Clay complex support-activators and catalyst compositions

Abstract

Disclosed are support-activators and catalyst compositions comprising the support-activators for the polymerization of olefins, where the support-activators include clay heteroadducts, also referred to as composites, prepared from colloidal phyllosilicates, such as colloidal montmorillonite clay, chemically modified with surfactants. In one aspect, the clay complex may comprise the contact product of a colloidal montmorillonite clay with a surfactant in a liquid vehicle but in the absence of any other reactant, such as a cationic polymetallate, and its use as a support-activator for metallocene precatalysts is also described. The use of a surfactant with a cationic polymetallate in the formation of a clay composite is also described.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 366,077, filed on June 9, 2022, and U.S. Patent Application No. 18 / 323,212, filed on May 24, 2023, each of which is incorporated by reference in its entirety. Technical Field

[0003] The present disclosure relates to catalyst compositions including a support-activator for producing polyethylene and processes for making and using the catalyst compositions. Background Art

[0004] In the industrial heterogeneous polymerization of olefins, support activators are usually used together with metallocene precatalysts. In general, support-activators have the dual role of activating metallocenes and serving as the template on which the growing polymer can be precipitated. Widely used support-activators include inorganic metal oxide supports, such as silica or aluminum oxide treated with cocatalysts or activators. One such support-activator is methylaluminoxane (MAO) on silica. However, the purchase or preparation cost of MAO is high, and MAO / silica needs multiple subsequent processing steps, such as washing, before it can be used.

[0005] Various clay support-activators have been studied in an attempt to reduce the cost and time required to prepare and use materials such as MAO / silica for metallocene activation. For example, U.S. Patents Nos. 6,531,552 (Japan Polychem Corporation), 6,825,371 (Mitsubishi Chemical Corporation), and 7,220,695 (ExxonMobil) describe treating clay-based supports, such as montmorillonite, with mineral acids, in some cases with additional components, such as surfactants. However, the reaction of acids with ion-exchange clays can result in the replacement of interlayer ions with protons, thereby destroying their porous structure that provides their catalytic activity. See, for example, Nascimento et al., Materials Research, 2015, 18 (2), 283-287; Tavani et al., 1999, 45 (295), 133-136; Kooli et al., Langmuir 2005, 21 (19), 8717-8723; and Tayano et al., Macromolecular Reaction Engineering, 2017, 11 (2), 1600017. Other limitations of the acid treatment method include the difficulty in isolating the modified clay. Other efforts to prepare support-activators include treating clay or organic polymer particles with a combination of surfactants and other components (such as organic amides) (Sumitomo Chemical Co., Ltd. U.S. Patent No. 9,200,093), but these methods and components are also complex and expensive. In addition, using only clay starting materials that exhibit the desired particle size and morphology in these methods may not provide support-activators with these properties.

[0006] Therefore, there remains a need to prepare and isolate economical high activity support-activators. This need is particularly evident in the production of metallocene-based polyolefins such as high clarity film resins. Such support-activators would present a significant cost advantage over currently used aluminoxane-based activators. It is also desirable to develop methods for producing support-activator particles having a uniform spherical morphology, which is very advantageous for producing the desired polymer morphology, ensuring reactor operability, and maintaining the activity of the support-activator. Summary of the invention

[0007] Various aspects of the present disclosure provide novel clay-based support-activators and processes for their preparation, catalyst compositions comprising the novel support-activators, methods for preparing the catalyst compositions, and processes for polymerizing olefins. On the one hand, chemically modified clay support-activators can readily activate metallocene compounds for olefin polymerization, and they are surprisingly easy and inexpensive to prepare and recover in high yields. Relative to acid-treated clay activators, the support-activators of the present disclosure can exhibit high polymerization activity and processability, wherein clay structural degradation and pore collapse (usually resulting in leaching of clay into solution) may occur during the activation process and hinder the easy separation and high polymerization activity of the resulting activator. In addition, the support-activators of the present disclosure retain their desired structural properties (e.g., high pore volume, shape, and size) under granulation / drying conditions (which typically result in high pore collapse in other support-activators).

[0008] The applicant's international patent application publication WO 2021 / 154204 (which is incorporated herein by reference in its entirety) discloses a new clay-based support-activator prepared by contacting a colloidal montmorillonite clay in a liquid carrier with a heterocoagulation agent comprising at least one cationic polymetalate, wherein a surfactant may be present if desired. The clay heteroadducts described in the disclosure are effective support-activators for metallocenes for olefin polymerization. When cationic polymetalates are used in an amount relative to the colloidal montmorillonite clay within a specific range, the montmorillonite heteroadducts can be easily separated from the resulting slurry by conventional filtration methods. The convenience of this filtration contrasts with the difficult separation of previous chemically modified clay support-activators, which may require several days of filtration or multiple washing and centrifugation steps.

[0009] It has now been unexpectedly discovered that clay-based support-activators having the desired spherical shape and size and activity for metallocene activation for olefin polymerization can be prepared when a colloidal montmorillonite clay in a liquid carrier is contacted with a surfactant agent, but in the absence of a cationic polymetalate. These clay-based support-activators are referred to as clay or montmorillonite "heteroadducts" or "complexes," or more specifically, "clay (or montmorillonite)-surfactant heteroadducts (or complexes)." Separation of these montmorillonite-surfactant heteroadducts can be accomplished using conventional filtration, without the need for centrifugation or high dilution of the reaction mixture, and without the need for extensive washing of the solids so obtained. The process provides solid clay heteroadducts that exhibit better activity than the corresponding untreated clay, comparable activity to more difficult to prepare pillared clay supports, and comparable activity to heteroagglomerated clays prepared using cationic polymetalates, thereby meeting the need.

[0010] It has further been discovered that various reagents used to prepare clay-based support-activators can be removed from the preparation process and still provide an active support-activator, thereby providing significant advantages in its production. In addition, 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 existing methods that require an organic liquid carrier.

[0011] Thus, the present disclosure provides a method for preparing a support-activator comprising a montmorillonite heteroadduct, the method comprising or consisting essentially of: in a first liquid carrier:

[0012] (a) colloidal montmorillonite clay; and

[0013] (b) contacting with 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 montmorillonite heteroadduct in the first liquid carrier; wherein the contacting step may occur in the absence of a specific reactant.

[0014] In various aspects of the present disclosure, the contacting step can be carried out in the following circumstances: [i] in the absence of: [A] a cationic polymetallate; [B] a non-layered silicate, a soluble silicate (e.g., 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 oxidant, or any combination thereof; [C] any or both of a cationic surfactant, a nonionic surfactant, or amphoteric surfactant; or (D) any combination thereof; [ii] in the absence of any other cationic reactant, other than the cationic surfactant (when present); or [iii] in the absence of any other reactant, other than the surfactant.

[0015] The method of contacting: (a) colloidal montmorillonite clay; and (b) a surfactant in a first liquid carrier may further include the step of isolating the montmorillonite heteroadduct from the slurry in the first liquid carrier. In some embodiments, the colloidal montmorillonite clay and the surfactant may be contacted at a ratio of 0.5 mmol to 5 mmol of surfactant per gram of colloidal montmorillonite clay, which works well in forming a montmorillonite heteroadduct having the disclosed advantageous characteristics (e.g., providing a colloidal montmorillonite clay that is easily filterable).

[0016] The present disclosure further provides a method of preparing a support-activator comprising a montmorillonite heteroadduct, the method comprising or consisting essentially of: in a first liquid carrier:

[0017] (a) colloidal montmorillonite clay; and

[0018] (b) contacting with 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 montmorillonite heteroadduct in the first liquid carrier;

[0019] The first liquid carrier is essentially composed of water, an organic liquid or a combination thereof.

[0020] The method may also further comprise the step of isolating the montmorillonite heteroadduct from the slurry in the first liquid carrier.

[0021] Once the montmorillonite heteroadduct has been separated from the slurry in the first liquid carrier as disclosed herein, the method of preparing the support-activator can further include the steps of suspending (or resuspending) the montmorillonite heteroadduct in a dispersion medium to provide a suspension of the montmorillonite heteroadduct in the dispersion medium; and spray drying the montmorillonite heteroadduct from the suspension to provide the support-activator in particulate form. In one aspect, the dispersion medium can contain water or consist essentially of water. The latter spray drying step can be referred to herein as "granulating" the montmorillonite heteroadduct.

[0022] It has also been recognized that when colloidal montmorillonite clay in a liquid carrier is contacted with a heterocoagulation agent comprising both a cationic polymetalate and a surfactant agent, the resulting clay-cationic polymetalate-surfactant heteroadduct can exhibit unexpectedly improved polymerization activity in combination with a metallocene. Thus, the present disclosure also presents a method of preparing a support-activator comprising a montmorillonite heteroadduct, the method comprising or consisting essentially of: applying in any order in a first liquid carrier:

[0023] (a) colloidal montmorillonite clay;

[0024] (b) cationic polymetallates; and

[0025] (c) contacting with 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 montmorillonite heteroadduct in the first liquid carrier.

[0026] If desired, the contacting step can also occur in the absence of a particular reactant. In various aspects, for example, the contacting step can be performed in the following circumstances: [i] in the absence of: [A] a non-layered silicate, a soluble silicate (e.g., 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 oxidant, or any combination thereof; [B] any or both of a cationic surfactant, a nonionic surfactant, or an amphoteric surfactant; or [C] any combination thereof; [ii] in the absence of any other cationic reactants, other than the cationic polymetalate and the cationic surfactant (when present); or [iii] in the absence of any other reactants, other than the cationic polymetalate and the surfactant. This method of preparing a clay-cationic polymetalate-surfactant heteroadduct can further include the step of isolating the heteroadduct from the slurry in the first liquid carrier. In one aspect, the method can further include the steps of suspending (or resuspending) the montmorillonite heteroadduct in a dispersion medium to provide a suspension of the montmorillonite heteroadduct in the dispersion medium; and spray drying the montmorillonite heteroadduct from the suspension to provide a support-activator in particulate form. In one aspect, the dispersion medium can comprise or consist essentially of water.

[0027] Compared to the corresponding clay-cationic polymetalate heteroadducts disclosed in Applicant's U.S. Patent Application Publication No. 2021 / 0230318 (which is incorporated herein by reference in its entirety), the clay-cationic polymetalate-surfactant heteroadducts can exhibit improvements in polymerization activity. In addition, these clay-cationic polymetalate-surfactant heteroadducts are convenient to prepare, easy to filter, and can be spray-dried from aqueous slurries in the absence of organic liquids to provide highly spherical support-activators.

[0028] On the other hand, providing a clay-cationic polymetalate-surfactant heteroadduct by spray drying can also be achieved by forming an aqueous spray-dried slurry of a preformed or separated clay-cationic polymetalate heteroadduct, the heteroadduct comprising a surfactant in the aqueous spray-dried slurry. That is, a clay-cationic polymetalate heteroadduct can be formed, as disclosed in the applicant's U.S. Patent Application Publication No. 2021 / 0230318. The clay-cationic polymetalate heteroadduct can then be separated and resuspended in an aqueous dispersion medium containing a surfactant to form a spray-dried suspension, and spray-dried. It is convenient to prepare heteroadducts in this way and provide clay-cationic polymetalate heteroadducts that are easy to filter, which can be spray-dried from an aqueous slurry in the absence of an organic liquid to provide a highly spherical carrier-activator. Therefore, the order of addition of the components can be changed, particularly with respect to the separation of the heteroadducts When adding a surfactant, and active and useful products can be produced with any order of addition.

[0029] The present disclosure also provides the montmorillonite heteroadduct itself. For example, a montmorillonite heteroadduct or a support-activator comprising a montmorillonite heteroadduct is provided, wherein the montmorillonite heteroadduct may comprise or consist essentially of the contact product of:

[0030] (a) colloidal montmorillonite clay; and

[0031] (b) a surfactant, wherein the surfactant comprises or is selected from a cationic surfactant, a nonionic surfactant, an amphoteric surfactant or any combination thereof.

[0032] According to various aspects of the present disclosure, the contact product may be present or may exist in the following circumstances: [i] the absence of: [A] a cationic polymetallate; [B] a non-layered silicate, a soluble silicate (e.g., 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 oxidant, or any combination thereof; [C] any or both of a cationic surfactant, a nonionic surfactant, or amphoteric surfactant; or [D] any combination thereof; [ii] the absence of any other cationic reactant, other than the cationic surfactant (when present); or [iii] the absence of any other reactant, other than the surfactant.

[0033] According to another aspect, a montmorillonite heteroadduct or a support-activator comprising a montmorillonite heteroadduct is provided, wherein the montmorillonite heteroadduct comprises or consists essentially of the contact product of:

[0034] (a) colloidal montmorillonite clay; and

[0035] (b) a surfactant comprising or selected from a cationic surfactant, a nonionic surfactant, an amphoteric surfactant or any combination thereof;

[0036] The first liquid carrier is essentially composed of water, an organic liquid or a combination thereof.

[0037] Yet another aspect of the present disclosure provides a support-activator comprising a montmorillonite heteroadduct comprising or consisting essentially of the contact product of:

[0038] (a) colloidal montmorillonite clay;

[0039] (b) cationic polymetallates; and

[0040] (c) a surfactant comprising or selected from a cationic surfactant, a nonionic surfactant, an amphoteric surfactant or any combination thereof.

[0041] In various aspects of the present disclosure, if desired, the contact product may be present or may exist in the following circumstances: [i] the absence of: [A] non-layered silicate, soluble silicate (e.g., sodium silicate), charged inorganic component, metal oxide, organic amide, anionic surfactant, inorganic acid, organic acid, inorganic base, organic base, oxidant or any combination thereof; [B] any or both of cationic surfactant, nonionic surfactant or amphoteric surfactant; or [C] any combination thereof; [ii] the absence of any other cationic reactant, other than the cationic polymetallate and cationic surfactant (when present); or [iii] the absence of any other reactant, other than the cationic polymetallate and surfactant.

[0042] The surfactant-treated clays (montmorillonite clay heteroadducts) of the present disclosure, whether clay-surfactant heteroadducts or clay-cationic polymetalate-surfactant heteroadducts, when subjected to a granulation and drying process of spray drying followed by calcination, form particles having higher sphericity, porosity, and particle uniformity relative to clay activators dried by other methods. Once granulated and dried as described herein, the clay heteroadducts also retain high olefin polymerization activity when activating metallocene compounds. This desirable performance is in contrast to the performance of clay activators that have been treated with cationic polymetalate salts alone in the absence of surfactant, which may lose polymerization activity and / or particle porosity when spray dried. Because the disclosed spray drying process can be performed on clay-surfactant heteroadducts and clay-cationic polymetalate-surfactant heteroadducts dispersed in an aqueous dispersion medium without the need for an organic liquid or a mixture of an organic liquid and an aqueous dispersion medium, the economic feasibility, safety, and environmental sustainability of the process are significantly improved compared to processes that require a dispersion medium containing an organic liquid.

[0043] The montmorillonite heteroadducts prepared in this way can be used very effectively in transition metal based olefin polymerization processes in combination with cocatalysts such as alkylaluminum compounds. 2 The montmorillonite heteroadduct-cocatalyst combination can provide a very active support-activator for metallocene olefin polymerization when compared to aluminoxane or borane-derived support-activators. In addition, the surfactants used in the process can also be very cheap and can be used with relatively cheap cocatalysts (such as alkyl aluminum compounds), especially compared to aluminoxane and borane-based activators.

[0044] Also disclosed herein is a catalyst system for olefin polymerization, the catalyst system comprising:

[0045] (a) at least one metallocene compound; and

[0046] (b) at least one support-activator according to any aspect of the present disclosure.

[0047] The catalyst system may 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 methylaluminoxane (MAO)). The support-activator of the catalyst system may also be absent any specific reactant not present in the contact product as described herein.

[0048] The present disclosure also provides a method of preparing a catalyst system, wherein the method comprises: providing in a second liquid carrier:

[0049] (a) at least one metallocene compound; and

[0050] (b) contacting at least one support-activator comprising a montmorillonite heteroadduct according to the present disclosure.

[0051] At least one support-activator may comprise a montmorillonite heteroadduct prepared according to any of the methods provided in the present disclosure. In such methods of preparing the catalyst system, the method may further comprise contacting at least one co-catalyst (such as an alkyl aluminum compound) and / or at least one co-activator (such as methylaluminoxane (MAO)) in a second liquid carrier, wherein the contacting may occur in any order. The support-activator may also be absent any specific reactant not present in the contact product as described herein.

[0052] In another aspect, the present disclosure provides a process for polymerizing olefins, the process comprising contacting at least one olefin monomer with a catalyst system under polymerization conditions to form a polyolefin, wherein the catalyst system comprises:

[0053] (a) at least one metallocene compound; and

[0054] (b) at least one support-activator comprising a montmorillonite heteroadduct according to the present disclosure.

[0055] As disclosed herein, at least one support-activator may also comprise a montmorillonite heteroadduct prepared according to any of the methods provided in the present disclosure, and the catalyst system may 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 methylaluminoxane (MAO). The support-activator may also be absent any specific reactant not present in the contact product as described herein.

[0056] These and other aspects, features and embodiments of the support-activator, catalyst composition, methods of making the composition and polymerization processes, and related compositions and methods are more fully described in the detailed description, figures, examples and claims provided herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] Figure 1 and Figure 2 An embodiment of the present disclosure is shown, which shows a scanning electron microscope (SEM) image of a powdered product formed by spray drying an aqueous slurry, wherein the solid component is a filtered adduct obtained by reacting tetramethylammonium bromide with tetramethylammonium bromide in deionized water in the process described in Example 21-E1. HPM-20 montmorillonite is obtained by contact.

[0058] Figure 3 and Figure 4An embodiment of the present disclosure is shown, which shows an SEM image of a powdered product formed by spray drying an aqueous slurry, wherein the solid component is a filtered adduct obtained by reacting aluminum chlorohydrate with HPM-20 montmorillonite is obtained by contact.

[0059] Figure 5 and Figure 6 An embodiment of the present disclosure is shown, which shows an SEM image of a powdered product formed by spray drying an aqueous slurry, wherein the solid component is a filtered adduct obtained by reacting tetrabutylammonium bromide with HPM-20 montmorillonite is obtained by contact.

[0060] Figure 7 and Figure 8 An embodiment of the present disclosure is shown, which shows that in the process described in Example 2-A1, azeotropic drying is carried out by using 1-butanol as an azeotropic agent to azeotropically dry aluminum chlorohydrate (ACH) with SEM image of the support-activator formed by contacting the adduct obtained with HPM-20 montmorillonite and subsequently calcining the dried product.

[0061] Fig. 9 and Fig.10 An embodiment of the present disclosure is shown, which shows an SEM image of a support-activator formed by spray drying an aqueous slurry, wherein the solid component is a filtered adduct obtained by reacting tetramethylammonium bromide with HPM-20 montmorillonite, wherein the spray-dried adduct is subsequently calcined.

[0062] Fig.11 and Fig.12 An embodiment of the present disclosure is shown, which shows an SEM image of a support-activator formed by spray drying an aqueous slurry and subsequently calcining the spray-dried product, wherein the solid component is a filtered adduct obtained by reacting aluminum chlorohydrate with aluminum in the process described in Comparative Example 20-D1. HPM-20 montmorillonite is obtained by contact.

[0063] Fig.13 and Fig.14 An embodiment of the present disclosure is shown, which shows an SEM image of a support-activator formed by spray drying an aqueous slurry and then calcining the spray-dried product, wherein the solid component is a filtered adduct obtained by reacting tetrabutylammonium bromide with HPM-20 montmorillonite is obtained by contact.

[0064] Fig.15 Another embodiment of the present disclosure is shown, which shows an optical microscope image of an ethylene-1-hexene copolymer derived from polymerization, wherein the support-activator is combined with a metallocene bis(1-butyl-3-methylcyclopentadienyl)zirconium dichloride and a triethylaluminum cocatalyst to form an active catalyst. The support-activator is formed by spray drying an aqueous slurry and then calcining the spray-dried product, wherein the solid component is a filtered adduct obtained by reacting tetramethylammonium bromide with tetramethylammonium bromide in the process described in Example 21-E1. HPM-20 montmorillonite is obtained by contact.

[0065] Fig.16 Another embodiment of the present disclosure is shown, which shows an optical microscope image of an ethylene-1-hexene copolymer derived from polymerization, wherein the support-activator is combined with a metallocene bis(1-butyl-3-methylcyclopentadienyl)zirconium dichloride and a triethylaluminum cocatalyst to form an active catalyst. The support-activator is formed by spray drying an aqueous slurry and then calcining the spray-dried product, wherein the solid component is a filtered adduct obtained by reacting tetrabutylammonium bromide with tetrabutylammonium bromide in the process described in Example 22-E2. HPM-20 montmorillonite is obtained by contact.

[0066] Fig.17 Another embodiment of the present disclosure is shown, which shows an optical microscope image of an ethylene-1-hexene copolymer derived from polymerization, wherein the support-activator is combined with a metallocene bis(1-butyl-3-methylcyclopentadienyl)zirconium dichloride and a triethylaluminum cocatalyst to form an active catalyst. In the process described in Example 2-A1, the support-activator is azeotropically dried by azeotropically drying aluminum chlorohydrate (ACH) with 1-butanol as an azeotroping agent. The adduct is formed by contacting with HPM-20 montmorillonite.

[0067] Fig.18 The results of the nitrogen adsorption / desorption BJH (Barrett, Joyner and Halenda) pore volume analysis of the calcined aluminum chlorohydrate (ACH) heteroagglomerated clay of Example 5-A4 are provided, providing the pore diameters (angstroms, ) versus cumulative pore volume (cubic centimeters per gram, cc / g). The recipe used to prepare the heteroadduct slurry used 1.54 mmol Al / g clay, and the sample was zeotropically dried and calcined to provide a zeotropic clay-ACH heteroadduct.

[0068] Fig.19 The results of the nitrogen adsorption / desorption BJH pore volume analysis of the calcined tetramethylammonium bromide heteroagglomerated clay of Example 11-B6 are provided, providing the pore diameters (angstroms, ) versus cumulative pore volume (cubic centimeters per gram, cc / g). The formulation used to prepare the heteroadduct slurry uses 2.48 mmol tetramethylammonium bromide / gram of clay in the absence of a cationic polymetalate to form a heteroagglomerated clay that is zeotropically dried and calcined to provide a zeotropic clay-surfactant heteroadduct.

[0069] Fig. 20 The results of the nitrogen adsorption / desorption BJH pore volume analysis of the calcined tetrabutylammonium bromide heteroagglomerated clay of Example 14-B9 are provided, providing the pore diameters (angstroms, ) versus cumulative pore volume (cubic centimeters per gram, cc / g). The formulation used to prepare the heteroadduct slurry uses 1.24 mmol tetramethylammonium bromide / gram of clay in the absence of a cationic polymetalate to form a heteroagglomerated clay that is zeotropically dried and calcined to provide a zeotropic clay-surfactant heteroadduct.

[0070] Fig.21 The results of the nitrogen adsorption / desorption BJH pore volume analysis of the calcined tetrabutylammonium bromide and aluminum chlorohydrate (ACH) hetero-agglomerated clay of Example 23-E3 are provided, providing the pore diameters (angstroms, ) versus cumulative pore volume (cubic centimeters per gram, cc / g). The formulation used to prepare the heteroadduct slurry used 1.24 mmol tetrabutylammonium bromide / g clay in combination with ACH to form a heteroagglomerated clay that was spray dried and calcined to provide a spray dried clay-ACH-surfactant heteroadduct.

[0071] Fig. 22 The results of the nitrogen adsorption / desorption BJH pore volume analysis of the calcined tetra-n-octylammonium bromide and aluminum chlorohydrate (ACH) hetero-agglomerated clay of Example 24-E4 are provided, and the pore diameters (angstroms, ) versus cumulative pore volume (cubic centimeters per gram, cc / g). The formulation used to prepare the heteroadduct slurry used 0.73 mmol tetra-n-octylammonium bromide / g clay in combination with ACH to form a hetero-agglomerated clay that was spray dried and calcined to provide a spray dried clay-ACH-surfactant hetero-adduct.

[0072] Fig.23 The results of nitrogen adsorption / desorption BJH pore volume analysis of the comparative example of the spray dried and calcined aluminum chlorohydrate (ACH) heteroagglomerated clay of Example 20-D1 are provided, and the pore diameters (angstroms, ) versus cumulative pore volume (cubic centimeters per gram, cc / g). The formulation used to prepare the heteroadduct slurry used 1.54 mmol aluminum chlorohydrate / g clay to form a heteroagglomerated clay that was spray dried and calcined to provide a spray dried clay-ACH heteroadduct.

[0073] Fig.24 The results of nitrogen adsorption / desorption BJH pore volume analysis of the spray-dried and calcined tetrabutylammonium bromide heteroagglomerated clay of Example 22-E2 are provided, providing the pore diameters (angstroms, ) versus cumulative pore volume (cubic centimeters per gram, cc / g). The formulation used to prepare the heteroadduct slurry used 0.73 mmol tetrabutylammonium bromide / g clay in the absence of a cationic polymetalate to form a heteroagglomerated clay that was spray dried and calcined.

[0074] Fig.25 The rotary evaporated and calcined The results of nitrogen adsorption / desorption BJH pore volume analysis of HPM-20 montmorillonite clay provide the pore diameters (angstroms, ) versus cumulative pore volume (cubic centimeters per gram, cc / g).

[0075] Fig.26 Provided is a method of preparing a polymetallic acid salt according to Example 21-E1 by reacting the polymetallic acid salt with the polymetallic acid salt in the absence of a cationic Powder XRD (X-ray diffraction) pattern of the calcined spray-dried product of HPM-20 montmorillonite clay in combination with tetramethylammonium bromide (TMABr).

[0076] Fig. 27 Provided is a method of preparing a polymetallic acid salt according to Example 22-E2 by mixing the polymetallic acid salt with the polymetallic acid salt in the absence of a cationic Powder XRD pattern of the calcined spray-dried product of HPM-20 montmorillonite in combination with tetrabutylammonium bromide (TBABr).

[0077] Fig.28 A method for preparing a cellulose ester according to Comparative Example 20-D1 by mixing the cellulose esters with the cellulose esters in the absence of a surfactant is provided. Powder XRD pattern of the calcined spray-dried product of HPM-20 montmorillonite combined with aluminum chlorohydrate (ACH).

[0078] Fig.29 The results are shown for adding 10.7 wt.% (weight percent) tetrabutylammonium bromide aqueous solution by volume to 1 wt.% Zeta potential titration in aqueous dispersion of HPM-20 bentonite, plotting the measured zeta potential versus mmol cation / g clay (millimoles cation per gram clay). A 30 second equilibrium delay was allowed after each titrant aliquot. mmol cation / g clay represents the cumulative millimoles of aqueous tetrabutylammonium bromide solution added during the titration.

[0079] Fig.30 The results are shown for adding a 7.9 wt.% (weight percent) tetramethylammonium bromide aqueous solution by volume to a 1 wt.% Zeta potential titration in aqueous dispersion of HPM-20 bentonite, plotting the measured zeta potential versus mmol cation / g clay (millimoles cation per gram clay). A 30 second equilibrium delay was allowed after each titrant aliquot. mmol cation / g clay represents the cumulative millimoles of aqueous tetramethylammonium bromide solution added.

[0080] Fig.31 and Fig.32 A comparative example of the present disclosure is shown, which shows SEM images of support-activators produced by the processes of Example 2-A1 and Example 3-A2, respectively, wherein the SEM images of the calcined support-activators are analyzed by scanning probe image processor (SPIP) software to provide particle boundaries depicted on these images for circularity calculations. Fig.31 and Fig.32 The support-activator was azeotropically dried by mixing aluminum chlorohydrate (ACH) with 1-butanol as an azeotroping agent in the absence of a surfactant as described in Examples 2-A1 and 3-A2, respectively. HPM-20 montmorillonite is contacted and the dried product is subsequently calcined to form.

[0081] Fig.33 An embodiment of the present disclosure is shown showing SEM images of a support-activator, wherein SEM images of the calcined support-activator are analyzed by Scanning Probe Image Processor (SPIP) software to provide particle boundaries delineated on these images for circularity calculations. Fig.33 Support-activator As described in Example 30-E2, tetrabutylammonium bromide and HPM-20 montmorillonite was contacted to form the isolated product, and the isolated product was dried azeotropically by rotary evaporation from an aqueous slurry prior to calcination. Fig.33 Images can be used with Figures 34 to 36 A spray dried and calcined sample of Example 22-E2 is shown for comparison.

[0082] Fig.34 , Fig.35 and Fig.36An example of the present disclosure is shown showing three different SEM images of a calcined support-activator that were analyzed by Scanning Probe Image Processor (SPIP) software to provide particle boundaries delineated on the images and used for circularity calculations. Fig.34 , Fig.35 and Fig.36 Support-activator As described in Example 22-E2, tetrabutylammonium bromide and HPM-20 montmorillonite is contacted to form, isolated by filtration, and the separated support-activator is spray dried from the aqueous suspension and subsequently calcined.

[0083] Fig.37 and Fig.38 Examples of the present disclosure are shown in which the support-activator produced by the processes of Example 2-A1 (azeotropic clay-aluminum chlorohydrate heteroadduct) and Example 30-E2 (non-azeotropic and rotary evaporated clay-tetrabutylammonium bromide heteroadduct) is combined with (η5-1-n-butyl-3-methyl-cyclopentadienyl)2ZrCl2 and triethylaluminum (TEA), respectively, and the resulting catalyst compositions are used to copolymerize ethylene and 1-hexene as described in these examples. The polymer particles obtained from these copolymerizations are collected and reacted by X2 was analyzed to determine the sphericity of the particles. Fig.37 and Fig.37 The volume weighted sphericity (SPHT3) of samples of polymer particles from Example 2-A1 and Example 30-E2 are plotted versus polymer particle size, respectively. Particle size distribution data and the number weighted average sphericity (SPHT0) of the entire particle distribution are also listed.

[0084] Fig.39 and Fig.40 A graph of volume weighted sphericity SPHT3 versus polymer particle size is shown for two samples of ethylene-1-hexene copolymer particles prepared using a metallocene catalyst composition comprising a 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 polymetalate, and these polymer particles were collected and filtered. X2 was analyzed to determine the particle sphericity. Particle size distribution data and the number-weighted average sphericity (SPHT0) of the entire particle distribution are also listed.

[0085] Fig.41Particle size distribution and cumulative volume curves for a sample of ethylene-1-hexene copolymer particles prepared using a metallocene catalyst composition comprising a support-activator from Example 31 are shown. The Q3[%] axis corresponds to the curve on the graph and represents the cumulative volume percentage value, which is the percentage of the total volume of particles below that particle size value. The P3[%] axis corresponds to the bar graph distribution and shows the percentage of the total volume of each bar or "slice" corresponding to the particle size. Example 31 Support-Activator is provided by spray drying a clay-tetrabutylammonium bromide heteroadduct in the absence of a cationic polymetalate, and these polymer particles are collected and filtered through X2 was analyzed to determine the particle size distribution. Fig.41 Data is collected for Fig.40 The same copolymer samples as the data in .

[0086] Fig.42 , Fig.44 and Fig.46 shows the use of the inclusion from Example 33 ( Fig.42 )、Instance 34( Fig.44 ) and Example 35 ( Fig.46 Particle size distribution and cumulative volume curves for three different samples of ethylene-1-hexene copolymer particles prepared with a metallocene catalyst composition containing a support-activator of Example 31 (clay-tetrabutylammonium bromide heteroadduct). These examples were derived from spray drying a sample of the support-activator of Example 31 (clay-tetrabutylammonium bromide heteroadduct), sieving the sample into three different size ranges, and calcining each sample before using it to prepare catalyst compositions and copolymers. The support-activator sieve fraction used to produce the copolymers was 19 μm (micrometers) to 37 μm (micrometers). Fig.42 )、37μm to 50μm( Fig.44 ) and 50μm to 74μm ( Fig.46 ).use X2 obtains polymer particle size distribution.

[0087] Fig.43 , Fig.45 and Fig.47 Presents the use of the included from Example 33 ( Fig.43 )、Instance 34( Fig.45 ) and Example 35 ( Fig.47 ) as a function of polymer particle size for samples of ethylene-1-hexene copolymer particles prepared from metallocene catalyst compositions containing a support-activator of Example 31 (clay-tetrabutylammonium bromide heteroadduct). These examples are derived from spray drying a sample of the support-activator of Example 31 (clay-tetrabutylammonium bromide heteroadduct), sieving the sample into three different size ranges, and calcining each sample before using it to prepare catalyst compositions and copolymers. The support-activator sieve fraction used to produce the copolymers was 19 μm (micrometers) to 37 μm (micrometers). Fig.43 )、37μm to 50μm( Fig.45 ) and 50μm to 74μm ( Fig.47 ).use X2 obtains polymer particle size distribution. DETAILED DESCRIPTION

[0088] In order to more clearly define the terms and phrases used herein, the following definitions are provided. If there is a conflict between any definition or usage provided by any document incorporated by reference herein and the definition or usage provided herein, the definition or usage provided herein shall prevail.

