dried as an aqueous slurry, without the addition of an azeotropic agent such as 1-butanol, 1-propanol, or other such organic liquids, has been a difficult problem. As discussed below, the data in Table 1 demonstrate this problem. Such a water-only spray drying process is highly desirable to improve the process economic viability and environmental sustainability compared to those that require an organic dispersion medium. Surprisingly, the present process enables spray drying from a water-only slurry, achieving the advantage of providing clay hetero-additives that maintain high porosity and activity after firing, characterized by a desirable highly spherical morphology that imparts excellent processing characteristics to the support activator, support catalyst, and resulting polymer.

[0208] Table 1 shows the property and polymerization data for clay-aluminum chlorohydrate (ACH) hetero-coagulants prepared in the absence of surfactant and dried by either an azeotropic or non-azeotropic process, fired to form a clay-ACH support activator. Runs 1-4 show that drying the clay-ACH support in an azeotropic mixture of 1-butanol and water, followed by firing, results in a high BJH porosity of greater than 0.25 cc / g. However, the fired clay-ACH hetero-additive of Run 5, dried as an aqueous slurry without the addition of 1-butanol or any organic liquid and then fired, has a low BJH porosity of 0.049 cc / g. The samples shown in Runs 1-4 also exhibit excellent polymerization activity (>2000 gPE / Table 2 g support activator / hour) when combined with bis(1-butyl-3-methylcyclopentadienyl) zirconium dichloride, while Run 5 exhibits minimal polymerization activity (<100 gPE / g support activator / hour) under similar conditions.

[0209] The data in Table 2 illustrate embodiments of the present disclosure. In one aspect, the addition of a surfactant to a clay dispersion in water and the evaporation of the aqueous slurry, without the addition of an azeotropic agent (such as 1-butanol, 1-propanol, or other organic solvents), followed by the firing of the clay adduct, produces a support activator having substantial BJH porosity as compared to fired clay prepared under similar conditions without surfactant species. For example, FIG. 25 provides the results of nitrogen adsorption / desorption BJH pore volume analysis of rotary evaporated and fired Volclay® HPM-20 montmorillonite clay prepared according to Example 1 by drying a 5 wt% dispersion of HPM-20. Specifically, this figure provides a plot of pore diameter (angstroms, Å) versus cumulative pore volume (cubic centimeters per gram, cc / g) for the clay only, prior to any adduct formation. The total BJH porosity of this sample is 0.06 cc / g. Thus, fired smectites such as the bentonite used in the present disclosure can have a BJH porosity of from about 0 cc / g to about 0.1 cc / g in the absence of surfactant reagents.

[0210] In contrast, embodiments of the clay-surfactant hetero-adduct support activators can have a BJH porosity greater than about 0.1 cc / g, e.g., 0.1 cc / g to over 0.3 cc / g. In other embodiments or aspects of the present disclosure, the BJH porosity of the clay-surfactant support activator can be from about 0.15 to 0.3 cc / g. Table 2 reports the porosity characteristics of such fired clay-surfactant hetero-coagulants having a BJH porosity of 0.1 cc / g to 0.3 cc / g, such as runs 2, 5, 7-14, and 18-21. Thus, the fired clay-surfactant hetero-coagulant is characterized by a BJH porosity that is about 150% (1.5×) to 200% (2×) of the BJH porosity of the corresponding fired clay lacking the surfactant, and can be characterized by a BJH porosity greater than 200% of the corresponding fired clay species lacking the surfactant. In embodiments, the spray-dried clay-surfactant support activator typically exhibits a BHJ porosity of a total BHJ porosity of approximately 0.1 to 0.3 cc / g, and there are some high-activity examples towards the lower limit of this porosity range, down to 0.12 cc / g. In contrast, the clay-ACH support activator can have a relatively high BJH porosity of about 0.5 to 0.7 cc / g.

[0211] The porosity of these clay-surfactant support activators can be compared to the porosity of other clay hetero-adducts. For example, as follows, tests were considered using only cationic polymethalate, only surfactant at different surfactant concentrations, and hetero-adducts (support activators) prepared using a combination of cationic polymethalate and surfactant.

[0212] The porosity data were obtained for a fired azeotrope-free (rotary-evaporated) clay-aluminum chlorohydrate (ACH)-surfactant hetero-adduct prepared according to Example 7-B2, and the hetero-coagulant was prepared by contacting the clay slurry with ACH and subsequently with 0.5 wt% trihexyltetradecylphosphonium bromide. The total BJH porosity of this type is 0.148 cc / g.

[0213] Porosity data was also obtained for a fired azeotropic (rotary evaporated) clay-surfactant heteroaddition prepared according to Example 13-B8, where the clay heterocoagulum was prepared by contacting the clay with 1 wt% tetrabutylammonium bromide (TBABr) in the absence of cationic polymethalate (0.62 mmol TBABr / g clay). The total BJH porosity of this type is 0.126 cc / g.

[0214] Porosity data was also obtained for a fired azeotropic (rotary evaporated) clay-surfactant heteroaddition prepared according to Example 14-B9, where the clay heterocoagulum was prepared by contacting the clay with 2 wt% tetrabutylammonium bromide in the absence of cationic polymethalate (clay). The total BJH porosity of this type is 0.162 cc / g.

[0215] In a further aspect, the measured BJH porosity of a fired heterocoagulant prepared by a combination of clay, surfactant, and an additional heterocoagulant such as aluminum chlorohydrate or polyaluminum chloride (cationic polymethalate) substantially exceeds the measured BJH porosity of a fired heterocoagulant prepared by a combination of clay and the additional heterocoagulant alone. As a baseline measurement, a fired azeotropic (rotary evaporated) clay heterocoagulum prepared by contacting the clay with an aqueous aluminum chlorohydrate (ACH) dispersion according to Example 5-A4 was found to have a total BJH porosity of 0.049 cc / g. However, when both cationic polymethalate and surfactant are used, the porosity can be substantially increased. This increase is shown by a fired azeotropic (rotary evaporated) clay-ACH-surfactant heteroaddition prepared according to Example 6-B1, where the fired clay heterocoagulum was prepared by contacting the clay with an aqueous aluminum chlorohydrate dispersion and 2 wt% tetraoctylammonium bromide. The total BJH porosity of this sample was found to be 0.287 cc / g.

[0216] In particular, fired hetero-coagulants prepared by the combination of clay and a surfactant (and optionally other hetero-coagulants such as aluminum chlorohydrate or polyaluminum chloride) can also exhibit high BJH porosity (>0.15 cc / g) even when pre-fired drying is carried out in the absence of an azeotropic agent. This unexpected result can be demonstrated, for example, in Table 2 (Run 2) and Table 3 (Runs 7 - 10). Thus, the addition of an azeotropic agent is not necessary to maintain the porosity of the clay-surfactant support. The ability to use pure water instead of an alcohol-water mixture (or other organic liquid with water) during the treatment of these support activators provides many practical economic and safety advantages in the use of these clay-surfactant supports.

[0217] The data in Table 2 also show that tetramethylammonium bromide in combination with clay provides a hetero-adduct with good activity, but that relatively high concentrations of tetramethylammonium bromide are usually required to achieve the desired activity. When using long-chain tetraalkylammonium, long-chain alkyltrimethylammonium, or long-chain alkylammonium surfactants in combination with smectite clay, excellent activity of the support activator is observed at lower relative surfactant concentrations.

[0218] In another aspect, the smectite clay adduct (heterocoagulate) can have an average particle size, for example, of 1 μm (micron) to 250 μm as a dried or fired average particle size. Unless otherwise stated, the particle sizes recited for the smectite clay adducts are for the dried or fired clay adduct particles measured as described herein. For example, the smectite clay adduct can have an average particle size of about 1 μm (micron), about 2 μm, about 3 μm, about 5 μm, about 7 μm, about 10 μm, about 12 μm, about 15 μm, about 18 μm, about 20 μm, about 25 μm, about 30 μm, about 35 μm, about 40 μm, about 45 μm, about 50 μm, about 55 μm, about 60 μm, about 65 μm, about 70 μm, about 75 μm, about 80 μm, about 85 μm, about 90 μm, about 95 μm, about 100 μm, about 110 μm, about 120 μm, about 125 μm, about 130 μm, about 140 μm, about 150 μm, about 160 μm, about 170 μm, about 175 μm, about 185 μm, about 200 μm, about 225 μm, or about 250 μm, or can have an average particle size within any range between these recited values. For example, the smectite clay adduct can have an average particle size of 1 μm (micron) to 250 μm, 2 μm to 125 μm, 3 μm to 100 μm, 5 μm to 150 μm, 5 μm to 80 μm, 7 μm to 70 μm, 10 μm to 100 μm, 10 μm to 60 μm, 15 μm to 80 μm, 15 μm to 50 μm, or 20 μm to 75 μm.

[0219] Zeta potential. The zeta potential of slurries of clay-surfactant adducts was measured as a function of the millimoles of surfactant added to slurries of smectite clay and compared to the zeta potential of slurries of clay-cationic polymethacrylate adducts. FIGS. 29 and 30 show zeta potential data for slurries of smectite clay titrated with aqueous solutions of tetrabutylammonium bromide and tetramethylammonium bromide, respectively, plotting the zeta potential of the slurry versus the millimoles of the specific tetraalkylammonium bromide added per gram of clay. mmol cation / g clay reflects the cumulative millimoles of the added tetraalkylammonium bromide aqueous solution.

[0220] As shown in these figures, surfactant titration never provides a zeta potential (in millivolts) that is zero or positive (+). In the tetrabutylammonium bromide titration (Figure 29), a zeta potential of approximately negative (-) 18 mV is the most positive potential observed, and in the tetramethylammonium bromide titration (Figure 30), a zeta potential of approximately negative (-) 43 mV is the most positive potential observed. When a slurry of smectite clay is titrated with an ammonium bromide solution (not shown), a zeta potential of approximately negative (-) 50 mV is the most positive potential observed. This behavior is in contrast to zeta potential titration using aluminum chlorohydrate as the titrant, where the zeta potential curve ranges from a negative (-) mV potential to a neutral to positive (+) mV potential as the amount of titrant increases.

[0221] The highest polymerization activity observed for smectite clay-tetraalkylammonium heteroadditives depends on the specific tetraalkylammonium surfactant used. For example, the highest polymerization activity observed for the smectite clay-tetrabutylammonium bromide heteroadditive occurs for those prepared using from about 1.25 mmol surfactant / g clay to about 2.5 mmol surfactant / g clay (see Table 2).

[0222] I. Powder XRD Structure of Spray-Dried Clay-Surfactant Heterocoagulants Powder XRD (X-ray diffraction) patterns of a series of spray-dried and calcined products are shown in FIGS. 26-28. These samples were not dried by azeotropic or non-azeotropic rotary evaporation of the liquid carrier, but rather the samples were spray-dried and calcined. FIG. 26 shows the powder XRD of a product calcined and spray-dried from a combination of Volclay® HPM-20 montmorillonite clay and tetramethylammonium bromide (TMABr) in the absence of cationic polymethalate, as in Example 21-E1. FIG. 27 shows the powder XRD pattern of a product calcined and spray-dried from a combination of Volclay® HPM-20 montmorillonite and tetrabutylammonium bromide (TBABr) in the absence of cationic polymethalate, according to Example 22-E2. FIG. 28 shows the powder XRD of a product calcined and spray-dried from a combination of Volclay® HPM-20 montmorillonite clay and aluminum chlorohydrate (ACH) in the absence of surfactant, according to Comparative Example 20-D1. In these XRD patterns, the peaks in the range of 20-30 degrees two-theta (2θ) (20-30° 2θ) arise from mineral impurities present in the starting colloidal clay.

[0223] In contrast to other clay-based materials such as those described by Jensen et al. in U.S. Patent Application Publication Nos. 2018 / 0142047 and 2018 / 0142048 (assigned to W.R. Grace), and those described in International Publication No. 2021 / 154204, the clay-surfactant heteroagglomerates of the present disclosure can exhibit a substantial d001 peak at 6-9 degrees two-theta (2θ) (6-9° 2θ), e.g., 7-8 degrees two-theta (2θ) (7-8° 2θ), in a powder XRD scan after filtration and calcination at 300° C. or higher. This feature is shown in the examples of FIGS. 26 and 27, which show the powder XRD patterns of spray-dried and calcined products obtained by combining either tetramethylammonium bromide (FIG. 26) or tetrabutylammonium bromide (FIG. 27) with Volclay® HPM-20 montmorillonite, respectively, and the samples differ only in the tetraalkylammonium surfactant used.

[0224] These features are in contrast to fired columnar adducts consisting of clay and aluminum chlorohydrate (where the aluminum chlorohydrate is added to the clay at a molar ratio exceeding 6 mmol Al / g clay) and tend to have a substantial d001 peak clearly defined at 4 - 6 degrees 2θ (4 - 6° 2θ) in a powder XRD scan. They are also different from cationic polymetallate - hetero adducts such as those prepared using aluminum chlorohydrate (ACH) and montmorillonite according to Comparative Example 20 - D1, the powder XRD scan of which is provided in FIG. 28. In this hetero adduct, the powder XRD shows little or virtually no columnarization (peak at 4.8 degrees 2θ - 5.2 degrees 2θ) compared to the mineral impurities present in the starting colloidal clay in the 2 - theta range of 20 - 30 degrees 2θ, and little or virtually no simple ion - exchanged clay (peak at 9 degrees 2θ - 10 degrees 2θ).

