WO2023239560A1 - Activateurs de support composites d'argile et compositions de catalyseur - Google Patents

Activateurs de support composites d'argile et compositions de catalyseur Download PDF

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Publication number
WO2023239560A1
WO2023239560A1 PCT/US2023/023644 US2023023644W WO2023239560A1 WO 2023239560 A1 WO2023239560 A1 WO 2023239560A1 US 2023023644 W US2023023644 W US 2023023644W WO 2023239560 A1 WO2023239560 A1 WO 2023239560A1
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WIPO (PCT)
Prior art keywords
surfactant
clay
acid
heteroadduct
smectite
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PCT/US2023/023644
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English (en)
Inventor
Kevin Chung
Michael D. Jensen
Yiqun Fang
Casey ZAMZOW
II Charles R. Johnson
Mary Lou Cowen
Jenny CHUN-YU CHEN
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Formosa Plastics Corporaton, U.S.A.
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Priority claimed from US18/323,212 external-priority patent/US20230399420A1/en
Application filed by Formosa Plastics Corporaton, U.S.A. filed Critical Formosa Plastics Corporaton, U.S.A.
Publication of WO2023239560A1 publication Critical patent/WO2023239560A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16—Clays or other mineral silicates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/06—Catalyst characterized by its size
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound

Definitions

  • support-activators serve the dual role of activating the metallocene and functioning as a template upon which the growing polymer chain can precipitate.
  • Widely used support-activators include an inorganic metal oxide support such as silica or alumina treated with a co-catalyst or an activator.
  • One such support-activator is methylaluminoxane (MAO) on silica.
  • MAO methylaluminoxane
  • MAO is expensive to procure or make, and MAO/silica requires multiple subsequent processing steps such as washings before it can be used.
  • Various clay support-activators have been investigated in an attempt to reduce the costs and time required to make and use materials such as MAO/silica for metallocene activation. For example, U.S.
  • Patent Nos.6,531,552 Japan Polychem Corporation
  • 6,825,371 Mitsubishi Chemical Corporation
  • 7,220,695 ExxonMobil
  • the reaction of acids with ion-exchanged clays can cause replacement of interlayer ions with protons, thereby destroying its porous structure which provided its catalytic activity.
  • Patent No.9,200,093 to Sumitomo Chemical Company are also complex and expensive.
  • merely using a clay starting material in these approaches which exhibits a desirable particle size and morphology may not provide a support-activator having these properties. Therefore, there remains a need for highly active support-activators which are economical to prepare and isolate. This need is particularly evident in the production of metallocene-based polyolefins such as high clarity film resins.
  • Such support-activators would present significant cost advantages over currently used aluminoxane-based activators.
  • aspects of this disclosure provide new clay-based support-activators and processes for their preparation, catalyst compositions comprising the new support-activators, methods for making the catalyst compositions, and processes for polymerizing olefins.
  • the chemically-modified clay support-activators can readily activate metallocene compounds toward polymerization of olefins, they are surprisingly easy and cost-effective to prepare and recover in high yield.
  • the support-activators of this disclosure can demonstrate high polymerization activities and processability relative to acid-treated clay activators, in which clay structure degradation and pore collapse (often resulting in leaching of clay into solution) can occur during the activation process and preclude facile isolation and high polymerization activity of the resulting activators. Furthermore, the support-activators of this disclosure retain their desirable structural properties (for example, high pore volume, shape, and size) under granulation/drying conditions which often result in a high degree of pore collapse in other support-activators.
  • the clay heteroadducts described in this publication are efficient support-activators for metallocenes for olefin polymerization.
  • the cationic polymetallate is used in an amount relative to the colloidal smectite clay within a specific range, the smectite heteroadduct can be easily isolated from the resulting slurry by a conventional filtration process.
  • clay- based support-activators are termed clay or smectite “heteroadducts” or “composites”, or more specifically “clay (or smectite)-surfactant heteroadducts (or composites)”.
  • the isolation of these smectite-surfactant heteroadducts can be achieved using a conventional filtration, without the need for centrifugation or high dilution of reaction mixtures, and without extensive washing of the solid thus obtained.
  • This process provides the solid clay heteroadduct exhibiting better activity than the corresponding untreated clay, comparable activities to the more difficult-to-prepare pillared clay supports, and comparable activities to the heterocoagulated clays prepared using a cationic polymetallate, thereby fulfilling a need. It has been further discovered that a wide range of reagents used for preparing clay-based support-activators can be eliminated from the preparative method and still provide an active support-activator, providing significant advantages in their production. Moreover, these clay heteroadducts can be spray-dried from a suspension of the heteroadduct in a dispersion medium consisting essentially of water to form the support-activator, which provides economic and environmental advantages over prior methods requiring an organic liquid carrier.
  • the present disclosure provides a method of making a support- activator comprising a smectite heteroadduct, the method comprising or consisting essentially of contacting 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 to provide a slurry of the smectite heteroadduct in the first liquid carrier; wherein the contacting step may occur in absence of specific reactants.
  • the contacting step may be carried out [i] in the absence of: [A] a cationic polymetallate; [B] a non-layered silicate, a soluble silicate (for example, sodium silicate), a charged inorganic component, a metal oxide, an organic amide, an anionic surfactant, an inorganic acid, an organic acid, an inorganic base, an organic base, an 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 for cationic surfactant when present; or [iii] in the absence of any other reactant, except for the surfactant.
  • a cationic polymetallate for example, sodium silicate
  • This method of contacting in a first liquid carrier (a) a colloidal smectite clay; and (b) a surfactant can further comprise the step of: isolating the smectite heteroadduct from the slurry in the first liquid carrier.
  • the colloidal smectite clay and the surfactant can be contacted in a ratio of from 0.5 millimoles to 5 millimoles of surfactant per gram of colloidal smectite clay which works well in forming the smectite heteroadduct having the disclosed favorable features, for example, in providing the colloidal smectite clay which is readily filterable.
  • the present disclosure further provides a method of making a support- activator comprising a smectite heteroadduct, the method comprising or consisting essentially of contacting 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 to provide a slurry of the smectite heteroadduct in the first liquid carrier; wherein the first liquid carrier consists essentially of water, an organic liquid, or a combination thereof.
  • This method also can further comprise the step of: isolating the smectite heteroadduct from the slurry in the first liquid carrier.
  • the method of making a support-activator can further comprise the steps of: suspending (or re-suspending) the smectite heteroadduct in a dispersion medium to provide a suspension of the smectite heteroadduct in the dispersion medium; and spray-drying the smectite heteroadduct from the suspension to provide the support-activator in particulate form.
  • the dispersion medium can comprise or consist essentially of water.
  • This latter spray-drying step may be referred to herein as “granulating” the smectite heteroadduct. It has also been realized that when a colloidal smectite clay in a liquid carrier is contacted with a heterocoagulation reagent comprising both a cationic polymetallate and a surfactant reagent, the resulting clay-cationic polymetallate-surfactant heteroadducts can show unexpectedly improved polymerization activities in combination with metallocenes.
  • this disclosure also demonstrates a method of making a support-activator comprising a smectite heteroadduct, the method comprising or consisting essentially of contacting in any order in a first liquid carrier: (a) a colloidal smectite clay; (b) a cationic polymetallate; and (c) 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 heteroadduct in the first liquid carrier. If desired, this contacting step also may occur in absence of specific reactants.
  • the contacting step may be carried out [i] in the absence of: [A] a non-layered silicate, a soluble silicate (for example, sodium silicate), a charged inorganic component, a metal oxide, an organic amide, an anionic surfactant, an inorganic acid, an organic acid, an inorganic base, an organic base, an oxidizing agent, or any combination thereof; [B] any one or any two of a cationic surfactant, a nonionic surfactant, or an amphoteric surfactant; or [C] any combination thereof; [ii] in the absence of any other cationic reactant, except for the cationic polymetallate and the cationic surfactant when present; or [iii] in the absence of any other reactant, except for the cationic polymetallate and the surfactant.
  • a non-layered silicate for example, sodium silicate
  • a soluble silicate for example, sodium silicate
  • This method of making the clay-cationic polymetallate-surfactant heteroadducts can further comprise the step of: isolating the heteroadduct from the slurry in the first liquid carrier.
  • the method can further comprise the steps of: suspending (or re-suspending) the smectite heteroadduct in a dispersion medium to provide a suspension of the smectite heteroadduct in the dispersion medium; and spray-drying the smectite heteroadduct from the suspension to provide the support-activator in particulate form.
  • the dispersion medium can comprise or consist essentially of water.
  • the clay-cationic polymetallate-surfactant heteroadducts can exhibit improvements in polymerization activity. Moreover, these clay-cationic polymetallate-surfactant heteroadducts are convenient to make, readily filterable, and can be spray-dried from an aqueous slurry in the absence of an organic liquid to provide highly spherical support-activators.
  • providing the clay-cationic polymetallate-surfactant heteroadducts by spray drying also may be achieved by forming an aqueous spray-drying slurry of a preformed or isolated clay-cationic polymetallate heteroadduct, which includes a surfactant in the aqueous spray-drying slurry. That is, the clay-cationic polymetallate heteroadduct can be formed as disclosed in Applicant’s U.S. Patent Appl. Publ. No. 2021/0230318. The clay-cationic polymetallate heteroadduct can then be isolated and re- suspended in an aqueous dispersion medium which includes a surfactant to form a spray- drying suspension and spray dried.
  • Preparing heteroadducts in this fashion is convenient and provides readily filterable clay-cationic polymetallate heteroadducts, which can be spray- dried from an aqueous slurry in the absence of an organic liquid, to provide highly spherical support-activators. Therefore, the order of addition of the components, particularly with respect to when the surfactant is added relative to the isolation of the heteroadduct, can be altered and an active and useful product can be produced with either order of addition.
  • This disclosure also provides the smectite heteroadducts themselves.
  • a smectite heteroadduct or a support-activator comprising a smectite heteroadduct, in which the smectite heteroadduct can comprise or consist essentially of a contact product in a first liquid carrier and in the absence of specific reactants, of: (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.
  • the contact product can occur or can be [i] in the absence of: [A] a cationic polymetallate; [B] a non-layered silicate, a soluble silicate (for example, sodium silicate), a charged inorganic component, a metal oxide, an organic amide, an anionic surfactant, an inorganic acid, an organic acid, an inorganic base, an organic base, an 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 for cationic surfactant when present; or [iii] in the absence of any other reactant, except for the surfactant.
  • a cationic polymetallate for example, sodium silicate
  • a smectite heteroadduct or a support-activator comprising a smectite heteroadduct, wherein the smectite heteroadduct comprises or consists essentially of a contact product in a first liquid carrier of: (a) a colloidal smectite clay; and (b) a surfactant comprising or selected from a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or any combination thereof; wherein the first liquid carrier consists essentially of water, an organic liquid, or a combination thereof.
  • a support-activator comprising a smectite heteroadduct, the smectite heteroadduct comprising or consisting essentially of a contact product in a first liquid carrier of: (a) a colloidal smectite clay; (b) a cationic polymetallate; and (c) a surfactant comprising or selected from a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or any combination thereof.
  • the contact product can occur or can be [i] in the absence of: [A] a non-layered silicate, a soluble silicate (for example, sodium silicate), a charged inorganic component, a metal oxide, an organic amide, an anionic surfactant, an inorganic acid, an organic acid, an inorganic base, an organic base, an oxidizing agent, or any combination thereof; [B] any one or any two of a cationic surfactant, a nonionic surfactant, or an amphoteric surfactant; or [C] any combination thereof; [ii] in the absence of any other cationic reactant, except for the cationic polymetallate and the cationic surfactant when present; or [iii] in the absence of any other reactant, except for the cationic polymetallate and the surfactant.
  • a non-layered silicate for example, sodium silicate
  • a soluble silicate for example, sodium silicate
  • surfactant-treated clays smectite clay heteroadducts
  • clay-surfactant heteroadducts or clay-cationic polymetallate-surfactant heteroadducts when subjected to the granulation and drying process of spray drying followed by calcination, constitute particles possessing higher sphericity, porosity, and particle uniformity relative to clay activators dried through other methods.
  • the clay heteroadducts Once granulated and dried as described herein, the clay heteroadducts also retain a high olefin polymerization activity when activating metallocene compounds.
  • the smectite heteroadducts prepared in this manner can be used very effectively in combination with co-catalysts such as alkyl aluminum compounds for transition metal-based olefin polymerization processes.
  • This smectite heteroadduct-co-catalyst combination can afford very active support-activators for metallocene olefin polymerizations when compared with traditional MAO-SiO2 or borane-derived support-activators.
  • the surfactant agents used in this process also can be very inexpensive and can be used with relatively inexpensive co-catalysts such as alkyl aluminum compounds, particularly compared to aluminoxane and borane-based activators.
  • a catalyst system for olefin polymerization comprising: (a) at least one metallocene compound; and (b) at least one support-activator according to any aspect of this disclosure.
  • This catalyst system can further comprise additional components, for example, at least one co-catalyst such as an alkyl aluminum compound and/or at least one co-activator such as methyl aluminoxane (MAO).
  • the support-activator of the catalyst system also can be absent any of the specific reactants which are absent from the contact product as described herein.
  • This disclosure also provides a method of making a catalyst system, in which 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 heteroadduct according to this disclosure.
  • the at least one support-activator can comprise a smectite heteroadduct prepared according to any method provided in this disclosure.
  • the method can further comprise contacting in the second liquid carrier at least one co-catalyst such as an alkyl aluminum compound and/or at least one co-activator such as methyl aluminoxane (MAO), in which the contacting can occur in any order.
  • co-catalyst such as an alkyl aluminum compound
  • at least one co-activator such as methyl aluminoxane (MAO)
  • the support-activator also may be absent any of the specific reactants which are absent from the contact product as described herein.
  • this disclosure provides for a process for polymerizing olefins comprising contacting at least one olefin monomer and a catalyst system under polymerization conditions to form a polyolefin, wherein the catalyst system comprises: (a) at least one metallocene compound; and (b) at least one support-activator comprising a smectite heteroadduct according to this disclosure.
  • the at least one support-activator also can comprise a smectite heteroadduct prepared according to any method provided in this disclosure, and the catalyst system can further comprise additional components, for example, at least one co-catalyst such as an alkyl aluminum compound and/or at least one co-activator such as methyl aluminoxane (MAO).
  • the support-activator also may be absent any of the specific reactants which are absent from the contact product as described herein.
  • FIG.1 and FIG.2 illustrate an embodiment of this disclosure, showing a scanning electron microscope (SEM) image of the powdered product formed by spray-drying an aqueous slurry in which the solid component is the filtered adduct obtained by contacting tetramethylammonium bromide and Volclay® HPM-20 montmorillonite in deionized water in the process described in Example 21-E1.
  • SEM scanning electron microscope
  • FIG.3 and FIG.4 illustrate an embodiment of this disclosure, showing an SEM image of the powdered product formed by spray-drying an aqueous slurry in which the solid component is the filtered adduct obtained by contacting aluminum chlorohydrate and Volclay® HPM-20 montmorillonite in the process described in Example 20-D1.
  • FIG.5 and FIG.6 illustrate an embodiment of this disclosure, showing an SEM image of the powdered product formed by spray-drying an aqueous slurry in which the solid component is the filtered adduct obtained by contacting tetrabutylammonium bromide and Volclay® HPM-20 montmorillonite in the process described in Example 22-E2.
  • FIG.7 and FIG.8 illustrate an embodiment of this disclosure, showing an SEM image of the support-activator formed by azeotropically drying the adduct obtained by contacting aluminum chlorhydrate (ACH) and Volclay® HPM-20 montmorillonite using 1- butanol as the azeotroping agent, and subsequently calcining the dried product in the process described in Example 2-A1.
  • ACH aluminum chlorhydrate
  • Volclay® HPM-20 montmorillonite 1- butanol as the azeotroping agent
  • FIG.9 and FIG.10 illustrate an embodiment of this disclosure, showing an SEM image of the support-activator formed by spray-drying an aqueous slurry in which the solid component is the filtered adduct obtained by contacting tetramethylammonium bromide and Volclay® HPM-20 montmorillonite in the process described in Example 21-E1, in which the spray-dried adduct was subsequently calcined.
  • FIG.11 and FIG.12 illustrate an embodiment of this disclosure, showing an SEM image of the support-activator formed by spray-drying an aqueous slurry in which the solid component is the filtered adduct obtained by contacting aluminum chlorhydrate and Volclay® HPM-20 montmorillonite in the process described in comparative Example 20-D1, and subsequently calcining the spray-dried product.
  • FIG.13 and FIG.14 illustrate an embodiment of this disclosure, showing an SEM image of the support-activator formed by spray-drying an aqueous slurry in which the solid component is the filtered adduct obtained by contacting tetrabutylammonium bromide and Volclay® HPM-20 montmorillonite in the process described in Example 22-E2, and subsequently calcining the spray-dried product.
  • FIG.15 illustrates another embodiment of this disclosure, showing an optical microscope image of an ethylene-1-hexene copolymer derived from a polymerization in which a support-activator was combined with the metallocene bis(1-butyl-3- methylcyclopentadienyl)zirconium dichloride and triethylaluminum co-catalyst to form the active catalyst.
  • the support-activator was formed by spray-drying an aqueous slurry in which the solid component was the filtered adduct obtained by contacting tetramethylammonium bromide and Volclay® HPM-20 montmorillonite in the process described in Example 21-E1, and subsequently calcining the spray-dried product.
  • FIG.16 illustrates another embodiment of this disclosure, showing an optical microscope image of an ethylene-1-hexene copolymer derived from a polymerization in which a support-activator was combined with the metallocene bis(1-butyl-3- methylcyclopentadienyl)zirconium dichloride and triethylaluminum co-catalyst to form the active catalyst.
  • the support-activator was formed by spray-drying an aqueous slurry in which the solid component was the filtered adduct obtained by contacting tetrabutylammonium bromide and Volclay® HPM-20 montmorillonite in the process described in Example 22-E2, and subsequently calcining the spray-dried product.
  • FIG.17 illustrates a further embodiment of this disclosure, showing an optical microscope image of an ethylene-1-hexene copolymer derived from a polymerization in which a support-activator was combined with the metallocene bis(1-butyl-3-methyl- cyclopentadienyl)zirconium dichloride and triethylaluminum co-catalyst to form the active catalyst.
  • the support-activator was formed by azeotropically drying the adduct obtained by contacting aluminum chlorohydrate (ACH) and Volclay® HPM-20 montmorillonite using 1- butanol as the azeotroping agent in the process described in Example 2-A1.
  • FIG.18 provides the results of a nitrogen adsorption/desorption BJH (Barrett, Joyner, and Halenda) pore volume analysis of the calcined aluminum chlorhydrate (ACH) heterocoagulated clay of Example 5-A4, providing a plot of pore diameter (Angstrom, ⁇ ) versus the cumulative pore volume (cubic centimeters per gram, cc/g) for the heteroadduct.
  • BJH Barrett, Joyner, and Halenda
  • pore volume analysis of the calcined aluminum chlorhydrate (ACH) heterocoagulated clay of Example 5-A4 providing a plot of pore diameter (Angstrom, ⁇ ) versus the cumulative pore volume (cubic centimeters per gram, cc/g) for the heteroadduct.
  • the recipe for the preparation of this heteroadduct slurry used 1.54 mmol Al/g clay, and the sample was dried non-azeotropically and calcined to provide the non-azeotroped clay-ACH heteroad
  • FIG.19 provides the results of a nitrogen adsorption/desorption BJH pore volume analysis of the calcined tetramethylammonium bromide heterocoagulated clay of Example 11-B6, providing a plot of pore diameter (Angstrom, ⁇ ) versus the cumulative pore volume (cubic centimeters per gram, cc/g) for the heteroadduct.
  • the recipe for the preparation of this heteroadduct slurry used 2.48 mmol tetramethylammonium bromide/g clay in the absence of a cationic polymetallate to form the heterocoagulated clay which was dried non-azeotropically and calcined to provide the non-azeotroped clay-surfactant heteroadduct.
  • FIG.20 provides the results of a nitrogen adsorption/desorption BJH pore volume analysis of the calcined tetrabutylammonium bromide heterocoagulated clay of Example 14-B9, providing a plot of pore diameter (Angstrom, ⁇ ) versus the cumulative pore volume (cubic centimeters per gram, cc/g) for the heteroadduct.
  • the recipe for the preparation of this heteroadduct slurry used 1.24 mmol tetramethylammonium bromide/g clay in the absence of a cationic polymetallate to form the heterocoagulated clay which was dried non-azeotropically and calcined to provide the non-azeotroped clay-surfactant heteroadduct.
  • FIG.21 provides the results of a nitrogen adsorption/desorption BJH pore volume analysis of the calcined tetrabutylammonium bromide and aluminum chlorohydrate (ACH) heterocoagulated clay of Example 23-E3, providing a plot of pore diameter (Angstrom, ⁇ ) versus the cumulative pore volume (cubic centimeters per gram, cc/g) for the heteroadduct.
  • the recipe for the preparation of this heteroadduct slurry used 1.24 mmol tetrabutylammonium bromide/g clay in combination with ACH to form the heterocoagulated clay which was spray-dried and calcined to provide the spray-dried clay-ACH-surfactant heteroadduct.
  • FIG.22 provides the results of a nitrogen adsorption/desorption BJH pore volume analysis of the calcined tetraoctylammonium bromide and aluminum chlorohydrate (ACH) heterocoagulated clay of Example 24-E4, providing a plot of pore diameter (Angstrom, ⁇ ) versus the cumulative pore volume (cubic centimeters per gram, cc/g) for the heteroadduct.
  • the recipe for the preparation of this heteroadduct slurry used 0.73 mmol tetraoctylammonium bromide/g clay in combination with ACH to form the heterocoagulated clay which was spray-dried and calcined to provide the spray-dried clay-ACH-surfactant heteroadduct.
  • FIG.23 provides the results of a nitrogen adsorption/desorption BJH pore volume analysis of a comparative example of the spray-dried and calcined aluminum chlorohydrate (ACH) heterocoagulated clay of Example 20-D1, providing a plot of pore diameter (Angstrom, ⁇ ) versus the cumulative pore volume (cubic centimeters per gram, cc/g) for the heteroadduct.
  • the recipe for the preparation of this heteroadduct slurry used 1.54 mmol aluminum chlorohydrate/g clay to form the heterocoagulated clay which was spray-dried and calcined to provide the spray-dried clay-ACH heteroadduct.
  • FIG.24 provides the results of a nitrogen adsorption/desorption BJH pore volume analysis of the spray-dried and calcined tetrabutylammonium bromide heterocoagulated clay of Example 22-E2, providing a plot of pore diameter (Angstrom, ⁇ ) versus the cumulative pore volume (cubic centimeters per gram, cc/g) for the heteroadduct.
  • the recipe for the preparation of this heteroadduct slurry used 0.73 mmol tetrabuthylammonium bromide/g clay in the absence of a cationic polymetallate to form the heterocoagulated clay which was spray-dried and calcined.
  • FIG.25 provides the results of a nitrogen adsorption/desorption BJH pore volume analysis of the rotary evaporated and calcined Volclay® HPM-20 montmorillonite clay prepared according to Example 1, providing a plot of pore diameter (Angstrom, ⁇ ) versus the cumulative pore volume (cubic centimeters per gram, cc/g) for the clay only, prior to any heteroadduct formation.
  • FIG.26 provides a powder XRD (X-ray diffraction) pattern of the calcined, spray-dried product from combining Volclay® HPM-20 montmorillonite clay and tetramethylammonium bromide (TMABr) absent a cationic polymetallate, prepared according to Example 21-E1.
  • TMABr tetramethylammonium bromide
  • FIG.27 provides a powder XRD pattern of the calcined spray-dried product from combining Volclay® HPM-20 montmorillonite and tetrabutylammonium bromide (TBABr) absent a cationic polymetallate, prepared according to Example 22-E2.
  • FIG.28 provides a powder XRD pattern of the calcined spray-dried product from combining Volclay® HPM-20 montmorillonite and aluminum chlorhydrate (ACH), absent a surfactant, prepared according to Comparative Example 20-D1.
  • FIG.29 illustrates a zeta potential titration for the volumetric addition of a 10.7 wt.% (weight percent) aqueous solution of tetrabutylammonium bromide into a 1 wt.% Volclay® HPM-20 bentonite aqueous dispersion, plotting the measured zeta potential versus the versus the mmol cation/g clay (millimoles of cation per gram of clay). An equilibration delay of 30 seconds was allowed after each titrant aliquot. The mmol cation/g clay indicates the cumulative millimoles of aqueous tetrabutylammonium bromide solution added during the titration.
  • FIG.30 illustrates a zeta potential titration for the volumetric addition of a 7.9 wt.% (weight percent) aqueous solution of tetramethylammonium bromide into a 1 wt.% Volclay® HPM-20 bentonite aqueous dispersion, plotting the measured zeta potential versus the mmol cation/g clay (millimoles of cation per gram of clay). An equilibration delay of 30 seconds was allowed after each titrant aliquot. The mmol cation/g clay indicates the cumulative millimoles of the aqueous tetramethylammonium bromide solution added.
  • FIG.31 and FIG.32 illustrate comparative embodiments of this disclosure, showing SEM images of the support-activators produced by the processes of Example 2-A1 and Example 3-A2, respectively, in which the SEM images of the calcined support-activators are analyzed by Scanning Probe Image Processor (SPIP) software to provide the particle boundaries which are depicted on the images, which are used for Circularity calculations.
  • SPIP Scanning Probe Image Processor
  • FIG.31 and FIG.32 support-activators were formed by azeotropically drying the adduct obtained by contacting aluminum chlorhydrate (ACH) and Volclay® HPM-20 montmorillonite in the absence of a surfactant, using 1-butanol as the azeotroping agent and subsequently calcining the dried product as described in Example 2-A1 and Example 3-A2, respectively.
  • FIG.33 illustrates an embodiment of this disclosure, showing an SEM image of the support-activator in which the SEM image of the calcined support-activator which is analyzed by Scanning Probe Image Processor (SPIP) software to provide the particle boundaries which are depicted on the image, which are used for Circularity calculations.
  • SPIP Scanning Probe Image Processor
  • FIG.33 support-activator was formed as described in Example 30-E2 by contacting tetrabutylammonium bromide and Volclay® HPM-20 montmorillonite in the absence of a cationic polymetallate, and the isolated product was dried by rotary evaporation non- azeotropically from an aqueous slurry prior to calcining.
  • the FIG.33 image can be compared with the spray-dried and calcined samples of Example 22-E2 shown in FIGS.34- 36.
  • FIG.34, FIG.35, and FIG.36 illustrate embodiments of this disclosure, showing three different SEM images of the calcined support-activators which are analyzed by Scanning Probe Image Processor (SPIP) software to provide the particle boundaries which are depicted on the images and which are used for Circularity calculations.
  • SPIP Scanning Probe Image Processor
  • the FIG.34, FIG.35, and FIG.36 support-activators were formed as described in Example 22-E2 by contacting tetrabutylammonium bromide and Volclay® HPM-20 montmorillonite in the absence of a cationic polymetallate which was isolated by filtration, and the isolated support- activator was spray-dried from an aqueous suspension and subsequently calcined.
  • FIG.37 and FIG.38 illustrate embodiments of this disclosure, in which support-activators produced by the processes of Example 2-A1 (azeotroped clay-aluminum chlorohydrate heteroadduct) and Example 30-E2 (clay-tetrabutylammonium bromide heteroadduct, non-azeotroped and rotary evaporated), respectively, were combined with ( ⁇ 5- 1-n-butyl-3-methyl-cyclopentadienyl)2ZrCl2 and triethylaluminum (TEA) and the resulting catalyst composition used to co-polymerize ethylene and 1-hexene as described in these Examples.
  • Example 2-A1 azeotroped clay-aluminum chlorohydrate heteroadduct
  • Example 30-E2 clay-tetrabutylammonium bromide heteroadduct, non-azeotroped and rotary evaporated
  • FIG.37 and FIG.37 each plot the volume-weighted sphericities (SPHT3) versus polymer particle size for a sample of the polymer particles from Example 2-A1 and Example 30-E2, respectively. Particle size distribution data and number-weighted average sphericity of the entire particle distribution (SPHT0) are also tabulated.
  • FIG.39 and FIG.40 illustrate plots of the volume-weighted sphericity SPHT3 versus polymer particle size for two samples of ethylene-1-hexene co-polymer particles prepared using a metallocene catalyst composition comprising the support-activator from Example 31.
  • the Example 31 support-activator was prepared by spray drying a clay- tetrabutylammonium bromide heteroadduct in the absence of a cationic polymetallate, and these polymer particles were collected and analyzed by a CAMSIZER® X2 to determine particle sphericity.
  • Particle size distribution data and number-weighted average sphericity of the entire particle distribution (SPHT0) are also tabulated.
  • FIG.41 illustrates the particle size distribution and cumulative volume curve for the sample of ethylene-1-hexene co-polymer particles prepared using a metallocene catalyst composition comprising the support-activator from Example 31.
  • the Q3[%] axis corresponds to the curve-line on the graph and represents the cumulative volume percent value, which is the percent of the total volume of the particles which is below that particle size value.
  • the P3[%] axis corresponds to the bar chart distribution and shows the percent of the total volume corresponding to each bar or “slice” of particle size.
  • Example 31 support-activator was provided by spray drying a clay-tetrabutylammonium bromide heteroadduct in the absence of a cationic polymetallate, and these polymer particles were collected and analyzed by a CAMSIZER® X2 to determine particle size distribution.
  • the FIG.41 data are for the same co-polymer sample used to collect the data in FIG.40.
  • FIG.42, FIG.44, and FIG.46 illustrate particle size distribution and cumulative volume curves for three different samples of ethylene-1-hexene co-polymer particles prepared using a metallocene catalyst composition comprising the support-activators from Example 33 (FIG.42), Example 34 (FIG.44), and Example 35 (FIG.46).
  • Example 31 support-activator (clay- tetrabutylammonium bromide heteroadduct), sieving this sample into three different size ranges, and calcining each sample, which was then used to prepare the catalyst compositions and co-polymers.
  • the support-activator sieved fractions used to produce the co-polymer are 19 ⁇ m (microns) to 37 ⁇ m (FIG.42), 37 ⁇ m to 50 ⁇ m (FIG.44), and 50 ⁇ m to 74 ⁇ m (FIG. 46). Polymer particle size distributions were obtained using a CAMSIZER® X2.
  • FIG.43, FIG.45, and FIG.47 present plots of the volume-weighted sphericities (SPHT3) versus polymer particle size for samples of the ethylene-1-hexene co- polymer particles prepared using metallocene catalyst compositions comprising the support- activators from Example 33 (FIG.43), Example 34 (FIG.45), and Example 35 (FIG.47).
  • SPHT3 volume-weighted sphericities
  • the support-activator sieved fractions used to produce the co-polymer are 19 ⁇ m (microns) to 37 ⁇ m (FIG.43), 37 ⁇ m to 50 ⁇ m (FIG.45), and 50 ⁇ m to 74 ⁇ m (FIG.47).
  • Polymer particle size distributions were obtained using a CAMSIZER® X2.
  • DETAILED DESCRIPTION OF THE DISCLOSURE In order to more clearly define the terms and phrases used herein, the following definitions are provided. To the extent that any definition or usage provided by any document incorporated herein by reference conflicts with the definition or usage provided herein, the definition or usage provided herein controls.
  • surfactant and similar terms such as “surfactant agent”, “surfactant compound”, “surfactant component”, or “surface active agent” and the like refer to chemical compounds or reagents capable of reducing surface tension between phases, for example, two liquid phases, a gas and a liquid phase, or a liquid and a solid phase. Many surfactant compounds contain a hydrophobic section or region and a hydrophilic section or region, for example, a polar region and a non-polar region, respectively.
  • the hydrophilic section may include, but not necessarily, a negatively charged moiety, a positively charged moiety, or hydrogen bonding moiety (such as a hydroxyl, other oxygen- containing group, and the like), while the hydrophobic section may include, but not necessarily, an alkyl or an aromatic group.
  • Surfactants are often characterized by the terms anionic, cationic, or nonionic, based upon whether their hydrophilic section includes a negatively charged moiety, a positively charged moiety, or hydrogen bonding moiety, respectively.
  • a surfactant in this disclosure can include cationic surfactants, nonionic surfactants, and amphoteric surfactants, and in some cases anionic surfactants which can be used in combination with a cationic surfactant, a nonionic surfactant, or amphoteric surfactant as explained herein, all of which are further described.
  • An “amphoteric” surfactant refers to surfactants which can include a positively charged moiety (or a moiety which can readily become positively charged by accepting a proton) and a negatively charged moiety (or a moiety which can readily become negatively charged by releasing a proton) in the same molecule.
  • amphoteric surfactant is used interchangeably with “amphoteric” surfactants based on the inclusion of both cationic and anionic moieties in the same molecule.
  • an “amphoteric” surfactant includes a portion which can react with an acid and a portion which can react with a base.
  • An “amphiprotic” surfactant is a type of amphoteric surfactant which either donate a proton (H + ) or accept a proton, examples of which is amino acids. Unless otherwise excluded, reference to an amphoteric or zwitterionic surfactant includes amphiprotic surfactants.
  • Nonionic surfactants such as amino acids may be considered a type of nonionic surfactant, however in this disclosure, the term “nonionic” surfactant is reserved for molecules which are not zwitterionic, such as poly(ethylene)glycol, poly(propylene)glycol, or cyclodextrins, whereas the term “amphoteric” surfactant is used for zwitterionic surfactants. Heterocoagulation reagent.
  • heterocoagulation reagent used herein to describe a compound or a composition comprising monomeric, oligomeric, or polymeric species existing in solution or as a colloidal suspension which, when combined with a colloidal clay dispersion in an appropriate ratio, forms a readily filterable solid (as defined herein).
  • heterocoagulation reagent is used herein to refer to the cationic surfactants, nonionic surfactants, and amphoteric surfactants described in this disclosure, as well as to the positively charged oligomeric or polymeric metal oxide containing species termed “polymetallates” or “polyoxometallates” such as aluminum chlorhydrate (ACH) described in detail in Applicant’s U.S. Patent Appl. Publ. No.2021/0230318, which is incorporated herein by reference in its entirety. These polymetallates are also termed “cationic polymetallates”. “Heterocoagulation” is a term in the art described by Lagaly in Ullmann’s Encyclopedia of Chemistry 2012.
  • the heterocoagulation reagent may include a surfactant only, a cationic polymetallate only, or a combination of a surfactant and a cationic polymetallate.
  • heterocoagulation is defined as the process by which negatively charged colloidal clay particles are combined with a heterocoagulation reagent to form a readily filterable solid, unless otherwise specified.
  • Most, but not all, of the heterocoagulation reagents described in this disclosure are positively charged species which combine with the 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, such as described by Cerbelaud et al.
  • Heteroadduct or heterocoagulate refers to the contact product obtained from combining a heterocoagulation reagent disclosed herein and a colloidal clay such as a colloidal smectite clay.
  • the agglomerate formed by the attraction of negatively charged colloidal clay particles with the heterocoagulation reagents of this disclosure is referred to as a “heteroadduct” or “heterocoagulate”, or sometimes referred to simply as an “adduct” or “coagulate”.
  • a heterocoagulation such as Wu Cheng et al. in U.S. Patent No.8,642,499, which is incorporated herein by reference, who uses the term “heterocoagulation”.
  • these terms refer to the “readily filterable” contact product of a heterocoagulation reagent and a colloidal clay, as defined herein. These terms are used to distinguish the readily filterable heterocoagulate from the contact product of a heterocoagulation reagent and a colloidal clay which are combined in a ratio that provides a product which is not readily filterable, for example, the product formed when following a pillared clay synthesis.
  • the terms “heteroadduct” and “heterocoagulate” and similar terms are also used when describing the formation of a heterocoagulated clay formed from contacting a clay with a cationic polymetallate, whether contact occurs in the presence of a surfactant or in the absence of a surfactant.
  • heteroadducts comprising the contact product of a clay with a cationic polymetallate are described in detail in U.S. Patent Appl. Publ. No.2021/0230318.
  • Other heterocoagulates of this disclosure can be prepared by contacting a colloidal clay and a surfactant in the absence of a cationic polymetallate. Accordingly, when not specified otherwise and as the context allows or requires, a “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. Polymetallate.
  • polymetallate cationic polymetallate
  • cationic polymetallate and similar terms such as “polyoxometallate”, are used interchangeably in this disclosure as they are in U.S. Patent Appl. Publ. No.2021/0230318 to refer to the water-soluble polyatomic cations that include two or more metal atoms (for example, aluminum, silicon, titanium, zirconium, or other metals) along with at least one bridging ligand between metals such as oxo, hydroxy and/or halide ligands.
  • metal atoms for example, aluminum, silicon, titanium, zirconium, or other metals
  • bridging ligand between metals such as oxo, hydroxy and/or halide ligands.
  • the “polymetallates” of this disclosure are usually referred to herein as “cationic polymetallates”.
  • the specific ligands can depend upon the precursor and other factors, such as the process for generating the polymetallate, the solution pH, and the like.
  • the polymetallates of this disclosure can be hydrous metal oxides, hydrous metal oxyhydroxides, and the like, including combinations thereof. Bridging ligands such as oxo ligands which bridge two or more metals can occur in these species, however, polymetallates can also include terminal oxo, hydroxyl, and/or halide ligands. While many known polymetallate species are anionic, and the suffix “-ate” is often used to reflect an anionic species, the polymetallate (polyoxometallate) species used according to this disclosure are cationic.
  • polymetallate compositions can contain multiple species in a suitable carrier such as in aqueous solution, depending upon, for example, the solution pH, the concentration, the starting precursor from which the polymetallate is generated in aqueous solution, and the like.
  • a suitable carrier such as in aqueous solution
  • these multiple species are referred to collectively as “polymetallates” or “polyoxometallates”, regardless of whether the compositions include or consist primarily of cationic polyoxometallates, polyhydroxymetallates, polyoxohydroxymetallate, or species that include other ligands such as halides, or mixtures of compounds.
  • polymetallates examples include but are not limted to polyaluminum oxyhydroxychlorides, aluminum chlorhydrate (ACH), polyaluminum chloride (PAC), or aluminum sesquichlorohydrate compositions, which can include linear, cyclic or cluster compounds. These compositions are referred to collectively as polymetallates, although the term “polymetallate” or “polyoxometallate” are also used to described a composition substantially comprising a single species. Both isopolymetallates, which contain a single type of metal, and heteropolymetallates, which contain more than one type of metal (or electropositive atoms such as phosphorus) are included in the general terms polymetallate or polyoxometallate.
  • the polymetallates according to this disclosure can be non-alkylating toward transition metal compounds such as metallocene compounds. That is, the subject polymetallates can be absent direct metal-carbon bonds as would be found in aluminoxanes or other organometallic species.
  • the polymetallate can be at least one aluminum polymetallate. Examples include, but are not limited to, aluminum chlorhydrate (ACH), also termed aluminum chlorohydrate, which encompasses multiple water soluble aluminum species, usually considered as having the general formula AlnCl3n-m(OH)m. These polymetallate species can be referred to as aluminum oxyhydroxychloride compounds or compositions.
  • polyaluminum chloride which is also not a single species, but a collection of multiple aluminum polymeric species which can include linear, cyclic, or cluster compounds, examples of which can contain from 2 to about 30 aluminum atoms, oxo, chloride, and hydroxyl groups.
  • aluminum polymetallates include, but are not limited to, compounds having the general formula [Al m O n (OH) x Cl y ] ⁇ zH 2 O such as aluminum sequichlorohydrate, and cluster-type species such as Keggin ions, for example, [AlO 4 Al 12 (OH) 24 (H 2 O) 12 ] 7+ ⁇ 7[Cl]-, sometimes referred to as “Al 13 -mer” polycation.
  • Polyaluminum chloride (PAC) can be produced by combining aqueous hydroxide with AlCl 3 , and the resulting mixture of aluminum species has a range of basicities.
  • Aluminum chlorhydrate is generally considered the most basic, and polyaluminum chloride (PAC) being less basic.
  • Readily Filterable The terms “readily filterable”, “readily filtered”, “easily filterable”, “easily filtered or separated” and the like are used herein to describe a composition according to this disclosure in which the solids in a mixture containing a liquid phase can be separated by filtration from the liquid phase without resorting to centrifugation, ultra-centrifugation, or dilute solutions of less than about 2 wt.% solids, long settling times followed by decanting the liquid away from solids, and other such techniques.
  • a readily filterable clay heteroadduct can be isolated or separated in good yield in a matter of minutes or less, or time periods of less than about one hour, from the soluble salts and byproducts of the synthesis, by passing a slurry comprising the heteroadduct through conventional filtering materials, such as sintered glass, metal or ceramic frits, paper, natural or synthetic matte-fiber and the like, under gravity or vacuum filtration conditions.
  • filtering materials such as sintered glass, metal or ceramic frits, paper, natural or synthetic matte-fiber and the like, under gravity or vacuum filtration conditions.
  • Colloids or suspensions as described by Lagaly in Ulmmann’s Encyclopedia of Chemistry 2012, that require long sedimentation times or ultrafiltration are not considered to be “filterable” in the context of this disclosure.
  • the readily filterable suspensions or slurries of this disclosure can afford clear filtrates upon filtration, while “non-readily-filterable” suspensions which take substantially longer to filter can contain particulate matter that is observable as a cloudy or non-clear filtrate to the naked eye, indicative of colloidal clay dispersions. Colloid.
  • Catalyst composition and catalyst system. Terms such as “catalyst composition,” “catalyst mixture,” “catalyst system,” and the like are used to represent the combination of recited components which ultimately form, or are used to form, the active catalyst according to this disclosure. The use of these terms does not depend upon any specific contacting steps, order of contacting, whether any reaction may occur between or among the components, or any product which may form from any contact of any or all of the recited components.
