JP2023523494A - Process for preparing catalysts and catalyst compositions - Google Patents

Abstract

A catalyst composition comprising a support activator and a support activator for polymerizing olefins in which the support activator comprises a clay heteroadduct, wherein the colloidal smectite clay chemically modified with a heterocoagulant is disclosed. prepared from colloidal phyllosilicates such as By limiting the amount of heterocoagulation reagent compared to the colloidal smectite clays described herein, smectite heteroadduct support activators are easily isolated from slurries obtained by conventional filtration processes. It is a porous and amorphous solid capable of activating metallocenes and related catalysts towards olefin polymerization. Related compositions and processes are disclosed. [Selection drawing] Fig. 1

Description

Cross-reference to related applications None

The present disclosure relates to catalyst compositions including support activators for producing polyethylene and processes for their preparation and use.

Compounds such as methylaluminoxane (MAO) and arylborane are commonly used as metallocene catalyst activators or cocatalysts for the polymerization of olefins. Heterogeneous catalyst systems are used in these polymerization systems because industrial scale production of polyolefin resins can use gas phase or slurry reactor platforms rather than solution phase conditions. Preparation and use of these heterogeneous polymerization catalysts can be complicated and expensive. For example, when catalyzing inorganic metal oxide supports such as silica or alumina, the additional use of cocatalysts or activators such as MAO and arylboranes is often required, which is time consuming and can be expensive. Synthesis of MAO and arylboranes themselves is atomically inefficient and requires multiple steps and inert conditions, which can increase the cost of using such activators.

Various support activators have been investigated in an attempt to reduce the high cost of aluminoxanes, arylboranes, and other expensive activators or cocatalysts. For example, McDaniel et al. US Pat. Nos. 6,107,230 and 9,670,296 of US Pat. work on. McDaniel et al. U.S. Pat. Nos. 6,632,894 and 7,041,753 also disclose a sol-gel matrix that can serve as a support activator for metallocenes, but which itself is costly to manufacture. describes the use of clay minerals in Other approaches are described, for example, by Suga et al. US Pat. No. 5,973,084 to Nikano et al. No. 6,531,552 to Murase et al. The use of chemically modified clay minerals is also found, such as in the work of US Pat. No. 9,751,961 to McCauley and US Pat. These approaches include process limitations such as low catalyst recovery yields, excessive preparation steps, difficulty in isolating modified clay minerals, or narrow preparation conditions under which clays can be modified and isolated.

Therefore, there remains a need to improve the ease and economy of preparation of support activators. This need is evident when chemically modified clay support activators with sufficient activity are desired for making metallocene-based polyolefins such as high clarity film resins. It eliminates the need for aluminoxanes and other expensive activators, is convenient and economical to prepare and recover in high yields, and/or has relatively high activity with polymerization catalysts such as metallocene compounds. It would be desirable to develop a clay-based support activator that demonstrates.

Aspects of the present disclosure provide new support activators and processes for their preparation, new catalyst compositions comprising support activators, methods of making catalyst compositions, and olefin polymerization processes. In one aspect, chemically modified clay support activators can readily activate metallocene compounds towards the polymerization of olefins, are surprisingly easy and inexpensive to prepare, and are recovered in high yields. can. In particular, the process and support activator of the present disclosure removes the chemically modified clay support activator from, for example, digestion of clay particles and leaching of the clay into the solution of the octahedral alumina layer during the activation process. Previous difficulties in isolation can be largely circumvented, making standard filtration very difficult as the size of the clay particles decreases.

A colloidal smectite clay, such as a dioctahedral smectite clay, is contacted in a liquid carrier (also referred to as a "diluent") with a heterocoagulation reagent comprising at least one cationic polymetallate to form a colloid within a specified range. It has been unexpectedly discovered that the use of heterocoagulation reagents in amounts compared to bulk smectite clays synthesize support activators containing isolated smectite heteroadducts. By limiting the amount of heterocoagulating reagent to the colloidal smectite clays described herein, smectite heteroadducts, also referred to as heterocoagulating smectites, can be readily isolated from slurries obtained by conventional filtration processes. can be released. The isolation process has often been difficult with previous chemically modified clay support activators that can take days for filtration or require multiple washing and centrifugation steps. Additionally, smectite heteroadduct support activators isolated according to the present disclosure can be used with little or no washing steps, further enhancing their utility, ease, and economy of preparation and use. be able to.

The smectite heteroadducts thus prepared can be used in conjunction with co-catalysts such as alkylaluminum compounds to provide metallocene olefin catalysts, especially when compared to conventional MAO- _SiO2 or borane-derived support activators. It provides a highly active support activator for polymerization. Heterocoagulants used in this process can be very inexpensive and can be used with co-catalysts such as alkylaluminum compounds and can also be very inexpensive compared to aluminoxanes and borane-based activators.

Additionally, isolation of the smectite heteroadduct can be accomplished using conventional filtration without the need for centrifugation or high dilution of the reaction mixture and without extensive washing of the resulting solid. This process provides solid clay heteroadducts that exhibit activity superior to the corresponding untreated clays and comparable or superior to the more difficult-to-preparate pillared clay supports, thereby addressing the need for Fulfill.

Further, unlike pillared clays, the heterocoagulated clay materials of the present disclosure are amorphous solids. The preparation of heterocoagulated clays provides three-dimensional structures, but non-columnar and non-crystalline and amorphous structures. Without intending to be bound by theory, it is believed that the regular crystal structure of the starting smectite is disrupted during the preparation of the clay heteroadduct, rather than simply extended upon contact with the cationic polymetalate, resulting in a non- It is believed to provide a crystalline, non-layered amorphous material.

Accordingly, in one aspect, the present disclosure provides a support activator comprising an isolated smectite heteroadduct, wherein the smectite heteroadduct comprises [1] a colloidal smectite clay, and [2] at least one an amount of a heterocoagulation reagent sufficient to provide a smectite heteroadduct slurry comprising a cationic polymetalate and having a zeta potential in the range of about positive 25 mV (+25 millivolts) to about negative 25 mV (−25 millivolts); of the contact product in a liquid carrier.

The present disclosure also provides, in another aspect, a method of making a support activator comprising a smectite heteroadduct, the method comprising:
a) providing a colloidal smectite clay;
b) colloidal smectite clay in an amount sufficient to provide a smectite heteroadduct slurry comprising at least one cationic polymetalate and having a zeta potential in the range of about positive 25 mV (millivolts) to about negative 25 mV; contacting the heterocoagulant reagent in a liquid carrier;
c) isolating the smectite heteroadduct from the slurry.

According to a further aspect, the present disclosure provides a catalyst composition for olefin polymerization, the catalyst composition comprising:
a) at least one metallocene compound;
b) optionally at least one cocatalyst;
c) at least one supported active agent comprising a calcined smectite heteroadduct, the smectite heteroadduct comprising [1] a colloidal smectite clay; and [2] at least one cationic polymetalate in a liquid carrier; and in an amount sufficient to provide a slurry of smectite heteroadducts having a zeta potential in the range of about positive 25 mV (millivolts) to about negative 25 mV. and an agent.

The present disclosure also provides, in another aspect, a method of making an olefin polymerization catalyst, the method comprising, in any order,
a) at least one metallocene compound;
b) optionally at least one cocatalyst;
c) at least one supported active agent comprising a calcined smectite heteroadduct, the smectite heteroadduct comprising [1] a colloidal smectite clay; and [2] at least one cationic polymetalate in a liquid carrier; and in an amount sufficient to provide a slurry of smectite heteroadducts having a zeta potential in the range of about positive 25 mV (millivolts) to about negative 25 mV. with an agent.

In one aspect, for example, an optional cocatalyst may be required to initiate efficient olefin polymerization, depending on the particular metallocene compound used to prepare the olefin polymerization catalyst, or it may It may be an alkylating agent that may not be necessary.

In a further aspect, a process for the polymerization of olefins is provided, the process comprising contacting at least one olefin monomer and a catalyst composition under polymerization conditions to form a polyolefin, the catalyst composition comprising:
a) at least one metallocene compound;
b) optionally at least one cocatalyst;
c) at least one supported active agent comprising a calcined smectite heteroadduct, the smectite heteroadduct comprising [1] a colloidal smectite clay; and [2] at least one cationic polymetalate in a liquid carrier; and in an amount sufficient to provide a slurry of smectite heteroadducts having a zeta potential in the range of about positive 25 mV (+25 millivolts) to about negative 25 mV (-25 millivolts). , and at least one supporting active agent.

These and other aspects, features and embodiments of the compositions, including support activator and catalyst compositions, methods of making the compositions, and polymerization processes and related methods, are described in the detailed description provided herein. , the drawings, the examples, and the claims.

A schematic representation of embodiments of the present disclosure is provided to illustrate a method of preparing, washing, and isolating a support activator comprising a calcined smectite heteroadduct of the present disclosure, the process comprising preparing, washing, and isolating a pillared clay. and methods of isolation. 1 provides powder XRD (X-ray diffraction) patterns of a series of fired products combining aluminum chlorohydrate (ACH) and Volclay® HPM-20 montmorillonite. All but the starting clay itself in the 6.4 mmol Al/g clay sample (top) representing the typically prepared Al ₁₃ pillared clay (Comparative Example 5), and the 0 mmol Al/g clay sample (Comparative Example 3). Samples were prepared according to the method of the invention according to the examples (see Examples 18, 20-21, and 23). An aqueous solution of 2.5 weight percent (wt %) aluminum chlorohydrate (ACH, measured density of 1.075 g/mL) in 0.62 weight percent Volclay® HPM-20 bentonite aqueous dispersion. Zeta potential titration with volumetric addition is shown and measured zeta potential is plotted against titer volume (mL). The titration setting was 0.5 mL per titration point followed by an equilibration delay of 30 seconds. The titration volume indicates the cumulative volume of added aluminum chlorohydrate aqueous solution. See also Table 4. FIG. 3 plots converted to zeta potential versus mass ratio of aluminum to clay. In particular, FIG. 4 shows 2.5 wt % aluminum chlorohydrate (ACH, measured density of 1.075 g/mL) in 0.62 wt % Volclay® HPM-20 bentonite aqueous dispersion. Zeta potential titrations for the addition of aqueous solutions are shown and the measured zeta potentials are plotted against Al content (mmol Al/g clay). The titer indicates the cumulative mmol of aluminum in the added aqueous ACH solution. 4.58% by weight UltraPAC® 290 polyaluminum chloride (empirically Al ₂ (OH) _2.5 Cl _3.5 ) in 1% by weight Volclay® HPM-20 bentonite aqueous dispersion. ) and the measured zeta potential is plotted against the titration volume (mL). The titration setting was 1 mL per titration point followed by an equilibration delay of 30 seconds. Titrated volume indicates the cumulative volume of UltraPAC® 290 polyaluminum chloride aqueous solution added. See also Table 5. Zeta potential titration for volumetric addition of 10 wt% aqueous dispersion of NYACOL® AL27 colloidal alumina in 0.75 wt% Volclay® HPM-20 bentonite aqueous dispersion (adjusted) and the measured zeta potential is plotted against titer volume (mL). The titration settings were 1 mL per titration point from 0 to 27 mL and 3 mL per subsequent titration point with an equilibration delay of 60 seconds. Titration volume indicates the cumulative volume of added NYACOL® AL27 aqueous colloidal alumina solution. See Example 11 and Table 6. Measured zeta potential showing zeta potential titration for volumetric addition of 2.5 wt% aqueous aluminum chlorohydrate (ACH) into 5 wt% AEROSIL® 200 fumed silica aqueous dispersion. is plotted against titration volume (mL). The titration setting was 1 mL per titration point and the equilibration delay was 60 seconds. The titration volume indicates the cumulative volume of aqueous ACH solution added. See Example 37. The plot of FIG. 7 is shown converted to zeta potential versus mass ratio of aluminum to clay. Specifically, FIG. 8 shows the zeta potential titration of 2.5 wt % aluminum chlorohydrate (ACH) aqueous solution added to 5 wt % AEROSIL® 200 fumed silica aqueous dispersion. and the measured zeta potentials are plotted against the Al content (mmol Al/g clay). The titer indicates the cumulative mmol of aluminum in the added aqueous ACH solution. Aluminum chlorohydrate (ACH) solution treated AEROSIL® 200 fumed silica aqueous dispersion containing 5% silica by weight in 1% by weight Volclay® HPM-20 bentonite aqueous dispersion. Zeta-potential titrations (adjusted) with volumetric addition are provided. The titration settings were 0.2 mL per titration point from 0 to 1.2 mL and 0.5 mL per subsequent titration point with an equilibration delay of 30 seconds. Since the titrant is a colloidal species, the zeta potential was adjusted using the method described in Example 11 to give the plot in FIG. See Example 38. Shows the results of nitrogen adsorption/desorption BJH (Barrett, Joyner, and Halenda) pore volume analysis of the aluminum chlorohydrate (ACH) heterocoagulated clay of Example 18, showing the cumulative pore volume (cubic centimeters per gram) for the heteroadducts. , cc/g) versus pore size (Angstroms, Å). The recipe for the preparation of this heteroadduct slurry used 1.76 mmol Al/g clay. 3 provides nitrogen adsorption/desorption BJH pore volume analysis results for comparative sheared and then azeotroped samples of Volclay® HPM-20 bentonite, but without further treatment, according to Comparative Example 3; Values are given for V 3-10 _nm greater than 55% of the volume V _3-30 nm. Provides nitrogen adsorption/desorption BJH pore volume analysis results of an untreated sample of Volclay® HPM-20 bentonite suspended in water, evaporated and calcined, but with no further treatment according to Comparative Example 1 values are shown for V _3-10 nm greater than 55% of the cumulative pore volume V 3-30 _nm . ¹ H NMR spectrum of 7-phenyl-2-methyl-indene in CDCl ₃ with contaminant CH ₂ Cl ₂ and water peaks identified and peak integrals indicated. ¹ H NMR spectrum of rac-dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dichloride in CDCl ₃ with peak integrals indicated.

To more clearly define the terms and phrases used herein, the following definitions are provided. To the extent a definition or usage provided by any document incorporated herein by reference conflicts with a definition or usage provided herein, the definition or usage provided herein shall control. do.

A. DEFINITIONS AND EXPLANATION OF TERMS Polymetalate. The term "polymetalate" and analogous terms such as "polyoxometalate" are used in this disclosure to refer to two or more metals together with at least one bridging ligand between the metals such as oxo, hydroxy and/or halide ligands. Used interchangeably to refer to water-soluble polyatomic cations containing atoms such as aluminum, silicon, titanium, zirconium, or other metals. Specific ligands can depend on the precursor and other factors such as the process of producing the polymetalate, solution pH, and the like. For example, the polymetalates of the present disclosure can be hydrated metal oxides, hydrated metal oxyoxides, etc., including combinations thereof. Bridging ligands, such as oxo ligands that bridge two or more metals, can occur in these species, but polymetalates can also include terminal oxo, hydroxyl, and/or halide ligands.

Although many known polymetalate species are anionic and the suffix "-ate" is often used to reflect anionic species, the polymetalate (polyoxometalate) species used according to this disclosure are Cationic. These materials, which may be referred to as compounds, species, or compositions, are known to those skilled in the art, such as in aqueous solution, depending on, for example, solution pH, concentration, starting precursors from which polymetalates are formed in aqueous solution, and the like. It will be appreciated that more than one species can be contained in a suitable carrier of. For clarity and convenience, these multiple species refer to species, or mixtures of compounds, in which the compositions comprise cationic polyoxometalates, polyhydroxymetalates, polyoxohydroxymetalates, or other ligands such as halides. Collectively referred to as "polymetallates" or "polyoxometalates", whether comprising or predominately of them. Examples of polymetalates include, but are not limited to, polyaluminum oxyhydroxychloride, aluminum chlorohydrate, polyaluminum chloride, or aluminum sesquichlorohydrate compositions, including linear, cyclic, or cluster compounds. can be These compositions are collectively referred to as polymetalates, although the terms "polymetalate" or "polyoxometalate" are also used to describe compositions comprising substantially a single species.

Both isopolymetalates containing a single type of metal and heteropolymetalates containing more than one type of metal (or electropositive atoms such as phosphorus) are included under the general term polymetalate or polyoxometalate. be For example, aluminum polymetallates such as those provided by aluminum chlorohydrate (ACH) or polyaluminum chloride (PAC) are examples of isopolymetalates. In a further example, the polymetalates of the present disclosure are subsequently It can be prepared from the first metal oxide to be treated. For example, the first metal oxide can comprise silica, alumina, zirconia, etc., including fumed silica, alumina, or zirconia, and the second metal oxide, metal halide, or metal oxyhalide can comprise It can be obtained from aqueous solutions or suspensions of metal oxides, hydroxides, oxyhalides, or halides such as _ZrOCl2 , ZnO, _NbOCl3 , B(OH) ₃ , _AlCl3 , or combinations thereof. Therefore, when different metals are used in the preparation, the resulting species are considered heteropolymetallates. Both isopolymetalates and heteropolymetalates may be referred to simply as "polymetalates."

In a further aspect, polymetalates according to the present disclosure can be non-alkylated with respect to transition metal compounds such as metallocene compounds. That is, the subject polymetalates can be devoid of direct metal-carbon bonds as found in aluminoxanes or other organometallic species.

Because the size and number or metal ions in polymetalate species can vary considerably, polymetalate can be considered to include both oligomeric or polymeric species. When polymetalates are described as “comprising,” “consisting of,” “consisting essentially of,” or “chosen from” certain materials such as polyaluminum chloride or aluminum sesquichlorohydrate, these materials It should be understood that the polymetallate species formed when is in contact with water or an aqueous base or the like are described according to the precursors from which they are produced. Thus, for convenience, and for the sake of certainty and clarity pursuant to 35 U.S.C. can be described.

In one aspect, a polymetalate according to the present disclosure can be at least one aluminum polymetalate. Examples include aluminum chlorohydrate (ACH), also known as aluminum chlorohydrate, which includes multiple water-soluble aluminum species, commonly regarded as having the general formula Al _n Cl _3n-m (OH) _m , but not limited to. These polymetalate species are sometimes referred to as aluminum oxyhydroxychloride compounds or compositions. Another polymetalate that can be used in accordance with the present disclosure is polyaluminum chloride (PAC ), examples of which can contain from 2 to about 30 aluminum atoms, oxo, chloride, and hydroxyl groups. Other examples of aluminum polymetalates include compounds having the general formula [Al _m O _n (OH) _x Cl _y ] zH ₂ O, such as aluminum sequichlorohydrate, and cluster-type species such as the Keggin ion, e.g. Sometimes referred to as "Al ₁₃ -mer" polycations, including but not limited to [AlO ₄ Al ₁₂ (OH) ₂₄ (H ₂ O) ₁₂ ] ⁷⁺ •7[Cl] ^- . For example, polyaluminum chloride (PAC) can be produced by combining aqueous hydroxides with _AlCl3 , and the resulting mixtures of aluminum species have varying basicities. Aluminum chlorhydrate (ACH) is generally considered the most basic, and polyaluminum chloride (PAC) is considered the least basic.

Clay heteroadducts or clay heterocoagulates according to the present disclosure include [1] a colloidal smectite clay, such as a dioctahedral smectite clay, and [2] at least one cationic polymetalate in a liquid carrier, such as an aqueous carrier. with a heterocoagulation reagent in an amount sufficient to provide a slurry of smectite heteroadduct having a zeta potential in the range of about +25 mV to about -25 mV. Once isolated, the smectite heteroadduct can be heated, dried and calcined to form the support activator described herein. Upon calcination, additional reactions of polymetalates initially intercalated or associated with smectite can occur, e.g., water can be driven from the intercalated polymetalates to form additional oxo groups. obtain. In this aspect, the term "polyoxometalate" can be particularly useful for irradiating the calcined product. In any event, the terms "polymetalate" and "polyoxometalate" are used interchangeably to describe compositions used to contact colloidal smectites.

The polymetalates of the present disclosure may also be referred to as "polycations," homopolycations and Both heteropolycations can be included. For example, hydrotalcite is [Mg ₆ Al ₂ (OH) ₁₆ ]CO ₃ .4H ₂ O, a heteropolycation according to the present disclosure.

Other examples of polymetalates provided by way of example only include the ε-Keggin cation [ε-PMo ₁₂ O ₃₆ (OH) ₄ {Ln(H ₂ O) ₄ } ₄ ] ⁵⁺ where Ln is La, Ce, Nd, or Sm). For example, Angew. Chem. , Int. Ed. 2002, 41, 2398. As another _example , lanthanides having the general formula [ _Ln2V12O32 ( _H2O ) ₈ {Cl}]Cl, where Ln can be Eu, Gd, _Dy , Tb, Ho or Er containing cationic heteropolyoxovanadium clusters. For example, RSC Adv. 2013, 3, 6299-6304.

Finally, references to "at least one" cationic polymetalate are used to refer to one or more sources of cationic polymetalate used to prepare the heterocoagulant reagent. That is, even when a single source of cationic polymetalate is used to prepare the heterocoagulant reagent in aqueous solution, and multiple species may occur, these multiple species may be of a single or single type of cationic May be collectively referred to as polymetalates. Thus, references to a plurality or more than one cationic polymetalate are intended to refer to precursor compositions or sources of one or more of the cationic polymetalates used to prepare the heterocoagulant reagent. be.

Heterocoagulant reagent. The terms "heterocoagulant", "heterocoagulant" and the like refer to readily filterable solids (as defined herein) when present in solution or when combined with a colloidal clay dispersion in appropriate proportions. It is used herein to describe a composition comprising any positively charged oligomeric or polymeric metal oxide-containing species as a colloidal suspension that forms a . "Heterocoagulant reagent" is used interchangeably with the terms "polymetalate" or "polyoxometalate" to any positively charged oligomeric or polymeric metal that functions to form a clay heteroadduct. It may refer to oxide-containing species. Thus, a "heterocoagulant reagent" has a zeta potential in the range of about +25 mV to about -25 mV when a composition comprising one or more cationic polymetalate species in a liquid carrier is contacted with colloidal smectite clay. It is emphasized that when used in sufficient quantity to provide a slurry, it forms readily filterable solids. "Heterocoagulation" is a term in the art and is described by Lagaly in Ullmann's Encyclopedia of Chemistry 2012. Within the context of this disclosure, "heterocoagulation", unless otherwise specified, means combining negatively charged colloidal clay particles with positively charged species of a heterocoagulation reagent to form a readily filterable solid. defined as the process of Heterocoagulation is also described in the art and herein, for example, Cerbelaud et al. Advances in Physics: X, 2017, vol. 2, 35-53, sometimes referred to as heteroaggregation.

Heteroadducts or heterocoagulants. Clay heteroadducts or clay heterocoagulates and similar terms such as "heterocoagulated clays" or "smectite heteroadducts" refer to the contact product obtained from the combination of heterocoagulant reagents and colloidal clays. Thus, aggregates formed by the attraction of negatively charged colloidal clay particles with positively charged species in the heterocoagulant reagent are referred to as "heteroadducts." Wu Cheng et al. US Pat. No. 8,642,499, which is incorporated herein by reference. In one aspect, these terms refer to the "readily filterable" contact product of heterocoagulant reagent and colloidal clay as defined herein. These terms include a heterocoagulant reagent that is combined in a ratio that provides a readily filterable heterocoagulant and a product that is not readily filterable, such as, for example, the product formed when following a columnar viscosity synthesis recipe; and Used to distinguish from colloidal clay contact products. For stilt clay recipes, the contact product cannot be easily filtered and centrifugation is generally required to separate the stilt clay product.

When describing the formation of a heterocoagulant clay using an aluminum-containing heterocoagulant reagent, and unless otherwise specified, the combination of a pillaring reagent such as an aluminoxychloride (also called a heterocoagulant reagent) with the clay is The ratio is expressed as mm (mmol or millimoles) Al/g clay and represents millimoles of Al to grams of clay in the pillared or heterocoagulant. Gu et al. , Clay and clay minerals, 1990, 38(5), 493-500, which is incorporated herein by reference. Unless otherwise specified, when the pillar or aluminoxychloride heterocoagulant reagent is present as a soluble solution, millimolar Al is calculated based on the weight % Al or weight % _Al2O3 content provided by the manufacturer _. . Alternatively, unless otherwise specified, millimoles of Al is the weight used in the recipe and the empirical formula provided by the manufacturer when starting with solid forms of pillars or heterocoagulation reagents dispersed in solution. determined by

Easily filterable. "readily filterable", "readily filtered", "easily filterable", "easily filtered or separated" Terms such as centrifugation, ultracentrifugation, or dilute solutions where the solids in the mixture containing the liquid phase are less than about 2% by weight solids, long settling times, followed by decanting the liquid from the solids; and other such techniques, to describe compositions according to the present disclosure that can be separated from the liquid phase by filtration. These terms generally refer to contact products of colloidal smectite clays and heterocoagulant reagents under certain conditions according to the present disclosure, isolated by centrifugation, high dilution and sedimentation or sedimentation tanks, or ultrafiltration. Used herein to describe an unnecessary clay heteroadduct. Thus, readily filterable clay heteroadducts include heteroadducts to conventional filtration materials such as sintered glass, metallic or ceramic frits, paper, natural or synthetic matte fibers under gravity or vacuum filtration conditions. By passing through a slurry, it can be isolated or separated from the soluble salts and by-products of the synthesis in good yields in a time period of minutes or less, or less than about an hour.

This disclosure provides several specific experimental and quantitative methods by which filterability can be assessed. For example, certain methods are provided for quantifying the filterability of heteroadduct slurries, indicating that the slurries are readily filterable, or can be considered readily filterable, when prepared according to the methods of the present disclosure. be done. Colloids or suspensions described by Lagaly in Ulmmann's Encyclopedia of Chemistry 2012 that require long precipitation times or ultrafiltration are not considered "filterable" in the context of this disclosure. The readily filterable suspensions or slurries of the present disclosure can yield a clear filtrate upon filtration, while the "not easily filterable" suspensions that require substantially longer time to filter have colloidal It may contain particulate matter observable as a visually cloudy or opaque filtrate, indicative of a clay dispersion. so that a support activator according to the present disclosure provides a slurry of smectite heteroadducts having a zeta potential near the upper (positive) boundary of about +25 mV (millivolts) or near the lower (negative) boundary of about −25 mV. When the heteroadducts are filtered as prepared, some degree of cloudiness can be observed in the filtrate, which indicates that the smectite heteroadducts provide a slurry with a zeta potential close to or near 0 mV. and darkened to be prepared using a ratio of heterocoagulant reagents.

colloid. "Colloid," "colloidal clay," "colloidal solution," "colloidal suspension," and similar terms are defined in Gerhard Lagaly in Ullmann's Encyclopedia of Industrial Chemistry, published January 15, 2007, "Colloids." used as defined in the chapter entitled These terms are used interchangeably.

Catalyst compositions and catalyst systems. Terms such as "catalyst composition," "catalyst mixture," and "catalyst system" refer to the combination of listed components that ultimately form or are used to form an active catalyst according to the present disclosure. used for The use of these terms may be formed from any particular contacting step, order of contacting, whether any reaction may occur between or among the components, or any contacting of any or all of the components listed. Not dependent on any product. The use of these terms also refers to 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. does not depend on These and similar terms therefore apply to the initially listed or starting components of the catalyst composition, whether the catalyst composition is heterogeneous or homogeneous, or includes soluble and insoluble components; and any product combination that can result from contacting these initially listed starting ingredients. The terms "catalyst" and "catalyst system" or "catalyst composition" can be used interchangeably and such use will be apparent to those skilled in the art from the context of this disclosure.

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

Activity of a reference or comparative catalyst composition refers to the polymerization activity of a catalyst composition comprising the comparative catalyst composition, the weight of the comparative ion exchange or pillared clay or the weight of the clay component used to prepare the clay heteroadduct. based on itself. Terms such as "increased activity" or "improved activity" mean that the comparative catalyst composition generally utilizes a different support activator or activator, such as pillared clay, or is catalyzed. The activity of a catalyst composition according to the present disclosure is demonstrated to be greater than that of a comparative catalyst composition using the same catalyst components, such as the metallocene compound and cocatalyst, except that the clay component used is not a heterocoagulated clay. For example, for increased or improved activity according to the present disclosure, using a standard set of ethylene homopolymerization conditions, about 300 grams or more of polyethylene polymer per gram of calcined heterocoagulated clay per hour (g/g/hr ) based on calcined clay heteroadducts. In this aspect, the standard set of ethylene homopolymerization conditions includes the following. A 2 L stainless steel reactor equipped with a marine impeller was set at about 500 rpm and slurry polymerization conditions included 1 L of purified isobutane diluent, 90° C. polymerization temperature, 450 psi total ethylene pressure, typically 30 or 60 run length of minutes, comprising a metallocene catalyst composition comprising (1-Bu-3-MeCp) ₂ ZrCl ₂ with triethylaluminum (TEAL) cocatalyst, optionally using the metallocene as a stock solution containing TEAL, Charge an amount to provide a metallocene to clay ratio of about 7×10 ⁻⁵ mmol metallocene/mg calcined clay. Generally, one alkylaluminum cocatalyst was used in the polymerization run and was usually selected from TEAL or triisobutylaluminum (TIBAL).

contact product. The term "contact product" is used herein in any manner and in any length to describe or require or imply a particular order, depending on the context of the present disclosure. It is used to describe a composition in which the components are combined or "contacted" together in any order, except where indicated. "Contact product" can include reaction products, but the respective components need not react with each other, and the term is used regardless of whether it can occur when the recited components are contacted. be done. For example, the listed components can be contacted by blending or mixing, or the components can be added in any order or added simultaneously to the liquid carrier to form the contact product. can be contacted by Additionally, contact of any component may occur in the presence or absence of any other component of the compositions described herein, unless otherwise stated, required or implied by the context in which the term is used. Combining or contacting the listed components or any additional materials can be carried out by any suitable method. Accordingly, the term "contact product" includes mixtures, blends, solutions, slurries, reaction products, etc., or combinations thereof. Similarly, the term "contacting" is used herein to refer to materials that can be blended, mixed, slurried, dissolved, reacted, treated, or otherwise contacted in any way.

Pore diameter (pore size). Nitrogen adsorption/desorption measurements were used to determine pore size and pore volume distribution using the BJH method. The International Union of Pure and Applied Chemistry (IUPAC) system for classifying porous materials (see Pure & Appl. Chem., 1994, 66, 1739-1758) and Klobes et al. , National Institute of Standards and Technology Special Publication 960-17, pore size is defined as follows: "Micropores" and "microporous" as used herein refer to pores present in a catalyst or catalyst support made according to the processes of the present disclosure that are less than 20 Å in diameter. "Mesoporous" and "mesoporous" as used herein, catalysts or Refers to the pores present in the catalyst support. "Macropores" and "macroporous" as used herein refer to pores present in a catalyst or catalyst support produced according to the process of the present disclosure having a diameter of 500 Å (50 nm) or greater. Point.

Each of the above definitions of micropores, mesopores, and macropores is defined such that no pores are counted twice when summing the percentages or values in the distribution of pore sizes (pore size distribution) for any given sample. considered distinct and non-overlapping.

"d50" means median pore size as determined by porosimetry. Thus, "d50" corresponds to the median pore size calculated based on the pore size distribution and is the pore size for which half the pore size has the larger diameter. The d50 values reported here are from E. P. Barrett, L.; G. Joyner andP. P. Halenda ("BJH"), "The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms," J. Am. Am. Chem. Soc. , 1951, 73(1), pp 373-380.

"Median pore diameter" (MPD) can be calculated, for example, based on volume, surface area, or based on pore size distribution data. Median pore size calculated by volume means the pore size in which half of the total pore volume lies. Median pore size calculated by surface area means that more than half of the total pore surface area is present. Similarly, the median pore size calculated based on the pore size distribution is half the pore size according to the determined pore size distribution described elsewhere herein, e.g., through derivation from a nitrogen adsorption-desorption isotherm. means the pore size with the larger diameter.

Transition metal catalyst. A "transition metal catalyst" is in its present form when contacted with a support activator of the present disclosure or with a co-catalyst capable of transferring or imparting a polymerization activating ligand to the transition metal catalyst. When used, it refers to a transition metal compound or composition that functions as or can be converted into an active olefin polymerization catalyst. The use of the term "catalyst" is not intended to reflect any particular mechanism or "transition metal catalyst" per se, when it is activated or it is capable of polymerization activation. It is not intended to represent an active site for catalytic polymerization when attached with a ligand. Transition metal catalysts are described according to the transition metal compound or compounds used in the process for preparing the polymerization catalyst and can include metallocene compounds and related compounds as defined herein.

cocatalyst. "Cocatalyst" refers to a chemical reagent, compound, or composition capable of liganding a metallocene capable of initiating polymerization when the metallocene is otherwise activated with a support activator used herein for In other words, "cocatalyst" is used herein to refer to a chemical reagent, compound, or composition capable of providing a polymerization-activatable ligand to a metallocene compound. Polymerization activatable ligands include alkyls such as methyl or ethyl, aryls and substituted aryls such as phenyl or tolyl, substituted alkyls such as benzyl or trimethylsilylmethyl (—CH ₂ SiM ₃ ), hydrides, silyls and trimethylsilyls. Hydrocarbyl substituents such as, but not limited to, Thus, in one aspect, the co-catalyst can be an alkylating agent, hydriding agent, silylating agent, and the like. There is no limitation on the mechanism by which the cocatalyst provides the polymerization-activatable ligand to the metallocene compound. For example, a cocatalyst can participate in a metathesis reaction to exchange an exchangeable ligand such as a halide or alkoxide on the metallocene compound for a polymerization activating/initiating ligand such as methyl or hydride. In one aspect, the co-catalyst is an optional component of the catalyst composition, eg, when the metallocene compound already includes a polymerization activating/initiating ligand, eg, methyl or hydride. In another aspect, as will be appreciated by those skilled in the art, the cocatalyst is used for other purposes, such as to remove water from the polymerization reactor or process, even when the metallocene compound contains a polymerization-activatable ligand. can do. According to a further aspect, as the context requires or permits, the term "cocatalyst" may refer to an "activator" or a "cocatalyst" as described herein. may be used interchangeably.

Activator. "Activator," as used herein, generally refers to a substance capable of converting a metallocene component into an active catalyst system capable of polymerizing olefins, and the mechanism by which such activation occurs. are intended to be independent. An "activator" is, for example, the contact product of a metallocene component with a component that provides an activatable ligand (such as an alkyl or hydride) to the metallocene when the metallocene compound does not already contain such ligands. can be converted into a catalytic system capable of polymerizing olefins. This term is used regardless of the actual activation mechanism. Exemplary activating agents can include, but are not limited to, support activating agents, aluminoxanes, organoboron or organoborate compounds, ionizing compounds such as ionizing ionic compounds, and the like. Aluminoxanes, organoboron or organoborate compounds, and ionizing compounds may be referred to as "activators" or "co-activators" when used in catalyst compositions in which a support activator is present. However, the catalyst composition is supplemented with one or more aluminoxanes, organoborons, organoborates, ionizing compounds, or other coactivators.

Support activator. The term "support activator" as used herein refers to solid forms of activators such as ion exchange clays, protonic acid treated clays, or pillared clays, and similar substances that also function as activators. refers to the insoluble support of Provide a catalyst system capable of polymerizing olefins when a support activator is combined with a metallocene and an activatable ligand, or optionally a cocatalyst capable of providing a metallocene and an activatable ligand do.

ion exchange clay. The term "ion-exchanged clay," as used herein, is defined by those of ordinary skill in the art in which the exchangeable ions of a naturally occurring or synthetic clay have been replaced by another selected ion or To be understood as selected ion-exchanged clays (also called "monoionic" or "monocationic" clays). Ion exchange can occur by treatment of the natural or synthetic clay with a selected source of cations, usually from a concentrated ionic solution such as a 2N aqueous solution of cations, comprising multiple exchange steps, for example three exchange steps. The exchanged clay can then be washed several times with deionized water to remove excess ions generated in the processing steps, see, for example, Sanchez, et al. , Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2013, 423, 1-10, and Kawamura et al. , Clay and Clay Minerals, 2009, 57(2), 150-160. Centrifugation is commonly used to isolate the clay from solution between ion treatments and washings.

metallocene compounds. The term "metallocene" or "metallocene compound" as used herein, regardless of the particular binding mode, for example, cycloalkadienyl-type ligands or alkadienyl-type ligands are η ⁵ -, η 3 -, η ³ -, or heteroatom analogues thereof, whether or not bound to the metal in the η ¹ -binding mode, and whether or not one or more of these binding modes are accessible by the ligand; Transition metal or lanthanide metal compounds containing at least one substituted or unsubstituted cycloalkadienyl-type ligand or alkadienyl-type ligand are described. In this disclosure, the term “metallocene” is also used to refer to compounds containing at least one π-bonded allylic ligand, where the η ³ -allyl is not part of a cycloalkadienyl-type or alkadienyl-type ligand; It can be used as the transition metal compound component of the catalyst compositions described herein. “Metallocene” thus includes substituted or unsubstituted η ³ -η ⁵ -cycloalkadienyl-type and η ³ -η ⁵ -alkadienyl-type ligands, their heteroatom analogues, and the cyclopentadienyl ligands, indenyl ligands, fluorenyl ligands, η ³ -allyl ligands, pentadienyl ligands, boratabenzenyl ligands, 1,2-azaborolyl ligands, 1,2-diaza-3,5-diborolyl ligands, Includes compounds with η ³ -allylic ligands including, but not limited to, substituted analogs, and partially saturated analogs thereof. Partially saturated analogues include compounds containing partially saturated η ⁵ -cycloalkadienyl-type ligands, examples of which are tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl, partially Examples include, but are not limited to, saturated fluorenyls, substituted analogues thereof, and the like. In some contexts, metallocenes are referred to simply as "catalysts" and, much likewise, the term "cocatalyst" is used herein to refer to, for example, organoaluminum compounds. Thus, metallocene ligands are defined in this disclosure as at least one substituted or at least one unsubstituted cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, allyl, boratabenzenyl, It includes 1,2-azaborolyl or 1,2-diaza-3,5-diborolyl ligands and can be considered to include substituted analogues thereof. For example, optional substituents may include halides, C ₁ -C ₂₀ hydrocarbyls, C ₁ -C ₂₀ heterohydrocarbyls, C ₁ -C ₂₀ organoheteryls, fused C ₄ -C ₁₂ carbocyclic moieties, or nitrogen, oxygen, sulfur or fused C ₄ -C ₁₁ heterocyclic moieties having at least one heteroatom independently selected from phosphorus.

Organoaluminum compounds and organoboron compounds. The terms organoaluminum compounds and organoboron compounds, as used herein, include neutral compounds such as _AlMe3 and _BEt3 , and anionic complexes such as _LiAlMe4 , _LiAlH4 , _NaBH4 and _LiBEt4 . Also includes Accordingly, unless otherwise specified, hydride compounds of aluminum and boron are included in the definitions of organoaluminum compounds and organoboron compounds, respectively, regardless of whether the compounds are neutral or anionic.

columnar clay. For the purposes of this disclosure, "pillared clay" is defined as a clay species having ordered layers with basal spacings substantially greater than 9 Å to 13 Å. When powdered clay samples are analyzed using an X-ray diffractometer capable of scanning 2-theta angles of 2° or greater, species containing such columnar ordering are usually substantively observed at 2-theta values of 2°-9°. It is observed to have a large peak. These are typically prepared by the introduction of pillaring agents, for example oxygen-containing inorganic cations such as the oxygen-containing cations of lanthanum, aluminum, or iron. Aluminum pillared clays are often prepared by contacting the pillaring agent with the clay in amounts ranging from about 5 mmol Al/g clay or 6 mmol Al/g clay, up to about 30 mmol Al/g clay. A typical pillared clay formulation contains the support activator disclosed herein at about 2.0 mmol Al/g clay or less, about 1.7 mmol Al/g clay or less, about 1.5 mmol Al/g clay or less. Prepared using less than or equal to about 1.3 mmol Al/g clay, or less than or equal to about 1.2 mmol Al/g clay, but greater than about 0.75 mmol Al/g clay, or greater than about 1.0 mmol Al/g clay This may be contrasted with the preparation of support activating agents according to the present disclosure, which may be performed. Thus, in one aspect, the pillar agents used to form the columnar viscosity can be selected from the same heterocoagulating reagents used to form the heterocoagulating clays of the present disclosure. As explained herein, some pillared clay species may form even during the preparation of the smectite heteroadducts disclosed herein.

intercalated. The term "intercalated" or "intercalation" is a term of art denoting the intercalation of material between layers of a clay substrate. These terms are used herein in a manner understood by those skilled in the art and as described in US Pat. No. 4,637,992, unless otherwise noted.

basal interval. The terms “basal spacing,” “basal d001 spacing,” or “d001 spacing,” when used in the context of smectite clays such as montmorillonite, generally refer to the angstrom or nanometer spacing between similar planes of adjacent layers within the clay structure. Refers to a distance expressed in meters. Thus, for example, in the 2:1 family of smectite clays, including montmorillonite, the basal distance is from the top of a tetrahedral sheet to the top of the next tetrahedral sheet in an adjacent 2:1 layer, with or without modification or strut formation. is the distance to and including the intervening octahedral sheets. Basal spacing values are measured using X-ray diffraction analysis (XRD) of the d001 plane. For example, natural montmorillonite found in bentronite has a basal spacing range of about 12 Å to about 15 Å. (See, for example, the Fifth National Conference on Clays and Clay Minerals, National Academy of Sciences, National Research Council, Publication 566, 1958: Proceedings of the Conference ce: "Heterogeneity In Montmorillonite", JL McAtee, Jr., pp. 279- 88 and Table 1 at p.282.) For XRD test methods for determining basal spacing see Pillared Clays and Pillared Layered Solids, R.E. A. Schoonheydt et al. , Pure Appl. Chem. , 71(12), 2367-2371, (1999), and US Pat. No. 5,202,295 (McCauley) at column 27, lines 22-43.

zeta potential. The term "zeta potential" as used herein refers to the stern layer (a layer of tightly attached counterions formed to neutralize the surface charge of colloidal particles) and the diffusion layer (rather than a stern layer) refers to the difference in electrical potential between the junction with the loosely attached ion cloud (which also exists far from the particle surface) and the bulk solution or slurry. This property is expressed in units of voltage, such as millivolts (mV). Zeta potential, as described in US Pat. No. 5,616,872, incorporated herein by reference, is the generation of ultrasound waves as a result of the application of an electrical potential across a colloidal suspension. can be obtained by quantifying the "sonic amplitude effect" (ESA).

hydrocarbyl group. The term "hydrocarbyl group," as used herein, refers to a monovalent, linear, branched, or cyclic group formed by removing a monovalent hydrogen atom from a parent hydrocarbon compound, Used according to art-recognized IUPAC definitions. Unless otherwise specified, hydrocarbyl groups can be aliphatic or aromatic, can be saturated or unsaturated, and can contain linear, cyclic, branched, and/or fused ring structures, any of which unless otherwise specifically excluded. See IUPAC Compendium of Chemical Terminology, ^2nd Ed (1997) at 190. Examples of hydrocarbyl groups include, but are not limited to, aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, cycloalkadienyl, alkynyl, aralkyl, aralkenyl, and aralkynyl groups.

heterohydrocarbyl groups. The term "heterohydrocarbyl" refers to a monovalent, linear, monovalent, straight-chain, It is used in this disclosure to include branched or cyclic groups. The parent heterohydrocarbon may be aliphatic or aromatic. Examples of "heterohydrocarbyl" groups include halide substituents, nitrogen substituents, phosphorus substituents, silicon substituents, oxygen substituents, and sulfur substituents in which the hydrogen is removed to form a carbon atom to generate a free valence. Hydrocarbyl groups are included. Examples _{of heterohydrocarbyl} groups include _-CH2OCH3 , _{-CH2SPh , -CH2NHCH3} , _{-CH2CH3NMe2 , -CH2SiMe3 , -CMe2SiMe3 , -CH2} (C _6H4-4 -OMe), _-CH2 ( _{C6H4-4 -} NHMe _{) , -CH2} ( _C6H4-4 - _{PPh2 )} , _{-CH2CH3PEt2 , -CH2Cl} , —CH ₂ (2,6-C ₆ H ₃ Cl ₂ ), and the like.

Heterohydrocarbyl includes both heteroaliphatic (including saturated and unsaturated) and heteroaromatic groups. Thus, heteroatom-substituted vinyl groups, heteroatom-substituted alkenyl groups, heteroatom-substituted dienyl groups, and the like are all encompassed by heterohydrocarbyl groups.

Organoheteryl group. The term "organoheteryl" group is also used according to the art-recognized IUPAC definition as a carbon-containing monovalent group, thus being organic but having its free valence at an atom other than carbon. . See IUPAC Compendium of Chemical Terminology, ^2nd Ed (1997) at 284. Organoheteryl groups can be linear, branched, or cyclic and can be alkoxy, aryloxy, organothio (or organylthio), organogermanium (or organylgermanium), acetamido, acetonylacetanate, alkylamido, dialkylamido. , arylamido, diarylamido, trimethylsilyl and other common groups. —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 , groups such as hexafluoroacetonylacetanate.