[0225] Thus, the spray - dried fired clay - surfactant hetero adducts of the invention described herein have a distinct microscopic structure that is clearly different from previously disclosed fired spray - dried clay - aluminum chlorohydrate hetero - coagulants and other clay - cationic polymetallate hetero - coagulants.

[0226] J. Morphology of Spray - Dried Clay - Surfactant Hetero - Coagulants and Polymers Produced Therefrom In one aspect, the fired, spray-dried clay-surfactant heteroagglomerate support activators and the support catalysts prepared therefrom were found to be essentially highly spherical and very consistently spherical, i.e., highly uniform in their spherical shape. The highly spherical nature can be measured by various means including sphericity (S), roundness (R), circularity (C), or combinations thereof. Surprisingly, the highly spherical and highly circular characteristics of the clay-surfactant heteroagglomerates could be achieved by spray drying from an aqueous suspension in the absence of any organic solvent. The clay heteroagglomerates, the polymer particles produced using the clay heteroagglomerates as support activators, and also the corresponding clay heteroagglomerates or polymer particles produced when the clay heteroagglomerates were azeotropically dried (1-butanol / water, rotary evaporation) or non-azeotropically dried (water only, rotary evaporation) were found to be significantly more spherical and circular than the corresponding clay heteroagglomerates or polymer particles.

[0227] This uniform spherical morphology can be highly advantageous for generating the desired polymer morphology and for ensuring reactor operability and maintaining the activity of the support activator. The morphology of the support activator according to the present disclosure is shown in the figures as follows. Figures 9, 10, 13, and 14 show SEM (scanning electron microscopy or surface electron microscopy) images of the fired support activators prepared according to the present disclosure. Figures 9 and 10 show SEM images of the fired support activators formed by spray drying an aqueous slurry of a heteroaddition formed by contacting tetramethylammonium bromide (TMABr) and Volclay® HPM-20 montmorillonite according to Example 21-E1. Figures 13 and 14 show SEM images of the fired support activators formed by spray drying an aqueous slurry of a heteroaddition formed by contacting tetrabutylammonium bromide (TBABr) and Volclay® HPM-20 montmorillonite according to Example 22-E2.

[0228] Comparative SEM images are provided as follows. FIGS. 11 and 12 show SEM images of a fired support activator formed by spray drying an aqueous slurry of a hetero-adduct formed by contacting aluminum chlorohydrate (ACH) and Volclay® HPM-20 montmorillonite in the absence of a surfactant according to Comparative Example 20-D1. FIGS. 7 and 8 show SEM images of a fired support activator formed by spray drying an aqueous slurry of a hetero-adduct formed by contacting aluminum chlorohydrate (ACH) and Volclay® HPM-20 montmorillonite, and subsequently azeotropic drying from an aqueous slurry containing 1-butanol as an azeotropic agent, as described in Comparative Example 2-A1.

[0229] The predominant spherical morphology of the fired, spray-dried clay-surfactant hetero-adduct particles (FIGS. 9, 10, 13, and 14) with minimal aggregate formation is in contrast to the SEM images of the fired - but not spray-dried - support activators derived from clay and aluminum chlorohydrate azeotropically dried from water and 1-butanol slurries (FIGS. 7 and 8), where the majority of the bright hetero-adduct particles are non-spherical particulate particles and / or are highly aggregated. The hetero-adducts spray-dried and fired from clay and aluminum chlorohydrate (FIGS. 11 and 12) exhibit some highly spherical particles, but this hetero-adduct is also characterized by many non-spherical and / or highly aggregated particles.

[0230] In addition, comparing the morphology of the fired support activators prepared according to the present disclosure from FIGS. 9, 10, 13, and 14 to those of the isolated support activators (which can simply be called clay-hetero-adducts) before firing from FIGS. 1, 2, 5, and 6 shows that firing of the spray-dried particles does not substantially alter the spherical morphology of the support activator particles. Thus, the description of the sphericity, roundness, and circularity of the smectite hetero-adducts after firing applies equally to the isolated but unfired smectite hetero-adducts.

[0231] Accordingly, one aspect of the present disclosure provides highly spherical, circular, and round clay-surfactant heteroadditives, support activators, and supported catalysts, and these parameters can be measured as follows. Aspects for determining these parameters can be found in the following references, each of which is hereby incorporated by reference in its entirety: (1) G.-C. Cho, J. Dodds, and J. C. Santamarina, Journal of Geotechnical and Geoenvironmental Engineering, 2006, 132(5), 591-602; (2) I. Cruz-Matiasa, D. Ayalab, D. Hillerc, S. Gutschd, M. Zachariasd, S. Estradee, and F. Peiroe, Journal of Computational Science 2019, 30, 28-40. Without intending to be bound by theory, the concepts of sphericity and roundness can be considered as three-dimensional (3D) concepts that can be adapted for two-dimensional (2D) measurements. Again, without intending to be bound by theory, the concept of circularity can be considered as a two-dimensional (2D) surrogate for sphericity.

[0232] In one aspect, the clay-surfactant heteroadditives, support activators, and supported catalysts of the present disclosure can be characterized as having an average particle sphericity of 0.60 or greater (≧0.60), and the sphericity of each particle is given by the formula:

Number

[0233] In a further aspect, the morphology of the polyethylene homopolymers and copolymers prepared using a support activator was observed to reflect the morphology of the clay-surfactant adduct, support activator, or support catalyst. As a result, the morphology of the polymer particles can function as a proxy for the morphology of the clay-surfactant adduct, support activator, or support catalyst particles. Thus, the particles of the clay-surfactant adduct, support activator, support catalyst, and polymer particles can have a volume-weighted average sphericity (SPHT3) or number average particle sphericity (SPHT0) of 0.60 or greater, 0.65 or greater, 0.70 or greater, 0.75 or greater, 0.80 or greater, 0.85 or greater, 0.87 or greater, 0.90 or greater, 0.92 or greater, or 0.95 or greater. The particles of the clay-surfactant adduct, support activator, support catalyst, and polymer particles can also have a volume-weighted average sphericity (SPHT3) or number average particle sphericity (SPHT0) of about 0.60, about 0.65, about 0.70, about 0.75, about 0.80, about 0.85, about 0.87, about 0.90, about 0.92, about 0.95, or any range of sphericity between these values. These sphericity values of the average SPHT0 and average SPHT3 can be obtained, inter alia, from multiple image analyses of falling particles passing through the sensing zone of a CAMSIZER® device such as a CAMSIZER® X2 device analysis.

[0234] In a further aspect, the sphericity of polymer particles produced by polymerization using a support catalyst comprising a clay-surfactant heteroaddition was able to be analyzed and quantified by particle shape and size analysis using a CAMSIZER® device and associated software. As noted above, in contrast to polymers produced from support catalysts containing non-spray dried heteroaddition samples (azeotropic or non-azeotropic), polymers produced from support catalysts containing spray dried heteroaddition samples were surprisingly found to exhibit an average volume weighted sphericity (SPHT3 from CAMSIZER® X2 measurement) of 0.75 or greater, 0.80 or greater, 0.85 or greater, or 0.90 or greater. These polymer particles can also have an average volume weighted sphericity (SPHT3) of about 0.75, about 0.80, about 0.85, about 0.87, about 0.90, about 0.92, about 0.95, or any range of sphericity between these values. In one aspect, these sphericity values also correspond to the numerical weighted average sphericity (SPHT0) from CAMSIZER® X2 device analysis.

[0235] Polymer particles obtained from ethylene-1-hexene copolymerization were collected using various calcined spray dried and calcined non-spray dried clay heteroaddition support activators and analyzed by a CAMSIZER® X2 dynamic image analyzer to determine particle sphericity and particle size as recorded in Table 6. Summaries of the corresponding sphericity plots and particle distribution characteristics are shown in FIGS. 37-40.

[0236] Figure 37 shows the sphericity analysis of polymer samples containing an azeotropic-dried (non-spray-dried) and calcined support activator obtained by contacting aluminum chlorohydrate with montmorillonite in the absence of a surfactant, using 1-butanol as an azeotropic agent, as described in Example 2-A1. The sphericity analysis in Figure 38 was performed on polymer samples containing a non-spray-dried support activator as described in Example 30-E2, where the support catalyst was obtained by contacting tetrabutylammonium bromide with montmorillonite in the absence of cationic polymethalate, and the isolated product was rotary-evaporated in the absence of an azeotropic agent before calcination. As shown in Table 6, and Figures 37 and 38, both of these polymer samples exhibit a low (<0.70) volume-weighted mean apparent sphericity (SPHT3).

[0237] In contrast, sphericity analysis of polymers prepared using the fired spray-dried support activator demonstrated improved sphericity of the support activator compared to azeotropic or non-azeotropic and non-spray-dried ones. Figures 39 and 40, which are sphericity data in Table 6, were obtained from two different polymer samples generated from two different support activator samples produced under different spray-drying conditions within the range shown in Example 31. Adjusting or optimizing the spray-drying parameters within the range of Example 31 to achieve the sphericity and span value reports in Table 6 is well within the ability of one of ordinary skill in the art. For example, reference is made to C. Arpagaus (2018), A Short Review on Nano Spray Drying of Pharmaceuticals. J. Nanomed. Nanosci.: JNAN-149. DOI: 10.29011 / 2577-1477.100049, which is incorporated herein by reference. This reference summarizes how adjusting process parameters such as inlet temperature, drying gas flow rate, spray mesh size, solid concentration, feed rate, etc. affects droplet size, particle size, and other properties. The main spray-drying parameters adjusted when preparing the support activator of interest were the concentration and feed rate in the aqueous slurry. Figures 39 and 40, and the data in Table 6, demonstrate a very high average sphericity for these samples.

[0238] Figure 41 shows particle size distribution data and cumulative volume curves for a sample of polymer powder used to obtain the data of Figure 40, generated using a catalyst prepared from the spray-dried clay-tetrabutylammonium bromide adduct support activator of Example 31. In the chart of Figure 41 and similar charts, the Q3 [%] axis corresponds to the curve on the graph and represents the cumulative volume percent value that is the percent of the total volume of particles below that particle size value. The P3 [%] axis corresponds to the bar graph distribution and shows the percent of the total volume corresponding to each bar or “slice” of particle size. The sphericity data of Figures 39 and 40 obtained with ethylene-1-hexene copolymer particles, and the particle size distribution data of Figure 41 were collected and analyzed by CAMSIZER® X2 as provided in the examples.

[0239] In a further aspect, the sieving can be carried out on smectite clay, spray-dried clay-surfactant adduct, support activator, or support catalyst, either before or after firing or other drying processes. Table 7 shows the sphericity and span data for ethylene-1-hexene copolymers derived from metallocene-catalyzed polymerization using a fired support activator from the spray-dried, unsieved clay-surfactant support activator of Example 31, and for sieved samples in Examples 33 - 35, of ethylene-1-hexene copolymers derived from a spray-dried and sieved clay-surfactant support activator. Table 7 shows that support activators with smaller particle sizes receive more benefit from sieving in terms of producing more spherical ethylene-1-hexene copolymers compared to unsieved support activators. Thus, by using certain sieved samples, the sphericity can be further improved if desired. Such a process can produce particles of clay, clay-surfactant adduct, support activator, or support catalyst having a narrower size distribution than the unsieved material, and having a number-weighted or volume-weighted average particle sphericity of 0.65 or greater, 0.70 or greater, 0.75 or greater, 0.80 or greater, 0.85 or greater, 0.87 or greater, 0.90 or greater, 0.92 or greater, or 0.95 or greater. These sieved samples of clay, clay-surfactant adduct, support activator, or support catalyst particles can also have an average volume-weighted sphericity (SPHT3) of about 0.75, about 0.80, about 0.85, about 0.87, about 0.90, about 0.92, about 0.95, or any range of sphericity between these values. Additionally, polymer powders produced from support catalysts containing such sieved spray-dried adduct samples can also exhibit a volume-weighted average sphericity of 0.75 or greater, 0.80 or greater, or 0.85 or greater, and furthermore have improved sphericity compared to polymer powders produced from support catalysts containing unsieved precursor spray-dried adducts, support activators, or support catalysts.

[0240] In another aspect, sieving can be used to improve the size uniformity of the clay-surfactant adduct, support activator, or support catalyst as compared to the unsieved precursor material. Sieving can be performed on the spray-dried clay-surfactant adduct, support activator, or support catalyst either before or after firing or other drying processes, providing a more uniform particle size distribution among the particles and having a lower span (=[d(0.9)-d(0.1)] / d(0.5)) as compared to the unsieved precursor material. For example, the sieving process can produce a spray-dried clay-surfactant adduct, support activator, or support catalyst having a particle size distribution with a span of 2 or less, 1.5 or less, 1.25 or less, 1 or less, or 0.75 or less. Additionally, the particle size distribution of the polymer powder produced from a support catalyst containing such sieved spray-dried adduct sample can exhibit a span of 2 or less, 1.5 or less, 1.25 or less, 1 or less, or 0.75 or less, and can exhibit a lower span as compared to the particle size distribution of the polymer powder produced from a support catalyst containing an unsieved spray-dried adduct, support activator, or support catalyst of the precursor. In a further aspect, the sieving process can produce, or the polymer powder produced therefrom can exhibit, a span of about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, about 0.9, about 1.0, about 1.1, about 1.2, about 1.3, about 1.4, about 1.5, about 1.6, about 1.7, about 1.8, about 1.9, about 2.0, or any range between any of the span values, either before or after firing or other drying processes on the spray-dried clay-surfactant adduct, support activator, or support catalyst.