  • the terms “activity”, “catalyst activity”, “catalyst composition activity” and the like refer to the polymerization activity of a catalyst composition comprising a dried or calcined clay heteroadduct as disclosed herein, which is typically expressed as weight of polymer polymerized per weight of catalyst clay support-activator only, absent any transition metal catalyst components such as a metallocene compound, any co-catalyst such as an organoaluminum compound, or any co-activators such as an aluminoxane, per hour of polymerization. In other words, the weight of polymer produced divided by the weight of calcined clay heteroadduct per hour, in units of g/g/hr (grams per gram per hour).
  • Activity of a reference or comparative catalyst composition refers to the polymerization activity of a catalyst composition comprising a comparative catalyst composition and is based upon the weight of a comparative ion-exchanged or pillared clay or other support-activator, or the weight of the clay component by itself that is used to prepare clay heteroadducts.
  • contact product is used herein to describe compositions wherein the components are combined together or “contacted” in any order, unless a specific order is stated or required or implied by the context of the disclosure, in any manner, and for any length of time.
  • contact product can include reaction products, it is not required for the respective components to react with one another, and this term is used regardless of any reaction which may or may not occur upon contacting the recited components.
  • the recited components can be contacted by blending or mixing or the components can be contacted by adding or combining the components in any order or simultaneously into or with a liquid carrier.
  • the contacting of any components can occur in the presence or absence of any other component of the compositions described herein.
  • Examples of contact products which would exclude certain components being used to form the contact product include the following.
  • the present disclosure describes a smectite heteroadduct comprising the contact product in a first liquid carrier and specifically in the absence of various reagents, or in the absence of other specified reagents or in the absence of any other reagent, of (a) a colloidal smectite clay, and (b) a surfactant.
  • the smectite heteroadduct can comprise the contact product in a first liquid carrier of (a) a colloidal smectite clay and (b) a surfactant, wherein the first liquid carrier consists essentially of water, an organic liquid, or a combination thereof.
  • a first liquid carrier of (a) a colloidal smectite clay and (b) a surfactant, wherein the first liquid carrier consists essentially of water, an organic liquid, or a combination thereof.
  • the term “contact product” includes mixtures, blends, solutions, slurries, reaction products, and the like, or combinations thereof.
  • the term “contacting” is used herein to refer to materials which may be blended, mixed, slurried, dissolved, reacted, treated, or otherwise contacted in some manner and in any order unless specified otherwise.
  • Pore diameter (pore size) and pore volume Nitrogen adsorption/desorption measurements were used to determine pore size and pore volume distributions using the BJH (Barrett, Joyner, and Halenda) pore volume analysis method. Based upon the International Union of Pure and Applied Chemistry (IUPAC) system for classifying porous materials (see Pure & Appl.
  • pore sizes are defined as follows. “Micropore” and “microporous” as used herein refers to pores present in catalysts or catalyst supports produced according to processes of the disclosure having a diameter of less than 20 ⁇ . “Mesopore” and “mesoporous” as used herein refers to pores present in catalysts or catalyst supports produced according to processes of the present disclosure having a diameter in a range of from 20 ⁇ to less than 500 ⁇ (that is from 2 nm to ⁇ 50 nm).
  • Micropore and “macroporous” as used herein refers to pores present in catalysts or catalyst supports produced according to processes of the present disclosure having a diameter equal to or greater than 500 ⁇ (50 nm).
  • ⁇ 50 nm
  • Each of the above definitions of micropore, mesopore and macropore are considered distinct and non-overlapping, such that pores are not counted twice when summing up percentages or values in a distribution of pore sizes (pore diameter distribution) for any given sample.
  • the term “d50” or “D50” means the median pore diameter as measured by porosimetry. Thus, “d50” corresponds to the median pore diameter calculated based on pore size distribution and is the pore diameter above which half of the pores have 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.
  • the “median pore diameter” (MPD) can be calculated based upon, for example, volume, surface area or based on pore size distribution data. Median pore diameter calculated by volume means the pore diameter above which half of the total pore volume exists.
  • Median pore diameter calculated by surface area means that pore diameter above which half of the total pore surface area exists.
  • median pore diameter calculated based on pore size distribution means the pore diameter above which half of the pores have a larger diameter according to the pore size distribution determined as described elsewhere herein, for example, through derivation from nitrogen adsorption-desorption isotherms. Transition metal catalyst.
  • a “transition metal catalyst” refers to a transition metal compound or composition which can function as, or be transformed into, an active olefin polymerization catalyst when contacted with the support-activator of this disclosure, either in its current form or when contacted with a co-catalyst which is capable of transferring or imparting a polymerization-activatable ligand to the transition metal catalyst. Therefore, “transition metal catalyst” includes transition metal species which can function as a catalyst and transition metal species which are “precatalysts” or “procatalyts” in that they can be transformed into a composition which can function as a catalyst.
  • transition metal catalyst is not intended to reflect any specific mechanism or that the “transition metal catalyst” itself represents an active site for catalytic polymerization when it is activated or when it has been imparted with a polymerization- activatable ligand.
  • the transition metal catalyst is described according to the transition metal compound or compounds used in the process for preparing a polymerization catalyst, and can include metallocene compounds and defined herein, and related compounds. Co-catalyst.
  • a “co-catalyst” is used herein to refer to a chemical reagent, compound, or composition which is capable of imparting a ligand to the transition metal compound such as a metallocene which can initiate polymerization when the metallocene is otherwise activated with the support-activator.
  • the “co-catalyst” is used herein to refer to a chemical reagent, compound, or composition which is capable of providing a polymerization-activatable ligand to a metallocene compound.
  • Polymerization- activatable ligands include, but are not limited to, hydrocarbyl groups such as alkyls such as methyl or ethyl, aryls and substituted aryls such as phenyl or tolyl, substituted alkyls such as benzyl or trimethylsilylmethyl (-CH 2 SiM 3 ), hydride, silyl and substituted groups such as trimethylsilyl, and the like. Therefore, in an aspect, a co-catalyst can be an alkylating agent, a hydriding agent, a silylating agent, and the like.
  • the co-catalyst provides a polymerization-activatable ligand to the metallocene compound.
  • the co-catalyst can engage in a metathesis reaction to exchange an exchangeable ligand such as a halide or alkoxide on the metallocene compound with a polymerization-activatable/initiating ligand such as methyl or hydride.
  • the co-catalyst is an optional component of the catalyst composition, for example, when the metallocene compounds already includes a polymerization-activatable/initiating ligand such as methyl or hydride.
  • a co- catalyst can be used for other purposes, such as to scavenge moisture from the polymerization reactor or process.
  • the term “co-catalyst” may refer to an “activator” which may be used interchangeably with “co- catalyst” as explained herein.
  • Activator refers generally to a substance that is capable of converting a metallocene component into an active catalyst system which can polymerize olefins, and is intended to be independent of the mechanism by which such activation occurs.
  • an “activator” can convert the contact product of a metallocene component and a component that provides an activatable ligand (such as an alkyl or a hydride) to the metallocene, for example, when the metallocene compound does not already comprise such a ligand, into a catalyst system which can polymerize olefins. This term is used regardless of the actual activating mechanism.
  • activators can include, but are not limited to a support-activator, aluminoxanes, organoboron or organoborate compounds, ionizing compounds such as ionizing ionic compounds, and the like.
  • Aluminoxanes, organoboron or organoborate compounds, and ionizing compounds may be referred to as “activators” or “co-activators” when used in a catalyst composition in which a support-activator is present, but the catalyst composition is supplemented by one or more aluminoxane, organoboron, organoborate, ionizing compounds, or other co-activators.
  • Support-Activator refers to an activator in a solid form, such as ion-exchanged-clays, protic-acid-treated clays, or pillared clays, and similar insoluble activators which also functions as a support.
  • the smectite heteroadducts according to this disclosure are support-activators.
  • Ion-exchanged clay The term “ion-exchanged clay” as used herein and as understood by the person skilled in the art refers to a clay in which the exchangeable ions of a naturally-occurring or synthetic clay have been replaced by or exchanged with another selected ion or ions.
  • Ion exchange can occur by treatment of the naturally-occurring or synthetic clay with a source of the selected cation, usually from concentrated ionic solutions such as 2 N aqueous solutions of the cation, including through multiple exchange steps, for example, three exchange steps.
  • the exchanged clay can be subsequently washed several times with deionized water to remove excess ions produced by the treatment process, for example as described 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.
  • centrifugation is used to isolate the clay from solution between ion treatments and washings. Metallocene compound.
  • metalocene or “metallocene compound” as used herein, describes a transition metal or lanthanide metal compound comprising at least one substituted or unsubstituted cycloalkadienyl-type ligand or alkadienyl-type ligand, including heteroatom analogs thereof, regardless of the specific bonding mode, for example, regardless of whether the cycloalkadienyl-type ligand or alkadienyl-type ligand are bonded to the metal in an ⁇ 5 -, ⁇ 3 -, or ⁇ 1 -bonding mode, and regardless of whether more than one of these bonding modes is accessible by such ligands.
  • the term “metallocene” is also used to refer to a compound comprising at least one pi-bonded allyl-type ligand in which the ⁇ 3 -allyl is not part of a cycloalkadienyl- type or alkadienyl-type ligand, which can be used as the transition metal compound component of the catalyst composition described herein.
  • metalocene includes compounds with substituted or unsubstituted ⁇ 3 to ⁇ 5 -cycloalkadienyl-type and ⁇ 3 to ⁇ 5 - alkadienyl-type ligands, ⁇ 3 -allyl-type ligands, including heteroatom analogs thereof, and including but not limited to cyclopentadienyl ligands, indenyl ligands, fluorenyl ligands, ⁇ 3 - allyl ligands, pentadienyl ligands, boratabenzenyl ligands, 1,2-azaborolyl ligands, 1,2-diaza- 3,5-diborolyl ligands, substituted analogs thereof, and partially saturated analogs thereof.
  • Partially saturated analogs include compounds comprising partially saturated ⁇ 5 - cycloalkadienyl-type ligands, examples of which include but are not limited to tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, substituted analogs thereof, and the like.
  • the metallocene is referred to simply as the “catalyst,” in much the same way the term “co- catalyst” is used herein to refer to, for example, an organoaluminum compound.
  • a metallocene ligand can be considered in this disclosure to include at least one substituted or at one unsubstituted cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, allyl, boratabenzenyl, 1,2-azaborolyl, or 1,2-diaza-3,5-diborolyl ligand, including substituted analogs thereof.
  • any substituent can be selected independently from a halide, a C1-C20 hydrocarbyl, a C1-C20 heterohydrocarbyl, a C1-C20 organoheteryl, a fused C4-C12 carbocyclic moiety, or a fused C4- C11 heterocyclic moiety having at least one heteroatom selected independently from nitrogen, oxygen, sulfur, or phosphorus.
  • Organoaluminum compounds and organoboron compounds include neutral compounds such as AlMe3 and BEt3 and also include anionic complexes such as LiAlMe4, LiAlH4, NaBH4, and LiBEt4, and the like.
  • Pillared clay is defined as a clay species in which ordered layers with basal spacing are substantially greater than 9 ⁇ to 13 ⁇ .
  • species containing such pillared ordering are typically observed to possess a substantial peak at 2 ⁇ values between 2° to 9°.
  • pillaring agents for example, an oxygen-containing inorganic cation such as an oxygen-containing cation of lanthanum, aluminum, or iron.
  • Aluminum pillared clays are often prepared by contacting the pillaring agent with the clay in an amount ranging from about 5 mmol Al/g clay or 6 mmol Al/g clay, up to about 30 mmol Al/g clay.
  • Intercalated The terms “intercalated” or “intercalation” are terms of the art which indicate insertion of a material into the interlayers of a clay substrate. The terms are used herein in the manner understood by the person of skill in the art, and as described in U.S. Patent No 4,637,992, unless otherwise noted. Basal spacing.
  • basal spacing when used in the context of smectite clays such as montmorillonite, refers to the distance, usually expressed in angstroms or nanometers, between similar faces of adjacent layers in the clay structure.
  • the basal distance is the distance from the top of a tetrahedral sheet to the top of the next tetrahedral sheet of an adjacent 2:1 layer and including the intervening octahedral sheet, with or without modification or pillaring.
  • Basal spacing values are measured using X-ray diffraction analysis (XRD) of the d001 plane.
  • Natural montmorillonite as found for example in bentonite has a basal spacing range of from about 12 ⁇ to about 15 ⁇ .
  • 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 U.S.
  • Zeta potential refers to the difference in electrical potential between the juncture of the Stern layer (a layer of firmly- attached counterions which forms to neutralize the surface charge of a colloidal particle) and diffuse layer (a cloud of loosely attached ions residing farther from the particle surface than the Stern layer), and the bulk solution or slurry. This property is expressed in units of voltage, for example millivolts (mV). Zeta potential can be derived by quantifying the “Electrokinetic Sonic Amplitude Effect” (ESA), which is the generation of ultrasound waves as a result of applying an electric potential across a colloidal suspension, as described in U.S.
  • ESA Electrokinetic Sonic Amplitude Effect
  • Hydrocarbyl group As used herein, the term “hydrocarbyl” group is used according to the art-recognized IUPAC definition, as a univalent, linear, branched, or cyclic group formed by removing a single hydrogen atom from a parent hydrocarbon compound. Unless otherwise specified, a hydrocarbyl group can be aliphatic or aromatic; saturated or unsaturated; and can include linear, cyclic, branched, and/or fused ring structures; unless any of these are otherwise specifically excluded. See IUPAC Compendium of Chemical Terminology, 2 nd Ed (1997) at 190.
  • hydrocarbyl groups include, but are not limited to, aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, cycloalkadienyl, alkynyl, aralkyl, aralkenyl, and aralkynyl groups and the like.
  • Heterohydrocarbyl group The term “heterohydrocarbyl” group is used in this disclosure to encompass a univalent, linear, branched, or cyclic group, 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.
  • heterohydrocarbon can be aliphatic or aromatic.
  • heterohydrocarbyl groups include halide-substituted, nitrogen-substituted, phosphorus-substituted, silicon-substituted, oxygen-substituted, and sulfur-substituted hydrocarbyl groups in which a hydrogen has been removed form a carbon atom to generate a free valence.
  • heterohydrocarbyl groups include, but are not limited to, -CH2OCH3, -CH2SPh, -CH2NHCH3, -CH2CH3NMe2, -CH2SiMe3, -CMe2SiMe3, -CH2(C6H4- 4-OMe), -CH2(C6H4-4-NHMe), -CH2(C6H4-4-PPh2), -CH2CH3PEt2, -CH2Cl, -CH2(2,6- C 6 H 3 Cl 2 ), and the like.
  • Heterohydrocarbyl encompasses both heteroaliphatic groups (including saturated and unsaturated groups) and heteroaromatic groups.
  • heteroatom- substituted vinylic groups heteroatom-substituted alkenyl groups, heteroatom-substituted dienyl groups, and the like are all encompassed by heterohydrocarbyl groups.
  • Organoheteryl group The term “organoheteryl” group is also used in accordance with its art-recognized IUPAC definition, as univalent group containing carbon, which is thus organic, but which has its free valence at an atom other than carbon. See IUPAC Compendium of Chemical Terminology, 2 nd Ed (1997) at 284.
  • An organoheteryl group can be linear, branched, or cyclic, and includes such common groups as alkoxy, aryloxy, organothio (or organylthio), organogermanium (or organylgermanium), acetamido, acetonylacetanato, alkylamido, dialkylamido, arylamide, diarylamido, trimethylsilyl, and the like.
  • Groups such as -OMe, -OPh, -S(tolyl), -NHMe, -NMe 2 , -N(aryl) 2 , -SiMe 3 , -PPh 2 , - O3S(C6H4)Me, -OCF2CF3, -O2C(alkyl), -O2C(aryl), -N(alkyl)CO(alkyl), -N(aryl)CO(aryl), - N(alkyl)C(O)N(alkyl)2, hexafluoroacetonylacetanato, and the like.
  • Organyl group Organyl group.
  • An organyl group can be linear, branched, or cyclic, and the term “organyl” may be used in conjunction with other terms, as in organylthio- (for example, MeS-) and organyloxy. Heterocyclyl group.
  • the IUPAC Compendium compares organyl groups to other groups such as heterocyclyl groups and organoheteryl groups.
  • heterocyclyl groups are defined as univalent groups formed by removing a hydrogen atom from any ring atom of a heterocyclic compound.
  • a piperidin-1-yl group and a piperidin-2-yl group shown below, wherein the lines drawn from the nitrogen atom or carbon atom represent an open valence and not a methyl group are heterocyclyl groups.
  • the piperidin-1-yl group is also considered an organoheteryl group
  • the piperidin-2-yl group is also considered a heterohydrocarbyl group.
  • the valence of a “heterocyclyl” can occur on any appropriate cyclic atom
  • the valence of a “organoheteryl” occurs on a heteroatom
  • the valence of a heterohydrocarbyl occurs on a carbon atom.
  • Hydrocarbylene group and hydrocarbylidene group is also considered an organoheteryl group
  • the piperidin-2-yl group is also considered a heterohydrocarbyl group.
  • hydrocarbylene is also defined according to its ordinary and customary meaning, as set out in the IUPAC Compendium of Chemical Terminology, 2 nd Ed (1997), as a divalent group formed by removing two hydrogen atoms from a hydrocarbon, the free valencies of which are not engaged in a double bond.
  • a hydrocarbylene group in which the free valencies are not engaged in a double bond is distinguished from a hydrocarbylidene group such as an alkylidene group.
  • a “hydrocarbylidene” group is a divalent group formed upon a hydrocarbon by removing two hydrogen atoms from the same carbon atom, the free valencies of which are part of a double bond.
  • An alkylidene group is an exemplary hydrocarbylidene and is defined as a divalent group formed upon an alkane by removing two hydrogen atoms from the same carbon atom, the free valencies of which are part of a double bond.
  • heterohydrocarbylene group and heterohydrocarbylidene group are used to refer to a divalent group formed by removing two hydrogen atoms from a parent heterohydrocarbon molecule, the free valencies of which are not engaged in a double bond. The hydrogen atoms can be removed from two carbon atoms, two heteroatoms, or one carbon and one heteroatom, such that the free valencies are not engaged in a double bond.
  • 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-, -and the like.
  • a “heterohydrocarbylidene” group is a divalent group formed upon a heterohydrocarbon by removing two hydrogen atoms from the same carbon atom, the free valencies of which are part of a double bond.
  • Halide and halogen are used herein to refer to the ions or atoms of fluorine, chlorine, bromine, or iodine, individually or in any combination, as the context and chemistry allows or dictates. These terms may be used interchangeably regardless of charge or the bonding mode of these atoms.
  • Polymer The term “polymer” is used herein generically to include olefin homopolymers, copolymers, terpolymers, and so forth.
  • a copolymer is derived from an olefin monomer and one olefin comonomer, while a terpolymer is derived from an olefin monomer and two olefin comonomers. Accordingly, “polymer” encompasses copolymers, terpolymers, and the like, derived from any olefin monomer and comonomer(s) disclosed herein. Similarly, an ethylene polymer would include ethylene homopolymers, ethylene copolymers, ethylene terpolymers, and so forth.
  • an olefin copolymer such as an ethylene copolymer
  • an olefin copolymer can be derived from ethylene and a comonomer, such as propylene, 1- butene, 1-hexene, or 1-octene. If the monomer and comonomer were ethylene and 1-hexene, respectively, the resulting polymer would be categorized an as ethylene/1-hexene copolymer.
  • the term “polymerization” includes homopolymerization, copolymerization, terpolymerization, and so forth.
  • a copolymerization process includes contacting one olefin monomer such as ethylene and one olefin comonomer such as 1-hexene to produce a copolymer.
  • olefin monomer such as ethylene
  • olefin comonomer such as 1-hexene
  • polyolefin types such as “HDPE” for high density polyethylene
  • HDPE high density polyethylene
  • polymer is not limited by molecular weight and therefore encompasses both lower molecular weight polymers, sometimes referred to as oligomers, as well as higher molecular weight polymers. Procatalyst or Precatalyst.
  • procatalyst or “precatalyst” as used herein means a compound that is capable of polymerizing, oligomerizing or hydrogenating olefins when activated by an aluminoxane, borane, borate or other acidic activator, whether a Lewis acid or a Br ⁇ nsted acid, or when activated by a support-activator as disclosed herein. Additional Explanations of Terms. The following additional explanations of terms are provided to fully disclosed aspects of the disclosure and claims. Several types of numerical ranges are disclosed herein, including but not limited to, numerical ranges of a number of atoms, basal spacings, weight ratios, molar ratios, percentages, temperatures, and so forth.
  • the Applicant when the Applicant discloses or claims a chemical moiety that has a certain number of carbon atoms, such as a C1 to C12 (or C1 toC12) alkyl group, or in alternative language having from 1 to 12 carbon atoms, the Applicant’s intent is to refer to a moiety that can be selected independently from an alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms, as well as any range between these two numbers (for example, a C1 to C6 alkyl group), and also including any combination of ranges between these two numbers (for example, a C2 to C4 and C6 to C8 alkyl group).
  • any range of numbers recited in the specification or claims such as that representing a particular set of properties, units of measure, conditions, physical states or percentages, is intended to literally incorporate expressly herein by reference or otherwise, any number falling within such range, including any subset of numbers within any range so recited.
  • any number R falling within the range is specifically disclosed.
  • R RL+k(RU ⁇ RL), wherein k is a variable ranging from 1% to 100% with a 1% increment, e.g., k is 1%, 2%, 3%, 4%, 5%....50%, 51%, 52%....95%, 96%, 97%, 98%, 99%, or 100%.
  • any numerical range represented by any two values of R, as calculated above is also specifically disclosed.
  • any general or specific structure presented also encompasses all conformational isomers, regioisomers, and stereoisomers that may arise from a particular set of substituents, unless stated otherwise.
  • the general or specific structure also encompasses all enantiomers, diastereomers, and other optical isomers whether in enantiomeric or racemic forms, as well as mixtures of stereoisomers, as would be recognized by a skilled artisan.
  • values or ranges may be expressed in this disclosure using the term “about”, for example, “about” a stated value, greater than or less than “about” a stated value, or in a range of from “about” one value to “about” another value.
  • a support-activator an organoaluminum compound
  • a metallocene compound is meant to encompass one, or mixtures or combinations of more than one (“at least one”), catalyst support-activator, organoaluminum compound, or metallocene compound, respectively.
  • the term “comprising” and variations thereof such as “comprises”, “comprised of”, “having”, “including,” and the like, as recited in transitional phrases or the specification, are inclusive and open-ended and do not exclude additional, unrecited elements or method steps.
  • describing a compound or composition as “consisting essentially of” should not be construed as “comprising,” as this phrase is intended to describe the recited component that includes materials which do not significantly alter composition or method to which the term is applied.
  • a precursor or catalyst component can consist essentially of a material which can include impurities commonly present in a commercially produced sample of the material when prepared by a certain procedure.
  • compositions or processes are described in terms of “comprising” various components or steps, the compositions and processes can also “consist essentially of” or “consist of” the various components or process steps.
  • a claim includes different features and/or feature classes (for example, a method step, feedstock features, and/or product features, among other possibilities)
  • the transitional terms comprising, consisting essentially of, and consisting of apply only to feature class to which is utilized and it is possible to have different transitional terms or phrases utilized with different features within a claim.
  • a method can comprise several recited steps (and other non-recited steps) but utilize a catalyst system preparation consisting of specific or alternatively consisting essentially of specific steps but utilize a catalyst system comprising recited components and other non-recited components.
  • the terms “substantial” and “substantially” as applied to any criteria such as a property, characteristic or variable means to meet the stated criteria in sufficient measure that one skilled in the art would understand that the benefit to be achieved, or the condition or property value desired is met.
  • the term “substantially” may be used when describing a metallocene catalyst or catalyst system which is substantially free of or substantially absent an aluminoxane, a borate activator, a protic-acid-treated clay, or a pillared clay.
  • substantially free can be used to describe a composition in which none of the recited component the composition is substantially free of was added to the composition, and only impurity amounts such as amounts derived from the purity limits of the other components or generated as a byproduct are present.
  • the composition when a composition is said to be “substantially free” of a particular component, the composition may have less than 10 wt.% of the component, less than 5 wt.% of the component, less than 3 wt.% of the component, less than 2 wt.% of the component, less than 1 wt.% of the component, less than 0.5 wt.% of the component, or less than 0.1 wt.% of the component.
  • the terms “optionally”, “optional” and the like with respect to a claim element 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 claim, and it is envisioned that the claim can encompass either or both alternatives.
  • 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), published on-line at http://old.iupac.org/reports/periodic_table/; version dated 19 Feb.2010. Reference to a “group” or “groups” of the Periodic Table as reflected in the Periodic Table of Elements using the IUPAC system for numbering groups of elements as Groups 1-18.
  • IUPAC International Union of Pure and Applied Chemistry
  • the support-activators of this disclosure can be formed by contacting an expanding-type clay such as smectite or dioctahedral smectite clay or a preformed smectite clay-cationic polymetallate heteroadduct with a surfactant in a liquid carrier, and there are several embodiments or aspects for the method and the resulting heteroadducts.
  • an expanding-type clay such as smectite or dioctahedral smectite clay or a preformed smectite clay-cationic polymetallate heteroadduct
  • a surfactant in a liquid carrier
  • a method of making a support-activator comprising a smectite heteroadduct comprising or consisting essentially of contacting 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 to provide a slurry of the smectite heteroadduct in the first liquid carrier.
  • This process can optionally involve the further addition of other reagents such as cationic polymetallates or metal oxides, however, the contacting step also may occur in absence of specific reactants as described hereinabove.
  • the contacting step may be carried out in the absence of a cationic polymetallate and other reactants, or the contacting step can be carried out in the absence of any other reactant, except for the surfactant.
  • this disclosure provides a method of making a support- activator comprising a smectite heteroadduct, the method comprising or consisting essentially of contacting in any order in a first liquid carrier: (a) a colloidal smectite clay; (b) a cationic polymetallate; and (c) 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 heteroadduct in the first liquid carrier.
  • this process can optionally involve the further addition of other reagents if desired, however, this contacting step also may occur in absence of specific reactants as described herein or in the absence of any other reactant if desired.
  • this disclosure provides for preforming a clay- cationic polymetallate heteroadduct, preparing an aqueous spray-drying slurry of a preformed or isolated clay-cationic polymetallate heteroadduct, which includes a surfactant in the aqueous spray-drying slurry.
  • the resulting heteroadducts can be spray-dried from an aqueous slurry in the absence of an organic dispersion medium or in the absence of an organic liquid (except for the surfactant), to provide highly spherical support-activators.
  • This process also may optionally involve the addition of other reagents if desired, however, this contacting step also may occur in absence of specific reactants as described herein or in the absence of any other reactant if desired.
  • the heterocoagulates produced according to the disclosed process can be conveniently isolated through simple filtration, and subsequently dried and calcined to provide a support-activator that is useful to support and activate metallocene catalysts towards olefin polymerization.
  • the calcined surfactant supports described herein possess improved porosity relative to calcined clays and calcined clay-polymetallate mixtures, even when dried by spray-drying from an aqueous slurry.
  • methods such as azeotropically removing the water using an organic liquid are often required to maintain porosity.
  • substantial BJH porosity remains when spray dried in the absence of an organic dispersion liquid.
  • Conventional treatments to activate the aforementioned clays to provide a clay-based support-activator include contacting the clay with mineral acids such as hydrochloric acid or sulfuric acid, which can include a surfactant treatment (see, for example, U.S. Patent No.7,220,695).
  • mineral acids such as hydrochloric acid or sulfuric acid
  • these treatments can reduce the structural integrity of the clay, likely because in the process of acidifying the clay, the clay structure itself is destroyed through peptization, such as is described in Clay Minerals, 2003, 38(1), 127-138.
  • acids are generally believed to be necessary to activate the clay, therefore previous approaches to addressing the stability of the resulting support-activator have not entirely removed the acid treatment.
  • the Applicant has unexpectedly discovered that cationic polymetallates are also unnecessary, as the subject clays can be activated in the presence of surfactants but in the absence of cationic polymetallates such as aluminum chlorhydrate (ACH), polyaluminum chloride (PAC), or aluminum sesquichlorohydrate compositions, and still provide highly active support-activators having desirable structural properties.
  • the resulting support-activators have a high porosity, particle uniformity, and high particle sphericity.
  • the support-activators can be calcined or otherwise dried to control any residual moisture present in the support.
  • the surfactant molecules or surfactant cations can intercalate between the clay layers, acting as pillars to support the layered structure, even in the absence of other prior activating components such as acids or polymetallates. It has further been unexpectedly discovered that the calcined surfactant-clay supports described herein possess improved olefin polymerization activity relative to their calcined clay or calcined clay-polymetallate analogs. Again, while not wishing to be bound by theory, the enhanced porosity obtained by combination of surfactants and clay is thought to enable the metallocene to access and form more catalytically active sites.
  • this disclosure provides a support-activator comprising a smectite heteroadduct which can be calcined, in which the smectite heteroadduct comprises or consists essentially of the isolated contact product in a first liquid carrier of (a) a colloidal smectite clay and (b) a surfactant reagent comprising or selected from [i] a cationic surfactant, [ii] a nonionic surfactant, or [iii] an amphoteric surfactant, or any combination thereof.
  • colloidal Smectite Clays In addition to the Definitions section, the following disclosure provides additional information related to the smectite clays.
  • An expanding-type clay such as smectite or the 2:1 dioctahedral smectite clay, or a combination of expanding-type clays, can be used in the preparation of the support- activator described herein.
  • These expanding-type clays may be described as phyllosilicates or phyllosilicate clays, because certain members of the clay minerals group of the phyllosilicates can be used.
  • Suitable starting clays can include layered, naturally occurring or synthetic smectites.
  • Starting clays can also include the dioctahedral smectite clays. Further, suitable starting clays may also include clays such as montmorillonites, sauconites, nontronites, hectorites, beidellites, saponites, bentonites, or any combination thereof. Smectites are 2:1 layered clay minerals that carry a lattice charge and can expand when solvated with water and alcohols. Therefore, suitable starting clays can include, for example, the monocation exchanged, dioctahedral smectites, such as the lithium-exchanged clays, sodium-exchanged clays, or potassium-exchanged clays, or a combination thereof.
  • Water can also be coordinated to the layered clay structural units, either associated with the clay structure itself or coordinated to the cations as a hydration shell.
  • the 2:1 layered clays When dehydrated, have a repeat distance or d001 basal spacing of from about 9 ⁇ (Angstrom) to about 12 ⁇ (Angstrom) in the powder X-ray Diffraction (XRD); or alternatively, in a range of from about 10 ⁇ (Angstrom) to about 12 ⁇ (Angstrom) in the powder X-ray Diffraction (XRD).
  • the layered smectite clays are termed 2:1 clays, because their structures are “sandwich” structures which include two outer sheets of tetrahedral silicate and an inner sheet of octahedral alumina which is sandwiched between the silica sheets. Therefore, these structures are also referred to as “TOT” (tetrahedral-octahedral-tetrahedral) structures. These sandwich structures are stacked one upon the other to yield a clay particle.
  • This arrangement can provide a repeated structure about every nine and one-half angstroms ( ⁇ ), as compared with the pillared or intercalated clays produced by the insertion of “pillars” of inorganic oxide material between these layers to provide a larger space between the natural clay layers.
  • the clay used to prepare the clay-heterocoagulate and support- activator can be a colloidal smectite clay.
  • the colloidal smectite clay can have an average particle size of greater than or equal to 10 ⁇ m (microns), greater than or equal to 5 ⁇ m, greater than or equal to 3 ⁇ m, greater than or equal to 2 ⁇ m, or greater than or equal to 1 ⁇ m, wherein the average particle size can also be less than or equal to 15 ⁇ m, less than or equal to 25 ⁇ m, less than or equal to 50 ⁇ m, less than or equal to 75 ⁇ m, less than or equal to 100 ⁇ m, less than or equal to 125 ⁇ m, less than or equal to 150 ⁇ m, less than or equal to 175 ⁇ m, less than or equal to 200 ⁇ m, less than or equal to 225 ⁇ m, or less than or equal to 250 ⁇ m.
  • the average particle size can also be less than or equal to 15 ⁇ m, less than or equal to 25 ⁇ m, less than or equal to 50 ⁇ m, less than or equal to 75 ⁇ m, less than or equal to 100 ⁇ m,
  • any ranges of clay particle sizes between these recited numbers are disclosed. If not specifically stated otherwise, any particle size recited herein for the smectite clay itself is the particle size designated by the supplier of the clay. While clays that are unable to give colloidal suspensions can be used, the use of these non-colloidal clays present additional processing and separation issues that are avoided by the use of colloidal clays. These upper and lower limits of average particle sizes of the colloidal smective clay are also applicable to the clay-surfactant heteroadduct (dry or calcined), and the supported metallocene catalysts (dry), as described herein.
  • the colloidal smectite clay can have an average particle size of, for example, from 1 ⁇ m (micron) to 250 ⁇ m.
  • the colloidal smectite clay can have an average particle size of about 1 ⁇ m (microns), about 2 ⁇ m, about 3 ⁇ m, about 5 ⁇ m, about 7 ⁇ m, about 10 ⁇ m, about 12 ⁇ m, about 15 ⁇ m, about 18 ⁇ m, about 20 ⁇ m, about 25 ⁇ m, about 30 ⁇ m, about 35 ⁇ m, about 40 ⁇ m, about 45 ⁇ m, about 50 ⁇ m, about 55 ⁇ m, about 60 ⁇ m, about 65 ⁇ m, about 70 ⁇ m, about 75 ⁇ m, about 80 ⁇ m, about 85 ⁇ m, about 90 ⁇ m, about 95 ⁇ m, about 100 ⁇ m, about 110 ⁇ m, about 120 ⁇ m, about 125 ⁇ m, about 130 ⁇ m, about 140 ⁇ m, about 150
  • the colloidal smectite clay can have an average particle size of from 1 ⁇ m to 250 ⁇ m, from 2 ⁇ m to 125 ⁇ m, from 3 ⁇ m to 100 ⁇ m, from 5 ⁇ m to 150 ⁇ m, from 5 ⁇ m to 80 ⁇ m, from 7 ⁇ m to 70 ⁇ m, from 10 ⁇ m to 100 ⁇ m, from 10 ⁇ m to 60 ⁇ m, from 15 ⁇ m to 80 ⁇ m, from 15 ⁇ m to 50 ⁇ m, or from 20 ⁇ m to 75 ⁇ m.
  • the particles sizes of commercial Volclay® HPM-20 bentonite provide suitable particle sizes for use according to this disclosure.
  • the colloidal smectite clay used according to this disclosure can be characterized by a minimum 99.00% finer than 200 mesh (74 microns) particle sizes.
  • the colloidal smectite clay used according to this disclosure can be characterized by a minimum 99.75% finer than 200 mesh (74 microns), and a minimum 99.00% finer than 325 mesh (44 microns) for the particle sizes.
  • the clay used to prepare the support-activator can be absent a bivalent or trivalent ion exchanged smectite, for example, Mg-exchanged or Al-ion exchanged montmorillonite which are described in U.S. Patent No.6,531,552.
  • the clay used to prepare the support-activator can be absent mica or synthetic hectorite, as described in U.S. Patent Nos.6,531,552 and 5,973,084.
  • the clay used to prepare the support-activator can be absent a trioctahedral smectite or can be absent vermiculite.
  • the smectite clay can also comprise structural units characterized by the following formula: (M A IV)8(M B VI)pO20(OH)4; wherein a) M A IV is a four-coordinate Si 4+ , wherein the Si 4+ is optionally partially substituted by a four-coordinate cation that is not Si 4+ (for example, the cation that is not Si 4+ can be selected independently from Al 3+ , Fe 3+ , P 5+ , B 3+ , Ge 4+ , Be 2+ , Sn 4+ , and the like); b) M B VI is a six-coordinate Al 3+ or Mg 2+ , wherein the Al 3+ or Mg 2+ is optionally partially substituted by a six-coordinate cation that is not Al 3+ or Mg 2+ (for example, the cation that is not Al 3+ or Mg 2+ can be selected independently from Fe 3+ , Fe 2+ , Ni 2+ , Co 2+
  • the smectite clay can be monocation exchanged with at least one of lithium, sodium, or potassium.
  • the Examples, data, and Aspects of the Disclosure section provide additional detailed information of the various aspects and embodiments of the smectite clay.
  • D. Surfactants The step of contacting the clay and the surfactant can be carried out using any suitable surfactant, which can include cationic surfactants, nonionic surfactants, amphoteric surfactants (including amphiprotic surfactants), and can include combinations thereof.
  • the contact product and the method of making a support-activator can be absent any one or any two of a cationic surfactant, a nonionic surfactant, or an amphoteric surfactant.
  • the colloidal smectite clay and the surfactant can be contacted in a ratio of from 0.5 millimoles to 5 millimoles of surfactant per gram of colloidal smectite clay.
  • the colloidal smectite clay and the surfactant can be provided or contacted in a ratio of from 0.75 millimoles to 4 millimoles, from 1 millimoles to 3.5 millimoles , from 1.25 millimoles to 3 millimoles, or from 1.5 millimoles to 2.75 millimoles of surfactant per gram of colloidal smectite clay.
  • the cationic surfactant can comprise or can be selected from a primary, a secondary, a tertiary, or a quaternary ammonium compound or phosphonium compound.
  • this disclosure may refer to the cationic surfactant comprising a cationic component and a counterion or anion.
  • the cationic surfactant can comprise or can be selected from an ammonium compound (salt), 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 selected independently from hydrogen, a substituted or an unsubstituted C1-C25 hydrocarbyl group, or a substituted or an unsubstituted C1- C25 heterohydrocarbyl group, in which any two or more of R 1 , R 2 , R 3 , and R 4 may be part of a ring structure, and wherein at least one of R 1 , R 2 , R 3 , and R 4 is a non- hydrogen moiety; and X- is selected from an organic or an inorganic monoanion, dianion, or trianion.
  • 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 selected independently from hydrogen, a substituted or an unsubstituted C1-C25 aliphatic group, a substituted or an unsubstituted C1- C25 heteroaliphatic group, a substituted or an unsubstituted C 6 -C25 aromatic group, or a substituted or an unsubstituted C4-C25 heteroaromatic group, in which any two or more of R 1 , R 2 , R 3 , and R 4 may be part of a ring structure, and wherein 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,
  • the cationic surfactant can comprise or can be selected from a phosphonium compound (salt), 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 is selected independently from hydrogen, a substituted or an unsubstituted C1-C25 hydrocarbyl group, or a substituted or an unsubstituted C1- C25 heterohydrocarbyl group, in which any two or more of R 1 , R 2 , R 3 , and R 4 may be part of a ring structure, and wherein at least one of R 1 , R 2 , R 3 , and R 4 is a non- hydrogen moiety; and X- is selected from an organic or an inorganic monoanion, dianion, or trianion.
  • a phosphonium compound salt having the following general formula: [R 1 R 2 R 3 R 4 P] + X-, wherein each R 1 , R 2 ,
  • the phosphonium compound can have the general formula [R 1 R 2 R 3 R 4 P] + X-, wherein R 1 , R 2 , R 3 , and R 4 are selected independently from hydrogen, a substituted or an unsubstituted C1-C25 aliphatic group, a substituted or an unsubstituted C1-C25 heteroaliphatic group, a substituted or an unsubstituted C 6 -C25 aromatic group, or a substituted or an unsubstituted C4-C25 heteroaromatic group, in which any two or more of R 1 , R 2 , R 3 , and R 4 may be part of a ring structure, and wherein 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, bromide, iodide, formate, a carboxylate
  • the cationic surfactant can comprise a cation selected from lauryltrimethylammonium, stearyltrimethylammonium, trioctylammonium, distearyldimethylammonium, distearyldibenzylammonium, cetyltrimethylammonium, benzylhexadecyldimethylammonium, dimethyldi-(hydrogenated tallow)ammonium, dimethylbenzyl-(hydrogenated tallow)ammonium, or any combination thereof.
  • the cation of the cationic surfactant can comprise or be selected from tetramethylammonium, tetraethylammonium, tetrabutylammonium, tetrapentylammonium, tetrahexylammonium, tetraoctylammonium, tetrabenzylammonium, cetylammonium, decylammonium, dodecylammonium, methyloctadecylammonium, ethyloctadecylammonium, butyloctadecylammonium, dimethyloctadecylammonium, diethyloctadecylammonium, dibutyloctadecylammonium, trimethyloctadecylammonium, triethyloctadecylammonium, tributyloctadecylammonium,
  • the counterion X- for the cationic component of the cationic surfactant can comprise or can be selected from organic anions or inorganic anions such as halides.
  • organic anions include but are not limited to formate, carboxylates such as 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 cationic components such as exemplified above, in combination with an anion comprising or selected from a halide ion or an anion of an inorganic Br ⁇ nsted acid.
  • examples of cationic surfactants include, but are not limited to, a chloride or a bromide of benzalkonium, benzethonium, methylbenzethonium, cetylpyridinium, alkyl-dimethyl dichlorobenzene ammonium, dequalinium, phenamylinium, cetrimonium, or cethexonium.
  • examples of cationic surfactants that can be used according to this disclosure include tetrabutylammonium bromide, dioctadecyldimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecylammonium chloride, trimethylstearylammonium chloride, cetyltrimethylammonium bromide, octenidine dihydrochloride, cetyl trimethylammonium bromide (CTAB), cetyl trimethylammonium chloride (CTAC), cetylpyridinium chloride (CPC), benzalkonium chloride (BAC), benzethonium chloride (BZT), dimethyldioctadecylammonium chloride, dioctadecyldimethylammonium bromide (DODAB), or combinations thereof.