[0089] A. Definition and Interpretation of Terms

[0090] Surfactants. The term "surfactant" and similar terms such as "surfactant agent", "surfactant compound", "surfactant component" or "surface active agent" refer to compounds or agents that can reduce the surface tension between phases (e.g., two liquid phases, a gas phase and a liquid phase or a liquid phase and a solid phase). Many surfactant compounds contain a hydrophobic portion or region and a hydrophilic portion or region, such as a polar region and a non-polar region, respectively. The hydrophilic portion may include but not necessarily include a negatively charged portion, a positively charged portion, or a hydrogen bonding portion (such as a hydroxyl group, other oxygen-containing groups, etc.), while the hydrophobic portion may include but not necessarily include an alkyl or aromatic group. Surfactants are generally characterized by the terms anionic, cationic or nonionic based on whether their hydrophilic portion includes a negatively charged portion, a positively charged portion, or a hydrogen bonding portion. Unless otherwise specified or excluded, the "surfactant" referred to in the present disclosure may include cationic surfactants, nonionic surfactants and amphoteric surfactants, and in some cases may include anionic surfactants that can be used in combination with cationic surfactants, nonionic surfactants or amphoteric surfactants, as explained herein, all of which will be further described.

[0091] "Amphoteric" surfactants are surfactants that can include a positively charged portion (or a portion that can easily become positively charged by accepting a proton) and a negatively charged portion (or a portion that can easily become negatively charged by releasing a proton) in the same molecule. Based on the inclusion of cationic and anionic portions in the same molecule, the term "zwitterionic" surfactants are used interchangeably with "amphoteric" surfactants. In one aspect, an "amphoteric" surfactant includes a portion that can react with an acid and a portion that can react with a base. An "amphiprotic" surfactant is an amphoteric surfactant that either donates a proton (H +), or accepting a proton, examples of which are amino acids. Unless otherwise excluded, reference to amphoteric or zwitterionic surfactants includes amphoteric (amphiprotic) surfactants. "Amphoteric" surfactants such as amino acids can be considered a type of nonionic surfactant, however, in this disclosure, the term "nonionic" surfactant is reserved for non-zwitterionic molecules, such as poly (ethylene) glycol, poly (propylene) glycol or cyclodextrin, while the term "amphoteric" surfactant is used for zwitterionic surfactants.

[0092] Heteroaggregating agents. The terms "heteroaggregating agent", "heteroaggregating agent", etc. are used herein to describe a compound or composition comprising a monomer, oligomer or polymer, which is present in a solution or as a colloidal suspension, and when it is present as a colloidal suspension in an appropriate ratio and combined with a colloidal clay dispersion, forms a solid that is easily filtered (as defined herein). Therefore, the term heteroaggregating agent is used herein to refer to the cationic surfactants, nonionic surfactants and amphoteric surfactants described in the present disclosure, as well as to refer to positively charged oligomeric or polymeric metal oxides containing substances called "polymetalates" or "polyoxometalates", such as aluminum chlorohydrate (ACH), which are described in detail in the applicant's U.S. Patent Application Publication No. 2021 / 0230318, which is incorporated herein by reference in its entirety. These polymetalates are also referred to as "cationic polymetalates". "Heteroaggregating" is a term of art described by Lagaly in Ullmann's Encyclopedia of Chemistry 2012. Therefore, the heteroaggregating agent can include only surfactants, only cationic polymetalates, or a combination of surfactants and cationic polymetalates.

[0093] In the context of the present disclosure, unless otherwise specified, "hetero-coacervation" is defined as a process in which negatively charged colloidal clay particles are combined with a hetero-coacervation agent substance to form a solid that is easily filtered. Most, but not all, hetero-coacervation agents described in the present disclosure are positively charged substances that are combined with negatively charged colloidal clay particles to form a solid hetero-adduct that is easily filtered. In the art and herein, hetero-coacervation is sometimes also referred to as hetero-aggregation, such as described in Cerbelaud et al. Advances in Physics: X, 2017, Vol. 2, 35-53.

[0094] Heteroadducts or heteroaggregates. The terms "heteroadducts," "heteroaggregates," "aggregates," "heterocomplexes," "complexes," and similar terms such as "clay composites," "heteroaggregate clays," or "montmorillonite heteroadducts," refer to the contact product obtained from combining the heteroaggregate agents disclosed herein with colloidal clays, such as colloidal montmorillonite clays. That is, agglomerates formed by attraction of negatively charged colloidal clay particles with heteroaggregate agents disclosed herein, such as cationic polymetallates, surfactants disclosed herein, or both cationic polymetallates and surfactants, are referred to as "heteroadducts" or "heteroaggregates," or sometimes simply "adducts" or "aggregates." Reference is made to U.S. Pat. No. 8,642,499 to WuCheng et al., which uses the term "heteroaggregate," which is incorporated herein by reference. In one aspect, as defined herein, these terms refer to the "readily filterable" contact product of a heteroaggregate agent and a colloidal clay. These terms are used to distinguish readily filterable heterocoacervates from the contact products of a heterocoacervating agent and colloidal clay combined in a ratio to provide a product that is not readily filterable, such as the product formed when following a pillared clay synthesis.

[0095] The terms "heteroadduct" and "heteroaggregate" and similar terms are also used when describing the formation of heteroaggregate clays formed by contacting clay with cationic polymetallates, whether the contact occurs in the presence or absence of a surfactant. These heteroadducts comprising the contact product of clay and cationic polymetallates are described in detail in U.S. Patent Application Publication No. 2021 / 0230318. Other heteroaggregates of the present disclosure can be prepared by contacting colloidal clay with a surfactant in the absence of a cationic polymetallate.

[0096] Thus, when not otherwise stated and when the context permits or requires, a "heteroadduct" or "heteroaggregate" may be a montmorillonite clay-surfactant heteroadduct, a montmorillonite clay-cationic polymetallate-surfactant heteroadduct, or simply a montmorillonite clay-cationic polymetallate heteroadduct.

[0097] Polymetallates. The terms "polymetallates", "cationic polymetallates", and similar terms such as "polyoxometallates" are used interchangeably in the present disclosure, as they are in U.S. Patent Application Publication No. 2021 / 0230318 to refer to water-soluble polyatomic cations, which include two or more metal atoms (e.g., aluminum, silicon, titanium, zirconium or other metals) and at least one bridging ligand between the metals, such as an oxy group, a hydroxyl group, and / or a halide ligand. For the sake of clarity, the "polymetallates" of the present disclosure are generally referred to herein as "cationic polymetallates". The specific ligand may depend on the precursor and other factors, such as the process for producing the polymetallates, the solution pH, and the like. For example, the polymetallates of the present disclosure may be hydrous metal oxides, hydrous metal hydroxide oxides, and the like, including combinations thereof. Bridging ligands such as oxy ligands that bridge two or more metals may appear in these substances, however, the polymetallates may also include terminal oxy groups, hydroxyl groups, and / or halide ligands.

[0098] Although many known polymetallate species are anionic, and the suffix "-ate" is often used to reflect anionic species, the polymetallate (polyoxometalate) species used in accordance with the present disclosure are cationic. These materials may be referred to as compounds, substances, or compositions, but one of ordinary skill in the art will appreciate that polymetallate compositions may contain a variety of species in a suitable carrier, such as in aqueous solution, depending on, for example, solution pH, concentration, starting precursors for producing polymetallates in aqueous solution, etc. For clarity and convenience, these various species are collectively referred to as "polymetallates" or "polyoxometallates," regardless of whether the composition includes or consists essentially of a cationic polyoxometallate, a polyhydroxymetallate, a polyhydroxymetallate, or a species including or consisting essentially of a mixture of other ligands or compounds such as halides. Examples of polymetallates include, but are not limited to, polyoxyhydroxyaluminum chloride, aluminum chlorohydrate (ACH), polyaluminum chloride (PAC), or aluminum sesquichlorohydrate compositions, which may include linear, cyclic, or clustered compounds. These compositions are collectively referred to as polymetallates, but the terms "polymetallates" or "polyoxometallates" are also used to describe compositions that essentially contain a single substance.

[0099] Homopolymetalates containing a single type of metal and heteropolymetalates containing more than one type of metal (or electropositive atoms, such as phosphorus) are included in the general term polymetalates or polyoxometalates. On the other hand, polymetalates according to the present disclosure can be non-alkylated to transition metal compounds such as metallocene compounds. That is, the polymetalates of the present disclosure can be free of direct metal-carbon bonds, such as those found in aluminoxanes or other organometallic materials.

[0100] In another aspect, the polymetallate may be at least one aluminum polymetallate. Examples include, but are not limited to, aluminum chlorohydrate (ACH), also known as aluminum chlorohydrate, which encompasses a variety of water-soluble aluminum species, generally considered to have the general formula Al n Cl 3n-m (OH) m These polymetallic acid salt species may be referred to as aluminum oxyhydroxychloride compounds or compositions. Another polymetallic salt that may be used in accordance with the present disclosure is polyaluminum chloride (PAC), which is also not a single species, but rather a collection of various aluminum polymeric species that may include linear, cyclic, or clustered compounds, examples of which may contain from 2 to about 30 aluminum atoms, oxy groups, chlorine, and hydroxyl groups. Other examples of polymetallic aluminum salts include, but are not limited to, those having the general formula [Al m O n (OH) x Cl y ]·zH 2 O compounds, such as aluminum sesquichlorohydrate, and cluster-type species, such as Keggin ions, for example [AlO 4 Al 12 (OH) 24 (H 2 O) 12 ] 7+ ·7[Cl] - , sometimes called "Al 13 -mer" polycation. Polyaluminium chloride (PAC) can be prepared by reacting aqueous hydroxide with AlCl 3 Aluminium is produced in combination and the resulting mixture of aluminium species has a range of basicities. Aluminium chlorohydrate (ACH) is generally considered to be the most basic, and polyaluminium chloride (PAC) is considered to be the weakest.

[0101] Readily Filterable. The terms "readily filterable," "easy to filter," "easily filterable," "easy to filter or separate," and the like are used herein to describe compositions according to the present disclosure wherein solids in a mixture containing a liquid phase can be separated from the liquid phase by filtration without resorting to centrifugation, ultracentrifugation, or dilute solutions of less than about 2 wt.% solids, decanting liquid from solids after prolonged settling, and other such techniques. These terms are generally used herein to describe clay heteroadducts that do not require separation by centrifugation, high dilution, and settling or settling tanks, or ultrafiltration. Thus, readily filterable clay heteroadducts can be separated from soluble salts and synthesis byproducts in good yields in a few minutes or less, or in less than about one hour, under gravity or vacuum filtration conditions, by passing a slurry containing the heteroadduct through a conventional filter material, such as sintered glass, metal or ceramic frit, paper, natural or synthetic matte fibers, and the like.

[0102] The present disclosure provides some specific experimental and quantitative methods by which "ease of filterability" can be assessed. Colloids or suspensions described by Lagaly in Ulmmann's Encyclopedia of Chemistry 2012 that require long periods of sedimentation or ultrafiltration are not considered "filterable" in the context of the present disclosure. For example, an easily filterable suspension or slurry of the present disclosure may provide a clear filtrate upon filtration, while a "not easily filterable" suspension takes much longer to filter and may contain particulate matter in the form of a turbid or unclear filtrate that is observable to the naked eye, which is indicative of a colloidal clay dispersion.

[0103] Colloid. The terms "colloid", "colloidal clay", "colloidal solution", "colloidal suspension" and similar terms are used as defined in the chapter "Colloids" of Ullmannn's Encyclopedia of Industrial Chemistry, published by Gerhard Lagaly on January 15, 2007. These terms are used interchangeably.

[0104] Catalyst Compositions and Catalyst Systems. Terms such as "catalyst composition," "catalyst mixture," "catalyst system," and the like are used to refer to the combination of listed components that ultimately form or are used to form an active catalyst according to the present disclosure. The use of these terms is not dependent on any particular contacting steps, contacting order, whether any reactions may occur between or among the components, or any products that may be formed from any contact of any or all of the listed components. The use of these terms is also not dependent on the nature of the active catalytic sites, or the fate of any cocatalyst, metallocene compound, or support-activator after contacting or combining any of these components in any order. Thus, these and similar terms encompass the combination of the initially listed components or starting components of the catalyst composition, as well as any products that may result from contacting these initially listed starting components, regardless of whether the catalyst composition is heterogeneous or homogeneous, or includes soluble and insoluble components. The terms "catalyst" and "catalyst system" or "catalyst composition" may be used interchangeably, and such use will be apparent to the skilled person from the context of the present disclosure.

[0105] Catalyst activity. Unless otherwise indicated, 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 disclosed herein, which is generally expressed simply as weight of polymer polymerized / weight of catalyst clay support-activator / polymerization hour, in the absence of any transition metal catalyst component (such as a metallocene compound), any cocatalyst (such as an organoaluminum compound), or any coactivator (such as an aluminoxane). In other words, the weight of polymer produced per hour divided by the weight of the calcined clay heteroadduct, in units of g / g / hr (grams per gram per hour).

[0106] The activity of a reference or comparative catalyst composition refers to the polymerization activity of the catalyst composition comprising the comparative catalyst composition and is based on the weight of the comparative ion exchange or pillared clay or other support-activator or the weight of the clay component itself used to prepare the clay heteroadduct. Terms such as "increased activity" or "enhanced activity" describe the activity of a catalyst composition according to the present disclosure that is greater than the activity of a comparative catalyst composition using the same catalyst components such as a metallocene compound and a cocatalyst, except that the comparative catalyst composition typically uses a different support-activator or activator such as a pillared clay, or the clay component used in the catalytic reaction is not a heteroaggregate clay. A standard set of ethylene homopolymerization conditions that can be used to compare activity is described in the Examples.

[0107] Contact Product. The term "contact product" is used herein to describe compositions in which the components are combined together or "contacted" in any order, and for any duration, unless the context of the present disclosure in any way states or requires or implies a particular order. Although a "contact product" may include a reaction product, it is not required that the individual components react with each other, and this term is used regardless of any reactions that may or may not occur upon contacting the listed components. To form the contact product, for example, the listed components may be contacted by blending or mixing, or may be contacted by adding the components to or combining with a liquid carrier in any order or simultaneously.

[0108] Unless otherwise specified or required or implied by the context in which the term is used, contact of any component may occur in the presence or absence of any other component of the composition described herein. Examples of contact products that do not include certain components used to form the contact product include the following. In some aspects, the present disclosure describes a montmorillonite heteroadduct comprising a contact product of (a) colloidal montmorillonite clay and (b) a surfactant in a first liquid carrier and specifically in the absence of various reagents or in the absence of other specific reagents or in the absence of any other reagents. In another example, the montmorillonite heteroadduct may comprise a contact product of (a) colloidal montmorillonite clay and (b) a surfactant in a first liquid carrier, wherein the first liquid carrier consists essentially of water, an organic liquid, or a combination thereof. By describing the contact product in a first liquid carrier consisting essentially of water or an organic liquid, or a combination thereof, once the montmorillonite heteroadduct is formed, additional reagents may be contacted with the montmorillonite heteroadduct, or additional reagents may be excluded from contacting the montmorillonite heteroadduct as specified.

[0109] The combining or contacting of the listed components or any additional materials can be carried out by any suitable method. Thus, the term "contact product" includes mixtures, blends, solutions, slurries, reaction products, etc. or combinations thereof. Similarly, unless otherwise specified, the term "contacting" is used herein to refer to materials that can be blended, mixed, slurried, dissolved, reacted, treated, or contacted in some other manner and in any order.

[0110] Pore ​​diameter (pore size) and pore volume. Nitrogen adsorption / desorption measurements are used to determine pore size and pore volume distribution using the BJH (Barrett, Joyner and Halenda) pore volume analysis method. Based on the porous material classification system of the International Union of Pure and Applied Chemistry (IUPAC) (see Pure & Appl. Chem., 1994, 66, 1739-1758) and Klobes et al., National Institute of Standards and Technology Special Publication 960-17, pore size is defined as follows. As used herein, "micropores" and "microporous" refer to pores with a diameter less than 100 microns that are present in a catalyst or catalyst support produced according to the process of the present disclosure. As used herein, "mesopores" and "mesopores" refer to pores with a diameter of between to less than As used herein, "macroporous" and "multi-macroporous" refer to pores with diameters equal to or greater than 100 nm that are present in a catalyst or catalyst support produced according to the process of the present disclosure. (50nm) pores.

[0111] Each of the above definitions of micropores, mesopores, and macropores is considered distinct and non-overlapping to ensure that pores are not counted twice when summing the percentages or values ​​of the pore size distribution (pore diameter distribution) for any given sample.

[0112] "d50" or "D50" means the median pore diameter as measured by porosimetry. Thus, "d50" corresponds to the median pore diameter calculated based on the pore size distribution, and half of the pore diameters are larger than this median. The d50 values ​​reported herein are based on nitrogen desorption, using the well-known calculation method described by EP Barrett, LG Joyner, and PP 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.

[0113] "Median pore diameter" (MPD) can be calculated, for example, based on volume, surface area, or based on pore size distribution data. A median pore diameter calculated by volume means that half of the total pore volume is greater than the median value. A median pore diameter calculated by surface area means that half of the total pore surface area is greater than the median value. Similarly, a median pore diameter calculated based on a pore size distribution means that half of the pores have a pore diameter greater than the median value according to a pore size distribution determined as described elsewhere herein, for example, by deduction from a nitrogen adsorption-desorption isotherm.

[0114] Transition Metal Catalysts. "Transition metal catalyst" refers to a transition metal compound or composition that, when contacted with a support-activator of the present disclosure, can act as or be converted into an active olefin polymerization catalyst, either in its present form or when contacted with a cocatalyst that is capable of transferring or rendering a polymerizable activated ligand to the transition metal catalyst. Thus, "transition metal catalyst" includes both transition metal species that can act as catalysts and transition metal species that are "precatalysts" or "main catalysts" because they can be converted into compositions that can act as catalysts.

[0115] The use of the term "catalyst" is not intended to reflect any particular mechanism, or that the "transition metal catalyst" itself represents an active site for catalyzing polymerization when the "transition metal catalyst" is activated or endowed with a polymerization-activatable ligand. Transition metal catalysts are described in terms of one or more transition metal compounds used in the process for preparing the polymerization catalyst, and may include metallocene compounds and related compounds as defined herein.

[0116] Cocatalyst. "Cocatalyst" is used herein to refer to a chemical reagent, compound or composition that can impart a ligand to a transition metal compound such as a metallocene, which can initiate polymerization when the metallocene is activated by a support-activator. In other words, "cocatalyst" is used herein to refer to a chemical reagent, compound or composition that can provide a polymerizable activated ligand to a metallocene compound. The polymerizable activated ligand includes, but is not limited to, a hydrocarbyl group, such as an alkyl group, such as a methyl or ethyl group, an aryl group and a substituted aryl group, such as a phenyl or tolyl group, a substituted alkyl group, such as a benzyl or trimethylsilylmethyl group (-CH 2 SiM 3 ), hydride, silyl and substituted groups, such as trimethylsilyl, etc. Therefore, on the one hand, the cocatalyst can be an alkylating agent, a hydrogenating agent, a silylating agent, etc. There is no restriction on the mechanism by which the cocatalyst provides a polymerizable activated ligand to the metallocene compound. For example, the cocatalyst can participate in a metathesis reaction to exchange the exchangeable ligand (such as a halide or alkoxide) on the metallocene compound with a polymerizable activated / initiating ligand (such as a methyl or hydride). On the one hand, the cocatalyst is an optional component of the catalyst composition, for example, when the metallocene compound already includes a polymerizable activated / initiating ligand (such as a methyl or hydride). On the other hand, as will be appreciated by those skilled in the art, even when the metallocene compound includes a polymerizable activated ligand, the cocatalyst can also be used for other purposes, such as sweeping moisture from a polymerization reactor or process. According to another aspect and as required or permitted by the context, the term "cocatalyst" can refer to an "activator", which can be used interchangeably with the "cocatalyst" explained herein.

[0117] Activator. As used herein, "activator" generally refers to a substance that can convert a metallocene component into an active catalyst system that can polymerize olefins, and is intended to be independent of the mechanism by which such activation occurs. "Activator" can convert the contact product of a metallocene component and a component that provides an activatable ligand (such as an alkyl or hydride) for the metallocene into a catalyst system that can polymerize olefins, for example, when the metallocene compound does not yet contain such a ligand. Regardless of the actual activation mechanism, this term is used. Exemplary activators can include, but are not limited to, carrier-activators, aluminoxanes, organoboron or organoborate compounds, ionizing compounds (such as ionizing ionic compounds), etc. Aluminoxanes, organoboron or organoborate compounds, and ionizing compounds can be referred to as "activators" or "co-activators" when used in catalyst compositions in which carrier-activators are present, but the catalyst composition is supplemented with one or more aluminoxanes, organoborons, organoborates, ionizing compounds, or other co-activators.

[0118] Support-activator. As used herein, the term "support-activator" refers to an activator in solid form, such as ion exchange clays, protonic acid treated clays or pillared clays, and similar insoluble activators that also serve as supports. When the support-activator is combined with a metallocene having an activatable ligand, or alternatively with a metallocene and a cocatalyst that can provide an activatable ligand, a catalyst system is provided that can polymerize olefins. Thus, the montmorillonite heteroadducts according to the present disclosure are support-activators.

[0119] Ion exchange clay. As used herein and as understood by those skilled in the art, the term "ion exchange clay" refers to a clay in which the exchangeable ions of a naturally occurring or synthetic clay have been replaced or exchanged with one or more ions of another selection. Ion exchange can be performed by treating a naturally occurring or synthetic clay with a selected cation source, typically from a concentrated ionic solution (such as a 2N cationic aqueous solution), the treatment comprising a plurality of exchange steps, e.g., three exchange steps. The exchange clay can then be washed several times with deionized water to remove excess ions produced during the treatment, e.g., 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. Typically, centrifugation is used to separate the clay from the solution between ion treatment and washing.

[0120] Metallocene compounds. As used herein, the term "metallocene" or "metallocene compound" describes a transition metal or lanthanide metal compound that contains at least one substituted or unsubstituted cycloalkadienyl-type ligand or alkanadienyl-type ligand, including heteroatom analogs thereof, regardless of the specific bonding pattern, for example, regardless of whether the cycloalkadienyl-type ligand or alkanadienyl-type ligand is η-substituted or η-substituted. 5 -、η 3 - or η 1 -bonding mode to the metal, regardless of whether more than one of these bonding modes is accessible to such ligands. In this disclosure, the term "metallocene" is also used to refer to compounds containing at least one π-bonded allylic ligand, where η 3 -allyl is not part of a cycloalkadienyl or alkanadienyl ligand, and the compound can be used as the transition metal compound component of the catalyst composition described herein. Therefore, "metallocene" includes substituted or unsubstituted η 3 To 5 -cycloalkadienyl type and η 3 To 5 -alkadienyl type ligand, η 3 -allyl type ligand compounds, including heteroatom analogs thereof, and including but not limited to cyclopentadienyl ligands, indenyl ligands, fluorenyl ligands, n-allyl ligands, 3 -allyl ligands, pentadienyl ligands, boron anion heterophenyl ligands, 1,2-nitrogen borocyclopentadienyl ligands, 1,2-diaza-3,5-diboryl ligands, substituted analogs thereof and partially saturated analogs thereof. Partially saturated analogs include partially saturated η 5 -Compounds of 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. In some cases, metallocenes are simply referred to as "catalysts", which is almost identical to the term "cocatalyst" used herein to refer to, for example, organoaluminum compounds. Therefore, metallocene ligands may be considered in the present disclosure to include at least one substituted or at least one unsubstituted cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, allyl, boron heterophenyl, 1,2-azaboryl or 1,2-diaza-3,5-diboryl ligands, including substituted analogs thereof. For example, any substituent may be independently selected from halides, C 1 -C 20 Hydrocarbon, C 1 -C 20 Heteroalkyl, C 1 -C 20 Organic hetero groups, condensed C 4 -C 12 A carbocyclic moiety or a fused C having at least one heteroatom independently selected from nitrogen, oxygen, sulfur or phosphorus4 -C 11 Heterocyclic moiety.

[0121] Organoaluminum compounds and organoboron compounds. As used herein, the terms organoaluminum compounds and organoboron compounds include compounds such as AlMe 3 and BEt 3 neutral compounds, and also include LiAlMe 4 、LiAlH 4 , NaBH 4 and LiBEt 4 Thus, unless otherwise stated, hydride compounds of aluminum and boron are included in the definitions of organoaluminum and organoboron compounds, respectively, whether the compound is neutral or anionic.

[0122] Pillared clay. In this disclosure, "pillared clay" is defined as a clay in which ordered layers with a basal spacing substantially greater than to Clay materials. When powdered clay samples are analyzed using an X-ray diffraction apparatus capable of scanning 2° or greater 2θ angles, it is often observed that materials containing such pillared order have substantial peaks at 2θ values ​​between 2° and 9°. These are typically prepared by introducing a pillaring agent, such as an oxygen-containing inorganic cation, such as an oxygen-containing cation of lanthanum, aluminum, or iron. Aluminum-pillared clays are often prepared by contacting a pillaring agent with the clay, with the amount used ranging from about 5 mmol Al / g clay or 6 mmol Al / g clay to up to about 30 mmol Al / g clay.

[0123] Insertion. The term "insertion" or "intercalation" is a term of art that refers to the insertion of a material into an intercalation layer of a clay matrix. Unless otherwise indicated, these terms are used herein in a manner understood by those skilled in the art and as described in U.S. Pat. No. 4,637,992.

[0124] Basal Spacing. The terms "basal spacing," "basal d001 spacing," or "d001 spacing," when used in the context of smectite clays such as montmorillonite, refer to the distance between like faces of adjacent layers in the clay structure, typically expressed in angstroms or nanometers. Thus, for example, in the smectite clays of the 2:1 family that includes montmorillonite, the basal distance is the distance from the top of a tetrahedral sheet to the top of the next tetrahedral sheet of the adjacent 2:1 layer, and includes intervening octahedral sheets, 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 in bentonite, has a basal spacing of about 1.5 Å. to about The XRD test method for determining the substrate 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. Pat. No. 5,202,295 (McCauley) at column 27, lines 22-43.

[0125] Zeta potential. As used herein, the term "zeta potential" refers to the potential difference between the junction of the fixed layer (a firmly attached layer of counterions that forms to neutralize the surface charge of the colloidal particles) and the diffuse layer (a loosely attached group of ions that is located farther from the particle surface than the fixed layer) and the bulk solution or slurry. This property is expressed in units of voltage, such as millivolts (mV). The zeta potential can be obtained by quantifying the "electrokinetic acoustic amplitude effect" (ESA), which is the generation of ultrasonic waves due to the application of an electric potential on a colloidal suspension, as described in U.S. Pat. No. 5,616,872, which is incorporated herein by reference.

[0126] Hydrocarbyl groups. As used herein, the term "hydrocarbyl" group is used according to the art-recognized IUPAC definition as a monovalent, straight-chain, branched, or cyclic group formed by removing a single hydrogen atom from a parent hydrocarbon compound. Unless otherwise specified, a hydrocarbyl group may be aliphatic or aromatic; saturated or unsaturated; and may include straight-chain, cyclic, branched, and / or fused ring structures; unless any of these are otherwise explicitly excluded. See IUPAC Compendium of Chemical Terminology, 2nd Edition (1997) p. 190. Examples of hydrocarbyl groups include, but are not limited to, aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, cycloalkadienyl, alkynyl, aralkyl, aralkenyl, and aralkynyl groups, etc.

[0127] Heteroalkyl groups. The term "heteroalkyl" group is used in this disclosure to encompass monovalent, straight-chain, branched or cyclic groups formed by removing a single hydrogen atom from a carbon atom of a parent "heteroalkyl" molecule, at least one of which is replaced by a heteroatom. The parent heteroalkyl can be aliphatic or aromatic. Examples of "heteroalkyl" groups include halogen-substituted, nitrogen-substituted, phosphorus-substituted, silicon-substituted, oxygen-substituted and sulfur-substituted hydrocarbon groups in which hydrogen has been removed from a carbon atom to produce a free valence. Examples of heteroalkyl groups include, but are not limited to, -CH 2 OCH 3 、-CH 2 SPh, -CH 2 NHCH 3 、-CH 2 CH 3 NMe 2 、-CH 2 SiMe 3 、-CMe 2 SiMe 3 、-CH 2 (C 6 H 4 -4-OMe), -CH 2 (C 6 H 4 -4-NHMe), -CH 2 (C 6 H 4 -4-PPh 2 ),-CH 2 CH 3 P E 2 、-CH 2 Cl, -CH 2 (2,6-C 6 H 3 Cl 2 )wait.

[0128] Heteroalkyl encompasses heteroaliphatic groups (including saturated and unsaturated groups) and heteroaromatic groups. Thus, heteroatom-substituted vinyl groups, heteroatom-substituted alkenyl groups, heteroatom-substituted diene groups, and the like are all included in heteroalkyl groups.

[0129] Organic heteroyl groups. The term "organic heteroyl" group is also used according to the IUPAC definition recognized in the art, as a monovalent group containing carbon, so it is organic, but has free valence on atoms other than carbon. See IUPAC Compendium of Chemical Terminology, 2nd edition (1997) page 284. Organic heteroyl groups can be straight chain, branched or cyclic, and include common groups such as alkoxy, aryloxy, organic thio (or organic thio), organic germanium (or organic germanium), acetamido, acetonyl acetamido, alkyl amide, dialkyl amide, aryl amide, diaryl amide, trimethylsilyl, etc. Groups such as -OMe, -OPh, -S (tolyl), -NHMe, -NMe 2 、-N(aryl) 2 、-SiMe 3 、-PPh 2 , -O 3 S(C 6 H 4 )Me、-OCF 2 CF 3 , -O 2 C(alkyl), -O 2 C(aryl), -N(alkyl)CO(alkyl), -N(aryl)CO(aryl), -N(alkyl)C(O)N(alkyl) 2 , hexafluoroacetonate, acetyl, etc.

[0130] Organic group. Organic group is used in this disclosure according to the IUPAC definition and refers to any organic substituent group having one free valence on a carbon atom, regardless of the functional type, for example, CH 3 CH 2 -, ClCH 2 C-、CH 3 C(=O)-, 4-pyridylmethyl, etc. The organyl group may be linear, branched or cyclic, and the term "organyl" may be used in conjunction with other terms, such as in organothio- (eg, MeS-) and organooxy.

[0131] Heterocyclic radical group.The IUPAC general catalog compares organic radical group with other groups such as heterocyclic radical group and organic heterocyclic radical group.These terms are in the IUPAC Compendium of Chemical Terminology, and the 2nd edition (1997) has the following statement, and it proves the convention of connecting "-yl" suffix on the part with the valence from missing hydrogen of molecule or group.Therefore, heterocyclic radical group is defined as the monovalent group formed by removing hydrogen atom from any ring atom of heterocyclic compound.For example, the piperidin-1-yl group and piperidin-2-yl group shown below are all heterocyclic radical groups, and the line wherein drawing from nitrogen-atom or carbon atom represents open valence rather than methyl group.

[0132]

[0133] However, piperidin-1-yl groups are also considered to be organoheteroyl groups, and piperidin-2-yl groups are also considered to be heteroalkyl groups. Thus, the valences of "heterocyclyl" can appear on any suitable ring atom, while the valences of "organoheteroyl" appear on heteroatoms, and the valences of heteroalkyl appear on carbon atoms.

[0134] Hydrocarbylene groups and alkylidene groups. As described in the IUPAC Compendium of Chemical Terminology, 2nd Edition (1997), "alkylene" groups are also defined according to their usual and customary meaning as divalent groups formed by removing two hydrogen atoms from a hydrocarbon, the free valencies of which do not participate in a double bond. Examples of alkylene groups include, for example, 1,2-phenylene, 1,3-phenylene, 1,3-propylene (-CH 2 CH 2 CH 2 -), cyclopentylene (=CC 4 H 8 ) or bridge (-CH 2 -) and does not form a double bond. The alkylene group in which the free valence does not participate in a double bond is different from the alkylidene group such as the alkylidene group.

[0135] A "hydrocarbyl" group is a divalent group formed on a hydrocarbon by removing two hydrogen atoms from the same carbon atom, the free valence of which is part of a double bond. An alkylidene group is an exemplary hydrocarbyl group and is defined as a divalent group formed on an alkane by removing two hydrogen atoms from the same carbon atom, the free valence of which is part of a double bond. Examples of alkylidene groups are =CHMe, CHEt, =CMe 2 , =CHPh or a methylene carbon with a double bond (=CH 2 )'s methylene group.

[0136] Heteroalkylene groups and heteroalkylene groups. Similar to the alkylene group, the term "heteroalkylene" group refers to a divalent group formed by removing two hydrogen atoms from a parent heteroalkyl molecule, the free valencies of which are not involved in a double bond. The hydrogen atoms can be removed from two carbon atoms, two heteroatoms, or one carbon and one heteroatom so that the free valencies are not involved in a double bond. Examples of "heteroalkylene" groups include, but are not limited to, -CH 2 OCH 2 -、-CH 2 NPH 2 -、-SiMe 2 (1,2-C 6 H 4 )SiMe 2 -、-CMe 2 SiMe 2 -、-CH 2 NCMe 3 -、-CH 2 CH 2 PMe-、-CH 2 [1,2-C 6 H 3 (4-OMe)]CH 2 -wait.