Organyl group. Organyl groups have one free valency at a carbon atom according to the IUPAC definition, for example CH ₃ CH ₂ —, ClCH ₂ C—, CH ₃ C(═O)—, 4-pyridylmethyl, etc., regardless of functional type. used in this disclosure to refer to any organic substituent. Organyl groups may be linear, branched or cyclic and the term "organyl" is used in conjunction with other terms such as organylthio- (eg MeS-) and organyloxy. may be

heterocyclyl group. The IUPAC Compendium compares organyl groups with other groups such as heterocyclyl and organoheteryl groups. These terms are described in the IUPAC Compendium of Chemical Terminology, ^2nd Ed (1997) as follows, which uses the "-yl" suffix from the missing hydrogen to a portion of a molecule or group with valences. indicates a convention for associating terms. A heterocyclyl group is thus defined as a monovalent group formed by removing a hydrogen atom from any ring atom of a heterocyclic compound. For example, in both the piperidin-1-yl and piperidin-2-yl groups shown below, the lines drawn from the nitrogen or carbon atoms represent the free valences and are heterocyclyl groups, not methyl groups. be.

However, the piperidin-1-yl group is also considered an organoheteryl group and the piperidin-2-yl group is also considered a heterohydrocarbyl group. Thus, "heterocyclyl" valences can occur on any suitable ring atom, while "organoheteryl" valences occur on heteroatoms and heterohydrocarbyl valences occur on carbon atoms.

hydrocarbylene and hydrocarbylidene groups; A "hydrocarbylene" group is also a divalent group formed by removing two hydrogen atoms from a hydrocarbon, as described in the IUPAC Compendium of Chemical Terminology, ^2nd Ed (1997). , is defined according to its common and customary meaning, with its free valences not engaged in double bonds. Examples of hydrocarbylene groups include, for example, 1,2-phenylene, 1,3-phenylene, 1,3-propanediyl (—CH ₂ CH ₂ CH ₂ —), cyclopentylidene (=CC ₄ H ₈ ), Alternatively, a methylene that does not form a double bond in a bridge (—CH ₂ —) can be mentioned. Hydrocarbylene groups whose free valences are not engaged in double bonds are distinguished from hydrocarbylidene groups such as alkylidene groups.

A "hydrocarbylidene" group is a divalent group formed from a hydrocarbon by removing two hydrogen atoms from the same carbon atom, the free valences of which are part of a double bond. An alkylidene group is an exemplary hydrocarbylidene, defined as a divalent group formed from an alkane by removing two hydrogen atoms from the same carbon atom, the free valences of which are part of the double bond. is. Examples of alkylidene groups such as =CHMe, CHEt, = _CMe2 , =CHPh, or methylene where the methylene carbon forms a double bond (= _CH2 ).

heterohydrocarbylene and heterohydrocarbylidene groups. The term "heterohydrocarbylene" group is used to refer to a divalent group analogous to a hydrocarbylene group and formed by removing two hydrogen atoms from the parent heterohydrocarbon molecule. A valence is not engaged in a double bond. Hydrogen atoms can be removed from two carbon atoms, two heteroatoms, or one carbon and one heteroatom such that the free valences are not engaged in double bonds. Examples of "heterohydrocarbylidene" groups include -CH ₂ OCH ₂ -, -CH ₂ NPhCH 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 -, and the like.

Analogously to hydrocarbylidene, a "heterohydrocarbylidene" group is a divalent group formed from a heterohydrocarbon by the removal of two hydrogen atoms from the same carbon atom, the free valence of which is two. Part of a double bond. Examples of heterohydrocarbylidene groups include, but are not limited to, groups such as = _CHNMe2 , =CHOPh, = _CMeNMeCH2Ph , = _CHSiMe3 , = _CHCH2Cl .

Halides and Halogens. The terms "halide" and "halogen" are used herein to refer to ions or atoms of fluorine, chlorine, bromine, or iodine, individually or in any combination, as the context and chemistry permits or dictates. used in These terms can be used synonymously regardless of the charge or bonding mode of these atoms.

polymer. The term "polymer" is used generically herein to include olefin homopolymers, copolymers, terpolymers, and the like. Copolymers are derived from an olefinic monomer and one olefinic comonomer, while terpolymers are derived from an olefinic monomer and two olefinic comonomers. Thus, "polymer" includes copolymers, terpolymers, etc. derived from any of the olefinic monomers and comonomers disclosed herein. Similarly, ethylene polymers include ethylene homopolymers, ethylene copolymers, ethylene terpolymers, and the like. Thus, olefin copolymers such as ethylene copolymers may be derived from ethylene and comonomers such as propylene, 1-butene, 1-hexene, or 1-octene. When the monomer and comonomer were ethylene and 1-hexene respectively, the resulting polymer is classified as an ethylene/1-hexene copolymer. Similarly, the term "polymerization" includes homopolymerization, copolymerization, tripolymerization, and the like. For example, a copolymerization process involves contacting one olefinic monomer, such as ethylene, with one olefinic comonomer, such as 1-hexene, to produce a copolymer. Known abbreviations for polyolefin types may be used herein, such as "HDPE" for high density polyethylene.

Where the context permits or requires, the term "polymer" is used herein to refer to inorganic compositions used in the preparation and formation of pillars in modified clays. For example, the pillars may be composed of polymeric cationic hydroxymetal complexes of metals such as aluminum, zirconium, and/or titanium, such as aluminum chlorohydrate complexes (also known as "salt hydrates" or "chlorine hydrates"). are known to form in smectite clays based on the use of Inorganic copolymers, including composites, are also known. See, for example, US Pat. No. 4,176,090 and US Pat. No. 4,248,739. Furthermore, unless explicitly stated otherwise, the term polymer is not limited by molecular weight and thus includes both low molecular weight polymers, sometimes referred to as oligomers, and high molecular weight polymers.

procatalyst. The term "procatalyst" as used herein, whether a Lewis or Bronsted acid, when activated by an aluminoxane, borane, borate or other acidic activator, or the present It means a compound that is capable of polymerizing, oligomerizing or hydrogenating olefins when activated by a support activator as disclosed herein.

Additional explanation of terms. Additional explanations of the following terms are provided in the Fully Disclosed Aspects and Claims of this disclosure.

Unless otherwise specified or required by context, the chemical formulas of the polymetalates used as heterocoagulants disclosed herein are empirical formulas. Thus, formulas such _as (Al,Mg) _2Si4O10 (OH) ₂ ( _{H2O ) 8} are empirical polymetalate formulas that can be considered to encompass oligomeric or polymeric species, _FeOx Formulas such as (OH) _y ( _H2O ) _z ] ⁿ⁺ can also be considered to include oligomers or polymers where the variable subscript need not be an integer.

Several types of numerical ranges are disclosed herein including, but not limited to, numerical ranges for number of atoms, basal spacing, weight ratios, molar ratios, percentages, temperature, and the like. When disclosing or claiming a range of any type, it is Applicant's intent that each number that such range could reasonably be encompassed by, consistent with the written description and context, the endpoints of the range, and any subranges and combinations of subranges subsumed therein. For example, applicant discloses or claims a chemical moiety having a certain number of carbon atoms, such as a C1-C12 (or _C1 - _C12 ) alkyl group, or an alternative language having 1-12 carbon atoms. Applicant's intention is to include alkyl groups having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms, and (e.g. C1-C6 alkyl groups) and any combination of ranges between these two numbers (e.g. C2-C4 and C6-C8 alkyl group). Applicant claims in scope or similar manner if, for any reason, applicant chooses to claim less than the full scale of the disclosure, e.g., in light of references not known to applicant at the time of filing We reserve the right to exclude or exclude individual members of any such range or group, including any subrange or combination of subranges within a group, where possible.

In another aspect, any range of numbers recited in the specification or claims that represent a particular set of properties, units of measure, conditions, physical states, or percentages may be referred to by reference, or Otherwise, any number falling within that range is expressly intended to be incorporated herein, including any subset of numbers within that range so recited. For example, when a numerical range is disclosed having a lower bound, RL, and an upper bound, RU, any numerical value R falling within that range is specifically disclosed. In particular, the following numbers R within the scope are specifically disclosed:
R = RL + k (RU - RL),
where k is a variable ranging from 1% to 100% with 1% increments, eg k is 1%, 2%, 3%, 4%, 5% . . . . 50%, 51%, 52%. . . . 95%, 96%, 97%, 98%, 99% or 100%. Moreover, any numerical range represented by any two values of R, as calculated above, is also specifically disclosed.

For any specific compound disclosed herein, any generic or specific structure presented is, unless otherwise indicated, all stereoisomers, positional isomers that can arise from a particular set of substituents. , and stereoisomers. Similarly, unless otherwise specified, generic or specific structures also refer to enantiomers, diastereomers, and other optical isomers (either in enantiomer or racemate form) as recognized by those skilled in the art. ), as well as mixtures of stereoisomers.

Unless otherwise stated, values or ranges are used in this disclosure by the term "about," e.g., "about," greater or less than the stated value, or "about," It can be expressed using a range from one value to "about" another value. When such values or ranges are expressed, other disclosed embodiments refer to the particular recited values, ranges between the particular recited values, and other values proximate to the particular recited values. including. In one aspect, use of the term "about" means ±15% of the stated value, ±10% of the stated value, ±5% of the stated value, or ±3% of the stated value. For example, when the term "about" is used as a modifier to or in connection with a variable, characteristic or condition, any numerical value, range, characteristic or condition disclosed herein may vary slightly from the stated range. The use of properties such as temperature, rate, time, concentration, amount, content, basal spacing, size including pore size, pore volume, surface area, etc. that deviate or differ from a single stated value. Practice of the present disclosure by those skilled in the art will result in the desired results described herein, such as the preparation of porous catalyst support particles with defined properties and their use in the preparation of active olefin polymerization catalysts and olefin polymerization processes employing such catalysts. It is meant to convey that it is flexible enough to reach.

The terms "a," "an," "the," etc. (eg, "this") are intended to include multiple alternatives, such as at least one, unless specified otherwise. For example, a disclosure of "support activator," "organoaluminum compound," or "metallocene compound" refers to one or more mixtures of one or more of the catalyst support activator, organoaluminum compound, or metallocene compound, respectively. or any combination is intended to be included.

The term "comprising" and variations thereof such as "comprise," "comprises of," "having," "including," etc. may be used in a transitional phrase or in the specification. are inclusive and open and do not exclude additional, unlisted elements or method steps. The transitional phrase “consisting of” and variations thereof excludes any element, step, or ingredient not specified in the claim. The transitional phrase "consists essentially of" substantially affects the scope of the claim to the specified components or steps as well as to the basic and novel features of the claimed invention. limited to ingredients or processes that do not give Unless otherwise indicated, a description of a compound or composition as "consisting essentially of" includes materials in which the phrase does not significantly alter the composition or the manner in which the term is applied. It should not be interpreted as "comprising" as it is intended to describe the listed components. For example, a precursor or catalyst component can consist essentially of a material that, when prepared by a particular procedure, can contain impurities commonly present in commercially manufactured samples of the material. . When a claim includes different features and/or feature classes (e.g., process steps, feedstock features, and/or product features, among other possibilities), the transition term is only the feature class utilized. Including, consisting essentially of, and consisting of, it is possible to have different transition terms or phrases utilized with different features within the claims. For example, a method may include some of the steps listed (and other steps not listed), but utilize specific or alternatively catalyst system preparations that consist essentially of specific steps. utilizes a catalyst system that includes the listed components and other unlisted components. When compositions and processes are described in terms of "comprising" various components or steps, the compositions and processes may also "consist essentially of" or "consist of" various components or process steps. .

Unless otherwise defined with respect to a particular property, characteristic or variable, the terms “substantial” and “substantially” as applied to any criterion such as a property, characteristic or variable refer to a benefit achieved or a desired It means meeting a stated criterion on a sufficient scale that one skilled in the art would understand that a condition or property value is met. For example, the term "substantially" when describing a metallocene catalyst or catalyst system that is substantially free or substantially absent of aluminoxanes, borate activators, protonic acid treated clays, or pillared clays. can be used for In other words, the terms "substantially" and "substantially" rationally describe the subject matter as its scope is understood by those of ordinary skill in the relevant art, and reduce the claimed subject matter to any prior art. play a differentiating role. In one aspect, "substantially free" is used to add to the composition the listed ingredients that the composition is substantially free of, and to limit the amount of impurities, e.g., purity limits of other ingredients. Compositions can be described in which only amounts derived from or produced as a by-product are present. In a further aspect, when a composition is said to be "substantially free" of a particular component, the composition is less than 20% by weight of the component, less than 15% by weight of the component, less than 10% by weight of the component, It can have less than 5% by weight, less than 3% by weight of the component, less than 2% by weight of the component, less than 1% by weight of the component, less than 0.5% by weight of the component, or less than 0.1% by weight of the component.

The terms "optionally", "optional", etc., 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 claims, and it is contemplated that the claims may encompass either or both alternatives.

References to the periodic table or groups of elements within the periodic table are published by the International Union of Pure and Applied Chemistry (IUPAC) and are available at http://old. iupac. Refers to the Periodic Table of the Elements published online at org/reports/periodic_table/ (edition February 19, 2010). Using the IUPAC system for numbering groups of elements as Groups 1-18, refers to a "group" or "groups" of the periodic table as reflected in the periodic table of the elements. To the extent that any group is identified by Roman numerals according to the Periodic Table of the Elements as set forth, for example, in "Hawley's Condensed Chemical Dictionary" (2001) (the "CAS" system), the group is designated to avoid confusion. further identifies one or more elements of and provides cross-references to numerical IUPAC identifiers.

Various patents, publications and documents are disclosed and referenced herein. Each reference cited in this disclosure, whether patent, publication, or other document, is hereby incorporated by reference in its entirety, unless otherwise indicated.

References that may provide some background information related to the present disclosure include, for example, U.S. Pat. Nos. 5,360,775, 5,753,577, 5,973,084, 6,107,230, 6,531,552, 6,559, 090, 6,632,894, 6,943,224, 7,041,753, 7,220,695, 9,751,961 and U.S. 2018/0142047 and 2018/0142048, each of which is incorporated herein by reference in its entirety. Additional publications that may provide some background information related to this disclosure are:
Gu, B.; Doner, H.; E. , Clay and Clay Minerals, 1991, 38(5), 493-500,
Covarrubias et al. , Applied Catalysis A: General, 347(2), 15 September 2008, 223-233,
Tayano et al. , Clay Science, 2016, 20, 49-58,
Tayano et al. , Macromolecular Reaction Engineering, 2017(11), 201600017,
Journal of Molecular Catalysis A: Chemical, 2016, 420, 228-236,
Clay Science, 2016, 20, 49-58,
Finevich et al. , Russian Journal of General Chemistry 2007, 77(12), 2265-2271,
Bibi, Singh, and Silvester, Applied Geochemistry, 2014, 51, 170-183,
Sharma et al. , Journal of Material Science, 2018, 53, 10095-10110,
Okada et al. , Clay Science, 2003, 12, 159-163,
Sucha et al. , Clay Minerals, 1996, 31, 333-335,
Vlasova et al. , Science of Sintering, 2003, 35, 155-166,
Kline and Fogler, Industrial & Engineering Chemistry Fundamentals, 1981, 20(2), 155-161,
Ocelli, Clay and Clay Minerals, 2000, 48(2), 304-308,
Kooli, Microporous and Mesoporous Materials; 2013, 167, 228-236,
Pergher and Bertella, Materials, 2017, 10, 712, and Tsvetkov et al. , Clay and Clay Minerals, 1990, 38(4), 380-390,
, each of which is incorporated herein by reference in its entirety.

B. Overview The support activator of the present disclosure starts with a slurry of expanded clay in a liquid carrier, such as a smectite or dioctahedral smectite clay, and has at least one cation prepared under the conditions specified herein. may be formed by contacting the clay in the slurry with a heterocoagulant reagent comprising a polymetalate. The heterocoagulated clay form is very conveniently isolated by filtration, then dried and calcined to provide a support activator useful for supporting and activating metallocene catalysts towards olefin polymerization. can do. Formation of clay heteroadducts in good yields controls the ratio or amount of heterocoagulation reagent used relative to clay, as measured by zeta potential measurements of the slurry in which the clay heteroadducts are formed. can be achieved by Thus, a clay heteroadduct comprises [1] a smectite clay, such as a colloidal smectite clay, and [2] at least one cationic polymetalate, and has a zeta potential in the range of about positive 25 mV (millivolts) to about negative 25 mV. and a sufficient amount of the heterocoagulating reagent to provide a slurry of the resulting clay heteroadduct having the contact product in the liquid.

The smectite clay is mixed with the just specified clay such that the resulting slurry has a zeta potential greater than about +25 mV, occurring between a cationic polymetalate such as aluminum chlorohydrate (ACH) and the colloidal smectite clay. When more moles per gram of the cationic polymetalate is used to contact the heterocoagulant reagent in the liquid carrier, greater than about 2.3 mmol Al/g clay, greater than about 2.5 mmol Al/g clay, about Using recipes of greater than 2.7 mmol Al/g clay, or greater than about 3.0 mmol Al/g clay (millimoles of Al per gram of clay), correspondingly large amounts of columnar clay can be formed. A slurry of the desired smectite heteroadduct can contain several corresponding pillared clays, as observed by X-ray powder diffraction (XRD), and the formation of some of the pillared clays is associated with support activation. Secondary or incidental to agent formation, but having too high a concentration of pillared clay relative to the clay heteroadduct, the support activator is such that the ease of separation of the support activator is compromised. , resulting in a loss of immediate filterability of the slurry. Contacting the smectite clay with the heterocoagulant reagent in the liquid carrier using a lower number of cationic polymetalates per gram of clay such that the resulting slurry has a zeta potential of less than about −25 mV, the cation less than about 0.5 mmol Al/g clay, less than about 0.6 mmol Al/g clay, or less than about 0.8 mmol Al/g clay when using polymetallate aluminum chlorohydrate (ACH) and colloidal smectite clay. Less than, or in some cases less than about 1.0 mmol Al/g clay (millimoles of Al per gram of clay) clay may be formed, leaving a significant amount of colloidal smectite clay.

Also, in contrast to pillared clay support activators and similar clay-based activators used to support and activate metallocene catalysts, the clay heteroadduct support activators of the present disclosure are: It has also been unexpectedly discovered to have little or no use in subsequent washing steps after isolation by filtration. That is, the isolated heteroadduct support activator can be obtained without extensive or time-consuming purification, washing, or other such purification steps commonly used with other clay-based supports. can be used directly in catalyst formation with metallocenes and cocatalysts such as aluminum alkyls. This advantage can provide substantial economic advantages and enhanced ease of use when preparing olefin polymerization catalysts.

Accordingly, in one aspect, the present disclosure provides a support activator comprising an isolated smectite heteroadduct, wherein the smectite heteroadduct comprises [1] a colloidal smectite clay; [2] at least one contacting in a liquid with a heterocoagulant reagent in an amount sufficient to provide a slurry of smectite heteroadducts comprising a cationic polymetalate and having a zeta potential in the range of about positive 25 mV (millivolts) to about negative 25 mV; Contains products.

The present disclosure also provides, in another aspect, a method of making a support activator comprising a smectite heteroadduct, the method comprising:
a) providing a colloidal smectite clay;
b) colloidal smectite clay in an amount sufficient to provide a smectite heteroadduct slurry comprising at least one cationic polymetalate and having a zeta potential in the range of about positive 25 mV (millivolts) to about negative 25 mV; and contacting the heterocoagulant reagent with the liquid carrier.

The method can further comprise c) isolating the smectite heteroadduct from the slurry.

According to a further aspect, the present disclosure provides a catalyst composition for olefin polymerization, the catalyst composition comprising:
a) at least one transition metal catalyst such as a metallocene compound;
b) optionally at least one cocatalyst;
c) at least one supported active agent comprising a calcined smectite heteroadduct, the smectite heteroadduct comprising [1] a colloidal smectite clay; and [2] at least one cationic polymetalate in a liquid carrier; and in an amount sufficient to provide a slurry of smectite heteroadducts having a zeta potential in the range of about positive 25 mV (millivolts) to about negative 25 mV. and an agent.

In a still further aspect, a method of making an olefin polymerization catalyst, the method comprising, in any order,
a) at least one transition metal catalyst such as a metallocene compound;
b) optionally at least one cocatalyst;
c) with at least one support activator comprising a calcined smectite heteroadduct as described in accordance with the present disclosure.

Yet another aspect of the present disclosure is an olefin polymerization process comprising contacting at least one olefin monomer and a catalyst composition under polymerization conditions to form a polyolefin, wherein the catalyst composition comprises:
a) at least one transition metal catalyst such as a metallocene compound;
b) optionally at least one cocatalyst;
c) at least one support activator comprising a calcined smectite heteroadduct as described herein.

The examples, data, and disclosure of this written description provide detailed information of various aspects and embodiments for making and using the support activator and catalyst compositions described herein. See the aspect of The following sections provide some specific details of the components used to prepare the catalyst composition and to polymerize olefins using the catalyst composition.

C. Colloidal Smectite Clays In addition to the definitions section, the following disclosure provides additional information related to smectite clays.

Expanded clays, such as smectites or 2:1 dioctahedral smectite clays, or combinations of expanded clays can be used in preparing the support activator described herein. These expanded clays can be described as phyllosilicates or phyllosilicate clays, as specific members of the phyllosilicate clay mineral group can be used. Suitable starting clays may include layered, naturally occurring or synthetic smectites. Starting clays can also include dioctahedral smectite clays. Additionally, suitable starting clays may also include clays such as montmorillonite, sauconite, nontronite, hectoronite, beidellite, saponite, bentonite, or any combination thereof. Smectites are 2:1 layered clay minerals that carry lattice charges and can be swollen when solvated with water and alcohols. Suitable starting clays therefore include, for example, monoion-exchanged dioctahedral smectites such as lithium-, sodium-, or potassium-exchanged clays, or combinations thereof.

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

Layered smectite clays are 2: Also called clay. These structures are therefore also referred to as "TOT" (tetrahedron-octahedron-octahedron) structures. These sandwich structures are stacked one on top of the other to produce clay particles. This configuration yields approximately 9 Angstroms and half Angstroms (Å) of A repeating structure can be provided to provide greater space between the natural clay layers.

In one aspect, the clay used to prepare the support activator can be a colloidal smectite clay. Thus, the smectite clay can have an average particle size of less than about 10 microns (microns), less than about 5 microns, less than about 3 microns, less than 2 microns, or less than 1 micron, where the average particle size is greater than about 15 nm, greater than about 25 nm, Greater than about 50 nm, or greater than about 75 nm. That is, any range of clay particle sizes between these recited numbers is disclosed. Clays that cannot give colloidal suspensions can be used, but they are less preferred than colloidal clays.

In one aspect, the clay used to prepare the support activator is a divalent or trivalent ion-exchanged smectite such as Mg-exchanged montmorillonite or It may lack Al-ion exchanged montmorillonite. In another aspect, the clay used to prepare the support activator is mica or synthetic hector, as described in US Pat. Nos. 6,531,552 and 5,973,084. You may be missing a light. In a further aspect, the clay used to prepare the support activator may lack trihedral smectite or may lack vermiculite.

In one aspect, the smectite clay also has the formula:
(M ^A IV) ₈ (M ^B VI) _p O ₂₀ (OH) ₄ (wherein
a) M ^A IV is tetracoordinated Si ⁴⁺ and Si ⁴⁺ is optionally partially substituted by tetracoordinated cations that are not Si ⁴⁺ (e.g. cations that are not Si ⁴⁺ are Al ³⁺ , Fe ³⁺ , P ⁵⁺ , B ³⁺ , Ge ⁴⁺ , Be ²⁺ , Sn ⁴⁺ etc.),
b) M ^B VI is hexacoordinated Al ³⁺ or Mg ²⁺ and the Al ³⁺ or Mg ²⁺ is optionally partially substituted by a hexacoordinated cation that is not Al ³⁺ or Mg ²⁺ (e.g. Al ³⁺ or the non-Mg ²⁺ cations can be independently selected from Fe ³⁺ , Fe ²⁺ , Ni ²⁺ , Co ²⁺ , Li ⁺ , Zn ²⁺ , Mn ²⁺ , Ca ²⁺ , Be ²⁺ etc.),
c) p is 4 for a cation with a +3 format charge or p is 6 for a cation with a +2 format charge;
d) Any charge deficiency caused by partial substitution of cations that are not Si ⁴⁺ in M ^A IV and/or by partial substitution of cations that are not Al ³⁺ or Mg ²⁺ in M ^B VI are determined by the structure Balanced by cations intercalated between units (e.g., cations intercalated between structural units are selected from monocations, dications, trications, other multications, or any combination thereof can include structural units characterized by

The examples, data, and aspects of the disclosure section provide additional details of various aspects and embodiments of smectite clays.

D. Cationic Polymetalates Used in Heterocoagulant Reagents In addition to the "Definitions" section and aspects of the present disclosure, the following additional information further describes cationic polymetalates.

As explained in the Definitions section, the term “polymetalate” and similar terms such as “polyoxometalate” are defined by the addition of at least one bridging ligand between metals such as oxo, hydroxy and/or halide ligands to Refers to polyatomic cations containing more than one metal (eg, aluminum, silicon, titanium, zirconium, or other metals). For example, the polymetalates can be hydrated metal oxides, hydrated metal oxyoxides, etc., and can include bridging ligands, such as oxo ligands, that can bridge two or more metals in these species, and terminal Oxo, hydroxyl, and/or halide ligands may also be included. Although many polymetalate species are anionic and the suffix "-ate" is often used to reflect anionic species, the polymetalate (polyoxometalate) compounds used in accordance with this disclosure are cationic. is.

The heterocoagulant reagents of the present disclosure can be positively charged species that, when combined in appropriate proportions with a colloidal suspension of clay, form an easily filtered, easily washed coagulum. Positively charged species include soluble polyoxometalate, polyhydroxylmetalate, and polyoxohydroxymetallate cations, and related partially halide-substituted cations such as linear, cyclic, or cluster compounds. are polyaluminum oxyhydroxychloride or aluminum chlorohydrate or polyaluminum chloride species. These compounds are collectively referred to as polymetalates. The latter aluminum compounds can contain from about 2 to about 30 aluminum atoms.

Useful heterocoagulation reagents also include any colloidal species characterized by a positive zeta potential when dispersed in aqueous solvent or mixed aqueous and organic solvents (eg, alcohols). For example, useful dispersions of heterocoagulant reagents can exhibit zeta potentials greater than (>)+20 mV (positive 20 mV>), zeta potentials greater than +25 mV, or zeta potentials greater than +30 mV. The starting colloidal clay may contain monovalent ions or species such as protons, lithium ions, sodium ions, or potassium ions, but at least some, some, most, substantially all, or all of these ions are , is replaced by the heterocoagulant during the formation of a readily filterable clay heteroadduct. As discussed below, protons, lithium ions, sodium ions, potassium ions, and the like do not provide the filterability provided by the cationic polymetalates of the present disclosure. This feature can be observed by the long filtration times that occur when preparing and isolating hydrochloric acid treated support activators such as Examples 40 and 41.

Furthermore, unlike treatments that use strong concentrated acids to leach Al ions from montmorillonite, clay heteroadduct formation does not leach Al ions from the clay. When using aluminium-containing heterocoagulation reagents such as ACH or PAC, the aluminum content of the support activator is much less than that of the corresponding pillared clay, but actually equals that of the starting clay. increase than

In one aspect, the heterocoagulant reagent can comprise a colloidal suspension of Bohemian (aluminum hydroxide oxide) that provides a positive zeta potential (e.g., fumed alumina), or a metal oxide such as a fumed metal oxide. can. In another aspect, the heterocoagulant reagent can comprise chemically modified or chemically treated metal oxides, such as fumed silica treated with aluminum chlorohydrate, whereby when in suspension , the chemically treated metal oxides give a positive zeta potential, as described below. In a further aspect, the heterocoagulant reagent is produced by treating a metal oxide or metal oxide hydroxide or the like with the reagent in a fluidized bed, wherein the reagent exhibits a positive zeta potential when dispersed in suspension. bring. Heterocoagulants can exhibit positive values greater than +20 mV prior to combination with the phyllosilicate clay component.

In one aspect, the cationic polymetalate is in an amount sufficient to provide a colloidal suspension of the chemically treated first metal oxide having a positive zeta potential, e.g., a positive zeta potential greater than 20 mV (millivolts). can include a first metal oxide chemically treated with a second metal oxide, metal halide, metal oxyhalide, or a combination thereof. That is, the chemically treated first metal oxide comprises a first metal oxide, [1] a second metal oxide, i.e. another different metal oxide, [2] a metal halide, [3] ] metal oxyhalides, or [4] combinations thereof. For example, the first metal oxide that is chemically treated may be fumed silica, fumed alumina, fumed silica-alumina, fumed magnesia, fumed zinc oxide, fumed titania, fumed zirconia, fumed ceria, etc., or Any combination thereof can be included. The second metal oxide, metal halide, or metal oxyhalide is a metal oxide, hydroxide, oxyhalide, such as _ZrOCl2 , ZnO, _NbOCl3 , B(OH) ₃ , _AlCl3 , or combinations thereof. It can be obtained from a halide, or an aqueous solution or suspension of a halide. For example, the treatment may consist of dispersing the fumed oxide in a solution of aluminum chlorohydrate. For fumed silica, which can exhibit a negative zeta potential in suspension, after treatment with aluminum chlorohydrate, a suspension of chemically treated fumed silica exhibits a positive zeta potential of greater than about +20 mV. indicate.

In another aspect, the cationic polymetalate composition comprises [1] fumed silica, fumed alumina, fumed silica alumina, fumed magnesia, fumed zinc oxide, fumed titania, fumed zirconia, fumed ceria, or [2] polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichlorohydrate, polyaluminumoxyhydroxychloride, or any combination thereof chemically treated. For example, the cationic polymetalate composition comprises or consists of aluminum chlorohydrate-treated fumed silica, aluminum chlorohydrate-treated fumed alumina, aluminum chlorohydrate-treated fumed silica-alumina, or any combination thereof. can be selected.

While not intending to be bound by theory, the treated metal oxides exhibit a core-shell structure of positively charged shell and negative core such that the surface exhibits a positive zeta potential greater than about +20 mV. , or a continuous structure of mixed negative and positive regions or atoms. Some fumed metal oxides, such as fumed alumina, may already exhibit positive zeta potentials prior to chemical treatment. Nevertheless, fumed metal oxides that have no zeta potential or positive zeta potentials less than about +20 mV may be chemically treated with species such as aluminum chlorohydrate, and after treatment have a potential of about +20 mV. colloidal suspensions with zeta potentials exceeding .

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

In another embodiment, the heterocoagulation reagent is described in Lewis, et al. any colloidal inorganic oxide particles such as colloidal ceria or colloidal zirconia as described by U.S. Pat. No. 4,637,992, or any positively charged colloidal metal oxide disclosed therein. obtain. In another aspect, the heterocoagulant reagent can include magnetite or ferrihydrite. For example, the cationic polymetalate comprises or consists of bohemian, fumed silica alumina, colloidal ceria, colloidal zirconia, magnetite, ferrihydrite, any positively charged colloidal metal oxide, or any combination thereof. can be selected.

In another aspect, the heterocoagulant reagent is a cationic oligomeric or polymeric aluminum species in solution, such as aluminum chlorohydrate, also known as aluminum chlorohydrate (ACH), polyaluminum chloride (PAC), aluminum sesquichloro. hydrates, or any combination or mixture thereof. For example, a cationic polymetalate heterocoagulant reagent has the following empirical formula:
_Al2 (OH) _{nClm ( H2O} ) _x ,
(where n+m=6 and x is a number from 0 to about 4) or any combination of species.

In one aspect, the cationic polymetalate can comprise or be selected from an aluminum species having the formula [ _AlO4 ( _Al12 (OH) ₂₄ ( _H2O ) ₂₀ ] ⁷⁺ , which is the so-called "Al ₁₃ -mer” polycation and is considered a precursor of the Al ₁₃ pillared clay.

When using aluminum chlorohydrate as a heterocoagulant or chemical treatment reagent for treating other metal oxides, commercially available aluminum chlorohydrate (ACH) solutions or solid powders can be utilized. Aluminum chlorhydrate solutions are referred to as polymeric cationic hydroxyaluminum complexes or aluminum chlorohydroxide and are monomer precursors with a general empirical formula of 0.5 [ _Al2 (OH) _5Cl ( _H2O ) ₂ ]. Refers to polymers that are formed from the body. Preparation of aluminum chlorohydrate solutions is described in U.S. Pat. treating the amount of aluminum metal with hydrochloric acid.

Alternatively, the aluminum chlorhydrate solution is obtained using various aluminum sources such as alumina (Al ₂ O ₃ ), aluminum nitrate, aluminum chlorhydrate or other aluminum salts, and treatment with acid or base. be able to. A number of species that can be present in such solutions, such as the tridecameric [AlO ₄ (Al ₁₂ (OH) ₂₄ (H ₂ O) ₂₀ ] ⁷⁺ (Al ₁₃ -mer) polycation, are described by reference Perry and Shafran, Journal of Inorganic Biochemistry, 2001, 87, 115-124, which is incorporated herein.The species disclosed in this work, either individually or in combination, are in such solutions. The species present can be used as cationic polymetalates for the heterocoagulation of smectite clays.

In one aspect, the aqueous aluminum chlorohydrate solution used in accordance with the present disclosure can have an aluminum content, calculated or expressed as weight percent Al ₂ O ₃ , in the range of about 15 weight percent to about 55 weight percent. can be used, but more dilute concentrations can be used. Use of more dilute solutions can be accompanied by adjustments in other reaction conditions such as time and temperature, as will be appreciated by those skilled in the art. Alternate aluminum concentrations in aqueous aluminum polymetalate solutions, such as aqueous aluminum chlorohydrate solutions, expressed in weight percent Al ₂ O ₃ , range from about 0.1 weight percent to about 55 weight percent Al ₂ O ₃ , about 0.1 weight percent. 5 wt% to about 50 wt% Al ₂ O ₃ , about 1 wt% to about 45 wt% Al ₂ O ₃ , about 2 wt% to about 40 wt% Al ₂ O ₃ , about 3 wt% to about 37 wt% Al ₂ O ₃ , about 4 wt % to about 35 wt % Al ₂ O ₃ , about 5 wt % to about 30 wt % Al ₂ O ₃ , or about 8 wt % to about 25 wt % Al ₂ O ₃ and each range includes all individual concentrations expressed in tenths (0.1) of the weight percent subsumed therein, and includes any subranges therein. For example, a statement of about 0.1 wt% to about 30 wt% Al ₂ O ₃ includes a statement of 10.1 wt% to about 26.5 wt% Al ₂ O ₃ . Conveniently, the solid polymetalate can be used as solid aluminum chlorohydrate and added to the slurry of colloidal clay when preparing the heterocoagulum. Accordingly, the concentrations disclosed above are exemplary rather than limiting.

In one aspect, the cationic polymetalate comprises at least one additional metal selected from aluminum, zirconium, chromium, iron, or combinations thereof, according to U.S. Pat. No. 5,059,568, which is incorporated herein by reference. and a soluble rare earth salt, wherein the at least one rare earth metal is cerium, lanthanum, or a combination thereof. In one aspect, the heterocoagulant reagent can comprise an aqueous solution of lanthanides and Al ₁₃ keggin ions, as described by McCauley in US Pat. No. 5,059,568. However, the calcined clay heteroadducts of the present disclosure prepared using Macquarie-type polymetalates do not provide uniform intercalation structures with base spacing greater than 13 Å (angstroms). While not wishing to be bound by theory, it is believed that this observation may result from the much lower amount of Ce--Al heterocoagulation reagent to colloidal clay ratio used in accordance with the present disclosure. This smaller amount results from the conditions of contacting the smectite clay with the heterocoagulant reagent in an amount sufficient to provide a slurry of smectite heteroadducts with zeta potentials in the range of about +25 mV (millivolts) to about -25 mV. .

In a further aspect, exemplary polymetalates of the present disclosure can include [1] ε-Keggin cation [ε-PMo ₁₂ O ₃₆ (OH) ₄ {Ln(H ₂ O) ₄ } ₄ ] ⁵⁺ , where Ln is La , Ce, Nd or _Sm , [2] a lanthanide-containing cationic heteropolyoxovanadium cluster having the general formula [ _Ln2V12O32 ( _H2O ) ₈ {Cl} _] Cl, where Ln is Eu , Gd, Dy, Tb, Ho or Er.

In another aspect, the heterocoagulant is a layered double hydroxide, eg Abend et al. , Colloid Polym. Sci. 1998, 276, 730-731, or synthetic hematite, hydrotalcite, or other positively charged layered materials including, but not limited to, those described in US Pat. No. 9,616,412, incorporated herein by reference. It can be a double hydroxide. Thus, cationic polymetalates used as heterocoagulant reagents can be layered double hydroxides or mixed metal layered hydroxides. For example, mixed metal layer hydroxides can be selected from Ni--Al, Mg--Al, or Zn--Cr--Al types with positive layer charges. In another aspect, the layered double hydroxide or mixed metal layered hydroxide is magnesium aluminum hydroxide nitrate, magnesium aluminum hydroxide sulfate, magnesium aluminum hydroxide chloride, Mg _x (Mg,Fe) ₃ (Si,Al) ₄ O ₁₀ (OH) ₂ (H ₂ O) ₄ (where x is a number between 0 and 1, eg about 0.33 for ferrosaponite), (Al,Mg) ₂ Si ₄ O ₁₀ (OH) ₂ (H ₂ O) ₈ , synthetic hematite, zinc white (basic zinc carbonate) Zn ₅ (OH) ₆ (CO ₃ ) ₂ , hydrotalcite [Mg ₆ Al ₂ (OH) ₁₆ ]CO ₃ 4H ₂ O, taconite [Ni ₆ Al ₂ (OH) ₆ ]CO ₃ 4H ₂ O, hydrocalumite [Ca ₂ Al(OH) ₆ ] OH 6H ₂ O, magaldrate [Mg ₁₀ Al ₅ (OH) ₃₁ ] ( SO ₄ ) ₂ mH ₂ O, pyroaurite [Mg ₆ Fe ₂ (OH) ₁₆ ]CO ₃ 4.5 H ₂ O, ettringite [Ca ₆ Al ₂ (OH) ₁₂ ](SO ₄ ) ₃ 26 H ₂ O, or may comprise or be selected from any combination thereof.

In a still further aspect, the heterocoagulant reagent is used as described by Oades, Clay and Clay Minerals, 1984, 32(1), 49-57 or by Cornell and Schwertmann in "The Iron Oxides: Structure, Properties, Reactions , Occurrences and Uses”, 2003, Second Edition, Wiley VCH. Thionic polymetalates have the empirical formula FeO _x (OH) _y (H ₂ O) _z ] ⁿ⁺ where 2×+y is (<)3, z is a number from 0 to about 4, and n is a number from 1 to 3).

The use of cations such as protons, lithium ions, sodium ions, or potassium ions, as described in Examples 40 and 41, results in clay heteroadducts such as those provided by the cationic polymetalates of the present disclosure. For example, these acid treated clays are generally not readily filterable. While not wishing to be bound by theory, Nakano et al. Monovalent ions such as protons from HCl or _H2SO4 in aqueous solutions as described in U.S. Pat. _No. 6,531,552 and references therein, even using dilute or concentrated acids , unable to form stable, readily filterable heterocoagulating clay adducts. Colloidal dispersions of smectites, such as bentronite or montmorillonite, have a persistent negative charge and therefore exhibit a persistent negative zeta potential even at low pH. Again, without wishing to be bound by theory, at high acid concentrations at low pH (<3) the smectite colloidal dispersion becomes less negative, leading to negative zeta potentials of about 30 mV (−30 mV). It may even come close. (See Duran et al., Journal of Colloid and Interface Science, 2000, 229, p 107-117, which is incorporated herein by reference). However, it is believed that the clay structure itself is disrupted by peptidization of the octahedral alumina layers before the colloidal clay approaches a neutralized or nearly neutralized surface charge. (See Tayano et al., Macromolecular Reaction Engineering, 2017, 11, 201600017 and Clay Science 2016, 20, 49-58, each of which is incorporated herein by reference.) Octahedral alumina from the TOT structure Leaching of layers and dissolution of clay in strongly acidic solutions is described, for example, in US Pat. No. 3,962,135, Bibi, Singh, and Silvester, "Dissolution kinetics of kaolinite, illite and montmorillonite under acid-sulfate conditions: a com Parative study”, prepared for Clay Minerals, Chapter 4 (https://ses.library.usyd.edu.au/bitstream/handle/2123/8647/Chapter%204_Dissolution%20of%20illite, %20 montmorillonite.pdf?sequence = 5 rated manuscripts), and also https://pdfs. semantic scholar. org/6836/3c9c293dfd4255f9ad88678e1770c63384d3. pdf, and Dudkin et al. Chemistry for Sustainable Development, 2004, 12, 327-330, and Okada, et al. , Clay Science, 2003, 12, 159-165, each of which is incorporated herein by reference.

Without wishing to be bound by theory, other aprotic monovalent cations such as lithium, sodium, or potassium ions are added at points where coagulation of colloidal smectite particles can occur with the respective salt. It has been observed that this is attributed to shielding and reduction of Columbic repulsion between smectite particles. The concentration of monocations at which coagulation occurs is referred to as the critical coagulation concentration, and the concentration of monovalent cations required to achieve coagulation is generally higher than that required when divalent or trivalent cations are used. is also significantly higher. Again, without wishing to be bound by theory, monovalent cationic clay products are difficult to filter and may require centrifugation or isolation by high dilution and settling tanks. Without washing and removing monovalent ion salts, coagulated clays do not yield metallocene-support-activator catalysts with sufficient practical activity. Furthermore, to the extent that simple ion intercalations, such as sodium-exchanged montmorillonite or aluminum-exchanged montmorillonite, can be evident in the powder XRD of calcined clay heteroadducts, these materials can occur as unwanted by-products or colloidal It is believed to result from incomplete reaction of the clay and polymetalate.

In another aspect, the colloidal smectite clay can comprise or be selected from colloidal montmorillonite, such as Volclay® HPM-20 bentronite. The heterocoagulant reagent can comprise or be selected from aluminum chlorohydrate, polyaluminum chloride, or aluminum sesquichlorohydrate.

According to one aspect, the cationic polymetalate has the formula:
[M(II) _1−x M(III) _x (OH) ₂ ]A _x/n mL (I)
[LiAl ₂ (OH) ₆ ] A _1/n mL (II)
(In the formula,
M(II) is at least one divalent metal ion;
M(III) is at least one trivalent metal ion,
A is at least one inorganic anion;
L is an organic solvent or water;
n is the valence of the inorganic anion A, or in the case of multiple anions A, their average valence;
x is a number from 0.1 to 1,
wherein m is a number from 0 to 10), may include or be selected from conjugates of Formula I or Formula II, or any combination of conjugates of Formula I or Formula II.

In this aspect, M(II) can be zinc, calcium, strontium, barium, iron, cobalt, nickel, cadmium, manganese, copper, or magnesium, and independently M(III) is iron, chromium, can be manganese, bismuth, cerium, or aluminum, and A is, for example, hydrogen carbonate (bicarbonate), sulfate, nitrate, nitrite, phosphate, chloride, bromide, fluoride, hydroxide , or a carbonate, n may be, for example, a number from 1 to 3, and L may be, for example, methanol, ethanol, or isopropanol, or water. Further to this aspect, the cationic polymetalate is selected from the complexes of Formula I, wherein M(II) is magnesium, M(III) is aluminum and A is carbonate. obtain.

In one aspect, the cationic polymetalate can comprise polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichlorohydrate, or polyaluminumoxyhydroxychloride, or combinations thereof. In a further aspect, the cationic polymetalate can comprise linear, cyclic, or cluster aluminum compounds containing, for example, 2-30 aluminum atoms. Colloidal smectite clay of millimoles (mmol) of aluminum (Al) in polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichlorohydrate, or polyaluminum oxyhydroxychloride in recipes for preparing smectite heteroadducts. to grams (g), for example, from about 0.75 mmol Al/g clay to about 2.0 mmol Al/g clay, from about 0.8 mmol Al/g clay to about 1.9 mmol Al/g clay, from about 1.0 mmol Al/g clay to about 1.9 mmol Al/g clay. 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 Can be in the clay range. Alternatively, per gram (g) of colloidal smectite clay in recipes for preparing smectite heteroadducts, in polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichlorohydrate, or polyaluminum oxyhydroxychloride millimoles (mmol) of aluminum (Al) in is, 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, ratios thereof or any range therebetween. Combinations of subranges can also be included.

In a further aspect, isolated or calcined smectites of colloidal smectite clays of millimoles (mmol) of aluminum (Al) in polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichlorohydrate, or polyaluminum oxyhydroxychloride The ratio of the heteroadduct to grams (g) is about 90% of the comparative ratio of millimoles of aluminum to grams of the colloidal clay used to prepare the pillared clay using the same colloidal smectite clay and heterocoagulant reagent. 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.