  • CTAB cetyl trimethylammonium bromide
  • CTC cetyl trimethylammonium chloride
  • the cationic surfactant can comprise or be selected from an aliphatic dialkyl benzyl ammonium compounds (also termed aliphatic alkyl benzyl ammonium compounds), which describes a class of quaternary ammonium compounds that include alkyl dimethyl benzyl ammonium chloride (ADBAC), in which the alkyl can include, for example, C12-C16 or C12-C14 alkyl.
  • aliphatic dialkyl benzyl ammonium” compound may be used to describe a family of quaternary ammonium compounds which may be prepared or are commercially available in the form of compound mixtures.
  • product or safety data sheets for commercially available “ADBAC” state that the commercial product includes includes a mixture of alkyl dimethyl benzyl ammonium chloride and alkyl (C12-C14) dimethyl (ethylbenzyl) ammonium chloride.
  • Such common commercial ammonium compounds can be used in accordance with this disclosure.
  • the surfactant can comprise, consist essentially of, or be selected from a nonionic surfactant.
  • amphoteric surfactants including amphiprotic surfactants
  • nonionic surfactants include but are not limited to a polyhydric alcohol, mono-alkyl and di-alkyl ethers of polyhydric alcohols, or the polyalkylene glycols thereof, and any combinations of more than one such nonionic surfactant can be used.
  • Suitable polyhydric alcohols may contain 2, 3, or more hydroxyl groups.
  • the polyhydric alcohol can have the formula CH2OH(CHOH)nCH2OH wherein 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 the mono- and di-methyl and the mono- and di-ethyl ethers of ethylene glycol, propylene glycol, and diethylene glycol.
  • Exemplary polyalkylene glycols include poly(ethylene)glycol and poly(propylene)glycol.
  • nonionic surfactant can comprise polyethoxylated tallow amine (also polyoxyethyleneamine or POEA).
  • POEA polyoxyethyleneamine
  • the nonionic surfactant reagent can comprise or be selected from saccharides such as mono-saccharides, di-saccharides, oligosaccharides, or mixtures thereof such as found in corn syrup solid mixtures derived from hydrolysis of corn starch.
  • Exemplary saccharides include glucose, fructose, mannose, maltose, lactose, sucrose, and the like.
  • Exemplary oligosaccharides include but are not limited to cyclodextrins and maltodextrins.
  • the nonionic surfactants used according to this disclosure can also comprise amino-modified saccharides such as glucosamine, and oxidized sugar acids such as glucoronic acid.
  • the nonionic surfactant can comprise a singular fatty acid or a mixture of several fatty acids. These species typically include a carbon chain of 6 to 21 carbons in length, which may optionally contain internal unsaturation, in which 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, linoelaidic acid, ⁇ -linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid, or any combination thereof.
  • the nonionic surfactant can comprise a fatty acid, examples of which are listed immediately above, condensed with an alcohol having one or multiple hydroxyl groups, such as methanol, ethanol, butanol, hexanol, or glycerol, for example, a monoglyceride, diglyceride, or triglyceride.
  • an alcohol having one or multiple hydroxyl groups such as methanol, ethanol, butanol, hexanol, or glycerol, for example, a monoglyceride, diglyceride, or triglyceride.
  • the nonionic surfactant can comprise an ethoxylate, a glycol ether, a fatty alcohol polyglycol ether, or combinations thereof, examples of which include but are not limited to octylphenol ethoxylate, polyethylene glycol tert-octylphenyl ether, ethylenediamine tetrakis(ethoxylate-block-propoxylate) tetrol, or ethylenediamine tetrakis(propoxylate-block-ethoxylate) tetrol.
  • the nonionic surfactant can comprise or can be selected from a hydrocarbyl (hydrocarbon)sulfonate having the formula R 1 SO2OR 2 , wherein R 1 and R 2 are selected independently from a substituted or an unsubstituted C1-C25 alkyl, C6-C25 aryl, C7-C25 aralkyl, or C7-C25 alkaryl.
  • the nonionic surfactant can comprise or be selected from: (a) a mono-saccharide, a di-saccharide, an oligosaccharide, or any combination thereof; or (b) glucose, fructose, mannose, maltose, lactose, sucrose, a cyclodextrin, a maltodextrin, an amino-modified saccharides such as glucosamine, an oxidized sugar acid such as glucoronic acid, or any combination thereof.
  • the nonionic surfactant according to this disclosure can comprise or be selected from a silane having the formula R 1 SiX3, R 1 R 2 SiX2, or R 1 R 2 R 3 SiX, wherein: R 1 , R 2 , and R 3 are selected independently from a substituted or an unsubstituted C1- C25 hydrocarbyl group, C1-C25 heterohydrocarbyl group, or any other group which is hydrolytically stable when bonded to silicon in the nonionic surfactant; and X is selected independently from a hydrolyzable group which is converted to a hydroxyl group (-OH) upon hydrolysis thereby forming a silanol.
  • a silane having the formula R 1 SiX3, R 1 R 2 SiX2, or R 1 R 2 R 3 SiX wherein: R 1 , R 2 , and R 3 are selected independently from a substituted or an unsubstituted C1- C25 hydrocarbyl group, C1-C25 heterohydrocarbyl group, or any other group
  • the substituents R 1 , R 2 , and R 3 can be selected independently from hydrogen, a substituted or an unsubstituted C1-C25 aliphatic group, a substituted or an unsubstituted C1- C25 heteroaliphatic group, a substituted or an unsubstituted C6-C25 aromatic group, or a substituted or an unsubstituted C4-C25 heteroaromatic group.
  • the X group can be selected from a C1-C25 alkoxy, a C1-C25 acyloxy, a halogen, or a C1-C25 amine.
  • the nonionic surfactant according to this disclosure can comprise or can be selected from a silyl alcohol having the formula R 4-n Si(OH) n , wherein n is 1 or 2, and R is selected from a C1 to C20 alkyl group or a C6 to C20 aryl group.
  • silanols include, but are not limited to, triphenylsilanol, dimethylphenylsilanol, diphenylsilanediol, triisopropylsilanol, or any combination thereof.
  • amphoteric surfactants are those surfactants which include a positively charged moiety (or a moiety which can readily become positively charged by accepting a proton) and a negatively charged moiety (or a moiety which can readily become negatively charged by releasing a proton) in the same molecule.
  • the term “zwitterionic” surfactant is used interchangeably with “amphoteric” surfactants based on the inclusion of both cationic and anionic moieties in the same molecule.
  • Amphiprotic” surfactants which either donate a proton (H + ) or accept a proton are included in the scope of “amphoteric” surfactants, unless otherwise excluded.
  • amphoteric or zwitterionic surfactant includes amphiprotic surfactants.
  • examples of amphoteric surfactants include an amino acid or a combination of amino acids, a polypeptide, or a protein.
  • the contacting step between the clay and the surfactant can be carried out under conditions, including a pH from about 2.5 to 9.5, in which the an amino acid or combination of amino acids are zwitterionic. While not intending to be bound by theory, it is thought that the cationic end of the zwitterionic amino acid can intercalate the clay layers like the aforementioned cationic surfactants.
  • amphoteric surfactant can comprise 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.
  • the amphoteric (zwitterionic) surfactants of this disclosure have both cationic and anionic moieties or centers attached to the same molecule.
  • Examples of cationic centers of an amphoteric (zwitterionic) surfactant include moieties comprising or selected from a primary amine, a secondary amine, a tertiary amine, or a quaternary ammonium cation.
  • Examples of anionic centers of an amphoteric surfactant include but are not limited to sulfates, sulfonates, phosphates, or carboxylates.
  • an amphoteric surfactant can comprise or can be selected from a sultaine, such as a hydroxysultaine compounds.
  • sultaines include, but are not limited to lauramidopropyl hydroxysultaine (ISOTAINE LAPHS); cocamidopropyl hydroxysultaine (ISOTAINE CAPHS); oleamidopropyl hydroxysultaine (ISOTAINE OAPHS); tallowamidopropyl hydroxysultaine (ISOTAINE TAPHS); erucamidopropyl hydroxysultaine (ISOTAINE EAPHS); and lauryl hydroxysultaine (ISOTAINE LHS).
  • the amphoteric surfactant can comprise or can be selected from a betaines, including the simple betaine N,N,N-trimethylglycine.
  • betaines which can be used according to this disclosure include cocamidopropyl betaine.
  • amphoteric surfactants which can comprise or be selected from biological amphoteric surfactants, such as compounds having a phosphate anion with an amine or ammonium moiety in the same molecule, examples of which include phospholipids, phosphatidylserine, phosphatidylethanolamine, phosphatidylcholine, and sphingomyelins.
  • amphoteric surfactants which can comprise or be selected from amino-N-oxides such as tertiary amine N-oxides, examples of which include lauryldimethylamine oxide, myristamine oxide, pyridine-N-oxide, N-methylmorpholine-N- oxide.
  • the amphoteric surfactants of this disclosure can comprise or be selected from a hydrocarbyl amine-N-oxide, such as as alkyl amine-N-oxide or an aryl amine-N-oxide.
  • amphoteric surfactant can comprise or can be selected from CHAPS, which is 3-[(3-cholamidopropyl)dimethylammonio]-1-propanesulfonate, also designated as 3- ⁇ Dimethyl[3-(3 ⁇ ,7 ⁇ ,12 ⁇ -trihydroxy-5 ⁇ -cholan-24-amido)propyl]azaniumyl ⁇ - propane-1-sulfonate.
  • CHAPS 3-[(3-cholamidopropyl)dimethylammonio]-1-propanesulfonate, also designated as 3- ⁇ Dimethyl[3-(3 ⁇ ,7 ⁇ ,12 ⁇ -trihydroxy-5 ⁇ -cholan-24-amido)propyl]azaniumyl ⁇ - propane-1-sulfonate.
  • the smectite heteroadduct described herein can be prepared by contacting in a first liquid carrier: (a) a colloidal smectite clay; and (b) a surfactant comprising from a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or any combination thereof to provide a slurry of the smectite heteroadduct in the first liquid carrier; wherein the contacting step further comprises contacting the colloidal smectite clay or the smectite heteroadduct with an anionic surfactant, before, during, or after the colloidal smectite clay is contacted with the cationic surfactant, the nonionic surfactant, the amphoteric surfactant, or the combination thereof.
  • the smectite heteroadduct formed from the smectite clay and the cationic surfactant, nonionic surfactant, and/or amphoteric surfactant can be subsequently contacted with an anionic surfactant.
  • the contact product of the colloidal smectite clay and the cationic surfactant can be further contacted with an anionic surfactant if desired, prior to isolating the heteroadduct, or prior to spray-drying a slurry of the heteroadduct.
  • an anionic surfactant can be used to contact the clay at the same time as the cationic surfactant when forming the heteroadduct.
  • the anionic surfactant used according to this disclosure can comprise or be selected from a sulfate surfactant, a sulfonate surfactant, a phosphate surfactant, carboxylate surfactant, or other anionic surfactants, examples of which include but are not limited to dialkyl sulfocarboxylic acid esters, alkaryl sulfonic acid salts, aralkyl sulfonic acid salts, alkyl sulfonic acid salts, aryl sulfonic acid salts, sulfosuccinic acid esters, fatty acid alkali salts, polycarboxylic acid salts, polyoxyethylene alkyl ether phosphoric acid ester salts, alkylnaphthalene sulfonic acid salts, wherein the salts
  • anionic surfactant examples include, but are not limited to, an alkyl ether sulfate compound or an alkenyl ether sulfate compound having the formula [RO(C 2 H 4 O) x SO 3 ]M wherein R is a C 8 to C 20 alkyl group or a C 8 to C 20 alkenyl group, x an integer from 1 to 30, inclusive, and M is a cation which imparts water solubility to the alkyl ether sulfate or an alkenyl ether sulfate.
  • Embodiments of the alkyl ether sulfates useful in this disclosure include the condensation products of ethylene oxide and monohydric alcohols having from 8 to 20 carbon atoms, for example from about 14 to about 18 carbon atoms.
  • the monohydric alcohols can be derived from natural sources (for example, fats, coconut oil, or tallow), or they can be synthetic. Lauryl alcohol (dodecanol) and straight chain alcohols derived from tallow are examples of useful alcohols.
  • 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 used as the alkyl ether sulfate.
  • the anionic surfactant can comprise or be selected from a carboxylate compound having the formula [RCOO]M, wherein R is a C 8 to C 21 alkyl group and M is a cation selected from sodium, potassium, or ammonium.
  • the anionic surfactant can comprise or can be selected from: (a) a sulfonate compound having the formula R'SO 3 Na, wherein R' is a C 8 to C21 alkyl group, a C8 to C21 aralkyl group, or a C8 to C21 alkaryl group; or (b) an alkyl sulfate having the formula R"OSO 3 M, wherein R" is a C 8 to C 21 alkyl group, and M is a cation selected from NH4 + , Na + , K + , 1 ⁇ 2 Mg 2+ , diethanolammonium, or triethanolammonium.
  • the anionic surfactant according to this disclosure can comprise or be selected from a sulfated polyoxyethylene alkylphenol with a formula of R"C6H4(OCH2CH2)nOSO3M wherein R" is C1 to C9 alkyl group, M is NH4 + , Na + , or triethanolamine, and n is an integer from 1 to 50, inclusive.
  • Embodiments of the anionic surfactant of this disclosure can comprise or be selected from: (a) an alkyl sulfate having the formula [(R 1 O)SO 2 O]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) sulfated polyoxyalkylene having the formula [R 1 (OCH2CH2)nOSO2O]M or [R 1 (OCH 2 C(CH 3 )CH 2 ) n OSO 2 O]M; or (e) sulfonated polyoxyalkylene having the formula [R 1 (OCH2CH2)nSO2O]M or [R 1 (OCH 2 C(CH 3 )CH 2 ) n SO 2 O]M; wherein: R 1 is selected independently from a substituted or an unsubstituted C1-C25 alkyl-, C6-C25
  • the anionic surfactant can comprise or can be selected from an alkali metal salt of a fatty acid having from about 8 to about 30 carbon atoms.
  • the anionic surfactant can comprise or be selected from an alkali metal salt of a fatty acid 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, linoelaidic acid, ⁇ -linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid, or any combination thereof.
  • the anionic surfactant can comprise or be selected from potassium oleate, dodecyl benzene sulfonate, dioctyl sulfosuccinate, 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, polyoxyethylene (POE) lauryl ether sodium sulfate, POE lauryl ether triethanolamine sulfate, POE lauryl ether ammonium sulfate, POE stearyl ether sodium sulfate, sodium stearoylmethyltaurate, triethanolamine dodecylbenzenesulfonate, sodium tetradecenesulfonate, sodium
  • the anionic surfactant can comprise or be selected from: (a) a substituted or an 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 an unsubstituted alkyl sulfate selected from methylsulfate, ethylsulfate, 1-propylsulfate, 2-propylsulfate, 3-methylbutylsulfate, trifluoromethanesulfate, trichlor
  • Embodiments of the anionic surfactants which can be used according to this disclosure include a sulfate, a sulfonate, a phosphate, carboxylate, or other anionic surfactants, examples of which include but are not limited to dialkyl sulfocarboxylic acid esters, alkyl aryl sulfonic acid salts, alkyl sulfonic acid salts, sulfosuccinic acid esters, fatty acid alkali salts, polycarboxylic acid salts, polyoxyethylene alkyl ether phosphoric acid ester salts, alkylnaphthalene sulfonic acid salts, wherein the salts can be selected from, for example, salts of an alkali metal such as lithium, sodium or potassium, an alkaline earth metal such as calcium or magnesium, or ammonium or hydrocarbylammonium;
  • the anionic surfactants include an anionic functional moiety such as a sulfate, sul
  • the anionic surfactant further comprises a counter ion, examples of which include, but are not limited to, NH4 + , Na + , K + , 1 ⁇ 2 Mg 2+ , diethanolammonium, or triethanolammonium.
  • a counter ion examples of which include, but are not limited to, NH4 + , Na + , K + , 1 ⁇ 2 Mg 2+ , diethanolammonium, or triethanolammonium.
  • polymetallate and similar terms such as “polyoxometallate” refer to the polyatomic cations that include two or more metals (for example, aluminum, silicon, titanium, zirconium, or other metals) along with at least one bridging ligand between metals such as oxo, hydroxy and/or halide ligands.
  • the polymetallates can be hydrous metal oxides, hydrous metal oxyhydroxides, and the like, and can include bridging ligands such as oxo ligands which bridge two or more metals can occur in these species, and can also include terminal oxo, hydroxyl, and/or halide ligands.
  • the polymetallate (polyoxometallate) compounds used according to this disclosure are cationic.
  • the heterocoagulation reagents of this disclosure can be positively-charged species that when combined in the appropriate ratio with a colloidal suspension of clay form a coagulate which is readily filtered and easily washed.
  • the positively charged species include soluble polyoxometallate, polyhydroxylmetallate and polyoxohydroxymetallate cations, and related cations partially halide substituted, such as polyaluminum oxyhydroxychlorides or aluminum chlorhydrate or polyaluminum chloride species that are linear, cyclic or cluster compounds.
  • Useful heterocoagulation reagents can also include any colloidal species that are characterized by a positive zeta potential when dispersed in an aqueous solvent or in a mixed aqueous and organic (for example, alcohol) solvent.
  • useful dispersions of the heterocoagulation reagents can exhibit greater than (>) +20 mV (positive 20 mV) zeta potential, greater than +25 mV zeta potential, or greater than +30 mV zeta potential.
  • the starting colloidal clay may include monovalent ions or species such as protons, lithium ions, sodium ions, or potassium ions, it is thought that at least a portion of these ions can be replaced by the heterocoagulation reagents during formation of the readily filterable clay heteroadduct.
  • the cationic polymetallate heterocoagulation reagent can comprise a colloidal suspension of boehmite (an aluminum oxide hydroxide) or a metal oxide such as a fumed metal oxide which affords a positive zeta potential (for example, fumed alumina).
  • the heterocoagulation reagent can comprise a chemically- modified or chemically-treated metal oxide, for example an aluminum chlorhydrate-treated fumed silica, such that when in suspension, the chemically-treated metal oxide affords a positive zeta potential, as described below.
  • the heterocoagulation reagent may be generated by treating a metal oxide or metal oxide hydroxide and the like in a fluidized bed with reagents which will afford a positive zeta potential when the agent is dispersed in a suspension.
  • the heterocoagulation agent can exhibit a positive value greater than +20 mV prior to combination with the phyllosilicate clay component.
  • the cationic polymetallate can include a first metal oxide which is chemically-treated with a second metal oxide, a metal halide, a metal oxyhalide, or a combination thereof in an amount sufficient to provide a colloidal suspension of the chemically-treated first metal oxide having a positive zeta potential, for example, a zeta potential of greater than positive 20 mV (millivolts). That is, the chemically-treated first metal oxide is the contact product of the first metal oxide with [1] a second metal oxide, that is, another different metal oxide, [2] a metal halide, [3] a metal oxyhalide, or [4] a combination thereof.
  • the first metal oxide which is chemically-treated can comprise fumed silica, fumed alumina, fumed silica-alumina, fumed magnesia, fumed zinc oxide, fumed titania, fumed zirconia, fumed ceria, and the like, or any combination thereof.
  • the second metal oxide, the metal halide, or the 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.
  • treatment may consist of dispersing the fumed oxide in a solution of aluminum chlorhydrate.
  • the cationic polymetallate composition can comprise or 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, which is chemically-treated with [2] polyaluminum chloride, aluminum chlorhydrate, aluminum sesquichlorohydrate, polyaluminum oxyhydroxychloride, or any combination thereof.
  • the cationic polymetallate composition can comprise or be selected from aluminum chlorhydrate-treated fumed silica, aluminum chlorhydrate-treated fumed alumina, aluminum chlorhydrate-treated fumed silica-alumina, or any combination thereof.
  • Some fumed metal oxides, such as fumed alumina may already exhibit a positive zeta potential before chemical treatment. Nevertheless, fumed metal oxides which possess no zeta potential, or a positive zeta potential less than about +20 mV, may also be chemically treated with species, such as aluminum chlorohydrate and the like, after which treatment, a colloidal suspension having a zeta potential greater than about +20 mV can be obtained.
  • the heterocoagulation reagent can include a mixture of metal oxides formed in the fuming process, or subsequent to the fuming process, that because of their composition, exhibits a positive zeta potential.
  • An example of this type fumed oxide is fumed silica-alumina.
  • the heterocoagulation reagent may include any colloidal inorganic oxide particles such as described by Lewis, et al. in U.S. Patent No. 4,637,992, which is incorporated herein by reference, such as colloidal ceria or colloidal zirconia or any positively charged colloidal metal oxide disclosed therein.
  • the heterocoagulation reagent may comprise magnetite or ferrihydrite.
  • the cationic polymetallate can comprise or be selected from boehmite, fumed silica-alumina, colloidal ceria, colloidal zirconia, magnetite, ferrihydrite, any positively charged colloidal metal oxide, or any combination thereof.
  • the heterocoagulation reagents can include a cationic oligomeric or polymeric aluminum species in solution, such as aluminum chlorohydrate, also known as aluminum chlorhydrate (ACH), polyaluminum chloride (PAC), aluminum sesquichlorohydrate, or any combination or mixture thereof.
  • the cationic polymetallate can comprises or can be selected from aluminum species having the formula [AlO 4 (Al 12 (OH) 24 (H 2 O) 20 ] 7+ , which is the so-called “Al 13 -mer” polycation and which is thought to be the precursor to Al13 pillared clays.
  • aluminum chlorhydrate When aluminum chlorhydrate is used as a heterocoagulation reagent or chemical treatment reagent for treating other metal oxides, aluminum chlorhydrate (ACH) solution or solid powder from commercial sources can be utilized.
  • Aluminum chlorhydrate solutions may be referred to as polymeric cationic hydroxy aluminum complexes or aluminum chlorhydroxides, which refers to the polymers formed from a monomeric precursor having the general empirical formula 0.5[Al2(OH)5Cl(H2O)2].
  • Preparation of aluminum chlorhydrate solution is described in U.S. Patent Nos.2,196,016 and 4,176,090, which are incorporated herein by reference, and can involve treating aluminum metal with hydrochloric acid in amounts which produce a composition having the formula indicated above.
  • the aluminum chlorhydrate solutions may be obtained using various sources of aluminum such as alumina (Al2O3), aluminum nitrate, aluminum chloride or other aluminum salts and treatment with acid or base.
  • Al2O3 alumina
  • Al nitrate aluminum nitrate
  • aluminum chloride aluminum salts
  • treatment with acid or base aluminum
  • the numerous species that can be present in such solutions, including the tridecameric [AlO4(Al12(OH)24(H2O)20] 7+ (Al13-mer) polycation, 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, either individually or in combination, which are present in such solutions can be used as cationic polymetallates for heterocoagulation of the smectite clay.
  • aqueous aluminum chlorhydrate solutions used according to this disclosure can have an aluminum content, calculated or expressed as the weight percent of Al 2 O 3 , in a range of from about 15 wt.% to about 55 wt.%, although more dilute concentrations can be used. Using more dilute solutions can be accompanied by adjusting other reaction conditions such as time and temperature, as will be appreciated by the person of ordinary skill in the art.
  • Alternative aluminum concentrations in aqueous aluminum polymetallate solutions such as aqueous aluminum chlorhydrate solutions, expressed as the weight percent of Al2O3, can include: from about 0.1 wt.% to about 55 wt.% Al2O3; from about 0.5 wt.% to about 50 wt.% Al 2 O 3 ; from about 1 wt.% to about 45 wt.% Al 2 O 3 ; from about 2 wt.% to about 40 wt.% Al2O3; from about 3 wt.% to about 37 wt.% Al2O3; from about 4 wt.% to about 35 wt.% Al 2 O 3 ; from about 5 wt.% to about 30 wt.% Al 2 O 3 ; or from about 8 wt.% to about 25 wt.% Al2O3; each range including every individual concentration expressed in tenths (0.1) of a weight percentage encompassed therein, and including any subranges therein.
  • the recitation of from about 0.1 wt.% to about 30 wt.% Al2O3 includes the recitation of from 10.1 wt.% to 26.5 wt.% Al2O3.
  • solid polymetallate aush as solid aluminum chlorhydrate can be used and added to the slurry of the colloidal clay when preparing the heterocoagulate. Therefore, the concentrations disclosed above are not limiting but rather exemplary.
  • the cationic polymetallate can comprise or can be selected from an oligomer prepared by copolymerizing (co-oligomerizing) soluble rare earth salts with a cationic metal complex of at least one additional metal selected from aluminum, zirconium, chromium, iron, or a combination thereof, according to U.S. Patent No.5,059,568, which is incorporated herein by reference, for example, where the at least one rare earth metal can be cerium, lanthanum, or a combination thereof.
  • the heterocoagulation reagent can comprise an aqueous solution of lanthanides and Al13 Keggin ions, such as described by McCauley in U.S. Patent No.5,059,568.
  • the calcined clay-heteroadducts of the present disclosure prepared using the McCauley type polymetallates do not afford a uniform intercalated structure with basal spacings of greater than 13 ⁇ (Angstroms).
  • this observation may result from the much smaller amount of Ce-Al heterocoagulation reagent-to-colloidal clay ratio used according to this disclosure. This smaller amount arises by the conditions of contacting the smectite clay and the heterocoagulation reagent in an amount sufficient to provide a slurry of the smectite heteroadduct having a zeta potential in a range of from about +25 mV (millivolts) to about - 25 mV.
  • exemplary polymetallates of this disclosure can include: [1] the ⁇ -Keggin cations [ ⁇ -PMo12O36(OH)4 ⁇ Ln(H2O)4 ⁇ 4] 5+ , wherein Ln can be La, Ce, Nd, or Sm; and [2] the lanthanide-containing cationic heteropolyoxovanadium clusters having the general formula [Ln 2 V 12 O 32 (H 2 O) 8 ⁇ Cl ⁇ ]Cl, wherein Ln can be Eu, Gd, Dy, Tb, Ho, or Er.
  • the heterocoagulation agent may be a layered double hydroxide, such as a magnesium aluminum 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, which are incorporated herein by reference.
  • the cationic polymetallate used as a heterocoagulation reagent can be a layered double hydroxide or a mixed metal layered hydroxide.
  • the mixed metal layered hydroxide can be selected from a Ni-Al, Mg-Al, or Zn-Cr-Al type having a positive layer charge.
  • the layered double hydroxide or mixed metal layered hydroxide can comprise or can be selected from magnesium aluminum hydroxide nitrate, magnesium aluminum hydroxide sulfate, magnesium aluminum hydroxide chloride, Mg x (Mg,Fe) 3 (Si,Al) 4 O 10 (OH) 2 (H 2 O) 4 (x is a number from 0 to 1, for example, about 0.33 for ferrosaponite), (Al,Mg) 2 Si 4 O 10 (OH) 2 (H 2 O) 8 , synthetic hematite, hydrozincite (basic zinc carbonate) Zn5(OH)6(CO3)2, hydrotalcite [Mg6Al2(OH)16]CO3 ⁇ 4H2O, tacovite [Ni6Al2(OH)6]CO3 ⁇ 4H2O, tacovi
  • the heterocoagulation reagent can include aqueous solutions of Fe polycations, as described by Oades, Clay and Clay Minerals, 1984, 32(1), 49- 57, or described by Cornell and Schwertmann in “The Iron Oxides: Structure, Properties, Reactions, Occurrences and Uses”, 2003, Second Edition, Wiley VCH.
  • the cationic polymetallate can comprise or can be selected from an iron polycation having an empirical formula FeOx(OH)y(H2O)z] n+ , wherein 2x+y is less than ( ⁇ ) 3, z is a number from 0 to about 4, and n is a number from 1 to 3.
  • the use of cations such as protons, lithium ions, sodium ions, or potassium ions and the like do not afford clay heteroadducts as provided by the cationic polymetallates of this disclosure, for example, the proton (acid)-treated clays generally are not readily filterable.
  • the colloidal smectite clay can comprise or be selected from colloidal montmorillonite, such as Volclay® HPM-20 bentonite.
  • the heterocoagulation reagent can comprise or be selected from aluminum chlorhydrate, polyaluminum chloride, or aluminum sesquichlorohydrate.
  • the cationic polymetallate can comprises or be selected from a complex of Formula I or Formula II or any combination of complexes of Formula I or Formula II, according to the following formulas: [M(II)1-xM(III)x(OH)2]Ax/n ⁇ m L (I) [LiAl 2 (OH) 6 ]A 1/n ⁇ m L (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, is their mean valence; and x is a number from 0.1 to 1; and m is a number from 0 to 10.
  • M(II) can be, for example, zinc, calcium, strontium, barium, iron, cobalt, nickel, cadmium, manganese, copper, or magnesium; independently, M(III) can be, for example, iron, chromium, manganese, bismuth, cerium, or aluminum;
  • A can be, for example, hydrogencarbonate (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.
  • the cationic polymetallate can be selected from a complex of Formula I, wherein M(II) is magnesium, M(III) is aluminum, and A can be carbonate.
  • the cationic polymetallate can comprises polyaluminum chloride, aluminum chlorhydrate, aluminum sesquichlorohydrate, or polyaluminum oxyhydroxychloride, or a combination thereof.
  • the cationic polymetallate can include linear, cyclic or cluster aluminum compounds containing, for example, from 2-30 aluminum atoms.
  • the ratio of millimoles (mmol) of aluminum (Al) in the polyaluminum chloride, aluminum chlorhydrate, aluminum sesquichlorohydrate, or polyaluminum oxyhydroxychloride to grams (g) of colloidal smectite clay in recipe for preparing the smectite heteroadduct can be in a range of, for example, from about 0.75 mmol Al/g clay to about 2.0 mmol Al/g clay, from about 0.8 mmol Al/g clay to about 1.9 mmol Al/g clay, from about 1.0 mmol Al/g clay to about 1.8 mmol Al/g clay, from about 1.1 mmol Al/g clay to about 1.8 mmol Al/g clay, or from about 1.1 mmol Al/g clay to about 1.7 mmol Al/g clay.
  • the millimoles (mmol) of aluminum (Al) in the polyaluminum chloride, aluminum chlorhydrate, aluminum sesquichlorohydrate, or polyaluminum oxyhydroxychloride per grams (g) of colloidal smectite clay in recipe for preparing the smectite heteroadduct 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 any ranges between any of these ratios or
  • the ratio of millimoles (mmol) of aluminum (Al) in the polyaluminum chloride, aluminum chlorhydrate, aluminum sesquichlorohydrate, or polyaluminum oxyhydroxychloride to grams (g) of colloidal clay in the recipe to prepare the isolated or calcined smectite heteroadduct can 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 a comparative ratio of millimoles of aluminum to grams of colloidal clay used for the preparation of a pillared clay using the same colloidal smectite clay and heterocoagulation reagent.
  • the ratio of aluminum regent to clay in a pillaring recipe is expressed in mmol Al/g clay, indicating the number of millimoles of Al in the aluminum chlorhydrate reagent versus the grams of clay in the recipe. Specifically, this ratio reflects the ratio employed in the synthesis recipe, not the ratio in the final pillared clay product.
  • the amount of Al used in the pillared clay preparation is far in excess of the amount of Al that eventually is intercalated between the layers in the final pillared clay solid.
  • the surfactant reagent can be contacted with the clay in any manner in a first liquid carrier. It has been found that adding the clay to the first liquid carrier and applying shear force to disperse the clay, followed by adding the surfactant to this dispersion works well.
  • the first liquid carrier can comprise or can be water, to which the clay is added and dispersed, followed by surfactant.
  • the surfactant reagent can be contacted with the clay dispersion through direct addition of the solid or neat liquid form of the surfactant reagent to a slurry/dispersion of the clay, or by contacting a liquid mixture in which the reagent is dissolved or slurried in an appropriate solvent with the clay slurry/dispersion. While the solid clay can be added under high shear conditions to a liquid surfactant or a liquid or solid surfactant dissolved or dispersed in a liquid carrier, more consistent results have been achieved by forming a well-dispersed clay suspension in a liquid carrier prior to adding the surfactant to the carrier.
  • the step of contacting the colloidal smectite clay with a heterocoagulation reagent, whether a surfactant, a cationic polymetallate, or a combination thereof, can be carried out using high shear conditions obtained from high rpm (revolutions-per-minute) to afford a clump-free dispersion.
  • a heterocoagulation reagent whether a surfactant, a cationic polymetallate, or a combination thereof
  • the smectite heteroadduct can be prepared by contacting a colloidal smectite clay and a surfactant in a “first” liquid carrier.
  • first liquid carrier refers to the medium in which the smectite heteroadduct is prepared
  • second liquid carrier refers to the medium in which the catalyst system is prepared by contacting the smectite heteroadduct and a transition metal or metallocene compound.
  • the organic compounds that can serve as a first liquid carrier can also serve as the second liquid carrier.
  • the first liquid carrier can comprise, consists essentially of, or be selected from water, an organic liquid, or a combination thereof.
  • the first liquid carrier can comprise or can consist essentially of water, an alcohol, an ether, a ketone, an ester, or any combination thereof.
  • the first liquid carrier can comprise or can 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.
  • the first liquid carrier can be water absent any organic liquid, so that the colloidal smectite clay and the surfactant are contacted in water only.
  • the step of contacting the colloidal smectite clay and the surfactant can comprises: the addition of the surfactant in solid or neat liquid form to a mixture of the colloidal smectite clay in the first liquid carrier; or the addition of a solution or a slurry of the surfactant to a mixture of the colloidal smectite clay in the first liquid carrier.
  • the contacting step can comprise: (a) adding the surfactant and adding the cationic polymetallate, simultaneously or in any order, to a mixture of the colloidal smectite clay in the first liquid carrier; or (b)(1) adding the cationic polymetallate to a mixture of the colloidal smectite clay in the first liquid carrier to form a smectite-cationic polymetallate heteroadduct, (2) isolating the smectite-cationic polymetallate heteroadduct, and (3) re-suspending the smectite-cationic polymetallate heteroadduct in a dispersion medium into which the surfactant is added before, after, or during the re-suspending step.
  • the step of contacting the colloidal smectite clay with the surfactant and/or the cationic polymetallate can occurs at a range of temperatures, 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) 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 ranges between any of these temperatures.
  • the result of contacting in the first liquid carrier the clay and the heterocoagulation regent, whether surfactant, cationic polymetallate, or a combination thereof, is the formation of a clay-heteroadduct (or “heterocoagulate”).
  • the clay-heteroadduct may be referred to as a clay-surfactant heteroadduct, a clay-cationic polymetallate-surfactant heteroadduct, or a clay-cationic polymetallate heterocoagulate if no surfactant is present.
  • the method of making a support-activator comprising a smectite heteroadduct can further comprise the step of: (i) isolating the smectite heteroadduct from the slurry in the first liquid carrier.
  • the process can further comprise (ii) washing the smectite heteroadduct with water, an organic liquid, or a combination thereof, and the process may still further comprise (iii) drying or calcining the smectite heteroadduct.
  • Isolating the smectite heteroadduct can comprise gravity filtering the slurry, vacuum filtering the slurry, subjecting the slurry to reduced pressure, heating the slurry, subjecting the slurry to rotary-evaporation, sparging a gas through the slurry, or any combination thereof.
  • the ease of isolating the smectite heteroadducts by filtering the slurry from the contacting step provides an advantage in their preparation and use as support-activators.
  • the isolating the smectite heteroadduct can comprise evaporating the first liquid carrier from the slurry to which an organic liquid azeotroping reagent has been added, or isolating the smectite heteroadduct is conducted in the absence of an azeotroping agent.
  • the step of isolating the smectite heteroadduct can be carried out without the use of ultrafiltration, centrifugation, or settling tanks.
  • the smectite heteroadduct can be washed, re-suspended in a liquid carrier and again filtered off, re-suspended in a dispersion medium prior to spray- drying, and the like.
  • the method of making a support-activator can further comprise the step of re-suspending the smectite heteroadduct in water, an organic liquid, or a combination thereof to form a suspension, and evaporating the water from the suspension to isolate the smectite heteroadduct or filtering the suspension to isolate the smectite heteroadduct.
  • the smectite heteroadduct obtained again can be washed water, an organic liquid, or a combination thereof and re-isolated.
  • the method can further comprise the step of measuring a conductivity of the suspension of the smectite heteroadduct in water, and if the conductivity is greater than 300 ⁇ S/cm, repeating the steps of washing the smectite heteroadduct and filtering the suspension to provide the washed smectite heteroadduct.
  • the isolated smectite heteroadduct can then be dried or calcined.
  • drying the smectite heteroadduct can be carried out by an azeotroping process or by a spray-drying process. Drying or calcining the smectite heteroadduct can also occur by heating the smectite heteroadduct in air, in an inert atmosphere, under vacuum, or a combination of these methods.
  • the heterocoagulate solid may be dried with azeotroping agents if desired.
  • Suitable azeotroping agents can include, but are not limited to, ethanol, 1- propanol, 1-butanol, 2-butanol, benzene, or acetonitrile.
  • the azeotroping agent can be combined with water in any manner, such as before or after the addition to the heterocoagulate solid.
  • the product can be directly carried through to subsequent calcination/drying steps without the addition of an azeotroping agents.
  • This method constitutes an advantageous embodiment, as it allows the drying steps to be conducted in the absence of organic solvents, providing a substantial economic and safety benefit.
  • processing of a shape of a clay-surfactant heterocoagulate that is, altering or fixing/setting a shape of the heterocoagulate, may be carried out by granulating, pulverizing or classifying before calcination.
  • the ion-exchange layered clay (aluminosilicate) having a shape previously processed may be subjected to chemical treatment.
  • a clay-surfactant heterocoagulate may be subjected to processing of a shape following calcination. Processing may occur before or after chemical treatment with an optional co-catalyst such as an organoaluminum compound and/or treatment with a polymerization catalyst.
  • an optional co-catalyst such as an organoaluminum compound and/or treatment with a polymerization catalyst.
  • the shape of a clay-surfactant heterocoagulate may be altered or fixed/set by methods referred to as “granulation” methods.
  • Examples of granulation methods that can be used include, but are not limited to, a stirring granulation process, a spraying (spray-drying) granulation process, a tumbling granulation process, a grinding granulation process, a bricketing granulation process, a compacting granulation process, an extruding granulation process, a fluidized layer granulation process, an emulsifying granulation process, a suspending granulation process, a press-molding granulation process, and the like.
  • a stirring granulation process a spraying (spray-drying) granulation process, a tumbling granulation process, a grinding granulation process, a bricketing granulation process, a compacting granulation process, an extruding granulation process, a fluidized layer granulation process, an emulsifying granulation process, a suspending granulation process, a press-molding granulation process, and the like
  • granulations methods that work well according to this disclosure include a stirring granulation process, a spraying granulation process, a tumbling granulation process, and a fluidizing granulation process, but the granulation method is not limited to these specific processes.
  • the clay-surfactant heteroadducts prepared in slurry form according to this disclosure unexpectedly exhibited an improved ease of isolation as compared to, for example, pillared clays which are prepared using the same smectite clay and cationic polymetallate heterocoagulation reagent, but in different amounts. Specifically, the clay heteroadducts could be readily isolated by filtration, unlike the pillared clays.
  • One method by which the filterability of the heterocoagulated clay- surfactant slurries may be assessed determines if the heterocoagulate is “readily filterable” by comparing the filtrate collected from a slurry of the heteroadduct versus the aqueous carrier in the initial slurry.
  • a slurry of the clay-surfactant heteroadduct is readily or easily filterable if the slurry is characterized by the following filtration behavior: (a) when filtration of a 2.0 wt.% aqueous slurry of the smectite heteroadduct is initiated from 0 hours to 2 hours after the colloidal smectite clay and the surfactant form the contact product, the proportion of a filtrate obtained at a filtration time of from 2 hours to 12 hours using either vacuum filtration or gravity filtration, based upon the weight of the first liquid carrier in the slurry of the smectite heteroadduct is in a range of (i) from about 30% to about 100% by weight of the first liquid carrier in the slurry before filtration, that is, of the initial slurry water weight, (ii) from about 40% to about 100% by weight of the first liquid carrier in the slurry, (iii) from about 50% to about 100% by weight of the first liquid carrier in the s
  • a small portion of water may be added to the slurry for additional washing and to recover extra slurry.
  • the feature of performing the filtration with 0 to 2 hours after the initial formation is specified because some non-heteroadduct slurries including some pillared clay slurry compositions can be filtered more easily after the slurry is allowed an initial settling period of several days, and this filterability would not be considered “readily filterable” according to these criteria.
  • the clay-surfactant heteroadduct slurry could be filtered using a 20 micron filter within several minutes after the contacting step between the colloidal clay and the surfactant.
  • a filter having a specified opening size can be easily identified by the person of ordinary skill, for example the 20 ⁇ m filter used in the examples, which allows the clay heteroadduct to meet both of these criteria, but no filter size will allow the pillared clay to meet both of these criteria.
  • this “readily filterable” test if a filter having too large of openings between the filter media is used, such that a pillared clay filtration meets the requirement of part (a) of the criteria above, it will fail part (b) and will not be considered readily filterable.
  • the clay heteroadduct would also fail part (b) when using such a large filter size, but reducing the filter size (for example, to about 20 ⁇ m) will allow the clay heteroadduct to meet both criteria (a) and (b), whereas the pillared clay slurry will fail part (a) when reducing the filter size, because the filter will clog and little or no liquid carrier will be filtered through.
  • either gravity or vacuum filtration can be used in the “readily filterable” test because at the point in time at which the measurements of the filtrates is specified (10 minutes after initiating the filtration), a proper filter size can be easily identified by the person of ordinary skill which will allow the clay heteroadduct to meet both criteria (a) and (b), whereas the pillared clay will fail at least one of criteria (a) and (b). G.
  • the method of making a support-activator can further comprise the steps of: suspending the smectite heteroadduct in a dispersion medium to provide a suspension of the smectite heteroadduct in the dispersion medium; and spray-drying the smectite heteroadduct from the suspension to provide the support-activator in particulate form.
  • a dispersion medium used for a starting slurry to be sprayed include water, an organic liquid, or a combination thereof.