[0241] To more closely examine how the form and particle size distribution of the clay-surfactant heteroadditive or support activator changed over a more narrow particle size distribution, a sample of the support activator was prepared according to Example 31, spray dried, then sieved into three separate fractions, and the catalyst and polymer were prepared from the three fractions described in Examples 33 - 35. These data are provided in Table 7 and FIGS. 42 - 47. FIGS. 42, 44, and 46 show the particle size distribution and cumulative volume curves for the copolymer powder samples, and FIGS. 43, 45, and 47 plot the volume weighted sphericity (SPHT3) against the polymer particle size for samples of the polymer particles of FIGS. 42, 44, and 46, respectively.

[0242] Specifically, FIGS. 42 and 43 show the particle size distribution and sphericity data for copolymer powder samples produced from the spray dried clay-tetrabutylammonium bromide support activator of Example 31 having a particle size of 19 μm (microns) to 37 μm. That is, the support activator used to generate the data in FIGS. 42 and 43 passed through a 37 μm sieve but was captured by a 19 μm sieve. Similarly, FIGS. 44 and 45 show the particle size distribution and sphericity data for copolymer powder samples produced from the spray dried clay-tetrabutylammonium bromide support activator of Example 31 having a particle size of 37 μm (microns) to 50 μm. Finally, FIGS. 46 and 47 show the particle size distribution and sphericity data for copolymer powder samples produced from the spray dried clay-tetrabutylammonium bromide support activator of Example 31 having a particle size of 50 μm (microns) to 74 μm. These sieved samples were collected, calcined, and combined with (η 5 -1-n-butyl-3-methyl-cyclopentadienyl)2ZrCl2 and triethylaluminum (TEA) to form a catalyst composition and used to copolymerize ethylene and 1-hexene as described herein. The polymer particles obtained from these copolymerizations using each size fraction of the support activator were collected and analyzed using a CAMSIZER® X2 to determine the particle size distribution.

[0243] These Table 7 data demonstrate that all samples in the narrow size range of Examples 33 to 35 exhibit an average volume weighted sphericity SPHT3 of 0.65 or greater, and that the SPHT3 sphericity increases with increasing particle size. The polymer produced using the 50 μm to 74 μm maximum fraction of clay heteroadditive (Example 35 and Figure 47) had the highest SPHT3 sphericity of 0.86. Comparing the first 17 gram samples of the clay heteroadditive used in the sieving process, these three fractions accounted for a significant 16.76 g out of the total 17 g starting sample. Thus, 98.6 wt% of the Example 31 sample was accounted for by these three size fractions.

[0244] In a further aspect, the clay-surfactant heteroadditive, support activator, and support catalyst of the present disclosure can be characterized as having an average particle roundness of 0.60 or greater, where roundness is given by the formula:

Number

[0245] According to a further aspect, the clay-surfactant heteroadditive, support activator, and support catalyst of the present disclosure can be characterized as having an average particle circularity of 0.60 or greater, where circularity is given by the formula: [Number] and is calculated according to the formula, where

[0246] A is the area of the two-dimensional image (silhouette) of the particle, and perimeter is the length of the path enclosing the two-dimensional image of the particle. According to another aspect, the clay-surfactant heteroadditive, support activator, support catalyst, and polymer particles prepared therefrom can also have an average particle circularity of 0.65 or greater, 0.70 or greater, 0.75 or greater, 0.80 or greater, 0.85 or greater, 0.87 or greater, 0.90 or greater, 0.92 or greater, or 0.95 or greater. The clay-surfactant heteroadditive, support activator, support catalyst, and polymer particles prepared therefrom can also have an average particle circularity of about 0.65, about 0.70, about 0.75, about 0.80, about 0.85, about 0.87, about 0.90, about 0.92, about 0.95, or any range between any of the circularity values of these particles.

[0247] In a further aspect regarding the morphology of the clay-surfactant heteroadditive, support activator, and support catalyst of the present disclosure, the clay-surfactant heteroadditive, support activator, and support catalyst, when spray-dried or spray-dried and calcined, can be characterized by any one or any combination of the following properties: (a) An average particle sphericity of 0.65 or greater, (b) An average particle roundness of 0.65 or greater, and (c) An average particle circularity of 0.65 or greater.

[0248] Furthermore, the clay-surfactant heteroadditives, support activators, and supported catalysts of the present disclosure, the clay-surfactant heteroadditives, support activators, and supported catalysts can be characterized by any one, or any combination, of the following properties when spray dried, or when spray dried and calcined: (a) An average particle sphericity of 0.75 or greater, (b) An average particle roundness of 0.75 or greater, and (c) An average particle circularity of 0.75 or greater.

[0249] In addition, the clay-surfactant heteroadditives, support activators, and supported catalysts of the present disclosure, the clay-surfactant heteroadditives, support activators, and supported catalysts can be characterized by any one, or any combination, of the following properties when spray dried, or when spray dried and calcined: (a) An average particle sphericity of 0.80, 0.85, 0.90, or greater, (b) An average particle roundness of 0.80, 0.85, 0.90, or greater, and (c) An average particle circularity of 0.80, 0.85, 0.90, or greater.

[0250] In a further aspect of the present disclosure, polymer particles produced from polymerization conducted with a metallocene-activated spray dried clay-surfactant heteroagglomerate support activator are also essentially highly spherical. A calcined spray dried support activator (see FIGS. 9, 10, 13, and 14) derived from clay and tetramethylammonium bromide (Example 21-E1) or tetrabutylammonium bromide (Example 22-E2) was combined with a metallocene bis(1-butyl-3-methylcyclopentadienyl) zirconium dichloride and triethylaluminum cocatalyst to form an active catalyst, which was used to produce an ethylene-1-hexene copolymer. Optical microscope images of these polymer particles are provided in FIGS. 15 and 16, respectively. These polymer particles are essentially highly spherical, like their parent catalyst particles.

[0251] In contrast, FIG. 17 shows an optical micrograph of a polymer resulting from copolymerizing ethylene and 1-hexene using the azeotropically dried clay-aluminum chlorohydrate (ACH) support activator described in Example 2-A1 (in the absence of a surfactant), with the support activator being a metallocene (η 5 -1-Bu-3-MeCp)2ZrCl2 and combined with a triethylaluminum cocatalyst to form an active catalyst. FIGS. 7 and 8 show SEM images of the support activator prepared in Example 2-A1 and used to produce the polymer in FIG. 17. Like the support activators of FIGS. 7 and 8, the polymer particles of FIG. 17 are granular, highly irregular, very non-spherical, and aggregated, in contrast to the polymer particles shown in FIGS. 15 and 16.

[0252] Thus, the spray drying process from a slurry of only water can be an effective method for achieving the highly spherical morphology desired for the support activator, which in turn, when introduced into the metallocene, cocatalyst, and monomer under polymerization conditions, can be shown to produce highly symmetric and spherical polymer particles. The responsiveness of the clay-surfactant adducts of the present disclosure to spray drying, particularly the retention of their polymerization activity when subjected to such a drying method, thus confers many advantages to the catalyst bed filling and polymer filling characteristics.

[0253] In a further aspect, the circularity (C) of the clay-surfactant adducts and support catalysts containing the clay-surfactant adducts can be analyzed and quantified via a scanning electron microscope (SEM) using subsequent image analysis. For example, the fired clay-surfactant adducts and support catalysts containing the clay-surfactant adducts can be analyzed via a scanning electron microscope and the circularity of the particles measured using subsequent image analysis using a method such as Scanning Probe Image Processor (SPIP) software. In this aspect, the circularity of the spray dried and fired adducts and catalysts can be measured and compared to the circularity of the fired adducts and catalysts dried using other means such as azeotropic drying.

[0254] When analyzing such SEM images using SPIP software, unless otherwise instructed, particles having a diameter exceeding 8 μm and less than 100 μm are selected for analysis, because such a range excludes fine matter that may be generated when gridding the fired heteroadditives and large particles that are likely to be artifacts of misrecognized fused particles, while still encompassing these particle sizes that are most relevant to the catalytic process and most common in the sample. This circularity analysis of particles with diameters > 8 μm and < 100 μm was performed using SPIP software to calculate the area (A) of the two-dimensional image of the particle and the length of the perimeter, which is the length of the path encompassing the two-dimensional image of the particle. The SEM images of individual particles were inspected before use in the calculations to exclude particles whose detected boundaries were accidentally fused with other particles, blocked by other particles, or interrupted by the boundaries of the SEM photograph. In each analysis, unless otherwise described, a sample of 10 or more particles was detected and subjected to this analysis to calculate the circularity (C).

[0255] In contrast to the circularity of the non-spray-dried heteroadditive samples, the heteroadditives produced according to the present disclosure and spray-dried from an aqueous suspension alone were characterized by an average particle circularity (C) of 0.80 or greater, 0.85 or greater, or 0.90 or greater. The circularity measurements of the spray-dried and non-spray-dried clay heteroadditives prepared as described herein are recorded in Table 5, and the corresponding SEM images are shown in FIGS. 31 to 36.

[0256] For example, as shown in the SEM images of FIGS. 31 and 32, the non-spray-dried support activator is obtained by azeotropically drying an adduct obtained by contacting aluminum chlorohydrate (ACH) and montmorillonite in the absence of a surfactant, using 1-butanol as the azeotroping agent, and subsequently firing the dried product as described in Example 2-A1 and Example 3-A2, respectively. The SEM of FIG. 33 shows a support activator formed as described in Example 30-E2 by contacting tetrabutylammonium bromide and montmorillonite in the absence of cationic polymethalate, and the isolated product was dried from an aqueous slurry by rotary evaporation in the absence of an azeotroping agent prior to firing. In all of the samples of FIGS. 31 to 33, the particles observed in these images exhibit a low circularity and / or a high proportion of particles outside the diameter range of 8 μm to 100 μm. Generally, such low circularity and very large or small particles are not desirable for the catalytic process.

[0257] In contrast, the SEM images of FIGS. 34, 35, and 36 show a support activator formed as described in Example 22-E2 by contacting tetrabutylammonium bromide and montmorillonite in the absence of cationic polymethalate, isolated by filtration, and subsequently spray-dried from an aqueous suspension and fired. In all of the samples of FIGS. 34 to 36, the particles observed in these images exhibit a very high circularity, and most of the particles are within the desirable diameter range of 8 μm to 100 μm, which is very advantageous for these support activators in the catalytic process.

[0258] K. Metallocene compound A clay-surfactant adduct (also referred to as a clay adduct) can be used as a substrate or catalyst support activator for one or more suitable polymerization catalyst precursors, such as metallocenes, other organometallic compounds, and / or organoaluminum compounds, etc., for preparing an olefin polymerization catalyst composition. Thus, in one aspect, when a clay adduct is prepared as disclosed herein and combined with an organometallic main group such as an alkylaluminum compound and a Group 4 organotransition metal compound such as a metallocene, an active olefin polymerization catalyst or catalyst system is provided.

[0259] The support activators of the present disclosure can be used with cocatalysts such as metallocene compounds (also referred to herein as metallocene catalysts) and organoaluminum compounds, and the resulting compositions exhibit catalytic polymerization activity in the absence or substantial absence of ion exchange, protic acid treatment, or pillared clays, or aluminoxane or borate activators. Previously, it has been thought that activators such as aluminoxane or borate activators are necessary to achieve catalytic polymerization activity with metallocene or single-site or coordination catalyst systems. However, when desired to impart an activatable alkyl ligand to the metallocene, a combination of a heteroatom adduct support activator, a metallocene, and a cocatalyst such as an aluminum alkyl compound provides an active catalyst that requires other activators such as aluminoxane or borate activators.

[0260] Metallocene compounds are well understood in the art, and those skilled in the art will recognize that any metallocene can be used with the support activators described in the present disclosure, including, for example, non-bridged (non-ansa) metallocene compounds or bridged (ansa) metallocene compounds, or both combinations thereof. Thus, one, two, or more metallocene compounds can be used with the clay-surfactant support activators of the present disclosure.

[0261] In one aspect, the metallocene can be a metallocene containing a Group 3-6 transition metal, or a metallocene containing a lanthanide metal or a combination of two or more metallocenes. For example, the metallocene can contain a Group 4 transition metal (titanium, zirconium, or hafnium). In a further aspect, the metallocene compound is, independently of each other, of the formula: (X 1 )(X 2 )(X 3 )(X 4 )M, wherein a) M is selected from titanium, zirconium, or hafnium, b) X 1 is selected from substituted or unsubstituted cyclopentadienyl, indenyl, fluorenyl, pentadienyl, allyl, boratabenzenyl, 1,2-azaborolyl, or 1,2-diaza-3,5-diborolyl, and any substituent is a halide, C1-C 20 hydrocarbyl, C1-C 20 heterohydrocarbyl, C1-C 20 organoheteryl, fused C4-C 12 carbocyclic moiety, or a fused C4-C 11 heterocyclic moiety having at least one heteroatom independently selected from nitrogen, oxygen, sulfur, or phosphorus, c) X 2 is selected from [1] substituted or unsubstituted cyclopentadienyl, indenyl, fluorenyl, pentadienyl, or allyl, and any substituent is selected from a halide, C1-C 20 hydrocarbyl, C1-C 20 heterohydrocarbyl, or C1-C 20 organoheteryl, or [2] is selected from a halide, hydride, C1-C 20 hydrocarbyl, C1-C 20 heterohydrocarbyl, C1-C 20 organoheteryl, fused C4-C 12 carbocyclic moiety, or a fused C4-C 11 heterocyclic moiety having at least one heteroatom independently selected from nitrogen, oxygen, sulfur, or phosphorus, d) X 1 and X 2 are optionally crosslinked by at least one linker substituent having 2 to 4 crosslinking atoms independently selected from C, Si, N, P, or B, and each available non-crosslinked valence of each crosslinking atom is unsubstituted (bonded to H) or substituted, and any substituent is a halide, C1-C 20 hydrocarbyl, C1-C 20 heterohydrocarbyl, or C1-C 20 organoheteryl, independently selected, and any hydrocarbyl, heterohydrocarbyl, or organoheteryl substituent can form a saturated or unsaturated cyclic structure with the crosslinking atom and / or X 1 or X 2 and e) [1] X 3 and X 4 are selected independently from halides, hydrides, C1-C 20 hydrocarbyls, C1-C 20 heterohydrocarbyls, or C1-C 20 organoheteryls, or [2] [GX A k X B 4-k - wherein G is B or Al, k is a number from 1 to 4, and X A at each occurrence is independently selected from H or a halide, and X B at each occurrence is selected independently from C1-C 12 hydrocarbyls, C1-C 12 heterohydrocarbyls, C1-C 12 organoheteryls, or [3] X 3 and X 4 are both C4-C 20 polyenes, or [4] X 3 and X 4 together with M form a substituted or unsubstituted, saturated or unsaturated C3-C6 metallacycle, and any substituent on the metallacycle moiety is a halide, C1-C 20 hydrocarbyl, C1-C 20 heterohydrocarbyl, or C1-C​20 a compound or combination of compounds having (selected independently of organoheteryl), or consisting of, consisting essentially of, or selectable from them.