In this aspect, the aluminum ingest to clay ratio in the recipe pillar is expressed in mmol Al/g clay, which indicates the number of mmoles of Al in the aluminum chlorohydrate reagent and the number of grams of clay in the recipe. Specifically, this ratio reflects the ratio used in the synthesis recipe, not the ratio of the final pillar clay product. As an example, considering the Al _13- type Keggin ion described in Ocelli, Clay and Clay Minerals, 2000, 48(2), 304-308, the amount of Al used to prepare the pillar clay is Much more than the amount of Al intercalated between layers in the solid. The use of excess aluminum reagent is used to provide maximum pillar content in the final product and to obtain the desired porosity and surface area of the final fired material. Kooli in Microporous and Mesoporous Materials; 2013, 167, 228-236 generally discloses that recipes require about 6 mmol Al/gram clay to optimize pillaring. A recent scale-up study and optimization of Al ₁₃ Keggin ion columnar viscosity, Pergher and Bertella in Materials, 2017, 10, 712, used 15 mmol Al/g clay and about 1 wt. % diluted dispersion is required.

E. Preparation and Properties of Clay Heteradducts (Heteroconsolidated Clays) Unlike pillared clays, the heteroconsolidated clays of the present disclosure are amorphous solids. Thus, the preparation of heterocoagulated clays provides three-dimensional structures, but non-columnar and non-crystalline and amorphous structures. Without intending to be bound by theory, it is believed that the regular crystal structure of the starting smectite is not simply extended upon contact with cationic polymetalates, as described, but rather clay heteroadducts is believed to break during the preparation of , providing a non-crystalline, non-ordered, non-lamellar amorphous material. Factors that can affect the formation of an amorphous three-dimensional structure include reaction time, reaction temperature, starting clay purity and clay particle size, drying method, etc., as described herein. In addition, it is readily determinable for each heterocoagulant reagent and clay system.

In preparing the clay heteroadduct, the heterocoagulant may be added to a slurry of colloidal clay, the colloidal clay may be added to a slurry or solution of the heterocoagulant, or the heterocoagulant and colloidal clay may be added to the liquid carrier. may be added at the same time or in overlapping periods. Alternatively, the heterocoagulant and colloidal clay can be added to the heel of the heteroadduct product, such as by adding the heterocoagulant and clay either as a solid or as a suspension to a vessel or reactor containing the water or hydrous heel. can be added at the same time.

In one aspect, the liquid carrier from which the clay heteroadduct is prepared can be water or an aqueous system to which additional ingredients such as alcohols and/or at least one surfactant can be added. Suitable surfactants may include anionic surfactants, cationic surfactants, or nonionic surfactants. Specific examples of liquid carriers or "diluents" and specific examples of surfactants are provided in the Aspects section of the disclosure.

As noted, the ratio of heterocoagulation reagent to clay used in the recipe provides a solidification product mixture such as a slurry having a zeta potential ranging from about positive (+) 25 mV (millivolts) to about negative (-) 25 mV. Defined as the giving ratio. Therefore, the amount of heterocoagulant added to a known clay sample, ie the ratio of cationic polymetalate (heterocoagulant) to clay, is determined by titrating the clay with the heterocoagulant. For example, if the heterocoagulant reagent comprises a cationic polymetalate of aluminum, the ratio of heterocoagulant reagent to clay can be reported in millimoles (mmol) of aluminum (Al) in the cationic polymetalate to grams (g) of clay. can. The actual amount of cationic polymetalate used to form the clay heteroadduct, i.e., the ratio of heterocoagulating agent to clay, may depend on factors such as the degree of positive charge of the cationic polymetalate, the zeta potential of the clay, and the like. The heterocoagulant reagent and clay are combined with the resulting slurry (dispersion) of heterocoagulant clay exhibiting a zeta potential in the range of about +25 mV to about -25 mV. Alternatively, the heterocoagulation reagent and the clay may be combined with the resulting dispersion of heterocoagulation clay at a voltage of about +22 mV to about -22 mV, about +20 mV to about -20 mV, about +18 mV to about -18 mV, about +15 mV to about -15 mV. , about +10 mV to about -10 mV, about +5 mV to about -5 mV, or about 0 mV.

As described in the Examples, the Colloidal Dynamic Zeta Probe Analyzer™ is a zeta potential measurement that involves dynamically tracking the evolving zeta potential during titration of a colloidal clay dispersion with a cationic polymetalate titrant. used for Exemplary results from zeta potential titrations are illustrated in the Figures and described in the Examples, with data presented in Tables 4-6, for example. For example, FIG. 3 plots the zeta potential of a series of dispersions formed during the titration of Volclay® HPM-20 montmorillonite with aluminum chlorohydrate (ACH), showing the cumulative titration volume of the added aqueous ACH solution. Plot (x) versus the zeta potential of the dispersion (mV, (y)). Similarly, FIG. 4 plots the cumulative mmol Al/g clay versus zeta potential (mV) of dispersions for the same titration. Samples of several solid products formed during this zeta potential titration of HPM-20 clay by ACH were collected and FIG. provides a powder XRD pattern of the sintered product of As a result, the comparison and correlation between mmol Al/g clay and zeta potential and the filterability of the resulting products revealed from this analysis that smectite heterogeneous compounds with zeta potentials ranging from about 25 mV (millivolts) When the clay and the heterocoagulant reagent comprising at least one cationic polymetalate are contacted in a liquid carrier in an amount or ratio that provides a slurry of the adduct, the resulting product is readily filterable and washed. It has been unexpectedly found that it can be used as a support activator with no or minimal washing and imparts high polymerization activity to supported metallocene catalysts.

In synthesis reactions or titrations using cationic polymetalates, calculating the ratio of millimoles of metal atoms in the polymetalate per mass of clay provides a useful index for comparisons between polymetalates. For example, in zeta-potential titrations using aluminum cationic polymetalates as heterocoagulant reagents, the ratio of millimoles of aluminum per clay mass is more directly proportional to the different Al-containing heterocoagulant reagents, as shown in the titration curve of FIG. allow for meaningful comparisons. Derivation of this value is performed by obtaining the aluminum weight percent of the heterocoagulant, which is typically provided directly by the manufacturer or as an aluminum oxide (eg, Al ₂ O ₃ ) equivalent percent. In the latter case, the aluminum weight percent can be derived from multiplying the aluminum weight percent in the empirical formula by the aluminum oxide weight percent. From this aluminum weight percent, the molar amount of aluminum heterocoagulant reagent can be determined to give the molar aluminum/clay mass ratio.

For example, FIG. 4 shows that the ratio of aluminum chlorohydrate (ACH) to Volclay® HPM-20 expressed in mmol Al/g of clay falling within the desired zeta potential range is 1.76 mmol Al/g clay. indicates that Actual ratios may vary slightly depending on aluminum chlorohydrate lot, method of preparation, contamination or age, and/or specific batches of Volclay® HPM-20. FIG. 2 shows the zeta potential titration of American Colloid Company's Volclay® HPM-20 with 22 wt % aluminum chlorohydrate from GEO Specialty Chemicals. Thus, mmol Al/g clay can be determined as the point at which the zeta potential of colloidal species in the mixture is less than +25 mV and greater than or equal to -25 mV, e.g. , provides a heterocoagulant solid that is readily isolated by conventional filtration methods such as using filter paper. Accordingly, immediate filtration of the resulting clay heteroadduct can be performed with or without vacuum assistance, belt filters, and the like.

The resulting heterocoagulated clay dispersions exhibit zeta potentials in the disclosed range centered around zero and provide readily isolatable (easily filterable) heteroadducts. Without wishing to be bound by theory, and without limiting the scope of zeta potentials disclosed and claimed herein, colloidal smectites (such as the dioctahedral smectites described herein) and When the amount of combined heterocoagulant reagents provides a particle dispersion with a zeta potential close to zero, the clay heteroadduct exhibits excellent retention such that the particles in the dispersion have little or no electrophoretic mobility. rate and filterability can be obtained. This zero zeta potential point can be considered the nominal target ratio of cationic polymetalate to colloidal clay. Aspects of electrophoretic mobility are described, for example, in Gu, et al. , Clay and clay minerals, 1990, 38(5), 493-500.

The experimentally derived ratio of heterocoagulant reagent (cationic polymetalate) to colloidal clay was determined by providing a dispersion of colloidal clay in water, adding the dispersion to a zeta potential measurement vessel, and increasing the initial zeta potential of the clay dispersion to It can be determined by measuring. A solution of the selected heterocoagulant is prepared and added in portions to the dispersion and the zeta potential of the dispersion is measured after each addition. The ratio of cationic polymetalate to colloidal clay used to prepare the readily filterable clay heteroadduct is determined by the heterocoagulation required to achieve zero or essentially zero zeta potential from the resulting zeta potential titration curve. Calculated by determining the ratio of reagents.

In a further aspect, when the zeta potential titration curve is ill-defined or discontinuous at or near zero potential (mV), extrapolation of the point closest to zero zeta potential is used to determine the zeta The crossing point at which the potential curve crosses from a negative to a positive zeta potential can be estimated, thus accounting for the nominal target ratio. In another aspect, if the zeta potential titration curve is discontinuous near zero and remains discontinuous at or near the zeta potential boundaries (e.g., ±20 mV or ±25 mV), the Linear extrapolation between points on the titration curve can be used to estimate the heterocoagulant to clay ratio useful to achieve the desired zeta potential. Examples of zeta probe (zeta potential) titrations and determination of nominal target ratios of heterocoagulation reagent to clay are provided in the Figures and Examples section of this disclosure. See, eg, FIGS. 2-8, Examples 8-12 and Example 38.

The ratio of aluminum (mmol Al) in aluminum chlorohydrate to grams of Volclay® HPM-20 colloidal montmorillonite, used to prepare the clay heteroadduct, was determined by the aluminum chlorohydrate to columnar HPM-20 clay. can be significantly lower, sometimes less than an order of magnitude, than the ratio of mmol Al/g clay used to prepare That is, by using the same cationic polymetalate and colloidal clay, but using a mmol Al/g clay ratio that exceeds the range defined by the zeta potential of about +25 mV to about -25 mV for the clay heteroadduct dispersion: A columnar clay is formed. Thus, the ratio of cationic polypolymetalate to colloidal clay to form the clay heteroadducts of the present disclosure is determined, for example, by W. et al., using lanthanide-containing-Al pillared clays as supporting actives. R. It differs from that used in US Patent Application Publication Nos. 2018/0142047 and 2018/0142048 to Grace.

Conversely, if the recipe contains too low a ratio of heterocoagulant reagent to clay to attempt to create a clay heteroadduct, ready filtration of the resulting contact product by conventional filtration means is not possible. This feature is exemplified in Example 19, a 0.30 mmol Al/g clay recipe for preparing clay heteroadducts using aluminum chlorohydrate (ACH) and HPM-20 clay, shown in FIG. If derived from zeta potential titration, a zeta potential of -44 mV is expected. Filtration of the resulting contact product was difficult and sample isolation and preparation required centrifugation to isolate the product. Products such as these may be conveniently referred to herein as "heteroadducts", even though they are outside the zeta potential range for ready filterability. Similarly, in Example 26, using a recipe of 0.30 mmol Al/g clay with powdered ALOXICOLL® 51P aluminum chlorhydrate (Parchem Fine and Specialty Chemicals) was difficult to process and isolate. A large contact product heteroadduct was obtained and centrifugation was required to isolate the product.

The starting clay particles, such as montmorillonite, are made permanent by ^isomorphic substitution of ^ions into one of the "TOT" layers, e.g. It carries a negative charge. Thus, the starting clay forms a dispersion or suspension in water as the negatively charged clay particles repel each other and become stabilized in a polar aqueous environment. Without wishing to be bound by theory, contacting a negatively charged colloidal clay with cations, such as the cationic polymetalates disclosed herein, results in coulombic attraction of the opposing charge and neutralization of the clay surface. It is thought to initially promote solidification of the colloidal clay through This neutralization precipitates the clay heteroadduct from the polar aqueous carrier as large flocculated or coagulated particles that are easily filterable. As additional cationic polymetalates are added to the coagulation composition in excess, such as when preparing ion exchange, protonic acid treatment or pillared clays, some or all of the aggregated surfaces are "recharged" as positively charged species. ”, thereby allowing resuspension in a polar carrier such as water. This resuspension provides a dispersion of highly charged species that are difficult to filter and block the filter media. It is believed that the clay heteroadducts of the present disclosure are formed under these high ratios, thereby avoiding refilling and resuspension of the clay heteroadducts. Thus, the near-zero zeta potential surface of the clay heteroadduct provides an easily filterable product, which, incidentally, substantially avoids pillar formation of the clay, and furthermore, uniformly distributes the pillar-forming and starting clays. Avoid intercalated clay structures. Surprisingly, even without pillars, these structures form thermally stable and strong structures that can serve as very active support activators for metallocenes.

In one aspect, FIG. 1 provides an overview of practical and desirable aspects of preparing neutral or weakly charged dispersions with low magnitude, near zero, or zero zeta potential. Filtration of clay heteroadducts with these properties proceeds rapidly and usually requires most sequential filtrations to produce a support with the desired surface area, porosity, and polymerization activity. In contrast, highly charged dispersions, such as the type resulting from the preparation of pillared clays, are not readily filterable and relatively expensive and cumbersome methods are used to obtain useful support activators. must be processed as

Also, W. R. Jensen et al. In contrast to other materials, such as those described by . may not be shown or substantially not shown. This feature is illustrated in the example of FIG. 2, which presents the powder XRD (X-ray diffraction) patterns of a series of fired products combining aluminum chlorohydrate (ACH) and Volclay® HPM-20 montmorillonite. , each sample differing in the amount of cationic polymetalate used to prepare the heterocoagulated clay. These samples were prepared according to Examples 18, 20-21, 23 and 25, except for the following examples. The sample marked as originating from the 6.4 mmol Al/g clay sample (top) represents a typical preparation of Al ₁₃ pillared clay (see Example 5). The XRD of the starting clay itself (bottom) is marked as coming from the 0 mmol Al/g clay sample (see Example 3).

Referring again to FIG. 2 and the Examples for preparing these samples, Examples 12 through 30 range from 0 mmol Al/g clay examined in this figure to 6.4 mmol Al, including some comparative examples. A preparative method for forming an ACH clay heteroadduct of /g clay is provided. As the XRD pattern below about 10 degrees 2-theta shown in Figure 2 shows, there are two major peak changes as the proportion of cationic polymetalate increases in the preparation recipe. First, the XRD peak at about 9 degrees 2-theta (2-theta) corresponding to the starting clay disappears, and the peak at about 9 degrees (2-theta) to about 10 degrees (2-theta) increases gradually as the proportion of cationic polymetalate increases. do. The disappearance of the 9-degree (2-theta) peak appears to indicate the course of the reaction to form a mostly amorphous heterocoagulated clay, and the subsequent 9-10-degree (2-theta) peak is the Al ³⁺ ion intercalating It likely represents a simple ion intercalation like ions and is characterized by a smaller basal spacing than earlier ion-exchange clays. As more polymetalate is added to the slurry, the peak grows at about 4 degrees (2-theta) to about 6 degrees (2-theta), with the tis peak representing the major product at 6.4 mmol Al/g clay. This 4-6 degree (2θ) peak likely corresponds to the Keggin ion-interacting pillar structure that forms as the concentration of added polymetalate increases. Since the clay concentrations in these experiments were not highly diluted (i.e. >1 wt% clay), the 6.4mmol Al/g clay product could not be easily isolated by simple filtration and It had to be isolated and washed using multiple centrifugation and decanting steps. In addition, the starting clay colloidal clay as a comparative sample also could not be easily filtered.

In one aspect, when aluminum chlorohydrate (ACH) is the heterocoagulant reagent and Volclay® HPM-20 montmorillonite is the colloidal clay, the zeta potential and XRD data show a zeta potential range of ±25 mV. , corresponding to a range from about 1 mmol Al/g clay to 1.8 mmol Al/g clay. Similarly, the ±15 mV zeta potential range where the clay heteroadducts are more charged corresponds to a range of about 1.3 mmol Al/g clay to 1.7 mmol Al/g clay. These data also indicated that a zeta potential of 0 (zero) mV for clay heteroadducts near zero charge corresponds to about 1.5 mmol Al/g clay. Figure 2 shows that at 1.52 mmol Al/g clay, powder XRD shows little or virtually no pillaring (4. 8 degrees (2-theta) to 5.2 degrees (2-theta)) and little or virtually no simple ion-exchange clay (9 degrees (2-theta) to 10 degrees (2-theta) XRD patterns).

While not wishing to be bound by theory, when using aluminum chlorohydrate and colloidal smectite, the nearly zero charge of the heteroadduct provided by the 1.5 mmol Al/g clay recipe is actually to Al ₁₃ represents less than about half the amount (ratio) of aluminum that can be incorporated into columnar smectites, and a much smaller fraction of the aluminum used in pillar recipes. For example, Schoonheydt et al. , Clay and Clay Minerals 1994, 42(5), 518-525, this amount being about 3-4 mmol Al/g clay actually incorporated. As noted above, the amount of heterocoagulation reagent that yields a zeta potential of the heteroadduct of 0 (zero) mV, which can be considered a preferred amount of about 1.5 mmol Al/g clay, is optimized at 15 mmol Al/g clay. This is less than the amount used in the pillar recipe. The clay heteroadducts of the present disclosure are characterized by the absence or substantial absence of regularly intercalated pillar structures, and the clay heteroadducts are more comparable and It was surprisingly found to provide more activity.

Clay heteroadducts of the present disclosure are described by Jensen et al. is not a regularly intercalated pillar structure as described in US Patent Application Publication Nos. 2018/0142047 and 2018/0142048. Specifically, the clay heteroadducts of the present disclosure are not or substantially microporous catalyst components comprising layered colloidal clays with multiple pillars intercalated between extended molecular layers of clay. is not regularly complex ion intercalation (“non-regularly intercalated”). Thus, the clay heteroadducts of the present disclosure are not regularly arranged and are derived from Al ₁₃ keggin ions or lanthanide-centered poly Al ₁₃ pillars such as U.S. Patent Application Publication Nos. 2018/0142047 and 2018/0142048. There is no evidence of consistent regularity imparted by consistent pillars and/or consistent intercalated aluminum oxide or hydroxide layers, such as does. However, powder XRD peaks indicating some pillaring can be detected, especially in some multiplicatively washed and filtered examples. For example, the XRD pattern of a 1.76 mmol Al/g clay sample corresponds approximately to a zeta potential of +23 mV, but the intensity of the peaks is substantially lower than that of a prismatic recipe using, for example, 6.4 mmol Al/g clay. relatively low.

Thus, in a further aspect, the calcined clay heteroadducts of the present disclosure do not exist in ordered domains, as evidenced by the lack of XRD peaks between 0 and 12 degrees 2-theta. This observation can be compared to simple monoatomic ion-exchange processes or complex polyatomic ion-exchange processes in which sodium ions (e.g. in the starting sodium montmorillonite) are exchanged for divalent, trivalent or polyvalent ions obtained after drying. and reflects the size of simple monoatomic ions or polyatomic ions such as Al ₁₃ Keggin ions, or other columnar species as evidenced by the relevant d001 basal spacing in XRD .

In one aspect, the isolated clay heteroadducts are collected, for example, by filtration and they are not washed. In another aspect, the isolated clay heteroadduct is minimally washed with a suitable washing liquid, eg, water, eg, only sufficient to provide some purification advantage. While not wishing to be bound by theory, for example, Schoonheydt et al. Clay and Clay Minerals 1994, 42(5), 518-525 have been observed to facilitate pillar cleaning. Thus, washing to the extent that pillar formation occurs appears to sacrifice the desired isolated clay heteroadduct to form the undesirable by-product pillared clay.

In another aspect of the disclosure, Jensen et al. In further contrast to regularly intercalated ion-exchange clays such as those disclosed in US Patent Application Publication Nos. 2018/0142047 and _2018/0142048 , the wash water has a negative AgNO3 test (chloride Extensive washing of the solid clay heteroadducts of the present disclosure is not necessary to impart high polymerization activity to the clay heteroadducts until they exhibit high polymerisation activity. In contrast, a single filtration of the immediate heteroadduct mixture containing about 5% by weight solids without dilute solution gives good polymerization activity in the final catalyst mixture. This feature is demonstrated, for example, in Examples 22, 24, 29-31, 33, and 35-36. For example, the difference in the preparation of the ACH clay heteroadduct between Example 22 and Example 23 is whether the product preparation used one filtration and two filtrations, the latter using Includes a single wash between Thus, in the preparation of clay heteroadduct Example 22 using single filtration, the filtrate obtained by filtering the slurry was characterized by a conductivity of 1988 μS/cm. In contrast, the clay heteroadduct Example 23 with two filtrations provided a conductivity of 87 μS/cm and washing between filtrates characterized by a nearly 23-fold difference. However, the polymerization activity of catalysts prepared using these support activators changed by only 10%, which one skilled in the art would recognize as within the range of variable bench-scale polymerization tests. .

Similarly, polymerizations using the support activators of Example 24 vs. Example 25 further point to the economically beneficial aspect of support activators, providing a single to two filtration of clay heteroadducts. Filtration again results in essentially the same polymerization activity. Specifically, the catalyst formed from a single filtration support activator showed 3581 g/g/hr compared to the 3547 g/g/hr observed for the catalyst formed from a dual filtration support activator. showed activity over time. The conductivity of the slurry of the single filtered product (Example 24) was 1500 μS/cm and the conductivity of the final slurry of the double filtered product (Example 25) was 180 μS/cm. Therefore, it was unexpectedly discovered that extensive washing of the clay heteroadducts was not necessary for good polymerization activity (again, US2018/0142047, US2018/0142048 (contrast with ).

Samples made according to Example 28 (additional washing step) and Example 29 (single filtration) using 1.52 mmol Al/g clay yielded 1404 g/g/h and 1513 g/g/h of catalyst, respectively. provided activity. In this comparison, the single-filtered heteroadduct slurry of Example 29, which had a conductivity of 1750 μS/cm, was washed and filtered twice after the first filtration, and the Example 28 sample had a slurry conductivity of 169 μS/cm. actually provided higher activity than In another aspect, and in further contrast to the supported active agents of U.S. Patent Application Publication Nos. 2018/0142047 and 2018/0142048, the clay heteroadduct slurry of the present disclosure, prior to isolation and use, Aging at room temperature or elevated temperature for at least 10 days is not required. Rather, the clay heteroadduct slurry of the present disclosure can be filtered immediately and then dried or calcined, thus providing a much more efficient synthesis of support activator.

The formation of heterocoagulants has not been found to be very temperature sensitive in that clays form heteroadducts with heterocoagulants over a wide range of temperatures. For example, clay heteroadduct formation proceeds in the range of about 20° C. to about 30° C., although temperatures ranging from about 0° C. to the boiling point of the slurry containing the clay heteroadduct can be used.

The pH of the solution containing the heterocoagulant can be adjusted to provide a minimum zeta potential of the heterocoagulant product, as described by Goldberg, et al, Clay and Clay Minerals, 1987, 35, 220-270. can be readily determined by experiment. The resulting heteroadducts isolated by this method can also be used with metallocenes for olefin polymerization. Further, this method for adjusting the zeta potential allows the heterocoagulant to clay ratio itself to be between the ±25 mV (or, alternatively, ±22 mV, ±20 mV, etc.) range disclosed herein. can be used if it does not result in a zeta potential of However, this pH adjustment method requires additional steps in the synthesis and isolation of the clay heteroadduct, and it has been observed that this method does not guarantee immediate filterability or optimal final polymerization activity. Without wishing to be bound by theory, it is believed that pH adjustment in such cases may result in protonated or hydroxylated clays, heterocoagulant reagents, and/or clay heteroadducts, It is believed that it may affect the properties of the heteroadduct and the ultimate catalytic activity.

In another aspect, the present disclosure provides for the removal of salts and small amounts of non-coagulated colloidal material formed in the preparation of heterocoagulation products. For example, soluble by-products such as sodium chloride, in addition to small amounts of colloidal material, are readily removed from the heterocoagulation product by simply filtering the heterocoagulation product after washing with water. Washing can be accomplished by resuspending the isolated heterocoagulum product in water with mechanical agitation or shaking to form a slurry, which can then be refiltered. This method generally requires multiple washing and separation steps using high speed centrifugation, decantation, pH change of pillar agent clay solutions, or large dilution and sedimentation tanks for separation of columnar viscosity products. Contrast with pillar process. Such additional steps take time and time to separate and clean the pillared or chemically treated clay mineral adduct from impurities such as its starting components, nano- or micro-sized quartz, and other inorganic metal oxides. add cost. Conversely, filtration of clay heteroadducts may be done in bulk through sintered glass frits, metal frits, common filter papers, felts or other filtration media, or continuously using moving belt filters. can be filtered effectively. Filtration is fast and practical, e.g., filtration takes no more than 1 minute, no more than about 5 minutes, no more than about 10 minutes, no more than about 15 minutes, no more than about 30 minutes, no more than about 1 hour, no more than about 2 hours, about It can be completed in 5 hours or less, about 8 hours or less, or about 24 hours or less.

The conductivity of the clay heteroadduct filtrate or slurry can be monitored using a commercially available conductance meter. In one aspect, the concentration of the slurry is within the range of about 1 wt% to about 10 wt% solids, about 2.5 wt% to about 10 wt% solids, or about 5 wt% to about 10 wt% solids. When the clay heteroadduct slurry has a /cm to about 15,000 μS/cm, alternatively about 1,000 μS/cm (1 mS/cm) to about 10,000 μS/cm (10 mS/cm).

The heterocoagulated solid may optionally be dried by azeotropic methods, as practiced in some examples. Azeotropic drying is believed to preserve pore volume and surface area during drying compared to simply heating the heterocoagulant solid. For example, the filtered smectite heteroadduct can be resuspended in a slurry with a solvent that lowers the boiling point of water present in the heterocoagulation product. This water lost during drying can be characterized as free water or chemically bound water. That is, the water lost during drying can come from free water located at the pores or outer surface of the heteroadduct and chemically bound water generated from dehydrated surface hydroxyls during the drying and calcination process. Various alcohols are useful as azeotropic agents including, but not limited to, 1-butanol, 1-hexanol, isopentanol, ethanol, and the like, including any combination thereof.

Freeze drying, flash drying, fluid bed drying, or any combination thereof can also be used to remove water from the clay heteroadduct. These methods, whether used alone or in combination during water removal, can help maintain pore volume and surface area during the drying process. In another embodiment, spray drying of the clay heteroadduct suspension can be used to control the support activator and supported catalyst particle morphology. For example, suspensions of clay heteroadducts in aqueous or organic solvents, or combinations of aqueous and organic solvents, can be spray dried. Dry or wet grinding and sieving can be used to refine the morphology, size and size distribution of the heterocoagulated clay. These methods can be used individually or in combination to achieve the desired support activator particle morphology, particle size and particle size distribution of the clay heteroadduct. Spray drying and/or sieving of the clay heteroadduct can be used and is known to those skilled in the art to remove fines or larger particles that pose problems in transporting or using the heteroadduct as a support activator. other methods can be used as well.

Heterosolidified solids can be calcined or heated in a fluidized bed, eg, at temperatures ranging from about 100°C to about 900°C. For example, the heterocoagulated smectite clay is calcined in a fluidized bed at temperatures ranging from about 100°C to about 900°C, from about 200°C to about 800°C, from about 250°C to about 600°C, or from about 300°C to about 500°C. or can be heated. Calcination can be carried out in an ambient atmosphere (air), for example calcination in dry air at a temperature in the range of at least 110° C., for example the temperature ranges from about 200° C. to about 800° C., and about Times ranging from 1 minute to about 100 hours can be carried out. For example, smectite heteroadducts can be prepared under the following conditions: a) a temperature ranging from about 110°C to about 600°C and a time ranging from about 1 hour to about 10 hours; using any one of a temperature and a time ranging from about 1.5 hours to about 8 hours, or c) a temperature ranging from about 200° C. to about 450° C. and a time ranging from about 2 hours to about 7 hours. and can be fired.

The clay heteroadduct is also heated at a temperature of from about 225° C. to about 700° C. for a time ranging from about 1 hour to about 10 hours, most preferably from about 250° C. to about 500° C. and from about 1 hour to about 10 hours. It may be baked for a range of hours. Alternatively, calcination in air is from 200°C to 750°C, 225°C to 700°C, 250°C to 650°C, 225°C to 600°C, 250°C to 500°C, 225°C to 450°C, or 200°C. Temperatures in the range of -400°C can be carried out. As indicated, a firing temperature selected from any single temperature or a range of two temperatures, for example a temperature in the range of 110° C. to 800° C. separated by at least 10° C. (i.e. 10° C.), is the final It can be used for developing catalytic activity.

Heat treatment such as calcination can be carried out in ambient atmosphere or under other such conditions that facilitate removal of water, for example calcination can be carried out in a carbon monoxide atmosphere. The use of such atmospheres may more efficiently remove surface hydroxyls at lower temperatures compared to temperatures used in ambient air calcination processes, thus maintaining greater pore volume and surface area during surface dehydration. . After calcination, the heterocoagulation product may be described as a continuous amorphous combination of clay particles and inorganic oxide particles, herein referred to as activator support or support activator and is called

Determination of the total porosity, pore volume distribution, and surface area of the activator supports of the present disclosure is accomplished by any method known in the art, such as analysis using nitrogen gas adsorption-desorption measurements. be able to. Adsorption or desorption isotherms describe the gas (in this case nitrogen) that adsorbs onto or desorbs from the surface of the analyte (clay heteroadduct) as the pressure increases or decreases, respectively, at constant temperature. Plot the volume of . The isothermal data can be analyzed using the BJH method to determine total pore volume and generate a pore size distribution, as described below, and the isothermal data can be analyzed using BET to determine surface area. can be analyzed using the method.

Heterocoagulation of smectite clays can provide activator supports that have substantial porosity and exhibit catalytic activation properties when metallocenes or olefins are combined with other polymerizable organotransition metal compounds. can. In one aspect, the calcined clay heteroadduct has from about 0.2 cc/g to about 3.0 cc/g, from about 0.3 cc/g to about 2.5 cc/g, or from about 0.5 cc/g to about 1.5 cc/g. BJH porosities in the range of 8 cc/g can be demonstrated. Calcined clay heteroadducts can also exhibit a BJH porosity of 0.5 cc/g or greater. Mineralized clay heteroadducts with porosities as low as about 0.2 cc/g can be used, e.g. Clay heteroadducts with porosities of less than about 0.2 cc/g are used, but bis(1-butyl-3-methylcyclopentadienyl)zirconium dichloride) is used to make the catalyst system. can exhibit lower polymerization activity, eg <200 g PE/g support activator/hr, when combined with metallocenes such as. In this disclosure, the term "g support activator" refers to grams of the calcined clay heteroadduct used to make the catalyst.

A comparison of the BJH porosity of clay and clay heteroadducts is shown in FIGS. The BJH pore volume analysis of the calcined, otherwise non-zeotropic, starting montmorillonite that was not treated with a heterocoagulant is shown in FIG. 11 (Example 1). The pore volume analysis of the starting montmorillonite that was sheared, then azeotroped and calcined, but otherwise untreated with a heterocoagulant, is shown in FIG. 12 (Example 3). Finally, the pore volume analysis of the aluminum chlorohydrate (ACH) heterocoagulated clay of Example 18 (1.76 mmol Al/g clay) is shown in FIG. Thus, in the absence of a heterocoagulant reagent, a calcined smectite such as bentonite can have a BJH porosity of about 0 cc/g to about 0.2 cc/g.

The cumulative pore volume between specified pore size boundaries can be determined using the BJH derived pore volume distribution. The cumulative pore volume of pore sizes from X nm (nanometers) to Y nm (V _XYnm ) (where X nm is the lower limit of the pore size and Y is the upper limit of the pore size) is calculated from the total pore size of the cumulative pore sizes of 0 nm to Y nm, Determined by subtracting the total pore size of the cumulative pore sizes from 0 nm to X nm. In situations where the total cumulative pore volume for either the upper or lower pore size limit is not available, this pore size is estimated by linear interpolation between the two nearest pore size points for which cumulative pore size data are available.

In one embodiment of the calcined clay heteroadduct, the total or cumulative pore volume of pores between 3-10 nm diameter (V _{3-10 nm} , or “small mesopores”) is equal to the total cumulative pore volume of pores between 3-30 nm It can contain less than 55% of the volume (V _3-30nm ). In a further aspect, V _{3-10 nm} can comprise less than 50% of the cumulative pore volume V _{3-30 nm} , or alternatively V _{3-10 nm} comprises less than 40% of the cumulative pore volume V _{3-30 nm} . can contain. This feature is illustrated by the data in FIG. 10 showing the BJH pore volume analysis of the smectite heteroadduct of Example 18, with a V _{3-10 nm} value of about 0.33 (V _{3-30 nm} ). This pore volume analysis contrasts with the BJH pore volume analysis of both the untreated non-azeotropic clay (Example 1, Figure 11) and the azeotropic clay (Example 3, Figure 12), both of which , V _{3-10 nm} are greater than 0.55 (V _{3-30 nm} ).

These pore volume characteristics of the clay heteroadducts of FIG. 10 of this disclosure contrast with those of the acid-treated clays of Murase et al., US Pat. We disclose that the total pore volume with a diameter of (V _{2-10 nm} ) accounts for 60%-100% of the total mesopore volume, ie all pore volumes between 2 nm and 50 nm. (See FIG. 1 and Table 1 of US Pat. No. 9,751,961). Specifically, Murase et al. reported that smaller mesopores of 2 nm to 10 nm account for the majority of the total mesopore volume (2 nm to 50 nm), and the total mesopore volume can be calculated, for example, by V _{2-10 nm} +V _{10-30 nm} +V _{30-50 nm} . revealing what it can do. In contrast, the clay heteroadducts of the present disclosure are characterized by smaller mesopore V _{3-10 nm} volumes that exceed V _{10-30 nm} alone. Without wishing to be bound by theory, the increase in the ratio of larger mesopores to the share of total porosity in the present disclosure may be related to diffusion and accessibility of metallocene compounds to ionization sites on the clay heteroadduct surface. is considered to promote This is in contrast to smaller mesopores, which impede, or may impede, diffusion of the metallocene to the surface containing the ionization sites, especially for metallocenes with gyration radii exceeding the smallest end of the mesopore diameter. It is believed that there is.

Further, for example, Uchino et al. The pore size distribution determined by the BJH method can be shown by plotting dV (log D) against pore diameter, as shown by US Pat. No. 6,677,411. The diameter that exhibits the highest value of this function can be denoted by the term _DM and is considered the most frequently occurring pore size. That is, D _M is the diameter corresponding to the highest value of DV (log D) in the 30 Å to 500 Å pore diameter region. The order value of _DM , which is the maximum value, is denoted by the term _DVM . In one aspect, this logarithmic differential pore volume distribution typically has a local maximum of about 30 Å to about 40 Å (Angstroms). This local maximum intensity can also be the global maximum _DVM . In one aspect, the intensity in _DVM can be up to about 200% of the intensity of the maximum value of dV(logD) between 200 Å and 500 Å. Alternatively, the intensity at _DVM can be up to about 120% of the intensity at the maximum of dV(logD) between 200 Å and 500 Å. Alternatively, the intensity in _DVM can still be up to about 100% of the intensity of the maximum value of dV(logD) between 200 Å and 500 Å. In another aspect, the maximum value of dV(logD) between 200 Å and 500 Å exceeds all values of dV(logD) between 30 Å and 200 Å. This is described, for example, in Uchino et al. U.S. Pat. No. 6,677,411, which is incorporated herein by reference, the maximum D _VM values have associated diameters D _M between 60 Å and 200 Å.

Similarly, Casty et al. US Pat. No. 7,220,695, defines a preferred embodiment in which the diameter D _M presenting the maximum _DVM value lies between 60 Å and 200 Å (Angstroms). In contrast, the most frequently occurring pore diameters D _M of the clay heteroadducts of the present disclosure lie either within the range of 30 Å to 40 Å, or within the range of 200 Å to 500 Å.

Furthermore, the differential logarithmic pore volume distribution in US Pat. No. 6,677,411 shows substantially lower intensity in the 200-500 Å range compared to the 60-200 Å range. The maximum value of dV(logD) in the range of 200 Å to 500 Å is typically less than 10% of the maximum value of dV(logD) in the range of 60 Å to 200 Å. In contrast, the clay heteroadducts of the present disclosure can provide dV (log D) maxima in the range of 200 Å to 500 Å, which are typically in the range of 60 Å to 200 Å ( greater than 100% of the maximum value of log D). Without wishing to be bound by theory, the presence of a greater proportion of larger mesopores in the clay heteroadducts of the present disclosure is due to easier metallocene diffusion to the ionization sites of the support activator. is considered desirable.

F. Filterability of Smectite Heteroadducts Clay heteroadducts prepared in slurry form within the zeta potential range according to the present disclosure, compared to similar pillared clays prepared using the same smectite clay and heterocoagulant reagents It showed unexpectedly improved ease of separation. Specifically, clay heteroadducts can be easily isolated by filtration, unlike pillared clays. This enhanced filterability compares, for example, the settling rate of a clay heteroadduct slurry with that of a similar pillared clay prepared using the same clay and a slurry containing the same amount of clay. was observed and quantified by

Slurry settling velocity comparisons for pillared and heterocoagulated clays, each prepared with 5 wt % HPM-20 clay aqueous dispersion, are shown in Table 1. Each slurry was prepared as described in the referenced examples, added to a graduated cylinder, and the settling rate was determined by observing the volume of a substantially clear layer with no haze of colloidal particles visible at the top of the slurry. Measured over time. In this comparison, the sedimentation rate of the heterocoagulated clay was significantly faster, eg, 5 times faster on a volume basis. Without wishing to be bound by theory, the increased particle size of heterocoagulated clay dispersions with zeta potentials in a relatively narrow range around 0 mV, e.g. Coagulation is believed to be favored over pillar-shaped clay particles that tend to remain.

Therefore, one way in which the filterability of a heterocoagulated clay slurry can be evaluated as "easily filterable" is to look at the settling velocity of the slurry compared to that of a columnar viscosity slurry. In one aspect, a composition such as a clay heteroadduct has a sedimentation rate of 2.5 wt% aqueous heterodeposit slurry (as described herein) of the same colloidal smectite clay, the same heterocoagulation 3x, 3.5x, 4x, 4.5x, 5x, 6x, 7x the sedimentation rate of a 2.5 wt% aqueous pillar clay slurry prepared using the reagent and the same liquid carrier If it is 10-fold, 8-fold, 9-fold, or 10-fold or more, it is easily or easily filterable, and the sedimentation rate is about 12 hours, about 18 hours, about 24 hours, about 30 hours from the start of the sedimentation test. , about 36 hours, about 48 hours, about 72 hours, about 95 hours, about 96 hours, or about 100 hours or more.

Further demonstration of filterability was observed by quantifying the filtration rate or filtration rate of the clay slurry, as shown in Table 2. When a pillared clay slurry and a heterocoagulated clay slurry using 5 g of clay each were prepared to a total mass of 250 g and filtered, the heterocoagulated clay slurry was filtered quickly and the filtrate water was separated quickly, while the pillared clay The slurry filtration rate was over 80% slower. Again, without wishing to be bound by theory, it is believed that increasing the particle size of the coagulated heterocoagulated clay allows for easier separation of the heterocoagulated clay particles and water, while increasing the columnar viscosity. It is believed that the smaller particle size causes plugging of the filter paper, slows separation, and requires longer filtration times and continuous filtration due to the need to replace the plugged filter paper.

Thus, in one aspect, the present disclosure provides another method of quantifying the filterability of heteroadduct slurries, demonstrating that the slurries are readily filterable and can be easily filtered. In one aspect, the composition, such as the clay heteroadduct, is such that the slurry exhibits the following filtration behavior:
[a] Filtering the 2.0 wt% aqueous heteroadduct slurry within a time period between 0 and 2 hours after the contacting step b) (i.e. after initial formation of the heteroadduct slurry) yields a smectite heteroadduct Based on the weight of the liquid carrier in the slurry, the percentage of filtrate obtained in a 10 minute filtration time using either vacuum filtration or gravity filtration is: (1) before filtration, i.e. the initial slurry water weight (2) from about 60% to about 100% by weight of the liquid carrier in the slurry; (3) from about 70% to about 70% by weight of the liquid carrier in the slurry; about 100% by weight, or (4) in the range of about 80% to about 100% by weight of the liquid carrier in the slurry before filtration;
[b] the filtrate from the heteroadduct slurry evaporates to yield a solid comprising less than 20%, less than 15%, or less than 10% of the initial combined weight of clay and heterocoagulant. , readily or readily filterable.

Some non-hetero-adduct slurries, including some pillared clay slurry compositions, can be filtered more easily after allowing an initial settling period of several days, thus allowing 0-2 hours after initial formation. A filtering feature is identified.

In the examples used to generate the Table 2 data, the heteroadduct slurry and the pillared viscosity slurry were filtered using a 20 micron filter several minutes after the colloidal clay and polymetalate contacting step. The water from the heteroadduct slurry was essentially filtered at the 10 minute mark after vacuum filtration was started, whereas the water from the pillared clay slurry was filtered 10 minutes after vacuum filtration was started. It wasn't. Either the filter spacing (e.g., 20 μm) or whether the filtration was done by gravity filtration or vacuum filtration by assessing “easily filterable” using a combination of the two characteristics listed above. need not be specified. That is, filters with specified aperture sizes are readily identifiable by those skilled in the art, for example, the 20 μm filters used in the examples indicate that the clay heteroadduct meets both of these criteria. However, neither filter size allows the pillared clay to meet both of these criteria.

An example of applying this "readily filterable" test is when using filters with too large openings between the filter media so that the pillar clay filtration meets the requirements of part [a] of the above criteria. , which fails partly [b] and is not considered readily filterable. When using such a large filter size, the clay heteroadduct also fails part [b], but by decreasing the filter size (e.g., about 20 μm), the clay heteroadduct shows criteria [a] and Both [b] can be satisfied, while the pillared clay fails part [a] when decreasing the filter size. This is because the filters are clogged and little or no liquid carrier is filtered.

Similarly, either gravity filtration or vacuum filtration can be used in the "easily filterable" test. Because when the filtrate measurements are specified (10 minutes after starting the filtration), the appropriate filter size allows the clay heteroadduct to meet both criteria [a] and [b]. This is because, on the other hand, pillared clay fails at least one of criteria [a] and [b], although it can be easily identified by a person of appropriate skill in the art.

In another aspect, another method of quantifying filterability is as follows. Compositions such as clay heteroadducts have the following filtration behavior when slurries:
[a] if the 2.0 wt% aqueous heteroadduct slurry is filtered within a time period of 0 hours to 2 hours after the contacting step b) to provide a first filtrate, then the second filtrate, the first to the filtrate is less than 0.25, less than 0.20, less than 0.10, less than 0.15, less than 0.10, less than 0.5, or about 0.0, and the second filtrate is Obtained from filtration of a 2.0% by weight slurry of a pillared clay prepared using a colloidal smectite clay, a heterocoagulant reagent, and a liquid carrier, the weight of the first filtrate and the weight of the second filtrate being: being measured after the same filtration time of 5, 10 or 15 minutes;
[b] the filtrate from the heteroadduct slurry evaporates to yield a solid comprising less than 20%, less than 15%, or less than 10% of the initial combined weight of clay and heterocoagulant. , can be considered readily filterable or readily filtered.

Thus, this test compares the filtrate collected from the heteroadduct slurry to the columnar viscosity, while the previous test compares the filtrate collected from the heteroadduct slurry to the aqueous carrier of the initial slurry.

G. Metallocene Compounds The calcined clay heteroadducts may be prepared with one or more suitable polymerization catalyst precursors, such as metallocenes, other organometallic compounds, and/or organoaluminum compounds, or the like, to prepare olefin polymerization catalyst compositions, or It can be used as a substrate for other catalytic components or as a catalyst support activator. Thus, in one aspect, when the clay heteroadduct is prepared as disclosed herein and combined with an organobase metal, such as an alkylaluminum compound, and a Group 4 organotransition metal compound, such as a metallocene, the active olefin A polymerization catalyst or catalyst system is provided.

The support activators of the present disclosure can be used with co-catalysts such as metallocene compounds (also referred to herein as metallocene catalysts) and organoaluminum compounds, and the resulting compositions are ion exchange, proton It exhibits catalytic polymerization activity in the absence or substantial absence of acid treatment, or pillared clay, or aluminoxane or borate activators. It has previously been thought that activators such as aluminoxane or borate activators are necessary to achieve polymerization catalytic activity in metallocene or single site or coordination catalyst systems. However, if desired to impart an activatable alkyl ligand to a metallocene, a combination of a heteroadduct support activator, a metallocene, and a cocatalyst such as an aluminum alkyl compound may be used for aluminoxane or borate activation. To provide an active catalyst that requires other activating agents such as agents.

Metallocene compounds are well understood in the art and one skilled in the art will appreciate that any metallocene includes, for example, both non-bridged (non-ansa) metallocene compounds or bridged (ansa) metallocene compounds, or combinations thereof. , can be used with the support activator described in this disclosure. Accordingly, one, two, or more metallocene compounds can be used with the clay heteroadduct support activator of the present disclosure.