[0137] Similar to the alkyl radical, the "heteroalkyl radical" group is a divalent group formed on the heteroalkyl by removing two hydrogen atoms from the same carbon atom, and its free valency is part of the double bond. Examples of heteroalkyl radicals include, but are not limited to, =CHNMe 2 , =CHOPh, =CMeNMeCH 2 Ph, =CHSiMe 3 , =CHCH 2 Cl and other groups.

[0138] Halides and halogens. The terms "halide" and "halogen" are used herein to refer to ions or atoms of fluorine, chlorine, bromine, or iodine, as the context and chemistry permit or dictate, used alone or in any combination. These terms are used interchangeably regardless of the charge or bonding pattern of these atoms.

[0139] Polymer. The term "polymer" is generally used herein to include olefin homopolymers, copolymers, terpolymers, etc. Copolymers are derived from an olefin monomer and an olefin comonomer, while terpolymers are derived from an olefin monomer and two olefin comonomers. Therefore, "polymer" encompasses copolymers, terpolymers, etc. derived from any olefin monomer and comonomer disclosed herein. Similarly, ethylene polymers will include ethylene homopolymers, ethylene copolymers, ethylene terpolymers, etc. Therefore, olefin copolymers such as ethylene copolymers can be derived from ethylene and comonomers, such as propylene, 1-butene, 1-hexene or 1-octene. If the monomer and comonomer are ethylene and 1-hexene, respectively, the resulting polymer will be classified as an ethylene / 1-hexene copolymer. Similarly, the term "polymerization" includes homopolymerization, copolymerization, terpolymerization, etc. For example, a copolymerization process includes contacting an olefin monomer such as ethylene and an olefin comonomer such as 1-hexene to produce a copolymer. Well-known abbreviations of polyolefin types such as "HDPE" can be used herein to represent high-density polyethylene. Furthermore, unless expressly stated otherwise, the term "polymer" is not limited by molecular weight, and thus encompasses lower molecular weight polymers (sometimes called oligomers) as well as higher molecular weight polymers.

[0140] Main catalyst or precatalyst. As used herein, the term "main catalyst" or "precatalyst" means a catalyst that is activated by an aluminoxane, borane, borate or other acidic activator (whether a Lewis acid or a Bronsted acid). A compound that is capable of polymerizing, oligomerizing or hydrogenating olefins when activated by a polyol (e.g., a polyol) or ... when activated by a support-activator as disclosed herein.

[0141] Additional Explanations of Terms The following additional explanations of terms are provided for the fully disclosed aspects of the present disclosure and claims.

[0142] Several types of numerical ranges are disclosed herein, including but not limited to numerical ranges for atomic numbers, interbasic spacing, weight ratios, molar ratios, percentages, temperatures, and the like. When any type of range is disclosed or claimed, applicants intend to disclose or claim individually every possible number that such range can reasonably encompass, consistent with the written description and context, and including the endpoints of the range and any subranges and combinations of subranges encompassed therein. For example, when applicants disclose or claim a chemical moiety having a certain number of carbon atoms, such as C1 to C12 (or C 1 To C 12) alkyl group, or in other words having 1 to 12 carbon atoms, applicants intend to refer to the moiety of alkyl groups that can be independently selected from having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms, and any range between these two numbers (e.g., C1 to C6 alkyl groups), and also including any combination of ranges between these two numbers (e.g., C2 to C4 and C6 to C8 alkyl groups). If for any reason applicants choose to claim less than the full extent of the present disclosure, for example, in view of references that applicants may not have known at the time of filing the application, applicants reserve the right to limit or exclude any individual member of any such range or group, including any subrange or combination of subranges within the group, which can be claimed by range or in any similar manner.

[0143] On the other hand, any numerical ranges recited in the specification or claims, such as numerical ranges representing a set of specific characteristics, units of measurement, conditions, physical states, or percentages, are intended to be expressly incorporated verbatim herein by reference or otherwise, any number falling within such range (including any subset of the numbers within any range so recited). For example, whenever a numerical range with a lower limit RL and an upper limit RU is disclosed, any number R falling within the range is specifically disclosed. Specifically, the following numbers R within the range are specifically disclosed:

[0144] R=RL+k(RU-RL),

[0145] Wherein k is a variable ranging from 1% to 100%, wherein the increment is 1%, for example, k is 1%, 2%, 3%, 4%, 5%, .... 50%, 51%, 52%, .... 95%, 96%, 97%, 98%, 99% or 100%. In addition, any numerical range represented by any two values ​​of R calculated as above is also specifically disclosed.

[0146] For any particular compound disclosed herein, unless otherwise stated, any general or specific structure presented also encompasses all conformational isomers, positional isomers, and stereoisomers that may result from a particular set of substituents. Similarly, unless otherwise stated, the general or specific structure also encompasses all enantiomers, diastereomers, and other optical isomers (whether enantiomers or racemic forms) and mixtures of stereoisomers as known to the skilled artisan.

[0147] Unless otherwise indicated, values ​​or ranges may be expressed in the present disclosure using the term "about", for example, "about" a specified value, greater than or less than "about" a specified value, or within a range from "about" one value to "about" another value. When such values ​​or ranges are expressed, other embodiments disclosed include specific listed values, ranges between specific listed values, and other values ​​close to specific listed values. In one aspect, the use of the term "about" means ±15% of the value, ±10% of the value, ±5% of the value, or ±3% of the value. For example, when the term "about" is used as a modifier of a variable, feature, or condition or is used in conjunction with it, it is intended to express that the numbers, ranges, features, and conditions disclosed herein are flexible enough to allow a person skilled in the art to practice the present disclosure using temperatures, rates, times, concentrations, amounts, contents, properties (such as substrate spacing, dimensions, including pore size, pore volume, surface area, etc.) that are slightly beyond the specified range or different from a single specified value to achieve the desired results described in the application, such as the preparation of porous catalyst carrier particles having defined characteristics and their use in the preparation of active olefin polymerization catalysts and in olefin polymerization processes using such catalysts.

[0148] Unless otherwise indicated, the terms "a", "an", "the", etc. (such as "this") are intended to include plural selections, such as at least one. For example, disclosure of "support-activator", "organoaluminum compound" or "metallocene compound" is intended to encompass a mixture or combination of one or more than one ("at least one") of a catalyst support-activator, an organoaluminum compound or a metallocene compound, respectively.

[0149] As recited in the transitional phrase or in the specification, the term "comprising" and variations thereof, such as "comprises," "comprised of," "having," "including," and the like, are inclusive and open-ended, and do not exclude additional, unrecited elements or method steps. The transitional phrase "consisting of" and variations thereof exclude any element, step, or ingredient not specified in the claim. The transitional phrase "consisting essentially of" limits the scope of a claim to the specified components or steps and to those components or steps that do not materially affect the basic and novel characteristics of the claimed invention. Unless otherwise indicated, describing a compound or composition as "consisting essentially of" should not be construed as "comprising," as the phrase is intended to describe the recited components, which include materials that do not significantly change the composition or method to which the term is applied. For example, a precursor or catalyst component may consist essentially of a material that, when prepared by a certain procedure, may include impurities commonly found in commercially produced samples thereof.

[0150] When 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.

[0151] When a claim includes different features and / or classes of features (e.g., process steps, feedstock features, and / or product features, among other possibilities), the transition terms comprising, consisting essentially of, and consisting of apply only to the class of features utilized, and it is possible to have different transition terms or phrases utilized with different features within the claim. For example, a process may include several of the recited steps (and other unrecited steps), but be prepared with a catalyst system that consists of, or alternatively consists essentially of, the specific steps, but utilizes a catalyst system that includes the recited components and other unrecited components.

[0152] Unless otherwise defined with respect to a specific attribute, feature, or variable, the terms "substantial" and "substantially" as applied to any standard such as an attribute, feature, or variable means that the specified standard is met to a sufficient degree that a person skilled in the art will understand the benefit to be achieved, or that the desired condition or attribute value is met. For example, the term "substantially" may be used when describing a metallocene catalyst or catalyst system that is substantially free of or substantially absent of aluminoxane, borate activator, protic acid treated clay, or pillared clay. In other words, the terms "substantial" and "substantially" are reasonably used to describe the subject matter so that its scope will be understood by a person skilled in the relevant art and to distinguish the claimed subject matter from any prior art. In one aspect, "substantially free of" may be used to describe a composition in which none of the listed components that the composition is substantially free of are added to the composition, and only impurities are present, such as amounts derived from the purity limits of other components or amounts produced as by-products. On the other hand, when a composition is referred to as being "substantially free" of a particular component, the composition can 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.

[0153] The terms "optionally," "optionally," and the like with respect to claim elements 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 contemplated that the claim may cover either or both alternatives.

[0154] References to the periodic table or groups of elements in the periodic table are to the periodic table published by the International Union of Pure and Applied Chemistry (IUPAC), published online at http: / / old.iupac.org / reports / periodic_table / ; version dated February 19, 2010. References to one or more "groups" of the periodic table, as reflected in the periodic table, use the IUPAC system for numbering groups of elements as groups 1-18. If any group is identified by Roman numerals according to the periodic table published, for example, in "Hawley's Condensed Chemical Dictionary" (2001) ("CAS" system), it will further identify the element or elements of the group to avoid confusion and provide a cross-reference to the numerical IUPAC identifier.

[0155] Various patents, publications and documents are disclosed and cited herein. Unless otherwise indicated, each reference cited in this disclosure, whether patent, publication or other document, is incorporated herein by reference in its entirety.

[0156] References that may provide some background information related to the present disclosure include, for example, U.S. Patent Nos. 4,169,926; 5,135,756; 5,308,811; 6,034,187; 6,531,552; 6,825,371; 6,838,507; 6,927,261; 7,220,695; 7,732,542; 8,642,499; and 9,200,093; each of which is incorporated herein by reference in its entirety. Other publications that may provide some background information related to the present disclosure include: Materials Research 2015, 18(2), 283-287; , 1999, 45(295), 133-136; Langmuir 2005, 21(19), 8717-8723; Macromolecular Reaction Engineering 2017, 11(2), 1600017; and Clay Minerals 2003, 38(1), 127-138; each of which is incorporated herein by reference in its entirety.

[0157] B. Overview

[0158] The support-activator of the present disclosure can be formed by contacting a swellable clay such as montmorillonite clay or dioctahedral montmorillonite clay or a preformed montmorillonite clay-cationic polymetallate heteroadduct with a surfactant in a liquid carrier, and there are multiple embodiments or aspects for the method and the resulting heteroadduct. For example, a method for preparing a support-activator comprising a montmorillonite heteroadduct is provided, the method comprising or consisting essentially of: contacting: (a) colloidal montmorillonite clay in a first liquid carrier; with (b) a surfactant, wherein the surfactant includes or is selected from a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or any combination thereof, to provide a slurry of the montmorillonite heteroadduct in the first liquid carrier. The process may optionally involve further addition of other reagents, such as a cationic polymetallate or a metal oxide, however, the contacting step may also occur in the absence of a specific reactant as described above. For example, the contacting step may be performed in the absence of a cationic polymetallate and other reactants, or the contacting step may be performed in the absence of any other reactants except the surfactant. An unexpected advantage of the disclosed method for preparing the support-activator is the observation that it provides the montmorillonite heteroadduct in the desired highly spherical particle form for forming highly spherical catalyst particles.

[0159] In another aspect, the present disclosure provides a method for preparing a support-activator comprising a montmorillonite heteroadduct, the method comprising or consisting essentially of: contacting, in any order, in a first liquid carrier: (a) colloidal montmorillonite clay; (b) a cationic polymetalate; 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 montmorillonite heteroadduct in the first liquid carrier. If desired, the process may optionally involve further addition of other reagents, however, if desired, the contacting step may also occur in the absence of a specific reactant as described herein or in the absence of any other reactants.

[0160] According to another aspect, the present disclosure provides a preformed clay-cationic polymetallate heteroadduct, an aqueous spray-dried slurry of a preformed or isolated clay-cationic polymetallate heteroadduct is prepared, the heteroadduct comprising a surfactant in the aqueous spray-dried slurry. The resulting heteroadduct can be spray-dried from the aqueous slurry in the absence of an organic dispersion medium or in the absence of an organic liquid (except for the surfactant) to provide a highly spherical support-activator. If desired, the method may also optionally involve the addition of other reagents, however, if desired, the contacting step may also occur in the absence of a specific reactant as described herein or in the absence of any other reactant.

[0161] The heteroagglomerates produced according to the disclosed process can be conveniently separated by simple filtration and subsequently dried and calcined to provide a support-activator that can be used to support and activate metallocene catalysts for olefin polymerization. It has been unexpectedly found that the calcined surfactant supports described herein have improved porosity relative to calcined clays and calcined clay-polymetalate mixtures, even when dried by spray drying from an aqueous slurry. When attempting to maintain the porosity of the separated contact product of clay and polymetalate during the drying process, methods such as azeotropic removal of water using an organic liquid are generally required to maintain the porosity. However, in the present clay-surfactant heteroadducts, when spray dried in the absence of an organic dispersing liquid, a large amount of BJH porosity is still retained.

[0162] Conventional treatments for activating the aforementioned clays to provide clay-based support-activators include contacting the clay with an inorganic acid such as hydrochloric acid or sulfuric acid, which may include a surfactant treatment (see, for example, U.S. Pat. No. 7,220,695). However, these treatments may reduce the structural integrity of the clay, perhaps because the clay structure itself is destroyed by peptization in the process of acidifying the clay, such as described in Clay Minerals, 2003, 38 (1), 127-138. However, it is generally believed that acid is necessary for activating clay, and therefore previous methods for addressing the stability of the resulting support-activator have not completely eliminated the acid treatment. Applicants have unexpectedly discovered that acid is unnecessary and even undesirable because the subject clay can be fully activated in the absence of an acid such as hydrochloric acid or sulfuric acid to provide a highly active support-activator with greater structural integrity.

[0163] In the applicant's prior patent applications, published as U.S. Patent Application Publication No. 2021 / 0230318 and International Application Publication No. WO2021 / 154204, montmorillonite clay was contacted with a cationic polymetalate (including in the presence of a surfactant) to form a heteroadduct that, upon calcination, acts as a highly active support-activator for metallocenes. In one aspect, the applicant has unexpectedly discovered that a cationic polymetalate is also unnecessary, as the subject clay can be activated in the presence of a surfactant but in the absence of a cationic polymetalate such as aluminum chlorohydrate (ACH), polyaluminum chloride (PAC), or aluminum sesquichlorohydrate compositions, and still provide a highly active support-activator having the desired structural properties. The resulting support-activator has high porosity, particle uniformity, and high particle sphericity.

[0164] In order to provide a measure of consistency and uniformity for the catalyst prepared from the support-activator and any resulting polymer, and due to the sensitivity of supported metallocene catalysts to moisture, the support-activator may be calcined or otherwise dried to control any residual moisture present in the support. However, calcination of existing support-activators is known to result in a significant reduction in support-activator porosity. While not intending to be bound by theory, it is believed that as the clay layers are swollen by the liquid carrier molecules under the support-activator preparation conditions, they subsequently tend to collapse as the liquid molecules are removed at elevated temperatures.

[0165] In the present disclosure, the introduction of bulky ionic or nonionic surfactant molecules described herein imparts improved thermal stability to these clay-based support-activators. While not intending to be bound by any mechanistic theory of how this occurs, it is believed that the surfactant molecules or surfactant cations can be inserted between the clay layers, acting as pillars for supporting the layered structure, even in the absence of other existing activating components such as acids or polymetallates.

[0166] It has been further unexpectedly discovered that the calcined surfactant-clay supports described herein have improved olefin polymerization activity relative to their calcined clay or calcined clay-polymetalate analogs. Again, while not wishing to be bound by theory, it is believed that the enhanced porosity obtained by the combination of surfactant and clay allows metallocenes to access and form more catalytically active sites. These improved activities and properties of surfactant-clay supports-activators are economically desirable and provide significant advantages for using them in olefin catalysis processes.

[0167] Thus, in one aspect, the present disclosure provides a support-activator comprising a montmorillonite heteroadduct that can be calcined, wherein the montmorillonite heteroadduct comprises or consists essentially of the isolated contact product of: (a) a colloidal montmorillonite clay and (b) a surfactant agent comprising or selected from [i] a cationic surfactant, [ii] a nonionic surfactant, or [iii] an amphoteric surfactant, or any combination thereof, in a first liquid vehicle.

[0168] C. Colloidal montmorillonite clay

[0169] In addition to the Definitions section, the following disclosure provides additional information related to montmorillonite clay.

[0170] Swelling clays (such as montmorillonite or 2:1 dioctahedral montmorillonite clays) or combinations of swelling clays can be used to prepare the support-activator described herein. These swelling clays can be described as phyllosilicates or phyllosilicate clays, because certain members of the clay mineral family of phyllosilicates can be used. Suitable starting clays can include layered, naturally occurring or synthetic montmorillonites. Starting clays can also include dioctahedral montmorillonite clays. In addition, suitable starting clays can also include clays such as montmorillonite, sauconite, nontronite, laponite, beidenite, saponite, bentonite or any combination thereof. Montmorillonite is a 2:1 layered clay mineral with a lattice charge, and can swell when dissolved with water and ethanol. Therefore, suitable starting clays can include, for example, single cation exchange dioctahedral montmorillonite, such as clays exchanged by lithium, clays exchanged by sodium or clays exchanged by potassium or a combination thereof.

[0171] Water can also coordinate to the layered clay building blocks, either bound to the clay structure itself or coordinated to cations as hydration shells. When dehydrated, the 2:1 layered clay has a powder X-ray diffraction (XRD) pattern of approximately (Angstroms) to about or alternatively, in powder X-ray diffraction (XRD), about (Angstroms) to about (Angstroms) range.

[0172] Layered montmorillonite clays are called 2:1 clays because their structure is a "sandwich" structure consisting of two outer tetrahedral silicate layers and an inner octahedral alumina layer sandwiched between layers of silicon dioxide. For this reason, these structures are also called "TOT" (tetrahedron-octahedron-tetrahedron) structures. These sandwich structures are stacked one on top of the other to create the clay particles. This arrangement provides approximately 100% carbon dioxide per 100 angstroms of clay, compared to pillared or sandwiched clays that are created by inserting "pillars" of inorganic oxide material between the layers to provide more space between the natural clay layers. The repetitive structure.

[0173] In one aspect, the clay used to prepare the clay-heteroagglomerate and the support-activator can be a colloidal montmorillonite clay. Thus, the colloidal montmorillonite clay can have an average particle size greater than or equal to 10 μm (micrometers), greater than or equal to 5 μm, greater than or equal to 3 μm, greater than or equal to 2 μm, or greater than or equal to 1 μm, wherein the average particle size can also be less than or equal to 15 μm, less than or equal to 25 μm, less than or equal to 50 μm, less than or equal to 75 μm, less than or equal to 100 μm, less than or equal to 125 μm, less than or equal to 150 μm, less than or equal to 175 μm, less than or equal to 200 μm, less than or equal to 225 μm, or less than or equal to 250 μm. That is, any clay particle size range between these listed numbers is disclosed. If not specifically stated otherwise, any particle size listed herein for the montmorillonite clay itself is the particle size specified by the clay supplier. Although clays that do not produce colloidal suspensions can be used, the use of these non-colloidal clays presents additional processing and separation problems that can be avoided by using colloidal clays. These upper and lower limits for the average particle size of the colloidal montmorillonite clay also apply to the clay-surfactant heteroadducts (dried or calcined) and supported metallocene catalysts (dried), as described herein.

[0174] In another aspect, the colloidal montmorillonite clay can have an average particle size of, for example, 1 μm (micrometer) to 250 μm. For example, the colloidal montmorillonite clay can have an average particle size of about 1 μm (micrometer), about 2 μm, about 3 μm, about 5 μm, about 7 μm, about 10 μm, about 12 μm, about 15 μm, about 18 μm, about 20 μm, about 25 μm, about 30 μm, about 35 μm, about 40 μm, about 45 μm, about 50 μm, about 55 μm, about 60 μm, about 65 μm, about 70 μm, about 75 μm, about 80 μm, about 85 μm, about 86 μm, about 87 μm, about 88 μm, about 89 μm, about 90 μm, about 91 μm, about 92 μm, about 93 μm, about 94 μm, about 95 μm, about 96 μm, about 97 μm, about 98 μm, about 99 μm, about 100 μm, about 101 μm, about 102 μm, about 103 μm, about 104 μm, about 105 μm, about 106 μm, about 107 μm, about 108 μm The present invention can be used to prepare the present invention in an average particle size of about 100 μm, about 200 μm, about 300 μm, about 500 μm, about 600 μm, about 800 μm, about 1000 μm, about 1500 μm, about 1600 μm, about 1700 μm, about 1750 μm, about 1850 μm, about 2000 μm, about 2250 μm or about 250 μm, or any particle size range between these listed numbers. For example, the colloidal montmorillonite clay may have an average particle size of 1 μm to 250 μm, 2 μm to 125 μm, 3 μm to 100 μm, 5 μm to 150 μm, 5 μm to 80 μm, 7 μm to 70 μm, 10 μm to 100 μm, 10 μm to 60 μm, 15 μm to 80 μm, 15 μm to 50 μm, or 20 μm to 75 μm.

[0175] According to another aspect, commercially available The particle size of HPM-20 bentonite provides a suitable particle size for use according to the present disclosure. For example, the colloidal montmorillonite clay used according to the present disclosure can be characterized by a particle size that is at least 99.00% smaller than 200 mesh (74 microns). On the other hand, the colloidal montmorillonite clay used according to the present disclosure can be characterized by a particle size that is at least 99.75% smaller than 200 mesh (74 microns) and at least 99.00% smaller than 325 mesh (44 microns).

[0176] In one aspect, the clay used to prepare the support-activator may be free of divalent or trivalent ion exchange montmorillonite, such as the Mg exchange or Al ion exchange montmorillonite described in U.S. Pat. No. 6,531,552. In another aspect, the clay used to prepare the support-activator may be free of mica or synthetic hectorite, such as described in U.S. Pat. Nos. 6,531,552 and 5,973,084. In yet another aspect, the clay used to prepare the support-activator may be free of octahedral montmorillonite or may be free of vermiculite.

[0177] In one aspect, the montmorillonite clay may also comprise structural units characterized by the formula:

[0178] (M A IV) 8 (M B VI) p O 20 (OH) 4 ;in

[0179] a)M A IV is four-coordinated Si 4+ , where the Si 4+ Optionally partially covered with non-Si 4+ Four-coordinated cations (e.g., non-Si 4+ The cations can be independently selected from Al 3+ , Fe 3+ , P 5+ , B 3+ ,Ge 4+ 、Be 2+ Sn 4+ etc.) replaced;

[0180] b)M B VI is hexacoordinated Al 3+ or Mg 2+ , where Al 3+ or Mg 2+ Optionally partially covered with non-Al 3+ or Mg 2+ Hexacoordinate cations (e.g., non-Al 3+ or Mg 2+ The cations can be independently selected from Fe3+ , Fe 2+ 、Ni 2+ 、Co 2+ , Li + 、Zn 2+ , Mn 2+ , Ca 2 + 、Be 2+ etc.) replaced;

[0181] c) p is four for a cation with a formal charge of +3, or p is 6 for a cation with a formal charge of +2; and

[0182] d) By A Non-Si at IV 4+ Any charge deficiency resulting from partial substitution of the cations and / or by the B Non-Al at VI 3+ or Mg 2+ Any charge deficit resulting from partial substitution of cations is balanced by cations inserted between the structural units (e.g., the cations inserted between the structural units can be selected from monocations, dications, trications, other polycations, or any combination thereof.

[0183] In another aspect, the montmorillonite clay can be mono-cation exchanged with at least one of lithium, sodium, or potassium.The examples, data, and aspects of this disclosure provide additional details of various aspects and embodiments of the montmorillonite clay.

[0184] D. Surfactant

[0185] The step of contacting the clay with a surfactant can be carried out using any suitable surfactant, which can include cationic surfactants, nonionic surfactants, amphoteric surfactants (including amphoteric surfactants), and can include combinations thereof. In one aspect, the contact product and the method of preparing the support-activator can be absent of any or both of a cationic surfactant, a nonionic surfactant, or an amphoteric surfactant.

[0186] According to one aspect, the colloidal montmorillonite clay and the surfactant can be contacted at a ratio of 0.5 to 5 millimoles of surfactant per gram of colloidal montmorillonite clay. For example, the colloidal montmorillonite clay and the surfactant can be provided or contacted at a ratio of 0.75 to 4 millimoles, 1 to 3.5 millimoles, 1.25 to 3 millimoles, or 1.5 to 2.75 millimoles of surfactant per gram of colloidal montmorillonite clay.

[0187] Cationic surfactants. In one aspect, the cationic surfactants may include or may be selected from primary, secondary, tertiary or quaternary ammonium compounds or phosphorus compounds. When describing a cationic surfactant, the disclosure may refer to a cationic surfactant comprising a cationic component and a counterion or anion. In one aspect, the cationic surfactant may include or may be selected from an ammonium compound (salt) having the following general formula:

[0188] [R 1 R 2 R 3 R 4 N] + X - ,in

[0189] Each R 1 , R 2 , R 3 and R 4 are independently selected from hydrogen, substituted or unsubstituted C 1 -C 25 A hydrocarbon group or a substituted or unsubstituted C 1 -C 25 A heteroalkyl group, wherein R 1 , R 2 , R 3 and R 4 Any two or more of may be part of a ring structure, and R 1 , R 2 , R 3 and R 4 is a non-hydrogen moiety; and

[0190] X - Selected from organic or inorganic monoanions, dianions or trianions.

[0191] In another aspect, the ammonium compound may have the general formula [R 1 R 2 R 3 R 4 N] + X - , where: R 1 , R 2 , R 3 and R 4 are independently selected from hydrogen, substituted or unsubstituted C 1 -C 25 Aliphatic groups, substituted or unsubstituted C 1 -C 25 Heteroaliphatic groups, substituted or unsubstituted C 6 -C 25 Aromatic groups or substituted or unsubstituted C 4 -C 25A heteroaromatic group, wherein R 1 , R 2 , R 3 and R 4 Any two or more of may be part of a ring structure, and wherein R 1 , R 2 , R 3 and R 4 At least one of X is a non-hydrogen moiety; and X - Selected from any suitable anion such as fluoride, chloride, bromide, iodide, formate, acetate, oxalate, nitrate, sulfate, sulfite, perchlorate, carbonate, bromate, chlorate, chlorite, hypochlorite or phosphate.

[0192] According to another aspect, the cationic surfactant may include or may be selected from a phosphorus compound (salt) having the following general formula:

[0193] [R 1 R 2 R 3 R 4 P] + X - ,in

[0194] Each R 1 , R 2 , R 3 and R 4 are independently selected from hydrogen, substituted or unsubstituted C 1 -C 25 A hydrocarbon group or a substituted or unsubstituted C 1 -C 25 A heteroalkyl group, wherein R 1 , R 2 , R 3 and R 4 Any two or more of may be part of a ring structure, and wherein R 1 , R 2 , R 3 and R 4 is a non-hydrogen moiety; and

[0195] X - Selected from organic or inorganic monoanions, dianions or trianions.

[0196] In another aspect, the phosphorus compound may have the general formula [R 1 R 2 R 3 R 4 P] + X - , where R 1 , R 2, R 3 and R 4 are independently selected from hydrogen, substituted or unsubstituted C 1 -C 25 Aliphatic groups, substituted or unsubstituted C 1 -C 25 Heteroaliphatic groups, substituted or unsubstituted C 6 -C 25 Aromatic groups or substituted or unsubstituted C 4 -C 25 A heteroaromatic group, wherein R 1 , R 2 , R 3 and R 4 Any two or more of may be part of a ring structure, and wherein R 1 , R 2 , R 3 and R 4 At least one of is a non-hydrogen moiety; and the counterion X - Selected from any suitable anion such as fluoride, chloride, bromide, iodide, formate, carboxylate such as acetate, oxalate, nitrate, sulfate, sulfite, perchlorate, carbonate, bromate, chlorate, chlorite, hypochlorite or phosphate.

[0197] In an embodiment, the cationic surfactant may include a cation selected from lauryltrimethylammonium, stearyltrimethylammonium, trioctylammonium, distearyldimethylammonium, distearyldibenzylammonium, hexadecyltrimethylammonium, benzylhexadecyldimethylammonium, dimethyldi-(hydrogenated tallow)ammonium, dimethylbenzyl-(hydrogenated tallow)ammonium, or any combination thereof.

[0198] According to some aspects, the cation of the cationic surfactant may include or be selected from tetramethylammonium, tetraethylammonium, tetrabutylammonium, tetrapentylammonium, tetrahexylammonium, tetraoctylammonium, tetrabenzylammonium, hexadecylammonium, decylammonium, dodecylammonium, methyloctadecylammonium, ethyloctadecylammonium, butyloctadecylammonium, dimethyloctadecylammonium, diethyloctadecylammonium, dibutyloctadecylammonium, trimethyloctadecylammonium, triethyloctadecylammonium, tributyloctadecylammonium, methyltridecylammonium, ethyltridecylammonium, butyltridecylammonium, N,N-dimethylaniline, N,N-diethylaniline, N,N-2,4,5-pentamethylaniline, N,N-dimethyloctadecyl ammonium, N,N-dimethyl-N,N-dipropylammonium, N,N-dimethyl-N,N-dihexylammonium, N,N-dipropyl-N,N-dihexylammonium, trimethyl phosphine, triethyl phosphine, tributyl phosphine, trihexyl phosphine, tetramethyl phosphine, tetraethyl phosphine, tetrapropyl phosphine, tetrabutyl phosphine, tetrahexyl phosphine, tetrabenzyl phosphine, trihexyltetradecyl phosphine, diallyldimethylammonium, triethylmethylammonium, tributylethylammonium, trimethylsulfonium ammonium, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium, glycidyltrimethylammonium, N,N-dimethyl-N-ethyl-N-propylammonium, N,N-dimethyl-N-ethyl-N-butylammonium, N,N-dimethyl-N- Ethyl-N-pentyl ammonium, N,N-dimethyl-N-ethyl-N-hexyl ammonium, N,N-dimethyl-N-ethyl-N-heptyl ammonium, N,N-dimethyl-N-ethyl-N-decyl ammonium, N,N-dimethyl-N-propyl-N-butyl ammonium, N,N-dimethyl-N-propyl-N-pentyl ammonium, N,N-dimethyl-N-propyl-N-hexyl ammonium, N,N-dimethyl-N-propyl-N-heptyl ammonium, N,N-dimethyl-N-butyl-N-hexyl ammonium, N,N-dimethyl-N-butyl-N-heptyl ammonium, N,N-dimethyl-N-pentyl-N-hexyl ammonium, trimethylheptyl ammonium, N,N-diethyl-N-methyl-N-propyl ammonium, N , N-diethyl-N-methyl-N-pentylammonium, N,N-diethyl-N-methyl-N-heptylammonium, N,N-diethyl-N-propyl-N-pentylammonium, triethylmethylammonium, triethylpropylammonium, triethylammonium, triethylheptylammonium, N,N-dipropyl-N-methyl-N-ethylammonium, N,N-dipropyl-N-methyl-N-pentylammonium, N,N-dipropyl-N-butyl-N-hexylammonium, N,N-dibutyl-N-methyl-N-pentylammonium, N,N-dibutyl-N-methyl-N-hexylammonium, trioctylmethylammonium, N-methyl-N-ethyl-N-propyl-N-pentylammonium, diethyldimethylphosphine, dibutyldiethylphosphine, or any combination thereof.

[0199] In various aspects, the counterion X for the cationic component of the cationic surfactant -Can include or can be selected from organic anions or inorganic anions such as halides. Exemplary 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 cationic surfactants include but are not limited to cationic components such as those exemplified above, with combinations of anions including or selected from halide ions or anions of inorganic Bronsted acids.

[0200] In one aspect, examples of cationic surfactants include, but are not limited to, chlorides or bromides of benzalkonium, benzethonium, methylbenzethonium, cetylpyridinium, alkyl-dimethyldichloroanilinium, dequalinium, phenylpentylium, cetrimide, or cetrimide.

[0201] On the other hand, examples of cationic surfactants that can be used according to the present disclosure include tetrabutylammonium bromide, dioctadecyldimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecylammonium chloride, trimethylstearylammonium chloride, hexadecyltrimethylammonium bromide, octenidine dihydrochloride, hexadecyltrimethylammonium bromide (CTAB), hexadecyltrimethylammonium chloride (CTAC), cetylpyridinium chloride (CPC), benzalkonium chloride (BAC), benzethonium chloride (BZT), dimethyldioctadecylammonium chloride, dioctadecyldimethylammonium bromide (DODAB), or a combination thereof.

[0202] In some embodiments, the cationic surfactant may include or be selected from aliphatic dialkylbenzylammonium compounds (also referred to as aliphatic alkylbenzylammonium compounds), which describe a class of quaternary ammonium compounds including alkyldimethylbenzylammonium chloride (ADBAC), wherein the alkyl group may include, for example, C 12 -C 16 or C 12 -C 14 The term "aliphatic dialkylbenzylammonium" compounds may be used to describe a family of quaternary ammonium compounds that may be prepared or commercially available as a mixture of compounds. For example, the product marketed as "ADBAC" or the safety data sheet states that the commercially available product includes alkyl dimethylbenzylammonium chloride and alkyl (C 12 -C 14 ) mixture of dimethyl(ethylbenzyl)ammonium chloride. Such common commercial ammonium compounds may be used in accordance with the present disclosure.