[0262] In a further aspect, optionally, X 1 and X 2 is a) EX 5 2, -EX 5 2EX 5 2-, -EX 5 2EX 5 EX 5 2-, or >C=CX 5 2, where E in each occurrence is independently selected from C or Si; b) -BX 5 -, -NX 5 -, or -PX 5 , or c) [-SiX 5 2(1,2-C6H4)SiX 5 2-], [-CX 5 2(1,2-C6H4)CX 5 2-], [-SiX 5 2(1,2-C6H4)CX 5 2-], [-SiX 5 2(1,2-C2H2)SiX 5 2-], [-CX 5 2(1,2-C6H4)CX 5 2-], or [-SiX 5 2(1,2-C6H4)CX 5 2-], where X in each occurrence 5 is independently selected from H, halide, C1-C 20 hydrocarbyl, C1-C 20 heterohydrocarbyl, or C1-C 20 organoheteryl, and any X substituent selected from hydrocarbyl, heterohydrocarbyl, or organoheteryl substituents 5 is a bridging atom, another X 5 substituent, X 1or X 2 can be crosslinked by a linker substituent selected from (), which can form a saturated or unsaturated cyclic structure). X 1 and X 2 Examples of suitable linker substituents that can crosslink X 20 hydrocarbylene groups, C1-C 20 hydrocarbylidene groups, C1-C 20 heterohydrocarbyl groups, C1-C 20 heterohydrocarbylidene groups, C1-C 20 heterohydrocarbylene groups, or C1-C 20 heterohydrocarbylidene groups. For example, X 1 and X 2 can be crosslinked by at least one substituent having the formula >EX 5 2, -EX 5 2EX 5 2-, or -BX 5 - (wherein E is independently C or Si, and each occurrence of X 5 is independently selected from halides, C1-C 20 aliphatic groups, C6-C 20 aromatic groups, C1-C 20 heteroaliphatic groups, C4-C 20 heteroaromatic groups, or C1-C 20 organoheteryl groups).

[0263] The embodiments section of this disclosure lists additional explanations and choices regarding the linking portion between X 1 and X 2 , regarding X 5 , and regarding certain linker substituents or X 5 substituents.

[0264] The embodiments section of this disclosure also lists additional explanations and choices regarding X 1 and X 2 , including specific substituents on X 1 and X 2 .

[0265] The aspect sections of the present disclosure also describe X 3 and X 4 and provide additional explanations and selections for X 3 and X 4 that include the specific substituents above.

[0266] The aspect sections of the present disclosure also provide some specific examples of metallocene compounds useful in combination with the support activators of the present disclosure.

[0267] When the supported metallocene catalyst is prepared and dried according to the present disclosure, prior to its use, in combination with a cocatalyst, the supported metallocene catalyst can have an average particle size, for example, of 1 μm (micron) to 250 μm, which is the average dry particle size. Unless otherwise stated, the particle sizes recited for the supported metallocene catalyst are for the dried supported catalyst particles measured as described herein. In one aspect, the supported metallocene catalyst can have an average particle size of about 1 μm (micron), about 2 μm, about 3 μm, about 5 μm, about 7 μm, about 10 μm, about 12 μm, about 15 μm, about 18 μm, about 20 μm, about 25 μm, about 30 μm, about 35 μm, about 40 μm, about 45 μm, about 50 μm, about 55 μm, about 60 μm, about 65 μm, about 70 μm, about 75 μm, about 80 μm, about 85 μm, about 90 μm, about 95 μm, about 100 μm, about 110 μm, about 120 μm, about 125 μm, about 130 μm, about 140 μm, about 150 μm, about 160 μm, about 170 μm, about 175 μm, about 185 μm, about 200 μm, about 225 μm, or about 250 μm, or any range of particle sizes between these recited values. For example, the supported metallocene catalyst can have an average particle size of 1 μm (micron) to 250 μm, 2 μm to 125 μm, 3 μm to 100 μm, 5 μm to 150 μm, 5 μm to 80 μm, 7 μm to 70 μm, 10 μm to 100 μm, 10 μm to 60 μm, 15 μm to 80 μm, 15 μm to 50 μm, or 20 μm to 75 μm.

[0268] Metallocene compounds are understood by those skilled in the art, and those skilled in the art will recognize and understand the methods for the production and use of metallocenes in olefin polymerization catalyst systems. Many metallocenes and processes for producing metallocenes and organotransition metal compounds are known in the art as disclosed in U.S. Patent Nos. 4,939,217, 5,210,352, 5,436,305, 5,401,817, 5,631,335, 5,571,880, 5,191,132, 5,480,848, 5,399,636, 5,565,592, 5,347,026, 5,594,078, 5,498,581, 5,496,781, 5,563,284, 5,554,795, 5,420,320, 5,451,649, 5,541,272, 5,705,478, 5,631,203, 5,654,454, 5,705,579, 5,668,230, 9,045,504, and 9,163,100, and U.S. Patent Application Publication No. 2017 / 0342175, the entire disclosures of which are incorporated herein by reference.

[0269] L. Cocatalyst According to one aspect, the present disclosure provides a catalyst composition for olefin polymerization, the catalyst composition comprising: a) at least one metallocene compound, and b) Optionally, at least one cocatalyst and c) at least one support activator as described herein. The cocatalyst includes compounds such as trialkylaluminum that are thought to impart ligands to the metallocene or activate the metallocene ligand, and this can initiate polymerization when the metallocene would otherwise be activated by the support activator. The cocatalyst can be considered optional, for example, in scenarios where the metallocene can already contain a polymerization activating / initiating ligand (such as methyl or hydride). It will be understood that the cocatalyst can be used for other purposes such as removing moisture from the polymerization reactor or process even when the metallocene compound contains a polymerization activating / initiating ligand or the like. Thus, the cocatalyst can include or be selected from, for example, alkylating agents, hydridizing agents, or silylating agents. The metallocene compound, support activator, and cocatalyst can be contacted in any order.

[0270] The cocatalyst can include or be selected from organoaluminum compounds, organoboron compounds, organozinc compounds, organomagnesium compounds, organolithium compounds, or any combination thereof.

[0271] The aspect section of this disclosure lists additional explanations and selections for each of organoaluminum compounds, organoboron compounds, organozinc compounds, organomagnesium compounds, and organolithium compounds.

[0272] In one aspect, for example, the cocatalyst has the formula Al(X A ) n (X B ) m , M x [AlX A 4], Al(X C ) n (X D ) 3-n , M x [AlX C4] Each of the variables of these formulas can be independently had, that is, it can be a neutral molecular compound or an ionic compound / salt of aluminum, including, consisting of, essentially consisting of, or selectable from at least one organoaluminum compound. For example, the cocatalyst can include, consist of, essentially consist of, or be selected from any combination such as trimethylaluminum, triethylaluminum (TEA), tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, ethyl-(3-alkylcyclopentadienyl)aluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, triisobutylaluminum (TIBAL), diethylaluminum chloride, ethyl-(3-alkylcyclopentadienyl)aluminum, etc.

[0273] In another aspect, for example, the cocatalyst has the formula B(X E ) q (X F ) 3-q , B(X E )3, or M y [BX E4) (Each of the variables in these formulas can be independently had, i.e., can be a neutral molecular compound or an ionic compound / salt of boron, and includes, consists of, consists essentially of, or can be selected from at least one organoboron compound. For example, the cocatalyst can include, consist of, consist essentially of, or can be selected from trimethylboron, triethylboron, tripropylboron, tributylboron, trihexylboron, trioctylboron, diethylboron ethoxide, diisobutylboron hydride, triisobutylboron, diethylboron chloride, di-3-pinanenylborane, pinacolborane, catecholborane, lithium borohydride, lithium triethylborohydride, etc., their Lewis base adducts, or combinations or mixtures thereof. In another aspect, the cocatalyst can include or can be a halogenated organoboron compound, for example, a fluorinated organoboron compound, and examples of these include tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)phenyl]boron, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, lithium tetrakis-(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoro-methyl)phenyl]borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)-phenyl]borate, and any combination or mixture thereof.)

[0274] In yet another aspect, for example, the cocatalyst has the formula M C (X G ) r (X H ) 2-rcomprising, consisting of, essentially consisting of, or selectable from at least one organozinc or organomagnesium compound that can be possessed independently, wherein each variable of this formula is defined in the aspect section of the present disclosure. For example, the cocatalyst can include, consist of, essentially consist of, or be selected from any combination of dimethylzinc, diethylzinc, diisopropylzinc, dicyclohexylzinc, diphenylzinc, butylethylmagnesium, dibutylmagnesium, n-butyl-sec-butylmagnesium, dicyclopentadienylmagnesium, ethylmagnesium chloride, butylmagnesium chloride, etc.

[0275] In yet another aspect, for example, the cocatalyst can include, consist of, essentially consist of, or be selected from at least one organolithium compound that can be possessed independently of the formula Li(X J ), wherein each variable of this formula is defined in the aspect section of the present disclosure. For example, the cocatalyst can include, consist of, essentially consist of, or be selected from methyllithium, ethyllithium, propyllithium, butyllithium (including n-butyllithium and t-butyllithium), hexyllithium, isobutyllithium, etc., or any combination thereof.

[0276] M. Optional coactivator In one aspect, if desired, in addition to the calcined smectite heteroadduct support activator, other activators can be used in the catalyst composition of the present disclosure. These are referred to as coactivators, and examples of optional coactivators include, but are not limited to, ion-exchanged clays, protic acid-treated clays, pillared clays, aluminoxanes, borate activators, aluminate activators, ionizing ionic compounds, solid oxides treated with electron-withdrawing anions, or any optional combination thereof. In one aspect, the catalyst system and polymerization method can be free of any coactivator, including any one of the coactivators described herein.

[0277] The aspect sections of this disclosure enumerate additional explanations and selections for each of these optional co-activators.

[0278] Aluminoxane. Using aluminoxane (also referred to as poly(hydrocarbylaluminum oxide) or organoaluminoxane), other catalyst components can be contacted in a solvent that is substantially inert to the reactants, intermediates, and products of the activation step, for example, a saturated hydrocarbon solvent or a solvent such as toluene. The catalyst composition thus formed may, if desired, be isolated, or the catalyst composition may be introduced into the polymerization reactor without isolation.

[0279] As will be understood by those skilled in the art, aluminoxane is an oligomer, and aluminoxane compounds can include linear structures, cyclic structures, or cage structures, or mixtures thereof. For example, a cyclic aluminoxane compound having the formula (R-Al-O) n wherein R can be a linear or branched alkyl having 1 to about 12 carbon atoms, and n can be an integer from 3 to about 12. The (AlRO) n moiety also constitutes a repeating unit in the linear aluminoxane, for example, having the formula: R(R-Al-O) n AlR2, wherein R can be a linear or branched alkyl having 1 to about 12 carbon atoms, and n can be an integer from 1 to about 75. For example, the R group can be a linear or branched C1-C8 alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl, and wherein n can represent an integer from 1 to about 50. Depending on the method of preparation, storage, and use of the organoaluminoxane, the value of n may vary within a single sample of aluminoxane, and such combinations or populations of organoaluminoxane species are typically present in any sample.

[0280] Organoaluminoxanes can be prepared by various procedures known in the art. For example, organoaluminoxane preparations are disclosed in U.S. Patent Nos. 3,242,099 and 4,808,561, each of which is hereby incorporated by reference in its entirety. In one embodiment, the aluminoxane can be prepared by reacting water present in an inert organic solvent with an aluminum alkyl compound such as AlR3 to form the desired organoaluminoxane compound. Alternatively, the organoaluminoxane may be prepared by reacting an aluminum alkyl compound such as AlR3 with a hydrated salt such as copper sulfate hydrate in an inert organic solvent.

[0281] In one embodiment, the aluminoxane compound can be methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, isopropyl-aluminoxane, n-butylaluminoxane, t-butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentyl-aluminoxane, iso-pentylaluminoxane, neopentylaluminoxane, or a combination thereof. In one aspect, methylaluminoxane (MAO), ethylaluminoxane (EAO), or isobutylaluminoxane (IBAO) can be used as an optional cocatalyst, and these aluminoxanes can be prepared from trimethylaluminum, triethylaluminum, or triisobutylaluminum, respectively. These compounds can be complex compositions and may be referred to as poly(methylaluminum oxide), poly(ethylaluminum oxide), and poly(isobutylaluminum oxide), respectively. In another aspect, the aluminoxane can be used in combination with a trialkylaluminum as disclosed in U.S. Patent No. 4,794,096, which is hereby incorporated by reference in its entirety.