In one aspect, the metallocene can be a metallocene comprising a Group 3-6 transition metal, or a metallocene comprising a lanthanide metal or a combination of two or more metallocenes. For example, metallocenes can include Group 4 transition metals (titanium, zirconium, or hafnium). In a further aspect, the metallocene compounds each independently have the formula:
(X ¹ ) (X ² ) (X ³ ) (X ⁴ ) M (wherein
a) M is selected from titanium, zirconium, or hafnium;
b) X ¹ is selected from substituted or unsubstituted cyclopentadienyl, indenyl, fluorenyl, pentadienyl, allyl, boratabenzenyl, 1,2-azaborolyl, or 1,2-diaza-3,5-diborolyl, optionally substituted group is independent of halide, C ₁ -C ₂₀ hydrocarbyl, C ₁ -C ₂₀ heterohydrocarbyl, C ₁ -C ₂₀ organoheteryl, fused C ₄ -C ₁₂ carbocyclic moiety, or nitrogen, oxygen, sulfur, or phosphorus independently selected from fused _C4 - _C11 heterocyclic moieties having at least one heteroatom selected as
c) X ² is selected from [1] substituted or unsubstituted cyclopentadienyl, indenyl, fluorenyl, pentadienyl, or allyl, with optional substituents being halides, C ₁ -C ₂₀ hydrocarbyl, C ₁ -C ₂₀ heterohydrocarbyl, or C ₁ -C ₂₀ organoheteryl, or [2] Halide, hydride, C ₁ -C ₂₀ hydrocarbyl, C ₁ -C ₂₀ heterohydrocarbyl, C ₁ -C ₂₀ organoheteryl, condensation selected from a _C4 - _C12 carbocyclic moiety or a fused _C4 - _C11 heterocyclic moiety having at least one heteroatom independently selected from nitrogen, oxygen, sulfur, or phosphorus;
d) X ¹ and X ² are optionally bridged by at least one linker substituent having 2 to 4 bridging atoms independently selected from C, Si, N, P, or B, each Each available non-bridging valence of a bridging atom is unsubstituted (bonded to H) or substituted, and any substituents are halides, C ₁ -C ₂₀ hydrocarbyls, C ₁ -C ₂₀ heterohydrocarbyls, or C ₁ any hydrocarbyl, heterohydrocarbyl, or organoheteryl substituent independently selected from _—C20 organoheteryl, can form a saturated or unsaturated cyclic structure with the bridging atom or with X ¹ or X ² ;
e) [1] X ³ and X ⁴ are independently selected from halide, hydride, C ₁ -C ₂₀ hydrocarbyl, C ₁ -C ₂₀ heterohydrocarbyl, or C ₁ -C ₂₀ organoheteryl, [2] [GX ^A _k X ^B _4-k ] ⁻ (wherein G is B or Al, k is a number from 1 to 4, and X ^A at each occurrence independently of H or halide selected and X ^B at each occurrence is independently selected from C ₁ -C ₁₂ hydrocarbyl, C ₁ -C ₁₂ heterohydrocarbyl, C ₁ -C ₁₂ organoheteryl), [3] X ³ and X ⁴ are together a C ₄ -C ₂₀ polyene, or [4] X ³ and X ⁴ together with M form an unsubstituted or unsubstituted, saturated or unsaturated C ₃ -C ₆ metallacycle moiety, Optional substituents on the metalacycle moiety are independently selected from halides, C ₁ -C ₂₀ hydrocarbyls, C ₁ -C ₂₀ heterohydrocarbyls, or C ₁ -C ₂₀ organoheteryls. comprising, consisting of, consisting essentially of, or selected from a combination of

According to a further aspect, optionally X ¹ and X ² are
a) >EX ⁵ ₂ , -EX ⁵ ₂ EX ⁵ ₂ -, -EX ⁵ ₂ EX ⁵ EX ⁵ ₂ -, or >C=CX ⁵ ₂ where E at each occurrence is independent of C or Si selected),
b) -BX ⁵ -, -NX ⁵ -, or -PX ⁵ , or 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 -], [-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 ⁵ ₂ (1,2-C ₆ H ₄ )CX ⁵ _2- ]
(wherein X ⁵ at each occurrence is independently selected from H, halide, C ₁ -C ₂₀ hydrocarbyl, C ₁ -C ₂₀ heterohydrocarbyl, or C ₁ -C ₂₀ organoheteryl;
Any ^X5 substituent selected from hydrocarbyl, heterohydrocarbyl, or organoheteryl substituents can form a saturated or unsaturated cyclic structure with a bridging atom, another ^X5 substituent, ^X1 , or ^X2 . are bridged by linker substituents selected from

Examples of suitable linker substituents capable of bridging X ¹ and X ² include C ₁ -C ₂₀ hydrocarbylene groups, C ₁ -C ₂₀ hydrocarbylene groups, C ₁ -C ₂₀ heterohydrocarbyl groups, Included are C ₁ -C ₂₀ heterohydrocarbylene groups, C ₁ -C ₂₀ heterohydrocarbylene groups, or C ₁ -C ₂₀ heterohydrocarbylidene groups. For example, X ¹ and X ² have the formula >EX ⁵ ₂ , -EX ⁵ ₂ EX ⁵ ₂ -, or -BX ⁵ -, where E is independently C or Si and X ⁵ is a halide, a C ₁ -C ₂₀ aliphatic group, a C ₆ -C ₂₀ aromatic group, a C ₁ -C ₂₀ heteroaliphatic group, a C ₄ -C ₂₀ heteroaromatic group, or a C ₁ -C ₂₀ organoheteryl (independently selected from groups).

The Aspects section of this disclosure lists additional explanations and preferences regarding the linking moiety between X ¹ and X ² , regarding X ⁵ , and regarding specific linker substituents or X ⁵ substituents.

The Aspects section of this disclosure also lists additional descriptions and preferences for X ¹ and X ² , including specific substituents on X ¹ and X ² .

The Aspects section of this disclosure also lists additional descriptions and preferences for X ³ and X ⁴ , including specific substituents on X ³ and X ⁴ .

The Aspects section of this disclosure also provides some specific examples of metallocene compounds useful in combination with the support activators of this disclosure.

Metallocene compounds are understood by those skilled in the art, and those skilled in the art will recognize and understand methods of making and using metallocenes in olefin polymerization catalyst systems. A number of metallocenes and processes for making metallocenes and organotransition metal compounds are described in U.S. Pat. 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 2017/0342175, which are incorporated herein by reference in their entirety.

H. Cocatalyst According to one aspect, the present disclosure provides a catalyst composition for olefin polymerization, the catalyst composition comprising: a) at least one metallocene compound;
b) optionally, at least one cocatalyst; and c) at least one support activator as described herein. Cocatalysts include compounds such as trialkylaluminums, which, when the metallocene is otherwise liganded to the metallocene, are capable of initiating polymerization when activated with a support activator. It is considered. A cocatalyst may be considered optional, for example, in scenarios where the metallocene may already contain a polymerization activating/initiating ligand (such as methyl or hydride). It is understood that even if the metallocene compound contains polymerization activating/initiating ligands, etc., the cocatalyst can be used for other purposes such as removing water from the polymerization reactor or process. Will. Thus, the co-catalyst may comprise or be selected from, for example, an alkylating agent, a hydrizinating agent, or a silylating agent. The metallocene compound, support activator, and cocatalyst can be contacted in any order.

The cocatalyst can include or be selected from an organoaluminum compound, an organoboron compound, an organozinc compound, an organomagnesium compound, an organolithium compound, or any combination thereof.

The Aspects section of this disclosure lists additional descriptions and selections for each of the organoaluminum compounds, organoboron compounds, organozinc compounds, organomagnesium compounds, and organolithium compounds.

In one aspect, for example, the cocatalyst has the formula Al(X ^A ) _n (X ^B ) _m , M ^x [AlX ^A ₄ ], Al(X ^C ) _n (X ^D ) _3-n , M ^x [AlX ^C ₄ ] (i.e., which may be a neutral molecular compound or an ionic compound/salt of aluminum). Each of these formula variables can be selected and defined in the Aspects section of this disclosure. For example, cocatalysts include trimethylaluminum, triethylaluminum (TEA), tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, ethyl-(3-alkylcyclopentadiyl)aluminum, diethylaluminum ethoxide, diisobutyl hydride. may comprise, consist of, consist essentially of, or be selected from any combination of aluminum, triisobutylaluminum (TIBAL), diethylaluminum chloride, ethyl-(3-alkylcyclopentadiyl)aluminum, etc. .

In another aspect, for example, the co-catalyst can be of the formula B(X ^E ) _q (X ^F ) _3-q or M ^y [BX ^E ₄ ] (ie, a neutral molecular compound or an ionic compound/salt of boron ), each of the variables of these formulas can comprise, consist of, consist essentially of, or be selected from at least one organoboron compound that can independently have Defined in the Aspects section. For example, cocatalysts include trimethylboron, triethylboron, tripropylboron, tributylboron, trihexylboron, trioctylboron, diethylboron ethoxide, diisobutylboron hydride, triisobutylboron, diethylboron chloride, di-3-pinanylborane, comprising, consisting of, consisting essentially of, or selected from pinacolborane, catecholborane, lithium borohydride, lithium triethylborohydride, and Lewis base adducts thereof, or combinations or mixtures thereof; can. In another aspect, the cocatalyst can comprise or 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, triphenylcarbenium tetrakis(pentafluorophenyl)borate, lithium tetrakis-(pentafluorophenyl)borate, N , N-dimethylanilinium tetrakis[3,5-bis(trifluoro-methyl)phenyl]borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)-phenyl]borate, and any combination or thereof and a mixture of

In yet another aspect, for example, the cocatalyst comprises or consists of at least one organozinc or organomagnesium compound that can independently have the formula M ^C (X ^G ) _r (X ^H ) _2-r can consist essentially of, or be selected from, where each variable of this formula is defined in the Aspects section of this disclosure. For example, cocatalysts include dimethylzinc, diethylzinc, diisopropylzinc, dicyclohexylzinc, diphenylzinc, butylethylmagnesium, dibutylmagnesium, n-butyl-sec-butylmagnesium, dicyclopentadienylmagnesium, ethylmagnesium chloride, butyl chloride. It can comprise, consist of, consist essentially of, or be selected from any combination, such as magnesium.

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

I. Optional Co-Activators In one aspect, if desired, other activators can be used in the catalyst compositions of the present disclosure in addition to the calcined smectite heteroadduct activator support. These are referred to as co-activators and examples of optional co-activators include ion exchange clays, protinated clays, pillared clays, aluminoxanes, borate activators, aluminate activators, ionizing ionic compounds, Solid oxides treated with electron-withdrawing anions, or any combination thereof, include, but are not limited to.

The Aspects section of this disclosure lists additional descriptions and preferences for each of these optional co-activators.

Aluminoxane. any solvent that is substantially inert to the reactants, intermediates, and products of the activation step, e.g., using aluminoxanes (also called poly(hydrocarbylaluminum oxides) or organoaluminoxanes); For example, other catalyst components can be contacted in a solvent such as a saturated hydrocarbon solvent or toluene. The catalyst composition thus formed may be isolated, if desired, or the catalyst composition may be introduced into the polymerization reactor without isolation.

As will be appreciated by those skilled in the art, aluminoxanes are oligomeric and aluminoxane compounds can include linear, cyclic, or caged structures, or mixtures thereof. For example, cyclic aluminoxane compounds having the formula (R—Al—O) _n , where R can be a straight or branched alkyl having 1 to about 12 carbon atoms, and n is , can be an integer from 3 to about 12. (AlRO) _n moieties also constitute repeating units in linear aluminoxanes, for example having the formula: R(R—Al—O) _n AlR ₂ , where R is from 1 to about 12 and n can be an integer from 1 to about 75. For example, the R group can be linear or branched C ₁ -C ₈ alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl, where n is 1 can represent an integer from to about 50. Depending on the method of preparation, storage, and use of the organoaluminoxane, the value of n may vary within a single sample of aluminoxane, and such combinations or populations of organoaluminoxane species are typically found in any sample. exist within.

Organoaluminoxanes can be prepared by a variety of procedures known in the art, for example, organoaluminoxane preparations are disclosed in US 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 present in an inert organic solvent with an aluminum alkyl compound such as _AlR3 to form the desired organoaluminoxane compound. Alternatively, organoaluminoxanes may be prepared by reacting an aluminum alkyl compound such as _AlR3 with a hydrated salt such as hydrated copper sulfate in an inert organic solvent.

In one embodiment, the aluminoxane compound is methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, isopropyl-aluminoxane, n-butylaluminoxane, t-butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane, 1-pentylaluminoxane, 2 -pentyl-aluminoxane, 3-pentyl-aluminoxane, iso-pentyl-aluminoxane, neopentyl-aluminoxane, or combinations thereof. In one aspect, methylaluminoxane (MAO), ethylaluminoxane (EAO), or isobutylaluminoxane (IBAO) can be used as optional cocatalysts, which are trimethylaluminum, triethylaluminum, or trimethylaluminum, respectively. It can be prepared from isobutylaluminum. These compounds can be of complex composition and are sometimes referred to as poly(methylaluminum oxide), poly(ethylaluminum oxide), and poly(isobutylaluminum oxide), respectively. In another aspect, an aluminoxane can be used in combination with a trialkylaluminum such as disclosed in US Pat. No. 4,794,096, which is incorporated herein by reference in its entirety.

In preparing a catalyst composition containing an optional aluminoxane, the molar ratio of aluminum to metallocene compound present in the aluminoxane in the composition is typically It can be lower than the molar ratio. In the absence of the support activator of the present disclosure, the aluminoxane amount is, for example, from about 1:10 mol Al/mol metallocene (mol Al/mol metallocene) to about 100,000:1 mol Al/mol metallocene, or about 5: 1 mol Al/mol metallocene to about 15,000:1 mol Al/mol metallocene. The relative amount of aluminoxane can be reduced when used in conjunction with the disclosed support activators. For example, the amount of any aluminoxane added to the polymerization zone can range from about 0.01 mg/L to about 1000 mg/L, from about 0.1 mg/L to about 100 mg/L, or from about 1 mg/L to about 50 mg/L. It can be less than the previous typical amount within the range. Alternatively, the aluminoxane can be used in amounts commonly used in the prior art, but with the additional use of the support activator of the present disclosure to obtain the additional benefits of such combinations. can be used.

Organoboron compounds. The catalyst compositions of the present disclosure can also optionally include an optional organoboron coactivator in addition to the listed components (support activator, metallocene, and optional cocatalyst). In one aspect, the organoboron compound can comprise or be selected from a neutral boron compound, a borate salt, or a combination thereof. For example, the organoboron compound may comprise or be selected from a fluoroorganoboron compound, a fluoroorganoborate compound, or a combination thereof, and any such fluorinated compound known in the art. can be used.

Thus, the term fluoroganoboron compound is used herein to ^refer to a neutral compound in the form BY _{3 and} the term fluoroganoboric acid compound is used to refer to a fluorogano- Used herein to refer to monoanionic salts of boron compounds, Y represents a fluorinated organic group. For convenience, fluoroorganoboron compounds and fluoroorganoborate compounds are typically referred to collectively by the organoboron compound or by either name as the context requires.

In one aspect, examples of fluoroganoboron compounds that can be used as co-activators include tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)phenyl]boron, etc. (these (including mixtures). Examples of fluoroganoborate compounds that can be used as optional co-activators include fluorinated arylborates, such as N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, fluorophenyl)borate, lithium tetrakis-(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoro-methyl)phenyl]borate, triphenylcarbeniumtetrakis[3,5-bis (trifluoromethyl)-phenyl]borate and the like, including, but not limited to, mixtures thereof.

The Aspects section of this disclosure lists additional descriptions and selections of optional fluoroorganoboron and fluoroorganoborate compound co-activators.

While not intending to be bound by theory, these fluoroorganoborates and fluoroorganoboron compounds are characterized by: It is believed to form a weakly coordinating anion when combined with a metallocene compound.

Generally, any amount of organoboron compound can be utilized as the optional co-activator. For example, in one aspect, the molar ratio of organoboron compound to metallocene compound in the composition is from about 0.1:1 moles of organoboron compound or organoborate compound per mole of metallocene (mol/mol) to about 10 : 1 mol/mol, or from about 0.5 mol/mol to about 10 mol/mol (moles of organoboron compound or organoboronate compound per mole of metallocene), or alternatively, from about 0.8 mol/mol to about 5 mol/mol (moles of organoboron compound or organoboric acid compound per mole of metallocene). However, it is understood that the amount can be reduced or adjusted downward in the presence of the clay heteroadduct support activator.

Ionized compounds. In a further aspect, any co-activator that may be used in addition to the listed components of the catalyst compositions of the present disclosure may comprise or be selected from ionizing compounds. Examples of ionizing compounds are disclosed in US Pat. Nos. 5,576,259 and 5,807,938, each of which is incorporated herein by reference in its entirety.

The Aspects section of this disclosure lists additional descriptions and selections of optional ionizing compound co-activators.

The term ionizing compound is a term of art and refers to compounds, particularly ionic compounds, that can function to enhance the activity of the catalyst composition. In one aspect, any fluoroganoborate compound described herein as an organoboron co-activator may also be considered, functioning as an ionizing compound co-activator. However, the range of ionizing compounds is broader than that of fluoroorganoborate compounds, as compounds such as fluoroorganoaluminates are encompassed by ionizing compounds.

Without intending to be bound by theory, it is believed that the ionizing compound can interact or react with the metallocene compound to convert the metallocene into a cationic or initial cationic metallocene compound, rendering the metallocene polymerically active. is considered to be activated at Again, without intending to be bound by theory, the ionizable compound is a metallocene, particularly a metallocene of formula (X ¹ )(X ² )(X ³ )(X ⁴ )M disclosed herein. It functions by completely or partially extracting anionic ligands from non-cycloalkadienyl ligands or non-alkadienyl ligands such as (X ³ ) or (X ⁴ ) to form cationic or initial cationic metallocenes It is considered possible. However, an ionizing compound can function as an activator (co-activator) regardless of any mechanism by which it functions. For example, an ionizing compound can ionize a metallocene, extract an ^X3 or ^X4 ligand in such a way as to form an ion pair, weaken a metal- ^X3 or metal- ^X4 bond, or simply ^X3 or ^X4. It may coordinate the ligand or any other mechanism by which activation may occur. Furthermore, the activating function of the ionizing compound is evident in the increased activity of the overall catalyst composition compared to catalyst compositions containing catalyst compositions without any ionizing compound, so that only metallocene ionizing compounds are present. need not be activated (co-activated).

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

Optional support activator. In a further aspect, optional co-activators that may be used in addition to the listed components of the catalyst compositions of the present disclosure include other support activators, sometimes referred to as activator supports. or can be selected from other support activators. These are referred to as co-activator supports when used in the catalyst compositions described herein. Examples of optional co-activator supports are U.S. Pat. Nos. 6,833,338 and 9,670,296, each of which is incorporated herein by reference in its entirety.

For example, an optional co-activator support can comprise or be selected from silica treated with at least one electron-withdrawing anion, alumina, silica-alumina, or silica-coated alumina. For example, silica-coated alumina can have a weight ratio of alumina to silica in this aspect 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 may comprise or be selected from fluoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate, etc., or combinations thereof.

In one aspect, the optional co-activator support is, for example, alumina fluoride, alumina chloride, alumina bromide, alumina sulfate, silica alumina fluoride, silica alumina chloride, silica alumina bromide, silica alumina sulfate, silica alumina may be selected from silica zirconia, chlorinated silica zirconia, brominated silica zirconia, silica zirconia sulfate, fluorinated silica titania, and the like, any or any combination thereof for use in the catalyst compositions disclosed herein; can be Alternatively, or additionally, the co-activator support may comprise or be selected from a solid oxide treated with an electron-withdrawing anion such as fluorinated silica alumina, or sulfated alumina.

Examples of co-activator supports can include, but are not limited to, those listed in the Embodiments section of this disclosure.

J. Preparation of the Catalyst Composition In the catalyst system, the relative concentrations or ratios of metallocenes, such as Group 4 metallocenes of formula (X ¹ )(X ² )(X ³ )(X ⁴ )M, and calcined clay heteroadducts are determined by the calcined clay It can be expressed as moles of M (metal) per gram of 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 range from 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 is from about 0.0005 mol M/g heteroadduct to about 0.00000005 mol M/g heteroadduct, or alternatively, about 0.0001 mol A range from M/g heteroadduct to 0.000001 mol M/g heteroadduct can be used. As with all ranges disclosed herein, these recited ranges include the endpoints within the recited range as well as intermediate values and subranges. These ratios reflect the catalyst recipe, ie, they are based on the amounts of the components that are combined to obtain the catalyst composition, regardless of what the ratios are in the final catalyst.

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

The catalyst composition can be prepared 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. Contacting can occur in any number of ways, such as by blending, contacting in a carrier liquid, feeding each component separately or in any order or combination to the reactor. For example, various combinations of components or compounds can be contacted with each other before being further contacted 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 respect to additional optional components that may be used in the catalyst systems disclosed herein, such as co-activators, ionizing ionic compounds, etc., the step of contacting using these optional components may optionally include: May occur in any order.

In one aspect, the catalyst composition is first prepared by combining a transition metal compound, such as a metallocene, with a cocatalyst, such as an organoaluminum compound, for a period of from about 1 minute to about 24 hours, or alternatively from about 1 minute to about 1 hour. , 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, which can then be contacted with the calcined clay heteroadduct to form the catalyst composition.

In another aspect, the metallocene, a cocatalyst such as an organoaluminum compound, and the calcined clay heteroadduct can be pre-contacted prior to introduction into the reactor. For example, the pre-contacting step can occur over a period of about 1 minute to about 6 months. In one aspect, for example, the pre-contacting step is 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. can occur. Additionally, any subset of the final catalyst components may be precontacted in one or more precontacting steps, each with its own precontacting period.

After any or all of the catalyst system components have been precontacted, the catalyst composition is said to include postcontacted components. For example, the catalyst composition can include a post-contacted metallocene, a post-contacted cocatalyst such as an organoaluminum compound, and a post-contacted calcined clay heteroduct component. In the field of catalytic technology, it is not uncommon for the specific and detailed nature of the active catalytic sites, as well as the specific nature and fate of each component used to make the active catalyst, to be precisely known. While not intending to be bound by theory, it can be assumed that the majority of the weight of the catalyst composition based on the relative weights of the individual components comprises the post-contacted calcined clay heteroadduct. Since the active sites and the nature of the post-contacted components are not precisely known, the catalyst composition may simply be described according to its components or may be referred to as comprising post-contacted compounds or components.

The polymerization activity of the catalyst composition is expressed as weight polymer per weight of support activator containing calcined smectite heteroadduct per unit time, e.g., grams polymer/gram (calcined) support activator/hour. (g/g/hr). That is, activity can be calculated based on the support activator alone, in the absence of any metallocene or cocatalyst component. This measurement allows comparison of various activator supports, including those with other activators where the metallocene, cocatalyst, and other conditions are the same or substantially the same. The activity values disclosed in the examples are based on the reaction between ethylene and isobutane using isobutane as the diluent and at a polymerization temperature of about 50° C. to about 150° C. (eg, at a temperature of 90° C.), unless otherwise specified. Combined pressures were measured under slurry polymerization conditions using a range of about 300 psi to about 800 psi, eg, 450 psi for the combined sum of ethylene and isobutane combined. Activity data are reported as the weight of polymer produced divided by the weight of calcined clay heteroadduct per hour.

Catalytic activity can be a function of metallocene and calcined clay heteroadducts, as well as other ingredients and conditions. Under the conditions described above, the weight-based activity of the calcined clay heteroadduct is about 1,000 grams per hour per gram of calcined clay heteroadduct (g PE/g heteroadduct/hour, or simply g /g/hr) can be exceeded. In another aspect, the activity by weight of the calcined clay heteroadduct is greater than about 2000 g/g/hr, greater than about 4,000 g/g/hr, greater than about 6,000 g/g/hr, greater than about 8,000 g/hr. g/hr, greater than about 10,000 g/g/hr, greater than about 15,000 g/g/hr, greater than about 25,000 g/g/hr, or greater than about 50,000 g/g/hr. The upper limit of each of these activities can be about 70,000 g/g/hr, such that the activities range above these disclosed values and below about 75,000 g/g/hr. obtain.

For example, in one aspect, using the conditions described herein, the activator support is about 500 g/g/hr, about 750 g/g/hr, about 1,000 g/g/hr, about 1 , 250 g/g/h, about 1,500 g/g/h, about 1,750 g/g/h, about 2,000 g/g/h, about 2,500 g/g/h, about 3,500 g/g/h hours, about 5,000 g/g/hr, about 7,500 g/g/hr, about 10,000 g/g/hr, about 12,500 g/g/hr, about 15,000 g/g/hr, about 17, 500 g/g/h, about 20,000 g/g/h, about 25,000 g/g/h, about 30,000 g/g/h, about 35,000 g/h, about 40,000 g/h, about 50, 000 g/g/hr, about 60,000 g/hr, about 70,000 g/hr, or about 75,000 g/hr, including any range between these values. Higher values of polymerization activity can be associated with clay supports with very high site densities, and these activity values can also be metallocene dependent. Thus, by applying the teachings herein, activity levels within a range between two of the recited values can be achieved, e.g., activity levels of 500-75,000 g/g /hr, and within the range of 1,000 to 50,000 g/g/hr, in the range of 2,000 to 40,000 g/g/hr, or in the range of 2,500 to 20,000 g/g/hr. can be obtained within range. The activities in the examples and data tables were evaluated using isobutane as the diluent, a polymerization temperature of 90° C., a combined ethylene and isobutane pressure of 450 psi and (1-n-butyl-3-methylcyclopentadienyl) ₂ ZrCl _{2 .} and triethylaluminum catalyst composition under slurry homopolymerization conditions.

In one aspect, no aluminoxane, such as methylaluminoxane, was required to activate the metallocene and form the catalyst composition. Methylaluminoxane (MAO) is an expensive activator compound and can significantly increase the cost of polymer production. Further, in another aspect, no organoboron compounds or ionizing compounds, such as borate compounds, were required to activate the metallocene and form the catalyst composition. Furthermore, no ion exchange, protonic acid treatment or pillared clays, which also require multi-step preparation increasing costs, were also required to activate the metallocene and form the catalyst composition. Thus, the active heterogeneous catalyst composition may be an olefin containing comonomer, if desired, in the absence of any aluminoxane, boron or borate compound, ion-exchanged, protonated, or pillared clay. It can be easily and inexpensively produced and used to polymerize monomers. MAO or other aluminoxanes, boron or borate compounds, ion-exchange clays, protinated clays, or pillared clays are not required in the disclosed catalyst system, although these compounds are included in other aspects of the present disclosure. can be used in reduced or typical amounts according to

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

In one aspect, homopolymers consist of monomeric residues having from 2 to about 20 carbon atoms per molecule, preferably from 2 to about 10 carbon atoms per molecule. Olefin monomers include ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 3-ethyl-1- It may comprise or be selected from hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and mixtures thereof. In one aspect, homopolymers of ethylene, homopolymers of propylene, and homopolymers of other olefins are encompassed by the present disclosure. In another aspect, copolymers of ethylene and at least one comonomer, and less commonly copolymers of two non-ethylene copolymers, are encompassed by the present disclosure.

If copolymers are desired, each monomer can have from about 2 to about 20 carbon atoms per molecule. Comonomers of ethylene include, for example, 3 to 20 per molecule such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, styrene, vinylcyclohexane and other olefins. aliphatic 1-olefins having 1,3 carbon atoms, and conjugated or Non-conjugated diolefins may include, but are not limited to, other such diolefins and mixtures thereof. In a further 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, based on the total weight of monomers and comonomers in the copolymer, to produce a copolymer that incorporates from about 0.01 wt. or about 0.01 wt% to about 5 wt% comonomer, or still about 0.1 wt% to about 4 wt% % comonomer can be introduced, or alternatively any amount of comonomer can be introduced into the reactor zone to provide the desired copolymer.

Typically, the catalyst composition can be used to homopolymerize ethylene or propylene, or to copolymerize ethylene with a comonomer, or to copolymerize ethylene and propylene. In another aspect, several comonomers may be polymerized with monomers in the same or different reactor zones to achieve desired polymer properties.

Other useful comonomers can include polar vinyl, conjugated and non-conjugated diene, acetylene and aldehyde monomers, which can be included, for example, in minor amounts in the terpolymer composition. For example, non-conjugated dienes useful as comonomers can be linear, hydrocarbon diolefins, or cycloalkenyl-substituted alkenes having 6 to 15 carbon atoms. Suitable non-conjugated dienes include, for example, (a) linear acyclic dienes such as 1,4-hexadiene and 1,6-octadiene, (b) 5-methyl-1,4-hexadiene, 3,7-dimethyl -1,6-octadiene, and branched acyclic dienes such as 3,7-dimethyl-1,7-octadiene, (c) 1,4-cyclohexadiene, 1,5-cyclo-octadiene and 1,7- monocyclic alicyclic dienes such as cyclododecadiene, (d) tetrahydroindene, norbornadiene, methyl-tetrahydroindene, dicyclopentene (DCPD), cyclo-(2.2.1)-hepta-2,5-diene, alkenyl , polycyclic alicyclic fused and bridged cyclic dienes such as alkylidene, 5-methylene-2-norbornene (MNB), 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4- cycloalkenyl and cycloalkylidene norbornenes such as cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, and 5-vinyl-2-norbornene (VNB), and (e) vinylcyclohexene, allylcyclohexene, vinylcyclo Cycloalkenyl-substituted alkenes such as octene, 4-vinylcyclohexene, allylcyclodecene and vinylcyclododecene are included. 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 diolefins include 5-ethylidene-2-norbornene (ENB), 1,4-hexadiene, dicyclopentadiene (DCPD), norbornadiene, and 5-vinyl-2-norbornene (VNB). Note that the terms "unconjugated diene" and "diene" are used interchangeably throughout this description.

The catalyst compositions are used to polymerize olefins and have a wide range of densities, e.g. The oligomeric and polymeric materials used can be made. The catalyst compositions disclosed herein are particularly useful for the production of copolymers. For example, the copolymer resin may have a density of 0.960 g/cc or less, preferably 0.952 g/cc or less, more preferably 0.940 g/cc or less. According to certain aspects of the present disclosure, densities below 0.91 g/cc can be achieved, down to 0.860 g/cc. When densities are described as being below a particular density, one lower limit for such densities can be about 0.860 g/cc. The copolymer resin can contain at least about 65 weight percent (wt%) ethylene units, ie, the weight percent of ethylene monomer actually incorporated into the copolymer resin. In another aspect, the copolymer resins of the present disclosure refer to the weight percent of the α-olefin comonomer actually incorporated into the copolymer resin, at least about 0.5 weight percent, such as 0.5 weight percent to 35 weight percent. of α-olefins (α-olefins).

Catalyst compositions prepared according to the present disclosure are prepared from: (a) ethylene/propylene copolymers, including "random copolymers" in which the commoners are randomly distributed along the polymer backbone or chain; (b) propylene units are derived from Random copolymers of propylene and ethylene, "propylene random copolymers", comprising about 60% by weight of the polymer comprising the polymer, and (c) one polymer in which one polymer comprises the other polymer, typically the matrix phase, and an elastomeric phase. Also useful are "impact copolymers," meaning two or more polymers dispersed in another polymer comprising. Polyalphaolefins having monomers containing more than 3 carbons can be prepared using the catalyst compositions described herein. Such oligomers and polymers are particularly useful as lubricants, for example.

Any number of polymerization methods or processes can be used with the catalyst compositions of the present disclosure. For example, slurry polymerization, gas phase polymerization, solution polymerization, and the like, including multiple reactor combinations, can be used. Multiple reactor combinations can be configured in series or parallel configurations, or combinations thereof, depending on the desired polymerization sequence. Examples of reactor systems and combinations include, for example, double slurry loops in series, multiple slurry tanks in series, or slurry loops combined with a gas phase, or polymerization of ethylene, propylene and α-olefins separately or together. There may be multiple combinations of these processes that may be performed. In another aspect, the gas phase reactor may comprise a fluidized bed reactor or a tubular reactor, the slurry reactor may comprise a vertical or horizontal loop or a stirred tank, the solution reactor may comprise a stirred tank or an autoclave reactor. may contain vessels. Thus, any polymerization known in the art that can produce polyolefins such as polyethylene, polypropylene, ethylene and α-olefin containing polymers including ethylene α-olefin copolymers, and more generally substituted olefins such as vinylcyclohexane. zone can be used. In one aspect, for example, a stirred reactor can be utilized for batch processes, and the reaction is then conducted continuously in a loop reactor, or in a continuously stirred reactor, or in a gas phase reactor. be able to.

A catalyst composition comprising the recited components is capable of polymerizing olefins in the presence of a diluent or liquid carrier, and these two terms are used herein even if the catalyst component is not soluble in the diluent or liquid carrier. used interchangeably in the specification. Suitable diluents used in slurry and solution polymerizations are known in the art and include hydrocarbons that are liquid under the reaction conditions. Furthermore, the term "diluent" as used in this disclosure does not necessarily imply that the material is inert, as the diluent may contribute to polymerization, such as bulk polymerization with propylene.

Suitable hydrocarbon diluents can include cyclohexane, isobutane, n-butane, propane, n-pentane, isopentane, neopentane, and n-hexane, as well as high boiling solvents such as ISOPAR™. Not limited. Isobutane works well as a diluent in slurry polymerizations. Examples of such slurry polymerization techniques are disclosed in U.S. Pat. Nos. 4,424,341; 4,501,885; 4,613,484; 597,892, the entire disclosures of which are incorporated herein by reference. When polymerizing propylene or other α-olefins, the propylene or α-olefins themselves may contain a solvent known in the art as bulk polymerization.

In various aspects and embodiments, a polymerization reactor suitable for use with a catalyst system includes at least one feed system, at least one feed system for the catalyst or catalyst components, at least one reactor system, at least one can include two polymer recovery systems, or any suitable combination thereof. Suitable reactors can further include any or a combination of a catalyst storage system, an extrusion system, a cooling system, a diluent recycling system, a monomer recycling system, and a comonomer recycling system or control system. Such reactors can optionally include continuous takeoff and direct recycling of catalyst, diluent, monomer, comonomer, inert gas, and polymer. In one aspect, the continuous process comprises the continuous introduction of monomer, comonomer, catalyst, if desired cocatalyst, and diluent into a polymerization reactor, and can include continuous removal from the

In one aspect, the polymerization process can be conducted over a wide temperature range, for example, the polymerization temperature can range from about 50°C to about 280°C, and in another aspect, the polymerization reaction temperature can range from about 70°C to about 70°C. °C to about 110 °C. The polymerization reaction pressure can be any pressure that does not terminate the polymerization reaction. In one aspect, the polymerization pressure can be from about atmospheric pressure to about 30,000 psig. In another aspect, the polymerization pressure can be from about 50 psig to about 800 psig.

The polymerization reaction can be carried out in an inert atmosphere, ie, substantially free of molecular oxygen, and under substantially anhydrous conditions, thus in the absence of water at the start of the reaction. Therefore, a dry inert atmosphere, such as dry nitrogen or dry argon, is typically used in the polymerization reactor.

In one aspect, hydrogen can be used in the polymerization process to control polymer molecular weight. In another embodiment, the method of deactivating the catalyst by adding carbon monoxide to the polymerization zone as described in U.S. Pat. No. 9,447,204, incorporated herein by reference, is used to control or runaway polymerization can be mitigated or stopped.

For the catalyst systems of the present disclosure, the polymerizations disclosed herein are generally carried out using loop reaction zone or batch processes, or slurry polymerization processes in gas phase zones utilizing fluidized or stirred beds. be done.

slurry loop. In one aspect, a typical polymerization method is the slurry polymerization process (also known as the "particle form process") disclosed, for example, in US Pat. No. 3,248,179, incorporated herein by reference. Other polymerization methods for slurry processes include loop reactors of the type disclosed in U.S. Pat. No. 3,248,179, and multiple stirred reactors either in series, in parallel, or combinations thereof. You can use what is available.

The polymerization reactor system may comprise at least one loop slurry reactor and may comprise vertical or horizontal loops, or a combination that may be independently selected from a single loop or a series of loops. Multiple loop reactors can include both vertical and horizontal loops. Slurry polymerization can be carried out in an organic solvent as carrier or diluent. Examples of suitable solvents include propane, hexane, cyclohexane, octane, isobutane, or combinations thereof. Olefin monomer, support, catalyst system components, and optional comonomers can be continuously fed to a loop reactor where polymerization occurs. Reactor effluent can be flash evaporated to separate solid polymer particles.

gas phase. In one aspect, a method for producing a polyolefin polymer according to the present disclosure is a gas phase polymerization process using, for example, a fluidized bed reactor. Reactors of this type and means for operating the reactor are described, for example, in U.S. Pat. , 566, 4,543,399, 4,882,400, 5,352,749, 5,541,270, EP-A-0802202, 839,380, each of which is incorporated herein by reference. These patents disclose gas phase polymerization processes in which the polymerization medium is mechanically agitated or fluidized by a continuous flow of gaseous monomer and diluent.

A gas phase polymerization system may employ a continuous recycle stream containing one or more monomers that are continuously circulated through a fluidized bed in the presence of a catalyst under polymerization conditions. A recycle stream can be withdrawn from the fluidized bed and recycled back to the reactor. At the same time, polymer product can be removed from the reactor and fresh monomer added to replace the polymerized monomer. Such gas phase reactors can include a process for multi-stage gas phase polymerization of olefins, the olefins being fed to a second polymerization zone with the catalyst-containing polymer formed in the first polymerization zone. while being polymerized in the gas phase in at least two independent gas phase polymerization zones.

Other gas phase processes contemplated by the disclosed polymerization processes include sequential or multi-step polymerization processes. In one aspect, gas phase processes that can be used in accordance with the present disclosure include US Pat. -A-0794200, EP-B1-0649992, EP-A-0802202 and EP-B-634421, all of which are incorporated herein by reference.

In one aspect of gas phase polymerization according to the present disclosure, the ethylene partial pressure is in a range suitable to provide practical polymerization conditions, such as 10 psi to 250 psi, such as 65 psi to 150 psi, 75 psi to 140 psi, or 90 psi to 120 psi. can vary in the range of In another aspect, the molar ratio of comonomer to ethylene in the gas phase is also in a range suitable to provide practical polymerization conditions, such as 0.0-0.70, 0.0001-0.25, More preferably, it can vary from 0.005 to 0.025, or from 0.025 to 0.05. According to one aspect, the reactor pressure can be maintained in a range suitable to provide practical polymerization conditions, such as 100 psi to 500 psi, 200 psi to 500 psi, or 250 psi to 350 psi.

According to a further aspect, in a fluidized gas bed process used to produce polymers, a gas stream containing one or more monomers is continuously passed through the fluidized bed in the presence of a catalyst under reactive conditions. can be circulated to A gas stream can be withdrawn from the fluidized bed and returned to the reactor, at the same time polymer product can be withdrawn from the fluidized bed and withdrawn from the reactor, and fresh monomer is added to replace the polymerized monomer. can do. For example, U.S. Pat. Nos. 4,543,399; 4,588,790; 5,028,670; 5,317,036; 5,405,922, 5,436,304, 5,543,471, 5,462,999, 5,616,661, and 5,668, 228, each of which is incorporated herein by reference in its entirety.

Alternatively, the antistatic compound may be fed to the polymerization zone at the same time as the finished catalyst. Alternatively, U.S. Pat. Nos. 7,919,569; 6,271,325; 6,281,306; 6,140; Antistatic compounds such as those described in US Pat. Nos. 432 and 6,117,955 can be used. For example, the clay heteroadduct can be contacted with or impregnated with one or more antistatic compounds. Antistatic compounds may be added at any point, for example they may be added at any point after calcination, such as up to and including the final catalyst preparation after contacting.

In another aspect, so-called "self-limiting" compositions can be added to the clay heteroadduct to inhibit chunking, fouling, or uncontrolled or runaway reactions in the polymerization zone. For example, U.S. Pat. Nos. 6,632,769, 6,346,584, and 6,713,573, each incorporated herein by reference, release catalyst poisons above a threshold temperature Disclosed are additives that can Typically, such compositions can be added at any point after firing to limit or stop polymerization activity above a desired temperature.

solution. Polymerization reactors can also include solution polymerization reactors in which the monomer is contacted with the catalyst composition by suitable agitation or other means. Solution polymerization can be carried out batchwise or continuously. An inert organic diluent or carrier containing an excess of monomer can be used and the polymerization zone is maintained at a temperature and pressure that results in the formation of a polymer solution in the reaction medium. Agitation can be used during polymerization to obtain better temperature control, to maintain a homogenous polymerization mixture throughout the polymerization zone, and suitable means for dissipating the heat of polymerization are utilized. The reactor can also contain a series of at least one separator that uses high and low pressures to separate the desired polymer.

Tubular reactors and high pressure LDPE. In yet another aspect, the polymerization reactor can comprise a tubular reactor, which can make the polymer by free radical initiation, or alternatively by using the disclosed catalysts. The tubular reactor can have several zones where fresh monomer, initiator, or catalyst and cocatalyst are added. For example, monomers can be contained in an inert gas stream and introduced into one zone of the reactor, and initiators, catalyst compositions and/or catalyst components can be contained in a gas stream and introduced into another zone of the reactor. can be introduced into the zone of These gas streams can then be mixed for polymerization and the heat and pressure can be adjusted appropriately to obtain optimum polymerization reaction conditions.

Combined or multiple reactors. In a further aspect, the catalysts and processes of the present disclosure are not limited by any possible reactor type or combination of reactor types. For example, the disclosed catalysts and processes can be used in a multiple reactor system, which can include coupled or connected reactors or unconnected multiple reactors to conduct polymerization. The polymer can be polymerized in one reactor under one set of conditions, then the polymer can be transferred to a second reactor for polymerization under different conditions.

In this aspect, the polymerization reactor system can include a combination of two or more reactors. The production of polymer in multiple reactors can be performed several times in at least two separate polymerization reactors interconnected by a transfer device to transfer the polymer obtained from the first polymerization reactor to the second reactor. wherein the polymerization conditions are different in individual reactors. Alternatively, polymerization in multiple reactors can involve manually transferring polymer from one reactor to subsequent reactors to continue the polymerization. Such reactors include multiple loop reactors, multiple gas reactors, combinations of loop reactors and gas reactors, combinations of autoclave reactors or solution reactors with gas or loop reactors, multiple solution reactors, or any combination including, but not limited to, multiple autoclave reactors and the like.

Polymers made using the disclosed catalysts and processes. The catalyst composition used in this process can produce high quality polymer particles without substantial reactor fouling. When using the catalyst composition in the loop reactor zone under slurry polymerization conditions, the particle size of the calcined heterocoagulation product should be from about 10 microns (μm) to about It can range from 1000 microns, from about 25 microns to about 500 microns, from about 50 microns to about 200 microns, or from about 30 microns to about 100 microns.

When the catalyst composition is used in the gas phase reactor zone, the particle size of the calcined heterocoagulation product is from about 1 micron to about 1000 microns, about 5 microns to provide good control of the polymer particles and the polymerization reaction. to about 500 microns, or from about 10 microns to about 200 microns, or from about 15 microns to about 60 microns.

Suitable particle sizes in other polymerization reactor systems, whether single or multiple, may be a function of the overall productivity of the catalyst and the optimum particle size and particle size distribution of the final polymer catalyst composite particles. For example, the optimum size and size distribution can be determined by the polymerization reactor system, e.g. whether it is large enough to clog downstream filters. Likewise, the optimal size and size distribution in the polymerization system is the ease with which the catalyst-polymer composite particles are melted and extruded into pellets, transported or handled within storage silos or extrusion equipment. can be balanced against

Polymers produced using the catalyst compositions of the present disclosure are formed into a variety of articles such as, for example, household containers and appliances, film products, car bumper components, drums, fuel tanks, pipes, geomembranes, and liners. can do. In one aspect, additives and modifiers can be added to the polymer to provide desired effects, such as desired combinations of physical, structural, and flow properties. While maintaining the desired polymer properties obtained for polymers produced using the transition metal or metallocene catalyst compositions disclosed herein by using the methods and materials described herein , it is believed that the article can be manufactured at a lower cost.