[0203] Nonionic surfactants. In another aspect, the surfactant can comprise, consist essentially of, or be selected from nonionic surfactants. In the present disclosure, for convenience, amphoteric surfactants (including amphoteric surfactants) are described together with non-amphoteric nonionic surfactants.

[0204] In one aspect, examples of nonionic surfactants include, but are not limited to, polyols, monoalkyl ethers and dialkyl ethers of polyols, or polyalkylene glycols thereof, and any combination of more than one such nonionic surfactant may be used. Suitable polyols may contain 2, 3 or more hydroxyl groups. In one aspect, the polyol may have the formula CH 2 OH(CHOH) n CH 2 OH, wherein n is an integer from 2 to 5. Exemplary polyols (also referred to as sugar alcohols) include glycerol, 1,2,4-butanetriol, erythritol, pentaerythritol, maltitol, xylitol and sorbitol. Exemplary polyol ethers include, but are not limited to, monomethyl ether and dimethyl ether of ethylene glycol, propylene glycol and diethylene glycol and monoethyl ether and diethyl ether. Exemplary polyalkylene glycols include poly (ethylene) glycol and poly (propylene) glycol. These compounds and their preparation methods are disclosed in Kirk-Othmer, Encyclopedia of Chemical Technology, Second Edition, Vol. 10, pp. 638-674, which are incorporated herein by reference. According to the present disclosure, polyol amines are also suitable nonionic surfactants. For example, nonionic surfactants can include polyethoxylated tallow amine (also polyoxyethylene amine or POEA).

[0205] On the other hand, the nonionic surfactant agent can include or be selected from sugar, such as monosaccharide, disaccharide, oligosaccharide or their mixture such as found in the corn syrup solid mixture derived from corn starch hydrolysis. Exemplary sugar includes glucose, fructose, mannose, maltose, lactose, sucrose etc. Exemplary oligosaccharide includes but is not limited to cyclodextrin and maltodextrin. The nonionic surfactant used according to the present disclosure can also include amino-modified sugar such as glucosamine and oxidized sugar acid such as glucuronic acid.

[0206] On the other hand, nonionic surfactant can comprise the mixture of single fatty acid or several fatty acids.These materials generally comprise the carbochain of 6 to 21 carbons in length, and it can optionally comprise internal unsaturation, and wherein carbochain is with carboxylic acid end-capping.Exemplary fatty acid comprises sad, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, ricinoleic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, hexadecenoic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, trans-linoleic acid, alpha-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid or its any combination.On the other hand, nonionic surfactant can comprise the fatty acid of the alcohol (such as methyl alcohol, ethanol, butanols, hexanol or glycerine, for example monoglyceride, diglyceride or triglyceride) condensation with one or more hydroxyl groups listed in its example above.

[0207] In an embodiment, the nonionic surfactant may comprise an ethoxylate, a glycol ether, a fatty alcohol polyglycol ether, or a combination thereof, examples of which include, but are not limited to, octylphenol ethoxylate, polyethylene glycol tert-octylphenyl ether, ethylenediaminetetra(ethoxylate-block-propoxylate)tetraol, or ethylenediaminetetra(propoxylate-block-ethoxylate)tetraol.

[0208] In an embodiment, the nonionic surfactant may include or may be selected from the group consisting of 1 SO 2 OR 2 Hydrocarbon (hydrocarbon) sulfonate, wherein R 1 and R 2 Independently selected from substituted or unsubstituted C 1 -C 25 Alkyl, C 6 -C 25 Aryl, C 7 -C 25 Arylalkyl or C 7 -C 25 Alkyl.

[0209] According to other embodiments, the nonionic surfactant may include or be selected from: (a) monosaccharides, disaccharides, oligosaccharides or any combination thereof; or (b) glucose, fructose, mannose, maltose, lactose, sucrose, cyclodextrin, maltodextrin, amino-modified sugars such as glucosamine, oxidized sugar acids such as glucuronic acid or any combination thereof.

[0210] In one aspect, the nonionic surfactant according to the present disclosure may include or be selected from the group consisting of: 1 SiX 3 , R 1 R 2 SiX 2 or R 1 R 2R 3 SiX silane, wherein:

[0211] R 1 , R 2 and R 3 Independently selected from substituted or unsubstituted C 1 -C 25 Hydrocarbyl group, C 1 -C 25 a heteroalkyl group or any other group that is hydrolytically stable when bonded to silicon in a nonionic surfactant; and

[0212] X is independently selected from hydrolyzable groups which, upon hydrolysis, are converted to hydroxyl groups (—OH), thereby forming silanols.

[0213] In this regard, the substituent R 1 , R 2 and R 3 may be independently selected from hydrogen, substituted or unsubstituted C 1 -C 25 Aliphatic groups, substituted or unsubstituted C 1 -C 25 Heteroaliphatic groups, substituted or unsubstituted C 6 -C 25 Aromatic groups or substituted or unsubstituted C 4 -C 25 In this regard, in addition, the X group can be selected from C 1 -C 25 Alkoxy, C 1 -C 25 Acyloxy, halogen or C 1 -C 25 While not intending to be bound by theory, it is believed that this type of silane can interact with the clay hydroxyl groups, thereby repelling water from adhering to the interior clay pore surfaces.

[0214] According to one aspect, the nonionic surfactant according to the present disclosure may include or may be selected from the group consisting of: 4- n Si(OH) n Silyl alcohol, wherein n is 1 or 2, and R is selected from C 1 To C 20 Alkyl group or C 6 To C 20 Examples of silanols include, but are not limited to, triphenylsilanol, dimethylphenylsilanol, diphenylsilanediol, triisopropylsilanol, or any combination thereof.

[0215] While not intending to be bound by theory, it is believed that high temperature drying (such as the type that occurs during calcination) may result in the loss of firmly adhered hydrogen-bonded water from the clay pore surface hydroxyls and cause these pores to collapse, thereby reducing BJH porosity. When the clay heteroadduct is contacted with silanols or with silanes containing hydrolyzable groups that convert to hydroxyls upon hydrolysis to form silanols, some of this water may be replaced by these hydroxyl-containing silanol compounds. In this way, these silanol compounds are believed to reduce the potential porosity collapse caused by high temperature treatment of the clay support.

[0216] Amphoteric surfactants. In one aspect, "amphoteric" surfactants are those surfactants that include a positively charged portion (or a portion that can easily become positively charged by accepting a proton) and a negatively charged portion (or a portion that can easily become negatively charged by releasing a proton) in the same molecule. Based on the inclusion of cationic and anionic portions in the same molecule, the term "zwitterionic" surfactants are used interchangeably with "amphoteric" surfactants. Proton-donating (H + "Amphiprotic" surfactants that accept protons are included within the scope of "amphoteric" surfactants unless otherwise excluded. In addition, reference to amphoteric or zwitterionic surfactants includes amphoteric surfactants unless otherwise excluded.

[0217] On the one hand, examples of amphoteric surfactants include amino acids or combinations of amino acids, polypeptides or proteins. When the surfactant includes amino acids, the contacting step between clay and surfactant can be carried out under conditions including a pH of about 2.5 to 9.5, wherein the amino acid or combination of amino acids is zwitterionic. Although not intended to be bound by theory, it is believed that the cationic end of zwitterionic amino acids can be inserted into the clay layer like the aforementioned cationic surfactants. In an embodiment, the amphoteric surfactant can include an amino acid selected from alanine, arginine, asparagine, aspartic acid (aspartate), cysteine, cystine, glutamic acid (glutamate), glutamine, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine or an amino acid of any combination thereof.

[0218] On the other hand, the amphoteric (zwitterionic) surfactants of the present disclosure have cationic and anionic moieties or centers attached to the same molecule. Examples of cationic centers of amphoteric (zwitterionic) surfactants include or are selected from the moieties of primary amines, secondary amines, tertiary amines, or quaternary ammonium cations. Examples of anionic centers of amphoteric surfactants include, but are not limited to, sulfate, sulfonate, phosphate, or carboxylate.

[0219] In one aspect, the amphoteric surfactant may include or may be selected from sulfobetaines, such as hydroxysulfobetaine compounds. Examples of sulfobetaines include, but are not limited to, lauroamidopropyl hydroxysulfobetaine (ISOTAINELAPHS); cocoamidopropyl hydroxysulfobetaine (ISOTAINECAPHS); oleamidopropyl hydroxysulfobetaine (ISOTAINEOAPHS); tallowamidopropyl hydroxysulfobetaine (ISOTAINETAHS); erucamidopropyl hydroxysulfobetaine (ISOTAINEEAPHS); and lauryl hydroxysulfobetaine (ISOTAINELHS).

[0220] In another aspect, the amphoteric surfactant may include or may be selected from betaines, including simple betaine N,N,N-trimethylglycine.Other examples of betaines that may be used according to the present disclosure include cocamidopropyl betaine.

[0221] On the other hand, amphoteric surfactants are provided, which may include or be selected from biological amphoteric surfactants, such as compounds having a phosphate anion and an amine or ammonium portion in the same molecule, examples of which include phospholipids, phosphatidylserine, phosphatidylethanolamine, phosphatidylcholine and sphingomyelin.

[0222] In an embodiment, the amphoteric surfactant may include or be selected from N-amine oxides, such as tertiary amine N-oxides, examples of which include lauryl dimethylamine oxide, myristic amine oxide, pyridine-N-oxide, N-methylmorpholine-N-oxide. The amphoteric surfactant of the present disclosure may include or be selected from hydrocarbon-N-amine oxides, such as alkyl-N-amine oxides or aryl-N-amine oxides.

[0223] In another aspect, the amphoteric surfactant may include or may be selected from CHAPS, which is 3-[(3-cholamidopropyl)dimethylamino]-1-propanesulfonate, also known as 3-{dimethyl[3-(3α,7α,12α-trihydroxy-5β-cholan-24-amino)propyl]azepinium}propane-1-sulfonate.

[0224] Anionic surfactant. In another aspect, the montmorillonite heteroadducts described herein can be prepared by contacting: (a) colloidal montmorillonite clay; and (b) a surfactant comprising a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or any combination thereof in a first liquid carrier to provide a slurry of the montmorillonite heteroadduct in the first liquid carrier; wherein the contacting step further comprises contacting the colloidal montmorillonite clay or the montmorillonite heteroadduct with an anionic surfactant before, during, or after the contacting of the colloidal montmorillonite clay with the cationic surfactant, the nonionic surfactant, the amphoteric surfactant, or a combination thereof. In one aspect, the montmorillonite heteroadduct formed from the montmorillonite clay and the cationic surfactant, the nonionic surfactant, and / or the amphoteric surfactant can be subsequently contacted with an anionic surfactant. For example, if desired, the contact product of the colloidal montmorillonite clay and the cationic surfactant can be further contacted with an anionic surfactant before isolating the heteroadduct or before spray drying the slurry of the heteroadduct. In another aspect, when forming the heteroadduct, the clay can be contacted with an anionic surfactant and a cationic surfactant simultaneously. While not intending to be bound by theory, it is believed that the use of anionic surfactants may enhance the ease of drying the montmorillonite heteroadduct.

[0225] In this regard, the anionic surfactant used according to the present disclosure may include or be selected from sulfate surfactants, sulfonate surfactants, phosphate surfactants, carboxylate surfactants or other anionic surfactants, examples of which include but are not limited to dialkyl sulfonate carboxylates, alkylaryl sulfonates, aralkyl sulfonates, alkyl sulfonates, aryl sulfonates, sulfosuccinates, fatty acid alkali salts, polycarboxylates, polyoxyethylene alkyl ether phosphate salts, alkyl naphthalene sulfonates, wherein the salt may be selected from alkali metals (such as lithium, sodium or potassium), alkaline earth metals (such as calcium or magnesium) or ammonium or alkyl ammonium salts.

[0226] Other aspects and embodiments of anionic surfactants include, but are not limited to, those having the formula [RO(C 2 H 4 O) x SO 3 ]M alkyl ether sulfate compound or alkenyl ether sulfate compound, wherein R is C 8 To C 20 Alkyl group or C 8 To C 20Alkenyl group, x is an integer of 1 to 30 (including end value), and M is a cation that imparts solubility to alkyl ether sulfate or alkenyl ether sulfate. Embodiments that can be used for alkyl ether sulfate of the present disclosure include condensation products of ethylene oxide and monohydric alcohols having 8 to 20 carbon atoms (e.g., about 14 to about 18 carbon atoms). Monohydric alcohols can be derived from natural sources (e.g., fat, coconut oil or tallow) or they can be synthetic. Lauryl alcohol (dodecanol) and the straight-chain alcohol derived from tallow are examples of useful alcohols. When such alcohols react with ethylene oxide (using about 1 to about 30 molar ratios of ethylene oxide (e.g., about 6 moles of ethylene oxide)), the mixture of the resulting molecular substances can have an average of about 6 moles of ethylene oxide / mole of alcohol, can be sulfated and neutralized, and used as alkyl ether sulfate.

[0227] In other aspects, the anionic surfactant may include or be selected from carboxylate compounds having the formula [RCOO]M, wherein R is C 8 To C 21 An alkyl group and M is a cation selected from sodium, potassium or ammonium.

[0228] According to another aspect, the anionic surfactant may include or may be selected from:

[0229] (a) having the formula R'SO 3 Sulfonate compounds of Na, wherein R' is C 8 To C 21 Alkyl group, C 8 To C 21 Aralkyl group or C 8 To C 21 an alkylaryl group; or

[0230] (b) having the formula R"OSO 3 M alkyl sulfate, wherein R" is C 8 To C 21 alkyl group, and M is selected from NH 4 + 、Na + , K + 、1 / 2Mg 2+ , diethanolammonium or triethanolammonium cation.

[0231] On the other hand, the anionic surfactant according to the present disclosure may include or be selected from the group consisting of: 6 H 4 (OCH 2 CH 2 ) n OSO 3 M sulfated polyoxyethylene alkylphenol, wherein R" is C 1 To C 9Alkyl group, M is NH 4 + 、Na + or triethanolamine, and n is an integer from 1 to 50, inclusive.

[0232] Examples of anionic surfactants disclosed herein may include or be selected from:

[0233] (a) having the formula [(R 1 O)SO 2 O]M alkyl sulfate;

[0234] (b) having the formula [R 1 SO 2 O]M alkyl sulfonates;

[0235] (c) having the formula [R 1 Alkyl sulfinates of S(O)O]M;

[0236] (d) having the formula [R 1 (OCH 2 CH 2 ) n OSO 2 O]M or [R 1 (OCH 2 C(CH 3 )CH 2 ) n OSO 2 O]M sulfated polyoxyalkylene; or

[0237] (e) having the formula [R 1 (OCH 2 CH 2 ) n SO 2 O]M or [R 1 (OCH 2 C(CH 3 )CH 2 ) n SO 2 Sulfonated Polymer

[0238] Alkylene oxide; wherein:

[0239] R 1 Independently selected from substituted or unsubstituted C 1 -C 25 Alkyl-, C 6 -C 25 Aryl-, C 7 -C 25 Aralkyl- or

[0240] C 7 -C25 Alkaryl;

[0241] M is a cation such as NH 4 + 、Na + , K + 、1 / 2Mg 2+ , diethanolammonium or triethanolammonium; and

[0242] n is an integer of 1 to 50.

[0243] In another aspect, the anionic surfactant may include or may be selected from an alkali metal salt of a fatty acid having from about 8 to about 30 carbon atoms. In an embodiment, the anionic surfactant may include 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, hexadecenoic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, trans-linoleic acid, alpha-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid, or any combination thereof.

[0244] According to other embodiments, the anionic surfactant may include or be selected from potassium oleate, dodecylbenzene sulfonate, dioctyl sulfosuccinate, sodium lauryl sulfonate, 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 sulfate, POE lauryl ether triethanolamine sulfate, POE lauryl ether ammonium sulfate, POE stearyl ether sulfate, sodium stearyl methyl taurate, triethanolamine dodecylbenzene sulfonate, sodium tetradecene sulfonate, sodium lauryl phosphate, or any combination thereof.

[0245] In another aspect, the anionic surfactant may include or be selected from:

[0246] (a) substituted or unsubstituted alkyl sulfonate selected from methane sulfonate, ethane sulfonate, 1-propane sulfonate, 2-propane sulfonate, 3-methylbutane sulfonate, trifluoromethane sulfonate, trichloromethane sulfonate, chloromethane sulfonate, 1-hydroxyethane sulfonate, 2-hydroxy-2-propane sulfonate, 1-methoxy-2-propane

[0247] Sulfonates or any combination thereof;

[0248] (b) substituted or unsubstituted alkyl sulfate selected from methyl sulfate, ethyl sulfate, 1-propyl sulfate, 2-propyl sulfate, 3-methylbutyl sulfate, trifluoromethane sulfate, trichloromethyl sulfate, chloromethyl sulfate, 1-hydroxyethyl sulfate, 2-hydroxy-2-propyl sulfate, 1-methoxy-2-propyl sulfate,

[0249] Sulfates or any combination thereof;

[0250] (c) a substituted or unsubstituted aryl sulfonate selected from benzenesulfonate, naphthalenesulfonate, p-toluenesulfonate, m-toluenesulfonate, 3,5-xylenesulfonate, trifluoromethoxybenzenesulfonate, trichloro-methoxybenzenesulfonate, trifluoromethylbenzenesulfonate, trichloromethylbenzene-sulfonate, fluorobenzenesulfonate, chlorobenzenesulfonate, 1-hydroxyethane-benzenesulfonate, 3-fluoro-4-methoxybenzenesulfonate or any combination thereof; or

[0251] (d) any combination thereof.

[0252] Examples of anionic surfactants that can be used according to the present disclosure include sulfates, sulfonates, phosphates, carboxylates or other anionic surfactants, examples of which include but are not limited to dialkyl sulfocarboxylates, alkylaryl sulfonates, alkyl sulfonates, sulfosuccinates, fatty acid alkali salts, polycarboxylates, polyoxyethylene alkyl ether phosphate salts, alkyl naphthalene sulfonates, wherein the salts can be selected from, for example, alkali metals (such as lithium, sodium or potassium), alkaline earth metals (such as calcium or magnesium), or ammonium or alkylammonium salts;

[0253] In one aspect, the anionic surfactant comprises an anionic functional moiety, such as sulfate, sulfonate, phosphate, or carboxylate, as well as other moieties described herein. In one aspect, the anionic surfactant further comprises a counterion, examples of which include, but are not limited to, NH 4 + 、Na + , K + 、1 / 2Mg 2+ , diethanolammonium or triethanolammonium.

[0254] E. Cationic polymetallates

[0255] In addition to the definitions section and aspects of the present disclosure, the following additional information further describes the cationic polymetallates.

[0256] As explained in the definition section, the term "polymetalate" and similar terms such as "polyoxometalate" refer to polyatomic cations including two or more metals (e.g., aluminum, silicon, titanium, zirconium or other metals) and at least one bridging ligand (such as an oxygen, hydroxyl and / or halide ligand) between the metals. For example, the polymetallic salt can be a hydrated metal oxide, a hydrated metal oxyhydroxide, etc., and can include bridging ligands (such as oxygen ligands bridging two or more metals can be present in these materials), and can also include terminal oxygen, hydroxyl and / or halide ligands. Although many polymetallic salt materials are anionic, and the suffix "-ate" is often used to reflect anionic materials, the polymetallic salt (polyoxometalate) complex used in accordance with the present disclosure is cationic.

[0257] The heterocoagulant of the present disclosure can be a positively charged substance that, when combined with a colloidal suspension of clay in an appropriate ratio, forms an easily filterable and easily washable coagulant. Positively charged substances include soluble polyoxometalates, polyhydroxymetal salts, and polyhydroxymetal oxometalate cations, as well as partially halide-substituted related cations, such as polyhydroxyaluminum oxychloride or aluminum chlorohydrate or polyaluminum chloride substances of linear, cyclic or clustered compounds. These compounds are collectively referred to as polymetallic salts. The latter aluminum compounds can contain from about 2 to about 30 aluminum atoms.

[0258] Useful heterocoagulants may also include any colloidal material characterized by a positive zeta potential when dispersed in an aqueous solvent or an aqueous and organic (e.g., alcohol) mixed solvent. For example, useful heterocoagulant dispersions may exhibit a zeta potential greater than (>) +20 mV (positive 20 mV), a zeta potential greater than +25 mV, or a zeta potential greater than +30 mV. Although the starting colloidal clay may include monovalent ions or species, such as protons, lithium ions, sodium ions, or potassium ions, it is believed that at least a portion of these ions may be replaced by the heterocoagulant during the formation of the readily filterable clay heteroadduct.

[0259] In one aspect, the cationic polymetallate heterocoagulation agent may comprise a colloidal suspension of boehmite (aluminum oxide hydroxide) or a metal oxide such as a fumed metal oxide (e.g., fumed alumina) that provides a positive zeta potential. In another aspect, the heterocoagulation agent may comprise a chemically modified or chemically treated metal oxide, such as fumed silica treated with aluminum chlorohydrate, such that when in suspension, the chemically treated metal oxide provides a positive zeta potential, as described below. In another aspect, the heterocoagulation agent may be produced by treating a metal oxide or metal oxide hydroxide, etc., with an agent in a fluidized bed, and when the agent is dispersed in the suspension, the agent will provide a positive zeta potential. Prior to combining with the phyllosilicate clay component, the heterocoagulation agent may exhibit a positive value greater than +20 mV.

[0260] In one aspect, the cationic polymetallate may include a first metal oxide chemically treated with a second metal oxide, metal halide, metal oxyhalide, or a combination thereof in an amount sufficient to provide a colloidal suspension of the chemically treated first metal oxide with a positive zeta potential, e.g., a zeta potential 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, i.e., another different metal oxide, [2] a metal halide, [3] a metal oxyhalide, or [4] a combination thereof. For example, the chemically treated first metal oxide may comprise fumed silica, fumed alumina, fumed silica-alumina, fumed magnesium oxide, fumed zinc oxide, fumed titanium dioxide, fumed zirconium oxide, fumed ceria, or the like, or any combination thereof. The second metal oxide, metal halide, or metal oxyhalide may be selected from a metal oxide, hydroxide, oxyhalide, or halide (e.g., ZrOCl 2 、ZnO、NbOCl 3 、B(OH) 3 、AlCl 3 or a combination thereof). For example, the treatment may consist of dispersing the fumed oxide in an aluminum chlorohydrate solution. Where the fumed silica may exhibit a negative zeta potential in suspension, after treatment with aluminum chlorohydrate, the suspension of chemically treated fumed silica exhibits a positive zeta potential greater than about +20 mV.

[0261] In another aspect, the cationic polymetallate composition may include or be selected from [1] fumed silica, fumed alumina, fumed silica-alumina, fumed magnesium oxide, fumed zinc oxide, fumed titanium oxide, fumed zirconium oxide, fumed cerium dioxide, or any combination thereof, and the cationic polymetallate composition is chemically treated with [2] polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichlorohydrate, polyoxyaluminum hydroxychloride, or any combination thereof. For example, the cationic polymetallate composition may include or be selected from aluminum chlorohydrate treated fumed silica, aluminum chlorohydrate treated fumed alumina, aluminum chlorohydrate treated fumed silica-alumina, or any combination thereof. Some fumed metal oxides such as fumed alumina may already exhibit a positive zeta potential prior to chemical treatment. However, fumed metal oxides that do not have a zeta potential or have a positive zeta potential of less than about +20 mV may also be chemically treated with substances such as aluminum chlorohydrate, and after treatment, a colloidal suspension having a zeta potential greater than about +20 mV may be obtained.

[0262] In another aspect, the heterocoagulation agent may include a mixture of metal oxides formed during or after a fuming process, the mixture exhibiting a positive zeta potential due to the metal oxide composition. An example of this type of fumed oxide is fumed silica-alumina.

[0263] In another embodiment, the heterocoagulant can include any colloidal inorganic oxide particles, such as the particles described by Lewis et al. in U.S. Pat. No. 4,637,992 (such as colloidal ceria or colloidal zirconia or any positively charged colloidal metal oxide disclosed therein), which is incorporated herein by reference. In another aspect, the heterocoagulant can include magnetite or ferrihydrite. For example, the cationic polymetallic salt can include or be selected from boehmite, fumed silica-alumina, colloidal ceria, colloidal zirconia, magnetite, ferrihydrite, any positively charged colloidal metal oxide, or any combination thereof.

[0264] In another aspect, the heterocoagulant may include a cationic oligomeric or polymeric aluminum species in solution, such as aluminum chlorohydrate, also known as aluminum chlorohydrate (ACH), polyaluminum chloride (PAC), aluminum sesquichlorohydrate, or any combination or mixture thereof. For example, the cationic polymetallate heterocoagulant may include or be selected from any combination of aluminum species or species having the following empirical formula:

[0265] Al 2 (OH) n Cl m (H 2 O) x ,

[0266] Wherein n+m=6, and x is a number from 0 to about 4.

[0267] In one aspect, the cationic polymetallate may include or may be selected from the group consisting of: 4 (Al 12 (OH) 24 (H 2 O) 20 ] 7+ Aluminum substance, which is the so-called "Al 13 -mer" polycation and is considered as Al 13 Precursors of pillared clays.

[0268] When aluminum chlorohydrate is used as a heteroaggregation agent or chemical treatment agent for treating other metal oxides, aluminum chlorohydrate (ACH) solutions or solid powders from commercial sources can be used. Aluminum chlorohydrate solutions can be referred to as polycationic hydroxyaluminum complexes or basic aluminum chloride, which refers to a polycationic hydroxyaluminum complex having a general empirical formula of 0.5 [Al 2 (OH) 5 Cl(H 2 O) 2] The preparation of aluminum chlorohydrate solutions is described in U.S. Pat. Nos. 2,196,016 and 4,176,090, which are incorporated herein by reference, and may involve treating aluminum metal with hydrochloric acid in an amount that produces a composition having the above formula.

[0269] Alternatively, various aluminum sources such as alumina (Al 2 O 3 ), aluminum nitrate, aluminum chloride or other aluminum salts and treated with acid or alkali to obtain aluminum chlorohydrate solution. Many substances (including tridecaned [AlO 4 (Al 12 (OH) 24 (H 2 O) 20 ] 7+ (Al 13 -mer) polycations) are described in Perry and Shafran, Journal of Inorganic Biochemistry, 2001, 87, 115-124, which is incorporated herein by reference. The substances disclosed in this study, either alone or in combination, present in such solutions can be used as cationic polymetallic salts for heteroagglomeration of montmorillonite clays.

[0270] In one aspect, the aqueous aluminum chlorohydrate solution used in accordance with the present disclosure may have a 2 O 3 The aluminum content, calculated or expressed as a weight percentage, can range from about 15 wt.% to about 55 wt.%, although more dilute concentrations can be used. As will be appreciated by one of ordinary skill in the art, the use of more dilute solutions can simultaneously adjust other reaction conditions, such as time and temperature. The concentration of substituted aluminum (as Al2O3) in an aqueous solution of an aluminum polymetalate, such as an aqueous solution of aluminum chlorohydrate, can be about 15 wt.% to about 55 wt.%, although more dilute concentrations can be used. As will be appreciated by one of ordinary skill in the art, the use of more dilute solutions can simultaneously adjust other reaction conditions, such as time and temperature. 2 O 3 The weight percentage of the Al 2 O 3 ; about 0.5wt.% to about 50wt.% Al 2 O 3 ; about 1wt.% to about 45wt.% Al 2 O 3 ; about 2wt.% to about 40wt.% Al 2 O 3 ; about 3wt.% to about 37wt.% Al 2 O 3 ; about 4wt.% to about 35wt.% Al 2 O 3; about 5wt.% to about 30wt.% Al 2 O 3 ; or about 8wt.% to about 25wt.% Al 2 O 3 ; Each range includes each individual concentration expressed as one-tenth (0.1) of the weight percent encompassed therein, and includes any sub-ranges therein. For example, about 0.1 wt.% to about 30 wt.% Al 2 O 3 References include 10.1 wt.% to about 26.5 wt.% Al 2 O 3 When convenient, a solid polymetallate, such as solid aluminum chlorohydrate, may be used and added to the slurry of colloidal clay when preparing the heteroagglomerate. Therefore, the concentrations disclosed above are not limiting but exemplary.

[0271] In one aspect, the cationic polymetallate may include or may be selected from oligomers prepared according to U.S. Pat. No. 5,059,568 by copolymerizing (co-oligomerizing) a soluble rare earth salt with a cationic metal complex of at least one additional metal selected from aluminum, zirconium, chromium, iron, or a combination thereof, which is incorporated herein by reference, for example, wherein the at least one rare earth metal may be cerium, lanthanum, or a combination thereof. In one aspect, the heterocoagulation agent may include a lanthanide and Al. 13 Aqueous solutions of Keggin ions, such as described by McCauley in U.S. Pat. No. 5,059,568. However, the calcined clay heteroadducts of the present disclosure prepared using McCauley-type polymetallic salts do not provide substrate spacings greater than (Angstroms). While not wishing to be bound by theory, it is believed that this observation may be due to the much smaller ratio of Ce-Al hetero-coagulant to colloidal clay used in accordance with the present disclosure. This smaller amount results from the contact conditions of the montmorillonite clay and the hetero-coagulant, which is sufficient to provide a slurry of montmorillonite hetero-adducts with a zeta potential in the range of about +25 mV (millivolts) to about -25 mV.

[0272] In another aspect, exemplary polymetallic acid salts of the present disclosure may include: [1] ε-Keggin cation [ε-PMo 12 O 36 (OH) 4 {Ln(H 2 O) 4} 4 ] 5+ , wherein Ln can be La, Ce, Nd or Sm; and [2] having the general formula [Ln 2 V 12 O32 (H 2 O) 8 {Cl}]Cl containing lanthanide cationic heteropolyoxyvanadium clusters, where Ln can be Eu, Gd, Dy, Tb, Ho or Er.

[0273] On the other hand, the heterocoagulant can be a layered double hydroxide, such as magnesium aluminum hydroxide nitrate described in 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. Pat. No. 9,616,412, which are incorporated herein by reference. Therefore, the cationic polymetallic salt used as a heterocoagulant can be a layered double hydroxide or a mixed metal layered hydroxide. For example, the mixed metal layered hydroxide can be selected from Ni-Al, Mg-Al or Zn-Cr-Al types having positively charged layers. On the other hand, the layered double hydroxide or mixed metal layered hydroxide can include or can be selected from magnesium aluminum hydroxide nitrate, magnesium aluminum hydroxide sulfate, aluminum hydroxide magnesium 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, iron soapstone is about 0.33), (Al, Mg) 2 Si 4 O 10 (OH) 2 (H 2 O) 8 , synthetic hematite, hydrozincite (basic zinc carbonate) Zn 5 (OH) 6 (CO 3 ) 2 、Hydrotalcite[Mg 6 Al 2 (OH) 16 ]CO 3 ·4H 2 O, carbon nickel aluminum stone [Ni 6 Al 2 (OH) 6 ]CO 3 ·4H 2 O, hydrocalumite [Ca 2 Al(OH) 6 ]OH·6H 2 O, magnesium plus aluminum [Mg 10 Al 5 (OH) 31](SO 4 ) 2 ·mH 2 O, ferromagnesian magnesia [Mg 6 Fe 2 (OH) 16 ]CO 3 4.5H 2 O, ettringite [Ca 6 Al 2 (OH) 12 ](SO 4 ) 3 ·26H 2 O or any combination thereof.

[0274] In yet another aspect, the heterocoagulant agent may include an aqueous solution of a Fe polycation, such as described in Oades, Clay and Clay Minerals, 1984, 32(1), 49-57 or Cornell and Schwertmann in "The Iron Oxides: Structure, Properties, Reactions, Occurrences and Uses", 2003, 2nd edition, Wiley VCH. The cationic polymetallate may include or may be selected from the group consisting of: x (OH) y (H 2 O) 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 does not provide clay heteroadducts as provided by the cationic polymetallates of the present disclosure, for example, these proton (acid) treated clays are generally not easily filterable.

[0275] In another aspect, the colloidal montmorillonite clay may include or be selected from colloidal montmorillonite clays such as HPM-20 bentonite. The heterocoagulant may include or be selected from aluminum chlorohydrate, polyaluminum chloride or aluminum sesquichlorohydrate.

[0276] According to one aspect, the cationic polymetallate may include 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 formula:

[0277] [M(II) 1-x M(III) x (OH) 2 ]A x / n ·m L (I)

[0278] [LiAl 2(OH) 6 ]A 1 / n ·m L (II)

[0279] in:

[0280] M(II) is at least one divalent metal ion;

[0281] M(III) is at least one trivalent metal ion;

[0282] A is at least one inorganic anion;

[0283] L is an organic solvent or water;

[0284] n is the valence of the inorganic anion A, or in the case of a plurality of anions A, their average valence; and

[0285] x is a number from 0.1 to 1; and

[0286] m is a number from 0 to 10.

[0287] In this regard: 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, hydrogen carbonate (bicarbonate), sulfate, nitrate, nitrite, phosphate, chloride, bromide, fluoride, hydroxide ion or carbonate; n can be, for example, a number from 1 to 3; and L can be, for example, methanol, ethanol or isopropanol or water. In this regard, in addition, the cationic polymetallate can be selected from the complex of formula I, wherein M (II) is magnesium, M (III) is aluminum, and A can be carbonate.