[0282] In the preparation of a catalyst composition comprising an optional aluminoxane, the molar ratio of aluminum present in the aluminoxane in the composition to the metallocene compound(s) can be lower than the typical molar ratios used in the absence of the support activator of the present disclosure. In the absence of the support activator of the present disclosure, the amount of aluminoxane can be, for example, from about 1:10 mol Al / mol metallocene (mol Al / mol metallocene) to about 100,000:1 mol Al / mol metallocene, or from about 5:1 mol Al / mol metallocene to about 15,000:1 mol Al / mol metallocene. When used in combination with the disclosed support activator, the relative amount of aluminoxane can be decreased. For example, the amount of optional aluminoxane added to the polymerization zone can be less than previous typical amounts in the range of about 0.01 mg / L to about 1000 mg / L, about 0.1 mg / L to about 100 mg / L, or about 1 mg / L to about 50 mg / L. Alternatively, the aluminoxane can be used in amounts typically used in the prior art, but the additional use of the support activator of the present disclosure is employed to obtain further advantages for such combinations.

[0283] An organoboron compound comprising an organic borate. The catalyst composition of the present disclosure can optionally further comprise an optional organoboron co-activator in addition to the listed components (support activator, metallocene, and optional cocatalyst). In one aspect, the organoboron compound can comprise or be selected from neutral boron compounds, borates, or combinations thereof. For example, the organoboron compound can comprise or be selected from fluoroorganoboron compounds, fluoroorganoborate compounds, or combinations thereof, and any such fluorinated compounds known in the art can be utilized.

[0284] Accordingly, the term fluoroorganoboron compound is used herein to refer to a neutral compound of the form BY3, and the term fluoroorganoborate compound is used to refer to a compound of the form [cation] + [BY4] -As used herein to refer to the monoanion salt of a fluoroorganoboron compound, Y represents a fluorinated organic group. For convenience, fluoroorganoboron compounds and fluoroorganoborate compounds are typically collectively referred to by either name, by an organic boron compound, or as the context requires.

[0285] In one aspect, examples of fluoroorganoboron compounds that can be used as a coactivator include, but are not limited to, tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)phenyl]boron, etc. (including mixtures thereof). Examples of fluoroorganoborate compounds that can be used as an optional coactivator include fluorinated aryl borates, such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, lithium tetrakis-(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, etc., and are not limited thereto, including mixtures thereof.

[0286] The aspect section of the present disclosure lists additional explanations and selections of optional fluoroorganoboron and fluoroorganoborate compound coactivators.

[0287] Without wishing to be bound by theory, these fluoroorganoborate and fluoroorganoboron compounds are thought to form weakly coordinating anions when combined with metallocene compounds, as disclosed in U.S. Patent No. 5,919,983, which is hereby incorporated by reference in its entirety.

[0288] Generally, any amount of an organoboron compound can be utilized as an optional cocatalyst. For example, in one aspect, the molar ratio of the organoboron compound to the metallocene compound in the composition can be from about 0.1:1 mole of the organoboron compound or organoboric acid compound (mol / mol) per mole of metallocene to about 10:1 mol / mol, or from about 0.5 mol / mol to about 10 mol / mol (moles of the organoboron compound or organoboric acid compound per mole of metallocene), or alternatively, can be in the range of about 0.8 mol / mol to about 5 mol / mol (moles of the organoboron compound or organoboric acid compound per mole of metallocene). However, it should be understood that in the presence of the clay heteroaddition support activator, the amount can be decreased or adjusted downward.

[0289] Ionizing compound. In a further aspect, the optional cocatalyst that can be used in addition to the listed components of the catalyst composition of the present disclosure can include, or can be selected from, ionizing compounds. Examples of ionizing compounds are disclosed in U.S. Patent Nos. 5,576,259 and 5,807,938, each of which is incorporated herein by reference in its entirety.

[0290] The aspect section of the present disclosure lists additional explanations and selections of optional ionizing compound cocatalysts.

[0291] The term ionizing compound is a term in the art and refers to a compound, particularly an ionic compound, that can function to enhance the activity of a catalyst composition. In one aspect, the fluoroguanoborate compounds described herein as optional organoboron cocatalysts can also be considered and function as ionizing compound cocatalysts. However, since compounds such as fluoroorganoaluminates are encompassed by ionizing compounds, the scope of ionizing compounds is broader than that of fluoroguanoborate compounds.

[0292] Although not intended to be bound by theory, the ionizing compound can interact or react with the metallocene compound to convert the metallocene into a cationic or pre-cationic metallocene compound, which is thought to activate the metallocene to polymerization activity. Again, although not intended to be bound by theory, the ionizing compound functions by completely or partially extracting an anionic ligand from a non-cycloalkadienyl ligand of a metallocene, particularly a metallocene of the formula (X 1 )(X 2 )(X 3 )(X 4 )M or a non-alkadienyl ligand such as (X 3 ) or (X 4 ) to form a cationic or pre-cationic metallocene. However, the ionizing compound can function as an activator (co-activator) regardless of the mechanism by which it functions. For example, the ionizing compound can ionize the metallocene and extract the X 3 or X 4 ligand in such a way as to form an ion pair, weaken the metal-X 3 or metal-X 4 bond, or simply coordinate to the X 3 or X 4 ligand or any other mechanism by which activation can occur. Further, since the activation function of the ionizing compound is evident in the improvement of the activity of the entire catalyst composition as compared to a catalyst composition containing no ionizing compound, the ionizing compound need not activate (co-activate) only the metallocene.

[0293] Examples of ionizing compounds include, but are not limited to, the list of compounds presented in the Aspects section of this disclosure.

[0294] Optional support activators. In a further aspect, optional co-activators that can be used in addition to the listed components of the catalyst compositions of the present disclosure can include other support activators, sometimes referred to as activator supports, or can be selected from other support activators. When used in the catalyst compositions described herein, these are referred to as co-activator supports. Examples of optional co-activator supports are disclosed in U.S. Patent Nos. 6,107,230, 6,653,416, 6,992,032, 6,984,603, 6,833,338, and 9,670,296, each of which is incorporated herein by reference in its entirety.

[0295] For example, the optional co-activator support can include, or can be selected from, silica, alumina, silica-alumina, or silica-coated alumina treated with at least one electron-withdrawing anion. For example, the silica-coated alumina can, in this aspect, have an alumina to silica weight ratio in the range of about 1:1 to about 100:1, or about 2:1 to about 20:1. The at least one electron-withdrawing anion can include, or can be selected from, fluoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate, etc., or combinations thereof.

[0296] In one aspect, the optional co-activator support can be selected from, for example, aluminum fluoride, aluminum chloride, aluminum bromide, aluminum sulfate, fluorinated silica-alumina, chlorinated silica-alumina, brominated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, chlorinated silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, etc., and any one or any combination thereof can be used in the catalyst compositions disclosed herein. Alternatively, or additionally, the co-activator support can include, or can be selected from, solid oxides treated with electron-withdrawing anions such as fluorinated silica-alumina, or sulfated alumina.

[0297] Examples of the cocatalyst support can include, but are not limited to, those listed in the aspect section of the present disclosure.

[0298] N. Catalyst System and Its Preparation One aspect provided by the present disclosure is the preparation of a catalyst system comprising a smectite heteroaddition and a transition metal precatalyst, particularly a metallocene. In one aspect, the catalyst system for olefin polymerization is (a) at least one metallocene compound, and (b) at least one supported activator according to any aspect of the present disclosure. The use of the term "catalyst system" encompasses the catalyst system containing these components, and the "catalyst system" can further include at least one cocatalyst such as an alkylaluminum compound and / or at least one cocatalyst such as methylaluminoxane (MAO) in combination with these components. The present disclosure also provides a method for preparing a catalyst system, the method comprising contacting (a) at least one metallocene compound and (b) at least one supported activator containing a smectite heteroaddition according to the present disclosure in a second liquid carrier. This method for preparing a catalyst system can further include contacting at least one cocatalyst such as an alkylaluminum compound and / or at least one cocatalyst such as methylaluminoxane (MAO) in the second liquid carrier, and the contacting can occur in any order.

[0299] In the catalyst system, the formula (X 1 )(X 2 )(X 3 )(X 4)The relative concentration or ratio of a metallocene such as a four-group metallocene of M and a calcined clay-surfactant heteroadduct can be expressed as the moles of M (metal) per gram of the calcined clay heteroadduct (mol M / g heteroadduct). In one embodiment, it has been found that the molar ratio of M per gram of the calcined clay heteroadduct can be in the range of about 0.025 mol M / g heteroadduct to about 0.000000005 mol M / g heteroadduct. In another embodiment, the moles of M per gram of the calcined clay heteroadduct can be used in the range of about 0.0005 mol M / g heteroadduct to about 0.00000005 mol M / g heteroadduct, or alternatively, in the range of about 0.0001 mol M / g heteroadduct to 0.000001 mol M / g heteroadduct. Similar to all ranges disclosed herein, these recited ranges include the endpoints within the recited ranges, as well as intermediate values and subranges. These ratios reflect the catalyst recipe, i.e., these ratios are based on the amounts of the components combined to obtain the catalyst composition regardless of what the ratios are in the final catalyst.

[0300] In a catalyst system, the relative concentration or ratio of a cocatalyst to the calcined clay heteroadduct can be expressed as the moles of the cocatalyst (e.g., an organoaluminum compound) per gram of the calcined clay heteroadduct (mol cocatalyst / g heteroadduct). In one embodiment, it has been found that the ratio of the number of moles of a cocatalyst such as an organoaluminum compound per gram of the calcined clay heteroadduct can be in the range of about 0.5 mol of cocatalyst / g of heteroadduct to about 0.000005 mol of cocatalyst / g of heteroadduct. In another embodiment, the molar ratio of the cocatalyst per gram of the calcined clay heteroadduct that can be used is within the range of about 0.1 mol cocatalyst / g heteroadduct to about 0.00001 mol cocatalyst / g heteroadduct, or alternatively, within the range of about 0.01 mol cocatalyst / g heteroadduct to about 0.0001 mol cocatalyst / g heteroadduct.

[0301] The catalyst composition can be produced by bringing a transition metal compound such as a metallocene, a calcined clay heteroadduct, and a cocatalyst such as an organoaluminum compound into contact under suitable conditions. The contact can occur in any number of ways, for example, by blending, contact in a carrier liquid, feeding the respective components separately or in any order or combination into a reactor. For example, various combinations of components or compounds can be brought into contact with each other before being further contacted with the remaining compound(s) or component(s) in the reactor. Alternatively, all three components or compounds can be brought into contact together before being introduced into the reactor. With respect to additional optional components that can be used in the catalyst systems disclosed herein, such as coactivators, ionizing ionic compounds, etc., the step of contacting using these optional components can occur in any way and in any order.

[0302] In one aspect, the catalyst composition can be prepared by first contacting a transition metal compound such as a metallocene with a cocatalyst such as an organoaluminum compound for a time of about 1 minute to about 24 hours, or alternatively about 1 minute to about 1 hour, at a contact temperature in the range of about 10°C to about 200°C, alternatively about 12°C to about 100°C, alternatively about 15°C to about 80°C, or alternatively about 20°C to about 80°C to form a first mixture, and then contacting this first mixture with a calcined clay heteroadduct to form the catalyst composition.

[0303] In another aspect, the metallocene, a cocatalyst such as an organoaluminum compound, and a calcined clay heteroadduct can be pre-contacted before being introduced into the reactor. For example, the pre-contact step can occur over a period of about 1 minute to about 6 months. In one aspect, for example, the pre-contact step can occur over a period of about 1 minute to about 1 week at a temperature of about 10°C to about 200°C, or about 20°C to about 80°C to provide an active catalyst composition. Further, any subset of the final catalyst components can also be pre-contacted in one or more pre-contact steps each having its own pre-contact period.

[0304] After precontacting any or all of the catalyst system components, the catalyst composition can be said to include postcontact components. For example, the catalyst composition can include a postcontact metallocene, a postcontact cocatalyst such as an organoaluminum compound, and a postcontact calcined clay heteroduct component. In the field of catalyst technology, it is not uncommon that the specific and detailed nature of the active catalyst sites, as well as the specific nature and fate of each component used to make the active catalyst, are not precisely known. While not intending to be bound by theory, the majority of the weight of the catalyst composition based on the relative weight of the individual components can be considered to include the postcontact calcined clay adduct. Since the nature of the active sites and the postcontact components are not precisely known, the catalyst composition can simply be described according to its components or can be referred to as including postcontact compounds or components.

[0305] As used herein, the first liquid carrier is the liquid carrier in which the smectite adduct is prepared, and the second liquid carrier is the liquid in which the catalyst system is prepared. The second liquid carrier can be any liquid carrier in which a metallocene can be contacted with the smectite adduct to prepare a supported precatalyst or catalyst without decomposing the metallocene or the smectite adduct. In embodiments, the second liquid carrier can include, consist essentially of, or be selected from cyclohexane, isobutane, n-butane, propane, n-pentane, isopentane, neopentane, n-hexane, naphtha, hydrotreated naphtha, Isopar™, at least one olefin, or any combination thereof. The second liquid carrier can further include at least one olefin.