Specific embodiment. In a more specific embodiment of the disclosure, a process is provided for making a catalyst composition, the process comprising:
(1) A suitable dioctahedral phyllosilicate clay is contacted with a heterocoagulant and easily filtered and less than 10 mS/cm, or less than 5 mS/cm, or from 1 mS/cm to 50 μS/cm, or 500 μS/cm forming a solid that is washed to a conductivity of ˜50 μS/cm;
(2) dehydrating and dehydroxylating the washed clay heteroadduct at or within a temperature range of from about -10°C to about 500°C to show no d001 peak at 2-theta less than 8 degrees, or and producing a calcined heterocoagulated clay adduct composition that exhibits substantially no, preferably no, or substantially no d001 peak at less than 10 degrees 2-theta. If there are peaks in the region of less than 10 degrees 2-theta, the major ones are 4 degrees 2-theta or more, or peaks with greater intensity than the peaks that the clay mineral itself would exhibit after firing at 300° C., for example, 8 degrees 2-theta. must be in the range of ~12 degrees 2-theta,
(3) mixing the calcined heterocoagulated clay adduct composition with, for example, bis(1-butyl-3-methylcyclopentadienyl)zirconium dichloride at a temperature in the range of 15° C. to 100° C. to form a mixture; and,
(4) after 1 minute to 1 hour, combining the mixture in part (3) with a trialkylaluminum such as triethylaluminum, trioctylaluminum or triisobutylaluminum to produce a catalyst composition. (Optionally "consist essentially of" or "consist of").

An alternative specific embodiment to that just described is to reverse the order of addition of the metallocene and trialkylaluminum in the immediately preceding steps (1)-(4).

The foregoing description is intended to be illustrative, not limiting, of the scope of the disclosure, which is further illustrated by the following examples. The examples should not be construed as limiting the scope of the disclosure. Rather, various other embodiments, aspects, modifications, and equivalents thereof may suggest themselves to those skilled in the art in light of the written description without departing from the spirit of the invention or the scope of the appended claims. can be pursued. Accordingly, the following examples are presented to provide a more detailed disclosure and explanation to those of ordinary skill in the art.

Reagents and General Procedures Unless otherwise stated, all reagents used to prepare the clay heteroadducts of the present disclosure were obtained from the commercial sources indicated and used "as is".

Volclay® HPM-20 bentonite aqueous dispersion (montmorillonite) manufactured by American Colloid Company is obtained from McCullough & Associates and is also referred to simply as HPM-20 or HPM-20 clay. A 50% aqueous solution of aluminum chlorohydrate (abbreviated as "ACH") and UltraPAC® 290 (polyaluminum chloride, empirically Al ₂ (OH) _2.5 Cl _3.5 ) were obtained from GEO Specialty Chemicals. Aluminum chlorohydrate powder (ALOXICOLL® 51P, empirically Al ₂ Cl(OH) ₅ ) and aluminum sesquichlorohydrate solution (ALOXICOLL® 31L) were obtained from Parchem Fine and Specialty Chemicals. Fumed silica (AEROSIL® 200) and fumed aluminum oxide aqueous dispersion (AERODISP® W400) were obtained from Evonik Industries AG. An aqueous dispersion of colloidal alumina (NYACOL® AL27) was prepared by Nano Technologies, Inc.; Obtained from

Unless otherwise noted, in the specification and examples, the clay dispersions, clay heteroadducts, pillared clays, and other compositions were run on a dual speed Conair™ Waring™ with timer. Can be prepared using a Commercial Lab Blender model 7010G. Blender speeds may be referred to as "low" speed blending versus "high" speed blending, as follows. A model 7010G blender was connected to a Staco energy variable transformer (model number 3PN1010B) and the blender speed was adjusted by changing the transformer settings. In the examples and specification, "slow" blending was achieved by setting the transformer from 0-50 and "fast" blending was achieved by setting the transformer from 50-100.

Conductivity was measured using a Eutech PCSTestr 35 or a radiometric analysis conductivity meter and measurements were made according to the instrument manual and references accompanying each instrument. Solution or slurry pH measurements were made using a Eutech PCSTestr 35 or Beckmann φ 265 laboratory pH meter.

Deionized water, referred to herein as Milli-Q® water, was prepared by first pretreating the water using a Prepak 1 pretreatment pack and then Millipore Milli-Q® Advantage A10 water. Obtained by further purifying water using a purification system. This water was typically used within 2 hours of collection.

Hexane, heptane, toluene and dichloromethane were dried over activated molecular sieves and degassed with nitrogen before use. Instrument grade isobutane used as a solvent for ethylene homopolymerization was purchased from Airgas and purified by passage through columns of activated carbon, alumina, 13× molecular sieves and finally from Diamond Tool and Die, Inc. Ultra high purity grade ethylene and hydrogen from an OxyClear™ gas purifier model number RGP-R1-500 from Airgas was obtained from Airgas. UHP (ultra high purity) ethylene was further purified by passage through columns of activated carbon, alumina, 13× molecular sieves, and an OxyClear™ gas purifier model number RGP-R1-500. UHP hydrogen was purified by passage through an OxyClear™ gas purifier model number RGP-R1-500. Purified propylene was obtained as a slipstream from a commercial polypropylene plant.

All preparations involving handling of organometallic compounds were performed under a nitrogen ( _N2 ) atmosphere using Schlenk techniques or in a glovebox.

Zeta Potential Measurements The zeta potentials of the colloidal suspensions disclosed herein were derived from measuring the electroacoustic effect when an electric field is applied to the suspension. The instrument used to make these measurements was a Colloidal Dynamic Zeta Probe Analyzer™. For example, zeta potential measurements were used to determine dispersed clay concentrations in 0.5 wt% to 1 wt% Volclay® HPM-20/water dispersions as follows. A 250 g to 300 g sample of the dispersion to be measured was transferred to a measuring vessel containing an axial bottom stirrer. The stirring speed was set fast enough to prevent settling or substantial settling of the dispersion, but slow enough to completely immerse the electroacoustic probe in the mixture when fully lowered. Met. Typically, the stirring speed was set at 250-350 rpm, often 300 rpm.

The Colloidal Dynamic Zeta Probe Analyzer™ measurement parameters used were as follows: 5 readings at 1 reading/min, particle density of 2.6 g/cc, dielectric constant of 4.5. An initial estimated colloid weight percentage (concentration _estimate ) of 0.7% to 1.0% by weight was typically entered into the Zeta Probe Analyzer™ software. A 5 wt % Volclay® HPM-20/water dispersion measured a zeta potential of −46 mV. In the equation below, where the final dispersed clay concentration is referred to as "conc", the final dispersed clay concentration can be calculated from the initial estimated concentration according to the following equation.
Concentration = _{Concentration Estimate} * (Measured Zeta Potential/(-46))

A Zeta Probe Analyzer™ was also used to dynamically track the evolving zeta potential during the titration of clay dispersions in either colloidal or non-colloidal solutions. Typically, the cationic polymetalate titrant (or other cationic titrant) is added at 0.5% to 5.0% by weight of the Volclay® HPM-20/water dispersion per titration point. 0.25 mL to 2.0 mL was added with an equilibration delay of 30 seconds to 120 seconds.

The Zeta Probe software uses the colloidal particle weight percentage not included in the colloidal titrant to calculate the zeta potential. Therefore, when the titrant was a colloidal species, the measured zeta potential was adjusted to reflect the excess colloidal content of the solution measured by the following method. Initially, the weights of titratable clay and titratable cationic species were determined by the following formulas, where ^* denotes multiplication, W denotes weight, and V denotes volume.
W _Titrant = V _Titrant * Density _Titrant * % Solids _Titrant
W _Clay = V _Total ^* Density _Titrant ^* Particle Concentration _Measurement

The density of a 5% Volclay® HPM-20 aqueous dispersion (titrant) was determined to be approximately 1.03 g/mL. The titration weight was scaled according to its particle density and compared to the particle density of titrated Volclay® HPM-20 (montmorillonite) to obtain the effective titration weight ( _Weffective ), which in this example is: calculated as
W _Effective = W _Titrant * Particle Density _Titrant / Particle Density _Titrant

The effective colloidal particle weight percentage (wt % _effective ) was then calculated to provide an estimate of the relative increase in colloid content compared to equivalent titrations using non-colloidal titrants. The reciprocal of this value was then multiplied by the measured zeta potential to determine the adjusted zeta potential as follows.
% _{effective by} weight = (W _effective + W _clay )/V _t
A = weight % _measured / weight % _effective
ZP _{adjustment value} = ZP _{measurement value} * A

As a function of titration volume and mmol Al/g clay, during zeta potential titrations of clay dispersions with cationic polymetalates, such as the titration of Volclay® HPM-20 montmorillonite with aluminum chlorohydrate (ACH). Zeta potential was measured before and during titration. Taking samples of the solid material formed at various points during the titration (e.g. 0 mmol Al/g clay, 1.17 mmol Al/g clay, 1.52 mmol Al/g clay, etc.), drying each sample, It was calcined and analyzed by powder XRD (X-ray diffraction).

As an example of a zeta-potential titration, FIG. 3 shows the zeta-potential of a series of dispersions obtained by titrating Volclay® HPM-20 montmorillonite with aluminum chlorohydrate (ACH), titrated volume versus dispersion. Figure 4 plots the zeta potential (mV) of the same titration of mmol Al/g clay vs. the dispersion. FIG. 2 provides powder XRD patterns of a series of calcined products collected during this zeta potential titration of HPM-20 clay by ACH.

Powder X-Ray Diffraction (XRD) Studies Powder X-ray patterns of clays and clay heteroadducts were obtained using standard X-ray powder diffraction techniques on a Bruker D8 daVinci instrument using a backloading holder and background Acquired using a Bragg Brentano geometry of the 'theta-theta' scan type with the silicon tip zeroed. The detector used was a linear silicon strip (LynxEYE) PSD detector. Test samples were placed in the sample holders of two circular goniometers enclosed in radiation-safe enclosures. The X-ray source was a 2.0 kW Cu X-ray tube maintained at 40 kV and 25 mA operating current. X-ray optics were standard Bragg Brentano focusing mode, X-rays diverged from a DS slit (0.6 mm) in the tube and hit the sample, followed by a position-sensitive X-ray detector (Lynx-Eye, Bruker -AXS) converged. Two circular goniometers of 250 mm diameter were computer controlled with independent stepper motors and optical encoders. Flat pressed powder samples were scanned at 0.8° (2-theta)/min (2-30 degrees 2-theta over 35 minutes). The software suite for data collection and evaluation was Windows-based. Data collection was automated using the Commander program by employing a BSML file and data was exported to the program DIFFRAC. Analyzed by EVA.

XRD test methods applied to the calcined clay heteroadducts disclosed herein to determine basal spacing are described, for example, by McCauley in US Pat. row). Bragg's equation or law that applies to clay is nλ=2d sin θ, where n is the number of repetitions, λ is 1.5418, d is the d001 spacing, and θ is the angle of incidence. is.

Pore Volume and Pore Volume Distribution The pore volume of the clay heteroadducts is reported as the cumulative volume in cc/g (cm ³ /g, cubic centimeters per gram) of all pores discernible by the nitrogen desorption method. For catalyst supports or carrier particles such as alumina powder, and clay and clay heteroadducts of the present disclosure, the pore size distribution and pore volume are according to S.W. Brunauer, P.; Emmett, andE. Teller in the J.D. Am. Chem. Soc. , 1939, 60, 309. E. T. See also ASTM D 3037, which identifies procedures for determining surface area using the nitrogen BET method, calculated with reference to nitrogen desorption isotherms (assuming cylindrical pores) by (or BET) techniques.

Pore volume distribution can be useful in understanding catalyst performance, and various attributes of pore volume distribution such as pore volume (total pore volume), percentage of pores in various size ranges, as well as dV The "pore mode", which describes the pore diameter corresponding to the local maximum in the (log D) vs. pore diameter distribution, is described by E.M. P. Barrett, L. G. Joyner, and P.S. P. Halenda ("BJH"), "The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms," J. Am. Am. Chem. Soc. , 1951, 73(1), pp 373-380.

surface area s.c. Brunauer, P.; Emmett, andE. Teller in the J.D. Am. Chem. Soc. , 1939, 60, 309. E. T. (or BET) technique using nitrogen desorption isothermal (assuming cylindrical pore) nitrogen adsorption desorption isotherm to determine surface area by nitrogen adsorption method and nitrogen BET method to determine surface area See also ASTM D 3037, which identifies procedures for All morphological properties related to weight, such as pore volume (PV) (cc/g, cubic centimeters per gram) or surface area (SA) (m ² /g, square meters per gram), are described in the art were normalized to the "metal-free standard" according to the well-known procedure in . However, unless otherwise specified, the morphological properties reported herein are on a "measured" basis without correction for metal content.

Polymerization Reactions Ethylene homopolymerizations were carried out in a dry 2 L stainless steel Parr autoclave reactor using 1 L of isobutane diluent. Table 3A shows comparative and inventive heterocoagulated clay supports using (1-n-butyl-3-methylcyclopentadienyl) ₂ ZrCl ₂ and triethylaluminum (AlEt ₃ ) as metallocene and cocatalyst. Properties and polymerization data for bodies are reported. Selected pressures and temperatures in the reactor for calculating the activity reported in Table 3A were maintained electronically by an ethylene mass flow controller or, alternatively, a jacketed temperature controller. Manually maintained using 450 total psi and 90°C. Table 3B reports the surface area and porosity properties of the comparative supports and the heterocoagulated clay supports of the invention.

Polymerization data using the support activator of the present disclosure and polymerization data using a comparative catalyst system are presented in Table 3A. Polymerization runs are labeled P1-P39 and the specific example number of the support used in each polymerization run is listed.

If hydrogen is used, use premixed gas feed tanks of purified hydrogen and ethylene to ensure that there is enough gas in the feed tanks so as not to significantly change the ratio of ethylene to hydrogen in the feed to the reactor. The desired total pressure was maintained at a constant pressure. The addition of hydrogen can affect the melt index of the polymer obtained with any given catalyst.

Prior to conducting a polymerization run, moisture was first removed from the reactor interior by preheating the reactor to at least 115° C. under a stream of dry nitrogen, which was maintained for at least 15 minutes. Agitation was provided by, for example, an impeller and a Magnadrive™ with a set point of 600 rpm. The metallocene catalyst for the polymerization runs in Table 3A was (1-n-butyl-3-methylcyclopentadienyl) ₂ ZrCl ₂ with triethylaluminum (AlEt ₃ or TEA) as cocatalyst or alkylating agent. and 1.8 mmol of AlEt ₃ (3 mL of 0.6 M solution of TEA in hexanes) was typically used for the polymerization runs in this table. Post-contacted catalyst components, i.e., a composition containing all listed catalyst system components previously contacted to form a composition, are prepared in an inert atmosphere glove box and transferred to a catalyst-filled tube or vessel. bottom. The contents of the catalyst-filled vessel were then charged to the reactor by flushing with 1 L of isobutane. The reactor temperature control system is then turned on and allowed to reach a temperature several degrees below the temperature setpoint, which typically took about 7 minutes. The reactor was brought to operating pressure by opening the ethylene manual feed valve and the polymerization run continued for the time reported in Table 3A, eg, 30 or 60 minutes.

Alternatively, the contents of the catalyst-filled tube can be forced into the reaction vessel with ethylene at a temperature several degrees below the setpoint temperature of the run, for example, about 10°C below the setpoint temperature. This method used two charging tubes. When running pressure was reached, the reactor pressure was controlled by a mass flow controller. Ethylene consumption and temperature were monitored electronically. During the course of the polymerization, the reactor temperature was maintained at the set point temperature ±2°C, except for the initial charge of catalyst during the first minutes of the run. After 60 minutes or the specified run time, the polymerization was stopped by shutting off the ethylene inlet valve and bubbling isobutane. The reactor was returned to ambient temperature. The polymer produced in the reaction was then removed from the reactor and dried, and the polymer weight was used to calculate the activity of a particular polymerization. Polymer melt indices, specifically melt index (MI) and high load melt index (HLMI), are obtained after stabilizing the polymer with butylated hydroxytoluene (BHT) according to ASTM procedures D618-05 and D1238-04C. rice field. Polymer density was measured according to ASTM D1505-03.

Catalyst and Polymer Characterization ¹ H NMR spectra of metallocene compounds were collected at room temperature by placing a 20 mg metallocene sample in a 10 mm NMR tube and adding 3.0 mL of CDCl ₃ . ¹ H NMR spectra were obtained on a Bruker AVANCE™ 400 NMR (400.13 MHz). Chemical shifts are reported in ppm (δ) relative to TMS or are referenced to the chemical shift of the residual solvent proton resonance. Coupling constants are reported in Hertz (Hz).

NMR measurements of isotactic pentad content in polypropylene were obtained by placing a 400 mg polymer sample in a 10 mm NMR tube into which tetrachloroethane-d2 and 1.7 g of o-dichlorobenzene were added. ¹³ C NMR spectra were obtained on a Bruker AVANCE™ 400 NMR (100.61 MHz, 90° pulses, 12 sec delay between pulses). Approximately 5000 transients were stored for each spectrum and the mmmm pentad peak (21.09 ppm) was used as a reference. Microstructural analysis was performed according to Busico, et al. Macromolecules, 1994, 27, 4521-4524.

Polypropylene melt flow rate (MFR) was determined at 230° C. under a load of 2.16 kg according to ASTM D-1238 procedure.

DSC and TA Instruments, Inc. Model: DSC Q1000 was used to obtain the melting point Tm of polypropylene according to the procedure of ASTM D-3417.

Nitrogen adsorption dissociation data for support activator and other materials were collected using an Anton Paar Autosorb iQ instrument. Representative measurements were performed as follows. 50 mg to 150 mg of calcined sample was weighed into the sample cell under an inert atmosphere and sealed with a stopper. The sample cell was inserted into the Autosorb iQ station and placed under vacuum. The samples were then cooled using liquid nitrogen. Nitrogen adsorption-desorption isotherms were recorded at 77 K and relative pressure P/P ₀ =0.05-1 (P ₀ =atmospheric pressure).

Example 1. Comparative Example of Calcined Clay Preparation A 700 mg sample of Volclay® HPM-20 clay in neat powder form was combined with 60 mL of deionized water. The mixture was vigorously stirred and rotary evaporated at 55° C. for 20-30 minutes. The resulting sample was then calcined at 300° C. for 6 hours to obtain 620 mg of gray powder. Nitrogen adsorption/desorption BJH pore volume analysis is plotted in FIG.

Example 2. Comparative Example of Azeotropic Clay Preparation A 5.16 g sample of Volclay® HPM-20 clay powder was placed in a round bottom flask and combined with 40 mL to 60 mL of n-butyl alcohol. The mixture was vigorously stirred and then rotary evaporated to dryness at 45°C. The drying process was stopped as soon as the alcohol was visibly evaporated. An odor of n-butyl alcohol was typically noticeable from samples after this process. A 5.39 g sample of wet clay was obtained and 4.46 g of this material was then calcined at 300° C. for 6 hours to give 3.3 g of black powder.

Example 3. Comparative Example of Azeotropic Clay Preparation After Shearing A 133 g sample was first rotary evaporated at 45° C.-55° C. to remove most of the water, then 50 mL of n-butanol was added. Rotoevaporation at 45°C was continued and drying was stopped as soon as the alcohol was visibly evaporated. A 3.2 g sample of this material was then calcined at 300° C. for 6 hours to yield 2.6 g of gray powder. BJH pore volume analysis of this material is shown in FIG.

Example 4. Preparation of Colloidal Clay Dispersion A Waring® blender was charged with 570 g of deionized water and while stirring, 30.0 grams of HPM-20 was added in small portions. The mixture was stirred at a high rate (revolutions per minute, rpm) to obtain a 5% by weight dispersion of the HPM-20 suspension with substantially no lumps or clumps. A 4.8 wt% dispersion of Volclay® HPM-20 clay is prepared using 20 g HPM-20 and 394 g water and stirred using a Waring® blender at high rpm. to obtain a clump-free dispersion, which was characterized by a conductivity of 908 μS/cm and a pH of 9.39.

Example 5. Comparative example of preparation of aluminum chlorohydrate (Al ₁₃ Keggin-ion) pillared clay using aluminum chlorohydrate solution (6.4 mmol Al/g clay). 100 g of the clay dispersion was charged, followed by 6.9 g of a 50% GEO aluminum chlorohydrate solution with a reported basicity of 83.47% while stirring. After adding the aluminum chlorohydrate, the mixture was stirred at high rate (rpm) for an additional 3 minutes. The pH of the mixture was measured as pH 4.23. Attempts to filter the resulting mixture through Fisherbrand™ P8 filter paper were unsuccessful. Therefore, two aliquots of the mixture were transferred to 50 milliliter plastic centrifuge tubes and the samples were centrifuged in a Beckmann Coulter Allegra 6 centrifuge at 3600 rpm for a total of 140 minutes. The resulting clear supernatant was decanted from each tube and replaced with deionized water. The sample was shaken to resuspend solids and centrifuged again. This process was repeated multiple times (typically 4-8 times) until the supernatant of one centrifuged sample obtained a conductivity of 67 μS/cm and a pH of 6.0. The supernatant was then decanted and the solids were transferred to an Erlenmeyer flask with approximately 70 mL of n-butanol using minimal deionized water. Rotary evaporation yielded 2.11 g of an off-white powder. A 437 mg sample of this powder was filled into a porcelain bowl and placed in an oven at 300° C. for 6 hours to yield 0.301 grams of dark gray powder.

Example 6. Reproducibility of preparation of aluminum chlorohydrate (Al ₁₃ Keggin-ion) pillared clay using aluminum chlorohydrate solution (6.4 mmol Al/g clay):
While stirring, slowly add 30 g of HPM-20 clay over 1-2 minutes to a Waring® blender containing 570 g of deionized Milli-Q® water and mix at low speed. A gray colloidal dispersion containing no or substantially no visible lumps or clumps was obtained. After this addition was complete, the resulting dispersion was blended at high speed for 5-10 minutes to give a slightly viscous mixture of a 5 weight percent aqueous dispersion of HPM-20 clay.

A 150 g portion of this 5 wt % HPM-20 aqueous dispersion was transferred to a Waring® blender and 9.35 g of the GEO aluminum chlorohydrate 50 wt % aqueous solution was pipetted into the vial, one at a time. added to the dispersion. The mixture was blended on high speed for 5 minutes, then divided into four 50 mL centrifuge tubes and centrifuged at 3000-3500 rpm for 30-60 minutes. The pH and conductivity of the supernatant were measured (Eutech PCSTester 35). The supernatant was decanted and the remaining wet solid was resuspended in deionized Milli-Q® water. The centrifugation process (centrifugation, supernatant pH/conductivity measurement, supernatant removal, and resuspension in deionized Milli-Q® water) was performed with a supernatant conductivity of 100-300 μS/cm. repeated until reaching A total of 6 centrifugations were performed, at which point the supernatant was discarded for the final hour. To the remaining wet solid was added 200 mL of 1-butanol and after rotary evaporation at 45° C., 9.75 g of wet solid was obtained. The wet solid was then ground with a pestle and mortar and 4.28 g of this solid was transferred to a porcelain crucible and calcined at 300° C. for 6 hours to give 1.65 g of gray-black powder.

Example 7. Comparative Example of Preparation of Aluminum Chlorhydrate (Al ₁₃ Keggin-Ion) Pillar Clay Using Powdered Aluminum Chlorhydrate (6.4 mg Al/g Clay) While stirring, a 30 g sample of HPM-20 clay was added to Slowly add to a Waring® blender containing 570 g of deionized Milli-Q® water over 2 minutes and stir at low speed to contain no or substantially no visible lumps or clumps. A gray colloidal dispersion was obtained which was essentially free of After the addition was complete, the dispersion was blended at high speed for 5-10 minutes to give a slightly viscous mixture of a 5 weight percent aqueous dispersion of HPM-20 clay.

A 100 g sample of this 5 wt% HPM-20 aqueous dispersion was transferred to a Waring® blender, 3.42 g of Parchem ALOXICOLL® 51P powder was weighed into a vial, and 35-40 g of deionized Diluted with Milli-Q® water and then added all at once to the dispersion. The mixture was blended at high speed for 5 minutes, then divided into four 50 mL centrifuge tubes and centrifuged at 3000-3500 rpm for 30-60 minutes. The pH and conductivity of the supernatant were measured (Eutech PCSTester 35). The supernatant was decanted and the remaining wet solid was resuspended in deionized Milli-Q® water. The centrifugation process (centrifugation, supernatant pH/conductivity measurement, supernatant removal, and resuspension in deionized Milli-Q® water) was performed with a supernatant conductivity of 100-300 μS/cm. (a final supernatant pH of 4.25, a conductivity of 225 μS/cm, and a total of 6 centrifugations were performed), at which point the supernatant was discarded for the final time. The remaining wet solid was combined with 100-200 mL of 1-butanol in a round bottom flask and rotary evaporated at 45° C. to give 5.54 g of wet solid, then ground with a pestle and mortar. A 1.8 g portion of this solid was transferred to a porcelain crucible and calcined at 300° C. for 6 hours to give 1.2 g of a gray-black powder.

Example 8. Gravimetric Determination of Colloidal Clay Content of 1% Volclay® HPM-20 Aqueous Dispersion A 60 g sample of a 5 wt % HPM-20 clay dispersion in water was ) with deionized water to give 300 g of an aqueous dispersion of 1 wt % HPM-20. A significant amount of settled clay was observed in this diluted dispersion after standing for 30 minutes to 1 hour. The colloidal portion was decanted and the sedimented portion was collected, dried and weighed. This process provided 900 mg of HPM-20 clay collected, corresponding to a colloidal content of 0.7% of the diluted dispersion. In a repeat of this experiment using 280-290 g of this 1% HPM-20 dispersion, 630 mg and 910 mg of solid clay were isolated, respectively, yielding colloid content values of 0.77 and 0.69 wt% for the diluted dispersion. Obtained.

Example 9. Zeta Potential Measurement of Aluminum Chlorhydrate/Volclay® HPM-20 Ratio in Clay Heteroadducts With stirring, 30 g of HPM-20 clay was dehydrated with 570 g of Milli-Q® over several minutes. Slow addition to a Waring® blender containing deionized water yielded a gray colloidal dispersion containing no or substantially no visible lumps or clumps. After the addition was complete, the dispersion was stirred at high speed for 5-10 minutes to give a slightly viscous mixture of a 5 wt% aqueous dispersion of HPM-20 clay. A 42 g portion of this 5 wt % HPM-20 aqueous dispersion was combined with 258 g of Milli-Q® deionized water to yield a 0.7 wt % HPM-20 aqueous dispersion. 280 g of this 0.7% by weight colloidal dispersion was then transferred to the measurement vessel of a Colloidal Dynamic Zeta Probe Analyzer™ containing an axial bottom stirrer. The stirring speed was set between 250 rpm and 350 rpm.

An initial colloid content estimate of 0.7 wt. was used to make zeta potential measurements to determine the actual colloidal content of the clay dispersion. Measurement of a 5 wt% HPM-20 aqueous dispersion yields a zeta potential measurement of -46 mV (negative 46 millivolts). Initial colloid content estimates were adjusted to match this zeta potential. In this case, the HPM-20 colloid content of the dispersion was determined to be 0.62%. The colloidal dynamic zeta probe measurement parameters were as follows: 5 readings, 1 reading/min, particle density of 2.6 g/cc, dielectric constant of 4.5.

A 2.5 wt% aqueous solution of aluminum chlorohydrate (ACH) was obtained by dilution of a 50 wt% aluminum chlorohydrate solution (GEO). A volumetric titration of a 2.5 wt% ACH solution in 0.7 wt% HPM-20 aqueous dispersion was then performed. The titration setting was 0.5 mL per titration point and the equilibration delay was 30 seconds, i.e., after addition of 0.5 mL of aqueous ACH, there was a 30 second delay to allow for equilibration prior to zeta potential measurement. did

Figure 3 and Table 4 report the results of this zeta potential titration for the volumetric addition of 2.5 wt% aqueous aluminum chlorohydrate (ACH) into the 0.7 wt% HPM-20 aqueous dispersion. , the measured zeta potential is plotted against the titration volume (mL). The titration volume indicates the cumulative volume of added aluminum chlorohydrate aqueous solution. Based on the amount of ACH solution and the measured density of the ACH solution of 1.075 g/mL, and the ACH molar aluminum/clay mass ratios used to achieve -20 mV, neutral, and +20 mV zeta potentials, Summarize.

Example 10. Zeta Potential Measurement of Polyaluminum Chloride UltraPAC® 290/Volclay® HPM-20 Ratio in Clay Heteradducts - Add slowly to a Waring® blender containing Q® deionized water and stir at low speed to obtain a gray colloid containing no or substantially no visible lumps or clumps. A dispersion was obtained. After the addition was complete, the dispersion was agitated by blending at high speed for 5-10 minutes to obtain a slightly viscous mixture of a 5 wt% aqueous dispersion of HPM-20 clay.

A 60 g portion of this 5 wt % HPM-20 aqueous dispersion was combined with 240 g of Milli-Q® deionized water to yield a 1 wt % HPM-20 aqueous dispersion. Approximately 280 g of the 1% by weight colloidal dispersion was transferred to the measurement vessel of a Colloidal Dynamic Zeta Probe Analyzer™ containing an axial bottom stirrer. Stirring speed was set as above.

Zeta potential measurements were performed on this diluted HPM-20 aqueous dispersion using an initial colloid content estimate of 1 wt% to determine the actual colloid content of the clay dispersion. Measurement of a 5 wt% HPM-20 aqueous dispersion yields a zeta potential measurement of -46 mV. Initial colloid content estimates are adjusted to match this zeta potential. In this case, the HPM-20 colloid content of the dispersion was estimated to be 0.67%. The colloidal dynamic zeta probe measurement parameters were as follows: 5 readings, 1 reading/min, particle density of 2.6 g/cc, dielectric constant of 4.5.

A 4.58 g sample of polyaluminum chloride (abbreviated as "PAC") UltraPAC® 290 (17.1% Al ₂ O ₃ content) was washed using Milli-Q® deionized water. Diluted into a 100 mL volumetric flask. A volumetric titration of this 4.58 wt% UltraPAC® 290 solution in the 1 wt% HPM-20 clay dispersion described above was then performed. The titration setting was 1 mL per titration point and the equilibration delay was 30 seconds.

Figure 5 and Table 5 report the results of these zeta potential measurements, where titration volume indicates the cumulative volume of the added 4.58 wt% UltraPAC® 290 aqueous solution, and the measured zeta potential is Plot against titration volume (mL). Table 5 summarizes the amount of UltraPAC® 290 dispersion used to achieve −20 m, neutral, and +20 mV zeta potentials.

Example 11. Zeta Potential Measurement of NYACOL® AL27 Colloidal Alumina/Volclay® HPM-20 Ratio in Clay Heteroadducts 1 wt % HPM-20 clay dispersion in 240 g Milli-Q® water was prepared by adding about 60 g of a 5 wt% HPM-20 aqueous dispersion. A 285 g to 300 g portion of the 1 wt % dispersion was transferred to the zeta probe measurement vessel and an initial zeta potential measurement was made to estimate the true particle wt % of the solution.

Zeta potential measurements were performed on this diluted HPM-20 aqueous dispersion to determine the actual colloidal content of the clay dispersion. Measurement of a 5 wt% HPM-20 aqueous dispersion yields a zeta potential measurement of -44.2 mV. Initial colloid content estimates are adjusted to match this zeta potential. In this case, the HPM-20 clay colloid content of the dispersion was determined to be 0.92%. The colloidal dynamic zeta probe measurement parameters were as follows: 5 readings, 1 reading/min, particle density of 2.6 g/cc, dielectric constant of 4.5.

A 100 g sample of commercially available NYACOL® AL27 colloidal alumina dispersion (20 wt % Al ₂ O ₃ ) was combined with 100 g of Milli-Q® deionized water to give a A 10 wt % Al ₂ O ₃ dispersion was obtained. A volumetric titration of this 10 wt% dispersion in the 1 wt% HPM-20 clay dispersion described above was then performed. (The 1 wt% HPM-20% concentration designation is based on the recipe rather than the zeta potential estimate, which was determined to be about 0.92 wt% because not all of the clay was colloidal at dilution.) Titration The settings were as follows. 1 mL per titration point from 0 mL to 27 mL and 3 mL per subsequent titration point with an equilibration delay of 60 seconds.

Figure 6 and Table 6 report the results of these measurements, where titrated volume indicates the cumulative volume of NYACOL® AL27 alumina dispersion added. In this example, the titrant is also a colloidal species. Zeta potentials were adjusted using the methods described above and the dates are provided in FIG. Table 6 summarizes the amount of NYACOL® AL27 dispersion used to achieve −20 m, neutral, and +20 mV zeta potentials.

Example 12. Preparation of Aluminum Chlorhydrate Clay Heteroadduct (1.76 mmol Al/g Clay) A Waring® blender was charged with 475.22 grams of deionized water. While stirring, 25.09 grams of HPM-20 clay from American Colloid was slowly added. After the clay addition was complete, the mixture was stirred at elevated temperature for 5 minutes to obtain a lump-free homogenous suspension, followed by 9.53 grams of aluminum chlorohydrate 50% by weight aqueous solution (GEO) with stirring. Add and continue stirring for 9 minutes. The mixture was poured into a high density polyethylene bottle. The Waring® flask was rinsed with 42.5 grams of deionized Milli-Q® water and the rinse was transferred to a bottle. The bottle was shaken to mix the contents well and the conductivity of the slurry was measured as 4.03 mS/cm and pH as 5.89.

A second batch of aluminum chlorohydrate clay heteroadduct was prepared by mixing 380.26 grams of deionized Milli-Q® water, 20.03 grams of HPM-20 clay, and 7.70 grams of aluminum chlorhydride. were prepared in the same manner using a rate 50 wt% aqueous solution (GEO). The conductivity of this batch was measured to be 3.64 mS/cm and the pH to 5.58. The contents of the second batch were transferred along with 30 grams of deionized water to the bottle containing the first batch of residual slurry. The bottle was shaken to give a gray slurry with no visible lumps. The combined batch had a final conductivity of 3.84 mS/cm and a final pH of 5.87.

Example 13. Comparative example of preparation of aluminum sesquichlorohydrate clay heteroadduct using powdered aluminum sesquichlorohydrate (ASCH, 6.4 mmol Al/g clay). In comparison, synthesis of an aluminum sesquichlorohydrate clay heteroadduct using powdered aluminum sesquichlorohydrate (ASCH) demonstrating the need to use multiple washes and centrifugations to isolate the product.

While stirring, slowly add 30 g of HPM-20 clay over 1-2 minutes to a Waring® blender containing 570 g of deionized Milli-Q® water and mix at low speed. to give a gray colloidal dispersion containing no or substantially no visible lumps or clumps. After the addition was complete, the dispersion was blended at high speed for 5-10 minutes to give a slightly viscous mixture of a 5 weight percent aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt % HPM-20 clay aqueous dispersion was transferred to a Waring® blender. A separate vial was charged with 3.53 g of ALOXICOLL® 31P powder and 35-40 mL of deionized Milli-Q® water, and the mixture was poured into the stirred dispersion all at once. The mixture was blended on high speed for 5 minutes, then split into four 50 mL centrifuge tubes and centrifuged at 3000-3500 rpm for 30-60 minutes. The pH and conductivity of the supernatant were measured (Eutech PCSTestr 35), the pH was 4.0 and the conductivity was 7300 μS/cm. The supernatant was decanted and the remaining wet solid was resuspended in deionized Milli-Q® water. The centrifugation process (centrifugation, supernatant pH/conductivity measurement, supernatant removal, and resuspension in deionized Milli-Q® water) was performed with a supernatant conductivity of 100-300 μS/cm. repeated until reaching A total of 6 centrifugations were required to achieve this conductivity with a final supernatant pH of 4.3 and a conductivity of 286 μS/cm. At this point the supernatant was discarded for the final hour and the remaining wet solids were combined with 100-200 mL of 1-butanol in a round bottom flask and rotary evaporated at 45°C to yield 5.82 g of wet solids. and then ground with a pestle and mortar. A 2.1 g sample of this solid was transferred to a porcelain crucible and calcined at 300° C. for 6 hours to yield 1.1 g of a gray-black powder.

Example 14. Spray Drying, Screening and Calcination of Unwashed Aluminum Chlorhydrate Clay Heteroadduct Retained on 325 Mesh Screen (1.76mmol Al/g Clay) Aluminum Chlorhydrate Clay Prepared According to Example 12 A portion of the heteroadduct (1.76 mmol Al/g clay) mixture (slurry) was spray dried using a Buchi B290 laboratory spray dryer. A portion of the spray dried clay heteroadduct was screened through a 325 mesh screen. Two grams of material retained on a 325 mesh screen was charged to a 300° C. oven and heated in air for 6 hours. While still hot, the material was transferred to a vacuum chamber and allowed to cool to room temperature under vacuum.

Example 15. Spray drying, screening, and calcining of unwashed aluminum chlorohydrate clay heteroadduct through a 325 mesh screen (1.76 mmol Al/g clay). A portion of the adduct (1.76 mmol Al/g clay) mixture (slurry) was spray dried using a Buchi B290 laboratory spray dryer. A portion of the spray dried clay heteroadduct was screened through a 325 mesh screen. Two grams of sloop screening material was charged to a 300° C. oven and heated in air for 6 hours. While still hot, the material was transferred to a vacuum chamber and allowed to cool to room temperature under vacuum.

Example 16. Spray dried and calcined washed aluminum chlorohydrate clay heteroadduct (1.76 mmol Al/g clay)
A portion of the aluminum chlorohydrate clay heteroadduct (1.76 mmol Al/g clay) slurry prepared according to Example 12 was filtered through Fisherbrand™ P8 filter paper using a Buchner funnel and vacuum. 158 grams of filter cake was then transferred to an HDPE bottle and resuspended in approximately 1.2 liters of deionized water by shaking. The conductivity of the slurry thus obtained was 114 μS/cm and the pH was 6.25. The slurry was again filtered through Fisherbrand™ P8 filter paper and left on the filter under vacuum overnight to yield 109.03 grams of a gray solid. A 97.07 gram sample of this solid was filled into an HDPE bottle with 452 g of deionized water and shaken until no lumps were visible in the slurry. The slurry had a conductivity of 112 μS/cm and a pH of 6.33. A portion of this aluminum chlorohydrate clay heteroadduct slurry was spray dried using a Buchi B290 laboratory spray dryer. A 1.77 gram sample of the spray dried material is loaded and baked in an oven at 300° C. for 6 hours in air. While still hot, the material was then transferred to a vacuum chamber and allowed to cool to room temperature under vacuum.

Example 17. Single filtered, azeotropic, and calcined aluminum chlorohydrate clay heteroadduct (1.76 mmol Al/g clay)
A 543 gram portion of the aluminum chlorohydrate clay heteroadduct (1.76 mmol Al/g clay) slurry prepared according to Example 12 was vacuum filtered through Fisherbrand™ brand P8 filter paper. The resulting filter cake was then resuspended in approximately 1 L of deionized water to yield a slurry with a conductivity of 114 μS and a pH of 6.25. The slurry was then vacuum filtered through Fisherbrand™ brand P8 paper and 11.5 grams of the filter cake from the clay heteroadduct retained on the filter paper was charged to an Erlenmeyer flask equipped with a stir bar. 200 mL of n-butanol was then added and the mixture was stirred until a slurry with no visible lumps or clumps was obtained. The stir bar was removed and the Erlenmeyer was rotary evaporated from a 45°C bath. An off-white powder containing some flakes and lumps was very gently ground to a uniform powder and 1.04 grams was charged into a porcelain crucible that was fired at 300° C. for 6 hours in air. The fired material was cooled under vacuum and 0.867 grams was transferred to an inert atmosphere glove box.

Example 18. Single filtration, azeotropic and calcining reproducibility of aluminum chlorohydrate clay heteroadduct (1.76 mmol Al/g clay) according to Example 17. Add slowly to a Waring® blender containing 570 g of deionized Milli-Q® water over a period of minutes and stir at low speed to contain no or substantially no visible lumps or clumps. A gray colloidal dispersion containing no After the addition was complete, the dispersion was blended at high speed for 5-10 minutes to give a slightly viscous mixture of a 5 weight percent aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt % HPM-20 clay aqueous dispersion was transferred to a Waring® blender and 1.91 g of the GEO aluminum chlorohydrate 50 wt % aqueous solution was pipetted into the vial and whisked once. was added to the dispersion at . The mixture solidified quickly and 70 mL of deionized Milli-Q® water was added to facilitate stirring. The mixture was then blended on high speed for 5 minutes before being vacuum filtered through Fisher P8 qualitative grade filter paper (coarse porosity). After 15-30 minutes of filtration, the filtrate pH and conductivity were measured (Eutech PCSTester 35), yielding a pH of 6.1 and a conductivity of 1516 μS/cm. The filtrate was discarded and the remaining wet solid was resuspended in 50-100 mL of deionized Milli-Q® water.

The filtration process (suspension of wet solids in deionized Milli-Q® water, vacuum filtration, and filtrate pH/conductivity measurement) was repeated again. The remaining wet solid was resuspended in 150-200 mL of 1-butanol and rotary evaporated at 45°C. The resulting solid was then ground with a pestle and mortar to give 5.18 g of a light gray powder. A 1.90 g portion of this solid was transferred to a porcelain crucible and calcined at 300° C. for 6 hours to yield 0.9 g of a gray-black powder. The powder XRD (X-ray diffraction) pattern of this sample is displayed in FIG. 2 and the BJH pore volume analysis of this sample is plotted in FIG.

Example 19. Comparative example of preparation of aluminum chlorohydrate (ACH) ion-exchanged clay (0.3 mmol Al/g clay) was slowly added to a Waring® blender containing water and stirred at low speed to give a gray colloidal dispersion containing no or substantially no visible lumps or clumps. . After the addition was complete, the dispersion was blended at high speed for 5-10 minutes to obtain a slightly viscous mixture of a 5 weight percent aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt % HPM-20 clay aqueous dispersion was transferred to a Waring® blender. A 0.325 g sample of GEO ACH aqueous dispersion (50 wt %) was pipetted into a vial, combined with 20 mL of deionized Milli-Q® water, and then poured into the clay dispersion all at once. The resulting mixture was then blended at high speed for 5 minutes and then vacuum filtered through Fisher P8 qualitative grade filter paper (coarse porosity). Filtration was slow (<1 drop/sec). Filtration was continued for 15-30 minutes, after which the filtrate pH and conductivity were measured (Eutech PCSTestr 35), yielding a pH of 7.3 and a conductivity of 487 μS/cm. The filtrate was discarded and the remaining wet solids were resuspended in 50 mL of deionized Milli-Q® water and centrifuged once at 3000-3500 rpm for 30-60 minutes. After removing the supernatant (measured conductivity 180 μS/cm), the remaining wet solid was resuspended in 50-100 mL 1-butanol and rotary evaporated at 45°C. The resulting solid was then ground with a pestle and mortar, and 1.7 g of powdered solid was transferred to a porcelain crucible and calcined at 300° C. for 6 hours to yield 0.8 g of gray-black powder.

Example 20. Preparation of Aluminum Chlorhydrate (ACH) Clay Heteroadduct (1.17 mmol Al/g Clay) With stirring, 30 g of Volclay® HPM-20 clay was added over 1-2 minutes to 570 g of deionized Milli - A gray colloidal dispersion that is slowly added to a Waring® blender containing Q® water and stirred at low speed to contain no or substantially no visible lumps or clumps. got After the addition was complete, the dispersion was blended at high speed for 5-10 minutes to obtain a slightly viscous mixture of a 5 weight percent aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt % HPM-20 clay aqueous dispersion was transferred to a Waring® blender. Then 1.27 g of a 50 wt % aqueous solution of GEO aluminum chlorohydrate was pipetted into the vial and added to the dispersion all at once. The mixture solidified quickly and 70 mL of deionized Milli-Q® water was added to facilitate stirring. The mixture was then blended on high speed for 5 minutes before being vacuum filtered through Fisher P8 qualitative grade filter paper (coarse porosity). After filtering for 15-30 minutes, the filtrate pH and conductivity were measured (Eutech PCSTestr 35), yielding a pH of 6.25 and a conductivity of 1166 μS/cm. The filtrate was discarded and the remaining wet solid was resuspended in 50-100 mL of deionized Milli-Q® water.

The filtration process (suspension of wet solids in deionized Milli-Q® water, vacuum filtration, filtrate pH/conductivity measurement) was continued until the conductivity of the resuspended slurry reached 100-300 μS/cm. repeated. In this case, one additional filtration was performed to obtain a slurry with a pH of 6.2 and a conductivity of 188 μS/cm. The remaining wet solid was resuspended in 150-200 mL of 1-butanol and rotary evaporated at 45°C. The solid was then ground with a pestle and mortar to give 2.97 g of light gray powder. A 1.7 g portion of this solid was transferred to a porcelain crucible and calcined at 300° C. for 6 hours to yield 1.0 g of a gray-black powder. The powder XRD (X-ray diffraction) pattern of this sample is shown in FIG.

Example 21. Preparation of Aluminum Chlorhydrate (ACH) Clay Heteroadduct (1.52 mmol Al/g Clay) With stirring, 30 g of Volclay HPM-20 clay was added to 570 g of deionized Milli for 1-2 minutes. - A gray colloidal dispersion that is slowly added to a Waring® blender containing Q® water and stirred at low speed to contain no or substantially no visible lumps or clumps. got After the addition was complete, the dispersion was blended at high speed for 5-10 minutes to give a slightly viscous mixture of a 5 weight percent aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt % HPM-20 clay aqueous dispersion was transferred to a Waring® blender. A 1.66 g sample of a 50 wt % aqueous solution of GEO aluminum chlorohydrate was pipetted into a vial and added to the dispersion all at once. The resulting mixture solidified rapidly and 80 mL of deionized Milli-Q® water was added to facilitate stirring. The mixture was then blended on high speed for 5 minutes before vacuum filtering through Fisher P8 qualitative grade filter paper (coarse porosity). After 15-30 minutes of filtration, the filtrate pH and conductivity were measured (Eutech PCSTester 35), yielding a pH of 6.2 and a conductivity of 1518 μS/cm. The filtrate was discarded and the remaining wet solid was resuspended in 50-100 mL of deionized Milli-Q® water.