  • water only can be used as the dispersion medium for spray-drying, which can be advantageous from a cost and environmental standpoint.
  • organic liquids sometimes referred to herein as organic solvents, even though the clay heteroadduct is not soluble therein
  • water examples include, but are not limited to, methanol, ethanol, i- propanol, n-propanol, n-butanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, xylene, and the like, including mixtures thereof.
  • water is used as a dispersion medium, without the presence of an organic liquid.
  • the dispersion medium can comprise or can consist essentially of water, an organic liquid, or a combination thereof, though one substantial advantage of this process is the ability to spray-dry the smectite heterocoagulate from an aqueous slurry in the absence of an organic liquid to obtain highly spherical particles of the smectite heterocoagulate.
  • suspending the smectite heteroadduct in a dispersion medium can occurs under high shear conditions.
  • the smectite heteroadduct can be maintained in the dispersion medium suspension for a period of time prior to spray-drying. While not intending to be bound by theory, it has been found that improved processing of the smectite heteroadduct may be achieved if it is maintained in dispersion medium suspension for a time.
  • the smectite heteroadduct can be suspended in the dispersion medium for a period of time of: (i) from 0.1 hour to 72 hours, from 0.25 hours 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 hours 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) 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.
  • the concentration of the clay heteroadduct in the starting slurry to be sprayed can be any concentration that provides a pumpable slurry.
  • the concentration of the clay heteroadduct in the slurry to be sprayed should be high enough to be energy efficient and provide a viable yield but not too high that the slurry cannot be pumped using the spray drying equipment.
  • the concentration of the clay heteroadduct in the starting slurry for the spraying granulation which produces 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%.
  • the concentration of the clay heteroadduct in the starting slurry for the spraying 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 ranges between any of these concentrations.
  • the upper limit of the clay heteroadduct concentration in the spray drying slurry may be influenced by the particular spray drying apparatus and the mechanical limits of the spray drying.
  • the lower limit of the clay heteroadduct concentration in the spray drying slurry may be influenced by concentrations which are low enough that insufficient evaporation occurs, leading to wet particles sticking to the spray dryer surface, or not producing the desired morphology such as spherical morphology.
  • the entrance temperature of hot air used in the spraying granulation method to produce spherical particles can vary depending upon a dispersion medium used.
  • the entrance temperature of hot air used in the spraying granulation can be from 80 °C to 260 °C, from 90 °C to 250 °C, or from 100 °C to 220 °C.
  • the entrance temperature of 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 ranges between any of these temperatures.
  • the smectite heteroadducts when isolated or dried by any means can then be subjected to calcining to provide a calcined support-activator which imparts activity to a polymerization catalyst.
  • calcined the smectite heterocoagulate solid by heating it is further dried and prepared for further treatment with a metallocene precatalyst and an optional co-catalysts and an optional co-activator.
  • This calcining thermal treatment also dries the clay heterocoagulate sufficiently to impart the high activity to the final catalyst.
  • Calcining treatment can be conducted in an ambient atmosphere (ambient pressure air), or under various conditions which facilitate removal of water.
  • the smectite heteroadduct can be heated or calcined under (a) an ambient atmosphere (air) which is not dried, or (b) a dry ambient atmosphere, wherein the dry ambient atmosphere includes air which has been passed through a drying column, or air which has a relative humidity of from about 0% to about 60%.
  • the smectite heteroadduct can be heated or calcined under an inert atmosphere such as nitrogen or under vacuum.
  • calcining can be conducted in a carbon monoxide atmosphere.
  • Calcining in atmospheres such as carbon monoxide can remove surface hydroxyls efficiently, and may allow the calcining to be effected at lower temperatures than would be required in an ambient atmosphere, helping preserve pore volume and surface area during dehydration of the surface, usually at temperatures of at least 100 °C.
  • Calcining the smectite heteroadduct can be carried out, for example, by heating the smectite heteroadduct in air, in an inert atmosphere, or under vacuum. In one aspect, calcining can be conducted in a fluidized bed.
  • the heterocoagulated solid can be calcined by heating at temperatures from: (i) from 100°C to 900°C, from 200°C to 800°C, from 200°C to 750°C, from 225°C to 700°C, from 225°C to 650°C, from 250°C to 650°C, from 250°C to 600°C, from 250°C to 500°C, from 225°C to 450°C, or from 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 5
  • the calcining temperature can be selected from any single temperature or calcining can be carried out over a range of two temperatures separated by at least 10°C, usually in the range of 110°C to 800 °C.
  • the temperatures used may be lower than those used in ambient air and/or the calcining time may be shorter than when calcining in ambient air.
  • calcining can be conducted in an ambient atmosphere (air), or in a dry ambient atmosphere (dry air), at a temperature from 110 °C, for example from about 200 °C, to 800 °C and for a time period from about 1 minute to about 100 hours.
  • the clay heteroadduct can be calcined in ambient air or dry air at a temperature from about 225 °C to about 700 °C for a time period from about 1 hour to about 10 hours, or at a temperature from about 250 °C to about 500 °C for a time period from about 1 hour to about 10 hours.
  • the smectite heteroadduct can calcined using any one of the following conditions: (a) a temperature ranging from about 110°C to about 600°C and for a time period ranging from about 1 hour to about 10 hours; (b) a temperature ranging from about 150°C to about 500°C and for a time period ranging from about 1.5 hours to about 8 hours; or (c) a temperature ranging from about 200°C to about 450°C and for a time period ranging from about 2 hours to about 7 hours.
  • the calcined heterocoagulated product can be described as a continuous, non-crystalline combination of clay and inorganic oxide particles, is highly effective towards activating a metallocene for olefin polymerization, and therefore can function as a support-activator, also termed an activator-support.
  • the calcined clay-surfactant heteroadduct can exhibit a nitrogen adsorption/desorption BJH porosity of: (i) from 0.1 cc/g to 3.0 cc/g, from 0.15 cc/g to 2.5 cc/g, from 0.25 cc/g to 2.0 cc/g, or from 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
  • Calcined clay-surfactant heteroadducts having a porosity as low as about 0.12 cc/g can be used in polymerization processes, as clay heteroadducts possessing ⁇ 0.1 cc/g BJH porosity typically exhibit low polymerization activity, for example, ⁇ 200 g PE/g support-activator/hr when combined with metallocenes such as bis(1-butyl-3- methylcyclopentadienyl)zirconium dichloride under polymerization reaction conditions.
  • polymerization activity is measured using the term “g support-activator”, which refers to the grams of the calcined clay-surfactant heteroadduct (or clay-surfactant- cationic polymetallate) used to make the catalyst.
  • g support-activator refers to the grams of the calcined clay-surfactant heteroadduct (or clay-surfactant- cationic polymetallate) used to make the catalyst.
  • Such a water-only spray drying process is highly desirable to improve the economic viability and environmental sustainability of the process over those requiring organic dispersion media.
  • the present process achieves the benefit of permitting spray-drying from a water-only slurry to provide a clay heteroadduct which maintains high porosity and activity after calcining, and which is characterized by a desirable, highly spherical morphology which imparts excellent processing characteristics to the support- activator, the supported catalyst, and the resulting polymer.
  • Table 1 presents the properties and polymerization data for clay-aluminum chlorohydrate (ACH) heterocoagulates prepared in the absence of a surfactant, dried by either an azeotroping or non-azeotroping process, and which have been calcined to form the clay- ACH support-activators.
  • Runs 1 through 4 illustrate that when clay-ACH supports are dried in azeotroping mixtures of 1-butanol and water and subsequently calcined, high BJH porosities in excess of 0.25 cc/g are obtained.
  • the calcined clay-ACH heteroadduct of Run 5 which has been dried as an aqueous slurry, without 1-butanol or any organic liquid being added, and subsequently calcined, possesses a low BJH porosity of 0.049 cc/g.
  • Samples illustrated in Runs 1 through 4 when combined with bis(1-butyl-3- methylcyclopentadienyl)zirconium dichloride, also demonstrate excellent polymerization activity (>2000 g PE/table 2g support-activator/hr), while Run 5 shows minimal polymerization activity ( ⁇ 100 g PE/g support-activator/hr) under analogous conditions.
  • Table 2 illustrate embodiments of the present disclosure.
  • FIG.25 provides the results of a nitrogen adsorption/desorption BJH pore volume analysis of the rotary evaporated and calcined Volclay® HPM-20 montmorillonite clay prepared according to Example 1, by drying a 5 wt.% dispersion of HPM-20.
  • this figure provides a plot of pore diameter (Angstrom, ⁇ ) versus the cumulative pore volume (cubic centimeters per gram, cc/g) for the clay only, prior to any heteroadduct formation.
  • the total BJH porosity of this sample is 0.06 cc/g.
  • the calcined smectites such as bentonites that are used in this disclosure may have BJH porosities from about 0 cc/g to about 0.1 cc/g.
  • embodiments of the clay-surfactant heteroadduct support- activators can have BJH porosities greater than about 0.1 cc/g, for example, from 0.1 cc/g to 0.3 cc/g.
  • the BJH porosity of the clay- surfactant heteroadduct support-activator can be about 0.15-0.3 cc/g.
  • Table 2 reports the porosity properties of such calcined clay-surfactant heterocoagulates, such as in Runs 2, 5, 7- 14, and 18-21, with BJH porosities of from 0.1 cc/g to 0.3 cc/g.
  • the calcined clay- surfactant heterocoagulate are characterized by BJH porosity that are about 150% (1.5 ⁇ ) to 200% (2 ⁇ ) of the BJH porosity of the corresponding calcined clay lacking the surfactant, and can be characterized by a BJH porosity that exceeds 200% of the corresponding calcined clay species lacking surfactant.
  • the spray-dried clay-surfactant support- activators typically exhibit a BHJ porosity of around 0.1-0.3 cc/g total BHJ porosity, and there are some high activity examples toward the lower end of this porosity range, even as low as 0.12 cc/g.
  • the clay-ACH support-activators can have BJH porosities as high as about 0.5-0.7 cc/g.
  • These clay-surfactant support-activator porosities can be compared with those of other clay heteroadducts. For example, tests were examined using heteroadducts (support-activators) prepared using a cationic polymetallate only, a surfactant only at different surfactant concentrations, and a combination of a cationic polymetallate and a surfactant, as follows.
  • the porosity data were obtained for the calcined, non-azeotroped (rotary evaporated) clay-aluminum chlorohydrate (ACH)-surfactant heteroadduct prepared according to Example 7-B2, in which the heterocoagulate is prepared through contacting the clay slurry with ACH followed by 0.5 wt% trihexyl tetradecyl phosphonium bromide.
  • the total BJH porosity of this species is 0.148 cc/g.
  • Porosity data were also obtained for the calcined, non-azeotroped (rotary evaporated) clay-surfactant heteroadduct prepared according to Example 14-B9, in which the clay heterocoagulate is prepared by contacting the clay with 2 wt.% tetrabutylammonium bromide in the absence of a cationic polymetallate.
  • the total BJH porosity of this species is 0.162 cc/g.
  • the measured BJH porosity of the calcined heterocoagulate prepared by combination of clay, a surfactant agent, and additional heterocoagulating agent such as aluminum chlorhydrate or polyaluminum chloride (cationic polymetallates) substantially exceeds the measured BJH porosity of the calcined heterocoagulate prepared by combination of the clay and additional heterocoagulating agent alone.
  • additional heterocoagulating agent such as aluminum chlorhydrate or polyaluminum chloride (cationic polymetallates)
  • porosity can substantially increase. This increase is depicted in the calcined, non-azeotroped (rotary evaporated) clay-ACH-surfactant heteroadduct prepared according to Example 6-B1, in which the calcined clay heterocoagulate was prepared through contacting clay with an aqueous aluminum chlorhydrate dispersion and 2 wt% of tetraoctylammonium bromide. The total BJH porosity of this sample was found to be 0.287 cc/g.
  • calcined heterocoagulates prepared by combination of clay and surfactants (and optionally other heterocoagulating agents such as aluminum chlorhydrate or polyaluminum chloride) can also exhibit high BJH porosity (>0.15 cc/g), even when pre- calcination drying is conducted in the absence of azetroping agents.
  • This unexpected result can be demonstrated, for example, in Table 2 (Run 2) and in Table 3 (Runs 7-10).
  • the addition of an azeotroping agent is not necessary to preserve the porosity of clay surfactant supports.
  • the smectite clay heteroadduct can have an average particle size of, for example, from 1 ⁇ m (micron) to 250 ⁇ m, which is the average dry or calcined particle size.
  • particle sizes recited for the smectite clay heteroadduct are for the dried or calcined clay-heteroadduct particles measured as described herein.
  • the smectite clay heteroadduct can have an average particle size of about 1 ⁇ m (microns), about 2 ⁇ m, about 3 ⁇ m, about 5 ⁇ m, about 7 ⁇ m, about 10 ⁇ m, about 12 ⁇ m, about 15 ⁇ m, about 18 ⁇ m, about 20 ⁇ m, about 25 ⁇ m, about 30 ⁇ m, about 35 ⁇ m, about 40 ⁇ m, about 45 ⁇ m, about 50 ⁇ m, about 55 ⁇ m, about 60 ⁇ m, about 65 ⁇ m, about 70 ⁇ m, about 75 ⁇ m, about 80 ⁇ m, about 85 ⁇ m, about 90 ⁇ m, about 95 ⁇ m, about 100 ⁇ m, about 110 ⁇ m, about 120 ⁇ m, about 125 ⁇ m, about 130 ⁇ m, about 140 ⁇ m, about 150 ⁇ m, about 160 ⁇ m, about 170 ⁇ m, about 175 ⁇ m, about 185 ⁇ m, about 200 ⁇ m, about 225
  • the smectite clay heteroadduct can have an average particle size of from 1 ⁇ m (micron) to 250 ⁇ m, from 2 ⁇ m to 125 ⁇ m, from 3 ⁇ m to 100 ⁇ m, from 5 ⁇ m to 150 ⁇ m, from 5 ⁇ m to 80 ⁇ m, from 7 ⁇ m to 70 ⁇ m, from 10 ⁇ m to 100 ⁇ m, from 10 ⁇ m to 60 ⁇ m, from 15 ⁇ m to 80 ⁇ m, from 15 ⁇ m to 50 ⁇ m, or from 20 ⁇ m to 75 ⁇ m. Zeta Potential.
  • FIG.29 and FIG.30 illustrate the zeta potential data for a slurry of smectite clay which was titrated with an aqueous solution of tetrabutylammonium bromide and tetramethylammonium bromide, respectively, which plot the slurry zeta potential vs.
  • the millimoles of the specific tetraalkylammonium bromide added per gram of clay The mmol cation/g clay reflects the cumulative millimoles of the aqueous tetraalkylammonium bromide solution added. As illustrated in these figures, the surfactant titration never provides a zeta potential (millivolts) which is zero or positive(+).
  • a zeta potential of about negative (-)18 mV is the most positive potential observed
  • a zeta potential of about negative (-)43 mV is the most positive potential observed.
  • a zeta potential of about negative (-)50 mV is the most positive potential observed.
  • the highest polymerization activity observed for the smectite clay- tetraalkylammonium heteroadducts depended upon the particular tetraalkylammonium surfactant employed. For example, the highest polymerization activity observed for the smectite clay-tetrabutylammonium bromide heteroadducts occurs for those prepared using from about 1.25 mmol surfactant/g clay to about 2.5 mmol surfactant/g clay (see Table 2).
  • FIGS.26-28 illustrate the powder XRD (x-ray diffraction) patterns of a series of spray-dried calcined products. These samples were not dried by either azeoptropically or non-azeotropically rotary evaporating the liquid carrier, but rather spray- drying and calcining the samples.
  • FIG.26 illustrates the powder XRD of the calcined, spray- dried product from combining Volclay® HPM-20 montmorillonite clay and tetramethylammonium bromide (TMABr) absent a cationic polymetallate, as in Example 21- E1.
  • TMABr tetramethylammonium bromide
  • FIG.27 illustrates the powder XRD of the calcined spray-dried product from combining Volclay® HPM-20 montmorillonite and tetrabutylammonium bromide (TBABr) absent a cationic polymetallate, according to Example 22-E2.
  • FIG.28 illustrates the powder XRD of the calcined spray-dried product from combining Volclay® HPM-20 montmorillonite and aluminum chlorhydrate (ACH), absent a surfactant, according to comparative Example 20- D1.
  • the peaks in the range of between 20-30 degrees 2 theta (2 ⁇ ) (20- 30 °2 ⁇ ) arise from the mineral impurities that exist in the starting colloidal clay.
  • the clay- surfactant heterocoagulates of this disclosure after filtration and calcination at 300 °C or higher, can exhibit a substantial d001 peak of between 6-9 degrees 2 theta (2 ⁇ ) (6-9 °2 ⁇ ), for example between 7-8 degrees 2 theta (2 ⁇ ) (7-8 °2 ⁇ ) in the powder XRD scan.
  • FIG.26 and FIG.27 present the powder XRD patterns of spray-dried and calcined products from combining either tetramethylammonium bromide (FIG.26) or tetrabutylammonium bromide (FIG.27), respectively, with Volclay® HPM-20 montmorillonite, the samples differing only in the tetraalkylammonium surfactant used.
  • the powder XRD indicates little or virtually no pillaring (peak between 4.8 degrees 2 ⁇ to 5.2 degrees 2 ⁇ ), and little or virtually no simple ion exchanged clay (peak between 9 degrees 2 ⁇ and 10 degrees 2 ⁇ ) relative to the mineral impurities that exist in the starting colloidal clay in the range of 2 theta between 20-30 degrees 2 ⁇ .
  • the inventive spray-dried calcined clay-surfactant heteroadducts described herein thus have distinctly different microscopic structures than previously disclosed calcined spray-dried clay-aluminum chlorhydrate heterocoagulates and other clay-cationic polymetallate heterocoagulates. J.
  • the calcined, spray-dried, clay-surfactant heterocoagulate support-activators and the supported catalysts prepared therefrom were found to be highly spherical in nature and very consistently spherical, that is, 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.
  • S sphericity
  • R roundness
  • C circularity
  • the highly spherical and highly circular properties of the clay-surfactant heterocoagulates could be achieved by spray-drying from an aqueous suspension, in the absence of any organic solvents.
  • the clay heterocoagulates and polymer particles produced using the clay heterocoagulates as support-activators also were found to be significantly more spherical and circular than the corresponding clay heterocoagulates or polymer particles produced when the clay heterocoagulate was azeotropically dried (1-butanol/water, rotatory evaporation) or non- azeotropically dried (water only, rotatory evaporation).
  • This uniform spherical morphology can be highly advantageous for producing desirable polymer morphologies, as well as for ensuring reactor operability, and maintaining the activity of the support-activator.
  • the morphologies of support-activators according to this disclosure are illustrated in the figures, as follows.
  • FIGS.9, 10, 13, and 14 present the SEM (scanning electron microscopy or surface electron microscopy) images of calcined support-activators prepared according to this disclosure.
  • FIG.9 and FIG.10 illustrate SEM images of the calcined support-activator formed by spray-drying an aqueous slurry of the heteroadduct formed from contacting tetramethylammonium bromide (TMABr) and Volclay® HPM-20 montmorillonite according to Example 21-E1.
  • TMABr tetramethylammonium bromide
  • Example 21-E1 Volclay® HPM-20 montmorillonite
  • FIG.13 and FIG.14 illustrate SEM images of the calcined support-activator formed by spray-drying an aqueous slurry of the heteroadduct formed from contacting tetrabutylammonium bromide (TBABr) and Volclay® HPM-20 montmorillonite according to Example 22-E2.
  • Comparative SEM images are provided as follows.
  • FIG.11 and FIG.12 illustrate SEM images of the calcined support-activator formed by spray-drying an aqueous slurry of the heteroadduct formed from contacting aluminum chlorhydrate (ACH) and Volclay® HPM-20 montmorillonite, in the absence of a surfactant, according to comparative Example 20-D1.
  • FIG.7 and FIG.8 illustrate SEM images of the calcined support-activator formed by spray-drying an aqueous slurry of the heteroadduct formed from contacting aluminum chlorhydrate (ACH) and Volclay® HPM-20 montmorillonite, which is subsequently azeotropically drying from an aqueous slurry that includes 1-butanol as the azeotroping agent, as described in comparative Example 2-A1.
  • ACH aluminum chlorhydrate
  • Volclay® HPM-20 montmorillonite Volclay® HPM-20 montmorillonite
  • one aspect of this disclosure provides for highly spherical, round, and circular clay-surfactant heteroadducts, support-activators, and supported catalysts, in which these parameters can be measured as follows. Aspects of determining these parameters can be found in the following references, each of which is incorporated herein by reference in its entirety: (1) G.-C. Cho, J. Dodds, and J. C.
  • the clay-surfactant heteroadducts, support-activators, and supported catalysts of this disclosure can be characterized as having an average particle sphericity of 0.60 or greater ( ⁇ 0.60), wherein the sphericity of each particle can be calculated according to the formula: r max-in is the radius of the largest inscribed circle of a two-dimensional image of a particle, and r min-cir is the radius of the smallest circumscribed circle of a two-dimensional image of the particle.
  • the average or mean particle sphericity can be measured as a number-weighted average sphericity deignated as “SPHT0”, or measured using a volume-weighted average sphericity designated as “SPHT3”.
  • an average sphericity without indicating whether the sphericity is a number-weighted average or a volume- weighted average is intended to refer to a volume-weighted average sphericity SPHT3.
  • such highly spherical particles may be obtained according to this disclosure by spray-drying from a water-only slurry, and high sphericity is maintained when calcining.
  • the morphologies of the polyethylene homopolymers and co-polymers prepared using the support-activators were observed to mirror the morphologies of the clay-surfactant heteroadducts, support-activators, or supported catalysts.
  • the morphology of the polymer particles can serve as a proxy for the morphology of the clay- surfactant heteroadduct, support-activator, or supported catalyst particle. Therefore, the particles of clay-surfactant heteroadducts, support-activators, supported catalysts, and polymer particles may have a volume-weighted average sphericity (SPHT3) or a number- averaged 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.
  • SPHT3 volume-weighted average sphericity
  • SPHT0 number- averaged particle sphericity
  • the particles of clay-surfactant heteroadducts, support-activators, supported catalysts, and polymer particles also may have a volume-weighted average sphericity (SPHT3) or a number-averaged particle sphericity (SPHT0) of 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 sphericities between these values.
  • SPHT3 volume-weighted average sphericity
  • SPHT0 number-averaged particle sphericity
  • the sphericity of the polymer particles produced by polymerizations employing the supported catalysts comprising clay-surfactant heteroadducts could be analyzed and quantified through particle shape and size analysis using a CAMSIZER® instrument and associated software.
  • the polymers produced from supported catalyst comprising any non-spray dried heteroadduct samples azeotroped or non-azeotroped
  • the polymers produced from supported catalyst comprising the spray-dried heteroadduct samples exhibited mean volume- weighted sphericities (SPHT3) from the CAMSIZER® X2 measurments) of 0.75 or greater, 0.80 or greater, 0.85 or greater, or 0.90 or greater.
  • These polymer particles also may have mean volume-weighted sphericities (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 sphericities between these values.
  • SPHT3 mean volume-weighted sphericities
  • these sphericity values also correspond to number-weighted average sphericities (SPHT0) from the CAMSIZER® X2 instrument analysis.
  • Polymer particles obtained from ethylene-1-hexene co-polymerizations were collected using various calcined spray-dried and calcined non-spray-dried clay heteroadduct support-activators and analyzed by a CAMSIZER® X2 Dynamic Image Analyzer to determine particle sphericity and particle size as recorded in Table 6. The corresponding sphericity plots and particle distribution characteristic summaries appear at FIG.37 through FIG.40.
  • FIG.37 presents the sphericity analysis on a polymer sample in which the supported catalyst comprised an azeotropically dried (non-spray dried) and calcined support- activator obtained by contacting aluminum chlorhydrate and montmorillonite in the absence of a surfactant, using 1-butanol as the azeotroping agent, as described in Example 2-A1.
  • the supported catalyst comprised an azeotropically dried (non-spray dried) and calcined support- activator obtained by contacting aluminum chlorhydrate and montmorillonite in the absence of a surfactant, using 1-butanol as the azeotroping agent, as described in Example 2-A1.
  • FIG.38 sphericity analysis was performed on a polymer sample in which the supported catalyst comprised a non-spray dried support-activator as described in Example 30-E2 from contacting tetrabutylammonium bromide and montmorillonite in the absence of a cationic polymetallate, with the isolated product being rotary evaporated in the absence of an azeotroping agent prior to calcining.
  • both of these polymer samples exhibits low ( ⁇ 0.70) volume-weighted average sphericities (SPHT3).
  • FIG.39 and FIG.40 sphericity data of Table 6 were obtained on two different polymer samples produced from two different support-activator samples which were produced under different spray-drying conditions within the ranges set out in Example 31. Adjusting or optimizing the spray-drying parameters within the ranges of Example 31 to achieve the sphericity and span values report in Table 6 are well within the abilities of the person of ordinary skill. See, for example, C. Arpagaus (2016), A Short Review on Nano Spray Drying of Pharmaceuticals.
  • FIG.41 shows particle size distribution data and cumulative volume curve for the sample of a polymer powder used to obtain the FIG.40 data, that is produced using a catalyst prepared from the spray dried, clay-tetrabutylammonium bromide heteroadduct support-activator of Example 31.
  • the Q3[%] axis corresponds to the curve-line on the graph and represents the cumulative volume percent value, which is the percent of the total volume of the particles which are below that particle size value.
  • the P3[%] axis corresponds to the bar chart distribution and shows the percent of the total volume corresponding to each bar or “slice” of particle size.
  • the sphericity data of FIG.39 and FIG.40 and the particle size distribution data of FIG.41 obtained on the ethylene-1-hexene co-polymer particles were collected and analyzed by a CAMSIZER® X2 as provided in the Examples.
  • sieving can be performed on the smectite clay, the spray- dried clay-surfactant heteroadducts, the support-activators, or the supported catalysts, either prior to or subsequent to a calcination or other drying process.
  • Table 7 presents sphericity and span data for ethylene-1-hexene co-polymers derived from metallocene-catalyzed polymerizations using calcined support-activators from spray-dried unsieved clay-surfactant support-activator of Example 31, and from spray-dried sieved clay-surfactant support- activator of the sieved samples in Examples 33-35.
  • Table 7 demonstrates that the smaller particle size support-activators benefit from sieving more than the larger particle size support- activators in terms of producing more spherical ethylene-1-hexene co-polymers as compared to the unsieved support-activator.
  • Such a process may produce particles of clay, clay- surfactant heteroadduct, support-activator, or supported catalyst having a more narrow size distribution then the unseived materials, and having 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 heteroadduct, support-activator, or supported catalyst particles also may have mean volume-weighted sphericities (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 sphericities between these values.
  • SPHT3 mean volume-weighted sphericities
  • polymer powder produced from supported catalyst comprising such sieved spray-dried heteroadduct samples also may exhibit volume-weighted average sphericities of 0.75 or greater, 0.80 or greater, or 0.85 or greater, and furthermore possess improved sphericity relative to polymer powder produced from supported catalyst comprising the unsieved precursor spray-dried heteroadduct, support-activator, or supported catalyst.
  • sieving also may be used to improve the size uniformity of the clay-surfactant heteroadduct, support-activator, or supported catalyst relative to the precursor un-sieved material.
  • the sieving process may produce spray-dried clay- surfactant heteroadducts, support-activators, or supported catalyst with a particle size distribution possessing a span of 2 or lower, 1.5 or lower, 1.25 or lower, 1 or lower, or 0.75 or lower.
  • the particle size distribution of polymer powder produced from supported catalyst comprising such sieved spray-dried heteroadduct samples may exhibit a span of 2 or lower, 1.5 or lower, 1.25 or lower, 1 or lower, or 0.75 or lower, and furthermore exhibit lower span relative to the particle size distribution of polymer powder produced from supported catalyst comprising the precursor unsieved spray-dried heteroadduct, support- activator, or supported catalyst.
  • the sieving process may produce spray- dried clay-surfactant heteroadducts, support-activators, or the supported catalysts, either prior to or subsequent to a calcination or other drying process, or the of polymer powder produced therefrom may 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 ranges between any of the span values.
  • FIG.42, FIG.44, and FIG.46 present the particle size distribution and cumulative volume curve for co-polymer powder samples, and FIG.43, FIG.
  • FIG.42 and FIG.43 illustrate particle size distribution and sphericity data for co-polymer powder samples produced from a spray dried clay-tetrabutyl- ammonium bromide support-activator of Example 31 with particles sizes between 19 ⁇ m (micron) and 37 ⁇ m. That is, the support-activator used to produce the FIG.42 and FIG.43 data pass through a 37 ⁇ m sieve but were captured on a 19 ⁇ m sieve.
  • FIG.44 and FIG.45 illustrate particle size distribution and sphericity data for co-polymer powder samples produced from the Example 31 spray dried clay-tetrabutylammonium bromide support- activator having particles sizes between 37 ⁇ m (micron) and 50 ⁇ m.
  • FIG.46 and FIG.47 illustrate particle size distribution and sphericity data for co-polymer powder samples produced from the Example 31 spray dried clay-tetrabutylammonium bromide support- activator having particles sizes between 50 ⁇ m (micron) and 74 ⁇ m.
  • the polymer made using largest fraction clay heteroadduct between 50 ⁇ m and 74 ⁇ m in size had the highest SPHT3 sphericity of 0.86.
  • these three fractions accounted for some 16.76 g of the total 17 g starting sample. Therefore, 98.6 wt% of the Example 31 sample was accounted for in these three size fractions.
  • the clay-surfactant heteroadducts, support-activators, and supported catalysts of this disclosure can be characterized as having an average particle roundness of 0.60 or greater, wherein roundness is calculated according to the formula: ri is the radius of the inscribed circle of the i th corner curvature of a two- dimensional image (silhouette) of a particle, n is the number of corners; and r max-in is the radius of the largest inscribed circle of the two-dimensional image of the particle.
  • the clay-surfactant heteroadducts, the support-activators, the supported catalysts, and the polymer particles prepared therefrom also may an average particle roundness 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 heteroadducts, support-activators, and supported catalysts, and the polymer particles prepared therefrom also may an average particle roundness 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 ranges between any of these particle roundness values.
  • the clay-surfactant heteroadducts, support- activators, and supported catalysts of this disclosure can be characterized as having an average particle circularity of 0.60 or greater, wherein circularity is calculated according to the formula: A is the area of a two-dimensional image (silhouette) of a particle, and perimeter is the length of the path encompassing the two-dimensional image of a particle.
  • the clay-surfactant heteroadducts, the support-activators, the supported catalysts, and the polymer particles prepared therefrom also may 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 heteroadducts, support-activators, supported catalysts, and the polymer particles prepared therefrom also may an average 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 ranges between any of these circularity values.
  • the clay- surfactant heteroadducts, support-activators, and supported catalysts when spray-dried or when spray-dried and calcined, can be characterized by any one of, 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.
  • the clay-surfactant heteroadducts, support-activators, and supported catalysts of this disclosure can be characterized by any one of, or any combination of, the following properties: (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.
  • the clay-surfactant heteroadducts, support-activators, and supported catalysts of this disclosure can be characterized by any one of, or any combination of, the following properties: (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.
  • the polymer particles produced from polymerizations conducted with metallocene-activated spray-dried clay-surfactant heterocoagulate support-activators also are highly spherical in nature.
  • the calcined, spray- dried support-activators derived from clay and tetramethylammonium bromide (Example 21- E1) or tetrabutylammonium bromide (Example 22-E2) (see FIGS.9, 10, 13, and 14) were combined with the metallocene bis(1-butyl-3-methylcyclopentadienyl)zirconium dichloride and triethylaluminum co-catalyst to form the active catalyst, which was used to produce an ethylene-1-hexene copolymer.
  • FIG.15 and FIG.16 Optical microscope images for these polymer particles are provided in FIG.15 and FIG.16, respectively. These polymer particles, like their parent catalyst particles, are highly spherical in nature.
  • FIG.17 shows an optical microscope image of the polymer derived from co-polymerizing ethylene and 1-hexene using the azeotropically dried, clay- aluminum chlorohydrate (ACH) support-activator (absent a surfactant) described in Example 2-A1, in which the support-activator was combined with the metallocene ( ⁇ 5 -1-Bu-3- MeCp)2ZrCl2 and triethylaluminum co-catalyst to form the active catalyst.
  • ACH clay- aluminum chlorohydrate
  • FIG.7 and FIG.8 illustrate SEM images of the support-activator prepared in Example 2-A1 and used to make the polymer in FIG.17.
  • the polymer particles of FIG.17 like the support-activator of FIGS. 7 and 8, are granular and quite irregular, highly non-spherical, and agglomerated, in contrast to the polymer particles shown in FIG.15 and FIG.16. Therefore, it can be seen that the spray-drying process from a water-only slurry can be effective method for achieving a desirable, highly spherical morphology for support-activators, which in turn can produce highly symmetric and spherical polymer particles once introduced to metallocene, co-catalyst, and monomer under polymerization conditions.
  • the calcined clay-surfactant heteroadducts and supported catalysts comprising the clay-surfactant heteroadducts can be can be analyzed through surface electron microscopy, with subsequent image analysis using methods such as Scanning Probe Image Processor (SPIP) software to measure circularity of the particles.
  • SPIP Scanning Probe Image Processor
  • the circularity of the spray-dried and calcined heteroadducts and catalysts can be measured and compared with the circularity of calcined heteroadducts and catalysts which were dried using other means such as azeotropic drying.
  • FIG.33 SEM illustrates a support-activator which was formed as described in Example 30-E2 by contacting tetrabutylammonium bromide and montmorillonite in the absence of a cationic polymetallate, and the isolated product was drying by rotary evaporation from an aqueous slurry in the absence of an azeotroping agent prior to calcining.
  • the particles observed in these images exhibit low circularity and/or a large proportion of the particles which fall outside the 8 ⁇ m to 100 ⁇ m diameter range. In general, such low circularity and exceptionally large or small particles are not desirable for catalytic processes.
  • FIG.34, FIG.35, and FIG.36 illustrate support-activators which were formed as described in Example 22-E2 by contacting tetrabutylammonium bromide and montmorillonite in the absence of a cationic polymetallate and which were isolated by filtration, and the isolated support-activators were subsequently spray-dried from an aqueous suspension and calcined.
  • the particles observed in these images exhibit a very high circularity and a large proportion of the particles fall within the desirable 8 ⁇ m to 100 ⁇ m diameter range, making these support-activators very advantageous for catalytic processes.
  • the clay-surfactant heteroadduct (also referred to as clay heteroadduct) 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 and the like, or other catalyst components in order to prepare an olefin polymerization catalyst composition. Therefore, in one aspect, when a clay heteroadduct is prepared as disclosed herein and combined with an organo-main group metal, such as alkylaluminum compounds and group 4 organotransition metal compound such as a metallocene, an active olefin polymerization catalyst or catalyst system is provided.
  • organo-main group metal such as alkylaluminum compounds and group 4 organotransition metal compound such as a metallocene
  • the support-activator of this disclosure can be used with metallocene compounds (also referred to herein as metallocene catalysts) and co-catalysts such as organoaluminum compounds, the resulting composition exhibits catalytic polymerization activity in the absence or substantial absence of an ion-exchanged, protic-acid-treated, or pillared clay, or aluminoxane or borate activators.
  • metallocene compounds also referred to herein as metallocene catalysts
  • co-catalysts such as organoaluminum compounds
  • heteroadduct support-activator metallocene, and co- catalyst such as aluminum alkyl compound if desired to impart an activatable alkyl ligand to the metallocene provides an active catalyst with the need for other activators such as aluminoxane or borate activators.
  • Metallocene compounds are well-understood in the art, and the skilled person will recognize that any metallocene can be used with the support-activator described in this disclosure, including for example, both non-bridged (non-ansa) metallocene compounds or bridged (ansa) metallocene compounds, or combinations thereof. Therefore, one, two, or more metallocene compounds can be used with the clay-surfactant support- activators of this disclosure.
  • the metallocene can be a metallocene comprising a group 3 to group 6 transition metal or a metallocene comprising a lanthanide metal or a combination of more than one metallocene.
  • the metallocene can comprise a group 4 transition metal (titanium, zirconium, or hafnium).
  • the metallocene compound can comprises, consists of, consists essentially of, or is selected from a compound or a combination of compounds, each independently having 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 a substituted or an unsubstituted cyclopentadienyl, indenyl, fluorenyl, pentadienyl, allyl, boratabenzenyl, 1,2-azaborolyl, or 1,2-diaza- 3,5-diborolyl, wherein any substituent is selected independently from a halide, a C1- C20 hydrocarbyl, a C1-C20 heterohydrocarbyl, a C1-C20 organoheteryl, a fused C4-C12 carbocyclic moiety, or a fused C4-C11 heterocycl
  • linker substituents which can bridge X 1 and X 2 include C1-C20 hydrocarbylene group, a C1-C20 hydrocarbylidene group, a C1-C20 heterohydrocarbyl group, a C1-C20 heterohydrocarbylidene group, a C1-C20 heterohydrocarbylene group, or a C1-C20 heterohydrocarbylidene group.
  • X 1 and X 2 can be bridged 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, X 5 in each occurrence is selected independently from a halide, a C1-C20 aliphatic group, a C6-C20 aromatic group, a C1-C20 heteroaliphatic group, a C4-C20 heteroaromatic group, or a C1-C20 organoheteryl group.
  • E is independently C or Si
  • X 5 in each occurrence is selected independently from a halide, a C1-C20 aliphatic group, a C6-C20 aromatic group, a C1-C20 heteroaliphatic group, a C4-C20 heteroaromatic group, or a C1-C20 organoheteryl group.
  • the Aspects section of this disclosure also recites additional description and selections for X 1 and X 2 , including specific substituents on X 1 and X 2 .
  • the Aspects section of this disclosure also recites additional description and selections for X 3 and X 4 , including specific substituents on X 3 and X 4 .
  • the Aspects section of this disclosure also provides some specific examples of metallocene compounds that are useful in combination with the support-activator of this disclosure.
  • the supported metallocene catalyst can have an average particle size of, for example, from 1 ⁇ m (micron) to 250 ⁇ m, which is the average dry particle size.
  • the supported metallocene catalyst can have an average particle size of about 1 ⁇ m (microns), about 2 ⁇ m, about 3 ⁇ m, about 5 ⁇ m, about 7 ⁇ m, about 10 ⁇ m, about 12 ⁇ m, about 15 ⁇ m, about 18 ⁇ m, about 20 ⁇ m, about 25 ⁇ m, about 30 ⁇ m, about 35 ⁇ m, about 40 ⁇ m, about 45 ⁇ m, about 50 ⁇ m, about 55 ⁇ m, about 60 ⁇ m, about 65 ⁇ m, about 70 ⁇ m, about 75 ⁇ m, about 80 ⁇ m, about 85 ⁇ m, about 90 ⁇ m, about 95 ⁇ m, about 100 ⁇ m, about 110 ⁇ m, about 120 ⁇ m, about 125 ⁇ m, about 130 ⁇ m, about 140 ⁇ m, about 150 ⁇ m, about 160 ⁇ m, about 170
  • the supported metallocene catalyst can have an average particle size of from 1 ⁇ m (micron) to 250 ⁇ m, from 2 ⁇ m to 125 ⁇ m, from 3 ⁇ m to 100 ⁇ m, from 5 ⁇ m to 150 ⁇ m, from 5 ⁇ m to 80 ⁇ m, from 7 ⁇ m to 70 ⁇ m, from 10 ⁇ m to 100 ⁇ m, from 10 ⁇ m to 60 ⁇ m, from 15 ⁇ m to 80 ⁇ m, from 15 ⁇ m to 50 ⁇ m, or from 20 ⁇ m to 75 ⁇ m.
  • Metallocene compounds are understood by the person skilled in the art, who will recognize and appreciate the methods of making and using the metallocene in olefin polymerization catalyst systems.
  • this disclosure provides a catalyst composition for olefin polymerization, the catalyst composition comprising: a) at least one metallocene compound; b) optionally, at least one co-catalyst; and c) at least one support-activator as described herein.
  • the co-catalyst includes compounds such as a trialkyl aluminum which are thought to impart a ligand to the metallocene or activate a metallocene ligand, which can then initiate polymerization when the metallocene is otherwise activated with the support-activator.
  • the co-catalyst may be considered optional, for example, in scenarios in which the metallocene may already include a polymerization-activatable/initiating ligand such as methyl or hydride. It will be understood that even when the metallocene compound includes such as a polymerization-activatable/initiating ligand, a co-catalyst can be used for other purposes, such as to scavenge moisture from the polymerization reactor or process.
  • the co- catalyst can comprise or be selected from, for example, an alkylating agent, a hydriding agent, or a silylating agent.
  • the metallocene compound, the support-activator, and the co- catalyst can be contacted in any order.
  • the co-catalyst can comprises or can be selected from an organoaluminum compound, an organoboron compound, an organozinc compound, an organomagnesium compound, an organolithium compound, or any combination thereof.
  • the Aspects section of this disclosure recites additional description and selections for each of the organoaluminum compound, organoboron compound, organozinc compound, organomagnesium compound, and organolithium compound.
  • the co-catalyst can comprise, consists of, consist essentially of, or be selected from at least one organoaluminum compound which can independently have 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 C 4 ], that is, can be neutral molecular compounds or ionic compounds/salts of aluminum, wherein each of the variables of these formulas is defined in the Aspects section of this disclosure.
  • the co-catalyst can comprise, consists of, consist essentially of, or be selected from trimethylaluminum, triethylaluminum (TEA), tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, ethyl-(3-alkylcyclopentadiyl)aluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, triisobutylaluminum (TIBAL), diethylaluminum chloride, ethyl-(3-alkylcyclopentadiyl)aluminum, and the like, including any combination thereof.