[0306] As disclosed, a catalyst system for olefin polymerization can comprise, or consist essentially of, (a) at least one metallocene compound and (b) at least one support activator according to the present disclosure. The catalyst system can also further comprise (c) at least one cocatalyst, (d) at least one co-activator, or a combination thereof. The catalyst system can also further comprise a fluid carrier. In the present disclosure, "fluid carrier" is used to describe a carrier in which the catalyst system and at least one olefin contact to form a polyolefin. Thus, since the polymerization using the catalyst system of the present disclosure can be carried out under conditions such as slurry or fixed-bed polymerization conditions, or under gas-phase polymerization conditions, the fluid carrier can be a liquid or a gas.

[0307] In one aspect, the fluid carrier can comprise, consist essentially of, or be selected from nitrogen; hydrocarbons such as cyclohexane, isobutane, n-butane, propane, n-pentane, isopentane, neopentane, n-hexane, naphtha, hydrotreated naphtha, or Isopar™; at least one olefin; or any combination thereof. However, the polymerization using the present catalyst system can be carried out using any fluid carrier that can be used with the supported catalyst. In another aspect, the fluid carrier can comprise, or consist essentially of, a liquid or gaseous hydrocarbon, ether, or a combination thereof, each of which independently has 2 to 20 carbon atoms.

[0308] O. Polymerization Activity of Isolated Clay-Heterocoagulants The data in Tables 1, 2, and 3 disclose the composition, surface area / pore volume characteristics, and polymerization activity of smectite clay support activators produced by contacting clay with either an exemplary cationic polymethalate (aluminum chloride hydrate), a surfactant, or a combination of a cationic polymethalate and a surfactant.

[0309] The heteroadditives of Table 1 and Table 2 are isolated by rotary evaporation drying under specified conditions, while the heteroadditives of Table 3 are isolated by spray drying from an aqueous slurry.

[0310] The polymerization activity of a catalyst composition containing a clay heteroadditive support activator can be expressed as the weight of the polymer per weight of the support activator containing the calcined smectite heteroadditive, per unit time, for example, grams of polymer / gram (calcined) support activator / hour (g / g / hour). That is, the activity can be calculated based on the support activator alone in the absence of any metallocene or cocatalyst component. This measurement enables comparison of various support activators, including those with other activators where the metallocene, cocatalyst, and other conditions are the same or substantially the same.

[0311] Unless otherwise specified, the activity disclosed in the examples was measured under slurry polymerization conditions using isobutane as a diluent, at a polymerization temperature of about 50 °C to about 150 °C (for example, at a temperature of 90 °C), and using a combined pressure of ethylene and isobutane in the range of about 300 psi to about 800 psi, for example, 450 psi for the combined total of ethylene and isobutane. The activity data are reported as the weight of the polymer produced divided by the weight of the calcined clay - surfactant heteroadditive per hour.

[0312] Catalytic activity can be a function of metallocene and calcined clay adducts, as well as other components and conditions. Under the conditions described above, the activity based on the weight of the calcined clay-surfactant adduct and the calcined clay-cationic polymethalate-surfactant adduct can exceed 1,000 grams of polyethylene (PE) polymer per gram of calcined clay adduct per hour (g PE / g adduct / hour, or simply g / g / hour or g / g / h). In another aspect, the catalytic activity based on the weight of the calcined clay adduct can be greater than 250 g / g / hour, greater than 500 g / g / hour, greater than 1,000 g / g / hour, greater than 1,500 g / g / hour, greater than 2,000 g / g / hour, greater than 3,000 g / g / hour, greater than 5,000 g / g / hour, greater than 7,500 g / g / hour, greater than 10,000 g / g / hour, greater than 15,000 g / g / hour, greater than 20,000 g / g / hour, greater than 30,000 g / g / hour, greater than 40,000 g / g / hour, greater than 50,000 g / g / hour, greater than 60,000 g / g / hour, greater than 70,000 g / g / hour, or greater than 80,000 g / g / hour. In some aspects, one upper limit of the activity can be about 100,000 g / g / hour so that the activity can be greater than the disclosed values and less than 100,000 g / g / hour.

[0313] For example, in one embodiment and using the conditions described herein, the support activator can have a polymerization activation activity of about 250 g / g / hour, about 300 g / g / hour, about 400 g / g / hour, about 500 g / g / hour, about 750 g / g / hour, about 1,000 g / g / hour, about 1,250 g / g / hour, about 1,500 g / g / hour, 1,750 g / g / hour, about 2,000 g / g / hour, about 2,500 g / g / hour, about 3,500 g / g / hour, about 5,000 g / g / hour, about 7,500 g / g / hour, about 10,000 g / g / hour, about 12,500 g / g / hour, about 15,000 g / g / hour, about 17,500 g / g / hour, about 20,000 g / g / hour, about 25,000 g / g / hour, about 30,000 g / g / hour, about 40,000 g / g / hour, about 50,000 g / g / hour, about 60,000 g / g / hour, about 70,000 g / g / hour, about 80,000 g / g / hour, about 90,000 g / g / hour, or about 100,000 g / g / hour, including any range between these values. Higher values of polymerization activity can associate with clay supports having extremely high site densities, and these activity values can also be dependent on the metallocene. Thus, by applying the teachings herein, an activity level within the range between two of the recited values can be achieved. For example, the activity level can be within the range of 250 to 35,000 g / g / hour, as well as within the range of 300 to 30,000 g / g / hour, 400 to 25,000 g / g / hour, or 500 to 20,000 g / g / hour. In one embodiment, the hetero-coagulation of the clay by the surfactant reagent provides a support activator having substantially increased polymerization activity compared to a seed prepared similarly without contact with the surfactant.

[0314] In one aspect, no aluminoxane, such as methylaluminoxane, was required to activate the metallocene and form the catalyst composition. Methylaluminoxane (MAO) is an expensive activator compound that can significantly increase the polymer production cost. Further, in another aspect, no organoboron compound or ionizing compound, such as a borate compound, was required to activate the metallocene and form the catalyst composition. Further, ion exchange, protonic acid treatment, or pillared clays, which also require multi-step preparation and increase the cost, were not required to activate the metallocene and form the catalyst composition. Thus, the active heterogeneous catalyst composition can be easily and inexpensively produced and used to polymerize olefin monomers, including comonomers if desired, in the absence of any aluminoxane compound, boron compound or boric acid compound, ion-exchanged, protonic acid-treated, or pillared clay. MAO or other aluminoxane, boron compound or borate compound, ion-exchanged clay, protonic acid-treated clay, or pillared clay is not required in the disclosed catalyst system, but these compounds can be used in reduced or typical amounts according to other aspects of the present disclosure.

[0315] The catalytic activities of the examples and Tables 1-3 were measured under slurry homopolymerization conditions for the homopolymerization of ethylene, using isobutane as the diluent, a polymerization temperature of 80 °C, and a combined total pressure of ethylene and isobutane of 350 psi, and a (η 5 -1-n-butyl-3-methyl-cyclopentadienyl)2ZrCl2 and triethylaluminum (AlEt3) catalyst composition, unless otherwise stated.

[0316] Throughout the present disclosure, the drying process of the support activator can be described as azeotropic (e.g., rotary evaporation from 1-butanol and water) and non-azeotropic (rotary evaporation from water only), or spray drying (from an aqueous suspension or a specified suspension). Further, the surface of the support activator can be made more hydrophobic by the addition of a surfactant in any of these drying processes. If desired, these methods can be combined, such as drying by an azeotropic or non-azeotropic process, followed by resuspending the adduct and spray drying from an aqueous slurry in the presence of a surfactant. The tightly bound water can then be removed from the dried adduct (support activator), for example, prior to their use as catalyst support activators, by calcination, heating in a fluidized bed, etc.

[0317] Table 1 reports the properties and polymerization data for azeotropic (1-butanol and water) and non-azeotropic (water only), calcined, clay-aluminum chlorohydrate (ACH) support activators. These support activators were prepared in the absence of a surfactant and were dried by (rotary) evaporation from a slurry rather than by spray drying. Runs 1-4 in Table 1 demonstrate that clay-ACH adducts that have undergone azeotropic drying exhibit very good catalytic activity when calcined (2000-4000 gPE / g support activator / hour), while Run 5 in Table 1 demonstrates that drying these adducts from a water-only slurry in the absence of an azeotropic agent produces a support with little to no catalytic activity (<200 gPE / g support activator / hour). Thus, attempts to dry clay-ACH support activators in this manner from an aqueous slurry without an organic azeotropic agent have resulted in a loss of activity and porosity from water-only drying.

[0318] In contrast, Runs 7 - 32 in Table 2 combine clay with surfactant tetraoctylammonium bromide, tetrabutylammonium bromide, and tetramethylammonium bromide, respectively, and then dry it by (rotary) evaporation from a slurry of only water in the absence of an azeotropic agent to produce a catalytically active species for ethylene polymerization. Runs 7 - 32 in Table 2 demonstrate activity in the range of 1000 - 3000 g PE / g support activator / hour. Run 2 in Table 2 uses clay combined with both a surfactant (tetraoctylammonium bromide) and aluminum chlorohydrate, dried as an aqueous-only slurry, to compare the activity of the clay - ACH - surfactant hetero - adduct. This sample also demonstrates enhanced polymerization activity (>2000 g PE / g support activator / hour) compared to Run 1 in Table 2 (<200 g PE / g support activator / hour), which is a species containing only clay and aluminum chlorohydrate in the absence of a surfactant.

[0319] Run 6 in Table 2 (Example 8 - B3) provides an example of forming a clay - aluminum chlorohydrate - surfactant hetero - adduct as a support activator in ethylene homopolymerization using the non - ionic surfactant dextrose. The activity of the sample is moderate (75 g PE / g support activator / hour), but its activity exceeds twice the activity provided by the clay - aluminum chlorohydrate hetero - adduct support activator of Run 1 in Table 2 (Example 5 - A4) in the absence of any type of surfactant.

[0320] Run 5 in Table 2 (Example 7 - B2) shows the use of the phosphonium salt cationic surfactant trihexyltetradecylphosphonium bromide to form a clay - surfactant hetero - adduct. The activity of this support activator in ethylene homopolymerization was found to be 184 g PE / g support activator / hour, which is slightly lower than that of most ammonium salt cationic surfactant hetero - adducts.

[0321] Finally, Runs 3 and 4 in Table 2 (Examples 28-C1 and 29-C2) are combined with smectite clay using ammonium bromide [NH4]Br instead of any hydrocarbylammonium surfactant. When the clay is combined with ammonium cations that have no hydrocarbyl moiety bonded to the ammonium nitrogen, little coagulation product of the clay and ammonium bromide was observed. Without intending to be bound by theory, it is believed that the same type of hetero-coagulum formed by the hydrocarbylammonium moiety is not formed in this reaction. The activity of this ammonium bromide-treated clay support activator in ethylene homopolymerization was found to be about 300 - 400 gPE / g support activator / hour.

[0322] Thus, in one aspect, a clay-surfactant support activator prepared in the absence of a cationic polymethalate according to the present disclosure can be combined with a metallocene pro-catalyst to obtain an olefin polymerization catalyst exhibiting surprising polymerization activity of about 300 gPE / g support activator / hour to about 2,500 gPE / g support activator / hour. Optionally, other hetero-coagulants (such as aluminum polyoxometalates) can be combined with the mixture of the clay and the surfactant. Thus, even a clay cationic polymethalate support activator, when prepared in the presence of a surfactant to form a clay-cationic polymethalate-cationic surfactant support activator, can exhibit a significant enhancement in activity (compare Run 1 and Run 2 in Table 2). A large increase in the BJH pore volume is observed with this increase in activity. The activity enhancement using a surfactant is not limited to cationic surfactants, and nonionic surfactants can also impart an improvement in the activity of the clay-cationic polymethalate support activator (compare Run 6 in Table 2).

[0323] While not desiring to be bound by theory, the increased porosity of the clay heteroaddition species reported in this disclosure is thought to facilitate the diffusion and accessibility of metallocene compounds to the ionized sites on the clay heteroaddition surface, enabling the increased polymerization activity of these clay-surfactant species.

[0324] Regarding the activity of the isolated spray-dried heteroagglomerates, the clay heteroadditions spray-dried from aqueous slurries have been found to exhibit surprisingly high sphericity, roundness, and circularity and to maintain excellent polymerization activity. This combination of properties confers process advantages in their use as polymerization support activators, such as providing excellent flow and packing properties for catalyst particles for use in catalyst bed systems.

[0325] The data in Table 3 show the characteristics and polymerization data for [1] clay-aluminum chlorohydrate (ACH) support activators, [2] clay-ACH-surfactant support activators, and [3] clay-surfactant support activators that have been spray-dried, calcined, and heteroagglomerated. Polymerization was carried out at a reactor pressure of 350 psi and 80 °C using (η 5 -1-n-butyl-3-methyl-cyclopentadienyl)2ZrCl2 as the metallocene and triethylaluminum (AlEt3) as the cocatalyst, and the percentages in Table 3 are weight percentages relative to the clay. The ACH component is present at a concentration of 1.54 mmol Al / g clay.

[0326] The results in Table 3 demonstrate the surprising finding that excellent polymerization activity can be achieved even in the absence of cationic polymethalate, using smectite clay-surfactant heteroadditions that have been spray-dried from aqueous slurries and calcined, as in Runs 3-6. These clay-surfactant heteroaddition data (Runs 3-6) are equivalent to those of the clay-ACH-surfactant heteroadditions spray-dried from aqueous slurries in Runs 7-10.