This filtration process (suspension of wet solids in deionized Milli-Q® water, vacuum filtration, filtrate pH/conductivity measurement) until the conductivity of the resuspended slurry reaches 100-300 μS/cm. repeated. In this case, one additional filtration was performed to obtain a slurry with a pH of 6.1 and a conductivity of 199 μS/cm. The remaining wet solid was resuspended in 150-200 mL of 1-butanol and rotary evaporated at 45°C. The resulting solid was then ground with a pestle and mortar to give 3.19 g of a light gray powder. A 1.65 g sample of this solid was transferred to a porcelain crucible and calcined at 300° C. for 6 hours to yield 0.9 g of a gray-black powder. The powder XRD pattern of this sample is shown in FIG.

Example 22. Comparative Example of Preparation of Aluminum Chlorhydrate (ACH) Clay Heteroadduct (2.5 mmol Al/g Clay) and Single Filtration With stirring, 30 g of HPM-20 clay was subjected to desorption of 570 g over 1-2 minutes. Add slowly to a Waring® blender containing ionic Milli-Q® water and stir at low speed to obtain a gray colloid containing no or substantially no visible lumps or clumps. A dispersion was obtained. After the addition was complete, the dispersion was blended at high speed for 5-10 minutes to give a slightly viscous mixture of a 5 weight percent aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt % HPM-20 clay aqueous dispersion was transferred to a Waring® blender. A 2.71 g sample of a 50 wt % aqueous solution of GEO aluminum chlorohydrate was pipetted into a vial and added to the dispersion all at once. The mixture quickly became viscous and 100 mL of deionized Milli-Q® water was added to facilitate stirring. The mixture was then blended on high speed for 5 minutes and then vacuum filtered through Fisher P8 qualitative grade filter paper (coarse porosity). After 15-30 minutes of filtration, the filtrate pH and conductivity were measured (Eutech PCSTester 35), yielding a pH of 4.72 and a conductivity of 1988 μS/cm. A portion of the wet solid filter cake was resuspended in 50-100 mL of 1-butanol and rotary evaporated at 45°C. The dried solid was then ground with a pestle and mortar to give 0.66 g of light gray powder. A 0.64 g portion of this solid was transferred to a porcelain crucible and calcined at 300° C. for 6 hours to yield 0.5 g of a gray-black powder.

Example 23. Preparation of aluminum chlorohydrate (ACH) clay heteroadduct and additional washing/filtration comparative example compared to Example 22 (2.5 mmol Al/g clay) While stirring, 30 g of HPM-20 clay was Slowly add over 1-2 minutes to a Waring® blender containing 570 g of deionized Milli-Q® water and stir at low speed to contain no visible lumps or clumps. Or a gray colloidal dispersion was obtained which was substantially free. After the addition was complete, the dispersion was blended at high speed for 5-10 minutes to give a slightly viscous mixture of a 5 weight percent aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt % HPM-20 clay aqueous dispersion was transferred to a Waring® blender. A 2.71 g sample of a 50 wt % aqueous solution of GEO aluminum chlorohydrate was pipetted into a vial and added to the dispersion all at once. The mixture quickly became viscous and 100 mL of deionized Milli-Q® water was added to facilitate stirring. The mixture was then blended on high speed for 5 minutes and then vacuum filtered through Fisher P8 qualitative grade filter paper (coarse porosity). After filtering for 15-30 minutes, filtrate pH and conductivity were measured (Eutech PCSTester 35). The filtrate was discarded and the remaining wet solid was resuspended in 50-100 mL of deionized Milli-Q® water.

The filtration process (suspension of wet solids in deionized Milli-Q® water, vacuum filtration, filtrate pH/conductivity measurement) was continued until the conductivity of the resuspended slurry reached 100-300 μS/cm. repeated. In this case, one additional filtration was performed to obtain a slurry with a pH of 4.67 and a conductivity of 87 μS/cm. The remaining wet solid was resuspended in 50-100 mL of 1-butanol and rotary evaporated at 45°C. The dried solid was then ground with a pestle and mortar to give 3.73 g of light gray powder. A 1.37 g portion of this solid was transferred to a porcelain crucible and calcined at 300° C. for 6 hours to give a 0.6 g grey-black powder. The powder XRD pattern of this sample is shown in FIG.

Example 24. Comparative Example of Preparation of Aluminum Chlorhydrate (ACH) Clay Heteroadduct (3.5 mmol Al/g Clay) and Single Filtration With stirring, 30 g of HPM-20 clay was subjected to desorption of 570 g over 1-2 minutes. Add slowly to a Waring® blender containing ionic Milli-Q® water and stir at low speed to obtain a gray colloid containing no or substantially no visible lumps or clumps. A dispersion was obtained. After the addition was complete, the dispersion was blended at high speed for 5-10 minutes to obtain a slightly viscous mixture of a 5 weight percent aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt % HPM-20 clay aqueous dispersion was transferred to a Waring® blender. A 3.80 g sample of 50 wt % aqueous solution of GEO aluminum chlorohydrate was pipetted into a vial and added to the dispersion all at once, and 20 mL of deionized Milli-Q® water was added to facilitate stirring. . The mixture was then blended on high speed for 5 minutes and then vacuum filtered through Fisher P8 qualitative grade filter paper (coarse porosity). After 15-30 minutes of filtration, the filtrate pH and conductivity were measured (Eutech PCSTester 35) to give a pH of 4.34 and a conductivity of 1500 μS/cm. A portion of the wet solid was resuspended in 50-100 mL of 1-butanol and rotary evaporated at 45°C. The dried solid was then ground with a pestle and mortar to give 0.74 g of light gray powder. A 0.62 g portion of this solid was transferred to a porcelain crucible and calcined at 300° C. for 6 hours to give a 0.5 g grey-black powder.

Example 25. Comparative Example of Aluminum Chlorhydrate (ACH) Clay Heteroadduct Preparation and Additional Washing/Filtration Compared to Example 24 (3.5 mmol Al/g Clay) Slowly add over 1-2 minutes to a Waring® blender containing 570 g of deionized Milli-Q® water and stir at low speed to contain no visible lumps or clumps. Or a gray colloidal dispersion was obtained which was substantially free. After the addition was complete, the dispersion was blended at high speed for 5-10 minutes to obtain a slightly viscous mixture of a 5 weight percent aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt % HPM-20 clay aqueous dispersion was transferred to a Waring® blender. A 3.80 g sample of a 50 wt % aqueous solution of GEO aluminum chlorohydrate was pipetted into a vial and added to the dispersion all at once. The mixture quickly became viscous and 20 mL of deionized Milli-Q® water was added to facilitate stirring. The mixture was then blended on high speed for 5 minutes and then vacuum filtered through Fisher P8 qualitative grade filter paper (coarse porosity). After filtering for 15-30 minutes, filtrate pH and conductivity were measured (Eutech PCSTester 35). The filtrate was discarded and the remaining wet solid was resuspended in 50-100 mL of deionized Milli-Q® water.

The filtration process (suspension of wet solids in deionized Milli-Q® water, vacuum filtration, filtrate pH/conductivity measurement) was continued until the conductivity of the resuspended slurry reached 100-300 μS/cm. repeated. In this case, one additional filtration was performed to obtain a slurry with a pH of 4.5 and a conductivity of 180 μS/cm. The remaining slurry was resuspended in 50-100 mL of 1-butanol and rotary evaporated at 45°C. The dried solid was then ground with a pestle and mortar to give 4.33 g of light gray powder. A 1.36 g portion of this solid was transferred to a porcelain crucible and calcined at 300° C. for 6 hours to give a 0.6 g grey-black powder. The powder XRD pattern of this sample is shown in FIG.

Example 26. Comparative Example of Preparation of Aluminum Chlorhydrate (ACH) Clay Heteroadduct Using Powdered ACH Reagent (0.3 mmol Al/g Clay) of deionized Milli-Q® water into a Waring® blender and stirred at low speed to obtain a gray color containing no or substantially no visible lumps or clumps. of colloidal dispersion was obtained. After the addition was complete, the dispersion was blended at high speed for 5-10 minutes to give a slightly viscous mixture of a 5 weight percent aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt % HPM-20 clay aqueous dispersion was transferred to a Waring® blender. Another vial was filled with 0.160 g of ALOXICOLL® 51P powder and 20 mL of deionized Milli-Q® water. The mixture was poured into the stirred dispersion all at once and 40 mL of deionized Milli-Q® water was added to facilitate stirring. The mixture was then blended on high speed for 5 minutes and then vacuum filtered through Fisherbrand™ P8 qualitative grade filter paper (coarse porosity). Filtration was slow (<1 drop/sec). After 15-30 minutes of filtration, the filtrate pH and conductivity were measured (Eutech PCSTester 35), yielding a pH of 6.5 and a conductivity of 780 μS/cm. The filtrate was discarded and the remaining wet solids were resuspended in 50 mL of deionized Milli-Q® water and centrifuged once at 3000-3500 rpm for 30-60 minutes. After removing the supernatant (conductivity 180 μS/cm), the remaining wet solid was resuspended in 50-100 mL 1-butanol and rotary evaporated. The resulting solid was then ground with a pestle and mortar, then transferred to a porcelain crucible and calcined at 300° C. for 6 hours to obtain a gray-black powder.

Example 27. Comparative Example of Preparation of Aluminum Chlorhydrate (ACH) Clay Heteroadduct Using Powdered ACH Reagent (0.6 mmol Al/g Clay) of deionized Milli-Q® water into a Waring® blender and stirred at low speed to obtain a gray color containing no or substantially no visible lumps or clumps. of colloidal dispersion was obtained. After the addition was complete, the dispersion was blended at high speed for 5-10 minutes to give a slightly viscous mixture of a 5 weight percent aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt % HPM-20 clay aqueous dispersion was transferred to a Waring® blender. A separate vial was filled with 0.4 g of ALOXICOLL® 51P powder and 20 mL of deionized Milli-Q® water. This mixture was poured all at once into the stirred dispersion. 40 mL of deionized Milli-Q® water was added to facilitate stirring. The mixture was then blended on high speed for 5 minutes and then vacuum filtered through Fisher P8 qualitative grade filter paper (coarse porosity). After 15-30 minutes of filtration, the filtrate pH and conductivity were measured (Eutech PCSTester 35) to give a pH of 7.2 and a conductivity of 180 μS/cm. The filtrate was discarded and the remaining wet solids were resuspended in 50 mL of deionized Milli-Q® water and centrifuged once at 3000-3500 rpm for 30-60 minutes. After removing the supernatant (conductivity 180 μS/cm), the remaining wet solid was resuspended in 50-100 mL 1-butanol and rotary evaporated at 45°C. The resulting solid was then ground with a pestle and mortar to give 2 g of a gray powder, which was then transferred to a porcelain crucible and calcined at 300° C. for 6 hours to give a grey-black powder.

Example 28. Preparation of aluminum chlorohydrate (ACH) clay heteroadduct using powdered ACH reagent and additional washing compared to Example 29 (1.52 mmol Al/g clay). , over 1-2 minutes, slowly added to a Waring® blender containing 570 g of deionized Milli-Q® water and stirred at low speed to contain no visible lumps or clumps. , or substantially no gray colloidal dispersion was obtained. After the addition was complete, the dispersion was blended at high speed for 5-10 minutes to give a slightly viscous mixture of a 5 weight percent aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt % HPM-20 clay aqueous dispersion was transferred to a Waring® blender. Another vial was filled with 0.812 g of ALOXICOLL® 51P powder and 20 mL of deionized Milli-Q® water. This mixture was poured all at once into the stirred dispersion. 20-40 mL of deionized Milli-Q® water was added to facilitate stirring. The mixture was then blended on high speed for 5 minutes and then vacuum filtered through Fisher P8 qualitative grade filter paper (coarse porosity). After filtering for 15-30 minutes, filtrate pH and conductivity were measured (Eutech PCSTester 35). The remaining wet solids were resuspended in 50-100 mL of deionized Milli-Q® water.

The filtration process (wet solid suspension in deionized Milli-Q® water, vacuum filtration, filtrate pH/conductivity measurement) was repeated until the conductivity of the supernatant reached 100-300 μS/cm. . In this case, two filtrations were performed to obtain a filtrate with a pH of 6.3 and a conductivity of 169 μS/cm. The remaining wet solid was resuspended in 150-200 mL of 1-butanol and rotary evaporated at 45°C. The solid was then ground with a pestle and mortar to give 3.44 g of light gray powder. A 1.5 g portion of this solid was transferred to a clay crucible and calcined at 300° C. for 6 hours to yield 1.0 g of a gray-black powder.

Example 29. Preparation of Aluminum Chlorhydrate (ACH) Clay Heteroadduct Using Powdered ACH Reagent and Single Filtration Compared to Example 28 (1.52 mmol Al/g Clay) , over 1-2 minutes, slowly added to a Waring® blender containing 570 g of deionized Milli-Q® water and stirred at low speed to contain no visible lumps or clumps. , or substantially no gray colloidal dispersion was obtained. After the addition was complete, the dispersion was blended at high speed for 5-10 minutes to give a slightly viscous mixture of a 5 weight percent aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt % HPM-20 clay aqueous dispersion was transferred to a Waring® blender. Another vial was filled with 0.812 g of ALOXICOLL® 51P powder and 20 mL of deionized Milli-Q® water. The mixture was poured into the stirred dispersion all at once and 20-40 mL of deionized Milli-Q® water was added to facilitate stirring. The mixture was then blended on high speed for 5 minutes and then vacuum filtered through Fisherbrand™ P8 qualitative grade filter paper. After 15-30 minutes of filtration, the filtrate pH and conductivity were measured (Eutech PCSTestr 35) to give a pH of 5.8 and a conductivity of 1750 μS/cm. A portion of the remaining wet solid was resuspended in 50-100 mL of 1-butanol and rotary evaporated at 45°C. The solid was then ground with a pestle and mortar to give 1 g of gray powder, which was then transferred to a porcelain crucible and calcined at 300° C. for 6 hours to give 0.6 g of gray-black powder.

Example 30. Preparation of aluminum chlorohydrate (ACH) clay heteroadduct using powdered ACH reagent (1.76 mmol Al/g clay). Add slowly to a Waring® blender containing Milli-Q® water and stir at low speed to obtain a gray colloidal dispersion containing no or substantially no visible lumps or clumps. I got the liquid. After the addition was complete, the dispersion was blended at high speed for 5-10 minutes to give a slightly viscous mixture of a 5 weight percent aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt % HPM-20 clay aqueous dispersion was transferred to a Waring® blender. Another vial was filled with 0.940 g of ALOXICOLL® 51P powder and 20 mL of deionized Milli-Q® water. This mixture was poured all at once into the stirred dispersion. 20-40 mL of deionized Milli-Q® water was added to facilitate stirring. The mixture was then blended on high speed for 5 minutes, then vacuum filtered through Fisherbrand™ P8 qualitative grade filter paper and washed with 100 mL of deionized Milli-Q® water. After 15-30 minutes of filtration, the filtrate pH and conductivity were measured (Eutech PCSTester 35) to give a pH of 6.1 and a conductivity of 1799 μS/cm. A portion of the remaining wet solid was resuspended in 50-100 mL of 1-butanol and rotary evaporated at 45°C. The solid was then ground with a pestle and mortar to give 1.07 g of gray powder, then transferred to a porcelain crucible and fired at 300° C. for 6 hours to give 0.9 g of gray-black powder.

Example 31. Preparation of aluminum sesquichlorohydrate clay heteroadduct (1.52 mmol Al/g clay) 30 g of HPM-20 clay was added to 570 g of deionized Milli-Q® water over 1-2 minutes while stirring. was added slowly to a Waring® blender containing and stirred at low speed to give a gray colloidal dispersion containing no or substantially no visible lumps or clumps. After the addition was complete, the dispersion was blended at high speed for 5-10 minutes to give a slightly viscous mixture of a 5 weight percent aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt % HPM-20 clay aqueous dispersion was transferred to a Waring® blender. A 1.30 g sample of the ALOXICOLL® 31 L solution was weighed into a vial and added to the dispersion along with enough deionized Milli-Q® water to facilitate stirring. The mixture was then blended at high speed for 5 minutes and the conductivity was measured (Eutech PCSTester 35) to give a conductivity of 2600 μS/cm. The mixture was then vacuum filtered through Fisherbrand™ P8 qualitative grade filter paper and washed briefly with 100 mL of deionized Milli-Q® water. After 15-30 minutes of filtration, a portion of the remaining wet solid was resuspended in 50-100 mL of water and the conductivity was measured again, typically between 100 μS/cm and 500 μS/cm. range (in this case the conductivity was 70 μS/cm). The suspension was then combined with 100-200 mL of 1-butanol and rotary evaporated at 45°C. The solid was then ground with a pestle and mortar to give 6.2 g of a gray powder, then 1.8 g of this solid was transferred to a porcelain crucible and calcined at 300° C. for 6 hours to yield 0.9 g of gray-black powder. A powder was obtained.

Example 32. Comparative Example of Preparation of Aluminum Sesquichlorohydrate Clay Heteroadduct (2.5 mmol Al/g Clay) With stirring, 30 g HPM-20 clay was added to 570 g Trademark) water was slowly added to a Waring® blender and stirred at low speed to give a gray colloidal dispersion containing no or substantially no visible lumps or clumps. After the addition was complete, the dispersion was blended at high speed for 5-10 minutes to give a slightly viscous mixture of a 5 weight percent aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt % HPM-20 clay aqueous dispersion was transferred to a Waring® blender. A 2.79 g sample of the ALOXICOLL® 31 L solution was weighed into a vial and added to the dispersion along with enough deionized Milli-Q® water to facilitate stirring. The mixture was then blended at high speed for 5 minutes and the conductivity was measured (Eutech PCSTester 35) to give a conductivity of 2800 μS/cm. The mixture was then vacuum filtered through Fisherbrand™ P8 qualitative grade filter paper and washed briefly with 100 mL of deionized Milli-Q® water. After 15-30 minutes of filtration, a portion of the remaining wet solid was resuspended in 50-100 mL or water and the conductivity was measured again (320 μS/cm), typically 100-500 μS. / cm. This suspension was then combined with 100-200 mL of 1-butanol and rotary evaporated at 45°C. The solid was then ground with a pestle and mortar to give 5.57 g of a gray powder, then 1.7 g of this solid was transferred to a porcelain crucible and calcined at 300° C. for 6 hours to give 1 g of gray-black powder. Obtained.

Example 33. Comparative example of preparation of polyaluminum chloride (PAC)-clay heteroadduct (0.5 mmol Al/g clay). A 177.28 gram sample was loaded into a Waring® blender. While stirring, 1.32 g of UltraPAC® 290 solution (GEO) was added to the HPM-20 clay slurry and then stirred at elevated temperature for 9 minutes. The gray heteroadduct sticky mass was then transferred in two portions to HDPE poly bottles with 210 grams of deionized water. The gray heteroadduct slurry was then shaken by hand for about 1 minute to obtain a pH of 4.31 and a conductivity of 1672 μS/cm. Filtering the slurry through Fisherbrand™ P8 coarse filter paper gave 28.03 g of wet cake, which was transferred to an HDPE bottle and 308 g of deionized water was also charged to it. The bottle was shaken to produce no lumps in the slurry, the pH was 4.76 and the conductivity was 200 μS/cm. The slurry was filtered through Fisherbrand™ P8 filter paper to give 22.30 g of wet cake, which was transferred with 200 mL of n-butanol to an Erlenmeyer equipped with a stir bar and stirred until no clamps were visible. . The stir bar was removed and the mixture was rotary evaporated from the 45° C. bath to give 9.49 g of an off-white powder that was lightly ground into a fine powder using a mortar and pestle. 1.10 grams of off-white powder was charged into a porcelain crucible and then oven at 300° C. and baked for 6 hours to yield 0.8960 grams of dark gray powder. The powder was cooled to ambient temperature under vacuum and then transferred to an inert atmosphere glovebox.

Example 34. Preparation of polyaluminum chloride (PAC)-clay heteroadduct (1.01 mmol Al/g clay) A 201.23 gram sample of the 5.0 wt% HPM-20 clay suspension prepared in Example 4 was placed in a Waring ® blender. While stirring, 3.036 g of UltraPAC® 290 solution (GEO) was added to the HPM-20 slurry. The resulting thick mass could not be blended by the Waring® blender and was transferred to an HDPE bottle with two deionized water grinds totaling 185g. The bottle was shaken by hand so that no clumps or clumps were visible. The resulting slurry had a pH of 3.8 and a conductivity of 26 mS/cm. The slurry was filtered through Fisherbrand™ coarse filter paper #8 and the clear filtrate yielded a conductivity of 5.2 mS/cm. A 61 g portion of the filter cake was then transferred to the original polymer bottle and resuspended by shaking in 328 g of deionized water until no lumps were visible. The conductivity obtained was 1116 μS/cm and the pH was 3.93. The slurry was then filtered through Fisherbrand™ P8 filter paper. The clear filtrate had a conductivity of 1200 μS/cm. A 9.95 g sample of filter cake was transferred to an Erlenmeyer flask. The remaining filter cake was resuspended in a new HDPE bottle in 281 g of deionized water with shaking to obtain a slurry with a pH of 4.11 and a conductivity of 150 μS/cm. After standing overnight, the slurry was filtered through Fisherbrand™ P8 paper and 18.25 g of filter cake and transferred to an Erlenmeyer flask with 100 mL of n-butanol. The flask was shaken to break up chunks, then rotary evaporated from a 40° C. bath to give 9.08 g of an off-white powder. A 2.384 g sample of the off-white powder was filled into a porcelain crucible and placed in a 300° C. oven for 6 hours to give 1.72 g of a gray powder which was placed under vacuum to cool to ambient temperature and then Placed in an inert atmosphere glove box.

Example 35. Comparative Example of Preparation of Polyaluminum Chloride (PAC)-Clay Heteroadduct (1.46 mmol Al/g Clay) , into a Waring® blender. While stirring, 4.36 g of UltraPAC® 290 solution from GEO Specialty Chemicals was added to the HPM-20 clay slurry. The flask was removed from the blender and rotated until a sticky gray mass could be stirred using the blender and then vigorously stirred for 9 minutes. The viscous mass was then poured into an HDPE polymer bottle with two parts total of 85 grams of deionized water to give a total of 275 grams of gray heteroadduct slurry and then shaken by hand for about 1 minute to give a slurry of 3.73 This resulted in a pH and conductivity of 6.79 mS/cm. The slurry was filtered through Fisherbrand™ P8 coarse filter paper, followed by resuspension of the filter cake in approximately 200 mL of deionized water to obtain a slurry conductivity of 1 mS/cm. The slurry was filtered and a 34 g portion of filter cake was transferred to a 500 mL Erlenmeyer with stir bar along with 200 mL of n-butanol. The mixture was stirred overnight to break up solid clumps. The removed stir bar was then removed and the mixture was rotary evaporated from a 45° C. bath to yield 10.78 g of an off-white powder that was lightly ground into a fine powder using a mortar and pestle. A 1.07 gram portion of the off-white powder was charged into a porcelain crucible and then fired at 300° C. for 6 hours to yield 0.8800 grams of dark gray powder. After the powder was cooled to ambient temperature under vacuum, it was transferred to an inert atmosphere glove box.

Example 36. Preparation of nano alumina clay heteroadduct (0.49 g alumina/g clay, 4.8 mmol Al/g clay) 30 g HPM-20 clay was added to 570 g deionized Milli-Q over 1-2 minutes while stirring. Add slowly to a Waring® blender containing water and stir at low speed to obtain a gray colloidal dispersion containing no or substantially no visible lumps or clumps. rice field. After the addition was complete, the dispersion was blended at high speed for 5-10 minutes to give a slightly viscous mixture of a 5 weight percent aqueous dispersion of HPM-20 clay.

An 80 g sample of a 5 wt % HPM-20 clay colloidal suspension was added to a graduated addition funnel. 9.7 g of NYACOL® AL-27 dispersion (20% Al ₂ O ₃ ) was added to a separate addition funnel to dilute the suspension to the 80 mL volume level. The solutions were added simultaneously to a Waring® blender containing 137 g of Milli-Q® water at low blending speed. The resulting mixture was then blended at high speed for about 5 minutes before being vacuum filtered through Fisher P8 qualitative grade filter paper. After 15-30 minutes of filtration, the filtrate pH and conductivity were measured (Eutech PCSTester 35), yielding a pH of 9.1 and a conductivity of 451 μS/cm. A portion of the remaining wet solid was resuspended in 50-100 mL of 1-butanol and rotary evaporated at 45°C. The resulting solid was then ground with a pestle and mortar to give 1.79 g of a light gray powder, 0.65 g of this powder was transferred to a porcelain crucible and calcined at 300° C. for 6 hours to give 0.53 g of A gray powder was obtained.

Example 37. Zeta-Potential Titration of Fumed Silica with Aluminum Chlorohydrate This and subsequent examples demonstrate a novel approach in which a "single" cationic polymetalate such as ACH can be combined with fumed silica to serve as a heterocoagulant reagent. We demonstrate that a cationic colloidal polymetalate system can be produced, resulting in the formation of a heterocoagulated clay when contacted with a colloidal clay.

A 15 g sample of AEROSIL® 200 fumed silica is combined with 277 g of deionized Milli-Q® water in a beaker. The mixture is dispersed using an ULTRA-TURRAX® dispersing tool at 5400 rpm for 10 minutes and at 7000 rpm for an additional 5 minutes to make a 5 wt% (by silica) dispersion. A 270 g portion of this dispersion is transferred to the measurement vessel of a Colloidal Dynamic Zeta Probe Analyzer™ containing an axial bottom stirrer. The stirring speed is set fast enough to prevent substantial settling of the dispersion, but slow enough to completely immerse the electroacoustic probe in the mixture when fully lowered. . A typical stirring speed is set at 250-350 rpm, often 300 rpm.

A 2.5 wt% aluminum chlorhydrate solution is prepared by diluting 6.16 g of an aqueous ACH solution (50 wt% aluminum chlorohydrate, GEO Specialty Chemicals) into 117 g of water. A volumetric zeta potential titration of the 2.5 wt % ACH solution in the 5 wt % AEROSIL® 200 dispersion described above is then performed. The titration setting is 1 mL per titration point and the equilibration delay is 60 seconds. The data obtained are shown in FIG. 7 for ACH-AEROSIL®200.

The zeta potential versus titer volume data from FIG. 7 is converted to zeta potential for the AEROSIL® 200 fumed silica mass ratio data plotted in FIG. From FIG. 8, 0.04 g of ACH/g AEROSIL® 200, corresponding to a zeta potential of about +30 mV, at a ratio above and below the approximate monolayer ratio for preparing heterocoagulant reagents. points were selected. The ratio of heterocoagulation reagent to clay is then adjusted in the usual manner, specifically the zeta potential of the clay with this ACH-fumed silica heterocoagulation reagent, as described in Examples 8-11. Determined by titration.

Example 38. Zeta Potential Titration of Clay with ACH-Fumed Silica and Measurement of ACH-SiO ₂ /Clay Ratio A 15 g sample of AEROSIL® 200 fumed silica was added to 277 g of deionized Milli-Q® in a beaker. ) combined with water. This mixture was dispersed using an ULTRA-TURRAX® dispersion tool at 6000-7000 rpm for 10 minutes, after which 7.86 g of GEO aluminum chlorohydrate (ACH) solution was added. This mixture was then dispersed at 7000 rpm for an additional 5 minutes to make a 5 wt% (by silica) ACH-AEROSIL® 200 fumed silica dispersion.

Separately, slowly add 30 g of HPM-20 clay over 1-2 minutes to a Waring® blender containing 570 g of deionized Milli-Q® water and stir at low speed to A gray colloidal dispersion containing no or substantially no visible lumps or clumps was obtained. After the addition was complete, the dispersion was stirred at high speed for 5-10 minutes to give a slightly viscous mixture of 5 wt% Volclay aqueous dispersion.

A 60 g sample of this 5 wt% HPM-20% aqueous dispersion was combined with 240 g of deionized Milli-Q® water to give, after shaking, a 1 wt% HPM-20% aqueous dispersion. rice field. About 280 g of the colloidal dispersion was transferred to the measurement vessel of the Colloidal Dynamic Zeta Probe Analyzer™ containing an axial bottom stirrer. Stirring speed was set as above. Zeta potential measurements were performed on this diluted HPM-20/water dispersion according to the Zeta Probe Analyzer™ manual to determine the actual colloidal content of the clay dispersion. A measurement of a 5 wt% HPM-20 aqueous dispersion yields a zeta potential measurement of -43 mV. Initial colloid content estimates are adjusted to match this zeta potential. In this case, the HPM-20 colloid content of the dispersion was estimated to be 0.86%. The colloidal dynamic zeta probe measurement parameters were as follows: 5 readings, 1 reading/min, particle density of 2.6 g/cc, dielectric constant of 4.5.

A volumetric titration of the ACH-AEROSIL® 200 fumed silica dispersion in the clay dispersion was then performed. The titration settings were 0.2 mL per titration point from 0 to 1.2 mL, 0.5 mL per titration point and beyond, with an equilibration delay of 30 seconds, resulting in the data shown in FIG. In this example, the titrant is also a colloidal species. Therefore, the zeta potential was adjusted using the method of Example 11 above, resulting in the plot of FIG. Therefore, the amounts of AEROSIL® 200 fumed silica in the ACH-AEROSIL® 200 fumed silica dispersions used to achieve −20 m, neutral, and +20 mV zeta potentials are shown in Table 7.

Example 39. Preparation ACH-fumed silica/clay heteroadduct (3.31 mmol Al/g clay)
A 15 g sample of AEROSIL® 200 fumed silica was combined with 277 g of deionized Milli-Q® water in a beaker and the mixture was dispersed using an ULTRA-TURRAX® dispersing tool to 6000 Dispersed at ~7000 rpm for 10 minutes. A sample of 7.86 g of GEO aluminum chlorohydrate solution was then added, followed by dispersion at 7000 rpm for an additional 5 minutes.

While stirring, slowly add 30 g of HPM-20 clay over 1-2 minutes to a Waring® blender containing 570 g of deionized Milli-Q® water and mix at low speed. to give a gray colloidal dispersion containing no or substantially no visible lumps or clumps. After the addition was complete, the dispersion was blended at high speed for 5-10 minutes to obtain a slightly viscous mixture of a 5 weight percent aqueous dispersion of HPM-20 clay.

A 57 mL sample of the AEROSIL® 200 dispersion was loaded into a graduated addition funnel and 80 g of the HPM-20 clay dispersion was transferred to a separate graduated addition funnel. The contents of the addition funnel were simultaneously added dropwise with stirring to 135 g of deionized Milli-Q® water in a Waring® blender. Once the addition was complete, the mixture was blended at high speed for 5-10 minutes and then vacuum filtered through Fisherbrand™ P8 qualitative grade filter paper. After filtering for 15-30 minutes, filtrate pH and conductivity were measured (Eutech PCSTester 35). The remaining wet solids were resuspended in 50-100 mL of deionized Milli-Q® water.

The filtration process (wet solid suspension in deionized Milli-Q® water, vacuum filtration, filtrate pH/conductivity measurement) was repeated until the filtrate conductivity reached 100-300 μS/cm. In this case, two additional filtrations were performed. The remaining wet solid was resuspended in 150-200 mL of 1-butanol and rotary evaporated at 45°C. The solid was then ground with a pestle and mortar to give 6.60 g of light gray powder. A 3.1 g portion of this solid was transferred to a porcelain crucible and calcined at 300° C. for 6 hours to yield 1.45 g of a gray-black powder.

Example 40. Preparation of HCl-Treated Clay (5.28 mmol H+/g Clay) With stirring, 30 g of HPM-20 clay was added to a Waring® containing 570 g of deionized Milli-Q® water for 1-2 minutes. Trademark) blender and stirred at low speed to give a gray colloidal dispersion containing no or substantially no visible lumps or clumps. After the addition was complete, the dispersion was blended at high speed for 5-10 minutes to give a slightly viscous mixture of a 5 weight percent aqueous dispersion of HPM-20 clay.

An 80 g sample of this 5 wt % HPM-20 clay aqueous dispersion was transferred to a Waring® blender. A 42.2 mL aliquot of 0.5 M HCl aqueous solution was measured into a graduated cylinder and then added all at once to the clay dispersion. The mixture was then blended on high speed for 5 minutes and then vacuum filtered through Fisher P8 qualitative grade filter paper (coarse porosity). After 2-3 hours of filtration, the filtrate was discarded and the remaining wet solid was resuspended in 80 mL of deionized Milli-Q® water. The pH and conductivity of the resulting suspension were measured (Eutech PCSTester 35) and gave a pH of 2.27 and a conductivity of 1560 μS/cm.

The suspension was vacuum filtered again for 2-3 hours. The filtrate was discarded again and the remaining wet solid was resuspended in 80 mL of deionized Milli-Q® water. The pH and conductivity of the resulting suspension were measured (Eutech PCSTestr 35) and gave a pH of 3.09 and a conductivity of 217 μS/cm. The remaining wet solid was resuspended in 150-200 mL of 1-butanol and rotary evaporated at 45°C. The solid was then ground with a pestle and mortar to give 0.58 g of light gray flakes. The solid was transferred to a clay crucible and calcined at 300° C. for 6 hours to give 0.45 g of gray powder.

Example 41. Preparation of HCl-treated clay (1.5 mmol H ⁺ /g clay) With stirring, 30 g of HPM-20 clay was added to Waring (1.5 mmol H + /g clay) containing 570 g of deionized Milli-Q® water for 1-2 minutes. blender and stirred at low speed to give a gray colloidal dispersion containing no or substantially no visible lumps or clumps. After the addition was complete, the dispersion was blended at high speed for 5-10 minutes to obtain a slightly viscous mixture of a 5 weight percent aqueous dispersion of HPM-20 clay.

An 80 g sample of this 5 wt % HPM-20 clay aqueous dispersion was transferred to a Waring® blender. A 12 mL aliquot of 0.5 M HCl aqueous solution was measured into a graduated cylinder and then added all at once to the clay dispersion, with 30 mL of deionized Milli-Q® water added to facilitate stirring. . The mixture was then blended on high speed for 5 minutes and then vacuum filtered through Fisher P8 qualitative grade filter paper (coarse porosity). After 2-3 hours of filtration, the filtrate was discarded and the remaining wet solid was resuspended in 80 mL of deionized Milli-Q® water. The pH and conductivity of the resulting suspension were measured (Eutech PCSTestr 35) and gave a pH of 2.56 and a conductivity of 4100 μS/cm.

The suspension was vacuum filtered again for 2-3 hours. The filtrate was discarded again and the remaining wet solid was resuspended in 80 mL of deionized Milli-Q® water. The pH and conductivity of the resulting suspension were measured (Eutech PCSTester 35) and gave a pH of 3.25 and a conductivity of 213 μS/cm. The remaining wet solid was resuspended in 150-200 mL of 1-butanol and rotary evaporated at 45°C. The resulting solid was then ground with a pestle and mortar to yield 1.73 g of light gray flakes. This solid was transferred to a clay crucible and calcined at 300° C. for 6 hours to give 1.2 g of gray powder.

Example 42. Slurry Settling Test of Heterocoagulated Clay (1.52 mmol Al/g Clay) Waring containing 760 g deionized Milli-Q® water with 40 g HPM-20 clay for 1-2 minutes while stirring. ® blender and stirred at low speed to give a gray colloidal dispersion containing no or substantially no visible lumps or clumps. After the addition was complete, the dispersion was blended at high speed for 5-10 minutes to obtain a slightly viscous mixture of a 5 weight percent aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt % HPM-20 clay aqueous dispersion was transferred to a Waring® blender. Then 1.66 g of a 50 wt % aqueous solution of GEO aluminum chlorohydrate was pipetted into the vial and added to the dispersion all at once. An additional 28 mL of deionized Milli-Q® water was added to the mixture to facilitate stirring. The mixture was blended on high speed for 5 minutes and then transferred to a bottle. The blender was washed with an additional 70 g of deionized Milli-Q® water to give 184 g of slurry.

The slurry was added to a 250 mL KIMAX® graduated cylinder until the 183 mL mark was reached and the slurry was allowed to stand. Over time, the slurry settled and formed a layer substantially free of visible colloidal particles. The volume of this clear layer was recorded periodically and after a settling time of 95 hours (hours), the clear layer volume, referred to as settling volume, was 15 mL.

Example 43. Comparative Example of Slurry Settling Test for ACH Columnar Viscosity (5.7 mmol Al/g Clay) A 5 wt % aqueous dispersion of HPM-20 clay was stirred slowly in 760 g of deionized Milli-Q® water. A gray colloid containing no visible lumps or clumps or substantially no A dispersion is obtained. After the addition was complete, the dispersion was blended at high speed for 5-10 minutes to give a slightly viscous 5 wt% aqueous dispersion of HPM-20 clay.

A 100 g portion of this 5 wt % HPM-20 clay aqueous dispersion was transferred to a Waring® blender. A 6.18 g sample of a 50 wt % aqueous solution of GEO aluminum chlorohydrate was pipetted into a vial and added to the dispersion all at once. An additional 13.8 mL of deionized Milli-Q® water was added to the mixture, then blended on high speed for 5 minutes, then transferred to a bottle. The blender was rinsed with an additional 30 g of deionized Milli-Q® water. A 50 g portion of Milli-Q® deionized water was then added to the mixture to give a 194 g slurry.

The slurry was added to a 250 mL KIMAX® graduated cylinder until the 183 mL mark was reached and the slurry was allowed to stand. Over time, the slurry settled and formed a layer substantially free of visible colloidal particles. The volume of this clear layer was recorded periodically and after a settling time of 95 hours (hours), the clear layer volume, referred to as settling volume, was 3 mL.

Example 44. Filtrate Quantitative Testing of Heterocoagulated Clay (1.52 mmol Al/g Clay) A 5 wt % aqueous dispersion of HPM-20 clay was prepared as described in Example 42.

A 100 g portion of this 5 wt % HPM-20 clay aqueous dispersion was transferred to a Waring® blender. Then 1.66 g of a 50 wt % aqueous solution of GEO aluminum chlorohydrate was pipetted into the vial and added to the dispersion all at once. An additional 38 mL of deionized Milli-Q® water was added to the mixture to facilitate stirring. The mixture was blended on high speed for 5 minutes and then transferred to a bottle. A total of 110 g of deionized Milli-Q® water was then added to the mixture to give a slurry with a total mass of 250 g.

The resulting mixture was then vacuum filtered through 11 cm Fisher P8 qualitative grade filter paper in a 550 mL Buchner funnel using a Welch 2034 DryFast™ diaphragm pump. After filtering for 10 minutes, 222 g of filtrate was obtained, leaving 24 g of wet cake. The resulting filtrate was rotary evaporated at 55° C. to give 0.23 g of solid residue.

Example 45. Comparative Example of Filtrate Quantitative Test of ACH Columnar Viscosity (5.7 mmol Al/g Clay) A 5 wt % aqueous dispersion of HPM-20 clay was prepared as described in Example 43. A 100 g portion of this 5 wt % HPM-20 clay aqueous dispersion was transferred to a Waring® blender. A 6.18 g sample of a 50 wt % aqueous solution of GEO aluminum chlorohydrate was pipetted into a vial and added to the dispersion all at once. Add an additional 44 g of deionized Milli-Q® water to the mixture, then blend on high speed for 5 minutes, then transfer to a bottle, then add 100 g of Milli-Q® deionized water to the mixture. to obtain a slurry with a total mass of 250 g.

The resulting mixture was then vacuum filtered through 11 cm Fisher P8 qualitative grade filter paper in a 550 mL Buchner funnel using a Welch 2034 DryFast™ diaphragm pump. After filtering for 20 minutes, 39 g of filtrate was obtained. The unfiltered mixture was allowed to settle for 96 hours, then vacuum filtered using the same filter paper grade and pump applied, resulting in an additional 172 g of filtrate with 40 g of wet cake remaining. rice field. The resulting filtrate was rotary evaporated at 55° C. to give 1.4 g of solid residue.

Example 46 Preparation of 7-Phenyl-2-methyl-indene Phenylboronic acid (3.05 g, 25.0 mmol), Pd ₂ (dba) ₃ (229 mg, 0.5 mmol) in toluene (50 mL) solution under nitrogen atmosphere. 25mmo, dba is dibenzylideneacetone), and P(t-Bu) ₃ (202mg, 1.00mmol) and ₇ -bromo _- 2- Methyl-1H-indene (5.23 g, 25.0 mmol) was added. The reaction mixture was vigorously stirred at 110° C. for about 18 hours after which time the mixture was cooled to ambient temperature and the solution was passed through silica gel and washed with dichloromethane. After removal of volatiles from the filtrate by rotary evaporation, the resulting crude product of 7-phenyl-2-methyl-1H-indene was purified by column chromatography (hexane) to give a colorless oil (4.41 g, 86 g). %) was obtained. The NMR spectrum of the product in CDCl ₃ containing traces of dichloromethane and water is shown in FIG.

Example 47. Preparation of ansametallocene ligand dimethylsilylenebis(2-methyl-4-phenylindenyl) Under _N2 atmosphere, n-BuLi (8.56 mL, 2.5 M in hexanes, 21.4 mmol) was added to 60 mL of dry toluene. and then added to a stirred solution of 7-phenyl-2-methyl-1H-indene (4.41 g, 21.4 mmol) at room temperature. After stirring for 6 hours at room temperature, the reaction mixture was cooled to −35° C. and a solution of dichlorodimethylsilane (1.29 mL, 10.7 mmol) in THF (5 mL) was added. The mixture was stirred and heated to 80° C. for about 18 hours. The resulting mixture was cooled to ambient temperature, the solution was passed through silica gel, washed with dichloromethane, and the volatiles were removed from the filtrate by rotary evaporation. The resulting crude product was purified by column chromatography (200:1 v:v hexane to Et ₂ O ratio) to give a yellow solid (2.65 g, 53% yield).

先の実施例の黄色固体ジメチルシリレンビス（２－メチル－４－フェニルインデニル）リガンドの一部（４１０ｍｇ、０．８７５ｍｍｏｌ）をメチルｔｅｒｔ－ブチルエーテル（２ｍＬ）中に溶解し、ジエチルエーテル（２ｍＬ）で希釈した。溶液を－３５℃に冷却し、ｎ－ＢｕＬｉの一部（ヘキサン中、０．７ｍＬ、２．５Ｍ）を撹拌しながら滴下した。得られた赤色溶液を室温に温め、一晩撹拌し、再び－３５℃に冷却した。次いで、冷たいリガンド溶液をヘキサン（１０ｍＬ）中のＺｒＣｌ_４（ＴＨＦ）_２（３３３ｍｇ、０．８７５ｍｍｏｌ）のスラリーに添加し、これを－３５℃に予め冷却した。得られたオレンジ色のスラリーを室温に温め、一晩撹拌した後、揮発性成分を真空下で除去し、残留固体をジクロロメタン（ＤＣＭ）で抽出した。ジクロロメタン抽出物をシリンジフィルターに通した後、オレンジ色の結晶が形成されるまで溶液を濃縮した。ヘキサンを添加して、より多くの生成物を沈殿させた。結晶性固体を濾過により収集し、高真空下で乾燥させた（２８０ｍｇ、収率５１％）。生成物をジクロロメタン（ＤＣＭ）／ヘキサン（１／１、ｖ：ｖ）中で再結晶して、１４５ｍｇの結晶を得、これをＤＣＭからさらに１回再結晶して、実質的に異性体的に純粋なｒａｃ－ジメチルシリレンビス（２－メチル－４－フェニルインデニル）ジルコニウムジクロリド６０ｍｇを得た。微量のジクロロメタンを含有するＣＤＣｌ_３中の再結晶化生成物の^１Ｈ ＮＭＲスペクトルを図１４に示す。 Example 48. Synthesis of rac-dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dichloride

A portion of the yellow solid dimethylsilylene bis(2-methyl-4-phenylindenyl) ligand from the previous example (410 mg, 0.875 mmol) was dissolved in methyl tert-butyl ether (2 mL) and diluted with diethyl ether (2 mL). diluted with The solution was cooled to −35° C. and a portion of n-BuLi (0.7 mL, 2.5 M in hexanes) was added dropwise with stirring. The resulting red solution was warmed to room temperature, stirred overnight and cooled to -35°C again. The cold ligand solution was then added to a slurry of ZrCl ₄ (THF) ₂ (333 mg, 0.875 mmol) in hexanes (10 mL), which was precooled to -35°C. After warming the resulting orange slurry to room temperature and stirring overnight, the volatiles were removed under vacuum and the residual solid was extracted with dichloromethane (DCM). After passing the dichloromethane extract through a syringe filter, the solution was concentrated until orange crystals formed. Hexane was added to precipitate more product. The crystalline solid was collected by filtration and dried under high vacuum (280 mg, 51% yield). The product was recrystallized in dichloromethane (DCM)/hexane (1/1, v:v) to give 145 mg of crystals, which were recrystallized once more from DCM to give substantially isomeric 60 mg of pure rac-dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dichloride were obtained. ^{A 1} H NMR spectrum of the recrystallized product in CDCl ₃ containing traces of dichloromethane is shown in FIG.