  • TAA triethylaluminum
  • TSA triethylaluminum
  • tributylaluminum trihexylaluminum
  • trioctylaluminum ethyl-(3-alkylcycl
  • the co-catalyst can comprise, consists of, consist essentially of, or be selected from at least one organoboron compound which can independently have the formula B(X E )q(X F )3-q, B(X E )3, or M y [BX E 4], that is, can be neutral molecular compounds or ionic compounds/salts of boron, wherein each of the variables of these formulas is defined in the Aspects section of this disclosure.
  • the co- catalyst can comprise, consists of, consist essentially of, or be selected from trimethylboron, triethylboron, tripropylboron, tributylboron, trihexylboron, trioctylboron, diethylboron ethoxide, diisobutylboron hydride, triisobutylboron, diethylboron chloride, di-3- pinanylborane, pinacolborane, catecholborane, lithium borohydride, lithium triethylborohydride, and the like, including a Lewis base adduct thereof, or any combination or mixture thereof.
  • the co-catalyst can comprise or can be a halogenated organoboron compound, for example a fluorinated organoboron compound, examples of which 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.
  • a fluorinated organoboron compound examples of which include tris(p
  • the co-catalyst can comprise, consists of, consist essentially of, or be selected from at least one organozinc or organomagnesium compound which can independently have the formula M C (X G )r(X H )2-r, wherein each of the variables of this formula is defined in the Aspects section of this disclosure.
  • the co-catalyst can comprise, consists of, consist essentially of, or be selected from dimethylzinc, diethylzinc, diisopropylzinc, dicyclohexylzinc, diphenylzinc, butylethylmagnesium, dibutylmagnesium, n-butyl-sec-butylmagnesium, dicyclopentadienylmagnesium, ethylmagnesium chloride, butylmagnesium chloride, and the like, including any combination thereof.
  • the co-catalyst can comprise, consists of, consist essentially of, or be selected from at least one organolithium compound which can independently have the formula Li(X J ), wherein each of the variables of this formula is defined in the Aspects section of this disclosure.
  • the co-catalyst can comprise, consists of, consist essentially of, or be selected from methyllithium, ethyllithium, propyllithium, butyllithium (including n-butyllithium and t-butyllithium), hexyllithium, iso- butyllithium, and the like, or any combination thereof.
  • optional co-activators include but are not limited to an ion-exchanged clay, a protic-acid-treated clay, a pillared clay, an aluminoxane, a borate activator, an aluminate activator, an ionizing ionic compound, a solid oxide treated with an electron withdrawing anion, or any combination thereof.
  • the catalyst system and polymerization method can be absent any co-activators, including any one of more of the co-activators described herein.
  • Aluminoxanes also referred to as poly(hydrocarbyl aluminum oxides) or organoaluminoxanes
  • Aluminoxanes can be used to contact the other catalyst components, for example, in any solvent which is substantially inert to the reactants, intermediates, and products of the activation step such as a saturated hydrocarbon solvent or a solvent such as toluene.
  • the catalyst composition formed in this manner may be isolated if desired or the catalyst composition may be introduced into the polymerization reactor without being isolated.
  • aluminoxanes are oligomeric, wherein the aluminoxane compound can comprise linear structures, cyclic, or cage structures, or mixtures thereof.
  • cyclic aluminoxane compounds having the formula (R-Al- O)n, wherein R can be a linear or branched alkyl having from 1 to about 12 carbon atoms, and n can be an integer from 3 to about 12.
  • the (AlRO) n moiety also constitutes the repeating unit in a linear aluminoxane, for example, having the formula: R(R-Al-O)nAlR2, wherein R can be a linear or branched alkyl having from 1 to about 12 carbon atoms, and n can be an integer from 1 to about 75.
  • 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.
  • 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 incorporated by reference herein, in its entirety.
  • an aluminoxane may be prepared by reacting water which is present in an inert organic solvent with an aluminum alkyl compound such as AlR 3 to form the desired organoaluminoxane compound.
  • organoaluminoxanes may be prepared by reacting an aluminum alkyl compound such as AlR 3 with a hydrated salt, such as hydrated copper sulfate, in an inert organic solvent.
  • the aluminoxane compound can be methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, iso-propyl-aluminoxane, n-butylaluminoxane, t- butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane, 1-pentylaluminoxane, 2- pentylaluminoxane, 3-pentyl-aluminoxane, iso-pentylaluminoxane, neopentylaluminoxane, or combinations thereof.
  • methyl aluminoxane (MAO), ethyl aluminoxane (EAO), or isobutyl aluminoxane (IBAO) can be used as optional co-catalysts, and these aluminoxanes can be prepared from trimethylaluminum, triethylaluminum, or triisobutylaluminum, respectively.
  • These compounds can be complex compositions, and are sometimes referred to as poly(methyl aluminum oxide), poly(ethyl aluminum oxide), and poly(isobutyl aluminum oxide), respectively.
  • aluminoxanes can be used in combination with a trialkylaluminium, such as disclosed in U.S.
  • Patent No.4,794,096 which is herein incorporated by reference in its entirety.
  • the molar ratio of the aluminum present in the aluminoxane to the metallocene compound(s) in the composition can be lower than the typical molar ratio that would be used in the absence of the support-activator of the present disclosure.
  • aluminoxane amounts can be, for example, from about 1:10 moles Al/moles 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.
  • the relative amounts of aluminoxane can be reduced.
  • the amount of optional aluminoxane added to a polymerization zone can be less than the previous typical amount within a range of about 0.01 mg/L to about 1000 mg/L, from about 0.1 mg/L to about 100 mg/L, or from about 1 mg/L to about 50 mg/L.
  • aluminoxane can be used in an amount typically used in the prior art, but with the additional use of a support-activator of the present disclosure in order to obtain further advantages for such a combination.
  • the catalyst compositions of this disclosure can also comprise an optional organoboron co-activator if desired, in addition to the recited components (support-activator, metallocene, and optional co-catalyst).
  • the organoboron compound can comprise or be selected form neutral boron compounds, borate salts, or combinations thereof.
  • the organoboron compounds can comprise or be selected from a fluoroorgano boron compound, a fluoroorgano borate compound, or a combination thereof, and any such fluorinated compounds known in the art can be utilized.
  • fluoroorgano boron compound is used herein to refer to the neutral compounds of the form BY3
  • fluoroorgano borate compound is used herein to refer to the monoanionic salts of a fluoroorgano boron compound of the form [cation] + [BY4] ⁇ , where Y represents a fluorinated organic group.
  • fluoroorgano boron and fluoroorgano borate compounds are typically referred to collectively by organoboron compounds, or by either name as the context requires.
  • fluoroorgano boron compounds that can be used as co-activators include, but are not limited to, tris(pentafluorophenyl)boron, tris[3,5- bis(trifluoromethyl)phenyl]boron, and the like, including mixtures thereof.
  • fluorinated aryl borates such as, N,N-dimethylanilinium tetrakis- (pentafluorophenyl)borate, triphenylcarbenium t
  • the molar ratio of the organoboron compound to the metallocene compound in the composition can be from about 0.1:1 mole of organoboron or organoborate compound per mole of metallocene (mol/mol) to about 10:1 mol/mol, or from about 0.5 mol/mol to about 10 mol/mol (mole of organoboron or organoborate compound per mole of metallocene), or alternatively in a range of from about 0.8 mol/mol to about 5 mol/mol (mole of organoboron or organoborate compound per mole of metallocene).
  • the amount can be reduced or adjusted downward in the presence of a clay-heteroadduct support-activator.
  • the optional co-activators which can be used in addition to the recited components of the catalyst compositions of this disclosure can comprise or can be selected from ionizing compounds.
  • ionizing compound examples 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.
  • the Aspects section of this disclosure recites additional description and selections for the optional ionizing compound co-activators.
  • the term ionizing compound is term of art and refers to a compound, particularly an ionic compound, which can function to enhance activity of the catalyst composition.
  • the fluoroorgano borate compounds described herein as optional organoboron co-activators can also be considered and function as ionizing compound co- activators.
  • the scope of the ionizing compounds is broader than the fluoroorgano borate compounds, as compounds such as fluoroorgano aluminate are encompassed by ionizing compounds. While not intending to be bound by theory, it is believed that the ionizing compounds may be capable of interacting or reacting with the metallocene compound and converting the metallocene into a cationic or an incipient cationic metallocene compound, which activates the metallocene to polymerization activity.
  • the ionizing compound may function by completely or partially extracting an anionic ligand from the metallocene, particularly a non- cycloalkadienyl ligand or non-alkadienyl ligand such as (X 3 ) or (X 4 ) of the metallocene formula (X 1 )(X 2 )(X 3 )(X 4 )M disclosed herein, to form a cationic or incipient cationic metallocene.
  • the ionizing compound can function as an activator (co-activator) regardless of any mechanism by which it functions.
  • the ionizing compound may ionize the metallocene, abstract an X 3 or X 4 ligand in a fashion as to form an ion pair, weakens the metal-X 3 or metal-X 4 bond, or simply coordinate to an X 3 or X 4 ligand, or any other mechanisms by which activation may occur. Further, it is not necessary that the ionizing compound activate (co-activate) the metallocene only, as the activation function of the ionizing compound is evident in the enhanced activity of catalyst composition as a whole, as compared to a catalyst composition containing catalyst composition that does not comprise any ionizing compound.
  • ionizing compounds include, but are not limited to, the list of compounds presented in the Aspects section of this disclosure.
  • Optional Support-Activators the optional co- activators which can be used in addition to the recited components of the catalyst compositions of this disclosure can comprise or can be selected from other support-activators, sometimes termed activator-supports, which when used in the catalyst compositions described herein are termed co-activator-supports.
  • activator-supports sometimes termed activator-supports, which when used in the catalyst compositions described herein are termed 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.
  • the optional co-activator-support may comprise or be selected from silica, alumina, silica-alumina, or silica-coated alumina which is treated with at least one electron-withdrawing anion.
  • the silica-coated alumina can have a weight ratio of alumina-to-silica in a range of from about 1:1 to about 100:1, or from about 2:1 to about 20:1, in this aspect.
  • the at least one electron-withdrawing anion can comprise or be selected from fluoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate, and the like, or combinations thereof.
  • the optional co-activator-supports can be selected from, for example, fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica- alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, and the like, any of which or any combinations of which can be employed in catalyst compositions disclosed herein.
  • the co-activator-support can comprise or be selected from solid oxides treated with an electron withdrawing anion such as fluorided silica-alumina, or sulfated alumina and the like.
  • co-activator-supports can include, but are not limited to, those listed in the Aspects section of this disclosure.
  • N. The Catalyst System and Its Preparation An aspect provided by this disclosure is the preparation of a catalyst system comprising the smectite heteroadduct and a transition metal precatalyst, particularly a metallocene.
  • the catalyst system for olefin polymerization can comprise: (a) at least one metallocene compound; (b) at least one support-activator according to any aspect of this disclosure.
  • the use of the term “catalyst system” encompasses a catalyst system comprising these components, and “catalyst system” can further comprise at least one co-catalyst such as an alkyl aluminum compound and/or at least one co-activator such as methyl aluminoxane (MAO) in combination with these components.
  • co-catalyst such as an alkyl aluminum compound and/or at least one co-activator such as methyl aluminoxane (MAO) in combination with these components.
  • MAO methyl aluminoxane
  • This disclosure also provides a method of making a catalyst system, in which 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 heteroadduct according to this disclosure.
  • This method of making a catalyst system can further comprise contacting in the second liquid carrier at least one co- catalyst such as an alkyl aluminum compound and/or at least one co-activator such as methyl aluminoxane (MAO), in which the contacting can occur in any order.
  • co- catalyst such as an alkyl aluminum compound
  • MAO methyl aluminoxane
  • the relative concentration or ratio of metallocene such as a group 4 metallocene of the formula (X 1 )(X 2 )(X 3 )(X 4 )M to the calcined clay-surfactant heteroadduct can be expressed as moles of M (metal) per grams of calcined clay heteroadduct (mol M/g heteroadduct).
  • M metal
  • mol M/g heteroadduct moles of M (metal) per grams of calcined clay heteroadduct
  • the ratio of moles of M per grams of calcined clay heteroadduct can be in a range of from about 0.025 mol M/g heteroadduct to about 0.000000005 mol M/g heteroadduct.
  • the moles of M per grams of calcined clay heteroadduct can be used in a range of from about 0.0005 mol M/g heteroadduct to about 0.00000005 mol M/g heteroadduct, or alternatively, from about 0.0001 mol M/g heteroadduct to 0.000001 mol M/g heteroadduct.
  • these recited ranges include the end points as well as intermediate values and subranges within the recited range.
  • These ratios reflect the catalyst recipe, that is, these ratios are based on the amount of the components combined to give the catalyst composition, regardless of what the ratio may be in the final catalyst.
  • the relative concentration or ratio of co-catalyst to the calcined clay heteroadduct can be expressed as moles of co-catalyst (for example, organoaluminum compound) per grams of calcined clay heteroadduct (mol co-catalyst/g heteroadduct).
  • co-catalyst for example, organoaluminum compound
  • mol co-catalyst/g heteroadduct mol co-catalyst/g heteroadduct
  • the ratio of moles of co-catalyst per grams of calcined clay heteroadduct that can be used is in a range of from about 0.1 mol co-catalyst/g heteroadduct to about 0.00001 mol co-catalyst/g heteroadduct, or alternatively, from about 0.01 mol co- catalyst/g heteroadduct to about 0.0001 mol co-catalyst/g heteroadduct.
  • Catalyst compositions can be produced by contacting the transition metal compound such as a metallocene, the calcined clay heteroadduct, and the co-catalyst such as an organoaluminum compound under suitable conditions.
  • Contacting can occur in any number of ways, for example by blending, by contact in a carrier liquid, by feeding each component into a reactor separately or in any order or combination.
  • various combinations of the components or compounds can be contacted with one another before being further contacted in a reactor with the remaining compound(s) or component(s).
  • all three components or compounds can be contacted together before being introduced into a reactor.
  • additional optional components which can be used in the catalyst system disclosed herein, such as co-activators, ionizing ionic compounds, and the like, contacting steps using these optional components can occur in any way and in any order.
  • the catalyst composition can be prepared by first contacting a transition metal compound such as a metallocene, with a co-catalyst such as an organoaluminum compound, for a time period of from about 1 minute to about 24 hours, or alternatively from about 1 minute to about 1 hour, at a contact temperature that can range from about 10°C to about 200°C, alternatively from about 12°C to about 100°C, alternatively from about 15°C to about 80°C, or alternatively from about 20°C to about 80°C, to form a first mixture, and this first mixture can then be contacted with a calcined clay heteroadduct to form the catalyst composition.
  • a transition metal compound such as a metallocene
  • a co-catalyst such as an organoaluminum compound
  • the metallocene, the co-catalyst such as an organoaluminum compound, and the calcined clay heteroadduct can be pre-contacted before being introduced into a reactor.
  • the pre-contacting step may occur over a time period of from about 1 minute to about 6 months.
  • the pre- contacting step may occur over a time period of from about 1 minute to about 1 week at a temperature from about 10°C to about 200°C or from about 20°C to about 80°C, to provide the active catalyst composition.
  • any subset of the final catalyst components also can be pre-contacted in one or more pre-contacting steps, each with its own pre-contacting time period.
  • a catalyst composition can comprise post-contacted components.
  • a catalyst composition can comprise a post-contacted metallocene, a post-contacted co-catalyst such as an organoaluminum compound, and a post-contacted calcined clay heterodduct component. It is not uncommon in the field of catalyst technology that the specific and detailed nature of the active catalytic site and 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 upon the relative weights of the individual components can be thought of as comprising the post-contacted calcined clay heteroadduct.
  • the catalyst composition may simply be described according to its components or referred to as comprising post-contacted compounds or components.
  • the first liquid carrier is the liquid carrier in which the smectite heteroadduct is prepared
  • 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 the metallocene can be contacted with the smectite heteroadduct to prepare the supported pre- catalyst or catalyst without degrading the metallocene or the smectite heteroadduct.
  • the second liquid carrier can comprise, consist essentially of, or be selected from cyclohexane, isobutane, n-butane, propane, n-pentane, isopentane, neopentane, n- hexane, naphtha, hydrogen-treated naphtha, Isopar TM , at least one olefin, or any combination thereof.
  • the second liquid carrier can further comprise at least one olefin.
  • the catalyst system for olefin polymerization can comprise or consist essentially of: (a) at least one metallocene compound; (b) at least one support- activator according to this disclosure.
  • the catalyst system may also further comprise: c) at least one co-catalyst; (d) at least one co-activator; or a combination thereof.
  • the catalyst system can also further comprise a fluid carrier.
  • a “fluid carrier” is used to describe the carrier in which the catalyst system and at least one olefin are contacted to form a polyolefin. Therefore, a fluid carrier can be a liquid or a gas because polymerization using the disclosed catalyst system can be conducted under conditions such as slurry or fixed bed polymerization conditions or under gas phase polymerization conditions.
  • the fluid carrier can comprise, consist essentially of, or be selected from: nitrogen; a hydrocarbon such as cyclohexane, isobutane, n-butane, propane, n- pentane, isopentane, neopentane, n-hexane, naphtha, hydrogen-treated naphtha, or Isopar TM ; at least one olefin; or any combination thereof.
  • a hydrocarbon such as cyclohexane, isobutane, n-butane, propane, n- pentane, isopentane, neopentane, n-hexane, naphtha, hydrogen-treated naphtha, or Isopar TM ; at least one olefin; or any combination thereof.
  • any fluid carrier that can be used with supported catalysts can be used to conduct the polymerization using the present catalyst system.
  • the fluid carrier can comprise or can consist essentially of a liquid or a gaseous hydrocarbon, an ether, or a combination thereof, each of which independently has from 2 to 20 carbon atoms.
  • O. Polymerization Activity of the Isolated Clay-Heterocoagulates The data in Tables 1, 2, and 3 disclose the compositions, surface area/pore volume properties, and polymerization activities of smectite clay support-activators produced by contacting the clay with either an exemplary cationic polymetallate (aluminum chloride hydrates), a surfactant, or a combination of a cationic polymetallate and a surfactant.
  • the heteroadducts Table 1 and Table 2 are isolated by rotary evaporation drying under the specified conditions, while the heteroadducts in Table 3 are isolated by spray-drying from an aqueous slurry.
  • the polymerization activities of the catalyst compositions comprising the clay heteroadduct support-activator can be expressed as the weight of polymer polymerized per weight of support-activator comprising the calcined smectite heteroadduct, per unit of time, for example, gram polymer/gram (calcined) support-activator/hour (g/g/hr). That is, activity can be calculated on the basis of the support-activator alone, absent any metallocene or co-catalyst components.
  • This measurement allows comparisons of the various support- activators, including with other activators, where the metallocene, co-catalyst, and other conditions are the same or substantially the same.
  • the activities disclosed in the Examples were measured under slurry polymerization conditions, using isobutane as the diluent, unless otherwise specified, and with a polymerization temperature of from about 50°C to about 150°C, (for example at a temperature of 90°C), and using a combined ethylene and isobutane pressure in a range of from about 300 psi to about 800 psi, for example 450 psi for the total combined ethylene and isobutane.
  • Activity data are reported as the weight of polymer produced divided by the weight of calcined clay-surfactant heteroadduct per hour.
  • Catalyst activity can be a function of the metallocene and the calcined clay heteroadduct, as well as other components and conditions.
  • the activity based on the weight of the calcined clay-surfactant heteroadducts and the calcined clay-cationic polymetallate-surfactant heteroadducts can be greater than 1,000 grams of polyethylene (PE) polymer per gram of calcined clay heteroadduct per hour (g PE/g heteroadduct/hr, or simply, g/g/hr or g/g/h).
  • PE polyethylene
  • the catalytic activity based on the weight of the calcined clay heteroadduct can be greater than 250 g/g/hr, greater than 500 g/g/hr, greater than 1000 g/g/hr, greater than 1500 g/g/hr, greater than 2000 g/g/hr, greater than 3,000 g/g/hr, greater than 5,000 g/g/hr, greater than 7,500 g/g/hr, greater than 10,000 g/g/hr, greater than 15,000 g/g/hr, greater than 20,000 g/g/hr, greater than 30,000 g/g/hr, greater than 40,000 g/g/hr, greater than 50,000 g/g/hr, greater than 60,000 g/g/hr, greater than 70,000 g/g/hr, or greater than 80,000 g/g/hr.
  • one upper limit for the activity can be about 100,000 g/g/hr, such that the activities can range from greater than these disclosed values, and less than 100,000 g/g/hr.
  • the support-activators can have a polymerization activity of about 250 g/g/hr, about 300 g/g/hr, about 400 g/g/hr, about 500 g/g/hr, about 750 g/g/hr, about 1,000 g/g/hr, about 1,250 g/g/hr, about 1,500 g/g/hr, 1,750 g/g/hr, about 2,000 g/g/hr, about 2,500 g/g/hr, about 3,500 g/g/hr, about 5,000 g/g/hr, about 7,500 g/g/hr, about 10,000 g/g/hr, about 12,500 g/g/hr, about 15,000 g/g/hr,
  • activity levels can be achieved that are in a range between two of the recited values recited, for example, activity levels can be obtained in the range of 250-35,000 g/g/hr, in the range as well as intermediate values and ranges such as 300-30,000 g/g/hr, 400-25,000 g/g/hr, or 500-20,000 g/g/hr.
  • the heterocoagulation of the clay with a surfactant reagent provides support-activators which possess substantially increased polymerization activity relative to analogously prepared species which are not contacted with a surfactant.
  • aluminoxane such as methyl aluminoxane was needed to activate the metallocene and form the catalyst composition.
  • Methyl aluminoxane (MAO) is an expensive activator compound which can greatly increase the polymer production costs.
  • no organoboron compound or ionizing compound, such as borate compounds were required to in order to activate the metallocene and form the catalyst composition.
  • ion-exchanged, protic-acid-treated or pillared clays which require similarly multi-step preparations which increase costs, were also not required to activate the metallocene and form the catalyst composition.
  • an active heterogeneous catalyst composition can be easily and inexpensively produced and used for polymerizing olefin monomers including comonomers if desired in the absence of any aluminoxane compounds, boron compounds or borate compounds, ion-exchanged-, protic-acid-treated- or pillared- clays.
  • MAO or other aluminoxanes, boron or borate compounds, ion-exchanged- clays, protic-acid-treated-clays, or pillared-clays are not required in the disclosed catalyst systems, these compounds can be used in reduced amounts or typical amounts according to other aspects of the disclosure.
  • the catalyst activities of the Examples and in Tables 1-3 were measured for homopolymerization of ethylene under slurry polymerization conditions, using isobutane as the diluent, and with a polymerization temperature of 80°C, and a combined ethylene and isobutane pressure of 350 total psi and ( ⁇ 5 -1-n-butyl-3-methyl-cyclopentadienyl) 2 ZrCl 2 and triethylaluminum (AlEt3) as metallocene and co-catalyst, unless otherwise noted.
  • the support-activators’ drying process may be described as azeotroped (for example, rotary evaporating from 1-butanol and water) and non- azeotroped (rotary evaporating from water only), or spray-dried (from an aqueous suspension or the suspension specified).
  • the surface of the support-activator can be made more hydrophobic by addition of a surfactant in any of these drying processes. If desired, these methods can be combined, such as drying by an azeotroping or non-azeotroping process followed by re-suspending the heteroadduct and spray drying from a aqueous slurry in the presence of a surfactant.
  • Tightly bound water can be subsequently removed from the dried heteroadduct (support-activator), for example by calcining, heating in a fluidized bed, and the like, prior to their use as catalyst support-activators.
  • Table 1 reports the properties and polymerization data for azeotroped (1- butanol and water) and non-azeotroped (water only), calcined, clay-aluminum chlorhydrate (ACH) support-activators. These support-activators were prepared in the absence of a surfactant, and they were not spray-dried but dried by (rotary) evaporation from the slurry.
  • Runs 1-4 of Table 1 demonstrate that the clay-ACH adducts which have undergone azeotropic drying exhibit very good catalytic activity when calcined (2000-4000 g PE/g support-activator/hr)
  • Run 5 of Table 1 demonstrates that the drying of these adducts from a slurry of water only, in the absence of an azeotroping agent, produces a support with little to no catalytic activity ( ⁇ 200 g PE/g support-activator/hr). Therefore, attempts to dry clay-ACH support-activators in this manner from an aqueous slurry without an organic azeotroping agent have resulted in a loss of activity and porosity from aqueous-only drying.
  • Runs 7-32 of Table 2 combine clay with surfactant agents tetraoctylammonium bromide, tetrabutylammonium bromide, and tetramethylammonium bromide respectively, and are subsequently dried by (rotary) evaporation from a water-only slurry in the absence of an azeotroping agent, produce catalytically active species for ethylene polymerization.
  • Runs 7-32 of Table 2 demonstrate activities in a range of from 1000-3000 g PE/g support-activator/hr.
  • Run 2 of Table 2 compares the activity of a clay-ACH-surfactant heteroadduct, utilizing clay combined with both a surfactant agent (tetraoctylammonium bromide) and an aluminum chlorhydrate, which is dried as an aqueous-only slurry.
  • This sample also demonstrates enhanced polymerization activity (>2000 g PE/g support- activator/hr) relative to Run 1 of Table 2 ( ⁇ 200 g PE/g support-activator/hr), which is a species containing only clay and the aluminum chlorhydrate, absent a surfactant.
  • Run 6 of Table 2 provides an example of using the nonionic surfactant dextrose to form a clay-aluminum chlorhydrate-surfactant heteroadduct as a support-activator in the ethylene homopolymerization. While the activity of the sample is modest (75 g PE/g support-activator/hr), its activity is more than twice the activity provided by the clay-aluminum chlorhydrate heteroadduct support-activator of Run 1 of Table 2 (Example 5-A4) which is absent a surfactant of any type.
  • Run 5 of Table 2 illustrates the use of the phosphonium salt cationic surfactant, trihexyl tetradecyl phosphonium bromide to form a clay-surfactant heteroadduct.
  • the activity of this support-activator in the ethylene homopolymerization was found to be 184 g PE/g support-activator/hr, somewhat lower than most of the ammonium salt cationic surfactant heteroadducts.
  • Runs 3 and 4 of Table 2 (Examples 28-C1 and 29-C2) use ammonium bromide [NH 4 ]Br rather than any hydrocarbyl ammonium surfactant to combine with the smectite clay.
  • clay-surfactant support-activators prepared in the absence of a cationic polymetallate according to this disclosure can be combined with a metallocene procatalyst to yield an olefin polymerization catalyst which exhibits surprising polymerization activities of from about 300 g PE/g support-activator/hr to about 2,500 g PE/g support-activator/hr.
  • other heterocoagulation agents such as aluminum polyoxometallates
  • clay-cationic polymetallate support-activators can exhibit a tremendous enhancement in activity when prepared in the presence of a surfactant to form clay-cationic polymetallate- cationic surfactant support-activators (compare Table 2 Run 1 and Run 2).
  • a large BJH pore volume enhancement is observed to accompany this increase in activity.
  • the activity enhancement using surfactants is not limited to cationic surfactants, as nonionic surfactants also impart improvements to the activity of the clay-cationic polymetallate support-activators (compare Table 2 Run 6).
  • clay heteroadduct species which are spray-dried from an aqueous slurry display a surprisingly high degree of sphericity, roundness, and circularity, and maintain excellent polymerization activities. This combination of properties imparts processing advantages in their use as polymerization support-activators such as providing superior flow and packing properties the catalyst particles for use in catalyst bed systems.
  • the data in Table 3 illustrate the properties and polymerization data for spray-dried, calcined, heterocoagulated [1] clay-aluminum chlorohydrate (ACH) support- activators, [2] clay-ACH-surfactant support-activators, and [3] clay-surfactant support- activators.
  • the polymerizations were performed at 350 psi reactor pressure and 80°C, using ( ⁇ 5 -1-n-butyl-3-methyl-cyclopentadienyl)2ZrCl2 as metallocene and triethylaluminum (AlEt3) as co-catalyst, and 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.
  • Table 3 demonstrate the surprising discovery that excellent polymerization activities can be achieved even in the absence of a cationic polymetallate using a smectite clay-surfactant heteroadduct which has been spray-dried from an aqueous slurry, in the absence of an organic liquid, and calcined, as in Runs 3-6.
  • These clay- surfactant heteroadduct data (Runs 3-6) are comparable to the clay-ACH-surfactant heteroadducts which has been spray-dried from an aqueous slurry in Runs 7-10.
  • Clay-surfactant heteroadduct data exhibit substantially better activities than the comparative low activities observed from clay-cationic polymetallate (ACH) heteroadducts prepared in the absence of a surfactant in Runs 1-2, which are spray- dried from an aqueous slurry.
  • ACH clay-cationic polymetallate
  • Runs 3 and 4 of Table 1 their polymerization activities exceed 2500 g/g/hr. This observation is consistent with the significant reduction in polymerization activity obtained when non-azeotropically drying clay-ACH heteroadducts from a water-only slurry as in Run 5 of Table 1.
  • the clay-surfactant heteroadducts and the clay-cationic polymetallate-surfactant heteroadducts can be spray dried and subsequently calcined which, when combined with a metallocene precatalyst, yield catalysts with high catalytic activity (1400-3000 g PE/g support-activator/hr) for olefin polymerization, as depicted in Table 3, Entries 3-10.
  • the spray drying process can be carried out on the clay- surfactant heteroadducts and the clay-cationic polymetallate-surfactant heteroadducts slurried in alcohol/water mixtures.
  • this spray drying process can be carried out on these heteroadducts slurried in water in the absence of an organic liquid.
  • the isolated heteroadducts can be re-suspended into a slurry which is subsequently spray dried.
  • the spray drying is performed on a slurry obtained from re-suspending the “filter cake” of the clay-surfactant adduct in a liquid carrier to be used for spray-drying and stirring or agitating, for example using high shear conditions, for a period of time.
  • the spray drying can be performed on a slurry obtained from re-suspending the filter cake of a clay-surfactant adduct in a liquid carrier to be used for spray-drying for a period of 15 minutes to 24 hours.
  • the spray drying can be performed on a slurry obtained from re-suspending the filter cake of the clay-surfactant adduct in a liquid carrier to be used for spray-drying and stirring or agitating the mixture for a period of 24 hours to 72 hours.
  • the advantages of using a surfactant agent can be realized when it is introduced at different times prior to spray-drying the resulting heterocoagulate. For example, Runs 3-6 of Table 3 illustrate the surfactant and the clay are contacted prior to the preparation of the spray-drying feed, that is, the clay-surfactant is formed and isolated and is subsequently re-suspended to prepare the spray-drying feed.
  • Runs 7-10 of Table 3 illustrate embodiments in which the surfactant agent can be introduced directly to the spray drying feed of an isolated and re-suspended clay-cationic polymetallate heteroadduct.
  • the clay-ACH heteroadduct was prepared and filtered off, and the resulting wet cake was re-suspended in water with the surfactant to form the spray-drying feed.
  • These samples were calcined after spray-drying and exhibited good porosities, with the tetrabutylammonium bromide sample (Runs 7-8, Example 23-E3) having a total BJH porosity of 0.273 cc/g.
  • Runs 7-10 of Table 3 are also referred to herein as forming a clay- cationic polymetallate-surfactant heteroadduct, although the method of making these is different from other heteroadducts in which the clay, ACH, and surfactant are contacted in the initial slurry of the clay.
  • the polymerization activities are demonstrated to range from about 500 g PE/g support-activator/hr to 2000 g PE/g support-activator/hr.
  • the polymers produced from these catalysts were compared with polymer particles produced from non-spray-dried support-activators, lower particle sizes and higher particle uniformities in the polymer particles were observed in the spray-dried heteroadduct polymers, which provides desirable operability advantages when these catalysts are introduced to fluidized reactor bed systems.
  • the data of Table 4 illustrates particle size distribution properties for the polyethylene homopolymer produced using [1] an azeotroped clay- aluminum chlorohydrate (ACH) support-activator produced in the absence of a surfactant (see comparative Example 2-A1 and Run 1 of Table 1), [2] an isolated clay-aluminum chlorohydrate (ACH) heteroadduct 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) heteroadduct spray-dried in the presence of tetraoctylammonium bromide surfactant (see Example 24-E4 and Run 10 of Table 3), demonstrating the higher uniformity coefficient of the inventive heteroadducts spray-dried in the presence of surfactants.
  • ACH azeotroped clay- aluminum chlorohydrate
  • the resulting smectite clay-cationic heteroadduct-surfactant heteroadduct can achieve a significantly greater polymerization activity as compared to the analogous clay-polymetallate heteroadducts prepared in the absence of a surfactant. 3.
  • a surfactant can be combined with a smectite clay in the absence of other additives, or a surfactant can be combined with a smectite clay and a cationic polymetallate, in any sequence or any manner to form the isolated heteroadduct.
  • a surfactant can be combined with a smectite clay with or without a cationic polymetallate to form a heteroadduct, or the surfactant can be used to contact a smectite clay-cationic polymetallate heteroadduct at the time of heteroadduct formation or later, for example, in preparing a spray-drying feed of the clay- polymetallate heteroadduct.
  • smectite clay-surfactant heteroadducts and smectite clay-cationic polymetallate-surfactant heteroadducts permits the heteroadducts to be spray-dried from a slurry in water only, without the need to use an organic liquid with the water such as in an azeotropic drying process, while still providing high polymerization activities.
  • Heteroadducts which are spray-dried from an aqueous slurry display a surprisingly high degree of sphericity, roundness, and circularity, which impart processing advantages in their use as polymerization support-activators such as providing superior flow and packing properties the catalyst particles for use in catalyst bed systems. 6.
  • Polymer particles produced using the inventive heteroadduct support-activators that have been spray-dried are characterized as having lower particle sizes and higher particle uniformities than their non-surfactant analogs, and these properties provide desirable operability advantages when these catalysts are introduced to fluidized reactor bed systems.
  • this disclosure describes a process of contacting at least one olefin monomer and the disclosed catalyst composition to produce at least one polymer (polyolefin).
  • polymer is used herein to include homopolymers, copolymers of two olefin monomers, and polymers of more than two olefin monomers such as terpolymers.
  • the catalyst composition can be used to polymerize at least one monomer to produce a homopolymer or a copolymer.
  • homopolymers are comprised of monomer residues which have from 2 to about 20 carbon atoms per molecule, preferably 2 to about 10 carbon atoms per molecule.
  • the olefin monomer can comprise or be selected from ethylene, propylene, 1- butene, 3-methyl-1-butene, 1-pentene, 3-methyl-l-pentene, 4-methyl-1-pentene, 1-hexene, 3- ethyl-1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and mixtures thereof.
  • homopolymers of ethylene, homopolymers of propylene, and homopolymers of other olefins are encompassed by this disclosure.
  • copolymers of ethylene and at least one comonomer and less commonly, copolymers of two non-ethylene copolymers are encompassed by this disclosure.
  • each monomer may have from about 2 to about 20 carbon atoms per molecule.
  • Comonomers of ethylene can include, but are not limited to, aliphatic 1-olefins having from 3 to 20 carbon atoms per molecule, such as, for example, 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
  • ethylene can be copolymerized with at least one comonomer comprising 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 which is sufficient to produce a copolymer that can incorporate from about 0.01 wt.% to about 10 wt.% comonomer or even beyond this range, based upon the total weight of the monomer and comonomer in the copolymer; alternatively, from about 0.01 wt.% to about 5 wt.% comonomer; alternatively still, from about 0.1 wt.% to about 4 wt.% comonomer; or alternatively still, any amount of comonomer can be introduced into a reactor zone that provides a desired copolymer.
  • the catalyst composition can be used to homopolymerize ethylene, or propylene, or copolymerize ethylene with a comonomer, or copolymerize ethylene and propylene.
  • comonomers may be polymerized with monomer in the same or different reactor zones to achieve the desired polymer properties.
  • Other useful comonomers can include polar vinyl, conjugated and non- conjugated dienes, acetylene and aldehyde monomers, which can be included for example in minor amounts in terpolymer compositions.
  • non-conjugated dienes useful as comonomers can be straight chain, hydrocarbon di-olefins or cycloalkenyl-substituted alkenes having from 6 to 15 carbon atoms.
  • Suitable non-conjugated dienes can include, for example: (a) straight chain acyclic dienes, such as 1,4-hexadiene and 1,6-octadiene; (b) branched chain acyclic dienes, such as 5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene; and 3,7-dimethyl-1,7-octadiene; (c) single ring alicyclic dienes, such as 1,4-cyclohexadiene; 1,5-cyclo-octadiene and 1,7-cyclododecadiene; (d) multi-ring alicyclic fused and bridged ring dienes, such as tetrahydroindene; nor
  • Particularly useful non-conjugated dienes include dicyclopentadiene, 1,4-hexadiene, 5-methylene-2-norbornene, 5-ethylidene-2- norbornene, and tetracyclo-(. ⁇ .-11,12)-5,8-dodecene.
  • Particularly useful diolefins include 5- ethylidene-2-norbornene (ENB), 1,4-hexadiene, dicyclopentadiene (DCPD), norbornadiene, and 5-vinyl-2-norbornene (VNB). Note that throughout this description the terms “non- conjugated diene” and “diene” are used interchangeably.
  • the catalyst compositions can be used for polymerizing olefins to make oligomeric and polymeric materials having a wide range of densities, for example, in a range of from about 0.66 g/mL (also, g/cc) to about 0.96 g/mL, which are used in numerous applications.
  • the catalyst compositions disclosed herein are particularly useful for the production of copolymers.
  • copolymer resins may have a density of 0.960 g/cc or less, preferably 0.952 g/cc or less, or more preferably 0.940 g/cc or less.
  • Copolymer resins can contain at least about 65 wt.% (percent by weight) of ethylene units, that is, the weight percent of ethylene monomers actually incorporated into the copolymer resin.
  • the copolymer resins of this disclosure can contain at least about 0.5 wt.%, for example, from 0.5 wt.% to 35 wt.% of an alpha-olefin ( ⁇ -olefin), referring to the weight percent of alpha-olefin comonomers actually incorporated into the copolymer resin.
  • ⁇ -olefin alpha-olefin
  • the catalyst compositions prepared according to the present disclosure are also useful for preparing: (a) ethylene/propylene copolymers, including “random copolymer” in which the commoner is distributed randomly along the polymer back-bone or chain; (b) “propylene random copolymer”, in which a random copolymer of propylene and ethylene comprising about 60 wt.% of the polymer derived from propylene units; and (c) “impact copolymer” meaning two or more polymers in which one polymer is dispersed in the other polymer, typically one polymer comprising a matrix phase and the other polymer comprising an elastomer phase.
  • the catalyst compositions described herein may further be used to prepare polyalphaolefins with monomers containing more than three carbons. Such oligomers and polymers are particularly useful, for example, as lubricants. Any number of polymerization methods or processes can be used with the catalyst compositions of this disclosure. For example, slurry polymerization, gas phase polymerization, and solution polymerization and the like, including multi-reactor combinations thereof, can be used. Multi-reactor combinations can be configured in a serial or parallel configuration, or a combination thereof, depending upon the desired polymerization sequence.
  • reactor systems and combinations can include, for example, dual slurry loops in series, multiple slurry tanks in series, or slurry loop combined with gas phase, or multiple combinations of these processes, in which polymerization of ethylene, propylene and alpha-olefins separately or together can be carried out.
  • gas phase reactors can comprise fluidized bed reactors or tubular reactors
  • slurry reactors can comprise vertical loops or horizontal loops or stirred tanks
  • solution reactors can comprise stirred tank or autoclave reactors.
  • any polymerization zone known in the art which can produce polyolefins such as ethylene and alpha-olefin-containing polymers including polyethylene, polypropylene, ethylene alpha-olefin copolymers, as well as more generally to substituted olefins such as vinylcyclohexane, can be utilized.
  • a stirred reactor can be utilized for a batch process, and then the reaction can be carried out continuously in a loop reactor or in a continuous stirred reactor or in a gas phase reactor.
  • the catalyst compositions comprising the recited components can polymerize olefins in the presence of a diluent or liquid carrier, and these two terms are used interchangeably herein, even if a catalyst component is not soluble in the diluent or liquid carrier.
  • Suitable diluents used in slurry and solution polymerization are known in the art and include hydrocarbons which are liquid under reaction conditions.
  • term “diluent” as used in this disclosure does not necessarily mean that the material is inert, as it is possible that a diluent can contribute to polymerization such as in bulk polymerizations with propylene.
  • Suitable hydrocarbon diluents can include, but are not limited to cyclohexane, isobutane, n-butane, propane, n-pentane, isopentane, neopentane, and n-hexane, and higher boiling solvents such as ISOPAR TM and the like.
  • Isobutane works well as the diluent in a slurry polymerization. Examples of such slurry polymerization technologies can be found in U.S. Patent Nos.4,424,341; 4,501,885; 4,613,484; 4,737,280; and 5,597,892; the entire disclosures of which are incorporated herein by reference.
  • polymerization reactors suitable for use with the catalyst system can comprise at least one raw material feed system, at least one feed system for catalyst or catalyst components, at least one reactor system, at least one polymer recovery system or any suitable combination thereof.
  • Suitable reactors can further comprise any, or combination of, a catalyst storage system, an extrusion system, a cooling system, a diluent recycling system, a monomer recycling system, and comonomer recycling system or a control system.
  • Such reactors can comprise continuous take-off and direct recycling of the catalyst, diluent, monomer, comonomer, inert gases, and polymer as desired.
  • continuous processes can comprise the continuous introduction of a monomer, a comonomer, a catalyst, a co-catalyst if desired, and a diluent into a polymerization reactor and the continuous removal from this reactor of a suspension comprising polymer particles and the diluent.
  • the polymerization methods can be carried out over a wide temperature range, for example, the polymerization temperatures may be in a range of from about 50°C to about 280°C, and in another aspect, polymerization reaction temperatures may be in a range of from about 70°C to about 110°C.