[0327] These clay-surfactant adduct data (runs 3 - 6) exhibit substantially better activity than the relatively low activity observed from clay-cationic polymethalate (ACH) adducts prepared in the absence of surfactant in runs 1 - 2, which are spray dried from an aqueous slurry. In particular, when these clay-cationic polymethalate (ACH) adducts are azeotroped but not spray dried, as in runs 3 and 4 of Table 1, their polymerization activity exceeds 2500 g / g / hour. This observation is consistent with the significant decrease in polymerization activity obtained when the clay-ACH adduct is non-azeotropically dried from a slurry of water only, as in run 5 of Table 1.

[0328] Thus, the clay-surfactant adducts and the clay-cationic polymethalate-surfactant adducts can be spray dried and subsequently calcined, and when combined with a metallocene pre-catalyst, yield a catalyst having a high catalytic activity (1400 - 3000 gPE / g support activator / hour) for olefin polymerization, as shown in Table 3, items 3 - 10. In an embodiment, the spray drying process can be carried out with the clay-surfactant adducts and the clay-cationic polymethalate-surfactant adducts slurried in an alcohol / water mixture. In other embodiments, this spray drying process can be carried out on these adducts slurried in water in the absence of an organic liquid.

[0329] In one aspect, when clay-surfactant adducts and clay-cationic polymethacrylate-surfactant adducts are isolated, for example, by filtering the slurry in which the adducts are prepared, the isolated adducts can be resuspended in the slurry and subsequently spray dried. For example, in an embodiment, spray drying is carried out for a certain period of time with a slurry obtained by resuspending the "filter cake" of the clay-surfactant adduct in a liquid carrier used for spray drying and stirring or agitating under high shear conditions and the like. In an embodiment, spray drying is carried out for a period of 15 minutes to 24 hours with a slurry obtained by resuspending the filter cake of the clay-surfactant adduct in a liquid carrier used for spray drying. In other embodiments, spray drying is carried out for a period of 24 minutes to 72 hours with a slurry obtained by resuspending the filter cake of the clay-surfactant adduct in a liquid carrier used for spray drying and stirring or agitating the mixture.

[0330] In one aspect, the advantage of using a surfactant can be realized when it is introduced at different times before spray drying the resulting heteroagglomerates. For example, Runs 3 - 6 in Table 3 show that the surfactant and clay are contacted before the preparation of the spray drying feed, i.e., the clay - surfactant is formed and isolated, and subsequently resuspended to prepare the spray drying feed. Alternatively, Runs 7 - 10 in Table 3 show embodiments where the surfactant can be introduced directly into the spray drying feed of the isolated and resuspended clay - cationic polymethacrylate heteroaddition product. In these runs (Examples 23 - E3 and 24 - E4), the clay - ACH heteroaddition product was prepared, filtered off, and the resulting wet cake was resuspended in water with the surfactant to form the spray drying feed. These samples were fired after spray drying and showed good porosity, with the tetrabutylammonium bromide samples (Runs 7 - 8, Example 23 - E3) having a total BJH porosity of 0.273 cc / g and the tetraoctylammonium bromide samples (Runs 9 - 10, Example 24 - E4) having a total BJH porosity of 0.123 cc / g. Without intending to be bound by theory, these latter Runs 7 - 10 in Table 3 are also referred to herein as forming clay - cationic polymethacrylate - surfactant heteroaddition products, but the method for making them is different from other heteroaddition products where the clay, ACH, and surfactant contact in the initial slurry of the clay.

[0331] Thus, in one aspect, when the spray-dried clay-surfactant adduct is calcined and the resulting support activator is combined with a metallocene and a cocatalyst to yield a polymerization catalyst, polymerization activity is demonstrated in the range of about 500 g PE / g support activator / hour to 2000 g PE / g support activator / hour. When polymers produced from these catalysts are compared to polymer particles produced from non-spray-dried support activators, lower particle size and higher particle uniformity in the polymer particles are observed for the spray-dried adduct polymers, providing desirable operability advantages when these catalysts are introduced into a fluidized reactor bed system. For example, the data in Table 4 show [1] an azeotropic clay-aluminum chlorohydrate (ACH) support activator produced in the absence of surfactant (see Comparative Example 2-A1 and Run 1 of Table 1), [2] an isolated clay-aluminum chlorohydrate (ACH) adduct spray-dried in the presence of tetrabutylammonium bromide surfactant (see Example 23-E3 and Run 7 of Table 3), and [3] an isolated clay-aluminum chlorohydrate (ACH) adduct spray-dried in the presence of tetraoctylammonium bromide surfactant (see Example 24-E4 and Run 10 of Table 3), for polyethylene homopolymers produced using, demonstrating the higher coefficient of uniformity of the adducts of the present invention spray-dried in the presence of surfactant.

[0332] Accordingly, the present disclosure demonstrates the utility of a process that minimizes the porosity loss typically associated with spray-dried clay slurries and enables the production of a catalyst that is both active and exhibits a desirable morphology for use in a catalyst bed.

[0333] Accordingly, at least the following unexpected results are provided and demonstrated through the present disclosure. 1. A smectite clay-surfactant adduct prepared in the absence of cationic polymethalate and in the absence of any other additives can provide a support activator capable of achieving excellent polymerization activity. 2. When the surfactant is used in combination with a smectite clay and a cationic polymethalate, the resulting smectite clay-cationic heteroaddition-surfactant heteroaddition can achieve significantly higher polymerization activity compared to similar clay-polymethalate heteroadditions prepared in the absence of the surfactant. 3. The surfactant can be combined with the smectite clay in the absence of other additives, or the surfactant can be combined with the smectite clay and the cationic polymethalate to form isolated heteroadditions in any order or by any means. For example, the surfactant can form a heteroaddition in combination with the smectite clay, regardless of the presence or absence of the cationic polymethalate, or the surfactant can be used to contact the smectite clay-cationic polymethalate heteroaddition during the formation of the heteroaddition, or afterwards, for example, when preparing a spray-dried feed of the clay-polymethalate heteroaddition. 4. The use of the surfactant to prepare the smectite clay-surfactant heteroaddition and the smectite clay-cationic polymethalate-surfactant heteroaddition enables spray drying of the heteroaddition from a slurry of only water, without the need to use an organic liquid such as an azeotropic drying process with water, and still provides high polymerization activity. 5. The heteroadditions spray dried from the aqueous slurry exhibit surprisingly high sphericity, roundness, and circularity, which impart process advantages to their use as polymerization support activators, such as providing excellent flow and packing characteristics to the catalyst particles for use in a catalyst bed system. 6. The polymer particles produced using the spray-dried heteroaddition support activator of the present invention are characterized by having a lower particle size and higher particle uniformity than their non-surfactant analogs, and these properties provide desirable operability advantages when these catalysts are introduced into a fluidized reactor bed system.

[0334] P. Polyolefins and Polymerization Processes In one aspect, the present disclosure describes a process of contacting at least one olefin monomer with a disclosed catalyst composition to produce at least one polymer (polyolefin). The term "polymer" is used herein to include homopolymers, copolymers of two olefin monomers, and polymers of more than two olefin monomers such as terpolymers. For convenience, polymers of two or more olefin monomers are simply referred to as copolymers. Thus, a catalyst composition can be used to polymerize at least one monomer to produce a homopolymer or a copolymer.

[0335] In one aspect, the homopolymer consists of monomer residues having from 2 to about 20, preferably from 2 to about 10 carbon atoms per molecule. Olefin monomers can include, or be selected from, ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 3-ethyl-1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and mixtures thereof. In one aspect, homopolymers of ethylene, homopolymers of propylene, and homopolymers of other olefins are encompassed by the present disclosure. In another aspect, copolymers of ethylene and at least one comonomer, and more generally copolymers of two non-ethylene comonomers, are encompassed by the present disclosure.

[0336] When a copolymer is desired, each monomer may have from about 2 to about 20 carbon atoms per molecule. As comonomers for ethylene, for example, there may be mentioned aliphatic 1-olefins having from 3 to 20 carbon atoms per molecule such as propylene, 1-butene, 2-butene, 1-pentene, 2-pentene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 3-ethyl-1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, styrene, vinylcyclohexane, and other olefins, and conjugated or non-conjugated diolefins such as 1,3-butadiene, isoprene, piperylene, 2,3-dimethyl-1,3-butadiene, 1,4-pentadiene, 1,7-hexadiene, and other such diolefins and mixtures thereof, but are not limited thereto. In a further aspect, ethylene may be copolymerized with at least one comonomer including or selected from 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, or 1-decene. An amount of comonomer can be introduced into a reactor zone sufficient to produce a copolymer incorporating from about 0.01 wt% to about 10 wt% of comonomer based on the total weight of monomers and comonomers in the copolymer, or alternatively from about 0.01 wt% to about 5 wt% of comonomer can be introduced, or alternatively still from about 0.1 wt% to about 4 wt% of comonomer can be introduced, or alte...

Claims

1. A support activator comprising a smectite heteroadduct, wherein the smectite heteroadduct is present in a first liquid support and in the absence of any other reactants. (a) Colloidal smectite clay and (b) comprising a contact product with a surfactant selected from cationic surfactants, nonionic surfactants, amphoteric surfactants, or any combination thereof, The smectite heteroadduct is subjected to a granulation process including a stirring granulation process, a spray drying granulation process, a rolling granulation process, a briquette granulation process, a compression granulation process, an extrusion granulation process, a fluid bed granulation process, an emulsification granulation process, a suspension granulation process, or a press molding granulation process. Support activator.

2. The support activator according to claim 1, wherein the colloidal smectite clay and the surfactant are in contact at a ratio of 0.5 to 5 mmol of surfactant per gram of colloidal smectite clay.

3. The support activator according to claim 1, wherein the smectite heteroadduct is isolated from the first liquid support.

4. The support activator according to claim 1, wherein the smectite clay comprises montmorillonite, souconite, nontronite, hectorite, byderite, saponite, bentonite, or any combination thereof.

5. The support activator according to claim 1, wherein the surfactant includes a cationic surfactant.

6. The surfactant comprises a cationic surfactant selected from primary, secondary, tertiary, or quaternary ammonium compounds or phosphonium compounds having the following formula: [R １ R ２ R ３ R ４ N] ＋ X － or [R １ R ２ R ３ R ４ P] ＋ X － , wherein, Each R １ , R ２ , R ３ , and R ４ However, hydrogen, substituted or unsubstituted C １ -C ２５ Hydrocarbyl group, or substituted or unsubstituted C １ -C ２５ Selected independently of heterohydrocarbyl groups, R １ , R ２ , R ３ , and R ４ Any two of these may be part of the ring structure, R １ , R ２ , R ３ , and R ４ At least one of them is a non-hydrogen part, X － The support activator according to claim 1, wherein the activator is selected from organic or inorganic monoanions.

7. The surfactant comprises a cationic surfactant selected from primary, secondary, tertiary, or quaternary ammonium compounds having the following formula: [R] １ R ２ R ３ R ４ N] ＋ X － In the formula, Each R １ , R ２ , R ３ , and R ４ However, hydrogen, substituted or unsubstituted C ２ -C ２５ Hydrocarbyl group, or substituted or unsubstituted C １ -C ２５ Selected independently of heterohydrocarbyl groups, R １ , R ２ , R ３ , and R ４ Any two of these may be part of the ring structure, R １ , R ２ , R ３ , and R ４ The support activator according to claim 6, wherein at least one of the members is a non-hydrogen portion.

8. The support activator according to claim 1, wherein the surfactant comprises a nonionic surfactant.

9. The support activator according to claim 8, wherein the nonionic surfactant is selected from ethoxylates, glycol ethers, fatty alcohol polyglycol ethers, or any combination thereof; amphoteric surfactants containing an anionic surfactant moiety and a cationic surfactant within the same molecule; or a combination thereof.

10. The nonionic surfactant is (a) A polyhydric alcohol containing two, three or more hydroxyl groups, a polyhydric alcohol having the formula CH₂OH(CHOH)nCH₂OH (where n is an integer from 2 to 5), a monoalkyl ether of a polyhydric alcohol, a dialkyl ether of a polyhydric alcohol, or any of these polyalkylene glycols, i.e., the polyalkylene glycol of the polyhydric alcohol, the monoalkyl ether of the polyhydric alcohol, or the dialkyl ether of the polyhydric alcohol, (b) Glycerol, 1,2,4-butanetriol, erythritol, pentaerythritol, maltitol, xylitol, sorbitol, ethylene glycol, propylene glycol, diethylene glycol, poly(ethylene) glycol, poly(propylene) glycol, or combinations thereof (c)(i) fatty acids comprising or selected from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, ricinoleic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoeladic acid, alpha-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid, or any combination thereof, or (ii) fatty acids of (c)(i) condensed with one or more alcohols having hydroxyl groups, (d) Hydrocarbyl (hydrocarbon) sulfonates having the formula R1 SO2 OR 2, wherein R1 and R2 are independently selected from substituted or unsubstituted C1-C25 alkyl-, C6-C25 aryl-, C7-C25 aralkyl-, or C7-C25 alkal-, (e) Glucose, fructose, mannose, maltose, lactose, sucrose, cyclodextrin, maltodextrin, glucosamine, glucoronic acid, or any combination thereof (f) A silane having the formula R1SiX3, R1R2SiX2, or R1R2R3SiX, wherein (i) R1, R2, and R3 are independently selected from substituted or unsubstituted C1-C25 hydrocarbyl groups, C1-C25 heterohydrocarbyl groups, or any other group that is hydrolyzably stable when bonded to silicon in the nonionic surfactant, and (ii) X is independently selected from C1-C25 alkoxys, C1-C25 acyloxys, halogens, or C1-C25 amines, or another hydrolyzable group that is converted to a hydroxyl group (-OH) upon hydrolysis, or (g) amino acids, selected from The support activator according to claim 8.