[0288] In one aspect, the cationic polymetallic acid salt may comprise polyaluminium chloride, aluminium chlorohydrate, aluminium sesquichlorohydrate or polyaluminium oxychloride or a combination thereof. In yet another aspect, the cationic polymetallic acid salt may comprise a linear, cyclic or cluster aluminium compound containing, for example, 2-30 aluminium atoms. In the formulation for preparing the montmorillonite heteroadduct, the ratio of the number of millimoles (mmol) of aluminium (Al) in polyaluminium chloride, aluminium chlorohydrate, aluminium sesquichlorohydrate or polyaluminium oxychloride to the number of grams (g) of colloidal montmorillonite clay may be, for example, in the range of about 0.75 mmol Al / g clay to about 2.0 mmol Al / g clay, about 0.8 mmol Al / g clay to about 1.9 mmol Al / g clay, about 1.0 mmol Al / g clay to about 1.8 mmol Al / g clay, about 1.1 mmol Al / g clay to about 1.8 mmol Al / g clay, or about 1.1 mmol Al / g clay to about 1.7 mmol Al / g clay. Alternatively, in the formulation for preparing the montmorillonite heteroadduct, the millimoles (mmol) of aluminum (Al) in the polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichlorohydrate or polyhydroxyaluminum oxychloride per gram (g) of colloidal montmorillonite clay 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 combinations of sub-ranges therebetween.

[0289] On the other hand, in the formulation used to prepare the isolated or calcined montmorillonite heteroadduct, the ratio of millimoles (mmol) of aluminum (Al) to grams (g) of colloidal clay in the polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichlorohydrate or polyaluminum oxyhydroxychloride 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 the comparative ratio of millimoles of aluminum to grams of colloidal clay used when preparing the pillared clay using the same colloidal montmorillonite clay and heterocoagulation agent.

[0290] In this regard, the ratio of aluminum reagent to clay in the pillaring formulation is expressed as mmol Al / g clay, which represents the number of millimoles of Al in the aluminum chlorohydrate reagent relative to the number of grams of clay in the formulation. Specifically, this ratio reflects the ratio used in the synthesis formulation, not the ratio in the final pillared clay product. As an example, consider the Al described in Ocelli, Clay and Clay Minerals, 2000, 48(2), 304-308. 13 Keggin ions, the amount of Al used in the preparation of the pillared clay far exceeds the amount of Al that will eventually be inserted between the solid layers of the final pillared clay. The use of excess aluminum reagent is used to provide the maximum pillar content in the final product and to obtain the porosity and surface area required for the final calcined material. Kooli in Microporous and Mesoporous Materials; 2013, 167, 228-236 discloses that about 6 mmol Al / gram of clay is usually required in the formulation to optimize pillaring. In recent studies on Al 13 In the scale-up study and optimization of Keggin ion-pillared clay, Pergher and Bertella in Materials, 2017, 10, 712 disclosed that in order to obtain a pillar with the desired substrate spacing and surface area, a dilute dispersion of 15 mmol Al / g clay and about 1 wt.% clay was required. F. Preparation, separation, and filterability of clay heteroaggregates

[0291] According to aspects of the present disclosure, the surfactant agent may be contacted with the clay in any manner in the first liquid vehicle. It has been found that adding the clay to the first liquid vehicle and applying shear forces to disperse the clay followed by adding the surfactant to the dispersion works well. The first liquid vehicle may include or may be water, to which the clay is added and dispersed, followed by the addition of the surfactant. The surfactant agent may be contacted with the clay dispersion by adding the surfactant agent in solid or pure liquid form directly to a slurry / dispersion of the clay or by contacting a liquid mixture in which the agent is dissolved or slurried in an appropriate solvent with the clay slurry / dispersion. Although solid clay may be added to a liquid surfactant or a liquid or solid surfactant dissolved or dispersed in a liquid vehicle under high shear conditions, more consistent results have been obtained by forming a well-dispersed clay suspension in a liquid vehicle before adding the surfactant to the vehicle.

[0292] The step of contacting the colloidal montmorillonite clay with the heterocoagulation agent (whether a surfactant, a cationic polymetallate, or a combination thereof) can be carried out using high shear conditions obtained by high rpm (revolutions per minute) to provide a dispersion without lumps. On a laboratory scale, this can be done using and on an industrial scale, a Cowles-type mixer or other high speed dispersion mixer may be used with suitable mixing speeds and high shear impellers as required.

[0293] The montmorillonite heteroadduct can be prepared by contacting a colloidal montmorillonite clay with a surfactant in a "first" liquid vehicle. Unless otherwise specified, the term "first" liquid vehicle refers to the medium in which the montmorillonite heteroadduct is prepared, while the "second" liquid vehicle refers to the medium in which the catalyst system is prepared by contacting the montmorillonite heteroadduct with a transition metal or metallocene compound. An organic compound that can serve as the first liquid vehicle can also serve as the second liquid vehicle.

[0294] In one aspect, the first liquid carrier may include, consist essentially of, or be selected from the group consisting of water, an organic liquid, or a combination thereof. For example, the first liquid carrier may include or consist essentially of water, an alcohol, an ether, a ketone, an ester, or any combination thereof. In an embodiment, the first liquid carrier may include or consist essentially of water, methanol, ethanol, n-propanol, isopropanol, n-butanol, diethyl ether, di-n-butyl ether, acetone, methyl acetate, ethyl acetate, or any combination thereof. For example, the first liquid carrier may be water without any organic liquid, such that the colloidal montmorillonite clay and the surfactant are in contact only in water.

[0295] In another aspect, the step of contacting the colloidal montmorillonite clay with the surfactant may include: adding the surfactant in solid or neat liquid form to the mixture of the colloidal montmorillonite clay in the first liquid carrier; or adding a solution or slurry of the surfactant to the mixture of the colloidal montmorillonite clay in the first liquid carrier. When the montmorillonite heteroadduct is prepared by a process of contacting the colloidal montmorillonite clay, the cationic polymetallate and the surfactant, the contacting step may include:

[0296] (a) adding a surfactant and a cationic polymetallate simultaneously or in any order to a mixture of colloidal montmorillonite clay in a first liquid carrier; or

[0297] (b) (1) adding a cationic polymetalate to a mixture of colloidal montmorillonite clay in a first liquid carrier to form a montmorillonite-cationic polymetalate heteroadduct, (2) isolating the montmorillonite-cationic polymetalate heteroadduct and (3) resuspending the montmorillonite-cationic polymetalate heteroadduct in a dispersion medium,

[0298] A surfactant is added to the dispersion medium before, after or during the resuspension step.

[0299] In embodiments, the step of contacting the colloidal montmorillonite clay with a surfactant and / or a cationic polymetallate may occur at a temperature range, for example: (i) about 5°C to about 90°C, about 10°C to about 50°C, or 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 range between any of these temperatures.

[0300] Thus, the result of contacting the clay with a heteroaggregate agent (whether a surfactant, a cationic polymetalate, or a combination thereof) in a first liquid carrier is the formation of a clay-heteroadduct (or "heteroaggregate"). Depending on the heteroaggregate agent, the clay-heteroadduct may be referred to as a clay-surfactant heteroadduct, a clay-cationic polymetalate-surfactant heteroadduct, or a clay-cationic polymetalate heteroaggregate (if no surfactant is present). Once the clay-heteroadduct is formed, removal of salts and other soluble byproducts of heteroaggregate preparation may be readily accomplished by isolating the heteroaggregate product, washing the heteroaggregate with water, and then simply filtering to isolate the heteroaggregate.

[0301] The method of preparing a support-activator comprising a montmorillonite heteroadduct may further include the steps of: (i) separating the montmorillonite heteroadduct from a slurry in a first liquid carrier. Once separated, the process may further include (ii) washing the montmorillonite heteroadduct with water, an organic liquid, or a combination thereof, and the process may still further include (iii) drying or calcining the montmorillonite heteroadduct. Separating the montmorillonite heteroadduct may include gravity filtering the slurry, vacuum filtering the slurry, subjecting the slurry to reduced pressure, heating the slurry, subjecting the slurry to rotary evaporation, bubbling a gas through the slurry, or any combination thereof. The ease with which the montmorillonite heteroadduct is separated by filtering the slurry from the contacting step provides advantages in their preparation and use as a support-activator. Separating the montmorillonite heteroadduct may include evaporating the first liquid carrier from a slurry to which an organic liquid entrainer has been added, or separating the montmorillonite heteroadduct may be performed in the absence of an entrainer. In any case, the step of separating the montmorillonite heteroadduct may be performed without the use of ultrafiltration, centrifugation, or a settling tank.

[0302] Once isolated, the montmorillonite heteroadduct may be washed, resuspended in a liquid carrier and filtered again, resuspended in a dispersion medium before spray drying, and the like. For example, the method of preparing the support-activator may further include the steps of resuspending the montmorillonite heteroadduct in water, an organic liquid, or a combination thereof to form a suspension, and evaporating water from the suspension to isolate the montmorillonite heteroadduct or filtering the suspension to isolate the montmorillonite heteroadduct. The reobtained montmorillonite heteroadduct may be washed with water, an organic liquid, or a combination thereof and reisolated. In one aspect, the method may further include the steps of measuring the conductivity of the suspension of the montmorillonite heteroadduct in water, and if the conductivity is greater than 300 μS / cm, repeating the steps of washing the montmorillonite heteroadduct and filtering the suspension to provide a washed montmorillonite heteroadduct.

[0303] The separated montmorillonite heteroadduct can then be dried or calcined. For example, drying the montmorillonite heteroadduct can be carried out by an azeotropic process or by a spray drying process. Drying or calcining the montmorillonite heteroadduct can also be carried out by heating the montmorillonite heteroadduct in air, in an inert atmosphere, under vacuum, or a combination of these methods.

[0304] In one aspect, if desired, the heterocoagulation solid can be dried with an azeotroping agent. Suitable entrainers can include, but are not limited to, ethanol, 1-propanol, 1-butanol, 2-butanol, benzene, or acetonitrile. In one aspect, the entrainer can be mixed with water in any manner, such as before or after addition to the heterocoagulation solid.

[0305] On the other hand, the product can be directly subjected to the subsequent calcination / drying step without the addition of an azeotropic agent.This process constitutes an advantageous embodiment because it allows the drying step to be carried out in the absence of an organic solvent, thereby providing significant economic and safety benefits.

[0306] In one aspect, the processing of the shape of the clay-surfactant heteroaggregate (i.e., changing or fixing / setting the shape of the heteroaggregate) can be performed by granulation, pulverization or classification prior to calcination. That is, the ion-exchange layered clay (aluminosilicate) having a previously processed shape can be chemically treated. Alternatively, the clay-surfactant heteroaggregate can undergo processing of the shape after calcination. Processing can be performed before or after chemical treatment with an optional cocatalyst (such as an organoaluminum compound) and / or treatment with a polymerization catalyst.

[0307] In one aspect, the shape of the clay-surfactant heteroagglomerate can be changed or fixed / set by a process called a "granulation" process. Examples of granulation methods that can be used include, but are not limited to, a stirring granulation process, a spray (spray drying) granulation process, a tumbling granulation process, a grinding granulation process, a briquetting granulation process, a compacting granulation process, an extrusion granulation process, a fluidized layer granulation process, an emulsification granulation process, a suspension granulation process, a compression molding granulation process, and the like. In another aspect, granulation methods that work well according to the present disclosure include a stirring granulation process, a spray granulation process, a tumbling granulation process, and a fluidized granulation process, but the granulation method is not limited to these specific processes.

[0308] The clay-surfactant heteroadducts prepared in slurry form according to the present disclosure unexpectedly exhibit improved ease of separation compared to, for example, pillared clays prepared using the same montmorillonite clay and cationic polymetallate heterocoagulation agent but in different amounts. Specifically, unlike the pillared clays, the clay heteroadducts can be quickly separated by filtration.

[0309] One way in which the filterability of a hetero-coagulated clay-surfactant slurry can be assessed is by determining whether the hetero-coagulated is "easily filterable" by comparing the filtrate collected from the hetero-adduct slurry to the aqueous carrier in the initial slurry. In one aspect, a slurry of a clay-surfactant hetero-adduct is easily or readily filterable if the slurry is characterized by the following filtering behavior:

[0310] (a) when filtering a 2.0 wt. % aqueous montmorillonite heteroadduct slurry beginning 0 to 2 hours after the colloidal montmorillonite clay and the surfactant form a contact product, the proportion of the filtrate obtained at a filtering time of 2 to 12 hours using vacuum filtration or gravity filtration (based on the weight of the first liquid vehicle in the montmorillonite heteroadduct slurry) is in the following ranges: (i) from about 30% to about 100% by weight of the first liquid vehicle in the slurry before filtration, i.e., the initial slurry water weight; (ii) from about 40% to about 100% by weight of the first liquid vehicle in the slurry; (iii) from about 50% to about 100% by weight of the first liquid vehicle in the slurry; or (iv) from about 60% to about 100% by weight of the first liquid vehicle in the slurry before filtration; and

[0311] (b) Upon evaporation, the filtrate from the heteroadduct slurry produces a clay solid comprising less than 20%, less than 15%, or less than 10% of the initial combined weight of montmorillonite clay and surfactant.

[0312] A small portion of water may be added to the slurry for additional washing and recovery of additional slurry. The feature of filtering between 0 hours and 2 hours after initial formation is specified because some non-heteroadduct slurries (including some pillared clay slurry compositions) may be filtered more quickly after the slurry has undergone an initial settling period of several days, and such filterability is not considered "readily filterable" under these standards.

[0313] In the present disclosure, the clay-surfactant heteroadduct slurry can be filtered using a 20 micron filter within a few minutes after the contacting step between the colloidal clay and the surfactant. In most cases, substantially all of the water from the heteroadduct slurry has been filtered out at the 10 minute mark after starting vacuum filtration. In contrast, substantially no water from a similar pillared clay slurry was filtered out 10 minutes after starting vacuum filtration.

[0314] By using a combination of the above two characteristics to assess "ease of filterability", it is not necessary to specify the filter spacing (e.g., 20 μm) nor is it necessary to specify whether the filtration is by gravity or vacuum. That is, one of ordinary skill can readily recognize that a filter with a particular opening size, such as the 20 μm filter used in the Examples, would allow the clay heteroadduct to meet both criteria, but no filter size would allow the pillared clay to meet both criteria.

[0315] As an example of applying this "easily filterable" test, if a pillared clay is filtered to meet the requirements of part (a) of the above criteria using a filter with too large openings between the filter media, it will not meet the requirements of part (b) and will not be considered easily filterable. When such a larger filter size is used, the clay heteroadduct will also not meet the requirements of part (b), but reducing the filter size (e.g., to about 20 μm) will allow the clay heteroadduct to meet both criteria (a) and (b), while when the filter size is reduced, the pillared clay slurry will not meet the requirements of part (a) because the filter will become clogged and little to no liquid carrier will be filtered through.

[0316] Likewise, either gravity filtration or vacuum filtration can be used for the "ease of filterability" test because, at the specified time point for measuring the filtrate (10 minutes after initiating filtration), an ordinary technician can easily determine the appropriate filter size that will result in the clay heteroadduct meeting criteria (a) and (b), while the pillared clay will not meet at least one of criteria (a) and (b).

[0317] G. Spray Drying and Calcination of Montmorillonite Clay-Heteroadduct

[0318] Once the montmorillonite heteroadduct has been isolated, the method for preparing the support-activator may further comprise the following steps:

[0319] suspending the montmorillonite heteroadduct in a dispersing medium to provide a suspension of the montmorillonite heteroadduct in the dispersing medium; and

[0320] The montmorillonite heteroadduct is spray dried from the suspension to provide the support-activator in particulate form.

[0321] Examples of dispersion media for the initial slurry to be sprayed include water, organic liquids or combinations thereof. For example, water alone can be used as a dispersion medium for spray drying, which is advantageous from a cost and environmental perspective. Examples of organic liquids (sometimes referred to herein as organic solvents, although the clay heteroadducts are insoluble therein) that can be used alone or in combination with water include, but are not limited to, methanol, ethanol, isopropanol, n-propanol, n-butanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, xylene, etc., including mixtures thereof. In one aspect, water is used as a dispersion medium without the presence of an organic liquid. In one aspect, the dispersion medium can comprise water, an organic liquid or a combination thereof or can be substantially composed of them, although a significant advantage of the process is the ability to spray dry montmorillonite heteroaggregates from aqueous slurries in the absence of an organic liquid to obtain highly spherical particles of the montmorillonite heteroaggregates. In an embodiment, suspending the montmorillonite heteroadducts in a dispersion medium can occur under high shear conditions.

[0322] In one aspect, once the isolated montmorillonite heteroadduct has been suspended in the dispersion medium to provide a spray drying dispersion (sometimes referred to herein as a "re-suspension" step, since the montmorillonite heteroadduct itself is separated from the suspension), the montmorillonite heteroadduct may 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 discovered that improved processing of the montmorillonite heteroadduct may be achieved if the montmorillonite heteroadduct is maintained in the dispersion medium suspension for a period of time. For example, the montmorillonite heteroadduct may be suspended in the dispersion medium for the following period of time prior to spray drying:

[0323] (i) 0.1 hours to 72 hours, 0.25 hours to 72 hours, 1 hour to 72 hours, 12 hours to 72 hours, 18 hours to 72 hours or 24 hours to 72 hours;

[0324] (ii) 0.1 hours to 48 hours, 0.25 hours to 48 hours, 1 hour to 48 hours, 12 hours to 48 hours, 18 hours to 48 hours or 24 hours to 48 hours; or

[0325] (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.

[0326] When a spray or spray drying granulation process is used, the concentration of the clay heteroadduct in the starting slurry to be sprayed can be any concentration that provides a pumpable slurry. In one aspect, the concentration of the clay heteroadduct in the slurry to be sprayed should be high enough to be energy efficient and provide a feasible yield, but not so high that the slurry cannot be pumped using a spray drying device. For example, the concentration of the clay heteroadduct in the starting slurry for spray granulation to produce spherical particles can be 0.1 wt% to 70 wt%, 1 wt% to 50 wt%, 5 wt% to 30 wt%, or 8 wt% to 25 wt%. For example, the concentration of the clay heteroadduct in the starting slurry for spray granulation can be about 0.1 wt%, about 0.5 wt%, about 1 wt%, about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, about 12 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 35 wt%, about 40 wt%, about 45 wt%, about 50 wt%, about 55 wt%, about 60 wt%, about 65 wt%, or about 70 wt%, or any range between any of these concentrations. In one aspect, the upper limit of the clay heteroadduct concentration in the spray drying slurry may be affected by the specific spray drying equipment and the mechanical limitations of spray drying. On the other hand, the lower limit of clay heteroadduct concentration in the spray drying slurry may be affected by a concentration that is low enough that insufficient evaporation occurs, resulting in wet particles sticking to the spray dryer surface, or not producing a desired morphology, such as a spherical morphology.

[0327] On the other hand, the inlet temperature of the hot air used to produce spherical particles in the spray granulation process can vary depending on the dispersion medium used. In one aspect, when the clay hetero-adduct is spray dried from a dispersion medium of only water, the inlet temperature of the hot air used in the spray granulation can be 80°C to 260°C, 90°C to 250°C, or 100°C to 220°C. For example, when the clay hetero-adduct is spray dried from a dispersion medium of only water, the inlet temperature of the hot air can be about 80°C, about 90°C, about 100°C, about 110°C, about 120°C, about 130°C, about 140°C, about 150°C, about 160°C, about 170°C, about 180°C, about 190°C, about 200°C, about 210°C, about 220°C, about 230°C, about 240°C, about 250°C, about 260°C, or any range between any of these temperatures.

[0328] The montmorillonite heteroadduct, when separated or dried by any means, can then be subjected to calcination to provide a calcined support-activator that imparts activity to the polymerization catalyst. By heating the calcined montmorillonite heteroagglomerate solid, it is further dried and prepared for further treatment with the metallocene precatalyst and optional cocatalyst and optional coactivator. The calcination heat treatment also fully dries the clay heteroagglomerate to impart high activity to the final catalyst. The calcination treatment can be carried out in ambient atmosphere (ambient pressure air) or under various conditions that are conducive to the removal of moisture.

[0329] In one aspect, the montmorillonite heteroadduct can be heated or calcined in (a) an undried ambient atmosphere (air) or (b) a dry ambient atmosphere, wherein the dry ambient atmosphere comprises air that has passed through a drying tower or air having a relative humidity of about 0% to about 60%. In another aspect, the montmorillonite heteroadduct can be heated or calcined under an inert atmosphere such as nitrogen or under vacuum. In another aspect, the calcination can be carried out in a carbon monoxide atmosphere. Calcination in an atmosphere such as carbon monoxide can effectively remove surface hydroxyls and can allow calcination to be carried out at a lower temperature (typically at a temperature of at least 100° C.) than that required in an ambient atmosphere, helping to maintain pore volume and surface area during surface dehydration.

[0330] Calcination of the montmorillonite heteroadduct can be carried out, for example, by heating the montmorillonite heteroadduct in air, in an inert atmosphere, or under vacuum. In one aspect, the calcination can be carried out in a fluidized bed. In another aspect, the heteroagglomerated solid can be calcined by heating at a temperature of (i) 100°C to 900°C, 200°C to 800°C, 200°C to 750°C, 225°C to 700°C, 225°C to 650°C, 250°C to 650°C, 250°C to 600°C, 250°C to 500°C, 225°C to 450°C, or 200°C to 400°C; or (ii) about 100°C, about 125°C, about 150°C, about 175°C, about 200°C, about 225°C, about 250 ... ℃, about 275℃, about 300℃, about 325℃, about 350℃, about 375℃, about 400℃, about 425℃, about 450℃, about 475℃, about 500℃, about 525℃, about 550℃, about 575℃, about 600℃, about 625℃, about 650℃, about 675℃, about 700℃, about 725℃, about 750℃, about 775℃, about 800℃, about 825℃, about 850℃, about 875℃, about 900℃, or any range between any of these temperatures.

[0331] In another aspect, the calcination temperature can be selected from any single temperature, or the calcination can be conducted within a range of two temperatures separated by at least 10° C., typically in the range of 110° C. to 800° C. As explained, when calcining in an atmosphere such as carbon monoxide, the temperatures used can be lower than those used in ambient air and / or the calcination times can be shorter than when calcining in ambient air.

[0332] In another aspect, the calcination can be carried out in an ambient atmosphere (air) or in a dry ambient atmosphere (dry air) at a temperature of 110° C. (e.g., about 200° C.) to 800° C. and a time period of about 1 minute to about 100 hours. In an embodiment, the clay heteroadduct can be calcined in ambient air or dry air at a temperature of about 225° C. to about 700° C. and a time period of about 1 hour to about 10 hours, or at a temperature of about 250° C. to about 500° C. and a time period of about 1 hour to about 10 hours.

[0333] In another aspect, the montmorillonite heteroadduct can be calcined using any of the following conditions: (a) a temperature in the range of about 110°C to about 600°C and a time period in the range of about 1 hour to about 10 hours; (b) a temperature in the range of about 150°C to about 500°C and a time in the range of about 1.5 hours to about 8 hours; or (c) a temperature in the range of about 200°C to about 450°C and a time in the range of about 2 hours to about 7 hours.

[0334] While not intending to be bound by theory, it is believed that after calcination, the calcined heteroagglomerated product can be described as a continuous, non-crystalline combination of clay and inorganic oxide particles that is very effective in activating metallocenes for olefin polymerization and can therefore act as a support-activator, also known as activator-support.

[0335] H. Characteristics of Clay Heteroagglomerates

[0336] Porosity and Particle Size. Hetero-agglomeration of clays with surfactant agents as described herein can provide support-activators with significant porosity that can enhance their activity as support-activators for metallocenes. In one aspect, the calcined clay-surfactant heteroadduct can exhibit a nitrogen adsorption / desorption BJH porosity of: (i) 0.1 cc / g to 3.0 cc / g, 0.15 cc / g to 2.5 cc / g, 0.25 cc / g to 2.0 cc / g, or 0.5 cc / g to 1.8 cc / g; (ii) about 0.10 cc / g, about 0.20 cc / g, about 0.30 cc / g, about 0.50 cc / g, about 0.75 cc / g, about 1.00 cc / g, about 1.25 cc / g, about 1.50 cc / g, about 1.75 cc / g, about 2.00 cc / g, about 2.25 cc / g, about 2.50 cc / g, about 2.75 cc / g, about 3.00 cc / g, about 3.25 cc / g, or about 3.50 cc / g. Calcined clay-surfactant heteroadducts having a porosity as low as about 0.12 cc / g can be used in the polymerization process because clay heteroadducts having a BJH porosity of <0.1 cc / g generally exhibit low polymerization activity, for example, <200 g PE / g support-activator / hr when combined with a metallocene such as bis(1-butyl-3-methylcyclopentadienyl)zirconium dichloride under polymerization reaction conditions. In the present disclosure, polymerization activity is measured using the term "g support-activator", which refers to the grams of calcined clay-surfactant heteroadduct (or clay-surfactant-cationic polymetalate) used to prepare the catalyst.

[0337] The preparation of calcined hetero-agglomerates (where the hetero-agglomerates are dried as aqueous slurries without the addition of entrainers such as 1-butanol, 1-propanol or other such organic liquids) that retain significant BJH porosity (≥ 0.1 cc / g) has been a challenging problem. The data in Table 1, as described below, illustrate this problem. This water-only spray drying process is highly desirable to improve the economic viability and environmental sustainability of the process compared to processes requiring an organic dispersion medium. Surprisingly, the present process achieves the advantage of allowing spray drying from a water-only slurry to provide a clay hetero-adduct that retains high porosity and activity after calcination and is characterized by a desirable highly spherical morphology that imparts excellent processing characteristics to the support-activator, supported catalyst and resulting polymer.

[0338] Table 1 presents the properties and polymerization data of clay-aluminum chlorohydrate (ACH) heteroagglomerates prepared in the absence of surfactant, dried by azeotropic or non-azeotropic processes, and calcined to form clay-ACH support-activator. Batches 1 to 4 show that high BJH porosities exceeding 0.25 cc / g are obtained when the clay-ACH support is dried in an azeotropic mixture of 1-butanol and water and then calcined. However, the calcined clay-ACH heteroadduct of batch 5, which has been dried as an aqueous slurry and then calcined without the addition of 1-butanol or any organic liquid, has a low BJH porosity of 0.049 cc / g. The samples shown in batches 1 to 4 also exhibited excellent polymerization activity (>2000 g PE / g support-activator / hr) when combined with bis(1-butyl-3-methylcyclopentadienyl)zirconium dichloride, while batch 5 showed minimal polymerization activity (<100 g PE / g support-activator / hr) under similar conditions.

[0339] The data in Table 2 illustrate embodiments of the present disclosure. In one aspect, adding a surfactant to a clay dispersion in water and evaporating the aqueous slurry without the addition of an azeotroping agent (such as 1-butanol, 1-propanol or other organic solvent) and then calcining the clay-heteroadduct produces a support-activator having a significant BJH porosity relative to a calcined clay prepared under similar conditions without the surfactant material. For example, Fig.25 A rotary evaporated and calcined dispersion prepared by drying a 5 wt.% HPM-20 dispersion according to Example 1 is provided. Results of nitrogen adsorption / desorption BJH pore volume analysis of HPM-20 montmorillonite clay. Specifically, the figure provides the pore size (angstroms, ) versus cumulative pore volume (cubic centimeters per gram, cc / g). The total BJH porosity of this sample is 0.06 cc / g. Thus, in the absence of a surfactant agent, the calcined montmorillonite such as bentonite used in the present disclosure may have a BJH porosity of about 0 cc / g to about 0.1 cc / g.

[0340] In contrast, embodiments of the clay-surfactant heteroadduct support-activator may have a BJH porosity greater than about 0.1 cc / g, for example, 0.1 cc / g to 0.3 cc / g. In other embodiments or aspects of the present disclosure, the clay-surfactant heteroadduct support-activator may have a BJH porosity of about 0.15 cc / g to 0.3 cc / g. Table 2 reports the porosity characteristics of such calcined clay-surfactant heteroagglomerates, such as in batches 2, 5, 7 to 14, and 18 to 21, where the BJH porosity is 0.1 cc / g to 0.3 cc / g. Thus, the calcined clay-surfactant heteroagglomerates are characterized by a BJH porosity that is about 150% (1.5×) to 200% (2×) of the BJH porosity of the corresponding calcined clay in the absence of surfactant, and may be characterized by a BJH porosity that exceeds 200% of the corresponding calcined clay material in the absence of surfactant. In the examples, the spray-dried clay-surfactant carrier-activator generally exhibits a BHJ porosity of about 0.1 cc / g to 0.3 cc / g total BHJ porosity, with some high activity examples near the lower end of this porosity range, even as low as 0.12 cc / g. In contrast, the clay-ACH carrier-activator can have a BJH porosity as high as about 0.5 cc / g to 0.7 cc / g.

[0341] These clay-surfactant support-activator porosities can be compared to the porosities of other clay heteroadducts. For example, heteroadducts (support-activators) prepared using only cationic polymetallates, only surfactants at different surfactant concentrations, and combinations of cationic polymetallates and surfactants were examined as described below.

[0342] Porosity data was obtained for a calcined non-azeotropic (rotary evaporated) clay-aluminum chlorohydrate (ACH)-surfactant heteroadduct prepared according to Example 7-B2, wherein the heteroagglomerate was prepared by contacting a clay slurry with ACH followed by 0.5 wt% trihexyltetradecylphosphonium bromide. The total BJH porosity of this material was 0.148 cc / g.

[0343] Porosity data was also obtained for a calcined non-azeotropic (rotary evaporated) clay-surfactant heteroadduct prepared according to Example 13-B8, wherein the clay heteroagglomerate was prepared by contacting the clay with 1 wt.% tetrabutylammonium bromide (TBABr) in the absence of a cationic polymetalate (0.62 mmol TBABr / g clay). The total BJH porosity of this material was 0.126 cc / g.

[0344] Porosity data was also obtained for a calcined non-azeotropic (rotary evaporated) clay-surfactant heteroadduct prepared according to Example 14-B9, wherein the clay heteroagglomerate was prepared by contacting the clay with 2 wt.% tetrabutylammonium bromide in the absence of a cationic polymetalate. The total BJH porosity of this material was 0.162 cc / g.

[0345] On the other hand, the measured BJH porosity of the calcined heteroagglomerates prepared by the combination of clay, surfactant agent and additional heteroagglomerates such as aluminum chlorohydrate or polyaluminum chloride (cationic polymetalate) significantly exceeds the measured BJH porosity of the calcined heteroagglomerates prepared by the combination of clay and additional heteroagglomerates. As a baseline measurement, the calcined non-azeotropic (rotary evaporated) clay heteroagglomerates prepared by contacting the clay with an aqueous aluminum chlorohydrate (ACH) dispersion according to Example 5-A4 were found to have a total BJH porosity of 0.049 cc / g. However, when both cationic polymetalate and surfactant are used, the porosity increases significantly. This increase is depicted in the calcined non-azeotropic (rotary evaporated) clay-ACH-surfactant heteroadduct prepared according to Example 6-B1, where the calcined clay heteroagglomerates were prepared by contacting the clay with an aqueous aluminum chlorohydrate dispersion and 2 wt% of tetraoctylammonium bromide. The total BJH porosity of this sample was found to be 0.287 cc / g.

[0346] It is noteworthy that the calcined heteroagglomerates prepared by the combination of clay and surfactant (and optionally, other heteroagglomerates such as aluminum chlorohydrate or polyaluminum chloride) can also exhibit high BJH porosity (>0.15 cc / g), even when the pre-calcined drying is carried out in the absence of an azeotroping agent. This unexpected result can be demonstrated, for example, in Table 2 (Batch 2) and Table 3 (Batches 7 to 10). Therefore, there is no need to add an azeotroping agent to maintain the porosity of the clay surfactant carrier. The ability to use pure water instead of alcohol-water mixtures (or other aqueous organic liquids) during the processing of these carrier-activators brings many practical economic and safety benefits to the use of these clay surfactant carriers.

[0347] The data in Table 2 also show that while the combination of tetramethylammonium bromide and clay provides heteroadducts that exhibit good activity, relatively high concentrations of tetramethylammonium bromide are generally required to achieve the desired activity. When a combination of long chain tetraalkylammonium, long chain alkyltrimethylammonium or long chain alkylammonium surfactants is used with montmorillonite clay, excellent activity of the support-activator is observed at lower relative surfactant concentrations.