Example 49. Propylene polymerization catalyzed by rac-dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dichloride, the calcined clay heteroadduct of Example 17, and trialkylaluminum Example 45-6 in a 2 mL toluene solution To 0 μmol of rac-dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dichloride was added 1.3 mL of tri-n-octylaluminum (TnOA, 1.2 mmol). The resulting solution was mixed with 75 mg of single-filtered, azeotropic, and calcined aluminum chlorohydrate clay heteroadduct (1.76 mmol Al/g clay) according to Example 17. The resulting slurry was shaken for 2 minutes and kept at room temperature for several hours before use.

Propylene polymerizations were carried out in a bench scale 2 liter reactor according to the following procedure. The reactor was first preheated to at least 100°C with a nitrogen purge to remove residual moisture and oxygen and then cooled to 50°C. Under nitrogen, 1 liter (L) of dry heptane was introduced into the reactor. When the reactor temperature was about 50° C., 2.0 mL of tri-n-octylaluminum (0.92 M in hexane) was added to the reactor, followed by the catalyst slurry prepared above. The reactor pressure was increased to 28.5 psig at 50° C. by introducing nitrogen.

The reactor temperature was then raised to 70° C. and the total reactor pressure was controlled at 90 psig by continuously introducing propylene into the reactor and the polymerization was allowed to proceed for 1 hour. After this, the reactor was vented to reduce the pressure to 0 psig and the reactor temperature was cooled to 50°C. The reactor was opened and 500 mL of methanol was added to the reactor contents and the resulting mixture was stirred for 5 minutes and then filtered to obtain the polymer product. The resulting polymer was vacuum dried at 80° C. for 6 hours. Polymers were evaluated for melt flow rate (MFR) and isotacticity, and catalytic activity was also measured. Table 8 below summarizes the propylene polymerization results for this example.

Example 50. Propylene polymerization catalyzed by rac-dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dichloride, the calcined clay heteroadduct of Example 16, and trialkylaluminum. Repeatedly using the spray dried and calcined washed clay heteroadduct, the polymerization was carried out at a temperature of 80°C instead of 70°C as in Example 49. Table 8 summarizes the propylene polymerization results of this example.

Example 51. Ethylene homopolymerization catalysis involves an inventive and relatively supportive and metallocene catalyst.
Ethylene homopolymerization was carried out at 450 psi and 90° C. using the previously described reaction procedures and conditions. Results are provided in Table 3A.

Although the invention herein has been described with reference to particular aspects or embodiments, it is to be understood that these aspects and embodiments are merely illustrative of the principles and applications of the invention. These and other descriptions according to this disclosure can further include various embodiments and aspects presented below.

Additional Examples Table 9 provides some practical and constructive examples of components that may be selected and used to prepare heterocoagulated clay activator supports, as well as the components used in conjunction with the activator supports. Figure 1 shows additional components that may be selected and used to produce an olefin polymerization catalyst. Any one or more of the compounds or compositions listed in each ingredient list may be selected independently of any other compound or composition set forth in any other ingredient list. can. For example, this table shows any one or more of component 1, any one or more of component 2, optionally any one of component A, as disclosed herein. It is disclosed that any one or more of the above and component B may be selected independently of each other and combined or contacted in any order to obtain a heterocoagulated clay activator support. As disclosed herein, any one or more of components 3 (metallocenes), optionally any one or more of components C, and optionally any one of components D One or more can be selected independently of each other and combined or contacted in any order with each other and with the heterocoagulated clay activator support to provide an olefin polymerization catalyst.

In Table 9, compounds understood by those skilled in the art such as TEA (triethylaluminum), TnOA (tri-n-octylaluminum), TiBA (triisobutylaluminum), MAO (methylaluminoxane), EAO (ethylaluminoxane), etc. Certain abbreviations are used. Unless otherwise specified, groups such as "hydrocarbyl" or "Si-containing hydrocarbyl" groups have 1 to about 12 carbons, such as, for example, methyl, n-propyl, phenyl, trimethylsilylmethyl, neopentyl, and the like. can be regarded as In Table 9, each group or substituent is independently selected from any other group of substituents. Thus, each "R" substituent is independently selected from any other R substituent, each "Q" group is independently selected from any other Q group, and so on.

Also with respect to Table 9, cocatalyst components are referred to as optional (optional component C) and include alkylating agents, hydriding agents, and the like. Cocatalyst components such as those described are typical in the formation of polymerization catalysts, as metallocenes are generally halide-substituted and can provide polymerization activating/initiating ligands such as methyl or hydrides. used for

Aspects of the present disclosure Aspect 1 . A catalyst composition for olefin polymerization, comprising:
a) at least one metallocene compound;
b) optionally at least one cocatalyst;
c) at least one supported active agent comprising a calcined smectite heteroadduct, the smectite heteroadduct comprising [1] a colloidal smectite clay; and [2] at least one cationic polymetalate in a liquid carrier; and in an amount sufficient to provide a slurry of smectite heteroadducts having a zeta potential in the range of about positive 25 mV (millivolts) to about negative 25 mV. A catalyst composition comprising:

Aspect 2. A process for the polymerization of olefins comprising contacting at least one olefin monomer and a catalyst composition under polymerization conditions to form a polyolefin, wherein the catalyst composition comprises:
a) at least one metallocene compound;
b) optionally at least one cocatalyst;
c) at least one supported active agent comprising a calcined smectite heteroadduct, the smectite heteroadduct comprising [1] a colloidal smectite clay; and [2] at least one cationic polymetalate in a liquid carrier; and in an amount sufficient to provide a slurry of smectite heteroadducts having a zeta potential in the range of about positive 25 mV (millivolts) to about negative 25 mV. A process, including an agent.

Aspect 3. A method for producing an olefin polymerization catalyst, the method comprising, in any order,
a) at least one metallocene compound;
b) optionally at least one cocatalyst;
c) at least one supported active agent comprising a calcined smectite heteroadduct, the smectite heteroadduct comprising [1] a colloidal smectite clay; and [2] at least one cationic polymetalate in a liquid carrier; and in an amount sufficient to provide a slurry of smectite heteroadducts having a zeta potential in the range of about positive 25 mV (millivolts) to about negative 25 mV. A method comprising contacting with an agent.

Aspect 4. A support activator comprising an isolated smectite heteroadduct, wherein the smectite heteroadduct comprises [1] a colloidal smectite clay, and [2] at least one cationic polymetalate, and has a zeta potential. support activation comprising the contact product of a heterocoagulant reagent in a liquid carrier in an amount sufficient to provide a slurry of smectite heteroadducts having a range of about positive 25 mV (millivolts) to about negative 25 mV. agent.

Aspect 5. A method of making a support activator, the method comprising:
a) providing a colloidal smectite clay;
b) colloidal smectite clay in an amount sufficient to provide a smectite heteroadduct slurry comprising at least one cationic polymetalate and having a zeta potential in the range of about positive 25 mV (millivolts) to about negative 25 mV; contacting the heterocoagulant reagent in a liquid carrier;
c) isolating the smectite heteroadduct from the slurry.

Aspect 6. the liquid carrier
water; alcohols such as methanol, ethanol, n-propanol, isopropanol, or n-butanol; ethers such as diethyl ether or di-n-butyl ether; ketones such as acetone; esters such as methyl acetate or ethyl acetate; comprising, consisting of, consisting essentially of, or selected from any combination of
optionally,
Anionic surfactants such as sulfates, sulfonates, phosphates, carboxylates, or other anionic surfactants, examples of which include dialkylsulfocarboxylic acid esters, alkylarylsulphonates , alkyl sulfonates, sulfosuccinates, fatty acid alkali salts, polycarboxylates, polyoxyethylene alkyl ether phosphate salts, alkyl naphthalene sulfonates. anionic surfactants, the salts of which may be selected from alkali metals such as lithium, sodium or potassium, alkaline earth metals such as calcium or magnesium, or salts of ammonium or hydrocarbylammonium;
Cationic surfactants such as primary, secondary or tertiary amines or ammonium compounds or quaternary ammonium compounds, examples of which are tetrabutylammonium bromide, dioctadecyldimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyl cationic surfactants, including but not limited to ammonium chloride, trimethylstearylammonium chloride, or cetyltrimethylammonium bromide;
Nonionic surfactants such as ethoxylates, glycol ethers, fatty alcohol polyglycol ethers, combinations thereof, or other nonionic surfactants, examples of which include octylphenol ethoxylate, polyethylene glycol tert- Nonionic surfactants, including but not limited to octylphenyl ether, ethylenediaminetetrakis(ethoxylate-block-propoxylate)tetrol, or ethylenediaminetetrakis(propoxylate-block-ethoxylate)tetrol, or the same molecule an amphoteric surfactant comprising an anionic surfactant portion and a cationic surfactant within, a surfactant comprising, consisting of, consisting essentially of, or selected from; The catalyst composition, olefin polymerization process, method of making an olefin polymerization catalyst, support activator, or method of making a support activator according to any one of aspects 1-5, comprising:

Aspect 7. The isolated smectite heteroadduct is [1] washed with water, [2] heated, dried, and/or calcined, or [3] washed with water, heated, dried, and/or A support activator according to any one of aspects 4 to 5, or a method for producing a support activator, which is calcined.

Aspect 8. The smectite heteroadduct is
A) isolated from the slurry by a filtration or azeotropic process; and/or b) isolated from the slurry without the use of ultrafiltration, centrifugation, or settling tanks. 3. The support activator or the method for producing the support activator according to 1.

Aspect 9. A support activator according to any one of aspects 4-5 or a process for producing a support activator according to any one of aspects 4-5, wherein the smectite heteroadduct is isolated from the slurry by ultrafiltration, centrifugation or a sedimentation tank. .

Aspect 10. The support of any one of aspects 4-5 or 7-9, wherein the isolated smectite heteroadduct is further dried or calcined by heating in air, in an inert atmosphere, or under vacuum. A method for producing a body activator or a support activator.

Aspect 11. 11. A support activator according to aspect 10 or a method of making a support activator according to aspect 10, wherein the heating is carried out to a temperature of at least about 100<0>C.

Aspect 12. Catalyst composition, olefin polymerization process, olefin polymerization catalyst according to any one of aspects 1 to 11, wherein the smectite clay is [1] natural or synthetic and/or [2] dioctahedral smectite clay. a method for producing a support activator, or a method for producing a support activator.

Aspect 13.
a) the smectite clay is colloidal, and/or b) the smectite clay has an average particle size of less than about 10 microns (microns), less than about 5 microns, less than about 3 microns, less than 2 microns, or less than 1 micron, and average 13. The catalyst composition, olefin polymerization process, method of making an olefin polymerization catalyst according to any one of aspects 1-12, wherein the particle size is greater than about 15 nm, greater than about 25 nm, greater than about 50 nm, or greater than about 75 nm. , a support activator, or a method for producing a support activator.

Aspect 14. The smectite clay comprises, consists of, consists essentially of, or is selected from montmorillonite, sauconite, nontronite, hectorite, beidellite, saponite, bentonite, or any combination thereof , a catalyst composition, an olefin polymerization process, a method of making an olefin polymerization catalyst, a support activator, or a method of making a support activator according to any one of aspects 1-13.

Aspect 15. A smectite clay has the following formula:
(M ^A IV) ₈ (M ^B VI) _p O ₂₀ (OH) ₄ (wherein
a) M ^A IV is tetracoordinated Si ⁴⁺ and the Si ⁴⁺ is optionally partially substituted by a tetracoordinated cation that is not Si ⁴⁺ ;
b) M ^B VI is hexacoordinated Al ³⁺ or Mg ²⁺ and the Al ³⁺ or Mg ²⁺ is optionally partially substituted by a hexacoordinated cation that is not Al ³⁺ or Mg ²⁺ ;
c) p is 4 for a cation with a +3 format charge or p is 6 for a cation with a +2 format charge;
d) Any charge deficiency caused by partial substitution of cations that are not Si ⁴⁺ in M ^A IV and/or by partial substitution of cations that are not Al ³⁺ or Mg ²⁺ in M ^B VI are determined by the structure The catalyst composition of any one of the preceding aspects, such as aspects 1-13, comprising structural units characterized by the cations intercalated between the units; A method for producing an olefin polymerization catalyst, a support activator, or a method for producing a support activator.

Aspect 16.
a) at each occurrence the cations that are not Si ⁴⁺ are independently selected from Al ³⁺ , Fe ³⁺ , P ⁵⁺ , B ³⁺ , Ge ⁴⁺ , Be ²⁺ , Sn ⁴⁺ and the like;
b) at each occurrence the cations that are not Al ³⁺ or Mg ²⁺ are independently selected from Fe ³⁺ , Fe ²⁺ , Ni ²⁺ , Co ²⁺ , Li ⁺ , Zn ²⁺ , Mn ²⁺ , Ca ²⁺ , Be ²⁺ and the like; and/or c) the catalyst composition of aspect 15, wherein the cations intercalated between structural units are selected from monocations, dications, trications, other multications, or any combination thereof, an olefin , a method for producing an olefin polymerization catalyst, a support activator, or a method for producing a support activator.

Aspect 17.
a) at each occurrence the cations that are not Si ⁴⁺ are independently selected from Al ³⁺ or Fe ³⁺ ;
b) at each occurrence the cations that are not Al ³⁺ or Mg ²⁺ are independently selected from Fe ³⁺ , Fe ²⁺ , Ni ²⁺ , or Co ²⁺ ;
c) the catalyst composition, olefin polymerization process, method of making an olefin polymerization catalyst, support activator, or support according to aspect 15, wherein the cations intercalated between structural units are selected from monocations A method for producing a body activator.

Aspect 18. 18. The catalyst composition, olefin polymerization process, method of making an olefin polymerization catalyst according to any one of aspects 1-17, wherein the smectite clay is monoion-exchanged with at least one of lithium, sodium, or potassium; A support activator, or a method for producing a support activator.

Aspect 19. 19. According to any one of aspects 1-18, wherein the cationic polymetalate comprises, consists of, consists essentially of, or is selected from cationic oligomeric species or cationic polymeric aluminum species. , a process for the polymerization of olefins, a method for preparing an olefin polymerization catalyst, a support activator, or a method for preparing a support activator.

Aspect 20. the cationic polymetalate comprises, consists of, consists essentially of, or is selected from polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichlorohydrate, or polyaluminum oxyhydroxychloride; The catalyst composition, olefin polymerization process, method of making an olefin polymerization catalyst, support activator, or method of making a support activator according to any one of aspects 1-18.

Aspect 21. The ratio of millimoles (mmol) of aluminum (Al) in the polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichlorohydrate, or polyaluminum oxyhydroxychloride to grams (g) of colloidal smectite clay is about 0.0. 2 mmol Al/g clay to about 2.5 mmol Al/g clay, about 0.5 mmol Al/g clay to about 2.2 mmol Al/g clay, about 0.75 mmol Al/g clay to about 2.0 mmol Al/g clay or from about 1.0 mmol Al/g clay to about 1.8 mmol Al/g clay. , or a method for producing a support activator.

Aspect 22. Isolated or calcined smectite heteroadducts of colloidal smectite clays of millimoles (mmol) of aluminum (Al) in polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichlorohydrate, or polyaluminum oxyhydroxychloride a ratio of millimoles of aluminum to grams of colloidal clay used in the preparation of the pillared clay using the same colloidal smectite clay and the heterocoagulant reagent is about 70% or less, not more than about 60 % or less, about 50% or less, about 45% or less, about 40% or less, or about 35% or less. or a method for producing a support activating agent.

Aspect 23. Catalyst composition, olefin polymerization process, olefin polymerization according to any one of aspects 1 to 18, wherein the cationic polymetalate comprises a linear, cyclic or cluster aluminum compound containing 2 to 30 aluminum atoms A method for producing a catalyst, a support activator, or a method for producing a support activator.

Aspect 24. the cationic polymetalate a second metal oxide, a metal halide in an amount sufficient to provide a colloidal suspension of the chemically treated first metal oxide having a zeta potential greater than positive 20 mV (millivolt); comprising, consisting of, consisting essentially of, or selected from a first metal oxide chemically treated with a metal oxide, a metal oxyhalide, or a combination thereof. A catalyst composition, an olefin polymerization process, a method for producing an olefin polymerization catalyst, a support activator, or a method for producing a support activator according to any one of the preceding claims.

Aspect 25. whether the first metal oxide comprises fumed silica, fumed alumina, fumed silica alumina, fumed magnesia, fumed zinc oxide, fumed titania, fumed zirconia, fumed ceria, or any combination thereof A catalyst composition according to aspect 24, consisting of, consisting essentially of, or selected from, a process for the polymerization of olefins, a process for the preparation of an olefin polymerization catalyst, a support activator, or a support A method for producing a body activator.

Aspect 26.
The first metal oxide comprises _SiO2 or _Al2O3 and _the second metal oxide, metal halide or metal oxyhalide comprises _ZrOCl2 , ZnO, _NbOCl3 , B(OH) ₃ , obtained from aqueous solutions or suspensions of metal oxides, hydroxides, oxyhalides, or halides such as AlCl ₃ , or combinations thereof;
Aspect 24, wherein the first metal oxide comprises _SiO2 and the second metal oxide, metal halide, or metal oxyhalide comprises _Al2O3 , ZnO, _AlCl3 , or combinations thereof _. A catalyst composition, an olefin polymerization process, a method for producing an olefin polymerization catalyst, a support activator, or a method for producing a support activator according to .

Aspect 27. a cationic polymetalate composition comprising:
fumed silica, fumed alumina, fumed silica alumina, fumed magnesia, chemically treated with polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichlorohydrate, polyaluminum oxyhydroxychloride, or any combination thereof Embodiments 1-18 comprising, consisting of, consisting essentially of, or selected from fumed zinc oxide, fumed titania, fumed zirconia, fumed ceria, or any combination thereof A catalyst composition, an olefin polymerization process, a method for producing an olefin polymerization catalyst, a support activator, or a method for producing a support activator according to any one of the preceding claims.

Aspect 28.
a) the colloidal smectite clay comprises colloidal montmorillonite such as HPM-20 Volclay;
b) the catalyst composition, olefin polymerization process, olefin polymerization catalyst of any one of aspects 1-18, wherein the heterocoagulant reagent comprises aluminum chlorohydrate, polyaluminum chloride, or aluminum sesquichlorohydrate. Method of manufacture, support activator, or method of manufacturing a support activator.

Aspect 29. the cationic polymetalate comprises or consists of bohemian, fumed silica alumina, colloidal ceria, colloidal zirconia, magnetite, ferrihydrite, any positively charged colloidal metal oxide, or any combination thereof; A catalyst composition according to any one of aspects 1 to 18, consisting essentially of or selected from, a process for the polymerization of olefins, a process for the preparation of an olefin polymerization catalyst, a support activator, or A method for producing a support activator.

Aspect 30 the cationic polymetalate comprises or consists of aluminum chlorohydrate-treated fumed silica, aluminum chlorohydrate-treated fumed alumina, aluminum chlorohydrate-treated fumed silica-alumina, or any combination thereof; A catalyst composition according to any one of aspects 1 to 18, consisting essentially of or selected from, a process for the polymerization of olefins, a process for the preparation of an olefin polymerization catalyst, a support activator, or A method for producing a support activator.

Aspect 31. A cationic polymetalate is
_Al2 (OH) _{nClm ( H2O} ) _x
Embodiments 1-18 comprising, consisting of, consisting essentially of, or selected from: wherein n+m=6 and x is a number from 0 to about 4 A catalyst composition, an olefin polymerization process, a method for producing an olefin polymerization catalyst, a support activator, or a method for producing a support activator according to any one of the preceding claims.

Aspect 32. Cationic polymetalates have the empirical formula 0.5 [Al ₂ (OH) ₅ Cl(H ₂ O) ₂ ] or [AlO ₄ (Al ₁₂ (OH) ₂₄ (H ₂ O) ₂₀ ] ⁷⁺ (“Al ₁₃ -mer ) a catalyst composition according to any one of aspects 1 to 18, comprising, consisting of, consisting essentially of, or selected from, a polycation, a process for the polymerization of olefins, an olefin A method for producing a polymerization catalyst, a support activator, or a method for producing a support activator.

Aspect 33. The cationic polymetalate is covalent with a cationic metal complex of at least one additional metal selected from aluminum, zirconium, chromium, iron, or combinations thereof and a soluble rare earth salt according to U.S. Pat. No. 5,059,568. 19. The catalyst composition according to any one of aspects 1-18, comprising, consisting of, consisting essentially of, or selected from an oligomer prepared by polymerizing an olefin polymerization process, A method for producing an olefin polymerization catalyst, a support activator, or a method for producing a support activator.

Aspect 34. 34. The catalyst composition, olefin polymerization process, method of making an olefin polymerization catalyst, support activator, or support of aspect 33, wherein the at least one rare earth metal is selected from cerium, lanthanum, or combinations thereof. A method for producing an activator.

Aspect 35. The cationic polymetalate has the formula:
[M(II) _1−x M(III) _x (OH) ₂ ]A _x/n mL (I)
[LiAl ₂ (OH) ₆ ] A _1/n mL (II)
(In the formula,
M(II) is at least one divalent metal ion;
M(III) is at least one trivalent metal ion,
A is at least one inorganic anion;
L is an organic solvent or water;
n is the valence of the inorganic anion A, or in the case of multiple anions A, their average valence;
x is a number from 0.1 to 1,
m is a number from 0 to 10); or selected therefrom.

Aspect 36.
M(II) comprises, consists of, consists essentially of, or is selected from zinc, calcium, strontium, barium, iron, cobalt, nickel, cadmium, manganese, copper, or magnesium ,
M(III) comprises, consists of, consists essentially of, or is selected from iron, chromium, manganese, bismuth, cerium, or aluminum;

A comprises, consists of, or consists of hydrogen carbonate (bicarbonate), sulfate, nitrate, nitrite, phosphate, chloride, bromide, fluoride, hydroxide, or carbonate consisting essentially of or selected from

n is a number from 1 to 3,
36. The catalyst composition of aspect 35, wherein L comprises, consists of, consists essentially of, or is selected from methanol, ethanol or isopropanol, or water, olefin polymerization process, olefin A method for producing a polymerization catalyst, a support activator, or a method for producing a support activator.

Aspect 37. 36. According to aspect 35, wherein the cationic polymetalate is selected from a complex of Formula I, wherein M(II) is magnesium, M(III) is aluminum and A is carbonate. A catalyst composition, an olefin polymerization process, a method of making an olefin polymerization catalyst, a support activator, or a method of making a support activator.

Aspect 38. 19. Any one of aspects 1-18, wherein the cationic polymetalate comprises, consists of, consists essentially of, or is selected from a layered double hydroxide or a mixed metal layered hydroxide. A catalyst composition, an olefin polymerization process, a method for producing an olefin polymerization catalyst, a support activator, or a method for producing a support activator according to .

Aspect 39. 39. Catalyst composition, olefin polymerization process, olefin polymerization according to aspect 38, wherein the mixed metal layered hydroxide is selected from Ni-Al, Mg-Al, or Zn-Cr-Al type with positive layer charge A method for producing a catalyst, a support activator, or a method for producing a support activator.

Aspect 40. Layered double hydroxides or mixed metal layered hydroxides are magnesium aluminum hydroxide nitrate, magnesium aluminum hydroxide sulfate, magnesium aluminum hydroxide chloride, Mg _x (Mg, Fe) ₃ (Si, Al) ₄ O ₁₀ (OH) ) ₂ (H ₂ O) ₄ (where x is a number between 0 and 1, eg about 0.33 for ferrosaponite), (Al,Mg) ₂ Si ₄ O ₁₀ (OH) ₂ (H ₂ O) ₈ , synthetic hematite, zinc oxide (basic zinc carbonate) Zn ₅ (OH) ₆ (CO ₃ ) ₂ , hydrotalcite [Mg ₆ Al ₂ (OH) ₁₆ ]CO ₃ 4H ₂ O, taconite [Ni ₆ Al ₂ (OH) ₆ ]CO ₃ 4H ₂ O, hydrocalumite [Ca ₂ Al(OH) ₆ ]OH 6H ₂ O, magaldrate [Mg ₁₀ Al ₅ (OH) ₃₁ ](SO ₄ ) ₂ . _mH2O , pyroaurite [ _{Mg6Fe2 (} OH) ₁₆ ]CO3 _{* 4.5H2O} , ettringite [ _{Ca6Al2 (} OH) ₁₂ ]( _SO4 ) ₃ * _26H2O , or any thereof 40. A catalyst composition according to aspect 39 comprising, consisting of, consisting essentially of, or selected from combinations, processes for polymerizing olefins, processes for preparing olefin polymerization catalysts, support activation. agent, or a method for producing a support activating agent.

Aspect 41. A cationic polymetalate has the empirical formula FeO _x (OH) _y (H ₂ O) _z ] ⁿ⁺ where 2x+y is (<)3, z is a number from 0 to about 4, and n is A catalyst according to any one of aspects 1 to 18, comprising, consisting of, consisting essentially of, or selected from an iron polycation having a number between 1 and 3 A composition, a process for polymerizing an olefin, a method for making an olefin polymerization catalyst, a support activator, or a method for making a support activator.

Aspect 42. When the smectite heteroadduct slurry is at a concentration of about 1% by weight or more, or at a concentration of about 2.5% by weight or more solids, or at a concentration of about 1% to about 10% by weight solids, about about 20,000 μS/cm to about 100 μS/cm, about 10,000 μS/cm to about 200 μS when 2.5% to about 10% by weight solids, or about 5% to about 10% by weight solids /cm, or a conductivity in the range of about 1000 μS/cm to about 300 μS/cm. , a support activator, or a method for producing a support activator.

Aspect 43. When the concentration of the slurry is about 1 wt. % solids by weight, or between about 5% and about 10% by weight solids, the smectite heteroadduct slurry is characterized by a conductivity of less than 10 mS/cm, less than 5 mS/cm, or less than 1 mS/cm. or wherein the smectite heteroadduct slurry is characterized by a conductivity in the range of 2 mS/cm to 10 μS/cm, 1 mS/cm to 50 μS/cm, or 500 μS/cm to 100 μS/cm. A catalyst composition, an olefin polymerization process, a method for producing an olefin polymerization catalyst, a support activator, or a method for producing a support activator according to any one of the preceding claims.

Aspect 44. Smectite heteroadducts, provided that:
a) a temperature ranging from about 110° C. to about 600° C. and a time ranging from about 1 hour to about 10 hours;
b) a temperature ranging from about 150° C. to about 500° C. and a time ranging from about 1.5 hours to about 8 hours, or c) a temperature ranging from about 200° C. to about 450° C. and from about 2 hours to about 44. The catalyst composition, olefin polymerization process, method of making an olefin polymerization catalyst, support of any one of aspects 1-43, wherein the catalyst composition is calcined using any one of the time in the range of 7 hours. An activator, or a method for producing a support activator.

Aspect 45. smectite heteroadducts in the range of 200°C to 750°C, 225°C to 700°C, 250°C to 650°C, 225°C to 600°C, 250°C to 500°C, 225°C to 450°C, or 200°C to 400°C 44. The catalyst composition, olefin polymerization process, method of making an olefin polymerization catalyst, support activator, or support activator according to any one of aspects 1-43, wherein the catalyst composition is calcined in air at a temperature of manufacturing method.

Aspect 46. 46. The catalyst composition, olefin polymerization process of any one of aspects 1-45, wherein the smectite heteroadduct is calcined in an atmosphere comprising air or carbon monoxide, or in an inert atmosphere such as nitrogen, A method for producing an olefin polymerization catalyst, a support activator, or a method for producing a support activator.

Aspect 47. 46. The catalyst composition, process for polymerization of olefins, method for making an olefin polymerization catalyst, support according to any one of aspects 1 to 45, wherein the smectite heteroadduct is calcined in air or carbon monoxide in a fluidized bed. A method for producing a body activator or a support activator.

Aspect 48. the smectite heteroadduct in an atmosphere of air containing carbon monoxide in a fluidized bed at a temperature in the range of 100°C to 900°C, 200°C to 800°C, 250°C to 600°C, or 300°C to 500°C; 44. The catalyst composition, olefin polymerization process, method of making an olefin polymerization catalyst, support activator, or method of making a support activator according to any one of aspects 1-43, which is calcined in an atmosphere. .

Aspect 49. 44. The catalyst composition, process for polymerization of olefins, method for producing an olefin polymerization catalyst, support activator according to any one of aspects 1 to 43, wherein the calcined smectite heteroadduct is calcined at a temperature of 250°C or higher. , or a method for producing a support activator.

Aspect 50. 44. The catalyst composition, process for polymerization of olefins, method for producing an olefin polymerization catalyst, support activator according to any one of aspects 1 to 43, wherein the calcined smectite heteroadduct is calcined at a temperature of 300°C or higher. , or a method for producing a support activator.

Aspect 51. 44. The catalyst composition, process for polymerization of olefins, method for producing an olefin polymerization catalyst, support activator according to any one of aspects 1 to 43, wherein the calcined smectite heteroadduct is calcined at a temperature of 350°C or higher. , or a method for producing a support activator.

Aspect 52. wherein the calcined smectite heteroadduct is free or substantially free of ordered domains characterized by powder X-ray diffraction (XRD) peaks ranging from 0 degrees 2-theta (2-theta) to 13 degrees 2-theta. 52. The catalyst composition, olefin polymerization process, method for producing an olefin polymerization catalyst, support activator, or method for producing a support activator according to any one of Claims 1 to 51.

Aspect 53. The calcined smectite heteroadduct has the following characteristics:
a) the presence or substantial absence of uniform intercalation structures in X-ray powder diffraction (XRD) having a d001 basal spacing of about 13 Å (Angstroms) or greater;
b) in the range of about 9 Å (Angstroms) to about 13 Å (Angstroms) in powder X-ray diffraction (XRD), or alternatively about 10 Å (Angstroms) to about 13 Å (Angstroms) in powder X-ray diffraction (XRD) or c) a combination of a) and b). The catalyst composition, olefin polymerization process, method for producing an olefin polymerization catalyst, support activator, or method for producing a support activator according to paragraph 1 above.

Aspect 54. a sample of the calcined smectite heteroadduct characterized by a non-smectite heteroadduct intercalation structure characterized by powder X-ray diffraction (XRD) peaks ranging from about 4 degrees 2-theta (2-theta) to about 5 degrees 2-theta; non-smectite heteroadduct intercalation structures are present at a concentration of less than 60 wt%, less than 50 wt%, less than 40 wt%, less than 30 wt%, less than 20 wt%, less than 10 wt%, or less than 5 wt% 52. The catalyst composition, olefin polymerization process, method of making an olefin polymerization catalyst, support activator, or method of making a support activator according to any one of aspects 1-51.

Aspect 55. from about 0.2 cc/g to about 3.0 cc/g, from about 0.3 cc/g to about 2.5 cc/g, or from about 0.5 cc/g to about 1.8 cc/g of the calcined smectite heteroadduct 55. The catalyst composition, process for polymerization of olefins, method for making an olefin polymerization catalyst, support activator, or manufacture of a support activator according to any one of aspects 1-54, exhibiting a range of BJH porosities. Method.

Aspect 56. _3-10 nm diameter (V _56. The catalyst composition, process for polymerization of olefins, process for preparing an olefin polymerization catalyst, support activator, or A method for producing a support activator.

Aspect 57. Calcined smectite heteroadducts exhibit a logarithmic differential pore volume distribution (dV(logD) versus pore size) with local maxima ranging from 30 Å (Angstroms) to 40 Å (D _VM(30-40) ), embodiments 1-56 A catalyst composition, an olefin polymerization process, a method for producing an olefin polymerization catalyst, a support activator, or a method for producing a support activator according to any one of the preceding claims.

Aspect 58. The calcined smectite heteroadduct has the highest value in the range of 30 Å (Angstroms) to 40 Å (D _VM(30-40) ), or in the range of 200 Å (Angstroms) to 500 Å (D _VM(200-500) ). 58. The catalyst composition of any one of aspects 1-57, characterized by a logarithmic differential pore volume distribution (dV(logD) vs. pore diameter) having (D _M , representing the most frequently occurring pore diameter), the olefin , a method for producing an olefin polymerization catalyst, a support activator, or a method for producing a support activator.

Aspect 59. 59. The catalyst composition, olefin polymerization process, method of making an olefin polymerization catalyst, support activator, or support activity according to aspect 58, wherein the local maximum D _VM(30-40) is the largest globally manufacturing method of the agent.

Aspect 60. Local maximum D _VM(30-40) is less than 210%, less than 150%, less than 120%, or less than 100% of the local maximum between 200 Å (Angstroms) and 500 Å (D _VM(200-500) ) 59. The catalyst composition, olefin polymerization process, method of making an olefin polymerization catalyst, support activator, or method of making a support activator according to aspect 58.

Aspect 61. Logarithmic differential pore size distribution (dV(logD) vs. pore diameter) with a local maximum from 200 Å (Angstroms) to 500 Å (D _VM(200-500) ) exceeding all values of dV(logD) from 30 Å (Angstroms) to 200 Å 59. The catalyst composition, process for polymerization of olefins, method for making an olefin polymerization catalyst, support activator, or method for making a support activator according to aspect 58, which exhibits a value.

Aspect 62. heterocoagulant reagent,
a) from about 1% to about 60% by weight calculated on Al ₂ O ₃ ;
b) about 5% to about 50% by weight calculated on Al ₂ O ₃ ;
b) from about 10% to about 45% by weight calculated on Al ₂ O ₃ ;
c) A catalyst composition, olefin polymerization process, according to any one of aspects 1 to 61, comprising an aluminum concentration in the range of about 15% to about 35% by weight calculated on Al ₂ O ₃ . , a method for producing an olefin polymerization catalyst, a support activator, or a method for producing a support activator.

Aspect 63. [1] colloidal smectite clay and [2] heterocoagulant reagent,
a) about positive (+) 22 mV (millivolts) to about negative (-) 22 mV;
b) about positive (+) 20 mV (millivolts) to about negative (-) 20 mV;
c) about positive (+) 18 mV (millivolts) to about negative (-) 18 mV;
d) about positive (+) 15 mV (millivolts) to about negative (-) 15 mV;
e) about positive (+) 12 mV (millivolts) to about negative (-) 12 mV;
f) about positive (+) 10 mV (millivolts) to about negative (-) 10 mV;
g) a smectite heteroadduct having a zeta potential in the range of about positive (+) 8 mV (millivolts) to about negative (-) 8 mV, or h) about positive (+) 5 mV (millivolts) to about negative (-) 5 mV. 63. The catalyst composition, olefin polymerization process, method of making an olefin polymerization catalyst, support activator, or support of any one of aspects 1-62, wherein the catalyst composition is contacted in an amount sufficient to provide a slurry of A method for producing a body activator.

Aspect 64. [1] colloidal smectite clay and [2] heterocoagulation reagent at 25°C ± 5°C for less than 1 hour, less than 45 minutes, less than 30 minutes, less than 20 minutes, less than 15 minutes, or less than 10 minutes; 64. The catalyst composition, olefin polymerization process, method of making an olefin polymerization catalyst, support activator, or method of making a support activator according to any one of aspects 1-63, which is contacted.

Aspect 65. After contacting [1] the colloidal smectite clay and [2] the heterocoagulant reagent, the smectite heteroadduct is isolated from the slurry by filtration without the use of ultrafiltration, centrifugation, or settling tanks. 65. The catalyst composition, process for polymerization of olefins, method of making an olefin polymerization catalyst, support activator, or method of making a support activator according to any one of aspects 1-64.

Aspect 66. 66. The catalyst composition, olefin polymerization process, method of making an olefin polymerization catalyst, support activator, or support activity according to any one of aspects 1-65, wherein the smectite heteroadduct is amorphous. manufacturing method of the agent.

Aspect 67. 67. Any one of aspects 1-66, wherein the catalyst composition or support activator further comprises an ion exchange clay, a protonic acid treated clay, a pillared clay, an aluminoxane, a boric acid coactivator, or any combination thereof. The catalyst composition, olefin polymerization process, method for producing an olefin polymerization catalyst, support activator, or method for producing a support activator according to any one of the preceding paragraphs.

Aspect 68. of aspects 1-66, wherein the catalyst composition or support activator is substantially free of ion exchange clays, protonic acid treated clays, pillared clays, aluminoxanes, boric acid coactivators, or any combination thereof. Catalyst composition, process for polymerization of olefins, method for making olefin polymerization catalyst, support activator, or method for making support activator according to any one of claims 1 to 3.

Aspect 69. 69. A process for preparing a support activator according to any one of aspects 5-68, wherein the smectite heteroadduct is subsequently dried and/or calcined.

Aspect 70. 70. Aspect 5-69, wherein the smectite heteroadduct is subsequently dried by heating, azeotropic drying, freeze drying, flash drying, fluid bed drying, spray drying, or any combination thereof. A method for producing a support activator.

Aspect 71. 71. A method for producing a support activator according to any one of aspects 5-70, wherein after isolating the smectite heteroadduct, the smectite heteroadduct is wet milled or dry milled.

Aspect 72. 72. A process for preparing a support activator according to any one of aspects 5-71, wherein the isolated smectite heteroadduct is dried to constant weight to obtain a dry smectite heteroadduct.

Aspect 73. Support activation according to any one of aspects 5-71, wherein the smectite heteroadduct is calcined at a temperature ranging from about 110° C. to about 900° C. for a period ranging from about 1 hour to about 12 hours. A method for producing the agent.

Aspect 74. The smectite heteroadduct has a catalyst productivity of at least about 1,500 g of polymer/g of support activator, or from about 1,500 g of polymer/g of support activator to about 30,000 g of polymer/g of support activator. 72. A method of making a support activator according to any one of aspects 5-71, wherein the support activator is calcined for a time and temperature sufficient to achieve a catalyst productivity in the range of the support activator of Aspects 5-71.

Aspect 75. [1] exposing the dried or calcined smectite heteroadduct to a vacuum followed by an inert atmosphere such as nitrogen or argon, optionally repeating the vacuum and inert gas cycle one or more times; calcining the smectite heteroadduct in a flowing gas of carbon monoxide, changing the flowing gas to an inert gas such as nitrogen or argon, and removing entrapped air from the dried or calcined smectite heteroadduct by 72. The method for producing a support activator according to any one of aspects 5 to 71, further comprising

Aspect 76. 76. A method of making a support activator according to any one of aspects 5-75, wherein the concentration of smectite heteroadduct solids in the slurry is at least about 5% by weight.

Aspect 77. Is the concentration of smectite heteroadduct solids in the slurry up to about 30%, up to about 25%, up to about 20%, up to about 15%, up to about 10%, up to about 5% by weight? or the concentration of smectite heteroadduct solids in the slurry ranges from about 2 wt% to about 30 wt%, from about 3 wt% to about 20 wt%, or from about 5 wt% to about 15 wt%. 77. A method for producing a support activator according to any one of 5 to 76.

Aspect 78. 78. Embodiment according to any one of aspects 5-77, wherein the contacting step is performed in the substantial absence of ion exchange clay, protonic acid treated clay, aluminoxane, boric acid co-activator, or any combination thereof. A method for producing a support activating agent according to

Aspect 79. 79. A method of making a support activator according to any one of aspects 5-78, wherein the contacting step is carried out within a temperature range of about 20°C to about 100°C.

Aspect 80. Smectite heteroadduct slurries exhibit the following filtration behavior:
[a] Filtering the heteroadduct slurry, having a heteroadduct concentration of 2.0% by weight in water, within a time period of 0 to 2 hours after the contacting step b) yields Based on the weight of the liquid carrier, the percentage of filtrate obtained in a 10 minute filtration time using either vacuum filtration or gravity filtration was: (1) about 50% by weight of the liquid carrier in the slurry prior to filtration; (2) from about 60% to about 100% by weight of the liquid carrier in the slurry before filtration; (3) from about 70% to about 100% by weight of the liquid carrier in the slurry before filtration; or (4) within the range of about 80% to about 100% by weight of the liquid carrier in the slurry prior to filtration;
[b] the filtrate from the heteroadduct slurry evaporates to yield a solid comprising less than 20%, less than 15%, or less than 10% of the initial combined weight of clay and heterocoagulant; 80. The support activator according to any one of aspects 4 to 79 or a method for producing a support activator.

Aspect 81. Smectite heteroadduct slurries exhibit the following filtration behavior:
[a] if a heteroadduct slurry having a heteroadduct concentration of 2.0% by weight in water is filtered within a time period of 0 hours to 2 hours after the contacting step b) to provide a first filtrate, The weight ratio of the filtrate of 2 to the first filtrate is less than 0.25, less than 0.20, less than 0.10, less than 0.15, less than 0.10, less than 0.5, or about 0.0 , a second filtrate obtained from filtration of a 2.0% by weight slurry of a pillared clay prepared using a colloidal zinc clay, a heterocoagulant reagent, and a liquid carrier; the weight of the filtrate of 2 is measured after the same filtration time of 5, 10 or 15 minutes;
[b] the filtrate from the heteroadduct slurry evaporates to yield a solid comprising less than 20%, less than 15%, or less than 10% of the initial combined weight of clay and heterocoagulant; 80. The support activator according to any one of aspects 4 to 79 or a method for producing a support activator.

Aspect 82. Smectite heteroadduct slurries are 3-fold, 3.5-fold, 4-fold higher than the settling rate of 2.5 wt% of aqueous pillared clay slurries prepared using colloidal smectite clay, heterocoagulant reagent, and liquid carrier characterized by a settling velocity of the 2.5 wt% composition of the aqueous heteroadduct slurry that is 6, 7, 8, 9, or 10 times greater, wherein the settling velocity is: Compared at about 12 hours, about 18 hours, about 24 hours, about 30 hours, about 36 hours, about 48 hours, about 72 hours, about 95 hours, about 96 hours, or about 100 hours or more from the start of the sedimentation test, 80. The support activator according to any one of aspects 4 to 79 or a method for producing a support activator.

Aspect 83. from at least one metallocene compound having olefin polymerization activity when the metallocene compound is activated by ion exchange clays, protonic acid treated clays, pillared clays, aluminoxanes, boric acid coactivators, or any combination thereof Selected the catalyst composition, olefin polymerization process, or method of making an olefin polymerization catalyst according to any one of aspects 1-3 and 6-68.

Aspect 84. Embodiments 1-3, 6-, wherein the metallocene compound comprises, consists of, consists essentially of, or is selected from a non-bridged (non-ansa) metallocene compound or a bridged (ansa) metallocene compound. 68, and 83. The catalyst composition, olefin polymerization process, or method of making an olefin polymerization catalyst of any one of paragraphs 68 and 83.

Aspect 85. Each metallocene compound independently has the formula:
(X ¹ ) (X ² ) (X ³ ) (X ⁴ ) M (wherein
a) M is selected from titanium, zirconium, or hafnium;
b) X ¹ is selected from substituted or unsubstituted cyclopentadienyl, indenyl, fluorenyl, pentadienyl, allyl, boratabenzenyl, 1,2-azaborolyl, or 1,2-diaza-3,5-diborolyl, optionally substituted group is independent of halide, C ₁ -C ₂₀ hydrocarbyl, C ₁ -C ₂₀ heterohydrocarbyl, C ₁ -C ₂₀ organoheteryl, fused C ₄ -C ₁₂ carbocyclic moiety, or nitrogen, oxygen, sulfur, or phosphorus independently selected from fused _C4 - _C11 heterocyclic moieties having at least one heteroatom selected as
c) X ² is selected from [1] substituted or unsubstituted cyclopentadienyl, indenyl, fluorenyl, pentadienyl, or allyl, with optional substituents being halides, C ₁ -C ₂₀ hydrocarbyl, C ₁ -C ₂₀ heterohydrocarbyl, or C ₁ -C ₂₀ organoheteryl, or [2] Halide, hydride, C ₁ -C ₂₀ hydrocarbyl, C ₁ -C ₂₀ heterohydrocarbyl, C ₁ -C ₂₀ organoheteryl, condensation selected from a _C4 - _C12 carbocyclic moiety or a fused _C4 - _C11 heterocyclic moiety having at least one heteroatom independently selected from nitrogen, oxygen, sulfur, or phosphorus;
d) X ¹ and X ² are optionally bridged by at least one linker substituent having 2 to 4 bridging atoms independently selected from C, Si, N, P, or B, each Each available non-bridging valence of a bridging atom is unsubstituted (bonded to H) or substituted, and any substituents are halides, C ₁ -C ₂₀ hydrocarbyls, C ₁ -C ₂₀ heterohydrocarbyls, or C ₁ any hydrocarbyl, heterohydrocarbyl, or organoheteryl substituent independently selected from _—C20 organoheteryl, can form a saturated or unsaturated cyclic structure with the bridging atom or with X ¹ or X ² ;
e) [1] X ³ and X ⁴ are independently selected from halide, hydride, C ₁ -C ₂₀ hydrocarbyl, C ₁ -C ₂₀ heterohydrocarbyl, or C ₁ -C ₂₀ organoheteryl, [2] [GX ^A _k X ^B _4-k ] ⁻ (wherein G is B or Al, k is a number from 1 to 4, and X ^A at each occurrence independently of H or halide selected and X ^B at each occurrence is independently selected from C ₁ -C ₁₂ hydrocarbyl, C ₁ -C ₁₂ heterohydrocarbyl, C ₁ -C ₁₂ organoheteryl), [3] X ³ and X ⁴ are together a C ₄ -C ₂₀ polyene, or [4] X ³ and X ⁴ together with M form an unsubstituted or unsubstituted, saturated or unsaturated C ₃ -C ₆ metallacycle moiety, Optional substituents on the metalacycle moiety are independently selected from halides, C ₁ -C ₂₀ hydrocarbyls, C ₁ -C ₂₀ heterohydrocarbyls, or C ₁ -C ₂₀ organoheteryls. 84. The catalyst composition of any one of aspects 1-3, 6-68, and 83, comprising, consisting of, consisting essentially of, or selected from a combination of an olefin or a method for producing an olefin polymerization catalyst.