11. A support activator comprising a smectite heteroadduct, wherein the smectite heteroadduct is present in a first liquid support and in the absence of any other reactants. (a) Colloidal smectite clay and (b) comprising a surfactant selected from amphoteric surfactants and a contact product thereof Support activator.

12. The support activator according to claim 11, wherein the amphoteric surfactant comprises a cationic portion and an anionic portion, the cationic portion being selected from a primary amine, a secondary amine, a tertiary amine, or a quaternary ammonium cation, and the anionic portion being selected from a sulfate, sulfonate, phosphate, or carboxylate.

13. The support activator according to claim 11, wherein the amphoteric surfactant is selected from amino acids, polypeptides, proteins, sultaine, hydroxysultaine, betaine, amine N-oxide, phospholipids, or sphingomyelin, or a combination thereof.

14. The support activator according to claim 11, wherein the amphoteric surfactant is selected from lauramidopropyl hydroxysultaine, cocamidopropyl hydroxysultaine, oleamidopropyl hydroxysultaine, taroamidopropyl hydroxysultaine, ercamidopropyl hydroxysultaine, lauryl hydroxysultaine, N,N,N-trimethylglycine, cocamidopropyl betaine, phosphatidylserine, phosphatidylethanolamine, phosphatidylcholine, lauryldimethylamine oxide, myristamine oxide, pyridine-N-oxide, N-methylmorpholine-N-oxide, 3-[(3-coramidopropyl)dimethylammonio]-1-propanesulfonate, or a combination thereof.

15. The smectite heteroadduct has the following properties: (i) The smectite heteroadduct has an average particle sphericity (SPHT3) of 0.65 or higher, (ii) The smectite heteroadduct has an average particle roundness of 0.65 or more, (iii) The support activator according to claim 1, characterized in that the smectite heteroadduct has an average particle circularity of 0.65 or more, one of these, or any combination thereof.

16. The support activator according to claim 1, wherein the smectite heteroadduct is characterized by an average particle sphericity of 0.70 or more, or an average particle circularity (SPHT3) of 0.70 or more.

17. The support activator according to claim 1, wherein the smectite heteroadduct is subjected to a spray drying granulation process.

18. The support activator according to claim 1, wherein the smectite heteroadduct is calcined.

19. A catalyst composition for olefin polymerization, wherein the catalyst composition is a) at least one metallocene compound, and b) A catalyst composition comprising at least one support activator comprising a calcined smectite heteroadduct, wherein the smectite heteroadduct comprises a contact product of [i] colloidal smectite clay and [ii] a surfactant selected from a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or any combination thereof, in a first liquid support and in the absence of any other reactants.

20. The catalyst composition according to claim 19, wherein the colloidal smectite clay and the surfactant are in contact at a ratio of 0.5 mmol to 5 mmol of surfactant per gram of colloidal smectite clay.

21. The catalyst composition is (c) at least one cocatalyst, (d) Fluid carrier, or The catalyst composition according to claim 20, further comprising such combinations.

22. The catalyst composition according to claim 21, wherein the at least one co-catalyst is selected from organoaluminum compounds, organoboron compounds, organozinc compounds, organomagnesium compounds, organolithium compounds, or any combination thereof.

23. The at least one metallocene compound is defined by the following formula: (X １ ) (X ２ ) (X ３ ) (X ４ ) has M, in the formula, (i) M is zirconium or hafnium, (ii) X １ However, it is a substituted or unsubstituted indenyl, fluorenyl, or cyclopentadienyl, and any substituent is C １ -C ２０ Hydrocarbil, C １ -C ２０ Heterohydrocarbyl, or condensed C ４ -C １２ Selected independently from the carbocyclic moiety, (iii)X ２ However, it is a substituted or unsubstituted indenyl or cyclopentadienyl, and any substituent is C １ -C ２０ Hydrocarbyl or C １ -C ２０ Selected independently from heterohydrocarbil, (iv) X ３ and X ４ However, halides, C １ -C ２０ Hydrocarbil, C １ -C ２０ Heterohydrocarbyl, or C １ -C ２０ Selected independently from organoheterils, (v) X １ and X ２ However, optionally, linked substituents > EX ５ ２ Bridged by, where E is selected from C or Si, and each X ５ However, C １ -C ２０ The catalyst composition according to claim 19, independently selected from hydrocarbyl.

24. The catalyst composition according to claim 19, wherein the smectite clay comprises montmorillonite, souconite, nontronite, hectorite, byderite, saponite, bentonite, or any combination thereof.

25. The catalyst composition according to claim 19, wherein the surfactant comprises a cationic surfactant.

26. The cationic surfactant is selected from primary, secondary, tertiary, or quaternary ammonium compounds or phosphonium compounds having the following formula: [R １ R ２ R ３ R ４ N] ＋ X － Or [R １ R ２ R ３ R ４ P] ＋ X － , wherein Each R １ 、R ２ 、R ３ 、and R ４ is independently selected from hydrogen, a substituted or unsubstituted C １ -C ２５ hydrocarbyl group, or a substituted or unsubstituted C １ -C ２５ heterohydrocarbyl group, and any two of R １ 、R ２ 、R ３ 、and R ４ can be part of a ring structure, and at least one of R １ 、R ２ 、R ３ 、and R ４ is a non-hydrogen moiety. X － The catalyst composition according to claim 25, wherein the catalyst is selected from organic or inorganic monoanions.

27. ​​The catalyst composition according to claim 19, wherein the surfactant comprises a nonionic surfactant.

28. The catalyst composition according to claim 27, wherein the nonionic surfactant is selected from ethoxylates, glycol ethers, fatty alcohol polyglycol ethers, or any combination thereof; amphoteric surfactants containing an anionic surfactant moiety and a cationic surfactant in the same molecule; or a combination thereof.

29. The nonionic surfactant is (a) A polyhydric alcohol containing two, three or more hydroxyl groups, a polyhydric alcohol having the formula CH₂OH(CHOH)nCH₂OH (where n is an integer from 2 to 5), a monoalkyl ether of a polyhydric alcohol, a dialkyl ether of a polyhydric alcohol, or any of these polyalkylene glycols, i.e., the polyalkylene glycol of the polyhydric alcohol, the monoalkyl ether of the polyhydric alcohol, or the dialkyl ether of the polyhydric alcohol, (b) Glycerol, 1,2,4-butanetriol, erythritol, pentaerythritol, maltitol, xylitol, sorbitol, ethylene glycol, propylene glycol, diethylene glycol, poly(ethylene) glycol, poly(propylene) glycol, or combinations thereof (c)(i) fatty acids comprising or selected from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, ricinoleic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoeladic acid, alpha-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid, or any combination thereof, or (ii) fatty acids of (c)(i) condensed with one or more alcohols having hydroxyl groups, (d) Hydrocarbyl (hydrocarbon) sulfonates having the formula R1 SO2 OR 2, wherein R1 and R2 are independently selected from substituted or unsubstituted C1-C25 alkyl-, C6-C25 aryl-, C7-C25 aralkyl-, or C7-C25 alkal-, (e) Glucose, fructose, mannose, maltose, lactose, sucrose, cyclodextrin, maltodextrin, glucosamine, glucoronic acid, or any combination thereof (f) A silane having the formula R1SiX3, R1R2SiX2, or R1R2R3SiX, wherein (i) R1, R2, and R3 are independently selected from substituted or unsubstituted C1-C25 hydrocarbyl groups, C1-C25 heterohydrocarbyl groups, or any other group that is hydrolyzably stable when bonded to silicon in the nonionic surfactant, and (ii) X is independently selected from C1-C25 alkoxys, C1-C25 acyloxys, halogens, or C1-C25 amines, or another hydrolyzable group that is converted to a hydroxyl group (-OH) upon hydrolysis, or (g) amino acids, selected from The catalyst composition according to claim 27.

30. The catalyst composition according to claim 19, wherein the surfactant includes an amphoteric surfactant.

31. The catalyst composition according to claim 30, wherein the amphoteric surfactant comprises a cationic moiety and an anionic moiety, the cationic moiety being selected from a primary amine, a secondary amine, a tertiary amine, or a quaternary ammonium cation, and the anionic moiety being selected from a sulfate, sulfonate, phosphate, or carboxylate.

32. The catalyst composition according to claim 30, wherein the amphoteric surfactant is selected from amino acids, polypeptides, proteins, sultaine, hydroxysultaine, betaine, amine N-oxide, phospholipids, or sphingomyelin, or a combination thereof.

33. The catalyst composition according to claim 30, wherein the amphoteric surfactant is selected from lauramidopropyl hydroxysultaine, cocamidopropyl hydroxysultaine, oleamidopropyl hydroxysultaine, taroamidopropyl hydroxysultaine, ercamidopropyl hydroxysultaine, lauryl hydroxysultaine, N,N,N-trimethylglycine, cocamidopropyl betaine, phosphatidylserine, phosphatidylethanolamine, phosphatidylcholine, lauryldimethylamine oxide, myristamine oxide, pyridine-N-oxide, N-methylmorpholine-N-oxide, 3-[(3-coramidopropyl)dimethylammonio]-1-propanesulfonate, or a combination thereof.

34. The smectite heteroadduct has the following properties: (i) The smectite heteroadduct has an average particle sphericity (SPHT3) of 0.65 or higher, (ii) The smectite heteroadduct has an average particle roundness of 0.65 or more, (iii) The catalyst composition according to claim 19, characterized in that the smectite heteroadduct has an average particle circularity of 0.65 or more, one of these, or any combination thereof.

35. The catalyst composition according to claim 19, wherein the smectite heteroadduct is characterized by an average particle sphericity (SPHT3) of 0.70 or more, or an average particle circularity of 0.70 or more.

36. The catalyst composition according to claim 19, wherein the smectite heteroadduct is subjected to a granulation process including a stirring granulation process, a spray drying granulation process, a rolling granulation process, a grinding granulation process, a briquette granulation process, a compression granulation process, an extrusion granulation process, a fluid bed granulation process, an emulsification granulation process, a suspension granulation process, or a press molding granulation process.

37. The catalyst composition according to claim 19, wherein the smectite heteroadduct is subjected to a spray drying granulation process.

38. The catalyst composition according to claim 19, wherein the smectite heteroadduct is calcined.

39. A process for polymerizing an olefin, comprising contacting at least one olefin monomer and a catalyst composition according to any one of claims 19 to 38 under polymerization conditions for forming a polyolefin, wherein the catalyst composition is a) at least one metallocene compound, and b) A process comprising at least one support activator comprising a calcined smectite heteroadduct, wherein the smectite heteroadduct comprises a contact product of [i] colloidal smectite clay and [ii] a surfactant selected from a cationic surfactant, an amphoteric surfactant, or a combination thereof, in a first liquid support and in the absence of any other reactants.

40. A process for polymerizing an olefin according to claim 39, wherein the at least one olefin monomer is selected from [a] ethylene or propylene, or [b] ethylene combined with at least one comonomer selected from propylene, 1-butene, 2-butene, 3-methyl-1-butene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 3-ethyl-1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1,3-butadiene, isoprene, piperylene, 2,3-dimethyl-1,3-butadiene, 1,4-pentadiene, 1,7-hexadiene, vinylcyclohexane, or any combination thereof.

41. A process for polymerizing an olefin according to claim 39, wherein the process comprises polymerization in a gas-phase reactor, a slurry loop, a double slurry loop in series, a plurality of slurry tanks in series, a slurry loop combined with a gas-phase reactor, a continuous stirring reactor in a batch process, or a combination thereof.

42. A method for producing a support activator containing a smectite heteroadduct, wherein the method comprises a first liquid support, (a) Colloidal smectite clay and (b) Providing a slurry of the smectite heteroadduct in the first liquid carrier by contacting a surfactant selected from a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or a combination thereof, The aforementioned contact step takes place in the absence of any other reactants. The smectite heteroadduct is subjected to a granulation process including a stirring granulation process, a spray drying granulation process, a rolling granulation process, a briquette granulation process, a compression granulation process, an extrusion granulation process, a fluid bed granulation process, an emulsification granulation process, a suspension granulation process, or a press molding granulation process. method.

43. (c) A method for producing a support activator according to claim 42, further comprising the step of isolating the smectite heteroadduct from the slurry.

44. (d) The steps of suspending the isolated smectite heteroadduct in a dispersion medium containing water to provide a suspension of the smectite heteroadduct in the dispersion medium, A method for producing the support activator according to claim 43, further comprising the step of (e) spray-drying the smectite heteroadduct from the suspension to provide the support activator in the form of fine particles.

45. (f) A method for producing the support activator according to claim 44, further comprising the step of calcining the support activator.

46. The smectite heteroadduct has the following properties: (i) The smectite heteroadduct has an average particle sphericity (SPHT3) of 0.65 or higher, (ii) The smectite heteroadduct has an average particle roundness of 0.65 or more, (iii) The smectite heteroadduct has an average particle circularity of 0.65 or more, a method for producing a support activator according to claim 42, characterized by any one of these or any combination thereof.

47. A support activator comprising a smectite heteroadduct, wherein the smectite heteroadduct is in a first liquid support and in the absence of any other reactants. (a) Colloidal smectite clay and (b) comprising a contact product with a surfactant selected from cationic surfactants, nonionic surfactants, amphoteric surfactants, or any combination thereof, The colloidal smectite clay and the surfactant come into contact at a ratio of 0.5 to 5 mmol of surfactant per gram of colloidal smectite clay. Support activator.

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