[0348] In another aspect, the montmorillonite clay heteroadduct (heteroadduct) can have an average particle size, for example, from 1 μm (micrometer) to 250 μm, which is an average dry or calcined particle size. Unless otherwise specified, the particle sizes listed for the montmorillonite clay heteroadduct are for the particle sizes of the dried or calcined clay-heteroadduct particles measured as described herein. For example, the montmorillonite clay heteroadduct can have an average particle size of about 1 μm (micrometer), about 2 μm, about 3 μm, about 5 μm, about 7 μm, about 10 μm, about 12 μm, about 15 μm, about 18 μm, about 20 μm, about 25 μm, about 30 μm, about 35 μm, about 40 μm, about 45 μm, about 50 μm, about 55 μm, about 60 μm, about 65 μm, about 70 μm, about 75 μm, about 80 μm, about 85 μm, about 86 μm, about 87 μm, about 88 μm, about 89 μm, about 90 μm, about 91 μm, about 92 μm, about 93 μm, about 94 μm, about 95 μm, about 96 μm, about 97 μm, about 98 μm, about 99 μm, about 100 μm, about 101 μm, about 102 μm, about 103 μm, about 104 μm, about 105 μm, about 106 μm, about 107 μm, about 108 μm, about 109 μm, about 110 μm, about 111 μm, about 112 μm, about 113 μm, about 114 μm, about 115 The average particle size of the present invention can be about 0 μm, about 85 μm, about 90 μm, about 95 μm, about 100 μm, about 110 μm, about 120 μm, about 125 μm, about 130 μm, about 140 μm, about 150 μm, about 160 μm, about 170 μm, about 175 μm, about 185 μm, about 200 μm, about 225 μm or about 250 μm, or any particle size range between these listed numbers. For example, the montmorillonite clay heteroadduct may have an average particle size of 1 μm (micrometer) to 250 μm, 2 μm to 125 μm, 3 μm to 100 μm, 5 μm to 150 μm, 5 μm to 80 μm, 7 μm to 70 μm, 10 μm to 100 μm, 10 μm to 60 μm, 15 μm to 80 μm, 15 μm to 50 μm, or 20 μm to 75 μm.

[0349] Zeta Potential. The zeta potential of slurries of clay-surfactant heteroadducts was measured as a function of the number of millimoles of surfactant added to the slurry of montmorillonite clay and compared to the zeta potential of slurries of clay-cationic polymetalate heteroadducts. Fig.29 and Fig.30 Zeta potential data for slurries of montmorillonite clay titrated with aqueous solutions of tetrabutylammonium bromide and tetramethylammonium bromide, respectively, are shown, plotting the zeta potential of the slurry versus the number of millimoles of the specific tetraalkylammonium bromide added per gram of clay. The mmol cation / g clay reflects the cumulative number of millimoles of aqueous tetraalkylammonium bromide added.

[0350] As shown in these figures, surfactant titrations never provide a zeta potential (mV) of zero or positive (+). For tetrabutylammonium bromide titrations ( Fig.29 ), a zeta potential of approximately negative (-) 18 mV is the most positive potential observed and for tetramethylammonium bromide titration ( Fig.30), a zeta potential of about negative (-) 43 mV was the most positive potential observed. When a slurry of montmorillonite clay was titrated with an ammonium bromide solution (not shown), a zeta potential of about negative (-) 50 mV was the most positive potential observed. This behavior is in contrast to a zeta potential titration using aluminum chlorohydrate as a titrant, where the zeta potential curve goes from a negative (-) mV potential through neutral to a positive (+) mV potential as the amount of titrant increases.

[0351] The highest polymerization activity observed for the montmorillonite clay-tetraalkylammonium heteroadducts depends on the specific tetraalkylammonium surfactant utilized. For example, the highest polymerization activity observed for the montmorillonite 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).

[0352] I. Powder XRD Structure of Spray-dried Clay-Surfactant Heteroaggregates

[0353] A series of powder XRD (x-ray diffraction) patterns of the spray-dried calcined products are presented in Figures 26 to 28 The samples were not dried by azeotropic or zeotropic rotary evaporation of the liquid carrier but rather by spray drying and calcining the samples. Fig.26 It is shown that as in Example 21-E1, by removing the polymetallic acid salt in the absence of a cationic Powder XRD of the calcined, spray-dried product of HPM-20 montmorillonite clay in combination with tetramethylammonium bromide (TMABr). Fig. 27 According to Example 22-E2, in the absence of a cationic polymetallate, Powder XRD of the calcined spray-dried product of HPM-20 montmorillonite in combination with tetrabutylammonium bromide (TBABr). Fig.28 According to Comparative Example 20-D1, in the absence of a surfactant, Powder XRD of calcined spray-dried product of HPM-20 montmorillonite combined with aluminum chlorohydrate (ACH). In these XRD patterns, the peaks in the range between 20 and 30 degrees 2θ (2θ) (20-30° 2θ) arise from mineral impurities present in the starting colloidal clay.

[0354] Compared to other clay-based materials such as those described by Jensen et al. in U.S. Patent Application Publication Nos. 2018 / 0142047 and 2018 / 0142048 (assigned to WR Grace) and those described in International Publication No. WO 2021 / 154204, the clay-surfactant heteroagglomerates of the present disclosure can exhibit a significant d001 peak between 6 and 9 degrees 2θ (2θ) (6-9°2θ) (e.g., between 7 and 8 degrees 2θ (2θ) (7-8°2θ)) in a powder XRD scan after filtration and calcination at 300°C or higher. This feature is Fig.26 and Fig. 27 These figures present the results of the experiments respectively performed by adding tetramethylammonium bromide ( Fig.26 ) or tetrabutylammonium bromide ( Fig. 27 )and Powder XRD patterns of the spray dried and calcined products obtained by combining HPM-20 montmorillonite with samples differing only in the tetraalkylammonium surfactant used.

[0355] These features are in contrast to calcined pillared adducts composed of clay and aluminum chlorohydrate (wherein the aluminum chlorohydrate is added to the clay at a molar ratio of more than 6 mmol Al / g clay), which tend to have a well-defined, significant d001 peak between 4 and 6 degrees 2θ (4-6° 2θ) in the powder XRD scan. They are also different from cationic polymetallate-heteroadducts, such as the type prepared according to Comparative Example 20-D1 using aluminum chlorohydrate (ACH) and montmorillonite, Fig.28 A powder XRD scan thereof is provided in . In this heteroadduct, the powder XRD indicates little or no pillaring (peak between 4.8 and 5.2 degrees 2θ) relative to the mineral impurities present in the starting colloidal clay in the 2θ range of 20 to 30 degrees 2θ, and little or no simple ion exchange clay (peak between 9 and 10 degrees 2θ).

[0356] Thus, the inventive spray-dried calcined clay-surfactant heteroadducts described herein have a distinct microstructure from previously disclosed calcined spray-dried clay-aluminum chlorohydrate heteroagglomerates and other clay-cationic polymetallate heteroagglomerates.

[0357] J. Morphology of spray-dried clay surfactant heteroagglomerates and polymers produced therefrom

[0358] On the one hand, it is found that the calcined, spray-dried clay-surfactant heteroaggregate support-activator and the supported catalyst prepared therefrom are highly spherical and very uniformly spherical in nature, that is, their spherical shape is highly uniform. The highly spherical property can be measured by various methods, including sphericity (S), roundness (R), roundness (C) or a combination thereof. Surprisingly, the highly spherical and highly rounded properties of the clay-surfactant heteroaggregate can be achieved by spray drying from an aqueous suspension in the absence of any organic solvent. It is also found that the clay heteroaggregates and polymer particles produced using the clay heteroaggregates as support-activators are significantly more spherical and rounder than the corresponding clay heteroaggregates or polymer particles produced when the clay heteroaggregates are azeotropically dried (1-butanol / water, rotary evaporation) or non-azeotropically dried (water only, rotary evaporation).

[0359] This uniform spherical morphology can be very beneficial for producing the desired polymer morphology as well as for ensuring reactor operability and maintaining the activity of the support-activator.The morphology of the support-activator according to the present disclosure is illustrated in the accompanying drawings as follows. Fig. 9 , 10 , 13 and 14 present SEM (scanning electron microscopy or surface electron microscopy) images of calcined support-activators prepared according to the present disclosure. Fig. 9 and Fig.10 The method of Example 21-E1 by spray drying of tetramethylammonium bromide (TMABr) and SEM image of the calcined support-activator formed by contacting HPM-20 montmorillonite with an aqueous slurry of the formed heteroadduct. Fig.13 and Fig.14 The method of Example 22-E2 by spray drying of tetrabutylammonium bromide (TBABr) and SEM image of the calcined support-activator formed by contacting HPM-20 montmorillonite with an aqueous slurry of the formed heteroadduct.

[0360] Comparative SEM images are provided below. Fig.11 and Fig.12 The results are shown in Table 2. Comparative Example 20-D1 was prepared by spray drying of aluminum chlorohydrate (ACH) in the absence of a surfactant. SEM image of the calcined support-activator formed by contacting HPM-20 montmorillonite with an aqueous slurry of the formed heteroadduct. Figure 7 and Figure 8 The results are shown in Table 2. The results are shown in Table 2. The results are shown in Table 2. SEM image of a calcined support-activator formed by contacting HPM-20 montmorillonite with an aqueous slurry of the formed heteroadduct, which was subsequently azeotropically dried from an aqueous slurry including 1-butanol as an azeotropic agent.

[0361] Predominantly spherical morphology of the calcined spray-dried clay-surfactant heteroadduct particles with minimal agglomerate formation ( Fig. 9 , 10 , 13 and 14) and from a water and 1-butanol slurry ( Figure 7 and 8 ) azeotropically dried calcined - but not spray dried - support-activator derived from clay and aluminum chlorohydrate, where it is apparent that most of the heteroadduct particles are non-spherical granular particles and / or highly agglomerated. Although the spray dried and calcined heteroadduct derived from clay and aluminum chlorohydrate ( Fig.11 and 12 ) shows some highly spherical particles, but the heteroadduct is also characterized by many non-spherical and / or highly agglomerated particles.

[0362] In addition, from Fig. 9 , 10 The morphology of the calcined support-activator prepared according to the present disclosure of 1, 13 and 14 is similar to that of the support-activator from Figure 1 , 2 By comparing the morphology of the isolated support-activator (which can be simply referred to as clay heteroadduct) before calcination of 5, 6, and 7, it can be seen that calcination of the spray-dried particles does not substantially change the spherical morphology of the support-activator particles. Therefore, the description of sphericity, roundness, and circularity of the calcined montmorillonite heteroadduct is also applicable to the montmorillonite heteroadduct that has been isolated but not yet calcined.

[0363] Thus, one aspect of the present disclosure provides highly spherical, round and circular clay-surfactant heteroadducts, support-activators and supported catalysts, wherein 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 JC Santamarina, Journal of Geotechnical and Geoenvironmental Engineering, 2006, 132 (5), 591-602; (2) I. Cruz-Matíasa, D. Ayalab, D. Hillerc, S. Gutschd, M. Zachariasd, S. Estradée and F. Peiróe, Journal of Computational Science 2019, 30, 28-40. While not intending to be bound by theory, the concepts of sphericity and roundness can be considered as 3-dimensional (3-D) concepts that can be applied to 2-dimensional (2-D) measurements. Again, while not intending to be bound by theory, the concept of circularity can be considered a 2-dimensional (2-D) representation of sphericity.

[0364] In one aspect, the clay-surfactant heteroadducts, support-activators, and supported catalysts of the present disclosure can be characterized as having an average particle sphericity of 0.60 or greater (≥0.60), wherein the sphericity of each particle can be calculated according to the following formula:

[0365] in

[0366] r 最大-内接 is the radius of the largest inscribed circle of the two-dimensional image of the particle, and

[0367] r 最小-外接 is the radius of the minimum circumscribed circle of the two-dimensional image of the particle.

[0368] The average (average or mean) particle sphericity can be measured as a number-weighted average sphericity designated as "SPHT0", or using a volume-weighted average sphericity designated as "SPHT3". Unless otherwise specified, reference to the average sphericity without specifying whether the sphericity is a number-weighted average or a volume-weighted average is intended to refer to the volume-weighted average sphericity SPHT3. As demonstrated herein, such highly spherical particles can be obtained according to the present disclosure by spray drying from a slurry of only water, and retain the high sphericity upon calcination.

[0369] On the other hand, it is observed that the morphology of polyethylene homopolymers and copolymers prepared using carrier-activators reflects the morphology of clay-surfactant heteroadducts, carrier-activators or supported catalysts. Therefore, the morphology of polymer particles can serve as a representative of the morphology of clay-surfactant heteroadducts, carrier-activators or supported catalyst particles. Therefore, particles of clay-surfactant heteroadducts, carrier-activators, supported catalysts and polymer particles can have a volume weighted average sphericity (SPHT3) or number average particle sphericity (SPHT0) of 0.60 or greater, 0.65 or greater, 0.70 or greater, 0.75 or greater, 0.80 or greater, 0.85 or greater, 0.87 or greater, 0.90 or greater, 0.92 or greater or 0.95 or greater. The particles of the clay-surfactant heteroadduct, support-activator, supported catalyst, and polymer particles may also have a volume weighted average sphericity (SPHT3) or number average particle sphericity (SPHT0) of about 0.60, about 0.65, about 0.70, about 0.75, about 0.80, about 0.85, about 0.87, about 0.90, about 0.92, about 0.95, or any sphericity range between these values. These sphericity values ​​for average SPHT0 and average SPHT3 may be obtained, among other things, from Instruments (such as The images were obtained by multiplex image analysis of falling particles in the sensing area analyzed by X2 instrument.

[0370] On the other hand, the sphericity of polymer particles produced by polymerization using a supported catalyst comprising a clay-surfactant heteroadduct can be measured using The instrument and associated software analyze and quantify by particle shape and size analysis. As described above, it was surprisingly found that the polymer produced from the supported catalyst comprising the spray dried heteroadduct sample exhibited an average volume weighted sphericity (SPHT3) of 0.75 or greater, 0.80 or greater, 0.85 or greater, or 0.90 or greater compared to the polymer produced from the supported catalyst comprising any non-spray dried heteroadduct sample (azeotropic or non-azeotropic). X2 measurement). These polymer particles can also have an average volume weighted sphericity (SPHT3) of about 0.75, about 0.80, about 0.85, about 0.87, about 0.90, about 0.92, about 0.95, or any sphericity range between these values. In one aspect, these sphericity values ​​also correspond to those from Number-weighted mean sphericity (SPHT0) analyzed by X2 instrument.

[0371] Polymer particles obtained from ethylene-1-hexene copolymerization using various calcined spray-dried and calcined non-spray-dried clay heteroadduct support-activators were collected and The X2 dynamic image analyzer was used to determine the particle sphericity and particle size, which are reported in Table 6. The corresponding sphericity graph and particle distribution characteristics are summarized in Figures 37 to 40 .

[0372] Fig.37 Sphericity analysis of polymer samples is presented, wherein the supported catalyst comprises an azeotropically dried (not spray dried) and calcined support-activator obtained by contacting aluminum chlorohydrate with montmorillonite using 1-butanol as an azeotroping agent in the absence of a surfactant, as described in Example 2-A1. The polymer samples were subjected to Fig.38 Sphericity analysis, wherein the supported catalyst comprises a non-spray dried support-activator as described in Example 30-E2 obtained by contacting tetrabutylammonium bromide with montmorillonite in the absence of a cationic polymetallate, wherein the isolated product is rotary evaporated in the absence of an azeotroping agent prior to calcination. As shown in Tables 6 and Fig.37 and Fig.38 As shown, both polymer samples exhibited low (<0.70) volume-weighted average sphericity (SPHT3).

[0373] In contrast, sphericity analysis of polymers prepared using calcined spray-dried support-activators showed that the sphericity of the support-activators was improved compared to those support-activators that were either azeotropic or non-azeotropic and not spray-dried. Fig.39 and Fig.40 Sphericity data is obtained on two different polymer samples produced by two different carrier-activator samples, which are produced under different spray drying conditions within the range specified in Example 31. It is entirely within the capabilities of ordinary technicians to adjust or optimize the spray drying parameters within the range of Example 31 to obtain the sphericity and span values ​​reported in Table 6. See, for example, C. Arpagaus (2018), A Short Review on Nano Spray Drying of Pharmaceuticals. J. Nanomed. Nanosci.: JNAN-149. DOI: 10.29011 / 2577-1477.100049, which is incorporated herein by reference. This reference summarizes how adjusting process parameters (such as inlet temperature, drying gas flow rate, spray net size, solid concentration, feed rate, etc.) affects droplet size, particle size and other characteristics. The main spray drying parameters adjusted in the preparation of the subject carrier-activator are the concentration in the aqueous slurry and the feed rate. Fig.39 and Fig.40 The data in Table 6 show that these samples have very high average sphericity.

[0374] Fig.41 Shown is the method for obtaining Fig.40 Particle size distribution data and cumulative volume curves for samples of polymer powder produced using the catalyst prepared from the spray-dried clay-tetrabutylammonium bromide heteroadduct support-activator of Example 31. Fig.41 In the graph and similar graphs, the Q3[%] axis corresponds to the curve on the graph and represents the cumulative volume percentage value, which is the percentage of the total volume of particles below that particle size value. The P3[%] axis corresponds to the bar graph distribution and shows the percentage of the total volume of each bar or "slice" corresponding to the particle size. Fig.39 and Fig.40 The sphericity data and Fig.41 The particle size distribution data is provided in the examples X2 to collect and analyze.

[0375] On the other hand, sieving can be performed on the montmorillonite clay, spray-dried clay-surfactant heteroadduct, support-activator or supported catalyst before or after calcination or other drying process. Table 7 presents the sphericity and span data of the calcined support-activator derived from metallocene-catalyzed polymerization ethylene-1-hexene copolymer using the spray-dried unscreened clay-surfactant support-activator from Example 31 and the spray-dried clay-surfactant support-activator from the sieved samples in Examples 33 to 35. Table 7 shows that, as compared with the unscreened support-activator, the support-activator with a smaller particle size benefits more from sieving than the support-activator with a larger particle size in terms of producing more spherical ethylene-1-hexene copolymers. Therefore, if desired, the sphericity can be further improved by using certain sieved samples. Such a process can produce particles of clay, clay-surfactant heteroadduct, support-activator or supported catalyst having a narrower size distribution than the unscreened material and having a number-weighted or volume-weighted average particle sphericity of 0.65 or greater, 0.70 or greater, 0.75 or greater, 0.80 or greater, 0.85 or greater, 0.87 or greater, 0.90 or greater, 0.92 or greater, or 0.95 or greater. Screened samples of these clay, clay-surfactant heteroadduct, support-activator or supported catalyst particles can also have an average volume-weighted sphericity (SPHT3) of about 0.75, about 0.80, about 0.85, about 0.87, about 0.90, about 0.92, about 0.95, or any sphericity range between these values. Additionally, polymer powders produced from supported catalysts comprising such sieved, spray-dried heteroadduct samples may also exhibit a volume weighted average sphericity of 0.75 or greater, 0.80 or greater, or 0.85 or greater, and further have improved sphericity relative to polymer powders produced from supported catalysts comprising unsieved precursor spray-dried heteroadducts, support-activators, or supported catalysts.

[0376] On the other hand, sieving can also be used to improve the size uniformity of the clay-surfactant heteroadduct, support-activator or supported catalyst relative to the precursor unscreened material. The spray-dried clay-surfactant heteroadduct, support-activator or supported catalyst can be sieved before or after calcination or other drying process to provide particles with a more uniform particle size distribution, i.e., a lower span (=[d(0.9)-d(0.1)] / d(0.5)) relative to the precursor unscreened material. For example, the sieving process can produce a spray-dried clay-surfactant heteroadduct, support-activator or supported catalyst having a particle size distribution with a span of 2 or less, 1.5 or less, 1.25 or less, 1 or less, or 0.75 or less. Additionally, the particle size distribution of a polymer powder produced from a supported catalyst comprising such a sieved spray-dried heteroadduct sample can exhibit a span of 2 or less, 1.5 or less, 1.25 or less, 1 or less, or 0.75 or less, and further exhibits a lower span relative to a particle size distribution of a polymer powder produced from a supported catalyst comprising a precursor unsieved spray-dried heteroadduct, support-activator, or supported catalyst. In another aspect, the sieving process can produce a spray-dried clay-surfactant heteroadduct, support-activator, or supported catalyst, or a polymer powder produced therefrom, before or after calcination or other drying process, can exhibit a span of about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, about 0.9, about 1.0, about 1.1, about 1.2, about 1.3, about 1.4, about 1.5, about 1.6, about 1.7, about 1.8, about 1.9, about 2.0, or any range between any of the span values.

[0377] In order to more closely examine how the morphology and particle size distribution of the clay-surfactant heteroadduct or support-activator varies over a narrower particle size distribution, a sample of support-activator was prepared according to Example 31, spray dried, then sieved into three separate fractions, and catalysts and polymers were prepared from the three fractions as described in Examples 33 to 35. These data are shown below in Tables 7 and Figures 42 to 47 Available in. Fig.42 , Fig.44 and Fig.46 The particle size distribution and cumulative volume curves of copolymer powder samples are presented, and Fig.43 , Fig.45 and Fig.47 The volume-weighted sphericity (SPHT3) is plotted against Fig.42 , Fig.44 and Fig.46 A graph showing the relationship between the polymer particle size of the sample containing polymer particles.

[0378] Specifically, Fig.42 and Fig.43 The particle size distribution and sphericity data for the copolymer powder samples produced by the spray-dried clay-tetrabutylammonium bromide support-activator of Example 31 are shown, wherein the particle size is between 19 μm (micrometers) and 37 μm. Fig.42 and Fig.43 The data carrier-activator passes through the 37μm sieve but is captured on the 19μm sieve. Similarly, Fig.44 and Fig.45 Particle size distribution and sphericity data for a copolymer powder sample prepared from the spray-dried clay-tetrabutylammonium bromide support-activator of Example 31 are shown, the sample having a particle size between 37 μm (micrometers) and 50 μm. Finally, Fig.46 and Fig.47 Particle size distribution and sphericity data are shown for copolymer powder samples prepared from the spray-dried clay-tetrabutylammonium bromide support-activator of Example 31, which have particle sizes between 50 μm (micrometers) and 74 μm. These sieved samples were collected, calcined, and compared to (η 5 -1-n-butyl-3-methyl-cyclopentadienyl) 2 ZrCl 2 and triethylaluminum (TEA) to form a catalyst composition for copolymerizing ethylene and 1-hexene as described herein. X2 Collect and analyze polymer particles obtained from these copolymerizations using each size fraction of support-activator to determine particle size distribution.

[0379] These Table 7 data reveal that all narrow size range samples of Examples 33 to 35 show an average volume weighted sphericity SPHT3 greater than or equal to 0.65, wherein the SPHT3 sphericity increases with increasing particle size. The polymers prepared using the largest fraction of clay heteroadducts with sizes between 50 μm and 74 μm (Examples 35 and Fig.47 ) had the highest SPHT3 sphericity of 0.86. When comparing the initial 17 gram sample of the clay heteroadduct used in the sieving process, these three fractions accounted for about 16.76 g of the total 17 g starting sample. Therefore, 98.6 wt% of the Example 31 sample accounted for these three size fractions.

[0380] In another aspect, the clay-surfactant heteroadducts, support-activators, and supported catalysts of the present disclosure may be characterized as having an average particle circularity of 0.60 or greater, wherein the circularity is calculated according to the following formula:

[0381] in

[0382] r i is the radius of the inscribed circle of the curvature of the ith corner point of the two-dimensional image (contour) of the particle, n is the number of corner points; and

[0383] r 最大-内接 is the radius of the largest inscribed circle of the two-dimensional image of the particle.

[0384] In another aspect, the clay-surfactant heteroadducts, support-activators, supported catalysts, and polymer particles prepared therefrom can also have an average particle circularity of 0.65 or greater, 0.70 or greater, 0.75 or greater, 0.80 or greater, 0.85 or greater, 0.87 or greater, 0.90 or greater, 0.92 or greater, or 0.95 or greater. The clay-surfactant heteroadducts, support-activators, and supported catalysts, and polymer particles prepared therefrom can also have an average particle circularity of about 0.65, about 0.70, about 0.75, about 0.80, about 0.85, about 0.87, about 0.90, about 0.92, about 0.95, or any range between any of these particle circularity values.

[0385] According to another aspect, the clay-surfactant heteroadducts, support-activators, and supported catalysts of the present disclosure may be characterized as having an average particle circularity of 0.60 or greater, wherein the circularity is calculated according to the following formula:

[0386] in

[0387] A is the area of ​​the two-dimensional image (outline) of the particle, and the perimeter is the length of the path that surrounds the two-dimensional image of the particle. According to another aspect, the clay-surfactant heteroadduct, support-activator, supported catalyst and polymer particles prepared therefrom can also have an average particle circularity of 0.65 or greater, 0.70 or greater, 0.75 or greater, 0.80 or greater, 0.85 or greater, 0.87 or greater, 0.90 or greater, 0.92 or greater or 0.95 or greater. The clay-surfactant heteroadduct, support-activator, supported catalyst and polymer particles prepared therefrom can also have an average particle circularity of about 0.65, about 0.70, about 0.75, about 0.80, about 0.85, about 0.87, about 0.90, about 0.92, about 0.95 or any range between any of these circularity values.

[0388] In another aspect related to the morphology of the clay-surfactant heteroadducts, support-activators, and supported catalysts of the present disclosure, the clay-surfactant heteroadducts, support-activators, and supported catalysts when spray dried or when spray dried and calcined can be characterized by any one or any combination of the following properties:

[0389] (a) an average particle sphericity of 0.65 or greater;

[0390] (b) an average particle roundness of 0.65 or greater; and

[0391] (c) Average particle circularity of 0.65 or more.

[0392] Furthermore, the clay-surfactant heteroadducts, support-activators, and supported catalysts of the present disclosure, when spray dried or when spray dried and calcined, may be characterized by any one or any combination of the following properties:

[0393] (a) an average particle sphericity of 0.75 or greater;

[0394] (b) an average particle roundness of 0.75 or greater; and

[0395] (c) Average particle circularity of 0.75 or more.

[0396] Additionally, the clay-surfactant heteroadducts, support-activators, and supported catalysts of the present disclosure, when spray dried or when spray dried and calcined, may be characterized by any one or any combination of the following properties:

[0397] (a) an average particle sphericity of 0.80, 0.85, 0.90 or greater;

[0398] (b) an average particle roundness of 0.80, 0.85, 0.90 or greater; and

[0399] (c) Average particle circularity of 0.80, 0.85, 0.90 or more.

[0400] In another aspect of the present disclosure, polymer particles produced by polymerization of a spray-dried clay-surfactant heterocoagulate support-activator activated with a metallocene are also highly spherical in nature. A calcined, spray-dried support-activator (see Example 21-E1) derived from clay and tetramethylammonium bromide (Example 21-E2) or tetrabutylammonium bromide (Example 22-E3) was prepared. Fig. 9 , 10 , 13 and 14) were combined with metallocene bis(1-butyl-3-methylcyclopentadienyl) zirconium dichloride and triethylaluminum cocatalyst to form an active catalyst for the production of ethylene-1-hexene copolymers. Optical microscope images of these polymer particles are shown in Fig.15 and Fig.16 These polymer particles, like their parent catalyst particles, are highly spherical in nature.

[0401] In contrast, Fig.17An optical microscope image of a polymer derived from the copolymerization of ethylene and 1-hexene using the azeotropically dried clay-aluminum chlorohydrate (ACH) support-activator described in Example 2-A1 (in the absence of surfactant) wherein the support-activator is coupled to a metallocene (η 5 -1-Bu-3-MeCp) 2 ZrCl 2 Combined with triethylaluminum cocatalyst to form an active catalyst. Figure 7 and Figure 8 The example 2-A1 prepared and used to prepare Fig.17 SEM image of the polymer support-activator in Fig.15 and Fig.16 Compared to the polymer particles shown, Fig.17 The polymer particles Figure 7 and 8 The support-activator is granular and rather irregular, highly non-spherical and agglomerated.

[0402] Thus, it can be seen that the spray drying process from a water-only slurry can be an effective method for achieving the desired highly spherical morphology of the support-activator, which can produce highly symmetrical and spherical polymer particles once the metallocene, cocatalyst and monomer are introduced under polymerization conditions. The amenability of the clay-surfactant heteroadducts of the present disclosure to spray drying (particularly their retention of polymerization activity when subjected to this drying method) thus confers many benefits to catalyst bed loading and polymer packing characteristics.

[0403] In another aspect, the circularity (C) of the clay-surfactant heteroadducts and supported catalysts comprising the clay-surfactant heteroadducts can be analyzed and quantified by surface electron microscopy (SEM) followed by subsequent image analysis. For example, the calcined clay-surfactant heteroadducts and supported catalysts comprising the clay-surfactant heteroadducts can be analyzed by surface electron microscopy followed by subsequent image analysis using methods such as scanning probe image processor (SPIP) software to measure the circularity of the particles. In this regard, the circularity of the spray dried and calcined heteroadducts and catalysts can be measured and compared to the circularity of the calcined heteroadducts and catalysts dried using other means such as azeotropic drying.

[0404] When analyzing such SEM images by the SPIP software, and unless otherwise stated, particles with diameters greater than 8 μm and less than 100 μm were selected for analysis, as such a range eliminates fines that may be produced when gridding calcined heteroadducts and eliminates large particles that are most likely artifacts of erroneously perceived molten particles, while still covering the particle sizes most relevant to the catalytic process and most common in the samples. Circularity analysis of >8 μm and <100 μm diameter particles uses the SPIP software to calculate the area (A) of the two-dimensional image of the particle as well as the perimeter length, which is the length of the path that encloses the two-dimensional image of the particle. SEM images of individual particles were checked before use in the calculations to eliminate particles whose detected boundaries were erroneously merged with other particles, obscured by other particles, or interrupted by the boundaries of the SEM photo. In each analysis, unless otherwise stated, a sample of 10 or more particles was detected and the analysis was performed to calculate circularity (C).

[0405] The heteroadducts prepared according to the present disclosure and spray dried from a water-only suspension are characterized by an average particle circularity (C) of 0.80 or greater, 0.85 or greater, or 0.90 or greater, compared to the circularity of the non-spray dried heteroadduct samples. The circularity measurements of the spray dried and non-spray dried clay heteroadducts prepared as described herein are recorded in Table 5, and the corresponding SEM images appear in Table 5. Figure 31 to Figure 36 .

[0406] For example, Fig.31 and Fig.32 As shown in the SEM images of , the non-spray-dried support-activator was obtained by azeotropically drying the adduct obtained by contacting aluminum chlorohydrate (ACH) with montmorillonite in the absence of a surfactant using 1-butanol as an azeotropic agent as described in Examples 2-A1 and 3-A2, respectively, and then calcining the dried product. Fig.33 SEM shows a support-activator formed as described in Example 30-E2 by contacting tetrabutylammonium bromide with montmorillonite in the absence of a cationic polymetalate, and the isolated product was dried by rotary evaporation from an aqueous slurry in the absence of an azeotroping agent prior to calcination. Figure 31 to Figure 33 In the sample, the particles observed in these images exhibit low circularity and / or a large portion of the particles fall outside the 8 μm to 100 μm diameter range. Generally, such low circularity and extremely large or small particles are not desirable for catalytic processes.

[0407] on the contrary, Fig.34 , Fig.35 and Fig.36The SEM image of shows a support-activator formed by contacting tetrabutylammonium bromide with montmorillonite in the absence of a cationic polymetalate as described in Example 22-E2 and separated by filtration, and then spray drying the separated support-activator from an aqueous suspension and calcining. Figure 34 to Figure 36 The particles observed in these images exhibit a very high degree of circularity in the samples, and the majority of the particles fall within the desired 8 μm to 100 μm diameter range, making these support-activators very favorable for catalytic processes.

[0408] K. Metallocene compounds

[0409] The clay-surfactant heteroadducts (also referred to as clay heteroadducts) can be used as a matrix or catalyst support-activator for one or more suitable polymerization catalyst precursors (such as metallocenes), other organometallic compounds and / or organoaluminum compounds, etc., or other catalyst components to prepare olefin polymerization catalyst compositions. Thus, in one aspect, when the clay heteroadducts are prepared as disclosed herein and combined with an organic main group metal (such as an alkyl aluminum compound) and a Group 4 organic transition metal compound (such as a metallocene), an active olefin polymerization catalyst or catalyst system is provided.

[0410] The support-activators of the present disclosure can be used with metallocene compounds (also referred to herein as metallocene catalysts) and cocatalysts (such as organoaluminum compounds), and the resulting compositions exhibit catalytic polymerization activity in the absence or substantial absence of ion exchange, protonic acid treated or pillared clays, or aluminoxane or borate activators. Previously, it was believed that activators (such as aluminoxane or borate activators) were necessary to achieve polymerization catalytic activity with metallocenes or single-site or coordination catalyst systems. However, if it is desired to impart an activatable alkyl ligand to the metallocene, the combination of heteroadduct support-activators, metallocenes, and cocatalysts (such as alkyl aluminum compounds) creates a need for an active catalyst that requires other activators (such as aluminoxane or borate activators).

[0411] Metallocene compounds are well known in the art, and those skilled in the art will recognize that any metallocene can be used with the support-activators described in the present disclosure, including, for example, non-bridged (non-ansa) metallocene compounds or bridged (ansa) metallocene compounds, or combinations thereof. Thus, one, two, or more metallocene compounds can be used with the clay-surfactant support-activators of the present disclosure.