  • the polymerization reaction pressure can be any pressure that does not terminate the polymerization reaction. In one aspect, polymerization pressures may be from about atmospheric pressure to about 30000 psig. In another aspect, polymerization pressures may be from about 50 psig to about 800 psig.
  • the polymerization reaction can be carried out in an inert atmosphere, that is, in an atmosphere substantially free of molecular oxygen and under substantially anhydrous conditions; thus, in the absence of water as the reaction begins.
  • a dry, inert atmosphere for example, dry nitrogen or dry argon
  • hydrogen can be used in a polymerization process to control polymer molecular weight.
  • a method of deactivating a catalyst by adding carbon monoxide to the polymerization zone as described in U.S. Patent No.9,447,204, which is incorporated by reference herein, may be used to mitigate or stop an uncontrolled, or runaway polymerization.
  • the polymerizations disclosed herein are commonly carried out using a slurry polymerization process in a loop reaction zone or a batch process, or a gas phase zone utilizing a fluidized bed or a stirrer bed. Slurry Loop.
  • a typical polymerization method is a slurry polymerization process (also known as the “particle form process”), which is disclosed, for example in U.S. Patent No.3,248,179, which is incorporated herein by reference.
  • Other polymerization methods for slurry processes can employ a loop reactor of the type disclosed in U.S. Patent No.3,248,179, and those utilized in a plurality of stirred reactors either in series, parallel, or combinations thereof.
  • the polymerization reactor system can comprise at least one loop slurry reactor, and can include vertical or horizontal loops or a combination, which can independently be selected from a single loop or a series of loops. Multiple loop reactors can comprise both vertical and horizontal loops.
  • the slurry polymerization can be performed in an organic liquid as the carrier or diluent.
  • suitable solvents include propane, hexane, cyclohexane, octane, isobutane, or combinations thereof.
  • Olefin monomer, carrier, catalyst system components, and any comonomer can be continuously fed to a loop reactor where polymerization occurs.
  • Reactor effluent can be flash evaporated to separate the solid polymer particles.
  • Gas Phase a method for producing polyolefin polymers according to the disclosure is a gas phase polymerization process, using for example a fluidized bed reactor. This type reactor, and means for operating the reactor, are described in, for example, U.S.
  • Gas phase polymerization systems can employ a continuous recycle stream containing one or more monomers continuously cycled through the fluidized bed in the presence of the catalyst under polymerization conditions. The recycle stream can be withdrawn from the fluidized bed and recycled back into the reactor.
  • gas phase reactors can comprise a process for multi- step gas-phase polymerization of olefins, in which olefins are polymerized in the gaseous phase in at least two independent gas-phase polymerization zones while feeding a catalyst- containing polymer formed in a first polymerization zone to a second polymerization zone.
  • Other gas phase processes contemplated by the disclosed polymerization process include series or multistage polymerization processes.
  • gas phase processes that can be used in accordance with the disclosure include those described in U.S.
  • the ethylene partial pressure may vary in a range suitable for providing practical polymerization conditions, for example, in a range of from 10 psi to 250 psi, for example, from 65 psi to 150 psi, from 75 psi to 140 psi, or from 90 psi to 120 psi.
  • a molar ratio of comonomer to ethylene in the gas phase also may vary in a range suitable for providing practical polymerization conditions, for example, in a range of from 0.0 to 0.70, from 0.0001 to 0.25, more preferably from 0.005 to 0.025, or from 0.025 to 0.05.
  • the reactor pressure can be maintained in a range suitable for providing practical polymerization conditions, for example, in a range of from 100 psi to 500 psi, from 200 psi to 500 psi, or from 250 psi to 350 psi, and the like.
  • a gaseous stream containing one or more monomers in a fluidized gas bed process used for producing polymers, can be continuously cycled through a fluidized bed in the presence of a catalyst under reactive conditions.
  • the gaseous stream can be withdrawn from the fluidized bed and recycled back into the reactor, and simultaneously, polymer product can be withdrawn from the fluidized bed and withdrawn from the reactor, while fresh monomer can be added to replace the polymerized monomer. See, for example, U.S.
  • antistatic compounds can be fed simultaneously with the finished catalyst into a polymerization zone.
  • antistatic compounds such as those described in US Patent Nos.7,919,569; 6,271,325; 6,281,306; 6,140,432 and 6,117,955, each of which is incorporated herein by reference in its entirety, can be used.
  • the clay heteroadduct can be contacted with or impregnated with one or more antistatic compounds.
  • Antistatic compounds may be added at any point, for example, they can be added any time after calcination such as up to and including the final post-contacted catalyst preparation.
  • so-called “self-limiting” compositions may be added to the clay heteroadduct to inhibit chunking, fouling, or uncontrolled or runaway reaction in the polymerization zone.
  • U.S. Patent Nos.6,632,769; 6,346,584; and 6,713,573, each of which is incorporated herein by reference disclose additives that can release a catalyst poison above a threshold temperature.
  • compositions can be added at any time after calcination, in order to limit or stop polymerization activity above a desired temperature.
  • Solution The polymerization reactor also can comprise a solution polymerization reactor, in which the monomer is contacted with the catalyst composition by suitable stirring or other means. Solution polymerizations can be effected in a batch manner, or in a continuous manner. A carrier comprising an inert organic diluent or excess monomer can be employed, and the polymerization zone is maintained at temperatures and pressures that will result in the formation of a solution of the polymer in the reaction medium.
  • the reactor can comprise a series of at least one separator that employs high pressure and low pressure to separate the desired polymer.
  • Tubular Reactors and High Pressure LDPE can be employed during polymerization to obtain better temperature control and to maintain uniform polymerization mixtures throughout the polymerization zone, and adequate means are utilized for dissipating the exothermic heat of polymerization.
  • the reactor also can comprise a series of at least one separator that employs high pressure and low pressure to separate the desired polymer.
  • Tubular Reactors and High Pressure LDPE can be employed in a series of at least one separator that employs high pressure and low pressure to separate the desired polymer.
  • Tubular Reactors and High Pressure LDPE can be employed in still another aspect, the polymerization reactor can comprise a tubular reactor, which can make polymers by free radical initiation or alternatively by employing the disclosed catalysts.
  • Tubular reactors can have several zones where fresh monomer, initiators, or catalysts and co-catalysts are added.
  • monomer can be entrained in an inert gaseous stream and introduced at one zone of the reactor, and initiators, the catalysts composition and/or catalyst components can be entrained in a gaseous stream and introduced at another zone of the reactor.
  • These gas streams can then be intermixed for polymerization, in which heat and pressure can be appropriately adjusted to obtain optimal polymerization reaction conditions.
  • Combined or Multiple Reactors the catalysts and processes of this disclosure are not limited by possible reactor types or combinations of reactor types.
  • the disclosed catalysts and processes can be used in multiple reactor systems which can comprise reactors combined or connected to perform polymerizations, or multiple reactors that are not connected.
  • the polymer can be polymerized in one reactor under one set of conditions, and then the polymer can be transferred to a second reactor for polymerization under a different set of conditions.
  • the polymerization reactor system can comprise the combination of two or more reactors.
  • Production of polymers in multiple reactors can include several stages in at least two separate polymerization reactors interconnected by a transfer device to transfer the polymers resulting from the first polymerization reactor into the second reactor, in which polymerization conditions are different in the individual reactors.
  • polymerization in multiple reactors can include the manual transfer of polymer from one reactor to subsequent reactors for continued polymerization.
  • Such reactors can include any combination including, but not limited to, multiple loop reactors, multiple gas reactors, a combination of loop and gas reactors, a combination of autoclave reactors or solution reactors with gas or loop reactors, multiple solution reactors, or multiple autoclave reactors, and the like.
  • Polymers Produced Using the Disclosed Catalysts and Processes The catalyst compositions used in this process can produce high quality polymer particles without substantially fouling the reactor.
  • the particle size of the calcined heterocoagulated product can be in a range of from about 10 microns ( ⁇ m) to about 1000 microns, from about 25 microns to about 500 microns, from about 50 microns to about 200 microns, or from about 30 microns to about 100 microns to provide good control of the polymer particle production during polymerization.
  • the particle size of the calcined heterocoagulated product can be in a range of from about 1 micron to about 1000 microns, from about 5 to about 500 microns, or from about 10 microns to about 200 microns, or from about 15 microns to about 60 microns, to provide good control of the polymer particle and polymerization reaction.
  • the suitable particle size in other polymerization reactor systems, whether single or multiple systems in series can be a function of the total productivity of the catalyst and the optimal particle size and particle size distribution of the final polymer-catalyst composite particle.
  • the optimal size and size distribution can be determined by the polymerization reactor system, such as whether the particles are easily fluidizable in a gas phase system but sufficiently large that they are not entrained in the fluidizing gas, which can result in plugging downstream filters.
  • the optimal size and size distribution in the polymerization system may be balanced against the ease with which they are conveyed or handled in storage silos or extrusion facilities when the catalyst-polymer composite particles are melted and extruded into pellets.
  • Polymers produced using the catalyst composition of this disclosure can be formed into various articles, such as, for example, household containers and utensils, film products, car bumper components, drums, fuel tanks, pipes, geomembranes, and liners.
  • additives and modifiers can be added to the polymer in order to provide desired effects, such as a desired combination of physical, structural and flow properties. It is believed that by using the methods and materials described herein, articles can be produced at a lower cost, while maintaining desired polymer properties obtained for polymers produced using transition metal or metallocene catalyst compositions as disclosed herein.
  • EXAMPLES The foregoing description is intended to illustrate and not limit the scope of the present disclosure, which is further illustrated by the following examples. The examples are not to be construed as imposing limitations upon the scope of the disclosure.
  • Volclay® HPM-20 bentonite aqueous dispersion (montmorillonite) manufactured by American Colloid Company was obtained from McCullough & Associates, and is also referred to as simply HPM-20 or HPM-20 clay.
  • a 50% aluminum chlorhydrate aqueous solution (abbreviated “ACH”) was obtained from GEO Specialty Chemicals.
  • ACH 50% aluminum chlorhydrate aqueous solution
  • the clay dispersions, clay heteroadducts, silicate composites, and other compositions were prepared using a dual-speed Conair TM Waring TM Commerical Lab Blender model 7010G, equipped with timer. Blender speeds may be referred to as “low” speed versus “high” speed blending as follows.
  • the Model 7010G blender was connected to a Staco Energy Variable Transformer (Model number 3PN1010B), and the blender speed was adjusted by changing the setting on the Transformer.
  • “low speed” blending was achieved by setting the Transformer between 0 to 50
  • “high speed” blending was achieved by setting the Transformer between 50 to 100.
  • Conductivity was measured using a Eutech PCSTestr 35 or a Radiometer Analytical conductivity meter and measurements were according to the instrument instruction manual and the references provided with each instrument.
  • the solution or slurry pH measurements were made using a Eutech PCSTestr 35 or Beckmann ⁇ 265 laboratory pH meter.
  • Milli-Q® water Deionized water referred to herein as Milli-Q® water was obtained by initially pretreating water using a Prepak 1 Pretreatment Pack, and then further purifying the water using a Millipore Milli-Q® Advantage A10 Water Purification System. This water was typically used within 2 hours of collection. Hexane, heptane, toluene and dichloromethane were dried over activated molecular sieves and degassed with nitrogen prior to use. Instrument grade isobutane, used as solvent for the ethylene homopolymerizations was purchased from Airgas and purified by passage through columns of activated charcoal, alumina, 13X molecular sieves, and finally an OxyClear TM gas purifier Model No.
  • RGP-R1-500 from Diamond Tool and Die, Inc. Ultra- high purity grade ethylene and hydrogen were obtained from Airgas.
  • the UHP (ultra-high purity) ethylene was further purified by passage through columns of activated charcoal, alumina, 13X molecular sieves, and an OxyClear TM gas purifier Model No. RGP-R1-500.
  • the UHP hydrogen was purified by passage through an OxyClear TM gas purifier Model No. RGP-R1-500.
  • Purified propylene was obtained as a slip stream from a commercial polypropylene plant. All preparations involving the handling of organometallic compounds were carried out under a dry nitrogen (N 2 ) atmosphere using Schlenk techniques or in a glove box.
  • Zeta Potential Measurements Zeta potentials of the colloidal suspensions disclosed herein were derived from measuring the electroacoustic effect upon application of electric field across the suspension.
  • the apparatus used to perform these measurements was a Colloidal Dynamics Zetaprobe AnalyzerTM.
  • zeta potential measurements were used to determine the dispersed clay concentration in a 0.5 wt.% (weight percent) to 1 wt.% Volclay® HPM- 20/water dispersion as follows. A 250 g to 300 g sample of the dispersion to be measured was transferred to the measurement vessel containing an axial bottom stirrer.
  • the stirring speed was set fast enough to prevent settling or substantial settling of the dispersion but slow enough to allow the electroacoustic probe to be fully immersed in the mixture when fully lowered.
  • the stirring speed was set between 250 rpm and 350 rpm, most often 300 rpm.
  • the Colloidal Dynamic Zetaprobe AnalyzerTM measurement parameters used were the following: 5 readings at 1 reading/minute; particle density of 2.6 g/cc; dielectric constant of 4.5.
  • An initial estimated colloidal weight percentage of 0.7 wt.% to 1.0 wt.% (concestimate) was typically entered into the Zetaprobe AnalyzerTM software.
  • the cationic surfactant or other cationic titrant was added to a 0.5 wt.% to 5.0 wt.% HPM-20/water dispersion at about 0.1 mL, 0.15 mL, 0.2 mL, or 0.25 mL per titration point, with an equilibration delay of from 30 seconds to 120 seconds.
  • the Zetaprobe software calculates zeta potential using a colloidal particle weight percentage which does not factor in the colloidal titrant.
  • the measured zeta potential was adjusted to reflect the extra colloidal content of the measured solution through the following method.
  • both the weight of the titrand clay and the titrant cationic species were determined by the following equations (where * indicates multiplication, W is weight, V is volume).
  • W titrant V titrant * density titrant * solids% titrant
  • Wclay Vtotal * densitytitrand * particle concentrationmeasured
  • the density for 5% HPM-20 aqueous dispersion (titrand) was determined to be approximately 1.03 g/mL.
  • the titrant weight was scaled according to its particle density relative to the particle density of the titrand HPM-20 (montmorillonite), to provide an effective titrant weight (W efftitrant ), which in this example was calculated as follows.
  • W efftitrant W titrant * particle density titrant / particle density titrand
  • the effective colloidal particle weight percentage (wt.% eff ) was then calculated, to provide an estimate of the relative increase in colloidal content compared to an equivalent titration using a non-colloidal titrant.
  • the inverse of this value was then multiplied by the measured zeta potential to determine an adjusted zeta potential as follows.
  • FIG.29 and FIG.30 illustrate zeta potential titrations for the volumetric addition of a 10.7 wt.% (weight percent) aqueous solution of tetrabutylammonium bromide (FIG.29) and a 7.9 wt.% aqueous solution of tetramethylammonium bromide (FIG.30) into a 1 wt.% Volclay® HPM-20 bentonite aqueous dispersion, respectively, plotting the measured zeta potential versus the millimoles of cation per gram of clay (mmol cation/g clay) calculated from the titrant volume.
  • Powder X-ray Diffraction Studies Powder X-ray patterns of clays and clay heteroadducts were obtained using standard X-ray powder diffraction techniques on a Bruker D8 daVinci instrument, with a Bragg Brentano geometry with a “theta-theta” scan type, using a Back-loading holder with zero background Silicon chip. The detector used was a Linear Silicon Strip (LynxEYE) PSD detector.
  • the test sample was placed in the sample holder of a two circle goniometer, enclosed in a radiation safety enclosure.
  • the X-ray source was a 2.0 kW Cu X-ray tube, maintained at an operating current of 40 kV and 25 mA.
  • the X-ray optics were the standard Bragg-Brentano para-focusing mode with the X-ray diverging from a DS slit (0.6 mm) at the tube to strike the sample and then converging at a position sensitive X-ray Detector (Lynx- Eye, Bruker-AXS).
  • the two-circle 250 mm diameter goniometer was computer controlled with independent stepper motors and optical encoders.
  • n ⁇ 2d ⁇ sin ⁇ , wherein n is the repeat number, ⁇ is 1.5418, d is d001 spacing and ⁇ is the angle of incidence.
  • Particle Size and Particle Size Distribution Polymer, support-activator, and catalyst particle sizes were determined as follows. As used herein, the terms d(0.1), d(0.5), and d(0.9), alternatively D10, D50, and D90 respectively, are used to indicate a particle size at which 10%, 50%, and 90% of the total volume of the particle sample consists of particles below the designated particle size.
  • a d(0.9) or D90 of 150 ⁇ m indicates that 90% of the total volume of particles in the sample have a particle size of less than 150 ⁇ m
  • a d(0.1) or D10 of 100 ⁇ m indicates that 10% of the total volume of particles in the sample have a particle size of less than 10 ⁇ m.
  • the width or narrowness of a particle size distribution can be given by its Span (also, “SPAN”), which is defined as (D90-D10)/(D50) or [d(0.9)-d(0.1)]/[d(0.5)].
  • Particles sizes for the support-activator or supported catalyst were determined using a Malvern MastersizerTM 2000 particle size analyzer using hexane solvent.
  • Particles sizes for the polymer were determined using a CAMSIZER® X2.
  • Particle Size and Shape Distribution Analysis of Polymer Powders The particle size distribution and shape distribution analysis of the ethylene homopolymer and ethylene-1-hexene co-polymer powders produced using support-activators of this disclosure were analyzed using a CAMSIZER® X2 Dynamic Image Analyzer. Support-activators were prepared as described in the cited Examples, and catalysts and polymers that were analyzed were prepare using the procedures detailed in Catalyst Preparation and Polymerization Reactions sections of these Examples.
  • Dry polymer powder samples of approximately 1-5 g (grams) were weighed into a vial and transferred to the ramp on the X-FALL module of the CAMSIZER® X2 Dynamic Image Analyzer.
  • the speed of the ramp vibration was set at a sufficient rate to ensure a constant stream of powder flow into the X-FALL module.
  • the remainder of the material was manually pushed in using a KimwipeTM.
  • SEM Surface Electron Microscopy
  • SPIP Scanning Probe Image Processor
  • the x-axis and y-axis lengths of the photograph, and z-axis (also referred to as the “working” distance) lengths are recorded, and used in the SPIP image analysis parameters.
  • the Smoothing Filter Size was set at 40 pixels, the Slope Noise reduction was set to 15-25%, and the Slope Image Threshold Percentile was adjusted as needed to obtain clear particle boundaries, and ranged from 50% to 76% depending on image.
  • the particle detection method used was the “Watershed Dispersion Segments” detection method. In analyzing such an SEM image by SPIP software, and unless otherwise indicated, particles having a diameter of greater than 8 ⁇ m and less than 100 ⁇ m in diameter were selected for analysis.
  • the SPIP software calculated the area (A) of a two-dimensional image of the particles and the perimeter length of the two-dimensional image of the particles to calculate circularity.
  • the SEM images of particles used for circularity calculations were individually examined to eliminate those for which the detected boundaries were incorrectly fused with other particles, occluded by other particles, or interrupted by the boundaries of the SEM photograph. In each analysis, unless otherwise stated, a sample of 10 or more particles were detected and subjected to this analysis to calculate circularity (C).
  • Pore Volume and Pore Volume Distribution Pore volumes of the clay heteroadducts are reported as the cumulative volume in cc/g (cm 3 /g, cubic centimeters per gram) of all pores discernable by nitrogen desorption methods.
  • the pore diameter distribution and pore volumes were calculated with reference to nitrogen desorption isotherm (assuming cylindrical pores) by the B.E.T. (or BET) technique as described by S. Brunauer, P. Emmett, and E. Teller in the J. Am. Chem. Soc., 1939, 60, 309; see also ASTM D 3037, which identifies the procedure for determining the surface area using the nitrogen BET method.
  • the pore volume distribution can be useful in understanding catalyst performance, and the pore volume (total pore volume), various attributes of pore volume distribution such as the percentage of pores in various size ranges, as well as “pore mode”, which describes the pore diameters corresponding to local maxima in the dV(log D) vs. pore diameter distribution, were derived from nitrogen adsorption-desorption isotherms based on the method described by E. P. Barrett, L. G. Joyner and P. P. Halenda (“BJH”), in “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.
  • Catalyst Preparation The preparation of a supported metallocene polymerization catalyst for ethylene homopolymerization or ethylene- ⁇ -olefin copolymerization may be carried out as exemplified by the following procedure. In a glove box under a nitrogen atmosphere, 4 mL of heptanes was added to a charge vessel. A 75 mg portion of calcined clay heteroadduct was weighed out and the calcined material was then dispensed into this charge vessel.
  • This process was used for both ethylene homopolymerization and ethylene- ⁇ -olefin (e.g.1-hexene) copolymerization, therefore, from 0 mL to 140 mL of 1-hexene was also added to the sample cylinder via syringe.
  • the sample cylinder was attached to a 2 L autoclave, and the material inside was pushed into the autoclave through isobutane flow.
  • the charge vessel was also attached to a 2 L autoclave, and the material inside was pushed into the autoclave through ethylene flow.
  • Polymerization Reactions Unless otherwise indicated, ethylene polymerizations were conducted in a dry, 2 L stainless steel Parr autoclave reactor using 1 L of isobutane diluent. Prior to conducting a polymerization run, moisture was first removed from the reactor interior by pre-heating the reactor to at least 115°C under a dry nitrogen flow, which was maintained for at least 15 minutes. Stirring was provided by an impellor and MagnadriveTM with a set point of, for example, 600 rpm.
  • the post-contacted catalyst components that is the composition containing all the listed catalyst system components that were previously contacted to form the composition, were prepared in an inert atmosphere glove box under dry nitrogen and transferred to a catalyst charge tube or vessel as described above.
  • the catalyst charge vessel contents were then charged to the reactor by flushing them in with 1 L of isobutane.
  • the reactor temperature control system was then turned on and is allowed to reach a few degrees lower than the temperature set-point, which typically took about 7 minutes.
  • the reactor was brought to run pressure by opening a manual feed valve for the ethylene, and polymerization runs were continued for 1 hour to provide the polymer and data in Tables 1-3.
  • the selected pressure and temperature in the reactor for calculating activities in Tables 1-3 were 350 total psi (0.3 psi H 2 and sufficient ethylene for 350 psi total) and 80°C.
  • a pre-mixed gas feed tank (“mixtank”) of purified hydrogen and ethylene (0.3 psi H2 and sufficient ethylene for 700 psi total) was used to maintain the desired total reactor pressure, with a large enough volume and a high enough pressure in the feed tank so as not to significantly change the ratio of ethylene- to-hydrogen in the feed to the reactor.
  • the contents of the catalyst charge tube can be pushed into the reaction vessel with ethylene at several degrees below the set point temperature of the run, for example, about 10 degrees centigrade below the set point temperature.
  • Polymer melt indices specifically, melt index (MI) and high load melt index (HLMI), were obtained after stabilization of the polymer with butylated hydroxytoluene (BHT) according to ASTM procedures D618-05 and D1238-04C. Polymer density was measured according to ASTM D1505-03. Tables 1-3 also report surface area and porosity properties of comparative supports and inventive heterocoagulated clay supports.
  • MI melt index
  • HLMI high load melt index
  • heterocoagulation agent(s) and the drying conditions for the various support-activator types, including calcined, heterocoagulated [1] clay- aluminum chlorohydrate (ACH) support-activators, [2] clay-ACH-surfactant support- activators, and [3] clay-surfactant support-activators.
  • ACH clay- aluminum chlorohydrate
  • clay-ACH-surfactant support- activators calcined, heterocoagulated [1] clay- aluminum chlorohydrate (ACH) support-activators
  • [2] clay-ACH-surfactant support- activators for the various support-activator types, including calcined, heterocoagulated [1] clay- aluminum chlorohydrate (ACH) support-activators, [2] clay-ACH-surfactant support- activators, and [3] clay-surfactant support-activators.
  • the specific Example number of the support used in each polymerization run is listed.
  • Catalyst and Polymer Characterization The 1 H NMR spectra of metallocene compounds were collected at room temperature by placing
  • the 13 C NMR spectra were acquired on a Bruker AVANCETM 400 NMR (100.61 MHz, 90° pulse, 12 s delay between pulse). About 5000 transients were stored for each spectrum, and the mmmm pentad peak (21.09 ppm) was used as reference.
  • the microstructure analysis was carried out as described by Busico, et al., Macromolecules, 1994, 27, 4521-4524.
  • the polypropylene Melt Flow Rate (MFR) was determined at 230°C under the load of 2.16 kg according to ASTM D-1238 procedure. Polypropylene melting temperature Tm was obtained according to ASTM D- 3417 procedure using DSC and TA Instrument, Inc. Model: DSC Q1000.
  • Table 1 presents the properties and polymerization data for clay-aluminum chlorohydrate (ACH) heterocoagulates prepared in the absence of a surfactant, dried by either an azeotroping or non-azeotroping process, and which have been calcined to form the clay- ACH support-activators.
  • Table 2 data illustrate embodiments of the present disclosure.
  • the addition of surfactant to a clay dispersion in water and evaporation of the aqueous slurry, without the addition of azeotroping agents (such as 1-butanol, 1-propanol, or other organic solvents), and subsequent calcination of the clay-heteroadduct produces support- activators with substantial BJH porosities relative to the calcined clay prepared under analogous conditions without the surfactant species.
  • Table 3 sets out the properties and polymerization data for spray-dried, calcined, heterocoagulated [1] clay-aluminum chlorohydrate (ACH) support-activators, [2] clay-ACH-surfactant support-activators, and [3] clay-surfactant support-activators.
  • the polymerizations were performed at 350 psi reactor pressure and 80°C, using ( ⁇ 5 -1-n-butyl-3- methyl-cyclopentadienyl)2ZrCl2 as metallocene and triethylaluminum (AlEt3) as co-catalyst, and 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.
  • Table 4 compares the polymer particle size distribution properties of polyethylene homopolymer produced using [1] a comparative azeotroped clay-aluminum chlorohydrate (ACH) heteroadduct support-activator produced in the absence of a surfactant, [2] a support-activator produced by spray-drying an isolated clay-aluminum chlorohydrate (ACH) heteroadduct in the presence of a tetrabutylammonium bromide surfactant, and [3] a support-activator produced by spray-drying an isolated clay-aluminum chlorohydrate (ACH) heteroadduct in the presence of a tetraoctylammonium bromide surfactant, as described herein.
  • ACH comparative azeotroped clay-aluminum chlorohydrate
  • Table 5 compares the average particle circularities obtained from SEM image analysis of various clay-support-activator samples using Scanning Probe Image Processor (SPIP) image analysis of the calcined support-activators.
  • the Table 5 circularity data are based on the image analysis of the samples illustrated in FIG.31 through FIG.36, and include: non-spray-dried, calcined support-activators formed from the combination of clay and aluminum chlorohydrate in an aqueous slurry (FIG.31 and FIG.32); non-spray- dried, calcined support-activator formed from combination of clay and tetrabutylammonium bromide in an aqueous slurry (FIG.33); and spray-dried, calcined support-activators formed from combination of clay and tetrabutylammonium bromide in an aqueous slurry (FIG.33 through FIG.36).
  • the spray-dried particles depicted in FIG.33 through FIG.36 exhibit substantially higher circularity and a larger proportion of 8-100 ⁇ m diameter particles as compared to those of FIG.31 through FIG.33 which were not spray-dried.
  • Table 6 compares the mean volume-weighted sphericities (SPHT3), the mean number-weighted sphericities (SPHT0), and the particle size data obtained from the CAMSIZER® analysis of polymer powder samples prepared from metallocene-catalyzed ethylene-1-hexene co-polymerizations using various calcined clay-support-activators.
  • the Table 6 mean sphericities are derived from the sphericity versus particle size plots in FIG.37 through FIG.40.
  • FIG.37 polymer data in Table 6 was derived using the support- activator of Example 2-A1 (azeotroped clay-aluminum chlorohydrate heteroadduct).
  • the FIG.38 polymer data in Table 6 was derived using the support-activator of Example 30-E2 (clay-tetrabutylammonium bromide heteroadduct, non-azeotroped and rotary evaporated).
  • the FIG.39 and FIG.40 polymer data in Table 6 were derived using the support-activator of Example 31 (large-scale preparations and spray drying of a clay-tetrabutylammonium bromide composite in the absence of a cationic polymetallate).
  • Table 6 shows that the spray- dried particles analyzed in FIG.39 and FIG.40 exhibit substantially higher volume-weighted average SPHT3 sphericities as compared to those of FIG.37 and FIG.38 which were not spray-dried.
  • Table 7 compares the mean volume-weighted sphericities (SPHT3), the mean number-weighted sphericities (SPHT0), and the particle size data for polymer particles, obtained from the CAMSIZER® analysis of ethylene-1-hexene co-polymer powder samples prepared using the calcined both sieved and unsieved support-activators prepared according to Example 31.
  • SPHT3 mean volume-weighted sphericities
  • SPHT0 mean number-weighted sphericities
  • This support-activator is a spray-dried (non-azeotroped) clay- tetrabutylammonium bromide heteroadduct prepared in the absence of a cationic polymetallate.
  • the Table 7 compares polymer particle data prepared using the non-sieved support-activator of Example 31, versus polymer data prepared using different size-range portions of this support-activator (Examples 33-35). In these examples, a clay heteroadduct was prepared and spray-dried as set out in Example 31, then sieved to provide more narrow size ranges of clay heteroadduct.
  • CAMSIZER® analysis data in Table 7 include data for polymer prepared from the unsieved Example 31 clay heteroadduct, and polymers obtained from support-activator particles captured between sieves having the openings of the following sizes: [1] between sieves with 19 ⁇ m (micron) and 37 ⁇ m openings (Example 33 and FIG.43), [2] between 37 ⁇ m and 50 ⁇ m opening sieves (Example 34 and FIG.45), and [3] between 50 ⁇ m and 74 ⁇ m opening sieves (Example 35 and FIG.47).
  • Samples designated “azeotroped” were dried from a slurry of water and 1-butanol azeotroping agent by rotary evaporation and were not spray-dried. Samples designated “non-azeotroped” or “not azeotroped” with no addional information were dried from a slurry of water in the absence of an azeotroping agent such as 1-butanol, by rotary evaporation and also were not spray-dried. Samples designated as “spray-dried” were spray-dried from a water-only suspension. Table 1.
  • C Drying was carried out by (i) azeotropically drying from a 1-butanol/water slurry (rotary evaporator), or (ii) non-azeotropically drying from an aqueous-only slurry (rotary evaporator).
  • D ACH component 1.75 mmol Al/g clay.
  • E ACH component 1.54 mmol Al/g clay.
  • ACH clay-aluminum chlorohydrate
  • a Polymerizations were performed at 350 psi reactor pressure and 80°C, using ( ⁇ 5 -1-n- butyl-3-methyl-cyclopentadienyl)2ZrCl2 and triethylaluminum (AlEt3) as metallocene and co-catalyst.
  • C Percentages are weight percents relative to the clay; ACH component, 1.54 mmol Al/g clay. Drying was carried out by non-azeotropically drying from an aqueous-only slurry (rotary evaporator). Table 3.
  • a Polymerizations were performed at 350 psi reactor pressure and 80°C, using ( ⁇ 5 -1-n- butyl-3- methyl-cyclopentadienyl) 2 ZrCl 2 and triethylaluminum (AlEt 3 ) as metallocene and co- catalyst.
  • C Drying was carried out by spray-drying from an aqueous slurry in the absence of an azeotroping agent. Table 4.
  • ACH azeotroped clay-aluminum chlorohydrate
  • a A Polymerizations were performed at 350 psi reactor pressure and 80°C, using ( ⁇ 5 -1-n- butyl-3-methyl-cyclopentadienyl)2ZrCl2 and triethylaluminum (AlEt3) as metallocene and co-catalyst.
  • B ACH aluminum chlorohydrate. Drying was carried out by (i) azeotropically drying from a 1-butanol/water slurry (rotary evaporator), or (ii) spray-drying from an aqueous slurry in the absence of an azeotroping agent.
  • Drying was carried out by (i) azeotropically drying from a 1-butanol/water slurry (rotary evaporator), (ii) non-azeotropically drying from an aqueous-only slurry (rotary evaporator), or (iii) spray-drying from an aqueous slurry in the absence of an azeotroping agent.
  • E Clay-heterocoagulates used in Run Nos.4 and 5 were produced under different spray-drying conditions within the ranges of Example 32.
  • A,B A Polymerizations were performed at 350 psi reactor pressure and 80°C, using ( ⁇ 5 -1- n-butyl-3-methyl-cyclopentadienyl)2ZrCl2 and triethylaluminum (AlEt3) as metallocene and co-catalyst, with 140 mL of 1-hexene introduced to the sample cylinder.
  • B Data obtained from CAMSIZER® X2 Dynamic Image Analyzer.
  • Drying was carried out by (i) azeotropically drying from a 1-butanol/water slurry (rotary evaporator), (ii) non-azeotropically drying from an aqueous-only slurry (rotary evaporator), or (iii) spray-drying from an aqueous slurry in the absence of an azeotroping agent.
  • E Clay-heterocoagulates used in Run Nos.3 and 4 were produced under different spray-drying conditions within the ranges of Example 31.
  • A,B A Polymerizations were performed at 350 psi reactor pressure and 80°C, using ( ⁇ 5 -1- n-butyl-3-methyl-cyclopentadienyl)2ZrCl2 and triethylaluminum (AlEt3) as metallocene and co-catalyst, with 140 mL of 1-hexene introduced to the sample cylinder.
  • B Obtained from CAMSIZER® X2 Dynamic Image Analyzer.
  • C Drying was carried out by spray-drying from an aqueous slurry in the absence of an azeotroping agent.
  • D The lower number is the sieve size opening which captured the spray-dried clay- heteroadduct sample, and the upper number is the larger sieve size opening which allowed the spray-dried clay-heteroadduct sample to pass through.
  • EXAMPLE 1 Preparation of a colloidal clay dispersion To a Waring® blender was charged 570 grams (g) of deionized Milli-Q® water, and with stirring, 30.0 g of Volclay® HPM-20 was added portion-wise. This mixture was stirred at a high rate (high revolutions per minute, rpm) to afford a substantially lump or clump-free, 5 wt.% (weight percent) dispersion or suspension of HPM-20 clay in water.
  • the filtrate pH and conductivity were measured (Eutech PCSTestr 35), to provide a pH of 6.1 and a conductivity of 1516 ⁇ S/cm.
  • the filtrate was discarded, and the remaining wet solid was re-suspended in 50 to 100 mL of deionized Milli-Q® water.
  • This filtration process of suspension of wet solid in deionized Milli-Q® water, vacuum filtration, and filtrate pH/conductivity measurement was repeated once more.
  • the remaining wet solid was then re-suspended in 150 to 200 mL of 1-butanol and rotary evaporated at 45°C.
  • the filtrate pH and conductivity were measured (Eutech PCSTestr 35), to provide a conductivity of 2640 ⁇ S/cm.
  • the filtrate was discarded, and the remaining wet solid was re-suspended in 50 to 100 mL of deionized Milli-Q® water.
  • the filtration process (suspension of wet solid in deionized Milli-Q® water, vacuum filtration, and filtrate pH/conductivity measurement) was repeated twice more. The remaining wet solid was then re-suspended in 400 mL of 1-butanol and rotary evaporated at 45°C.
  • the dispersion was blended at high speed for 5-10 minutes to obtain a slightly viscous mixture of 5 wt.% aqueous dispersion of HPM-20.
  • a 100 g portion of this 5 wt.% aqueous dispersion of HPM-20 was transferred into a Waring® blender, and 1.66 g of GEO aluminum chlorohydrate 50 wt.% aqueous solution was pipetted into a vial and was added all at once to the dispersion.
  • the mixture coagulated rapidly, and 80 mL of deionized Milli-Q® water was added in order to facilitate stirring.
  • the mixture was then blended at high speed for 5 minutes, then suction filtered through Fisherbrand TM P8 Qualitative-Grade Filter Paper (coarse porosity). After allowing 15-30 minutes for the filtration, the filtrate pH and conductivity were measured (Eutech PCSTestr 35), to provide a pH of 6.2 and a conductivity of 1518 ⁇ S/cm. The filtrate was then discarded and the remaining wet solid was re-suspended in 50-100 mL of deionized Milli-Q® water.
  • the filtration process (suspension of wet solid in deionized Milli-Q® water, suction filtration, filtrate pH/conductivity measurement) was repeated until the conductivity of the re-suspended slurry reached 100-300 ⁇ S/cm. In this case, two of these filtration cycles were performed to obtain a slurry with a pH of 6.1 and a conductivity of 199 ⁇ S/cm.
  • the remaining wet solid was re-suspended in 150-200 mL of 1-butanol and rotary evaporated at 45 °C. The resulting solid was ground in a mortar and pestle to obtain 3.19 g of a light grey powder.
  • the mixture was then stirred at a high rate (rpm) for an additional 5-10 minutes, subsequently vacuum filtered through Fisherbrand TM P8 Qualitative-Grade Filter Paper (coarse porosity), and washed with an additional 100 g of Milli-Q® deionized water. The filtrate was then discarded, and the remaining wet solid was re-suspended in 50 to 100 mL of deionized Milli-Q® water to form a slurry.
  • the slurry conductivity was measured as 820 ⁇ S (microsiemens)uS/cm using a Eutech PCSTestr 35.
  • Example of a non-azeotroped clay-aluminum chlorohydrate (ACH)- surfactant (tetraoctylammonium bromide) composite A Waring® blender was charged with 200 g of the colloidal clay dispersion (5 wt.% clay) prepared according to Example 1, followed by, with stirring, 4 g (2 wt.%) of tetraoctylammonium bromide followed by 3.29 g of 50 % GEO aluminum chlorhydrate solution with reported basicity of 83.47% and. A 50 mL porition of deionized water was added to enable continued stirring of the mixture.
  • ACH non-azeotroped clay-aluminum chlorohydrate
  • the mixture was stirred at a high rate (rpm) for an additional 5-10 minutes, and subsequently vacuum filtered through Fisherbrand TM P8 Qualitative-Grade Filter Paper (coarse porosity). After allowing 15 to 30 minutes for the filtration, the filtrate conductivity was measured as 1325 ⁇ S/cm using a Eutech PCSTestr 35. The filtrate was discarded, and the remaining wet solid was re-suspended in 50 mL of deionized Milli-Q® water to form a slurry. The slurry conductivity was measured as 290 ⁇ S/cm (Eutech PCSTestr 35).
  • ACH clay-aluminum chlorohydrate
  • a Waring® blender containing 570 g of deionized Milli-Q® water while stirring at low speed to afford a grey colloidal dispersion containing no or substantially no visible lumps or clumps.
  • the dispersion was blended at high speed for 5 to 10 minutes to obtain a slightly viscous mixture of 5 wt.% aqueous dispersion of HPM-20 clay.
  • a 200 g portion of this 5 wt.% aqueous dispersion of HPM-20 clay was transferred into a Waring® blender, and 3.295 g of 50 wt% aluminum chlorhydrate from GEO, and 1 g of trihexyltetradecylphosphonium bromide (0.18 mmol cation/g clay) was added all at once to the dispersion.
  • the dispersion conductivity was measured as 1340 ⁇ S/cm.
  • a 100 mL portion of deionized Milli-Q® water was added to this dispersion, and the mixture was subsequently filtered.
  • Example of a non-azeotroped clay-aluminum chlorohydrate (ACH)- dextrose composite A Waring® blender was charged with 200 g of the colloidal clay dispersion (5 wt.% clay) prepared according to Example 1, followed by, with stirring, 4 g of dextrose and 3.29 g of 50 % GEO aluminum chlorhydrate solution with reported basicity of 83.47% and 4 g of dextrose. The mixture coagulated rapidly, and 100 mL of deionized water was added to enable continued stirring of the mixture. Following these additions, the mixture was stirred at a high rate (rpm) for an additional 5-10 minutes, and subsequently vacuum filtered through Fisherbrand TM P8 Qualitative-Grade Filter Paper (coarse porosity.
  • Example of non-azeotroped, clay-tetramethylammonium bromide composite in the absence of a cationic polymetallate (1.69 mmol cation/g clay) A Waring® blender was charged with 100 g of the colloidal clay dispersion (5 wt.% clay) prepared according to Example 1, followed by, with stirring, 1.3 g of tetramethylammonium bromide. The mixture coagulated rapidly, and 100 mL of deionized water was added to enable continued stirring of the mixture. After these additions were performed, the mixture was stirred at a high rate (rpm) for an additional 5- 10 minutes, and subsequently vacuum filtered through Fisherbrand TM P8 Qualitative- Grade Filter Paper (coarse porosity).
  • the filtrate conductivity was measured as 98 ⁇ S/cm using a Eutech PCSTestr 35.
  • the filtrate was discarded, and the remaining wet solid was re-suspended in 50 to 100 mL of deionized Milli-Q® water to form a slurry.
  • This slurry was rotary evaporated to dryness, and the resulting solid was ground with a mortar and pestle to obtain 2.73 g of a powder.
  • the powder was charged to a porcelain crucible and calcined for 6 hours at 300 °C.
  • the calcined material was cooled down under vacuum and weighed in a glove box under an inert atmosphere to provide 2.4 g of calcined powder.
  • EXAMPLE 10-B Example of a non-azeotroped, clay-tetramethylammonium bromide composite in the absence of a cationic polymetallate (2.60 mmol cation/g clay) A Waring® blender was charged with 200 g of the colloidal clay dispersion (5 wt.% clay) prepared according to Example 1, followed by, with stirring, 4 g of tetramethylammonium bromide. The mixture coagulated rapidly, and 100 mL of deionized water was added to enable continued stirring of the mixture.