[0412] In one aspect, 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. For example, the metallocene can comprise a Group 4 transition metal (titanium, zirconium, or hafnium). In another aspect, the metallocene compound can comprise, consist of, consist essentially of, or be selected from a compound or a combination of compounds, each independently having the following formula:

[0413] (X 1 )(X 2 )(X 3 )(X 4 )M, where

[0414] a) M is selected from titanium, zirconium or hafnium;

[0415] b)X 1 is selected from substituted or unsubstituted cyclopentadienyl, indenyl, fluorenyl, pentadienyl, allyl, boron anion heterophenyl, 1,2-azaboryl or 1,2-diaza-3,5-diboryl, wherein any substituent is independently selected from halide, C 1 -C 20 Hydrocarbon, C 1 -C 20 Heteroalkyl, C 1 -C 20 Organic hetero groups, condensed C 4 -C 12 A carbocyclic moiety or a fused C having at least one heteroatom independently selected from nitrogen, oxygen, sulfur or phosphorus 4 -C 11 Heterocyclic moiety;

[0416] c)X 2 Selected from: [1] substituted or unsubstituted cyclopentadienyl, indenyl, fluorenyl, pentadienyl or allyl, wherein any substituent is independently selected from halide, C 1 -C 20 Hydrocarbon, C 1 -C 20 Heteroalkyl or C 1 -C 20 Organic heterogeneity;

[0417] or [2] halides, hydrides, C 1 -C 20 Hydrocarbon, C 1 -C 20 Heteroalkyl, C 1 -C 20 Organic hetero groups, condensed C 4 -C 12 A carbocyclic moiety or a fused C having at least one heteroatom independently selected from nitrogen, oxygen, sulfur or phosphorus 4 -C11 Heterocyclic moiety;

[0418] d) wherein at least one linker substituent having 2 to 4 bridging atoms independently selected from C, Si, N, P or B optionally bridges X 1 and X 2 , wherein each available non-bridging valence of each bridging atom is unsubstituted (bonded to H) or substituted, wherein any substituent is independently selected from halide, C 1 -C 20 Hydrocarbon, C 1 -C 20 Heteroalkyl or C 1 -C 20 An organic hetero group, wherein any hydrocarbon, heterohydrocarbon or organic hetero group substituent may form a bridging atom or X 1 or X 2 Saturated or unsaturated ring structure;

[0419] e)[1]X 3 and X 4 independently selected from halides, hydrides, C 1 -C 20 Hydrocarbon, C 1 -C 20 Heteroalkyl or C 1 -C 20 Organic heterocyclic group; [2] [GX A k X B 4-k ] - , wherein G is B or Al, k is a number from 1 to 4, and X A is independently selected at each occurrence from H or halide, and X B In each occurrence, independently selected from C 1 -C 12 Hydrocarbon, C 1 -C 12 Heteroalkyl, C 1 -C 12 Organic heterocyclic group; [3]X 3 and X 4 Together is C 4 -C 20 Polyene; or [4]X 3 and X 4 Together with M, it forms a substituted or unsubstituted, saturated or unsaturated C 3 -C 6 A metal ring moiety, wherein any substituent on the metal ring moiety is independently selected from halides, C 1 -C 20 Hydrocarbon, C 1 -C 20Heteroalkyl or C 1 -C 20 Organic heterogeneity.

[0420] According to another aspect, if necessary, X 1 and X 2 The bridge may be via a linker substituent selected from:

[0421] a)>EX 5 2 、-EX 5 2 EX 5 2 -、-EX 5 2 EX 5 EX 5 2 -or>C=CX 5 2 , wherein E at each occurrence is independently selected from C or Si;

[0422] b)-BX 5 -、-NX 5 -or-PX 5 -;or

[0423] c)[-SiX 5 2 (1,2-C 6 H 4 )SiX 5 2 -]、[-CX 5 2 (1,2-C 6 H 4 )CX 5 2 -]、[-SiX 5 2 (1,2-C 6 H 4 )CX 5 2 -],

[0424] [-SiX 5 2 (1,2-C 2 H 2 )SiX 5 2 -]、[-CX 5 2 (1,2-C 6 H 4 )CX 5 2 -] or [-SiX 52 (1,2-C 6 H 4 )CX 5 2 -];

[0425] Where X 5 is independently selected at each occurrence from H, halide, C 1 -C 20 Hydrocarbon, C 1 -C 20 Heteroalkyl or C 1 -C 20 Organic heterogeneity;

[0426] and wherein any X selected from a hydrocarbon, heterohydrocarbon or organic hetero substituent 5 Substituents can be attached to bridge atoms, another X 5 Substituent, X 1 or X 2 Forming saturated or unsaturated ring structures.

[0427] Can bridge X 1 and X 2 Examples of suitable linker substituents include C 1 -C 20 Hydrocarbylene group, C 1 -C 20 Hydrocarbyl group, C 1 -C 20 Heteroalkyl groups, C 1 -C 20 Heteroalkyl groups, C 1 -C 20 Heteroalkylene group or C 1 -C 20 For example, X 1 and X 2 It can be obtained by having the formula>EX 5 2 、-EX 5 2 EX 5 2 -or-BX 5 - is bridged by at least one substituent, wherein E is independently C or Si, X 5 is independently selected at each occurrence from halides, C 1 -C 20 Aliphatic group, C 6 -C 20 Aromatic groups, C 1 -C 20 Heteroaliphatic group, C 4 -C 20 Heteroaromatic groups or C1 -C 20 Organic heteroyl group.

[0428] The aspects of this disclosure list the following aspects: 1 With X 2 The connection between X 5 and with respect to specific linker substituents or X 5 Additional description and selection of substituents.

[0429] The aspects of this disclosure also list X 1 and X 2 (Including X 1 and X 2 Additional description and selection of specific substituents above.

[0430] The aspects of this disclosure also list X 3 and X 4 (Including X 3 and X 4 Additional description and selection of specific substituents above.

[0431] The aspects section of the present disclosure also provides some specific examples of metallocene compounds used in combination with the support-activators of the present disclosure.

[0432] Once the supported metallocene catalyst is prepared and dried according to the present disclosure, and before it is used in combination with a cocatalyst, the supported metallocene catalyst can have, for example, an average particle size of 1 μm (micrometer) to 250 μm, which is an average dry particle size. Unless otherwise specified, the particle size listed for the supported metallocene catalyst is for dry supported catalyst particles measured as described herein. On the one hand, the supported metallocene catalyst can have about 1 μm (micrometer), about 2 μm, about 3 μm, about 5 μm, about 7 μm, about 10 μm, about 12 μm, about 15 μm, about 18 μm, about 20 μm, about 25 μm, about 30 μm, about 35 μm, about 40 μm, about 45 μm, about 50 μm, about 55 μm, about 60 μm, about 65 μm, about 70 μm, about 75 μm, about 80μm, about 85μm, about 90μm, about 95μm, about 100μm, about 110μm, about 120μm, about 125μm, about 130μm, about 140μm, about 150μm, about 160μm, about 170μm, about 175μm, about 185μm, about 200μm, about 225μm or about 250μm or an average particle size range between these listed numbers. For example, the supported metallocene catalyst can have an average particle size of 1 μm (micrometer) to 250 μm, 2 μm to 125 μm, 3 μm to 100 μm, 5 μm to 150 μm, 5 μm to 80 μm, 7 μm to 70 μm, 10 μm to 100 μm, 10 μm to 60 μm, 15 μm to 80 μm, 15 μm to 50 μm, or 20 μm to 75 μm.

[0433] Those skilled in the art are familiar with metallocene compounds and will recognize and appreciate methods of preparing and using metallocenes in olefin polymerization catalyst systems. Many metallocenes and methods of preparing metallocenes and organotransition metal compounds are known in the art, such as disclosed in U.S. Pat. Nos. 4,939,217; 5,210,352; 5,436,305; 5,401,817; 5,631,335; 5,571,880; 5,191,132; 5,480,848; 5,399,636; 5,565,592; 5,347,026; 5,594,078; 5,498,581; 5 , 496,781; 5,563,284; 5,554,795; 5,420,320; 5,451,649; 5,541,272; 5,705,478; 5,631,203; 5,654,454; 5,705,579; 5,668,230; 9,045,504; and 9,163,100 and U.S. Patent Application Publication No. 2017 / 0342175, the entire disclosures of which are incorporated herein by reference.

[0434] L. Promoter

[0435] According to one aspect, the present disclosure provides a catalyst composition for olefin polymerization, the catalyst composition comprising: a) at least one metallocene compound;

[0436] b) optionally, at least one cocatalyst; and c) at least one support-activator as described herein. Cocatalysts include compounds such as trialkylaluminum, which are believed to give the metallocene a ligand that can then initiate polymerization when the metallocene is otherwise activated with a support-activator. Cocatalysts can be considered optional, for example, in cases where the metallocene may already include a polymerizable activating / initial ligand (such as a methyl or hydride). It should be understood that even when the metallocene compound includes, for example, a polymerizable activating / initial ligand, the cocatalyst can be used for other purposes, such as sweeping moisture from a polymerization reactor or process. Thus, the cocatalyst may include or be selected from, for example, an alkylating agent, a hydrogenating agent, or a silylating agent. The metallocene compound, the support-activator, and the cocatalyst may be contacted in any order.

[0437] The co-catalyst may include or may be selected from an organoaluminum compound, an organoboron compound, an organozinc compound, an organomagnesium compound, an organolithium compound, or any combination thereof.

[0438] Additional descriptions and selections for each of the organoaluminum compounds, organoboron compounds, organozinc compounds, organomagnesium compounds, and organolithium compounds are listed in the aspects section of the present disclosure.

[0439] In one aspect, for example, the cocatalyst can comprise, consist 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 a neutral molecular compound or ionic compound / salt of aluminum, wherein each of the variables in these formulas is defined in the aspects of the present disclosure. For example, the cocatalyst can include trimethylaluminum, triethylaluminum (TEA), tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, ethyl-(3-alkylcyclopentanediyl)aluminum, ethoxydiethylaluminum, diisobutylaluminum hydride, triisobutylaluminum (TIBAL), diethylaluminum chloride, ethyl-(3-alkylcyclopentanediyl)aluminum, etc., including any combination thereof, or consisting of, consisting essentially of, or selected from them.

[0440] In another aspect, for example, the cocatalyst can comprise, consist 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 a neutral molecular compound or ionic compound / salt of boron, wherein each variable in the variables of these formulas is defined in the aspects of the present disclosure. For example, the cocatalyst can include trimethylboron, triethylboron, tripropylboron, tributylboron, trihexylboron, trioctylboron, diethylethoxyboron, diisobutylboron hydride, triisobutylboron, diethylboron chloride, di-3-pinylborane, pinacolborane, catecholborane, lithium borohydride, lithium triethylborohydride, etc., including Lewis base adducts thereof, or any combination or mixture thereof, or consisting of, consisting essentially of, or selected from thereof. In another aspect, the cocatalyst may comprise or may be a halogenated organoboron compound, such as a fluorinated organoboron compound, examples of which include tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)phenyl]boron, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbonium tetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbonium tetrakis[3,5-bis(trifluoromethyl)-phenyl]borate, and any combination or mixture thereof.

[0441] In another aspect, for example, the cocatalyst can comprise, consist 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 in the formula is defined in the aspects section of the present disclosure. For example, the cocatalyst can comprise dimethyl zinc, diethyl zinc, diisopropyl zinc, dicyclohexyl zinc, diphenyl zinc, butylethyl magnesium, dibutyl magnesium, n-butyl-sec-butyl magnesium, dicyclopentadienyl magnesium, ethyl magnesium chloride, butyl magnesium chloride, and the like, including any combination thereof, or consisting of, consisting essentially of, or selected from.

[0442] In another aspect, for example, the co-catalyst can comprise, consist 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 in the formula is defined in the aspects section of the present disclosure. For example, the cocatalyst can comprise, consist of, consist essentially of, or be selected from methyllithium, ethyllithium, propyllithium, butyllithium (including n-butyllithium and tert-butyllithium), hexyllithium, isobutyllithium, or the like, or any combination thereof.

[0443] M. Optional co-activator

[0444] In one aspect, if desired, in addition to the calcined montmorillonite heteroadduct support-activator, other activators may also be used in the catalyst composition of the present disclosure. These are called co-activators, and optional co-activator examples include, but are not limited to, ion exchange clays, protic acid treated clays, pillared clays, aluminoxanes, borate activators, aluminate activators, ionizing ionic compounds, solid oxides treated with electron-withdrawing anions, or any combination thereof. In one aspect, the catalyst system and polymerization method may be free of any co-activator, including one of the plurality of co-activators described herein.

[0445] Additional descriptions and selections for each of these optional co-activators are listed in the Aspects section of the present disclosure.

[0446] Aluminoxane. Aluminoxanes (also known as poly(hydrocarbyl aluminum oxides) or organoaluminoxanes) can be used to contact the other catalyst components, for example, in any solvent that 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 can be isolated if desired, or the catalyst composition can be introduced into the polymerization reactor without isolation.

[0447] As will be appreciated by those skilled in the art, aluminoxanes are oligomers, wherein the aluminoxane compound may contain a linear structure, a cyclic or cage structure, or a mixture thereof. For example, a cyclic aluminoxane compound has the formula (R-Al-O) n , wherein R may be a straight or branched chain alkyl group having 1 to about 12 carbon atoms, and n may be an integer from 3 to about 12. (AlRO) n The moiety also constitutes a repeating unit in a linear aluminoxane, for example, having the formula: R(R-Al-O) n AHr 2 , wherein R can be a straight or branched alkyl group having 1 to about 12 carbon atoms, and n can be an integer from 1 to about 75. For example, the R group can be a straight or branched C 1 -C 8 An alkyl group may be selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl, and wherein n may represent an integer from 1 to about 50. Depending on how the organoaluminoxane is prepared, stored, and used, the value of n may vary in a single sample of aluminoxane, and combinations or populations of such organoaluminoxane species are typically present in any sample.

[0448] Organoaluminoxanes can be prepared by various procedures known in the art, for example, those disclosed in U.S. Pat. Nos. 3,242,099 and 4,808,561, each of which is incorporated herein by reference in its entirety. In one aspect, aluminoxanes can be prepared by reacting water in an inert organic solvent with an alkyl aluminum compound such as AlR 3 Alternatively, the organoaluminoxane may be prepared by reacting an alkylaluminum compound such as AlR 3 It is prepared by reaction with a hydrated salt such as hydrated copper sulfate in an inert organic solvent.

[0449] In one embodiment, the aluminoxane compound can be methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, n-butylaluminoxane, tert-butylaluminoxane, sec-butylaluminoxane, isobutylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane, neopentylaluminoxane or a combination thereof. In one aspect, methylaluminoxane (MAO), ethylaluminoxane (EAO) or isobutylaluminoxane (IBAO) can be used as an optional cocatalyst, and these aluminoxanes can be prepared from trimethylaluminum, triethylaluminum or triisobutylaluminum, respectively. These compounds can be complex compositions and are sometimes referred to as poly(methylaluminum oxide), poly(ethylaluminum oxide) and poly(isobutylaluminum oxide), respectively. On the other hand, aluminoxanes can be used in combination with trialkylaluminum, as disclosed in U.S. Pat. No. 4,794,096, which is incorporated herein by reference in its entirety.

[0450] When preparing a catalyst composition comprising an optional aluminoxane, the molar ratio of aluminum present in the aluminoxane to the metallocene compound in the composition can be lower than the typical molar ratio used in the absence of the support-activator of the present disclosure. In the absence of the support-activator of the present disclosure, the amount of aluminoxane can be, for example, from about 1:10 moles of Al / mole of metallocene (molAl / mol metallocene) to about 100,000:1mol Al / mol metallocene or from about 5:1mol Al / mol metallocene to about 15,000:1mol Al / mol metallocene. When used in combination with the disclosed support-activator, the relative amount of aluminoxane can be reduced. For example, the amount of the optional aluminoxane added to the polymerization zone can be less than the previous typical amount in the range of about 0.01 mg / L to about 1000 mg / L, about 0.1 mg / L to about 100 mg / L, or about 1 mg / L to about 50 mg / L. Alternatively, the aluminoxane can be used in the amount commonly used in the prior art, but the support-activator of the present disclosure is used in addition to obtain other advantages of this combination.

[0451] Organoboron compounds include organic borates. In addition to the components (support-activator, metallocene and optional co-catalyst) described in detail, the catalyst composition of the present disclosure may also include an optional organoboron co-activator if desired. In one aspect, the organoboron compound may include or be selected from a neutral boron compound, a borate or a combination thereof. For example, the organoboron compound may include or be selected from a fluorine organoboron compound, a fluorine organoborate compound or a combination thereof, and any such fluorine compound known in the art may be used.

[0452] Therefore, the term fluoroorgano boron compound is used herein to refer to BY 3 The term fluoroorgano borate compound is used herein to refer to a neutral compound of the form + [BY 4 ] - The monoanionic salts of fluoroorgano boron compounds of the form of wherein Y represents a fluorinated organic group. For convenience, fluoroorgano boron and fluoroorgano borate compounds are often collectively referred to as organoboron compounds, or either name is used as the context requires.

[0453] In one aspect, examples of fluoroorganic 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. Examples of fluoroorganic borate compounds that can be used as optional co-activators include, but are not limited to, fluorinated aryl borates, such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbonium tetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbonium tetrakis[3,5-bis(trifluoromethyl)-phenyl]borate, and the like, including mixtures thereof.

[0454] Additional description and selection of optional fluoroorgano boron and fluoroorgano borate compound co-activators are listed in the Aspects section of the present disclosure.

[0455] While not intending to be bound by theory, it is believed that these fluoroorgano borates and fluoroorgano boron compounds form weakly coordinating anions when combined with metallocene compounds, such as disclosed in US Pat. No. 5,919,983, which is incorporated herein by reference in its entirety.

[0456] Typically, any amount of organoboron compound can be used as an optional co-activator. For example, in one aspect, the molar ratio of the organoboron compound to the metallocene compound in the composition can be from about 0.1:1 mole of organoboron or organoborate compound (mol / mol) per mole of metallocene to about 10:1 mol / mol, or from about 0.5 mol / mol to about 10 mol / mol (moles of organoboron or organoborate compound per mole of metallocene), or alternatively from about 0.8 mol / mol to about 5 mol / mol (moles of organoboron or organoborate compound per mole of metallocene). However, it should be understood that if a clay heteroadduct support-activator is present, the amount can be reduced or adjusted downward.

[0457] Ionizing compounds. In another aspect, in addition to the listed components of the catalyst composition of the present disclosure, the optional co-activator that may be used may include or may be selected from an ionizing compound. Examples of ionizing compounds are disclosed in U.S. Pat. Nos. 5,576,259 and 5,807,938, each of which is incorporated herein by reference in its entirety.

[0458] Additional description and selection of optional ionizing compound co-activators are listed in the Aspects section of the present disclosure.

[0459] The term ionizing compound is a term of art and refers to a compound, particularly an ionizing compound, which can act to enhance the activity of the catalyst composition. In one aspect, the fluoroorgano borate compounds described herein as optional organoboron co-activators can also be considered and used as ionizing compound co-activators. However, the scope of ionizing compounds is broader than that of fluoroorgano borate compounds, such as compounds encompassed by ionizing compounds, such as fluoroorganoaluminates.

[0460] While not intending to be bound by theory, it is believed that the ionizing compound may be able to interact or react with the metallocene compound and convert the metallocene into a cationic or initial cationic metallocene compound, which activates the polymerization activity of the metallocene. Likewise, while not intending to be bound by theory, it is believed that the ionizing compound may function by completely or partially extracting anionic ligands from the metallocene, particularly non-cycloalkadienyl ligands or non-alkadienyl ligands, such as the metallocenes of formula (X) disclosed herein. 1 )(X 2 )(X 3 )(X 4 )M's(X 3 ) or (X 4 ) to form a cation or initial cation metallocene. However, an ionizing compound can act as an activator (co-activator) regardless of the mechanism by which it acts. For example, an ionizing compound can ionize a metallocene to capture X in the form of an ion pair.3 or X 4 Ligand, weakening metal-X 3 or Metal-X 4 key, or simply with X 3 or X 4 ligand coordination, or any other mechanism by which activation may occur. Furthermore, the ionizing compound need not solely activate (co-activate) the metallocene, as the activating function of the ionizing compound is significant in the enhanced activity of the catalyst composition as a whole compared to a catalyst composition containing a catalyst composition that does not contain any ionizing compound.

[0461] Examples of ionizing compounds include, but are not limited to, the list of compounds presented in the Aspects section of the present disclosure.

[0462] Optional Support-Activators. In another aspect, in addition to the listed components of the catalyst compositions of the present disclosure, optional co-activators that may be used may include or may be selected from other support-activators, sometimes referred to as activator-supports, when used in the catalyst compositions described herein, referred to as co-activator-supports. Examples of optional co-activator-supports are disclosed in U.S. Pat. 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.

[0463] For example, the optional co-activator-support can include or be selected from silica, alumina, silica-alumina, or silica-coated alumina treated with at least one electron-withdrawing anion. For example, in this aspect, the silica-coated alumina can have an alumina to silica weight ratio ranging from about 1:1 to about 100:1, or from about 2:1 to about 20:1. The at least one electron-withdrawing anion can include or be selected from fluoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate, etc., or a combination thereof.

[0464] In one aspect, the optional co-activator-support can be selected from, for example, fluorinated alumina, chlorided alumina, brominated alumina, sulfated alumina, fluorinated silica-alumina, chlorided silica-alumina, brominated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, chlorided silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, and the like, any one of which or any combination thereof can be used in the catalyst compositions disclosed herein. Alternatively or additionally, the co-activator-support can comprise or be selected from a solid oxide treated with an electron-withdrawing anion such as fluorinated silica-alumina or sulfated alumina, and the like.

[0465] Examples of co-activator-supports can include, but are not limited to, those listed in the Aspects section of the present disclosure.

[0466] N. Catalyst system and its preparation

[0467] One aspect provided by the present disclosure is the preparation of a catalyst system comprising a montmorillonite heteroadduct and a transition metal precatalyst (particularly a metallocene). In one aspect, the catalyst system for olefin polymerization may comprise:

[0468] (a) at least one metallocene compound;

[0469] (b) at least one support-activator according to any aspect of the present disclosure.

[0470] The use of the term "catalyst system" encompasses a catalyst system comprising these components, and the "catalyst system" may further comprise at least one co-catalyst (such as an alkyl aluminum compound) and / or at least one co-activator (such as methylaluminoxane (MAO) in combination with these components). The present disclosure also provides a method of preparing a catalyst system, wherein the method comprises contacting in a second liquid carrier: (a) at least one metallocene compound; and (b) at least one support-activator comprising a montmorillonite heteroadduct according to the present disclosure. The method of preparing the catalyst system may further comprise contacting in a second liquid carrier at least one co-catalyst (such as an alkyl aluminum compound) and / or at least one co-activator (such as methylaluminoxane (MAO)), wherein the contacting may occur in any order.

[0471] In the catalyst system, a metallocene such as (X 1 )(X 2 )(X 3 )(X 4The relative concentration or ratio of the Group 4 metallocene (or metal) of calcined clay-surfactant heteroadduct (or metal) to the calcined clay-surfactant heteroadduct can be expressed as moles of M (metal) per gram of calcined clay heteroadduct (mol M / g heteroadduct). In one aspect, it has been found that the molar ratio of M per gram of calcined clay heteroadduct can be in the range of about 0.025 mol M / g heteroadduct to about 0.000000005 mol M / g heteroadduct. In another aspect, the moles of M per gram of calcined clay heteroadduct can be used in the range of about 0.0005 mol M / g heteroadduct to about 0.00000005 mol M / g heteroadduct, or alternatively, in the range of about 0.0001 mol M / g heteroadduct to 0.000001 mol M / g heteroadduct. As in all ranges disclosed herein, the recited range includes the endpoints as well as the intermediate values ​​and subranges within the recited range. These ratios reflect the catalyst formulation, that is, the ratios are based on the amounts of the components combined to produce the catalyst composition, regardless of the ratios found in the final catalyst.

[0472] The relative concentration or ratio of the cocatalyst to the calcined clay heteroadduct in the catalyst system can be expressed as the number of moles of cocatalyst (e.g., organoaluminum compound) per gram of calcined clay heteroadduct (mol cocatalyst / g heteroadduct). In one aspect, it has been found that the molar ratio of the cocatalyst, such as the organoaluminum compound, per gram of calcined clay heteroadduct can be in the range of about 0.5 mol cocatalyst / g heteroadduct to about 0.000005 mol cocatalyst / g heteroadduct. In another aspect, the molar ratio of the cocatalyst per gram of calcined clay heteroadduct can be used in the range of about 0.1 mol cocatalyst / g heteroadduct to about 0.00001 mol cocatalyst / g heteroadduct, or alternatively, in the range of about 0.01 mol cocatalyst / g heteroadduct to about 0.0001 mol cocatalyst / g heteroadduct.

[0473] The catalyst composition can be produced by contacting a transition metal compound (such as a metallocene, a calcined clay heteroadduct) and a cocatalyst (such as an organoaluminum compound) under suitable conditions. The contact can be carried out in a variety of ways, such as by blending, by contacting in a carrier liquid, by adding each component to a reactor alone or in any order or combination. For example, various combinations of components or compounds can be contacted with each other before further contact with the remaining compounds or components in the reactor. Alternatively, all three components or compounds can be contacted together before being introduced into the reactor. With regard to additional optional components that can be used in the catalyst system disclosed herein, such as co-activators, ionizing ionic compounds, etc., the step of contacting using these optional components can be carried out in any manner and in any order.

[0474] In one aspect, the method for preparing the catalyst composition can first contact a transition metal compound (such as a metallocene) with a cocatalyst (such as an organoaluminum compound) for about 1 minute to about 24 hours, or alternatively about 1 minute to about 1 hour, and the contact temperature can range from about 10°C to about 200°C, alternatively about 12°C to about 100°C, alternatively about 15°C to about 80°C, or alternatively about 20°C to about 80°C to form a first mixture, and then the mixture can be contacted with a calcined clay heteroadduct to form a catalyst composition.

[0475] In another aspect, the metallocene, the cocatalyst (such as an organoaluminum compound), and the calcined clay heteroadduct can be precontacted prior to introduction into the reactor. For example, the precontacting step can be carried out for a period of about 1 minute to about 6 months. In one aspect, for example, the precontacting step can be carried out at a temperature of about 10° C. to about 200° C. or about 20° C. to about 80° C. for a period of about 1 minute to about 1 week to provide an active catalyst composition. In addition, any subset of the final catalyst components can also be precontacted in one or more precontacting steps, each step having its own precontacting time.

[0476] After any or all of the catalyst system components are pre-contacted, it can be said that the catalyst composition comprises the contacted components. For example, the catalyst composition can comprise the contacted metallocene, the contacted co-catalyst (such as an organoaluminum compound) and the contacted calcined clay heteroadduct component. In the field of catalyst technology, it is not uncommon that the specific and detailed properties of active catalytic sites and the specific properties and results of each component used to prepare the active catalyst are not accurately known. Although it is not intended to be bound by theory, based on the relative weights of the various components, the majority of the weight of the catalyst composition can be considered to comprise the contacted calcined clay heteroadduct. Because the properties of the active sites and the contacted components are not accurately known, the catalyst composition can be simply described according to its components, or referred to as comprising the contacted compounds or components.

[0477] As used herein, the first liquid carrier is the liquid carrier in which the montmorillonite heteroadduct is prepared, and the second liquid carrier is the liquid in which the catalyst system is prepared. The second liquid carrier can be any liquid carrier in which a metallocene can be contacted with a montmorillonite heteroadduct to prepare a supported precatalyst or catalyst without degrading the metallocene or the montmorillonite heteroadduct. In an embodiment, the second liquid carrier can include, consist essentially of, or be selected from the following: cyclohexane, isobutane, n-butane, propane, n-pentane, isopentane, neopentane, n-hexane, naphtha, hydrotreated naphtha, Isopar TM , at least one olefin, or any combination thereof. The second liquid carrier may further comprise at least one olefin.

[0478] As disclosed, the catalyst system for olefin polymerization may include or consist essentially of the following: (a) at least one metallocene compound; (b) at least one support-activator according to the present disclosure. The catalyst system may also further include: c) at least one co-catalyst; (d) at least one co-activator; or a combination thereof. The catalyst system may also further include a fluid carrier. In the present disclosure, "fluid carrier" is used to describe a carrier in which the catalyst system is contacted with at least one olefin to form a polyolefin. Thus, the fluid carrier may be a liquid or a gas, since the polymerization performed using the disclosed catalyst system can be carried out under conditions such as slurry or fixed bed polymerization conditions or under gas phase polymerization conditions.

[0479] In one aspect, the fluid carrier may comprise, consist essentially of, or be selected from the group consisting of nitrogen; hydrocarbons such as cyclohexane, isobutane, n-butane, propane, n-pentane, isopentane, neopentane, n-hexane, naphtha, hydrotreated naphtha, or Isopar; TM ; at least one olefin; or any combination thereof. However, any fluid carrier that can be used with a supported catalyst can be used for polymerization using the present catalyst system. In another aspect, the fluid carrier can include or can consist essentially of a liquid or gaseous hydrocarbon, an ether, or a combination thereof, each of which independently has 2 to 20 carbon atoms.

[0480] O. Polymerization Activity of Isolated Clay-Heteroaggregates

[0481] The data in Tables 1, 2 and 3 disclose the composition, surface area / pore volume characteristics and polymerization activity of montmorillonite clay support-activators produced by contacting the clay with an exemplary cationic polymetallate (aluminum chlorohydrate), a surfactant, or a combination of a cationic polymetallate and a surfactant.

[0482] The heteroadducts in Tables 1 and 2 were isolated by rotary evaporation drying under the indicated conditions, while the heteroadducts in Table 3 were isolated by spray drying from an aqueous slurry.

[0483] The polymerization activity of a catalyst composition comprising a clay heteroadduct support-activator can be expressed as the weight of polymer polymerized per weight of support-activator comprising a calcined montmorillonite heteroadduct per unit time, e.g., grams of polymer per gram of (calcined) support-activator per hour (g / g / hr). That is, the activity can be calculated based solely on the support-activator, without the presence of any metallocene or cocatalyst components. This measurement allows comparison of various support-activators, including comparison with other activators, where the metallocene, cocatalyst, and other conditions are the same or substantially the same.

[0484] Unless otherwise stated, the activities disclosed in the examples are measured under slurry polymerization conditions, using isobutane as the diluent, and the polymerization temperature is from about 50°C to about 150°C (e.g., at a temperature of 90°C), and the combined ethylene and isobutane pressure used is in the range of about 300 psi to about 800 psi, for example, the total combined ethylene and isobutane pressure is 450 psi. The activity data is reported as the weight of polymer produced per hour divided by the weight of the calcined clay-surfactant heteroadduct.

[0485] The catalyst activity can be a function of the metallocene and calcined clay heteroadduct as well as other components and conditions. Under the above conditions, the activity based on the weight of the calcined clay-surfactant heteroadduct and the calcined clay-cationic polymetallate-surfactant heteroadduct 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). In another aspect, 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. In some aspects, an upper limit for the activity can be about 100,000 g / g / hr, such that the activity can range from greater than these disclosed values ​​to less than 100,000 g / g / hr.

[0486] For example, in one aspect and using the conditions described herein, the support-activator can have a flow rate 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 g / g / hr, about 12,500 g / g / hr, about 15,000 g / g / hr, about 17,500 g / g / hr, about 20,000 g / g / hr, about 25,000 g / g / hr, about 30,000 g / g / hr, about 40,000 g / g / hr, about 50,000 g / g / hr, about 60,000 g / g / hr, about 70,000 g / g / hr, about 80,000 g / g / hr, about 90,000 g / g / hr, or about 100,000 g / g / hr, including any ranges between these values. Higher polymerization activity values ​​may be associated with clay supports having very high site density, and these activity values ​​may also be metallocene dependent. Thus, by applying the teachings herein, activity levels within a range between the two values ​​recited can be obtained, for example, activity levels within a range of 250 g / g / hr to 35,000 g / g / hr can be obtained, as well as intermediate values ​​and ranges such as 300 g / g / hr to 30,000 g / g / hr, 400 g / g / hr to 25,000 g / g / hr, or 500 g / g / hr to 20,000 g / g / hr. In one aspect, heteroagglomeration of clay with a surfactant agent provides a carrier-activator having significantly increased polymerization activity relative to a similarly prepared material not contacted with a surfactant.

[0487] In one aspect, no aluminoxane (such as methylaluminoxane) is required to activate the metallocene and form the catalyst composition. Methylaluminoxane (MAO) is an expensive activator compound that greatly increases the production cost of the polymer. In addition, on the other hand, no organic boron compound or ionizing compound (such as borate compound) is required to activate the metallocene and form the catalyst composition. In addition, no ion exchange, protonic acid treatment or pillared clay similar to multi-step preparation that requires increased cost is required to activate the metallocene and form the catalyst composition. Therefore, in the absence of any aluminoxane compound, boron compound or borate compound, ion exchange, protonic acid treatment or pillared clay, active heterogeneous catalyst compositions can also be easily and cheaply produced and used for polymerizing olefin monomers, and comonomers can also be included if necessary. Although MAO or other aluminoxanes, boron or borate compounds, ion exchange clays, protonic acid treated clays or pillared clays are not necessary in the disclosed catalyst system, according to other aspects of the present disclosure, these compounds can be used to reduce the number or typical number of uses.

[0488] Unless otherwise stated, the catalyst activities in the Examples and Tables 1 to 3 were measured for homopolymerization of ethylene under slurry polymerization conditions using isobutane as the diluent and wherein the polymerization temperature was 80°C and the combined ethylene and isobutane pressure was 350 psi total and (η 5 -1-n-butyl-3-methyl-cyclopentadienyl) 2 ZrCl 2 and triethylaluminum (AlEt 3 ) as metallocene and co-catalyst.

[0489] Throughout this disclosure, the drying process of the support-activator can be described as azeotropic (e.g., rotary evaporation from 1-butanol and water) and non-azeotropic (rotary evaporation from water alone) or spray drying (from an aqueous suspension or a specified suspension). In addition, the surface of the support-activator can be made more hydrophobic by adding a surfactant in any of these drying processes. If desired, these methods can be combined, such as drying by azeotropic or non-azeotropic processes, followed by resuspending the heteroadduct and spray drying from an aqueous slurry in the presence of a surfactant. The tightly bound water can then be removed from the dried heteroadduct (support-activator) before it is used as a catalyst support-activator, for example by calcining, heating in a fluidized bed, etc.

[0490] Table 1 reports the properties and polymerization data of azeotropic (1-butanol and water) and non-azeotropic (water only), calcined clay-aluminum chlorohydrate (ACH) support-activators. These support-activators were prepared in the absence of surfactants and were not spray dried, but dried by (rotary) evaporation from a slurry. While batches 1 to 4 of Table 1 show that clay-ACH adducts that have been subjected to azeotropic drying exhibit very good catalytic activity upon calcination (2000-4000 g PE / g support-activator / hr), batch 5 of Table 1 shows that drying these adducts from a water-only slurry in the absence of an entrainer produced supports that were almost inactive (<200 g PE / g support-activator / hr). Thus, attempts to dry clay-ACH support-activators from aqueous slurries without organic entrainers in this manner have resulted in a loss of activity and porosity from aqueous drying alone.

[0491] In contrast, batches 7 to 32 of Table 2, respectively, combined clay with the surfactants tetraoctylammonium bromide, tetrabutylammonium bromide, and tetramethylammonium bromide, and subsequently dried by (rotary) evaporation from a water-only slurry in the absence of an azeotroping agent to produce catalytically active materials for ethylene polymerization. Batches 7 to 32 of Table 2 demonstrated activities in the range of 1000 to 3000 g PE / g support-activator / hr. Batch 2 of Table 2 compares the activity of clay-ACH-surfactant heteroadducts using clay in combination with a surfactant (tetraoctylammonium bromide) and aluminum chlorohydrate, which was dried to a water-only slurry. This sample also exhibited enhanced polymerization activity (>2000 g PE / g support-activator / hr) relative to batch 1 of Table 2 (<200 g PE / g support-activator / hr), which is a material containing only clay and aluminum chlorohydrate without surfactant.

[0492] Batch 6 (Example 8-B3) of Table 2 provides an example of using the nonionic surfactant dextrose to form a clay-aluminum chlorohydrate-surfactant heteroadduct as a support-activator in ethylene homopolymerization. Although the activity of the sample was modest (75 g PE / g support-activator / hr), its activity was more than twice that provided by the clay-aluminum chlorohydrate heteroadduct support-activator of Batch 1 (Example 5-A4) of Table 2 (which did not have any type of surfactant present).

[0493] Batch 5 (Example 7-B2) of Table 2 illustrates the use of a phosphonium salt cationic surfactant, trihexyltetradecylphosphonium bromide, to form a clay-surfactant heteroadduct. The activity of this support-activator in ethylene homopolymerization was found to be 184 gPE / g support-activator / hr, slightly lower than the activity of most ammonium salt cationic surfactant heteroadducts.

[0494] Finally, batches 3 and 4 of Table 2 (Examples 28-C1 and 29-C2) were prepared using ammonium bromide [NH 4 ]Br rather than any hydrocarbyl ammonium surfactant was combined with montmorillonite clay. When the clay was combined with ammonium cations without the hydrocarbyl moiety bound to the ammonium nitrogen, no significant condensation products of the clay and ammonium bromide were observed. Although not intending to be bound by theory, it is believed that the same type of heterocondensates formed with the hydrocarbyl ammonium moiety are not formed in this reaction. This ammonium bromide treated clay support-activator was found to be active in ethylene homopolymerizations of about 300 to 400 g PE / g support-activator / hr.

[0495] Therefore, on the one hand, the clay-surfactant carrier-activator prepared in the absence of cationic polymetallate according to the present disclosure can be combined with a metallocene primary catalyst to produce an olefin polymerization catalyst, which exhibits a surprising polymerization activity of about 300 g PE / g carrier-activator / hr to about 2,500 g PE / g carrier-activator / hr. Optionally, other hetero-coagulants (such as aluminum polyoxometalates) can be combined with clay and surfactant mixtures. Therefore, when prepared in the presence of a surfactant to form a clay-cationic polymetallate-cationic surfactant carrier-activator, even the clay-cationic polymetallate carrier-activator can also show a huge enhancement of activity (Compare Table 2 Batch 1 and Batch 2). It is observed that with the increase of activity, the BJH pore volume increases significantly. The activity enhancement using a surfactant is not limited to a cationic surfactant, because a nonionic surfactant also improves the activity of a clay-cationic polymetallate carrier-activator (Compare Table 2 Batch 6).

[0496] While not intending to be bound by theory, it is believed that the increased porosity of the clay heteroadduct materials reported in this disclosure facilitates diffusion of metallocene compounds and access to ionized sites on the clay heteroadduct surface, thereby enabling increased polymerization activity of these clay-surfactant materials.

[0497] With respect to the activity of the isolated spray dried heteroagglomerates, it has been found that the clay heteroadducts spray dried from aqueous slurries exhibit surprisingly high degrees of sphericity, roundness and circularity, while maintaining excellent polymerization activity. This combination of properties imparts processing advantages when used as polymerization support-activators, such as providing excellent flow and packing characteristics for catalyst particles for use in catalyst bed systems.

[0498] The data in Table 3 show the properties and polymerization data of spray dried, calcined, hetero-agglomerated [1] clay-aluminum chlorohydrate (ACH) support-activator, [2] clay-ACH-surfactant support-activator, and [3] clay-surfactant support-activator. Polymerizations were conducted at 350 psi reactor pressure and 80°C using (η 5 -1-n-butyl-3-methyl-cyclopentadienyl) 2 ZrCl 2 As metallocene, triethylaluminum (AlEt 3 ) as a co-catalyst; and the percentages in Table 3 are weight percentages relative to clay. The ACH component is present at a concentration of 1.54 mmol Al / g clay.

[0499] The results in Table 3 demonstrate the surprising discovery that, even in the absence of cationic polymetallates, excellent polymerization activity can be achieved using montmorillonite clay-surfactant heteroadducts that have been spray dried from an aqueous slurry in the absence of an organic liquid and calcined, such as batches 3 to 6. These clay-surfactant heteroadduct data (batches 3 to 6) are comparable to the clay-ACH-surfactant heteroadducts that have been spray dried from an aqueous slurry in batches 7 to 10.

[0500] These clay-surfactant heteroadduct data (batches 3 to 6) show significantly better activity than the relatively lower activity observed for the clay-cationic polymetallate (ACH) heteroadducts prepared in the absence of surfactant from batches 1 to 2, which were spray dried from aqueous slurries. Notably, when these clay-cationic polymetallate (ACH) heteroadducts were azeotroped without spray drying, such as batches 3 and 4 of Table 1, their polymerization activities exceeded 2500 g / g / hr. This observation is consistent with the significantly reduced polymerization activity obtained when the clay-ACH heteroadduct was non-azeotropically dried from a slurry of only water, such as batch 5 of Table 1.

[0501] Thus, the clay-surfactant heteroadducts and clay-cationic polymetalate-surfactant heteroadducts can be spray dried and subsequently calcined to produce catalysts with high catalytic activity (1400 to 3000 g PE / g support-activator / hr) for olefin polymerization when combined with a metallocene precatalyst, as shown in Table 3, entries 3 to 10. In embodiments, the spray drying process can be performed on the clay-surfactant heteroadducts and clay-cationic polymetalate-surfactant heteroadducts slurried in an alcohol / water mixture. In other embodiments, the spray drying process can be performed on these heteroadducts slurried in water in the absence of an organic liquid.

[0502] In one aspect, once the clay-surfactant heteroadduct is separated from the clay-cationic polymetallate-surfactant heteroadduct, for example, by filtering the slurry in which the heteroadduct is prepared, the separated heteroadduct can be resuspended in the slurry and subsequently spray dried. For example, in an embodiment, the slurry obtained from resuspending the "filter cake" of the clay-surfactant adduct in a liquid carrier is spray dried for spray drying and stirring or agitation, for example, using high shear conditions for a period of time. In an embodiment, the slurry obtained from resuspending the filter cake of the clay-surfactant adduct in a liquid carrier can be spray dried for spray drying for a period of 15 minutes to 24 hours. In other embodiments, the slurry obtained from resuspending the filter cake of the clay-surfactant adduct in a liquid carrier can be spray dried for spray drying and stirring or agitating the mixture for a period of 24 hours to 72 hours.

[0503] In one aspect, when introducing surfactants at different times before the spray-dried obtained heteroagglomerates, the advantages of using surfactants can be realized. For example, batches 3 to 6 of Table 3 show that surfactants are contacted with clay before the preparation of spray-dried feed, that is, clay-surfactant formation and separation, and then resuspended to prepare the spray-dried feed. Alternatively, batches 7 to 10 of Table 3 show embodiments in which surfactant reagents can be directly introduced into the spray-dried feed of separated and resuspended clay-cationic polymetallate heteroadducts. In these batches (Examples 23-E3 and 24-E4), clay-ACH heteroadducts are prepared and filtered, and the resulting wet cake is resuspended in water together with surfactant to form spray-dried feed. These samples were calcined after spray drying and exhibited good porosity, with the tetrabutylammonium bromide samples (batches 7 to 8, Example 23-E3) having a total BJH porosity of 0.273 cc / g and the tetraoctylammonium bromide samples (batches 9 to 10, Example 24-E4) having a total BJH porosity of 0.123 cc / g. While not intending to be bound by theory, these latter batches 7 to 10 of Table 3 are also referred to herein as forming clay-cationic polymetalate-surfactant heteroadducts, although the method of making these differs from other heteroadducts in which the clay, ACH and surfactant are contacted in an initial slurry of the clay.

[0504] Thus, in one aspect, once the spray-dried clay-surfactant heteroadducts are calcined and the resulting support-activator is combined with a metallocene and a cocatalyst to produce a polymerization catalyst, polymerization activities ranging from about 500 g PE / g support-activator / hr to 2000 g PE / g support-activator / hr are demonstrated. When the polymers produced by these catalysts are compared to polymer particles produced by non-spray-dried support-activators, lower particle size and higher particle uniformity of the polymer particles are observed in the spray-dried heteroadduct polymers, which provides desirable operability advantages when introducing these catalysts into fluidized reactor bed systems. For example, the data in Table 4 show the particle size distribution characteristics of polyethylene homopolymers produced using [1] an azeotropic clay-aluminum chlorohydrate (ACH) support-activator produced in the absence of surfactant (see Comparative Example 2-A1 and Batch 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 Batch 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 Batch 10 of Table 3), thereby demonstrating the higher uniformity coefficient of the inventive heteroadducts spray dried in the presence of surfactant.

[0505] Thus, the present disclosure demonstrates the practical use of a process that minimizes the porosity loss typically associated with spray drying clay slurries, which process is capable of producing a catalyst that is both active and exhibits the desired morphology for use in a catalyst bed.

[0506] Thus, at least the following unexpected results are provided and demonstrated throughout this disclosure.

[0507] 1. Montmorillonite clay-surfactant heteroadducts prepared in the absence of cationic polymetallates and in the absence of any other additives can provide support-activators that can achieve excellent polymerization activities.

[0508] 2. When a surfactant is used in combination with montmorillonite clay and a cationic polymetalate, the resulting montmorillonite clay-cation heteroadduct-surfactant heteroadduct can achieve significantly higher polymerization activity than similar clay-polymetalate heteroadducts prepared in the absence of a surfactant.

[0509] 3. The surfactant can be combined with the montmorillonite clay in the absence of other additives, or the surfactant can be combined with the montmorillonite clay and the cationic polymetalate in any order or in any manner to form a separate heteroadduct. For example, the surfactant can be combined with the montmorillonite clay with or without the cationic polymetalate to form the heteroadduct, or the surfactant can be used to contact the montmorillonite clay-cationic polymetalate heteroadduct during or after the heteroadduct is formed, for example, when preparing a spray drying feed for the clay-polymetalate heteroadduct.

[0510] 4. The use of surfactants to prepare montmorillonite clay-surfactant heteroadducts and montmorillonite clay-cationic polymetallate-surfactant heteroadducts allows spray drying of the heteroadducts from a slurry in water alone without the need to use an organic liquid with the water, such as in an azeotropic drying process, while still providing high polymerization activity.

[0511] 5. The heteroadducts spray dried from aqueous slurries exhibit surprisingly high degrees of sphericity, roundness and circularity, which impart processing advantages in their use as polymerization support-activators, such as providing excellent flow and packing characteristics for catalyst particles for use in catalyst bed systems.

[0512] 6. The polymer particles produced using the spray dried heteroadduct support-activators of the present invention are characterized by lower particle size and higher particle uniformity than their non-surfactant analogs, and these characteristics provide desirable operability advantages when these catalysts are introduced into fluidized reactor bed systems.

[0513] P. Polyolefins and Polymerization Processes

[0514] On the one hand, the present disclosure describes a process for contacting at least one olefin monomer with a disclosed catalyst composition to produce at least one polymer (polyolefin). The term "polymer" as used herein includes homopolymers, copolymers of two olefin monomers, and polymers of more than two olefin monomers, such as terpolymers. For convenience, polymers of two or more olefin monomers are referred to as copolymers. Therefore, the catalyst composition can be used for polymerizing at least one monomer to produce a homopolymer or a copolymer.

[0515] On the one hand, homopolymer comprises each molecule has 2 to about 20 carbon atoms, preferably each molecule has 2 to about 10 carbon atoms monomer residues.Olefin monomer can comprise or be selected from ethene, propylene, 1-butylene, 3-methyl-1-butylene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 3-ethyl-1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and mixtures thereof.On the one hand, homopolymer of ethene, homopolymer of propylene and homopolymer of other olefins are all contained in the present disclosure.On the other hand, the multipolymer of ethene and at least one comonomer, and the multipolymer of two kinds of uncommon non-ethylene copolymers, are also all contained in the present disclosure.

[0516] When copolymers are desired, each monomer may have from about 2 to about 20 carbon atoms per molecule. Comonomers of ethylene may 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, vinyl cyclohexane and other olefins; and conjugated or non-conjugated dienes, such as 1,3-butadiene, isoprene, piperylene, 2,3-dimethyl-1,3-butadiene, 1,4-pentadiene, 1,7-hexadiene and other such dienes and mixtures thereof. In another aspect, 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 sufficient to produce a copolymer that can incorporate from about 0.01 wt.% to about 10 wt.% comonomer, or even beyond this range, based on the total weight of monomer and comonomer in the copolymer; alternatively, from about 0.01 wt.% to about 5 wt.% comonomer; still alternatively, from about 0.1 wt.% to about 4 wt.% comonomer; or still alternatively, any amount of comonomer can be introduced into a reactor zone to provide the desired copolymer.

[0517] Typically, the catalyst composition can be used for homopolymerization of ethylene or propylene, or copolymerization of ethylene with a comonomer, or copolymerization of ethylene and propylene. On the other hand, several comonomers can be polymerized with the monomer in the same or different reactor zones to obtain the desired polymer properties.

[0518] Other useful comonomers can include polar vinyl, conjugated and non-conjugated dienes, acetylene and acetaldehyde monomers, which can be included in the terpolymer composition in small amounts, for example. For example, the non-conjugated diene that can be used as a comonomer can be a straight chain hydrocarbon diene or a cycloalkenyl substituted olefin having 6 to 15 carbon atoms. Suitable non-conjugated dienes may 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) monocyclic alicyclic dienes, such as 1,4-cyclohexadiene; 1,5-cyclooctadiene and 1,7-cyclododecadiene; (d) polycyclic alicyclic fused and bridged cyclic dienes, such as tetrahydroindene; norbornadiene; methyl-tetrahydroindene; dicyclopentadiene (DCPD); dicyclo- (2.2.1)-hept-2,5-diene; alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes, such as 5-methylene-2-norbornene (MNB), 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene and 5-vinyl-2-norbornene (VNB); and (e) cycloalkenyl substituted olefins, such as vinylcyclohexene, allylcyclohexene, vinylcyclooctene, 4-vinylcyclohexene, allylcyclodecene and vinylcyclododecene. Particularly useful non-conjugated dienes include dicyclopentadiene, 1,4-hexadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene and tetracyclo-(.Δ.-11,12)-5,8-dodecene. Particularly useful dienes include 5-ethylidene-2-norbornene (ENB), 1,4-hexadiene, dicyclopentadiene (DCPD), norbornadiene, and 5-vinyl-2-norbornene (VNB). Note that throughout this disclosure, the terms "non-conjugated diene" and "diene" are used interchangeably.

[0519] Catalyst compositions can be used for polymerizing olefins to prepare oligomers and polymer materials with a wide range of densities, for example in the range of about 0.66 g / mL (also referred to as g / cc) to about 0.96 g / mL, which are used in many applications. Catalyst compositions disclosed herein are particularly suitable for producing copolymers. For example, the density of the copolymer resin can be 0.960 g / cc or less, preferably 0.952 g / cc or less, or more preferably 0.940 g / cc or less. According to certain aspects of the present disclosure, a density less than 0.91 g / cc or even as low as 0.860 g / cc can be achieved. When density is described as being less than a specific density, a lower limit of such density can be about 0.860 g / cc. The copolymer resin can contain at least about 65 wt.% (weight percent) of ethylene units, that is, the weight percent of ethylene monomers actually incorporated into the copolymer resin. In another aspect, the copolymer resins of the present disclosure can contain at least about 0.5 wt.%, such as 0.5 wt.% to 35 wt.% alpha-olefin (α-olefin), which refers to the weight percent of the α-olefin comonomer actually incorporated into the copolymer resin.

[0520] The catalyst compositions prepared according to the present disclosure can also be used to prepare: (a) ethylene / propylene copolymers, including "random copolymers" in which the interpolymers are randomly distributed along the polymer backbone or chain; (b) "propylene random copolymers" in which the random copolymer of propylene and ethylene contains about 60 wt.% of a polymer derived from propylene units; and (c) "impact copolymers" refer to two or more polymers in which one polymer is dispersed in another polymer, typically one polymer comprising a matrix phase and the other polymer comprising an elastomeric phase. The catalyst compositions described herein can further be used to prepare polyalphaolefins having monomers, wherein the monomers contain more than three carbons. Such oligomers and polymers are par...

Claims

1. A support-activator comprising a montmorillonite heteroadduct comprising the contact product of: (a) colloidal montmorillonite clay; and (b) a surfactant selected from a cationic surfactant, a nonionic surfactant, an amphoteric surfactant or any combination thereof.

2. The support-activator of claim 1, wherein the colloidal montmorillonite clay is contacted with the surfactant at a ratio of 0.5 to 5 millimoles of surfactant per gram of colloidal montmorillonite clay.

3. The support-activator of claim 1, wherein the montmorillonite heteroadduct is isolated from the first liquid vehicle.

4. The support-activator of claim 1, wherein the montmorillonite clay comprises montmorillonite, sauconite, nontronite, hectorite, beidellite, saponite, bentonite, or any combination thereof.

5. The support-activator of claim 1, wherein the surfactant comprises a cationic surfactant.

6. The support-activator of claim 1, wherein the surfactant comprises a cationic surfactant selected from primary, secondary, tertiary or quaternary ammonium compounds or phosphorus compounds having the formula: [R 1 R 2 R 3 R 4 N] + X - or [R 1 R 2 R 3 R 4 P] + X - ,in Each R 1 , R 2 , R 3 and R 4 are independently selected from hydrogen, substituted or unsubstituted C1-C 25 A hydrocarbon group or a substituted or unsubstituted C1-C 25 A heteroalkyl group, wherein R 1 , R 2 , R 3 and R 4 Any two of may be part of a ring structure, and wherein R 1 , R 2 , R 3 and R 4 is a non-hydrogen moiety; and X - Selected from organic or inorganic monoanions.

7. The support-activator of claim 1, wherein the surfactant comprises a nonionic surfactant.

8. The carrier-activator according to claim 1, wherein the surfactant comprises: A nonionic surfactant, wherein the nonionic surfactant is selected from: ethoxylates, glycol ethers, fatty alcohol polyglycol ethers or any combination thereof; Amphoteric surfactants comprising an anionic surfactant portion and a cationic surfactant in the same molecule; or a combination thereof.

9. The support-activator of claim 1, wherein the surfactant comprises a nonionic surfactant selected from the group consisting of: (a) a polyol containing 2, 3 or more hydroxyl groups, having the formula CH2OH(CHOH) wherein n is an integer from 2 to 5 n A polyol of CH2OH, a monoalkyl ether of a polyol, a dialkyl ether of a polyol, or a polyalkylene glycol of any of these, i.e. a polyalkylene glycol of said polyol, said monoalkyl ether of a polyol, or said dialkyl ether of a polyol; (b) glycerol, 1,2,4-butanetriol, erythritol, pentaerythritol, maltitol, xylitol, sorbitol, ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol or a combination thereof; (c)(i) a fatty acid comprising or selected from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, ricinoleic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, hexadecenoic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, trans-linoleic acid, alpha-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid, or any combination thereof, or (ii) a fatty acid of (c)(i) condensed with an alcohol having one or more hydroxyl groups; (d) having the formula R 1 SO2OR 2 Hydrocarbon (hydrocarbon) sulfonate, wherein R 1 and R 2 are independently selected from substituted or unsubstituted C1-C 25 Alkyl-, C6-C 25 Aryl-, C7-C 25 Arylalkyl- or C7-C 25 Alkaryl; (e) glucose, fructose, mannose, maltose, lactose, sucrose, cyclodextrin, maltodextrin, glucosamine, glucuronic acid, or any combination thereof, (f) having the formula R 1 SiX3, R 1 R 2 SiX2 or R 1 R 2 R 3 SiX silane, wherein: (i)R 1 , R 2 and R 3 are independently selected from substituted or unsubstituted C1-C 25 Hydrocarbon group, C1-C 25 A heteroalkyl group or any other group that is hydrolytically stable when bonded to silicon in the nonionic surfactant; and (ii) X is independently selected from C1-C 25 Alkoxy, C1-C 25 Acyloxy, halogen or C1-C 25 An amine or another hydrolyzable group that is converted to a hydroxyl group (-OH) upon hydrolysis; or (g) Amino acids.

10. The support-activator of claim 1, wherein the surfactant comprises an amphoteric surfactant.

11. The support-activator according to claim 10, wherein the amphoteric surfactant comprises a cationic portion and an anionic portion, wherein the cationic portion is selected from a primary amine, a secondary amine, a tertiary amine or a quaternary ammonium cation, and the anionic portion is selected from a sulfate, a sulfonate, a phosphate or a carboxylate.

12. The carrier-activator of claim 1, wherein the surfactant comprises an amphoteric surfactant selected from the group consisting of amino acids, polypeptides, proteins, sulfobetaines, hydroxysulfobetaines, betaines, N-amine oxides, phospholipids, or sphingomyelins, or combinations thereof.

13. The carrier-activator according to claim 1, wherein the surfactant comprises an amphoteric surfactant selected from the group consisting of lauramidopropyl hydroxysulfobetaine, cocoamidopropyl hydroxysulfobetaine, oleamidopropyl hydroxysulfobetaine, tallowamidopropyl hydroxysulfobetaine, erucamidopropyl hydroxysulfobetaine, lauryl hydroxysulfobetaine, N,N,N-trimethylglycine, cocoamidopropyl betaine, phosphatidylserine, phosphatidylethanolamine, phosphatidylcholine, lauryl dimethylamine oxide, myristicamine oxide, pyridine-N-oxide, N-methylmorpholine-N-oxide, 3-[(3-cholamidopropyl)dimethylammonio]-1-propanesulfonate, or a combination thereof.

14. The support-activator of claim 1, wherein the montmorillonite heteroadduct is characterized by any one or any combination of the following properties: (i) the montmorillonite heteroadduct has an average particle sphericity of 0.65 or greater; (ii) the montmorillonite heteroadduct has an average particle roundness of 0.65 or more; and (iii) The montmorillonite heteroadduct has an average particle circularity of 0.65 or more.

15. The support-activator of claim 1 wherein the montmorillonite heteroadduct is characterized by an average particle sphericity of 0.75 or greater or an average particle circularity of 0.75 or greater.

16. A catalyst composition for olefin polymerization, the catalyst composition comprising: a) at least one metallocene compound; and b) at least one support-activator comprising a calcined montmorillonite heteroadduct comprising the contact product of: [1] a colloidal montmorillonite clay and [ii] a surfactant selected from a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or any combination thereof, in a first liquid vehicle and in the absence of any other reactants.

17. The catalyst composition of claim 16, wherein the colloidal montmorillonite clay is contacted with the surfactant at a ratio of 0.5 to 5 millimoles of surfactant per gram of colloidal montmorillonite clay.

18. The catalyst composition of claim 16, wherein the catalyst composition further comprises: (c) at least one promoter; (d) a fluid carrier; or Its combination.

19. The catalyst composition of claim 18, wherein the at least one co-catalyst is selected from an organoaluminum compound, an organoboron compound, an organozinc compound, an organomagnesium compound, an organolithium compound, or any combination thereof.

20. The catalyst composition of claim 16, wherein the at least one metallocene compound has the formula: (X 1 )(X 2 )(X 3 )(X 4 )M, where (i) M is zirconium or hafnium; (ii)X 1 is a substituted or unsubstituted indenyl, fluorenyl or cyclopentadienyl, wherein any substituent is independently selected from C1-C 20 Hydrocarbon, C1-C 20 Heteroalkyl or fused C4-C 12 Carbocyclic moiety; (iii)X 2 is a substituted or unsubstituted indenyl or cyclopentadienyl, wherein any substituent is independently selected from C1-C 20 Hydrocarbon or C1-C 20 heteroalkyl; (iv)X 3 and X 4 independently selected from halides, C1-C 20 Hydrocarbon, C1-C 20 Heteroalkyl or C1-C 20 Organic heterocyclic groups; and (v)X 1 and X 2 By connecting the substituent>EX 5 2 optionally bridged, wherein E is selected from C or Si, and each X 5 Independently selected from C1-C 20 Hydrocarbon.

21. The catalyst composition of claim 16, wherein the montmorillonite clay comprises montmorillonite, sauconite, nontronite, hectorite, beidellite, saponite, bentonite, or any combination thereof.

22. The catalyst composition of claim 16, wherein the surfactant comprises a cationic surfactant.

23. The catalyst composition of claim 16, wherein the surfactant comprises a cationic surfactant selected from a primary, secondary, tertiary or quaternary ammonium compound or a phosphorus compound having the formula: [R 1 R 2 R 3 R 4 N] + X - or [R 1 R 2 R 3 R 4 P] + X - ,in Each R 1 , R 2 , R 3 and R 4 are independently selected from hydrogen, substituted or unsubstituted C1-C 25 A hydrocarbon group or a substituted or unsubstituted C1-C 25 A heteroalkyl group, wherein R 1 , R 2 , R 3 and R 4 Any two of may be part of a ring structure, and wherein R 1 , R 2 , R 3 and R 4 is a non-hydrogen moiety; and X - Selected from organic or inorganic monoanions.

24. The catalyst composition of claim 16, wherein the surfactant comprises a nonionic surfactant.

25. The catalyst composition of claim 16, wherein the surfactant comprises: A nonionic surfactant, wherein the nonionic surfactant is selected from: ethoxylates, glycol ethers, fatty alcohol polyglycol ethers or any combination thereof; Amphoteric surfactants comprising an anionic surfactant portion and a cationic surfactant in the same molecule; or a combination thereof.

26. The catalyst composition of claim 16, wherein the surfactant comprises a nonionic surfactant selected from the group consisting of: (a) a polyol containing 2, 3 or more hydroxyl groups, having the formula CH2OH(CHOH) wherein n is an integer from 2 to 5 n A polyol of CH2OH, a monoalkyl ether of a polyol, a dialkyl ether of a polyol, or a polyalkylene glycol of any of these, i.e. a polyalkylene glycol of said polyol, said monoalkyl ether of a polyol, or said dialkyl ether of a polyol; (b) glycerol, 1,2,4-butanetriol, erythritol, pentaerythritol, maltitol, xylitol, sorbitol, ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol or a combination thereof; (c)(i) a fatty acid comprising or selected from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, ricinoleic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, hexadecenoic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, trans-linoleic acid, alpha-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid, or any combination thereof, or (ii) a fatty acid of (c)(i) condensed with an alcohol having one or more hydroxyl groups; (d) having the formula R 1 SO2OR 2 Hydrocarbon (hydrocarbon) sulfonate, wherein R 1 and R 2 are independently selected from substituted or unsubstituted C1-C 25 Alkyl-, C6-C 25 Aryl-, C7-C 25 Arylalkyl- or C7-C 25 Alkaryl; (e) glucose, fructose, mannose, maltose, lactose, sucrose, cyclodextrin, maltodextrin, glucosamine, glucuronic acid, or any combination thereof, (f) having the formula R 1 SiX3, R 1 R 2 SiX2 or R 1 R 2 R 3 SiX silane, wherein: (i)R 1 , R 2 and R 3 are independently selected from substituted or unsubstituted C1-C 25 Hydrocarbon group, C1-C 25 A heteroalkyl group or any other group that is hydrolytically stable when bonded to silicon in the nonionic surfactant; and (ii) X is independently selected from C1-C 25 Alkoxy, C1-C 25 Acyloxy, halogen or C1-C 25 An amine or another hydrolyzable group that is converted to a hydroxyl group (-OH) upon hydrolysis; or (g) Amino acids.

27. The catalyst composition of claim 16, wherein the surfactant comprises an amphoteric surfactant.

28. The catalyst composition of claim 16, wherein the surfactant comprises an amphoteric surfactant, and the amphoteric surfactant comprises a cationic portion and an anionic portion, wherein the cationic portion is selected from a primary amine, a secondary amine, a tertiary amine, or a quaternary ammonium cation, and the anionic portion is selected from a sulfate, a sulfonate, a phosphate, or a carboxylate.

29. The catalyst composition of claim 16, wherein the surfactant comprises an amphoteric surfactant selected from the group consisting of amino acids, polypeptides, proteins, sulfobetaines, hydroxysulfobetaines, betaines, N-amine oxides, phospholipids, or sphingomyelins, or combinations thereof.

30. The catalyst composition of claim 16, wherein the surfactant comprises an amphoteric surfactant selected from the group consisting of lauroyl hydroxysulfonate, cocoamidopropyl hydroxysulfonate, oleamidopropyl hydroxysulfonate, tallowamidopropyl hydroxysulfonate, erucamidopropyl hydroxysulfonate, lauryl hydroxysulfonate, N,N,N-trimethylglycine, cocoamidopropyl betaine, phosphatidylserine, phosphatidylethanolamine, phosphatidylcholine, lauryl dimethylamine oxide, myristicamine oxide, pyridine-N-oxide, N-methylmorpholine-N-oxide, 3-[(3-cholamidopropyl)dimethylammonio]-1-propanesulfonate, or a combination thereof.

31. The catalyst composition of claim 16, wherein the montmorillonite heteroadduct is characterized by any one or any combination of the following properties: (i) the montmorillonite heteroadduct has an average particle sphericity of 0.65 or greater; (ii) the montmorillonite heteroadduct has an average particle roundness of 0.65 or more; and (iii) The montmorillonite heteroadduct has an average particle circularity of 0.65 or more.

32. The catalyst composition of claim 16, wherein the montmorillonite heteroadduct is characterized by an average particle sphericity of 0.75 or greater or an average particle circularity of 0.75 or greater.

33. A process for polymerizing olefins, the process comprising contacting at least one olefin monomer with a catalyst composition under polymerization conditions to form a polyolefin, wherein the catalyst composition comprises: a) at least one metallocene compound; b) at least one support-activator comprising a calcined montmorillonite heteroadduct comprising the contact product of: [1] a colloidal montmorillonite clay and [ii] a surfactant selected from a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or any combination thereof, in a first liquid vehicle and in the absence of any other reactants.

34. The process for polymerizing olefins according to claim 33, wherein the at least one olefin monomer is selected from [a] ethylene or propylene or [b] a combination of ethylene and at least one comonomer selected from the group consisting of 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.

35. The process for polymerizing olefins according to claim 33, 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 a combination thereof.

36. A method of preparing a support-activator comprising a montmorillonite heteroadduct, the method comprising: (a) colloidal montmorillonite clay; and (b) contacting with a surfactant selected from a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or any combination thereof to provide a slurry of the montmorillonite heteroadduct in the first liquid carrier; wherein the contacting step occurs in the absence of any other reactants.

37. The method for preparing a carrier-activator according to claim 36, further comprising the steps of: (c) separating the montmorillonite heteroadduct from the slurry.

38. The method for preparing a carrier-activator according to claim 37, further comprising the steps of: (d) suspending the separated montmorillonite heteroadduct in a dispersion medium comprising water to provide a suspension of the montmorillonite heteroadduct in the dispersion medium; and (e) spray drying the montmorillonite heteroadduct from the suspension to provide the support-activator in particulate form.

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