  • EXAMPLE 11-B6 Example of a non-azeotroped, clay-tetramethylammonium bromide composite in the absence of a cationic polymetallate (3.38 mmol cation/g clay) A Waring® blender was charged with 100 g of the colloidal clay dispersion (5 wt.% clay) prepared according to Example 1, followed by, with stirring, 2.6 g of tetramethylammonium bromide. The mixture coagulated rapidly, and 100 mL of deionized water was added to enable continued stirring of the mixture.
  • the mixture was stirred at a high rate (rpm) for an additional 5- 10 minutes, and subsequently vacuum filtered through Fisherbrand TM P8 Qualitative- Grade Filter Paper (coarse porosity). After allowing 15 to 30 minutes for the filtration, the filtrate was discarded, and the remaining wet solid was re-suspended in 50 to 100 mL of deionized Milli-Q® water to form a slurry. This slurry was rotary evaporated to dryness, and the resulting solid was ground with a mortar and pestle to obtain 3.22 g of a powder. The powder was charged to a porcelain crucible and calcined for 6 hours at 300 °C.
  • the mixture was stirred at a high rate (rpm) for an additional 5- 10 minutes, and subsequently vacuum filtered through Fisherbrand TM P8 Qualitative- Grade Filter Paper (coarse porosity). After allowing 15 to 30 minutes for the filtration, the filtrate conductivity was measured as 142 ⁇ S/cm using a Eutech PCSTestr 35. The filtrate was discarded, and the remaining wet solid was re-suspended in 50 to 100 mL of deionized Milli-Q® water to form a slurry. This slurry was rotary evaporated to dryness, and the resulting solid was ground with a mortar and pestle to obtain 2.69 g of a powder.
  • Example of a non-azeotroped, clay-tetrabutylammonium bromide composite in the absence of a cationic polymetallate (0.62 mmol cation/g clay) A Waring® blender was charged with 200 g of the colloidal clay dispersion (5 wt.% clay) prepared according to Example 1, followed by, with stirring, 2 g of tetrabutylammonium bromide (1 wt.% relative to dispersion).
  • the mixture coagulated rapidly, and 150 mL of deionized water was added to enable continued stirring of the mixture. After these additions were performed, the mixture was stirred at a high rate (rpm) for an additional 5-10 minutes, and subsequently vacuum filtered through Fisherbrand TM P8 Qualitative-Grade Filter Paper (coarse porosity). After allowing 15 to 30 minutes for the filtration, the filtrate was then discarded, and the remaining wet solid was re-suspended in 50 mL of deionized Milli-Q® water to form a slurry. The slurry conductivity was measured as 105 ⁇ S/cm using a Eutech PCSTestr 35.
  • Example of a non-azeotroped, clay-2 wt.% tetrabutylammonium bromide composite in the absence of a cationic polymetallate (1.24 mmol cation/g clay) A Waring® blender was charged with 200 g of the colloidal clay dispersion (5 wt.% clay) prepared according to Example 1, followed by, with stirring, 4 g of tetrabutylammonium bromide. The mixture coagulated rapidly, and 200 mL of deionized water was added to enable continued stirring of the mixture.
  • the mixture was stirred at a high rate (rpm) for an additional 5- 10 minutes, and subsequently vacuum filtered through Fisherbrand TM P8 Qualitative- Grade Filter Paper (coarse porosity). After allowing 15 to 30 minutes for the filtration, the filtrate’s conductivity was measured as 1325 ⁇ S/cm using a Eutech PCSTestr 35. The filtrate was then discarded, and the remaining wet solid was re-suspended in 50 mL of deionized Milli-Q® water to form a slurry. The slurry conductivity was measured as 350 ⁇ S/cm using a Eutech PCSTestr 35.
  • Example of a non-azeotroped, clay-3 wt.% tetrabutylammonium bromide composite in the absence of a cationic polymetallate (1.86 mmol cation/g clay) A Waring® blender was charged with 200 g of the colloidal clay dispersion (5 wt.% clay) prepared according to Example 1, followed by, with stirring, 6 g of tetrabutylammonium bromide. The mixture coagulated rapidly, and 100 mL of deionized water was added to enable continued stirring of the mixture.
  • the mixture was stirred at a high rate (rpm) for an additional 5- 10 minutes, and subsequently vacuum filtered through Fisherbrand TM P8 Qualitative- Grade Filter Paper (coarse porosity). The filtrate was then discarded, and the remaining wet solid was re-suspended in 50 mL of deionized Milli-Q® water to form a slurry.
  • the slurry conductivity was measured as 700 ⁇ S/cm using a Eutech PCSTestr 35. A 40 g portion of this slurry was combined with 50 mL water and rotary evaporated at 50 °C to dryness, and the resulting solid was ground with a mortar and pestle to a uniform powder.
  • EXAMPLE 16-B11 Example of a non-azeotroped, clay-4 wt.% tetrabutylammonium bromide composite in the absence of a cationic polymetallate (2.48 mmol cation/g clay) A Waring® blender was charged with 200 g of the colloidal clay dispersion (5 wt.% clay) prepared according to Example 1, followed by, with stirring, 8 g of tetrabutylammonium bromide.
  • Example of a non-azeotroped, clay-2 wt.% tetraoctylammonium bromide composite, absent a cationic polymetallate (0.73 mmol cation/g clay) A Waring® blender was charged with 200 g of the colloidal clay dispersion (5 wt.% clay) prepared according to Example 1, followed by, with stirring, 4 g of tetraoctylammonium bromide. After this addition was performed, the mixture was stirred at a high rate (rpm) for an additional 5-10 minutes, and subsequently vacuum filtered through Fisherbrand TM P8 Qualitative-Grade Filter Paper (coarse porosity). The filtration took approximately 5 hours.
  • Example of a non-azeotroped, clay-3 wt.% tetraoctylammonium bromide composite, absent a cationic polymetallate (1.10 mmol cation/g clay) A Waring® blender was charged with 100 g of the colloidal clay dispersion (5 wt.% clay) prepared according to Example 1, followed by, with stirring, 3 g of tetraoctylammonium bromide. After this addition was performed, the mixture was stirred at a high rate (rpm) for an additional 5-10 minutes, and subsequently vacuum filtered through Fisherbrand TM P8 Qualitative-Grade Filter Paper (coarse porosity). The filtration was carried out overnight.
  • Example of a non-azeotroped, clay-4 wt.% tetraoctylammonium bromide composite, absent a cationic polymetallate (1.46 mmol cation/g clay) A Waring® blender was charged with 100 g of the colloidal clay dispersion (5 wt.% clay) prepared according to Example 1, followed by, with stirring, 4 g of tetraoctylammonium bromide. After this addition was performed, the mixture was stirred at a high rate (rpm) for an additional 5-10 minutes, and subsequently vacuum filtered through Fisherbrand TM P8 Qualitative-Grade Filter Paper (coarse porosity). The filtration was carried out overnight.
  • Comparative example of a large-scale preparation and spray drying of a clay-aluminum chlorohydrate (ACH) heteroadduct wet cake A 5 wt.% dispersion of HPM-20 in deionized water was prepared, and a 600 g portion of this dispersion was added, with stirring, to 9.885 g 50% aluminum chlorohydrate (ACH) solution (GEO). The mixture coagulated rapidly, and 50-100 mL of deionized water was added to enable continued stirring of the mixture.
  • ACH clay-aluminum chlorohydrate
  • Example of a large-scale preparation and spray drying of a clay-etramethylammonium bromide composite wet cake, absent a cationic polymetallate A 355 g sample of a 5 wt.% dispersion of HPM-20 in deionized water was prepared and stirred, and 9.25 g of tetramethylammonium bromide solid was added tohe stirred slurry. The mixture coagulated rapidly, and 50-100 mL of deionized water was added to enable continued stirring of the mixture.
  • Example of a large-scale preparation and spray drying of a clay-etrabutylammonium bromide composite wet cake, absent a cationic polymetallate A 600 g sample of a 5 wt.% dispersion of HPM-20 in deionized water was prepared and stirred, and 12 g tetrabutylammonium bromide solid was added to the stirred slurry. The mixture coagulated rapidly, and 50-100 mL of deionized water was added to enable continued stirring of the mixture. After these additions were performed,he mixture was stirred at a high rate (rpm) for an additional 5-10 minutes, and subsequently vacuum filtered through FisherbrandTM P8 Qualitative-Grade Filter Paper (coarse porosity).
  • Example 23-E3 Example of the preparation and spray-drying of a clay-aluminum chlorohydrate (ACH)-tetrabutyl ammonium bromide composite by adding the surfactant tohe spray-drying feed A Waring® blender was charged with 800 g of the colloidal clay dispersion (5 wt.% clay) prepared according to Example 1, followed by, with stirring, 13.18 g of 50 % aluminum chlorhydrate solution (GEO).
  • ACH clay-aluminum chlorohydrate
  • GEO aluminum chlorhydrate solution
  • Example of the preparation and spray-drying of a clay-aluminum chlorohydrate (ACH)-tetraoctyl ammonium bromide composite by adding the surfactant tohe spray-drying feed A Waring® blender was charged with 800 g of the colloidal clay dispersion (5 wt.% clay) prepared according to Example 1, followed by, with stirring, 13.18 g of 50 % aluminum chlorhydrate solution (GEO). The mixture coagulated rapidly, and 200 mL Milli-Q® deionized water was added to enable continued stirring of the mixture.
  • ACH clay-aluminum chlorohydrate
  • a cationic polymetallate (1.24 mmol cation/g clay)
  • 30 g of Volclay® HPM-20 clay was added slowly over the course of 1 to 2 minutes into a Waring® blender containing 570 g of deionized Milli-Q® water while stirring at low speed to afford a grey colloidal dispersion containing no or substantially no visible lumps or clumps.
  • the dispersion was blended at high speed for 5 to 10 minutes to obtain a slightly viscous mixture of 5 wt.% aqueous dispersion of HPM-20 clay.
  • the dispersion was blended at high speed for 5 to 10 minutes to obtain a slightly viscous mixture of 5 wt.% aqueous dispersion of HPM-20 clay.
  • a 100 g portion of this 5 wt.% aqueous dispersion of HPM-20 clay wasransferred into a Waring® blender, and 1.65 g of dodecylammonium bromide was added all at once to the dispersion. Immediate coagulation was observed, and 70 g of deionized Milli-Q® water was added to improve blending. The mixture was filtered over 15-30 minutes, and an additional 100g of deionized Milli-Q® water was added during the filtration.
  • a cationic polymetallate (1.24 mmol cation/g clay)
  • 30 g of Volclay® HPM-20 clay was added slowly over the course of 1 to 2 minutes into a Waring® blender containing 570 g of deionized Milli-Q® water while stirring at low speed to afford a grey colloidal dispersion containing no or substantially no visible lumps or clumps.
  • the dispersion was blended at high speed for 5 to 10 minutes to obtain a slightly viscous mixture of 5 wt.% aqueous dispersion of HPM-20 clay.
  • the dispersion was blended at high speed for 5 to 10 minutes to obtain a slightly viscous mixture of 5 wt.% aqueous dispersion of HPM-20 clay.
  • a 100 g portion of this 5 wt.% aqueous dispersion of HPM-20 clay wasransferred into a Waring® blender, and 607 mg of ammonium bromide was added all at once to the dispersion. No significant coagulation was observed.
  • This mixture was dried on a rotovap at 50 °C, and the resulting solid was then ground with a mortar and pestle to obtain 1.86 g of a light grey powder.
  • the dispersion was blended at high speed for 5 to 10 minutes to obtain a slightly viscous mixture of 5 wt.% aqueous dispersion of HPM-20 clay.
  • a 100 g portion of this 5 wt.% aqueous dispersion of HPM-20 clay wasransferred into a Waring® blender, and 1214 mg of ammonium bromide was added all at once to the dispersion. No significant coagulation was observed.
  • This mixture was dried on a rotovap at 50 °C, and the resulting solid was then ground with a pestle and mortar to obtain 1.86 g of a light grey powder.
  • EXAMPLE 30-E2 Large-scale preparation and non-azeotroped drying of a clay-etrabutylammonium bromide composite wet cake, absent a cationic polymetallate A 10 kg sample of a 5 wt.% dispersion of HPM-20 in deionized water was prepared and stirred, and 200 g tetrabutylammonium bromide solid was added to the stirred slurry. The mixture was stirred using a drill with paint mixer attachment, and allowed to coagulate overnight.
  • the mixture was pressure homogenized at around 800 to 1200 psi, with the end product mixture having a solids content of about 3 wt% to 6 wt%.
  • This feed was introduced to a spray dryer using a rotary atomizer, with the following settings: drying N2 gas flow rate 100 kg/hr; inletemperature 220 °C; rotary atomizer speed was selected in the range of 17,000-35,000 RPM; feed rate was selected in the range of 4.5-6.0 kg/hr. Approximately 150 to 390 g of spray-dried powder were obtained from multiple spray drying runs under the stated conditions. EXAMPLE 32.
  • the mixture was pressure homogenized at around 800 to 1200 psi, with the end product mixture having a solids content of about 3 wt% to 6 wt%.
  • This feed was introduced to a spray dryer using a rotary atomizer, with the following settings: drying N2 gas flow rate, 100 kg/hr; inletemperature 220 °C; rotary atomizer speed was selected in the range of 30,000-35,000 RPM; feed rate was selected in the range of 5.4-5.5 kg/hr. Approximately 120 g to 150 g of spray-dried powder were obtained from multiple spray drying runs under the stated conditions. EXAMPLE 33.
  • a 17 g sample of the spray-dried clay-tetrabutylammonium bromide heteroadduct prepared according to Example 31 was added to the 74 micron sieve. After 45 minutes of shaking,he material on the sieve with 19 micron openings was collected, yielding 0.700 of a powder. This 19-37 ⁇ m sample was used to prepare a polymerization catalyst, which washen used to prepare an ethylene-1-hexene copolymer as described herein in the Catalyst Preparation and Polymerization Reactions sections of the Examples. The resulting polymer was characterized as shown in Table 7. EXAMPLE 34.
  • a 17 g sample of the spray-dried clay-tetrabutylammonium bromide heteroadduct prepared according to Example 31 was added to the 74 micron sieve. After 45 minutes of shaking,he material on the sieve with 50 micron openings was collected, yielding 3.29 of a powder.
  • This 50-74 ⁇ m sample was used to prepare a polymerization catalyst, which washen used to prepare an ethylene-1-hexene copolymer as described herein in the Catalyst Preparation and Polymerization Reactions sections of the Examples.
  • the resulting polymer was characterized as shown in Table 7.
  • Table 8 illustrates some actual or constructive examples of componentshat can be selected and used to prepare the clay composite support-activator, and additional components that can be selected and used in combination with the support- activator to generate the olefin polymerization catalyst. Any one or more than one of the compounds or compositions set out in each component listing can be selectedndependently of any other compound or composition set out in any other componentisting.
  • this table discloses that any one or more than one of Component 1, any one or more than one of Component 2, optionally any one or more than one of Component A, and optionally any one or more than one of Component B, can be selectedndependently of each other and combined or contacted in any order to provide the heterocoagulated clay support-activator, as disclosed herein.
  • Any one or more than one of Component 3 (metallocene), optionally any one or more than one of Component C, and optionally any one or more than one of Component D can be selected independently of each other and combined or contacted in any order with each other and the heterocoagulated clay support-activator to provide an olefin polymerization catalyst, as disclosed herein.
  • Table 8 Actual and constructive examples of components that can be selected ndependently and used to prepare a clay composite support-activator and an olefin polymerization catalyst.
  • TEA triethylaluminum
  • TnOA tri-n-octylaluminum
  • TiBA triisobutylaluminum
  • MAO methylaluminoxane
  • EAO ethylaluminoxane
  • groups such as “hydrocarbyl” or “Si-containing hydrocarbyl” groups may be considered to have from 1 to about 12 carbons, such as for example, methyl, n-propyl, phenyl, trimethylsilylmethyl, neopentyl, and the like.
  • each group or substituent is selected indepdendently of any other group of substituent. Therefore, each “R” substituent is selected independently of any other R substituent, each “Q” group is selected independently of any other Q group, and the like.
  • the co-catalyst component is referred to as optional (Optional Component C), and includes alkylating agents, hydriding agents andhe like.
  • a co-catalyst component such as those listed is typically used in the formation ofhe polymerization catalyst because the metallocene is commonly halide-substituted andhe co-catalyst can provide a polymerization-activatable/initiating ligand such as methyl or hydride.
  • a support-activator comprising a smectite heteroadduct, the smectite heteroadduct comprising or consisting essentially of a contact product in a firstiquid carrier of: (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 to provide a slurry of the smectite heteroadduct in the first liquid carrier; wherein the contact product occurs or is: [i] in the absence of: [A] a cationic polymetallate; [B] a non-layered silicate, a soluble silicate (for example, sodium silicate), a charged inorganic component, a metal oxide, an organic amide, an anionic surfactant, an inorganic acid, an organic acid, an inorganic base, an organic base, an oxidizing agent,
  • a support-activator comprising a smectite heteroadduct, the smectite heteroadduct comprising or consisting essentially of a contact product in a firstiquid carrier of: (a) a colloidal smectite clay; and (b) a surfactant comprising or selected from a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or any combination thereof; wherein the first liquid carrier consists essentially of water, an organic liquid, or a combination thereof.
  • a firstiquid carrier of: (a) a colloidal smectite clay; and (b) a surfactant comprising or selected from a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or any combination thereof; wherein the first liquid carrier consists essentially of water, an organic liquid, or a combination thereof.
  • a support-activator comprising a smectite heteroadduct, the smectite heteroadduct comprising or consisting essentially of a contact product in a firstiquid carrier of: (a) a colloidal smectite clay; (b) a cationic polymetallate; and (c) a surfactant comprising or selected from a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or any combination thereof.
  • a non-layered silicate for example, sodium silicate
  • a soluble silicate for example, sodium silicate
  • anionic surfactant
  • Aspect 5 The support-activator according to any of the preceding Aspects, wherein the contact product comprises a slurry of the smectite heteroadduct inhe first liquid carrier.
  • Aspect 6 The support-activator according to any of the preceding Aspects, wherein the contact product comprises a slurry of the smectite heteroadduct inhe first liquid carrier from which the smectite heteroadduct is readily filterable accordingo the following criteria: (i) when filtration of a 2.0 wt.% aqueous slurry of the smectite heteroadduct isnitiated from 0 hours to 2 hours after the colloidal smectite clay and the surfactant formhe contact product, the proportion of a filtrate obtained at a filtration time of from 2 hourso 12 hours using either vacuum filtration or gravity filtration, based upon the weight ofhe first liquid carrier in the slurry of the smectite heteroadduct is in
  • Aspect 7 The support-activator according to any of the preceding Aspects, wherein the smectite heteroadduct is isolated from the first liquid carrier.
  • Aspect 8 The support-activator according to any of the preceding Aspects, wherein the smectite heteroadduct, upon calcination, provides the support- activator which imparts activity to a polymerization catalyst.
  • Aspect 9 The support-activator according to any of the preceding Aspects, wherein the smectite heteroadduct is spray-dryable from a suspension of the smectite heteroadduct in a dispersion medium.
  • the smectite heteroadduct further comprises the contact product of an anionic surfactant.
  • Aspect 11 The support-activator according to any of the preceding Aspects, wherein the smectite heteroadduct is spray-dryable from a suspension of the smectite heteroadduct in a dispersion medium to provide the support-activator in particulate form which, following calcination, is characterized by any one of, or any combination of, the following properties: (i) the smectite heteroadduct has an average particle sphericity of 0.65 or greater; (ii) the smectite heteroadduct has an average particle roundness of 0.65 or greater; and (iii) the smectite heteroadduct has an average particle circularity of 0.65 or greater.
  • a catalyst system for olefin polymerization comprising: (a) at least one metallocene compound; (b) at least one support-activator according to any of the preceding Aspects.
  • Aspect 13 The catalyst system according to Aspect 12, wherein the catalyst system further comprises: (c) at least one co-catalyst; (d) at least one co-activator; or a combination thereof.
  • Aspect 14 The catalyst system according to any of Aspects 12-13, wherein the catalyst system further comprises a fluid carrier.
  • a method of making a support-activator comprising a smectite heteroadduct comprising or consisting essentially of contacting 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 to provide a slurry of the smectite heteroadduct in the first liquid carrier; wherein the contacting step occurs: [i] in the absence of: [A] a cationic polymetallate; [B] a non-layered silicate, a soluble silicate (for example, sodium silicate), a charged inorganic component, a metal oxide, an organic amide, an anionic surfactant, annorganic acid, an organic acid, an inorganic base, an organic base, an oxidizing agent, or any combination thereof; [C] any one or any one or
  • a method of making a support-activator comprising a smectite heteroadduct comprising contacting 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 to provide a slurry of the smectite heteroadduct in the first liquid carrier; wherein the first liquid carrier consists essentially of water, an organic liquid, or a combination thereof.
  • a method of making a support-activator comprising a smectite heteroadduct comprising or consisting essentially of contacting in any order in a first liquid carrier: (a) a colloidal smectite clay; (b) a cationic polymetallate; and (c) 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 heteroadduct in the first liquid carrier.
  • the step of contacting the colloidal smectite clay, the cationic polymetallate, and the surfactant comprises: (a) adding the surfactant and adding the cationic polymetallate, simultaneously orn any order, to a mixture of the colloidal smectite clay in the first liquid carrier; or (b)(1) adding the cationic polymetallate to a mixture of the colloidal smectite clayn the first liquid carrier to form a smectite-cationic polymetallate heteroadduct, (2)solating the smectite-cationic polymetallate heteroadduct, and (3) re-suspending the smectite-cationic polymetallate heteroadduct in a dispersion medium into which the surfactant is added before, after, or during the re-suspending step.
  • Aspect 19 The method of making a support-activator according to any of Aspects 15-18, wherein the contacting step further comprises contacting the colloidal smectite clay or the smectite heteroadduct with an anionic surfactant, before, during, or after the colloidal smectite clay is contacted with the cationic surfactant, the nonionic surfactant, the amphoteric surfactant, or the combination thereof.
  • the contacting step further comprises contacting the colloidal smectite clay or the smectite heteroadduct with an anionic surfactant, before, during, or after the colloidal smectite clay is contacted with the cationic surfactant, the nonionic surfactant, the amphoteric surfactant, or the combination thereof.
  • Aspect 21 The method of making a support-activator according to any of Aspects 15-20, wherein the step of contacting the colloidal smectite clay with the surfactant and/or the cationic polymetallate occurs under high shear conditions.
  • Aspect 23 The method of making a support-activator according to any of Aspects 15-22, wherein the step of contacting the colloidal smectite clay and the surfactant comprises: the addition of the surfactant in solid or neat liquid form to a mixture of the colloidal smectite clay in the first liquid carrier; or the addition of a solution or a slurry of the surfactant to a mixture of the colloidal smectite clay in the first liquid carrier.
  • Aspect 24 The method of making a support-activator according to any of Aspects 15-22, wherein the step of contacting the colloidal smectite clay and the surfactant comprises: the addition of the surfactant in solid or neat liquid form to a mixture of the colloidal smectite clay in the first liquid carrier; or the addition of a solution or a slurry of the surfactant to a mixture of the colloidal smectite clay in the first liquid carrier.
  • Aspect 25 The method of making a support-activator according to any of Aspects 15-24, further comprising the steps of: (i) isolating the smectite heteroadduct from the slurry in the first liquid carrier.
  • Aspect 26 The method of making a support-activator according to Aspect 25, further comprising the step of: (ii) washing the smectite heteroadduct with water, an organic liquid, or a combination thereof.
  • Aspect 27 The method of making a support-activator according to Aspect 24, further comprising the step of: (iii) drying or calcining the smectite heteroadduct.
  • Aspect 28 The method of making a support-activator according to any of Aspects 15-24, further comprising the steps of: (i) isolating the smectite heteroadduct from the slurry in the first liquid carrier.
  • Aspect 26 The method of making a support-activator according to Aspect 25, further comprising the
  • the method of making a support-activator according to any of Aspects 25-27, wherein the step of isolating the smectite heteroadduct comprises or is selected from gravity filtering the slurry, vacuum filtering the slurry, subjecting the slurryo reduced pressure, heating the slurry, subjecting the slurry to rotary-evaporation, sparging a gas through the slurry, or any combination thereof.
  • Aspect 29 The method of making a support-activator according to any of Aspects 25-28, wherein the step of isolating the smectite heteroadduct comprises or is selected from filtering the slurry, evaporating the first liquid carrier from the slurry, or a combination thereof.
  • Aspect 30 The method of making a support-activator according to any of Aspects 25-27, wherein the step of isolating the smectite heteroadduct comprises or is selected from gravity filtering the slurry, vacuum filtering the s
  • Aspect 31 The method of making a support-activator according to any of Aspects 25-29, wherein the step of isolating the smectite heteroadduct comprises or is selected from evaporating the first liquid carrier from the slurry to which an organic liquid azeotroping reagent has been added.
  • Aspect 31 The method of making a support-activator according to any of Aspects 25-29, wherein the step of isolating the smectite heteroadduct is conducted in the absence of an azeotroping agent.
  • Aspect 32 The method of making a support-activator according to any of Aspects 25-29, wherein the step of isolating the smectite heteroadduct is conducted in the absence of an azeotroping agent.
  • Aspect 33 The method of making a support-activator according to any of Aspects 25-31, wherein the step of isolating the smectite heteroadduct is carried out without the use of ultrafiltration, centrifugation, or settling tanks.
  • Aspect 33 The method of making a support-activator according to any of Aspects 25-32, further comprising the step of re-suspending the smectite heteroadduct in water, an organic liquid, or a combination thereof to form a suspension, and evaporatinghe water from the suspension to isolate the smectite heteroadduct.
  • Aspect 34 The method of making a support-activator according to any of Aspects 25-31, wherein the step of isolating the smectite heteroadduct is carried out without the use of ultrafiltration, centrifugation, or settling tanks.
  • Aspect 35 The method of making a support-activator according to any of Aspects 25-34, further comprising the step of washing the smectite heteroadduct with water, an organic liquid, or a combination thereof.
  • Aspect 36 The method of making a support-activator according to any of Aspects 25-32, further comprising the step of re-suspending the smectite heteroadduct in water, an organic liquid, or a combination thereof to form a suspension, and filtering the suspension to isolate the smectite heteroadduct.
  • the method of making a support-activator according to Aspect 36 further comprising the step of measuring a conductivity of the suspension ofhe smectite heteroadduct in water, and if the conductivity is greater than 300 ⁇ S/cm, repeating the steps of washing the smectite heteroadduct and filtering the suspension to provide the washed smectite heteroadduct.
  • Aspect 38 The method of making a support-activator according to any of Aspects 25-37, further comprising the step of drying or calcining the smectite heteroadduct.
  • Aspect 39 The method of making a support-activator according to Aspect 36, further comprising the step of measuring a conductivity of the suspension ofhe smectite heteroadduct in water, and if the conductivity is greater than 300 ⁇ S/cm, repeating the steps of washing the smectite heteroadduct and filtering the suspension to provide the washed sme
  • Aspect 38 The method of making a support-activator according to Aspect 38, further comprising the step of drying the smectite heteroadduct by an azeotroping process or by a spray-drying process.
  • Aspect 40 The method of making a support-activator according to Aspect 38, further comprising the step of drying or calcining the smectite heteroadduct by heating in air, heating in an inert atmosphere, heating under vacuum, or a combinationhereof.
  • Aspect 41 The method of making a support-activator according to any of Aspects 25-40, further comprising the step of grinding the smectite heteroadduct to a uniform powder.
  • Aspect 42 The method of making a support-activator according to any of Aspects 25-40, further comprising the step of grinding the smectite heteroadduct to a uniform powder.
  • Aspect 43 The method of making a support-activator according to any of Aspects 15-42, further comprising the step of spray drying the slurry of the smectite heteroadduct in the first liquid carrier. Aspect 44.
  • Aspect 45 The method of making a support-activator according to Aspect 44, wherein the dispersion medium comprises or consists essentially of water, an organic liquid, or a combination thereof.
  • the dispersion medium comprises, consists essentially of, or is selected from water, methanol, ethanol, i-propanol, n-propanol, n-butanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, xylene, or a combination thereof.
  • Aspect 47 The method of making a support-activator according to Aspect 44-46, wherein the step of suspending the smectite heteroadduct in a dispersion medium occurs under high shear conditions.
  • Aspect 49 The method of making a support-activator according to any of Aspects 44-48, wherein the suspension of the smectite heteroadduct comprises the dispersion medium and the smectite heteroadduct in a concentration of: (i) from 0.1 wt% to 70 wt%, alternatively from 1 wt% to 50 wt%, or alternatively from 5 wt% to 30 wt% in the suspension; or (ii) about 1 wt%, about 2 wt%, about 5 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about 30 wt%, about 40 wt%, about 50 wt%, about 60 wt%, or about 70 wt%.
  • Aspect 50 The method of making a support-activator according to any of Aspects 44-49, wherein the step of spray drying the suspension of the smectite heteroadduct comprises a spray drying process wherein air at a temperature of from 80 °Co 260 °C, from 100 °C to 220 °C, or from 120 °C to 200 °C is used in the spray drying process.
  • Aspect 51 The method of making a support-activator according to any of Aspects 44-50 further comprising the step of: (f) calcining the smectite heteroadduct by heating the smectite heteroadduct in air,n an inert atmosphere, or under vacuum.
  • Aspect 52 The method of making a support-activator according to any of Aspects 44-49, wherein the step of spray drying the suspension of the smectite heteroadduct comprises a spray drying process wherein air at a temperature of from 80 °Co 260 °C, from
  • a method of making a catalyst system comprising contacting in a second liquid carrier: (a) at least one metallocene compound; and (b) at least one support-activator comprising a smectite heteroadduct according to any of Aspects 1-11.
  • Aspect 53. A method of making a catalyst system, the method comprising contacting in any order in a second liquid carrier: (a) at least one metallocene compound; and (b) at least one support-activator comprising a smectite heteroadduct prepared according to any of Aspects 15-51.
  • Aspect 55 A process for polymerizing olefins comprising contacting ateast one olefin monomer and a catalyst system under polymerization conditions to form a polyolefin, wherein the catalyst system comprises: (a) at least one metallocene compound; and (b) at least one support-activator comprising a smectite heteroadduct according to any of Aspects 1-11.
  • Aspect 56 A process for polymerizing olefins comprising contacting ateast one olefin monomer and a catalyst system under polymerization conditions to form a polyolefin, wherein the catalyst system comprises: (a) at least one metallocene compound; and (b) at least one support-activator comprising a smectite heteroadduct according to any of Aspects 1-11.
  • a process for polymerizing olefins comprising contacting ateast one olefin monomer and a catalyst system under polymerization conditions to form a polyolefin, wherein the catalyst system comprises: (a) at least one metallocene compound; and (b) at least one support-activator comprising a smectite heteroadduct prepared according to any of Aspects 15-51.
  • Aspect 57 The process for polymerizing olefins according to any of Aspects 55-56, wherein the catalyst system further comprises: (c) at least one co-catalyst; (d) at least one co-activator; or a combination thereof.
  • Aspect 59 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein when the smectite heteroadduct is spray dried and calcined, and the resulting smectite heteroadduct has an average particle sphericity of 0.70 or greater wherein sphericity is calculated according to the formula r max-in is the radius of the largest inscribed circle of a two-dimensional image of a particle, and r min-cir is the radius of the smallest circumscribed circle of a two-dimensionalmage of the particle.
  • Aspect 60 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to Aspect 59, wherein when the smectite heteroadduct is spray dried and calcined, and the resulting smectite heteroadduct has an 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.
  • Aspect 61 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to Aspect 59, wherein when the smectite heteroadduct is spray dried and calcined, and the resulting smectite heteroadduct has an average particle sphericity
  • Aspect 62 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to Aspect 61, wherein when the smectite heteroadduct is spray dried and calcined, and the resulting smectite heteroadduct has an average roundness of 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.
  • Aspect 63 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to Aspect 61, wherein when the smectite heteroadduct is spray dried and calcined, and the resulting smectite heteroadduct has an average roundness of 0.75 or greater, 0.80 or greater, 0.85 or greater, 0.87 or
  • Aspect 64 is the area of a two-dimensional image (silhouette) of a particle, and perimeter ishe length of the path encompassing the two-dimensional image of a particle.
  • Aspect 65 is
  • Aspect 66 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the first liquid carrier comprises, consists essentially of, or is selected from water, an organic liquid, or a combination thereof.
  • Aspect 67 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the first liquid carrier comprises or consists essentially of water, an alcohol, an ether, a ketone, an ester, or any combination thereof.
  • Aspect 68 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the first liquid carrier comprises or
  • the first liquid carrier comprises or consists essentially of water, methanol, ethanol, n-propanol, sopropanol, n-butanol, diethyl ether, di-n-butyl ether, acetone, methyl acetate, ethyl acetate, or any combination thereof.
  • Aspect 70 The catalyst system or the process for polymerizing olefins according to any of the preceding Aspects, wherein the fluid carrier comprises, consists essentially of, or is selected from a gas or a liquid.
  • Aspect 71 The fluid carrier comprises, consists essentially of, or is selected from a gas or a liquid.
  • the fluid carrier comprises, consists essentially of, or is selected from: nitrogen; a hydrocarbon such as cyclohexane, isobutane, n-butane, propane, n-pentane, isopentane, neopentane, n-hexane, naphtha, hydrogen-reated naphtha, or Isopar TM ; at least one olefin; or any combination thereof.
  • a hydrocarbon such as cyclohexane, isobutane, n-butane, propane, n-pentane, isopentane, neopentane, n-hexane, naphtha, hydrogen-reated naphtha, or Isopar TM ; at least one olefin; or any combination thereof.
  • the fluid carrier comprises, consists essentially of, or is selected from a liquid or a gaseous hydrocarbon, an ether, or a combination thereof, each of which independently has from 2 to 20 carbon atoms.
  • the second liquid carrier comprises, consists essentially of, or is selected from cyclohexane, isobutane, n-butane, propane, n-pentane, isopentane, neopentane, n-hexane, naphtha, hydrogen-treated naphtha, Isopar TM , at least one olefin, or any combination thereof.
  • the secondiquid carrier comprises, consists essentially of, or is selected from any one or combination of the fluid carriers.
  • Aspect 76. The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the smectite clays [1] natural or synthetic, and/or [2] a dioctahedral smectite clay.
  • Aspect 77 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the smect
  • the smectite clay comprises, consists of, consists essentially of, or is selected from montmorillonite, sauconite, nontronite, hectorite, beidellite, saponite, bentonite, or any combination thereof.
  • the colloidal smectite clay can have an average particle size of from 1 ⁇ m (micron) to 250 ⁇ m, for example, about 1 ⁇ m (microns), about 2 ⁇ m, about 3 ⁇ m, about 5 ⁇ m, about 7 ⁇ m, about 10 ⁇ m, about 12 ⁇ m, about 15 ⁇ m, about 18 ⁇ m, about 20 ⁇ m, about 25 ⁇ m, about 30 ⁇ m, about 35 ⁇ m, about 40 ⁇ m, about 45 ⁇ m, about 50 ⁇ m, about 55 ⁇ m, about 60 ⁇ m, about 65 ⁇ m, about 70 ⁇ m, about 75 ⁇ m, about 80 ⁇ m, about 85 ⁇ m, about 90 ⁇ m, about 95 ⁇ m, about 100 ⁇ m,
  • Aspect 80 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the smectite clay comprises structural units characterized by the following formula: (M A IV)8(M B VI)pO20(OH)4; wherein M A IV is a four-coordinate Si 4+ , wherein the Si 4+ is optionally partially substituted by a four-coordinate cation that is not Si 4+ ; M B VI is a six-coordinate Al 3+ or Mg 2+ , wherein the Al 3+ or Mg 2+ is optionally partially substituted by a six-coordinate cation that is not Al 3+ or Mg 2+ ; p is four for cations with a +3 formal charge, or p is 6 for cations with a +2 formal charge; and any charge deficiency that is created by the partial substitution of a
  • Aspect 81 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to Aspect 80, wherein: in each occurrence, the cation that is not Si 4+ is independently selected from Al 3+ , Fe 3+ , P 5+ , B 3+ , Ge 4+ , Be 2+ , Sn 4+ , and the like; in each occurrence, the cation that is not Al 3+ or Mg 2+ is independently selected from Fe 3+ , Fe 2+ , Ni 2+ , Co 2+ , Li + , Zn 2+ , Mn 2+ , Ca 2+ , Be 2+ , and the like; and/or the cations intercalated between structural units are selected from monocations, dications, trications, other multications, or any combination thereof.
  • Aspect 82 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to Aspect 80, wherein: in each occurrence, the cation that is not Si 4+ is independently selected from Al 3+ or Fe 3+ ; and in each occurrence, the cation that is not Al 3+ or Mg 2+ is independently selected from Fe 3+ , Fe 2+ , Ni 2+ , or Co 2+ . the cations intercalated between structural units are selected from monocations.
  • Aspect 83 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to Aspect 80, wherein: in each occurrence, the cation that is not Si 4+ is independently selected from Al 3+ or Fe 3+ ; and in each occurrence, the cation that is not Al 3+ or Mg 2+
  • Aspect 84. The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the smectite heteroadduct comprises both crystalline domains and amorphous domains.
  • SPAN particle size distribution parameter
  • Aspect 87 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the smectite heteroadduct is calcined by heating in air, in an inert atmosphere, or under vacuum, and wherein the heating is carried out to a temperature of at least about 100°C.
  • Aspect 88 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the smectite heteroadduct is calcined by heating in air, in an inert atmosphere, or under vacuum, and wherein the heating is carried out to a temperature of at least about 100°C.
  • Aspect 90 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the smectite heteroadduct is heated or calcined at a single temperature or within or over a range of twoemperatures separated by at least 10° C, in the range of from 110°C to 800°C.
  • Aspect 91 Aspect 91.
  • air air
  • a dry ambient atmosphere includes air which has been passed through a drying column, or air which has a relative humidity of from about 0% to about 60%.
  • Aspect 95 Aspect 95.
  • Aspect 96 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the smectite heteroadduct is calcined, and the calcined smectite heteroadduct is characterized by a BJH porosity of: (i) from 0.1 cc/g to 3.0 cc/g, from 0.15 cc/g to 2.5 cc/g, from 0.25 cc/g to 2.0 cc/g, or from 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/
  • Aspect 97 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the smectite heteroadduct is isolated and calcined, and the calcined smectite heteroadduct is characterized by a BJH porosity which exceeds 200% of a BJH porosity of an analogous calcined smectite which has been analogously prepared as the smectite heteroadduct, but which has not been contacted with the surfactant.
  • Aspect 98 Aspect 98.
  • Aspect 99 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the smectite heteroadduct is calcined and the calcined smectite heteroadduct exhibits a combined cumulative pore volume of pores between 3-10 nm diameter (V3-10nm) which is less than 55%, less than 50%, less than 45%, or less than 40% of the combined cumulative pore volume of pores between 3-30 nm (V3-30nm).
  • V3-10nm 3-10 nm diameter
  • dV log D
  • the smectite heteroadduct comprises the contact product of a colloidal smectite clay and a cationic surfactant, and is calcined and the calcined smectite heteroadduct exhibits a powder X-ray diffraction (XRD) d001 peak from 6 degrees 2 theta to 9 degrees 2 theta.
  • XRD powder X-ray diffraction
  • the smectite heteroadduct comprises the contact product of a colloidal smectite clay and a cationic surfactant, and is calcined and the calcined smectite heteroadduct exhibits a powder X-ray diffraction (XRD) d001 peak from 7 degrees 2 theta to 8 degrees 2 theta.
  • XRD powder X-ray diffraction
  • Aspect 104 Aspect 104.
  • Aspect 105 Aspect 105.
  • the surfactant comprises is absent any two of a cationic surfactant, a nonionic surfactant, an amphoteric surfactant.
  • Aspect 107 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the surfactant is absent a cationic surfactant.
  • Aspect 108. The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the surfactant is absent a nonionic surfactant.
  • Aspect 109 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the surfactant is absent a nonionic surfactant.
  • Aspect 110. The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the cationic surfactant comprises or is selected from a primary, a secondary, a tertiary, or a quaternary ammonium compound or phosphonium compound.
  • the cationic surfactant can comprise or can be selected from an ammonium compound (salt), havinghe 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 selected independently from hydrogen, a substituted or an unsubstituted C1-C25 hydrocarbyl group, or a substituted or an unsubstituted C1-C25 heterohydrocarbyl group, in which any two of R 1 , R 2 , R 3 , and R 4 may be part of a ring structure, and wherein at least one of R 1 , R 2 , R 3 , and R 4 is a non-hydrogen moiety; and X- is selected from an organic or an inorganic monoanion,
  • Aspect 112 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to Aspect 111, wherein: R 1 , R 2 , R 3 , and R 4 are selected independently from hydrogen, a substituted or an unsubstituted C1-C25 aliphatic group, a substituted or an unsubstituted C1-C25 heteroaliphatic group, a substituted or an unsubstituted C6-C25 aromatic group, or a substituted or an unsubstituted C4-C25 heteroaromatic group, in which any two of R 1 , R 2 , R 3 , and R 4 may be part of a ring structure; and X- is selected from any suitable anion, such as fluoride, chloride, bromide, iodide, formate, acetate, oxalate, nitrate, sulfate,
  • Aspect 113 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the cationic surfactant can comprise or can be selected from a phosphonium compound (salt), havinghe following general formula: [R 1 R 2 R 3 R 4 P] + X-, wherein each R 1 , R 2 , R 3 , and R 4 is selected independently from hydrogen, a substituted or an unsubstituted C1-C25 hydrocarbyl group, or a substituted or an unsubstituted C1-C25 heterohydrocarbyl group, in which any two of R 1 , R 2 , R 3 , and R 4 may be part of a ring structure, and wherein at least one of R 1 , R 2 , R 3 , and R 4 is a non-hydrogen moiety; and X- is selected from an organic or an in
  • Aspect 114 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to Aspect 113, wherein: R 1 , R 2 , R 3 , and R 4 are selected independently from hydrogen, a substituted or an unsubstituted C1-C25 aliphatic group, a substituted or an unsubstituted C1-C25 heteroaliphatic group, a substituted or an unsubstituted C6-C25 aromatic group, or a substituted or an unsubstituted C4-C25 heteroaromatic group, in which any two of R 1 , R 2 , R 3 , and R 4 may be part of a ring structure; and the counterion is selected from any suitable anion, such as fluoride, chloride, bromide, iodide, formate, a carboxylate such as acetate, oxalate, nitrate
  • Aspect 115 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the cationic surfactant comprises a cation selected from lauryltrimethylammonium, stearyltrimethylammonium, trioctylammonium, distearyldimethylammonium, distearyldibenzylammonium, cetyltrimethylammonium, benzylhexadecyldimethylammonium, dimethyldi-(hydrogenated tallow)ammonium, dimethylbenzyl-(hydrogenated tallow)ammonium, or any combination thereof.
  • the cationic surfactant comprises a cation selected from lauryltrimethylammonium, stearyltrimethylammonium, trioctylammonium, distearyldimethylammonium, distearyl
  • Aspect 116 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the cationic surfactant comprises a cation selected from tetramethylammonium, tetraethylammonium,etrabutylammonium, tetrapentylammonium, tetrahexylammonium, tetraoctylammonium,etrabenzylammonium, cetylammonium, decylammonium, dodecylammonium, methyloctadecylammonium, ethyloctadecylammonium, butyloctadecylammonium, dimethyloctadecylammonium, diethyloctadecylammonium, dibutyloctadecyl
  • Aspect 117 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the cationic surfactant comprises an anion selected from a halide, such as chloride or bromide.
  • the cationic surfactant comprises or is selected from a chloride or bromide of benzalkonium, benzethonium, methylbenzethonium, cetylpyridinium, alkyl-dimethyl dichlorobenzene ammonium, dequalinium, phenamylinium, cetrimonium, or cethexonium.
  • the cationic surfactant comprises or is selected from a chloride or bromide of benzalkonium, benzethonium, methylbenzethonium, cetylpyridinium, alkyl-dimethyl dichlorobenzene ammonium, dequalinium, phenamylinium, cetrimonium, or cethexonium.
  • the cationic surfactant comprises or is selected from tetrabutylammonium bromide, dioctadecyldimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecylammonium chloride, trimethylstearylammonium chloride, cetyltrimethylammonium bromide, octenidine dihydrochloride, cetyl trimethylammonium bromide (CTAB), cetyl trimethylammonium chloride (CTAC), cetylpyridinium chloride (CPC), benzalkonium chloride (BAC), benzethonium chloride (BZT), dimethyldioctadecylammonium chloride, dioctadec
  • Aspect 120 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the nonionic surfactant comprises, or is selected from a non-amphoteric surfactant.
  • nonionic surfactant comprises, further comprises, or is selected from: an ethoxylate, a glycol ether, a fatty alcohol polyglycol ether, or any combinations thereof.
  • nonionic surfactant comprises, further comprises, or is selected from: (a) a polyhydric alcohol containing 2, 3, or more hydroxyl groups, a polyhydric alcohol having the formula CH2OH(CHOH)nCH2OH wherein n is an integer from 2 to 5, a mono-alkyl ether of a polyhydric alcohol, a di-alkyl ether of a polyhydric alcohol, or a polyalkylene glycol of any of these, that is, a polyalkylene glycol of the polyhydric alcohol, the mono-alkyl ether of a polyhydric alcohol, or the di-alkyl ether of a polyhydric alcohol; (b) glycerol, 1,2,4-butanetriol, erythritol, pentaerythr
  • Aspect 123 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the nonionic surfactant comprises, further comprises, or is selected from a hydrocarbyl (hydrocarbon)sulfonate having the formula R 1 SO 2 OR 2 , wherein R 1 and R 2 are selectedndependently from a substituted or an unsubstituted C1-C25 alkyl-, C6-C25 aryl-, C7-C25 aralkyl-, or C7-C25 alkaryl.
  • a hydrocarbyl (hydrocarbon)sulfonate having the formula R 1 SO 2 OR 2 , wherein R 1 and R 2 are selectedndependently from a substituted or an unsubstituted C1-C25 alkyl-, C6-C25 aryl-, C7-C25 aralkyl
  • nonionic surfactant comprises, further comprises, or is selected from: (a) a mono-saccharide, a di-saccharide, an oligosaccharide, or any combinationhereof; or (b) glucose, fructose, mannose, maltose, lactose, sucrose, a cyclodextrin, a maltodextrin, an amino-modified saccharides such as glucosamine, an oxidized sugar acid such as glucoronic acid, or any combination thereof.
  • the nonionic surfactant comprises, further comprises, or is selected from a silane having the formula R 1 SiX3, R 1 R 2 SiX2, or R 1 R 2 R 3 SiX, wherein: R 1 , R 2 , and R 3 are selected independently from a substituted or an unsubstituted C1-C25 hydrocarbyl group, C1-C25 heterohydrocarbyl group, or any other group which is hydrolytically stable when bonded to silicon in the nonionic surfactant; and X is selected independently from a hydrolyzable group which is converted to a hydroxyl group (-OH) upon hydrolysis thereby forming a silanol.
  • a silane having the formula R 1 SiX3, R 1 R 2 SiX2, or R 1 R 2 R 3 SiX wherein: R 1 , R 2 , and R 3 are selected independently from a substituted or an unsubstituted C1-C25 hydrocarbyl group, C1-C25 heterohydrocarbyl group, or any other group which
  • Aspect 126 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to Aspect 125, wherein: R 1 , R 2 , and R 3 are selected independently from hydrogen, a substituted or an unsubstituted C1-C25 aliphatic group, a substituted or an unsubstituted C1-C25 heteroaliphatic group, a substituted or an unsubstituted C6-C25 aromatic group, or a substituted or an unsubstituted C4-C25 heteroaromatic group.
  • Aspect 127 Aspect 127.
  • the nonionic surfactant comprises, further comprises, or is selected from a silyl alcohol having the formula R 4-n Si(OH) n , wherein n is 1 or 2, and R is selected from a C1 to C20 alkyl group or a C6 to C20 aryl group.
  • R is selected from a C1 to C20 alkyl group or a C6 to C20 aryl group.
  • nonionic surfactant comprises, further comprises, or is selected from triphenylsilanol, dimethylphenylsilanol, diphenylsilanediol, triisopropylsilanol, or any combination thereof.
  • the nonionic surfactant comprises or is selected from octylphenol ethoxylate, polyethylene glycol tert- octylphenyl ether, ethylenediamine tetrakis(ethoxylate-block-propoxylate) tetrol, ethylenediamine tetrakis(propoxylate-block-
  • the amphoteric surfactant comprises a cationic moiety and an anionic moiety, wherein the cationic moietys selected from a primary amine, a secondary amine, a tertiary amine, or a quaternary ammonium cation, and the anionic moiety is selected form a sulfate, a sulfonate, a phosphate, or a carboxylate.
  • the amphoteric surfactant comprises a cationic moiety and an anionic moiety, wherein the cationic moietys selected from a primary amine, a secondary amine, a tertiary amine, or a quaternary ammonium cation, and the anionic moiety is selected form a sulfate, a sulfonate, a phosphate, or a carboxylate.
  • amphoteric surfactant comprises, further comprises, or is selected from an amino acid, a polypeptide, a protein, or a combination thereof.
  • amphoteric surfactant comprises, further comprises, or is selected from an amino acid or a combination of amino acids
  • the contacting step is carried out under conditions,ncluding a pH from about 2.5 to 9.5, in which the an amino acid or combination of amino acids are zwitterionic.
  • amphoteric surfactant comprises, further comprises, or is selected from 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 combinationhereof.
  • Aspect 135. The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the amphoteric surfactant comprises, further comprises, or is selected from a sultaine, a hydroxysultaine, a betaine, an amine N-oxide (such as a tertiary amine N-oxide, a hydrocarbyl amine N- oxide, an alkyl amine N-oxide, or an aryl amine N-oxide), a phospholipid, or a sphingomyelin.
  • a sultaine such as a tertiary amine N-oxide, a hydrocarbyl amine N- oxide, an alkyl amine N-oxide, or an aryl amine N-oxide
  • a phospholipid such as a tertiary amine N-oxide
  • amphoteric surfactant comprises, further comprises, or is selected from: (a) lauramidopropyl hydroxysultaine (ISOTAINE LAPHS), cocamidopropyl hydroxysultaine (ISOTAINE CAPHS), oleamidopropyl hydroxysultaine (ISOTAINE OAPHS), tallowamidopropyl hydroxysultaine (ISOTAINE TAPHS), erucamidopropyl hydroxysultaine (ISOTAINE EAPHS), lauryl hydroxysultaine (ISOTAINE LHS), or a combination thereof; (b) N,N,N-trimethylglycine, cocamidopropyl betaine, a phosphatidylserine, phosphatidylethanolamine, phosphatidyl
  • Aspect 137 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the anionic surfactant comprises, further comprises, or is selected from a sulfate surfactant, a sulfonate surfactant, a phosphate surfactant, carboxylate surfactant, or other anionic surfactants, examples of which include but are not limited to dialkyl sulfocarboxylic acid esters, alkaryl sulfonic acid salts, aralkyl sulfonic acid salts, alkyl sulfonic acid salts, aryl sulfonic acid salts, sulfosuccinic acid esters, fatty acid alkali salts, polycarboxylic acid salts, polyoxyethylene alkyl ether phosphoric acid ester salts, alkylnaphthalene
  • Aspect 138 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the anionic surfactant comprises, further comprises, or is selected from an alkyl ether sulfate compound or an alkenyl ether sulfate compound having the formula [RO(C2H4O)xSO3]M wherein R is a C 8 to C20 alkyl group or a C 8 to C20 alkenyl group, x an integer from 1 to 30, inclusive, and M is a cation which imparts water solubility to the alkyl ether sulfate or an alkenyl ether sulfate.
  • Aspect 139 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the anionic surfactant comprises, further comprises, or is selected from a carboxylate compound having the formula [RCOO]M, wherein R is a C8 to C21 alkyl group and M is a cation selected from sodium, potassium, or ammonium.
  • ROO]M carboxylate compound having the formula [RCOO]M, wherein R is a C8 to C21 alkyl group and M is a cation selected from sodium, potassium, or ammonium.
  • the anionic surfactant comprises, further comprises, or is selected from: (a) a sulfonate compound having the formula R'SO 3 Na, wherein R' is a C 8 to C2 1 alkyl group, a C8 to C21 aralkyl group, or a C8 to C21 alkaryl group; or (b) an alkyl sulfate having the formula R"OSO 3 M, wherein R" is a C 8 to C2 1 alkyl group, and M is a cation selected from NH4 + , Na + , K + , 1 ⁇ 2 Mg 2+ , diethanolammonium, orriethanolammonium.
  • Aspect 141 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the anionic surfactant comprises, further comprises, or is selected from a sulfated polyoxyethylene alkylphenol with a formula of R"C6H 4 (OCH 2 CH 2 ) n OSO 3 M wherein R" is C1 to C 9 alkyl group, M is NH4 + , Na + , or triethanolamine, and n is an integer from 1 to 50, inclusive.
  • the anionic surfactant comprises, further comprises, or is selected from a sulfated polyoxyethylene alkylphenol with a formula of R"C6H 4 (OCH 2 CH 2 ) n OSO 3 M wherein R" is C1 to C 9 alkyl group, M is NH4 + , Na + , or triethanolamine, and n is an integer from
  • the anionic surfactant comprises, further comprises, or is selected from: (a) an alkyl sulfate having the formula [(R 1 O)SO2O]M; (b) an alkyl sulfonate having the formula [R 1 SO 2 O]M; (c) an alkyl sulfinate having the formula [R 1 S(O)O]M; (d) sulfated polyoxyalkylene having the formula [R 1 (OCH2CH2)nOSO2O]M or [R 1 (OCH 2 C(CH 3 )CH 2 ) n OSO 2 O]M; (e) sulfonated polyoxyalkylene having the formula [R 1 (OCH2CH2)nSO2O]M or [R 1 (OCH 2 C(CH 3 )
  • Aspect 143 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the anionic surfactant comprises, further comprises, or is selected from an alkali metal salt of a fatty acid having from about 8 to about 30 carbon atoms.
  • the anionic surfactant comprises, further comprises, or is selected from an alkali metal salt of a fatty acid having from about 8 to about 30 carbon atoms.
  • the anionic surfactant comprises, further comprises, or is selected from an alkali metal salt of a fatty acid 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,inoleic acid, linoelaidic acid, ⁇ -linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid, or any combination thereof.
  • a fatty acid selected from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, ricinoleic acid, behenic acid, lignoc
  • Aspect 145 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the anionic surfactant comprises or is selected from potassium oleate, dodecyl benzene sulfonate, dioctyl sulfosuccinate, sodium laurylsulfonate, sodium stearate, sodium lauryl sulfate, sodium myristyl sulfate, potassium lauryl sulfate, ammonium lauryl sulfate,riethanolamine lauryl sulfate, sodium cetyl sulfate, sodium stearyl sulfate, polyoxyethylene (POE) lauryl ether sodium sulfate, POE lauryl ether triethanolamine sulfate, POE lauryl ether ammonium sulfate, PO
  • Aspect 146 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the anionic surfactant comprises, further comprises or is selected from: (a) a substituted or an 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 an unsubstituted alkyl sulfate selected from methyls
  • Aspect 147 The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the anionic surfactant further comprises a counter ion selected from NH 4 + , Na + , K + , 1 ⁇ 2 Mg 2+ , diethanolammonium, or triethanolammonium.
  • a counter ion selected from NH 4 + , Na + , K + , 1 ⁇ 2 Mg 2+ , diethanolammonium, or triethanolammonium.
  • metallocene compound comprises, further comprises, consists of, consists essentially of, or is selected from a non-bridged (non-ansa) metallocene compound or a bridged (ansa) metallocene compound.
  • Aspect 150 whereinhe metallocene compound comprises, further comprises, consists of, consists essentially of, or is selected from a non-bridged (non-ansa) metallocene compound or a bridged (ansa) metallocene compound.
  • he metallocene compound comprises, consists of, consists essentially of, or is selected from a compound or a combination of compounds, each independently having 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 a substituted or an unsubstituted cyclopentadienyl, indenyl, fluorenyl, pentadienyl, allyl, boratabenzenyl, 1,2-azaborolyl, or 1,2-diaza-3,5-diborolyl, wherein any substituent is selected independently from a halide, a C1-C20 hydrocarbyl, a C1-C20 heterohydrocarbyl, a C1-C20 organo
  • Aspect 152 The catalyst system, the method of making a catalyst system, or the process for polymerizing olefins according to any of Aspects 150-151, wherein X 1 and X 2 are bridged by a linker substituent selected from a C1-C20 hydrocarbylene group, a C1-C20 hydrocarbylidene group, a C1-C20 heterohydrocarbyl group, a C1-C20 heterohydrocarbylidene group, a C1-C20 heterohydrocarbylene group, or a C1-C20 heterohydrocarbylidene group.
  • Aspect 153 Aspect 153.
  • Aspect 150-152 The catalyst system, the method of making a catalyst system, or the process for polymerizing olefins according to any of Aspects 150-152, wherein X 1 and X 2 are bridged 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, X 5 in each occurrence is selected independently from a halide, a C1-C20 aliphatic group, a C6-C20 aromatic group, a C1-C20 heteroaliphatic group, a C4-C20 heteroaromatic group, or a C1-C20 organoheteryl group.
  • Aspect 154 Aspect 154.
  • X 5 n each occurrence is selected independently from a halide, a C1-C18 or C1-C12 alkyl group, a C2-C18 or C2-C12 alkenyl group, a C6-C18 or C6-C12 aromatic group, a C4-C18 or C4-C12 heteroaromatic group, a C1-C18 or C1-C12 heterohydrocarbyl group, a C1-C21 or C1-C15 organosilyl group, a C1-C18 or C1-C12 alkyl halide (haloalkyl) group, a C1-C18 or C1-C12 organophosphorus group, or a C1-C18 or C1-C12 organonitrogen group.
  • Aspect 155 The catalyst system, the method of making a catalyst system, or the process for polymerizing olefins according to any of Aspects 150-154, wherein X 1 and X 2 are bridged by a linker substituent selected from silylene, methylsilylene, dimethylsilylene, diisopropylsilylene, dibutylsilylene, methylbutylsilylene, methyl-t- butylsilylene, dicyclohexylsilylene, methylcyclohexylsilylene, methylphenylsilylene, diphenylsilylene, ditolylsilylene, methylnaphthylsilylene, dinaphthylsilylene, cyclodimethylenesilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenesilylene, or cycloheptamethylenesilylene.
  • Aspect 156 The catalyst system, the method of making a catalyst system, or the process for polymerizing olefins according to any of Aspects 150-155, wherein X 1 s selected from a substituted or an unsubstituted cyclopentadienyl, indenyl, or fluorenyl, wherein any substituent is selected independently from a halide, a C1-C20 aliphatic group, a C6-C20 aromatic group, a C1-C20 heteroaliphatic group, a C4-C20 heteroaromatic group, or a C1-C20 organoheteryl group.
  • Aspect 157 Aspect 157.
  • X 1 selected from a substituted or an unsubstituted cyclopentadienyl, indenyl, or fluorenyl, wherein any substituent is selected independently from a halide, a C1-C18 or C1-C12 alkyl group, a C2-C18 or C2-C12 alkenyl group, a C6-C18 or C6-C12 aromatic group, a C4-C18 or C4-C12 heteroaromatic group, a C1-C21 or C1-C15 organosilyl group, a C1-C18 or C1-C12 alkyl halide (haloalkyl) group, a C1-C18 or C1-C12 organophosphorus group, or a C1-C18 or C1-C12 organonitrogen group.
  • Aspect 158 The catalyst system, the method of making a catalyst system, or the process for polymerizing olefins according to any of Aspects 150-157, wherein X 1 , X 2 , or both X 1 and X 2 are selected independently from a substituted or an unsubstituted cyclopentadienyl, indenyl, or fluorenyl, wherein any substituent is selected independently from: (a) a silicon group having the formula -SiH3, -SiH2R, -SiHR2, -SiR3, -SiR2(OR), - SiR(OR) 2 , or -Si(OR) 3 ; (b) a phosphorus group having the formula -PHR, -PR2,-P(O)R2, -P(OR)2, - P(O)(OR) 2 , -P(NR2)2, or -P(O)(NR2)2; (c) a boron group having the formula
  • Aspect 159 The catalyst system, the method of making a catalyst system, or the process for polymerizing olefins according to any of Aspects 150-158, wherein X 1 , X 2 , or X 1 and X 2 are substituted with a fused carbocyclic or heterocyclic moiety selected from pyrrole, furan, thiophene, phosphole, imidazole, imidazoline, pyrazole, pyrazoline, oxazole, oxazoline, isoxazole, isoxazoline, thiazole, thiazoline, isothiozoline, or a partially saturated analogs thereof.
  • Aspect 160 The catalyst system, the method of making a catalyst system, or the process for polymerizing olefins according to any of Aspects 150-158, wherein X 1 , X 2 , or X 1 and X 2 are substituted with a fused carbocyclic or heterocyclic moiety selected from pyrrole
  • X 2 s selected from: [1] a substituted or an unsubstituted cyclopentadienyl, indenyl, or fluorenyl, wherein any substituent is selected independently from a halide, a C1-C20 aliphatic group, a C6-C20 aromatic group, a C1-C20 heteroaliphatic group, a C4-C20 heteroaromatic group, or a C1-C20 organoheteryl group; or [2] a halide, a C1-C20 aliphatic group, a C6-C20 aromatic group, a C1-C20 heteroaliphatic group, a C4-C20 heteroaromatic group, or a C1-C20 organoheteryl group.
  • Aspect 161 The catalyst system, the method of making a catalyst system, or the process for polymerizing olefins according to any of Aspects 150-160, wherein X 2 s selected from: [1] a substituted or an unsubstituted cyclopentadienyl, indenyl, or fluorenyl, wherein any substituent is selected independently from a halide, a C1-C18 or C1- C12 alkyl group, a C2-C18 or C2-C12 alkenyl group, a C6-C18 or C6-C12 aromatic group, a C4-C18 or C4-C12 heteroaromatic group, a C1-C2 1 or C1-C1 5 organosilyl group, a C1-C18 or C1-C12 alkyl halide (haloalkyl) group, a C1-C18 or C1-C12 organophosphorus group, or a C1-C18 or C1-
  • X 3 and X 4 are selected independently from a halide, a hydride, a C1-C20 aliphatic group, a C6-C20 aromatic group, a C1-C20 heteroaliphatic group, a C4-C20 heteroaromatic group, or a C1-C20 organoheteryl group; [2] X 3 and X 4 together are a substituted or an unsubstituted 1,3-butadiene having from 4 to 20 carbon atoms; or [3] X 3 and X 4 together with M form a substituted or an unsubstituted, saturated or unsaturated C4-C 5 metallacycle moiety, wherein any substituent on the metallacycle moiety is selected independently from a halide, a C1-C20 aliphatic group, a C
  • Aspect 164 The catalyst system, the method of making a catalyst system, or the process for polymerizing olefins according to any of Aspects 150-163, wherein: [1] X 3 and X 4 are selected independently from a halide, a hydride, a C1-C18 or C1-C12 alkyl group, a C2-C18 or C2-C12 alkenyl group, a C6-C18 or C6-C12 aromatic group, a C4-C18 or C4-C12 heteroaromatic group, a C1-C21 or C1-C15 organosilyl group, a C1-C18 or C1-C12 alkyl halide (haloalkyl) group, a C1-C18 or C1-C12 organophosphorus group, or a C1-C18 or C1-C12 organonitrogen group; or [2] X 3 and X 4 together are a substituted or an unsubstituted 1,3-
  • Aspect 165 The catalyst system, the method of making a catalyst system, or the process for polymerizing olefins according to any of Aspects 150-164, wherein X 3 and X 4 are selected independently from [1] a halide, a hydride, a borohydride, an aluminum hydride; or [2] a substituted or an unsubstituted C1-C18 aliphatic group, C1-C12 alkoxide group, C6-C10 aryloxide group, C1-C12 alkylsulfide group, C6-C10 arylsulfide group, wherein any substituent is selected independently from a halide, a C1-C10 alkyl, or a C6-C10 aryl; or [3] an amido group or a phosphido group, wherein any substituent is selected independently from a C1-C10 alkyl or a C6-C10 aryl.
  • Aspect 166 The catalyst system, the method of making a catalyst system, or the process for polymerizing olefins according to any of Aspects 148-150, wherein the metallocene compound comprises, further comprises, consists of, consists essentially of, or is selected from a metallocene compound having the formula (X 1 )(X 2 )(X 3 )(X 4 )M, wherein: (i) M is zirconium or hafnium; (ii) X 1 is a substituted or unsubstituted indenyl, fluorenyl, or cyclopentadienyl wherein any substituent is selected independently from a C1-C20 hydrocarbyl, a C1-C20 heterohydrocarbyl, or a fused C4-C12 carbocyclic moiety; (iii) X 2 is a substituted or unsubstituted indenyl or cyclopentadienyl, wherein any substituent is selected independently
  • Aspect 167 The catalyst system, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein he metallocene compound comprises, further comprises, consists of, consists essentially of, or is selected from (a) M is zirconium or hafnium; (b) R 1 through R 14 , in each occurrence, are selected independently from H, a C1- C12 hydrocarbyl group, or a C1-C12 heterohydrocarbyl group; (c) Y is carbon or silicon; and (d) Q is selected independently Cl, Br, a C1-C12 hydrocarbyl group, or a C1-C12 heterohydrocarbyl group.
  • Aspect 168 Aspect 168.
  • he metallocene compound comprises, further comprises, consists of, consists essentially of, or is selected from bis(1-butyl-3-methylcyclopentadienyl)zirconium dichloride, bis(1,2,3-trimethylcyclopentadienyl)zirconium dichloride, bis(1,2,4- rimethylcyclopentadienyl)zirconium dichloride, bis-(1,2,3,4-etramethylcyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(1,3-diethylcyclopentadienyl)- zirconium dichloride, bis(indenyl)zirconium dichloride, bis(4-methyl-1-indenyl)zirconium dichlor
  • Aspect 169 The catalyst system, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, whereinhe catalyst system further comprises a co-catalyst.
  • Aspect 170 The method of making a catalyst system according to any ofhe preceding Aspects, wherein the contacting step further comprises contacting, in any order, the metallocene compound and the support-activator with a co-catalyst.
  • Aspect 172. The catalyst system, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, whereinhe co-catalyst comprises, further comprises, consists of, consists essentially of, or is selected from an organoaluminum compound, an organoboron compound, an organozinc compound, an organomagnesium compound, an organolithium compound, or any combination thereof.
  • X A is selected independently from: [1] a hydride, a C1-C20 hydrocarbyl, or a C1-C20 heterohydrocarbyl; [2] a hydride, a C1-C20 aliphatic group, a C6-C20 aromatic group, a C1- C20 heteroaliphatic group, or a C4-C20 heteroaromatic group; or [3] two X A together
  • Aspect 174 The catalyst system, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, whereinhe co-catalyst comprises, further comprises, consists of, consists essentially of, or is selected from an organoaluminum compound or a combination of organoaluminum compounds, each independently having the formula: Al(X C ) n (X D ) 3-n or M x [AlX C 4 ], wherein n is a number from 1 to 3, inclusive; X C is selected independently from a hydride or a C1-C20 hydrocarbyl; X D is a formal anionic species selected independently from: fluoride; chloride; bromide; iodide; bromate; chlorate; perchlorate; hydrocarbylsulfate; hydrocarbylsulfite; sulfamate; hydrocarbylsulfide, hydrocarbylcarbonate; hydrogen-carbonate (bicarbon
  • Aspect 175. The catalyst system, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, whereinhe co-catalyst comprises, further comprises, consists of, consists essentially of, or is selected from: [1] trimethylaluminum, triethylaluminum (TEA), tripropylaluminum,ributylaluminum, trihexylaluminum, trioctylaluminum, ethyl-(3- alkylcyclopentadiyl)aluminum, diethylaluminum ethoxide, diisobutylaluminum hydride,riisobutylaluminum (TIBAL), diethylaluminum chloride, or any combination or mixturehereof; or [2] ethyl-(3-alkylcyclopentadiyl)aluminum, triisobutylaluminum (TI
  • Aspect 176 The catalyst system, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, whereinhe co-catalyst comprises, further comprises, consists of, consists essentially of, or is selected from an organoboron compound or a combination of organoboron compounds, each independently having the formula: B(X E )q(X F )3-q, B(X E )3, or M y [BX E 4], wherein q is from 1 to 3, inclusive; X E is selected independently from: [1] a hydride, a C1-C20 hydrocarbyl, or a C1-C20 heterohydrocarbyl; [2] a hydride, a C1-C20 aliphatic group, a C6-C20 aromatic group, a C1- C20 heteroaliphatic group, or a C4-C20 heteroaromatic group; [3] a fluorinated C1-C20
  • Aspect 177 The catalyst system, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, whereinhe co-catalyst comprises, further comprises, consists of, consists essentially of, or is selected from [1] trimethylboron, triethylboron, tripropylboron, tributylboron, trihexylboron,rioctylboron, diethylboron ethoxide, diisobutylboron hydride, triisobutylboron, diethylboron chloride, di-3-pinanylborane, pinacolborane, catecholborane, lithium borohydride, lithium triethylborohydride, a Lewis base adduct thereof, or any combination or mixture thereof; or [2] tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)phenyl
  • Aspect 178 The catalyst system, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, whereinhe co-catalyst comprises, further comprises, consists of, consists essentially of, or is selected from an organozinc or organomagnesium compound or a combination of organozinc and/or organomagnesium compounds, each independently having the formula: M C (X G ) r (X H ) 2-r , wherein M C is zinc or magnesium; r is a number from 1 to 2, inclusive; X G is selected independently from: [1] a hydride, a C1-C20 hydrocarbyl, or a C1-C20 heterohydrocarbyl; or [2] a hydride, a C1-C20 aliphatic group, a C6-C20 aromatic group, a C1-C20 heteroaliphatic group, or a C4-C20 heteroaromatic group; and X H
  • Aspect 179 The catalyst system, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, whereinhe co-catalyst comprises, further comprises, consists of, consists essentially of, or is selected from: [1] dimethylzinc, diethylzinc, diisopropylzinc, dicyclohexylzinc, diphenylzinc, or any combination thereof; [2] butylethylmagnesium, dibutylmagnesium, n-butyl-sec- butylmagnesium, dicyclopentadienylmagnesium, or any combination thereof; or [3] any combination of any organozinc co-catalyst from group [1] and any organomagnesium co- catalyst from group [2].
  • Aspect 180 The catalyst system, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, whereinhe co-catalyst comprises, further comprises, consists of, consists essentially of, or is selected from an organolithium compound having the formula: Li(X J ), wherein X J is selected independently from: [1] a hydride, a C1-C20 hydrocarbyl, or a C1-C20 heterohydrocarbyl; or [2] a hydride, a C1-C20 aliphatic group, a C6-C20 aromatic group, a C1-C20 heteroaliphatic group, or a C4-C20 heteroaromatic group.
  • X J is selected independently from: [1] a hydride, a C1-C20 hydrocarbyl, or a C1-C20 heterohydrocarbyl; or [2] a hydride, a C1-C20
  • Aspect 181 The catalyst system, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, whereinhe co-catalyst comprises, further comprises, consists of, consists essentially of, or is selected from methyllithium, ethyllithium, propyllithium, butyllithium (including n- butyllithium and t-butyllithium), hexyllithium, iso-butyllithium, or any combinationhereof.
  • the catalyst system the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, whereinhe catalyst system further comprises a co-activator which comprises or is selected from anon-exchanged clay, a protic-acid-treated clay, a pillared clay, an aluminoxane, a borate compound, an aluminate compound, an ionizing ionic compound, a solid oxide treated with an electron withdrawing anion, or any combination thereof.
  • a co-activator which comprises or is selected from anon-exchanged clay, a protic-acid-treated clay, a pillared clay, an aluminoxane, a borate compound, an aluminate compound, an ionizing ionic compound, a solid oxide treated with an electron withdrawing anion, or any combination thereof.
  • catalyst system the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, whereinhe catalyst system further comprises a co-activator which comprises or is selected from anonic ionizing compound.
  • a co-activator which comprises or is selected from anonic ionizing compound.
  • the ioniconizing compound comprises, consists of, consists essentially of, or is selected from tri(n- butyl)ammonium tetrakis(p-tolyl)borate, trimethylammonium tetraphenylborate,riethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n- butyl)ammonium tetraphenylborate, tri(t-butyl)ammonium tetraphenylborate, N,N- dimethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, N,N- dimethyl-(2,4,6-trimethylanilinium) tetraphenylborate, tropillium tetraphenylborate
  • Aspect 185 The catalyst system, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, whereinhe catalyst system further comprises a co-activator which comprises or is selected from a solid oxide treated with an electron withdrawing anion.
  • a co-activator which comprises or is selected from a solid oxide treated with an electron withdrawing anion.
  • the solid oxide comprises, consists of, consists essentially of, or is selected from silica, alumina, silica-alumina, silica-coated alumina, silica-zirconia, silica-titania, aluminum phosphate, heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination thereof; and ⁇ b) the electron-withdrawing anion comprises, consists of, consists essentially of, or is selected from fluoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate, fluorophosphate, fluorosulfate, or any combination thereof.
  • Aspect 188 The process for polymerizing olefins according to any of the preceding Aspects, wherein the polyolefin comprises, consists of, consists essentially of, or is selected from an olefin homopolymer or an olefin copolymer.
  • Aspect 189 The process for polymerizing olefins according to any of the preceding Aspects, wherein the polyolefin comprises, consists of, consists essentially of, or is selected from an olefin homopolymer, the homopolymer comprising olefin monomer residues having from 2 to about 20 carbon atoms per monomer molecule.
  • Aspect 190 The process for polymerizing olefins according to any of the preceding Aspects, wherein the polyolefin comprises, consists of, consists essentially of, or is selected from an olefin homopolymer, the homopolymer comprising olefin monomer residues having from 2 to about
  • the olefin monomer comprises, consists of, consists essentially of, or is 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, or 1-decene.
  • the olefin monomer comprises, consists of, consists essentially of, or is 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, or 1-decene.
  • the polyolefin comprises, consists of, consists essentially of, or is selected from an ethylene-olefin comonomer copolymer, the copolymer comprising ⁇ -olefin comonomer residues having from 3 to about 20 carbon atoms per monomer molecule.
  • Aspect 192. The process for polymerizing olefins according to Aspect 191, wherein the olefin comonomer is selected from an aliphatic C 3 to C20 olefin, a conjugated or nonconjugated C3 to C20 diolefin, or any mixture thereof.
  • olefin comonomer is 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.
  • Aspect 194 The process for polymerizing olefins according to any of the preceding Aspects, wherein the catalyst system exhibits an ethylene polymerization activity of greater than or equal to 250 g/g/hr (grams of polyethylene per gram of the support-activator per hour), greater than or equal to 300 g/g/hr (grams of polyethylene per gram of the support-activator per hour), greater than or equal to 500 g/g/hr (grams of polyethylene per gram of the support-activator per hour), greater than or equal to 1000 g/g/hr (grams of polyethylene per gram of the support-activator per hour), greater than or equal to 1500 g/g/hr, greater than or equal to 2000 g/g/hr, or greater than or equal to 2500 g/g/hr.
  • Aspect 195 The process for polymerizing olefins according to any of the preceding Aspects, wherein the polymerization conditions comprise [a] a metallocene compound to calcined smectite heteroadduct ratio of about 7 ⁇ 10 ⁇ 5 mmol metallocene compound /mg calcined smectite heteroadduct, and [b] other standard conditions as described in the specification.
  • the catalyst system comprises an organoaluminum compound and a calcined smectite heteroadduct in a relative concentration expressed in moles of organoaluminum compound per gram of calcined smectite heteroadduct in a range of from about 0.5 to about 0.000005, from about 0.1 to about 0.00001, or from about 0.01 to about 0.0001.
  • Aspect 198 The process for polymerizing olefins according to any of the preceding Aspects, wherein the process comprises at least one slurry polymerization, ateast one gas phase polymerization, at least one solution polymerization, or any multi- reactor combinations thereof.
  • Aspect 198 The process for polymerizing olefins according to any of the preceding Aspects, wherein the process comprises polymerization in a gas phase reactor, a slurry loop, dual slurry loops in series, multiple slurry tanks in series, a slurry loop combined with a gas phase reactor, a continuous stirred reactor in a batch process, or combinations thereof.
  • Aspect 199 Aspect 199.
  • the process for polymerizing olefins comprising contacting at least one olefin monomer and a catalyst system under polymerization conditions to form a polyolefin, wherein the catalyst system is prepared according to Aspect 201.
  • the support-activator or the catalyst system when used for polymerizing olefins or the process for polymerizing olefins according to any of the preceding Aspects which produces a polyolefin having a particle size distribution parameter (SPAN), calculated as (D90-D10)/(D50), of 10.0 or less, 7.5 or less, 5.0 or less, 3.0 or less, 2.7 or less, 2.5 or less, 2.2 or less, 2.0 or less, 1.8 or less , 1.6 or less, 1.4 oress, 1.2 or less, 1.0 or less, or 0.8 or less.
  • Aspect 204 Aspect 204.
  • the support-activator or the catalyst system when used for polymerizing olefins or the process for polymerizing olefins according to any of the preceding Aspects, wherein: the smectite clay or the smectite heteroadduct is sieved to provide at least one size fraction having an average particle size (d50) of from 15 ⁇ m (micron) to 80 ⁇ m; and the support-activator, the catalyst system, or the process for polymerizing olefins produces a polyolefin having a particle size distribution parameter (SPAN), calculated as (D90-D10)/(D50), of 10.0 or less, 7.5 or less, 5.0 or less, 3.0 or less, 2.7 or less, 2.5 oress, 2.2 or less, 2.0 or less, 1.8 or less , 1.6 or less, 1.4 or less, 1.2 or less, 1.0 or less, or 0.8 or less.
  • SPAN particle size distribution parameter
  • Aspect 205 The support-activator or the catalyst system when used for polymerizing olefins or the process for polymerizing olefins according to any of the preceding Aspects, which produces a polyolefin having a volume-weighted mean sphericity (SPHT3) 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.
  • SPHT3 volume-weighted mean sphericity
  • SPHT3 volume-weighted mean sphericity
  • the cationic polymetallate comprises, consists of, consists essentially of, or is selected from: fumed silica, fumed alumina, fumed silica-alumina, fumed magnesia, fumed zinc oxide, fumed titania, fumed zirconia, fumed ceria, or any combination thereof, which is chemically-treated with polyaluminum chloride, aluminum chlorhydrate, aluminum sesquichlorohydrate, polyaluminum oxyhydroxychloride, or any combination thereof.
  • the support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein: a) the colloidal smectite clay comprises colloidal montmorillonite, such as HPM- 20 Volclay; and b) the cationic polymetallate comprises aluminum chlorhydrate, polyaluminum chloride, or aluminum sesquichlorohydrate.
  • the colloidal smectite clay comprises colloidal montmorillonite, such as HPM- 20 Volclay
  • the cationic polymetallate comprises aluminum chlorhydrate, polyaluminum chloride, or aluminum sesquichlorohydrate.
  • the cationic polymetallate comprises, consists of, consists essentially of, or is selected from boehmite, fumed silica-alumina, colloidal ceria, colloidal zirconia, magnetite, ferrihydrite, any positively charged colloidal metal oxide, or any combination thereof.
  • the cationic polymetallate comprises, consists of, consists essentially of, or is selected from aluminum chlorhydrate-treated fumed silica, aluminum chlorhydrate-treated fumed alumina, aluminum chlorhydrate-treated fumed silica-alumina, or any combination thereof.
  • the cationic polymetallate comprises, consists of, consists essentially of, or is selected from aluminum species having the empirical formula 0.5[Al2(OH)5Cl(H2O)2] or [AlO4(Al12(OH)24(H2O)20] 7+ (“Al13-mer”) polycation.
  • the cationic polymetallate comprises, consists of, consists essentially of, or is selected from an oligomer prepared by copolymerizing soluble rare earth salts with a cationic metal complex of at least one additional metal selected from aluminum, zirconium, chromium,ron, or a combination thereof, according to U.S. Patent No.5,059,568.
  • the cationic polymetallate comprises, consists of, consists essentially of, or is selected from a complex of Formula I or Formula II or any combination of complexes of Formula I or Formula II, according to the following formulas: [M(II)1-xM(III)x(OH)2]Ax/n ⁇ m L (I) [LiAl 2 (OH) 6 ]A 1/n ⁇ m L (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,s their mean valence; and
  • M(II) comprises, consists of, consists essentially of, or is selected from zinc, calcium, strontium, barium, iron, cobalt, nickel, cadmium, manganese, copper, or magnesium
  • M(III) comprises, consists of, consists essentially of, or is selected from iron, chromium, manganese, bismuth, cerium, or aluminum
  • A comprises, consists of, consists essentially of, or is selected from hydrogencarbonate (bicarbonate), sulfate, nitrate, nitrite, phosphate, chloride, bromide, fluoride, hydroxide, or carbonate.
  • n is a number from 1 to 3; and L comprises, consists of, consists essentially of, or is selected from methanol, ethanol or isopropanol, or water.
  • Aspect 218 A catalyst composition, a process for polymerizing olefins, a method of making an olefin polymerization catalyst, a support-activator, or a method of making a support-activator according to Aspect 215, wherein the cationic polymetallate is selected from a complex of Formula I, wherein M(II) is magnesium, M(III) is aluminum, and A is carbonate
  • Aspect 221. The support-activator, the catalyst system, the method of making a support-activator, the method of making a catalyst system, or the process for polymerizing olefins according to any of the preceding Aspects, wherein the cationic polymetallate comprises, consists of, consists essentially of, or is selected from an iron polycation having an empirical formula FeOx(OH)y(H2O)z] n+ , wherein 2x+y is less than ( ⁇ ) 3, z is a number from 0 to about 4, and n is a number from 1 to 3.
  • the cationic polymetallate comprises, consists of, consists essentially of, or is selected from an iron polycation having an empirical formula FeOx(OH)y(H2O)z] n+ , wherein 2x+y is less than ( ⁇ ) 3, z is a number from 0 to about 4, and n is a number from 1 to 3.
  • the cationic polymetallate comprises, consists of, consists
  • a catalyst system a process for polymerizing olefins, a method of making an catalyst system, a support-activator, or a method of making a support-activator according to any one of Aspects 1-221, wherein the catalyst system, processes, methods, and support-activators are any catalyst system, processes, methods, and support-activators disclosed herein.

Abstract

Sont divulgués des activateurs de support et des compositions de catalyseur comprenant les activateurs de support pour la polymérisation d'oléfines dans lesquelles l'activateur de support comprend un hétéroadduit d'argile, également appelé composite, préparé à partir d'un phyllosilicate colloïdal tel qu'une argile smectique colloïdale, qui est chimiquement modifié avec un tensioactif. Selon un aspect, le composite d'argile peut comprendre le produit de contact d'une argile smectique colloïdale et d'un tensioactif dans un support liquide, mais en l'absence de tout autre réactif tel qu'un polymétallate cationique, et leur utilisation en tant qu'activateurs de support pour des précatalyseurs métallocènes. L'invention concerne également l'utilisation de tensioactifs avec des polymères cationiques dans la formation de composites d'argile.
PCT/US2023/023644 2022-06-09 2023-05-26 Activateurs de support composites d'argile et compositions de catalyseur WO2023239560A1 (fr)

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