Aspect 86. X ¹ and X ² are
a) >EX ⁵ ₂ , -EX ⁵ ₂ EX ⁵ ₂ -, -EX ⁵ ₂ EX ⁵ EX ⁵ ₂ -, or >C=CX ⁵ ₂ where E at each occurrence is independent of C or Si selected),
b) -BX ⁵ -, -NX ⁵ -, or -PX ⁵ , or 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 —],
[-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 ⁵ ₂ (1 , 2-C ₆ H ₄ )CX ⁵ ₂ -]
(wherein X ⁵ at each occurrence is independently selected from H, halide, C ₁ -C ₂₀ hydrocarbyl, C ₁ -C ₂₀ heterohydrocarbyl, or C ₁ -C ₂₀ organoheteryl;
Any ^X5 substituent selected from hydrocarbyl, heterohydrocarbyl, or organoheteryl substituents can form a saturated or unsaturated cyclic structure with a bridging atom, another ^X5 substituent, ^X1 , or ^X2 . 86. The catalyst composition, olefin polymerization process, or method of making an olefin polymerization catalyst according to aspect 85, wherein the catalyst composition is crosslinked by a linker substituent selected from:

Aspect 87. X ¹ and X ² are C ₁ -C ₂₀ hydrocarbylene group, C ₁ -C ₂₀ hydrocarbylidene group, C ₁ -C ₂₀ heterohydrocarbyl group, C ₁ -C ₂₀ heterohydrocarbylidene group, C ₁ - _86. The catalyst composition, olefin polymerization process, or olefin polymerization catalyst of aspect 85, which is bridged by a linker substituent selected from a C ₂₀ heterohydrocarbylene group, or a C 1 -C ₂₀ heterohydrocarbylene group. Production method.

Aspect 88. X ¹ and X ² are of the formula >EX ⁵ ₂ , -EX ⁵ ₂ EX ⁵ ₂ -, or -BX ⁵ -, where E is independently C or Si, and X ⁵ at each occurrence is from halides, C ₁ -C ₂₀ aliphatic groups, C ₆ -C ₂₀ aromatic groups, C ₁ -C ₂₀ heteroaliphatic groups, C ₄ -C ₂₀ heteroaromatic groups, or C ₁ -C ₂₀ organoheteryl groups 86. The catalyst composition, olefin polymerization process, or method of making an olefin polymerization catalyst according to aspect 85, wherein the catalyst composition is crosslinked by at least one substituent having an independently selected

Aspect 89. X ⁵ at each occurrence is a halide, a C ₁ -C ₁₈ or C 1 _{-C 12} alkyl group, a C ₂ -C ₁₈ or C ₂ -C ₁₂ alkenyl group, a C ₆ -C ₁₈ or C ₆ -C ₁₂ aromatic group C ₄ -C ₁₈ or C ₄ -C ₁₂ heteroaromatic group, C ₁ -C ₁₈ or C 1 -C ₁₂ heterohydrocarbyl group, C _{1 -C 21} or C ₁ -C ₁₅ organosilyl group, C independently from ₁ -C ₁₈ or C ₁ -C ₁₂ halogenated alkyl (haloalkyl) groups, C ₁ -C ₁₈ or C ₁ -C ₁₂ organic phosphorous groups, or C ₁ -C ₁₈ or C ₁ -C ₁₂ organic nitrogen groups 89. The catalyst composition, olefin polymerization process, or method of making an olefin polymerization catalyst according to any one of aspects 86-88, wherein the catalyst composition is selected as:

Aspect 90. X ¹ and X ² are silylene, methylsilylene, dimethylsilylene, diisopropylsilylene, dibutylsilylene, methylbutylsilylene, methyl t-butylsilylene, dicyclohexylsilylene, methylcyclohexylsilylene, methylphenylsilylene, diphenylsilylene, ditolylsilylene, methyl bridged by a linker substituent selected from naphthylsilylene, dinaphthylsilylene, cyclodimethylsilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexymethylenesilylene, or cycloheptamethylene, embodiment 85 A catalyst composition, an olefin polymerization process, or a method for producing an olefin polymerization catalyst according to .

Aspect 91. X ¹ is selected from substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl, and optional substituents are independently halides, C ₁ -C ₂₀ aliphatic groups, C ₆ -C ₂₀ aromatic groups , C ₁ -C ₂₀ heteroaliphatic groups, C ₄ -C ₂₀ heteroaromatic groups, or C ₁ -C ₂₀ organoheteryl groups. , an olefin polymerization process, or a method for producing an olefin polymerization catalyst.

Aspect 92. X ¹ is selected from substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl, any substituents being independently halides, C ₁ -C ₁₈ or C ₁ -C ₁₂ alkyl groups, C ₂ —C ₁₈ or C ₂ -C ₁₂ alkenyl group, C ₆ -C ₁₈ or C ₆ -C ₁₂ aromatic group, C ₄ -C ₁₈ or C ₄ -C ₁₂ heteroaromatic group, C ₁ -C ₂₁ or C ₁ -C ₁₅ organosilyl group, C ₁ -C ₁₈ or C ₁ -C ₁₂ halogenated alkyl (haloalkyl) group, C ₁ -C ₁₈ or C ₁ -C ₁₂ organophosphorus group, or C ₁ -C ₁₈ or C 91. The catalyst composition, olefin polymerization process, or method of making an olefin polymerization catalyst according to any one of aspects 85-90, independently selected from ₁ -C ₁₂ organic nitrogen groups.

Aspect 93. X ¹ , X ² , or both X ¹ and X ² are independently selected from substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl, and optional substituents are
a) a silicon group having the formula —SiH ₃ , —SiH ₂ R, —SiHR ₂ , —SiR ₃ , —SiR ₂ (OR), —SiR(OR) ₂ , or —Si(OR) ₃ ,
b) Formulas —PHR, —PR ₂ , —P(O)R ₂ , —P(OR) ₂ , —P(O)(OR) ₂ ,
a phosphorus group with —P(NR ₂ ) ₂ or —P(O)(NR ₂ ) ₂ ,
c) a boron group having the formula —BH ₂ , —BHR, —BR ₂ , —BR(OR), or —B(OR) ₂ ;
d) germanium groups having the formula -GeH ₃ , -GeH ₂ R, -GeHR ₂ , -GeR ₃ , -GeR ₂ (OR), -GeR(OR) ₂ , or -Ge(OR) ₃ , or e) them wherein R at each occurrence is independently selected from C ₁ -C ₂₀ hydrocarbyl groups. Compositions, olefin polymerization processes, or methods of making olefin polymerization catalysts.

Aspect 94. X ¹ , X ² , or X ¹ and X ² are pyrrole, furan, thiophene, phosphorus, imidazole, imidazoline, pyrazole, pyrazoline, oxazole, oxazoline, isoxazole, isoxazoline, thiazole, thiazoline, isothiozoline, or portions thereof 91. The catalyst composition, olefin polymerization process, or method of making an olefin polymerization catalyst according to any one of aspects 85-90, substituted with a fused carbocyclic or heterocyclic moiety selected from polysaturated analogues. .

Aspect 95. X ² is [1]substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl, and optional substituents are halides, C ₁ -C ₂₀ aliphatic groups, C ₆ -C ₂₀ aromatic groups , a C ₁ -C ₂₀ heteroaliphatic group, a C ₄ -C ₂₀ heteroaromatic group, or a C ₁ -C ₂₀ organoheteryl group, substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl , or [2] halides, C ₁ -C ₂₀ aliphatic groups, C ₆ -C ₂₀ aromatic groups, C ₁ -C ₂₀ heteroaliphatic groups, C ₄ -C ₂₀ heteroaromatic groups, or C ₁ - C ₂₀ organoheteryl group.

Aspect 96. X ² is [1]substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl, and optional substituents are halides, C ₁ -C ₁₈ or C ₁ -C ₁₂ alkyl groups, C ₂ - C ₁₈ or C ₂ -C ₁₂ alkenyl group, C ₆ -C ₁₈ or C ₆ -C ₁₂ aromatic group, C ₄ -C ₁₈ or C ₄ -C ₁₂ heteroaromatic group, C ₁ -C ₂₁ or C ₁ —C ₁₅ organosilyl group, C ₁ -C ₁₈ or C ₁ -C ₁₂ halogenated alkyl (haloalkyl) group, C ₁ -C ₁₈ or C ₁ -C ₁₂ organophosphorus group, or C ₁ -C ₁₈ or C ₁ substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl or [2] halides, C _{1 -C 18} or C ₁ -C ₁₂ alkyl groups, independently selected from —C 12 organic nitrogen groups; ₂ - _C18 or _C2 - _C12 alkenyl groups, _C6 - _C18 or _C6 - _C12 aromatic groups, _C4 - _C18 or _C4 - _C12 heteroaromatic groups, _C1 - _C21 or C ₁ -C ₁₅ organosilyl groups, C ₁ -C ₁₈ or C ₁ -C ₁₂ halogenated alkyl (haloalkyl) groups, C ₁ -C ₁₈ or C ₁ -C ₁₂ organophosphorus groups, or C ₁ -C ₁₈ or C ₁ -C ₁₂ organic nitrogen groups.

Aspect 97. at least one of X ¹ , X ² or the linking substituents between X ¹ and X ² has the formula —(CH ₂ ) _n CH═CH ₂ , where n is 1-10; 97. The catalyst composition, olefin polymerization process, or method of making an olefin polymerization catalyst according to any one of aspects 85 to 96, wherein the catalyst composition is substituted with a C ₃ -C ₁₂ olefin group having a C 3 -C 12 olefin group.

Aspect 98. [1] X ³ and X ⁴ are halide, hydride, C ₁ -C ₂₀ aliphatic group, C ₆ -C ₂₀ aromatic group, C ₁ -C ₂₀ heteroaliphatic group, C ₄ -C ₂₀ hetero [2] X ³ and X ⁴ are both substituted or unsubstituted 1,3-butadiene having from 4 to 20 carbon atoms independently selected from aromatic groups or C ₁ -C ₂₀ organoheteryl groups; or [3] X ³ and X ⁴ together with M form a substituted or unsubstituted, saturated or unsaturated C ₄ -C ₅ metalacycle moiety and any substituent on the metalacycle moiety is halogen C ₁ -C ₂₀ aliphatic group, C ₆ -C ₂₀ aromatic group, C ₁ -C ₂₀ heteroaliphatic group, C ₄ -C ₂₀ heteroaromatic group, or C ₁ -C ₂₀ organoheteryl group 98. The catalyst composition, olefin polymerization process, or method of making an olefin polymerization catalyst according to any one of aspects 85-97, wherein the catalyst composition is selected as:

Aspect 99. [1] X ³ and X ⁴ are halide, hydride, C ₁ -C ₁₈ or C ₁ -C ₁₂ alkyl group, C ₂ -C ₁₈ or C ₂ -C ₁₂ alkenyl group, C ₆ -C ₁₈ or C ₆ -C ₁₂ aromatic group, C ₄ -C ₁₈ or C ₄ -C ₁₂ heteroaromatic group, C ₁ -C ₂₁ or C ₁ -C ₁₅ organosilyl group, C ₁ -C ₁₈ or C ₁ -C ₁₂ independently selected from a halogenated alkyl (haloalkyl) group, a C ₁ -C ₁₈ or C ₁ -C ₁₂ organic phosphorous group, or a C ₁ -C ₁₈ or C ₁ -C ₁₂ organic nitrogen group, or [2 ] X ³ and X ⁴ are both substituted or unsubstituted 1,3-butadiene having 4 to 18 carbon atoms, or [3] X ³ and X ⁴ together with M are substituted or unsubstituted , a saturated or unsaturated C ₄ -C ₅ metallacycle moiety, and optional substituents on the metallacycle moiety are halides, C ₁ -C ₁₈ or C ₁ -C ₁₂ alkyl groups, C ₂ -C ₁₈ or C ₂ -C ₁₂ alkenyl group, C ₆ -C ₁₈ or C ₆ -C ₁₂ aromatic group, C ₄ -C ₁₈ or C ₄ -C ₁₂ heteroaromatic group, C ₁ -C ₂₁ or C ₁ -C ₁₅ organosilyl groups, C ₁ -C ₁₈ or C ₁ -C ₁₂ halogenated alkyl (haloalkyl) groups, C ₁ -C ₁₈ or C ₁ -C ₁₂ organophosphorus groups, or C ₁ -C ₁₈ or C ₁ -C 98. The catalyst composition, olefin polymerization process, or method of making an olefin polymerization catalyst according to any one of aspects 85-97, independently selected from ₁₂ organic nitrogen groups.

Embodiment 100. X ³ and X ⁴ are [1] halide, hydride, borohydride, aluminum hydride, or [2] substituted or unsubstituted C ₁ -C ₁₈ aliphatic group, C ₁ -C ₁₂ alkoxide group, C ₆ -C ₁₀ aryloxide groups, C ₁ -C ₁₂ alkyl sulfide groups, C ₆ -C ₁₀ aryl sulfide groups, wherein the optional substituents are halides, C ₁ -C ₁₀ alkyl or C ₆ -C substituted or unsubstituted C ₁ -C ₁₈ aliphatic groups, C ₁ -C ₁₂ alkoxide groups, C ₆ -C ₁₀ aryloxide groups, C _{1 -C 12} alkyl sulfide groups, independently selected from 10 aryl; a C ₆ -C ₁₀ aryl sulfide group, or [3] an amide group or a phosphate group, wherein the optional substituents are independently selected from C ₁ -C ₁₀ alkyl or C ₆ -C ₁₀ aryl; 98. The catalyst composition, olefin polymerization process, or method of making an olefin polymerization catalyst according to any one of aspects 85-97, independently selected from an amide group or a phosphate group.

Aspect 101. The metallocene compound is bis(cyclopentadienyl)zirconium dichloride, bis-(methylcyclopentadienyl)zirconium dichloride, bis(1,2-dimethylcyclopentadienyl)zirconium dichloride, bis(1,3-dimethylcyclopenta dienyl)zirconium dichloride, bis(1-butyl-3-methylcyclopentadienyl)zirconium dichloride, bis(1,2,3-trimethylcyclopentadienyl)zirconium dichloride, bis(1,2,4-trimethylcyclo) pentadienyl)zirconium dichloride, bis-(1,2,3,4-tetramethylcyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium dichloride, bis-(ethylcyclopentadienyl)zirconium Dichloride, bis(1,2-diethylcyclopentadienyl)zirconium dichloride, bis(1,3-diethylcyclopentadienyl)zirconium dichloride, bis(isopropylcyclopentadienyl)zirconium dichloride, bis(phenylpropylcyclopentad) yenyl)zirconium dichloride, bis(t-butylcyclopentadienyl)zirconium dichloride, bis(indenyl)-zirconium dichloride, bis(4-methyl-1-indenyl)zirconium dichloride, bis(5-methyl-1-indenyl)zirconium dichloride zirconium)zirconium dichloride, bis(6-methyl-1-indenyl)zirconium dichloride, bis(7-methyl-1-indenyl)zirconium dichloride, bis(5-methoxy-1-indenyl)-zirconium dichloride, bis(2,3 -dimethyl-1-indenyl)zirconium dichloride, bis(4,7-dimethyl-1-indenyl)zirconium dichloride, bis(4,7-dimethoxy-1-indenyl)zirconium dichloride, (indenyl)(fluorenyl)zirconium dichloride, bis (Fluorenyl)zirconium dichloride, bis(trimethylsilylcyclopentadienyl)zirconium dichloride, bis(trimethylgermylcyclopentadienyl)zirconium dichloride, bis(trimethylstannylcyclopentadienyl)zirconium dichloride, bis(trifluoromethylcyclopenta) dienyl)zirconium dichloride, (cyclopentadienyl)-(methylcyclopentadienyl)zirconium dichloride, (cyclopentadienyl)(dimethylcyclopentadienyl)zirconium dichloride, (cyclopentadienyl)(trimethylcyclopentadienyl) enyl)zirconium dichloride, (cyclopentadienyl)(tetramethylcyclopentadienyl)zirconium dichloride, (cyclopentadienyl)(pentamethylcyclopentadienyl)zirconium dichloride, (cyclopentadienyl)(ethylcyclopentadienyl) (enyl)zirconium dichloride, (cyclopentadienyl)(diethylcyclopentadienyl)zirconium dichloride, (cyclopentadienyl)(triethylcyclopentadienyl)zirconium dichloride, (cyclopentadienyl)(tetraethylcyclopentadienyl) Zirconium dichloride, (cyclopentadienyl)(pentaethylcyclopentadienyl)-zirconium dichloride, (cyclopentadienyl)(fluorenyl)zirconium dichloride, (cyclopentadienyl)(2,7-di-t-butylfluoro olenyl)-zirconium dichloride, (cyclopentadienyl)(octahydrofluorenyl)zirconium dichloride, (cyclopentadienyl)(4-methoxyfluorenyl)zirconium dichloride, (methylcyclopentadienyl)-(t -butylcyclopentadienyl)zirconium dichloride, (methylcyclopentadienyl)(fluorenyl)zirconium dichloride, (methylcyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, (methylcyclopentadienyl) pentadienyl)(octahydrofluorenyl)zirconium dichloride, (methylcyclopentadienyl)(4-methoxyfluorenyl)-zirconium dichloride, (dimethylcyclopentadienyl)(fluorenyl)-zirconium dichloride, (dimethylcyclo pentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, (dimethylcyclopentadienyl)(octahydrofluorenyl)zirconium dichloride, (dimethylcyclopentadienyl)(4-methoxyfluoro olenyl)zirconium dichloride, (ethylcyclopentadienyl)(fluorenyl)zirconium dichloride, (ethylcyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, (ethylcyclopentadienyl) (octahydrofluorenyl)zirconium dichloride, (ethylcyclopentadienyl)(4-methoxyfluorenyl)zirconium dichloride, (diethylcyclopentadienyl)-(fluorenyl)zirconium dichloride, (diethylcyclopentadienyl) ( 2,7-di-t-butylfluorenyl)zirconium dichloride, (diethylcyclopentadienyl)(octahydrofluorenyl)zirconium dichloride, (diethylcyclopentadienyl)(4-methoxyfluorenyl)zirconium dichloride , or any combination thereof, comprising, consisting of, consisting essentially of, or selected from, any one of aspects 1-3, 6-68, or 83. A catalyst composition, an olefin polymerization process, or a method of making an olefin polymerization catalyst.

Aspect 102. The catalyst composition, olefin polymerization process, or method of making an olefin polymerization catalyst of any one of aspects 1-3, 6-68, or 83-101, wherein the catalyst composition further comprises a co-catalyst.

Aspect 103. Embodiments 1-3, 6-68, or 83-102, wherein the contacting step further comprises contacting the metallocene compound and the support activator with a cocatalyst, in any order. A catalyst composition, an olefin polymerization process, or a method of making an olefin polymerization catalyst.

Aspect 104. The catalyst composition, the olefin polymerization process of any one of aspects 1-3, 6-68, or 83-103, wherein the cocatalyst comprises an alkylating agent, a hydriding agent, or a silylating agent, or A method for producing an olefin polymerization catalyst.

Aspect 105. the cocatalyst comprises, consists of, consists essentially of, or consists of an organoaluminum compound, an organoboron compound, an organozinc compound, an organomagnesium compound, an organolithium compound, or any combination thereof; Selected the catalyst composition, olefin polymerization process, or method of making an olefin polymerization catalyst according to any one of aspects 1-3, 6-68, or 83-104.

Aspect 106. The cocatalyst comprises, consists of, consists essentially of, or is selected from an organoaluminum compound, or a combination of organoaluminum compounds, each independently having the formula:
Al(X ^A ) _n (X ^B ) _m or M ^x [AlX ^A ₄ ] (wherein
a) n+m=3, where n and m are not limited to integers;
b) X ^A is [1] hydride, C ₁ -C ₂₀ hydrocarbyl, or C ₁ -C ₂₀ heterohydrocarbyl, [2] hydride, C ₁ -C ₂₀ aliphatic group, C ₆ -C ₂₀ aromatic group, C ₁ -C ₂₀ heteroaliphatic group, or C ₄ -C ₂₀ heteroaromatic group, or [3] two X ^A together are C ₄ -C ₅ hydrocarbylene groups wherein the remaining X ^A are independently selected from hydrides, C ₁ -C ₂₀ hydrocarbyls, or C ₁ -C ₂₀ heterohydrocarbyls;
c) X ^B is independently selected from [1] a halide or a C ₁ -C ₂₀ organoheteryl, or [2] a halide, a C ₁ -C ₁₂ alkoxide group, or a C ₆ -C ₁₀ aryloxide group;
d) the catalyst composition, olefin polymerization process of any one of aspects 1-3, 6-68, or 83-104, wherein M ^x is selected from Li, Na, or K; Or a method for producing an olefin polymerization catalyst.

Aspect 107. The cocatalyst comprises, consists of, consists essentially of, or is selected from an organoaluminum compound, or a combination of organoaluminum compounds, each independently having the formula:
Al(X ^C ) _n (X ^D ) _3-n or M ^x [AlX ^C ₄ ] (wherein
a) n is a number from 1 to 3, including
b) X ^C is independently selected from hydrides or C ₁ -C ₂₀ hydrocarbyls;
c) X ^D is fluoride, chloride, bromide, iodide, bromate, chlorate, perchlorate, hydrocarbyl sulfate, hydrocarbyl sulfite, sulfamate, hydrocarbyl sulfide, hydrocarbonate, hydrogen carbonate salts (bicarbonates), carbamates, nitrites, hydrogen nitrites, bicarbonates, bicarbonates, dihydrocarbyl phosphates, selenate, sulfites, carbonates, oxalates, phosphates, Phosphate, selenate, selenide, sulfide, oxide, sulfamate, azide, alkoxide, amide, amide, hydrocarbon amide, dihydrocarbylamide, dihydrocarbylamide, ^RA [CON(R)] _q (wherein R ^A at each occurrence is independently H or a substituted or unsubstituted C ₁ -C ₂₀ hydrocarbyl group and q is a number from 1 to 4, inclusive), and R ^B [CO ₂ ] _r (wherein R ^B at each occurrence is independently H or a substituted or unsubstituted C ₁ -C ₂₀ hydrocarbyl group, r is a number from 1 to 3, and ) is an independently selected formal anionic species,
d) M ^x is selected from Li, Na, or K).

Aspect 108. The co-catalyst is [1] trimethylaluminum, triethylaluminum (TEA), tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, ethyl-(3-alkylcyclopentadiyl)aluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, triisobutylaluminum (TIBAL), diethylaluminum chloride or any combination thereof, or [2]ethyl-(3-alkylcyclopentazyl)aluminum, triisobutylaluminum (TIBAL), trioctylaluminum, or any thereof or [3] any combination of any one or more cocatalysts [1] and any one or more cocatalysts [2]. 105. The catalyst composition, process for polymerization of olefins, or method of making an olefin polymerization catalyst according to any one of aspects 1-3, 6-68, or 83-104, which comprises or is selected from.

Aspect 109. The cocatalyst and coactivator comprise, consist of, consist essentially of, or are selected from an organoboron compound, or a combination of organoboron compounds, each independently having the formula:
B(X ^E ) _q (X ^F ) _3-q , B(X ^E ) ₃ or M ^y [BX ^E ₄ ] (wherein
a) q is a number from 1 to 3, including
b) X ^E is [1] hydride, C ₁ -C ₂₀ hydrocarbyl, or C ₁ -C ₂₀ heterohydrocarbyl, [2] hydride, C ₁ -C ₂₀ aliphatic group, C ₆ -C ₂₀ aromatic group, C ₁ -C ₂₀ heteroaliphatic group, or C ₄ -C ₂₀ heteroaromatic group, [3] fluorinated C ₁ -C ₂₀ hydrocarbyl, or fluorinated C ₁ -C ₂₀ heterohydrocarbyl, or [4] independently from a fluorinated C ₁ -C ₂₀ aliphatic group, a fluorinated C ₆ -C ₂₀ aromatic group, a fluorinated C ₁ -C ₂₀ heteroaliphatic group, or a fluorinated C ₄ -C ₂₀ heteroaromatic group selected,
c) X ^F is independently selected from [1] halide or C ₁ -C ₂₀ organoheteryl, or [2] halide, C ₁ -C ₁₂ alkoxide group, or C ₆ -C ₁₀ aryloxide group;
d) the catalyst composition, olefin polymerization process of any one of aspects 1-3, 6-68, or 83-104, wherein M ^y is selected from Li, Na, or K; Or a method for producing an olefin polymerization catalyst.

Aspect 110. [1] trimethylboron, triethylboron, tripropylboron, tributylboron, trihexylboron, trioctylboron, diethylboron ethoxide, diisobutylboron hydride, triisobutylboron, diethylboron chloride, di-3-pinanylborane, pinacolborane, catecholborane, lithium borohydride, lithium triethylborohydride, Lewis base adducts thereof, or combinations or mixtures thereof, or [2]tris(pentafluorophenyl)boron, tris[3,5 -bis(trifluoromethyl)phenyl]boron, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)borate, N,N - dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)-phenyl]borate, and combinations or mixtures thereof , the catalyst composition of any one of aspects 1-3, 6-68, or 83-104, consisting of, consisting essentially of, or selected from, a process for the polymerization of olefins, , or a method for producing an olefin polymerization catalyst.

Aspect 111. the cocatalyst comprises, consists of, consists essentially of, or is selected from an organozinc or organomagnesium compound, or a combination of organozinc and/or organomagnesium compounds, each independently formula:
M ^C (X ^G ) _r (X ^H ) _2-r (wherein
a) M ^C is zinc or magnesium,
a) r is a number from 1 to 2, including
b) X ^G is [1] hydride, C ₁ -C ₂₀ hydrocarbyl, or C ₁ -C ₂₀ heterohydrocarbyl, or [2] hydride, C ₁ -C ₂₀ aliphatic group, C ₆ -C ₂₀ aromatic independently selected from a C ₁ -C ₂₀ heteroaliphatic group, or a C ₄ -C ₂₀ heteroaromatic group;
c) X ^H is independently selected from [1] halide or C ₁ -C ₂₀ organoheteryl, or [2] halide, C ₁ -C ₁₂ alkoxide group, or C ₆ -C ₁₀ aryloxide group ), consisting of, consisting essentially of, or selected from, An olefin polymerization process or a method for producing an olefin polymerization catalyst.

Aspect 112. The co-catalyst is [1] dimethylzinc, diethylzinc, diisopropylzinc, dicyclohexylzinc, diphenylzinc, or any combination thereof, [2] butylethylmagnesium, dibutylmagnesium, n-butyl-sec-butylmagnesium, dicyclo pentadienylmagnesium, or any combination thereof, or any combination of any organozinc cocatalyst from group [1] with any organomagnesium cocatalyst from group [2] , the catalyst composition of any one of aspects 1-3, 6-68, or 83-104, consisting of, consisting essentially of, or selected from, a process for the polymerization of olefins, , or a method for producing an olefin polymerization catalyst.

Aspect 113. The cocatalyst has the formula:
Li(X ^J ) (wherein
X ^J is [1] hydride, C ₁ -C ₂₀ hydrocarbyl, or C ₁ -C ₂₀ heterohydrocarbyl, or [2] hydride, C ₁ -C ₂₀ aliphatic group, C ₆ -C ₂₀ aromatic group , a C ₁ -C ₂₀ heteroaliphatic group, or a C ₄ -C ₂₀ heteroaromatic group). , or a method of making an olefin polymerization catalyst according to any one of aspects 1-3, 6-68, or 83-104, wherein the catalyst composition, olefin polymerization process, or method of making an olefin polymerization catalyst is selected from.

Aspect 114. The cocatalyst comprises or consists of methyllithium, ethyllithium, propyllithium, butyllithium (including n-butyllithium and t-butyllithium), hexyllithium, iso-butyllithium, or any combination thereof or consisting essentially of or selected from, the catalyst composition of any one of aspects 1-3, 6-68, or 83-104, an olefin polymerization process, an olefin polymerization catalyst, manufacturing method.

Aspect 115. the catalyst composition comprises an ion exchange clay, a protonic acid treated clay, a pillared clay, an aluminoxane, a borate coactivator, an aluminate coactivator, an ionizing ion compound, a solid oxide treated with an electron-withdrawing anion; or any combination thereof, the catalyst composition, olefin polymerization process, or olefin A method for producing a polymerization catalyst.

Aspect 116. The catalyst composition, olefin polymerization process, or method of making an olefin polymerization catalyst of any one of aspects 1-3, 6-68, or 83-104, wherein the catalyst composition further comprises an ionic ionizing compound. .

Aspect 117. The ionic ionization compound is tri(n-butyl)ammonium tetrakis(p-tolyl)borate, trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate , tri(t-butyl)ammonium tetraphenylborate, N,N-dimethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, N,N-dimethyl-(2,4,6-trimethylanilinium ) tetraphenylborate, tropylium tetraphenylborate, triphenylcarbenium tetraphenylborate, triphenylphosphonium tetraphenylborate triethylsilylium tetraphenylborate, benzene (diazonium) tetraphenylborate, trimethylammonium tetrakis(pentafluorophenyl)borate, Triethylammonium tetrakis(pentafluorophenyl)borate, Tripropylammonium tetrakis(pentafluorophenyl)borate, Tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, Tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate , N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis ( pentafluorophenyl)borate, tropylium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylphosphonium tetrakis(pentafluorophenyl)borate, triethylsilylium tetrakis(pentafluorophenyl)borate, benzene (diazonium) tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, dimethyl(t-butyl) ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylanilinium tetrakis -(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, tropylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylphosphonium tetrakis-(2,3, 4,6-tetrafluorophenyl)borate, triethylsilylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate , trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammonium tetrakis(perfluoronaphthyl)borate, tripropylammonium tetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammonium tetrakis(perfluoronaphthyl)borate, tri( t-butyl)ammonium tetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-dimethyl-( 2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate, tropylium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate , triethylsilylium tetrakis(perfluoronaphthyl)borate, benzene(diazonium) tetrakis(perfluoronaphthyl)borate, trimethylammonium tetrakis(perfluorobiphenyl)borate, triethylammonium tetrakis(perfluorobiphenyl)borate, tripropylammonium tetrakis(perfluoronaphthyl)borate fluorobiphenyl)borate, tri(n-butyl)ammonium tetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammonium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-diethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate, tropylium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylphosphonium tetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate, benzene(diazonium)tetrakis(perfluorobiphenyl)borate, trimethylammonium tetrakis ( 3,5-bis(trifluoromethyl)phenyl)borate, triethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tripropylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate , tri(n-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(t-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N -dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-diethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethyl-( 2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tropylium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis (3,5-bis(trifluoromethyl)phenyl)borate, triphenylphosphonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylsilyliumtetrakis(3,5-bis(trifluoromethyl)phenyl )borate, benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate and dicyclohexylammonium tetrakis(pentafluorophenyl)borate, etc. additional trisubstituted phosphonium salts such as dialkylammonium salts of, tri(o-tolyl)phosphoniumtetrakis(pentafluorophenyl)borate, tri(2,6-dimethylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate, or any of them 117. The catalyst composition, olefin polymerization process, or method of making an olefin polymerization catalyst according to aspect 116, comprising, consisting of, consisting essentially of, or selected from a combination of:

Aspect 118. The catalyst composition of any one of aspects 1-3, 6-68, or 83-104, wherein the catalyst composition further comprises a co-activator comprising a solid oxide treated with an electron-withdrawing anion. , an olefin polymerization process, or a method for producing an olefin polymerization catalyst.

Aspect 119.
a) the solid oxide is silica, alumina, silica-alumina, silica-coated alumina, silica-zirconia, silica-titania, aluminum phosphate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, and comprising, consisting of, consisting essentially of, or selected from mixed oxides, or any combination thereof;
b) the electron withdrawing anion comprises or consists of fluoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate, fluorophosphate, fluorosulfate, or any combination thereof; 119. The catalyst composition, olefin polymerization process, or method of making an olefin polymerization catalyst according to aspect 118, which consists of, consists essentially of, or is selected from.

Aspect 120. The co-activator is alumina fluoride, alumina chloride, alumina bromide, alumina sulfate, silica alumina fluoride, silica alumina chloride, silica alumina bromide, silica silica alumina sulfate, silica zirconia fluoride, silica zirconia chloride, silica bromide 119. The catalyst composition of aspect 118, comprising, consisting of, consisting essentially of, or selected from zirconia, sulfated silica zirconia, fluorinated silica titania, or any combination thereof; An olefin polymerization process or a method for producing an olefin polymerization catalyst.

Aspect 121. Any of aspects 1-3, 6-68, or 83-120, wherein the catalyst composition further comprises a support or diluent, or wherein the contacting in any order occurs in the support or diluent. The catalyst composition, olefin polymerization process, or method of making an olefin polymerization catalyst of any one of claims 1 to 3.

Aspect 122. The carrier or diluent comprises, consists of, consists essentially of, or is selected from a hydrocarbon, an ether, or a combination thereof, each having from 1 to 20 carbon atoms. 122. The catalyst composition, olefin polymerization process, or method of making an olefin polymerization catalyst according to aspect 121.

Aspect 123. The carrier or diluent comprises or is made from cyclohexane, isobutane, n-butane, propane, n-pentane, isopentane, neopentane, n-hexane, Isopar™, at least one olefin, or any combination thereof. 122. The catalyst composition, olefin polymerization process, or method of making an olefin polymerization catalyst according to aspect 121, which consists of, consists essentially of, or is selected from.

Aspect 124. 122. The catalyst composition, olefin polymerization process, or preparation of an olefin polymerization catalyst according to aspect 121, wherein the carrier or diluent comprises, consists of, consists essentially of, or is selected from at least one olefin. Method.

Aspect 125. A support activator for a polyolefin having a catalyst activity of about 300 grams per gram of calcined smectite heteroadduct per hour (g/g/hr) or greater, [1] about 7×10 ⁻⁵ under polymerization conditions comprising a ratio of metallocene compound to calcined smectite heteroadduct of mmol metallocene compound/mg calcined smectite heteroadduct; 124. The catalyst composition, olefin polymerization process, or method of making an olefin polymerization catalyst according to any one of Clauses 1-3, 6-68, or 83-124.

Aspect 126. per gram of calcined smectite heteroadduct in the range of from about 0.5 to about 0.000005, from about 0.1 to about 0.00001, or from about 0.01 to about 0.0001. The catalyst composition of any one of aspects 1-3, 6-68, or 83-125, comprising the organoaluminum compound and the calcined smectite heteroadduct, in relative concentrations expressed in moles of the organoaluminum compound; An olefin polymerization process or a method for producing an olefin polymerization catalyst.

Aspect 127. Any of aspects 1-3, 6-68, or 83-126, wherein the process comprises at least one slurry polymerization, at least one gas phase polymerization, at least one solution polymerization, or any multi-reactor combination thereof. The catalyst composition, olefin polymerization process, or method of making an olefin polymerization catalyst of any one of claims 1 to 3.

Aspect 128. The process comprises polymerization in a gas phase reactor, a slurry loop, double slurry loops in series, multiple slurry tanks in series, a slurry loop combined with a gas phase reactor, a continuously stirred reactor in a batch process, or combinations thereof. The olefin polymerization process of any one of aspects 1-3, 6-68, or 83-127, comprising:

Aspect 129. 128. Any one of aspects 1-3, 6-68, or 83-128, wherein the polyolefin comprises, consists of, consists essentially of, or is selected from an olefin homopolymer or an olefin copolymer. The olefin polymerization process described in section.

Aspect 130. Embodiments 1- wherein the polyolefin comprises, consists of, consists essentially of, or is selected from an olefin homopolymer comprising olefin monomer residues having from 2 to about 20 carbon atoms per monomer molecule. 3, 6-68, or 83-129.

Aspect 131. The olefin monomer is ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 3-ethyl-1- 131. The olefin polymerization process according to aspect 130, selected from hexene, 1-heptene, 1-octene, 1-nonene, or 1-decene.

Aspect 132. The polyolefin comprises, consists of, consists essentially of, or is selected from an ethylene-olefin comonomer copolymer, the copolymer having from 3 to about 20 carbon atoms per monomer molecule of an α-olefin comonomer residue. The olefin polymerization process of any one of aspects 2, 6-68, or 83-129, comprising:

Aspect 133. 133. The olefin polymerization process according to aspect 132, wherein the olefin comonomer is selected from an aliphatic C ₃ -C ₂₀ olefin, a conjugated or non-conjugated C ₃ -C ₂₀ diolefin, or any mixture thereof.

Aspect 134. the olefin comonomer is 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- 133. The olefin polymerization process according to aspect 132, selected from pentadiene, 1,7-hexadiene, vinylcyclohexane, or any combination thereof.

Aspect 135.
a) a metallocene compound and a cocatalyst for [1] about 1 minute to about 24 hours, or about 1 minute to about 1 hour, and [2] about 10°C to about 200°C, or about 15°C to about contacting to form a first mixture at a temperature of 80° C., then
b) contacting the first mixture with a support activator comprising a calcined smectite heteroadduct to form the catalyst composition, according to any one of aspects 3, 6-68, or 83-126. A method for producing an olefin polymerization catalyst.

Aspect 136. A support activator comprising a metallocene compound, a cocatalyst, and a calcined smectite heteroadduct is subjected to [1] for a time of from about 1 minute to about 6 months, or from about 1 minute to about 1 week, and [2] about 10 C. to about 200.degree. C., or from about 15.degree. C. to about 80.degree. C. to form an olefin polymerization catalyst. manufacturing method.

Aspect 137. The catalyst composition of any one of aspects 3, 6-68, or 83-126, or 135-136.

Aspect 138. 137. A process for polymerization of olefins comprising contacting at least one olefin monomer and a catalyst composition under polymerization conditions to form a polyolefin, wherein the catalyst composition is prepared according to aspect 137.

Aspect 139. 139. Any one of aspects 1-138, wherein the catalyst composition, process, method, and support activator is any catalyst composition, process, method, and support activator disclosed herein. The catalyst composition, olefin polymerization process, method for producing an olefin polymerization catalyst, support activator, or method for producing a support activator according to paragraph 1 above.

Claims (23)

1. A support activator comprising an isolated smectite heteroadduct, said smectite heteroadduct comprising: [1] a colloidal smectite clay; and [2] at least one cationic polymetallate; and in a liquid carrier in an amount sufficient to provide a slurry of said smectite heteroadduct having a zeta potential in the range of about positive (+) 25 mV (millivolts) to about negative (-) 25 mV. A support activator comprising the contact product of 2. The support activator of claim 1, wherein the smectite clay comprises montmorillonite, sauconite, nontronite, hectorite, beidellite, saponite, bentonite, or any combination thereof. The cationic polymetalate comprises a cationic polyaluminate selected from polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichlorohydrate, or polyaluminum oxyhydroxychloride, or any combination thereof. Item 2. The support activator according to item 1. The cationic polymetalate comprises a cationic polyaluminate selected from polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichlorohydrate, polyaluminum oxyhydroxychloride, or any combination thereof, and the cationic polyaluminum wherein the ratio of millimoles (mmol) of aluminum (Al) in the salt to grams (g) of colloidal smectite clay ranges from about 0.2 mmol Al/g clay to about 2.5 mmol Al/g clay. Item 2. The support activator according to item 1. the cationic polymetalate in an amount sufficient to provide a colloidal suspension of the chemically treated first metal oxide having a zeta potential greater than positive (+) 20 mV (millivolts); 2. The support activator of claim 1, comprising a first metal oxide that is chemically treated with a compound, a metal halide, a metal oxyhalide, or a combination thereof. Fumed silica, fumed alumina, fumed silica, wherein said cationic polymetalate is chemically treated with polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichlorohydrate, polyaluminum oxyhydroxychloride, or any combination thereof 2. The support activator of claim 1, comprising alumina, fumed magnesia, fumed zinc oxide, fumed titania, fumed zirconia, fumed ceria, or any combination thereof. The slurry of the smectite heteroadduct is characterized by a conductivity in the range of 2 mS/cm to 10 μS/cm when the concentration of the slurry is in the range of about 1% to about 10% by weight solids; 2. The support activator of claim 1, wherein the segregated smectite heteroadduct is calcined. The calcined smectite heteroadduct has a BJH porosity ranging from about 0.2 cc/g to about 3.0 cc/g and less than 55% of the total cumulative pore volume (V 3-30 _nm ) of the 3-30 nm pores. A support activator according to claim 1, which exhibits a total cumulative pore volume of pores with a diameter of 3-10 nm (V _{3-10 nm} ). an amount of said colloidal smectite clay and said heterocoagulant reagent sufficient to provide a slurry of said smectite heteroadduct having a zeta potential in the range of about positive (+) 20 mV (millivolts) to about negative (−) 20 mV; 2. The support activator of claim 1, wherein the support activator is contacted with. an amount of said colloidal smectite clay and said heterocoagulant reagent sufficient to provide a slurry of said smectite heteroadduct having a zeta potential in the range of about positive (+) 15 mV (millivolts) to about negative (−) 15 mV; 2. The support activator of claim 1, wherein the support activator is contacted with. The smectite heteroadduct is isolated from the slurry by filtration without the use of ultrafiltration, centrifugation, or a settling tank, and the isolated smectite heteroadduct is washed with [1] optionally water. 2. The support activator of claim 1, which is washed [2] dried and/or calcined. Providing said slurry of said smectite heteroadduct has the following filtration behavior:
(a) after contacting step b), if an aqueous slurry of 2.0% by weight of said smectite heteroadduct is filtered within a time period of 0 hours to 2 hours, said Based on the weight of liquid carrier, the percentage of filtrate obtained in a 10 minute filtration time using either vacuum filtration or gravity filtration is from about 50% by weight of said liquid carrier in said slurry prior to filtration. in the range of about 100% by weight;
(b) said filtrate from said heteroadduct slurry, when evaporated, yields solids comprising less than 20% of the initial combined weight of clay and heterocoagulant. support activator. A catalyst composition for olefin polymerization, comprising:
a) at least one metallocene compound;
b) optionally at least one cocatalyst;
c) at least one supported active agent comprising a calcined smectite heteroadduct, said smectite heteroadduct comprising [1] a colloidal smectite clay; and [2] at least one cationic polymetalate in a liquid carrier. and in an amount sufficient to provide a slurry of said smectite heteroadduct having a zeta potential in the range of about positive (+) 25 mV (millivolts) to about negative (−) 25 mV. and at least one supported activator comprising: The at least one metallocene compound has the formula:
(X ¹ ) (X ² ) (X ³ ) (X ⁴ ) M (wherein
a) M is selected from titanium, zirconium, or hafnium;
b) X ¹ is selected from substituted or unsubstituted cyclopentadienyl, indenyl, fluorenyl, pentadienyl, allyl, boratabenzenyl, 1,2-azaborolyl, or 1,2-diaza-3,5-diborolyl, optionally substituted group is independent of halide, C ₁ -C ₂₀ hydrocarbyl, C ₁ -C ₂₀ heterohydrocarbyl, C ₁ -C ₂₀ organoheteryl, fused C ₄ -C ₁₂ carbocyclic moiety, or nitrogen, oxygen, sulfur, or phosphorus independently selected from fused _C4 - _C11 heterocyclic moieties having at least one heteroatom selected as
c) X ² is selected from [1] substituted or unsubstituted cyclopentadienyl, indenyl, fluorenyl, pentadienyl, or allyl, with optional substituents being halides, C ₁ -C ₂₀ hydrocarbyl, C ₁ -C ₂₀ heterohydrocarbyl, or C ₁ -C ₂₀ organoheteryl, or [2] halide, hydride, C ₁ -C ₂₀ hydrocarbyl, C ₁ -C ₂₀ heterohydrocarbyl, C ₁ -C ₂₀ selected from an organoheteryl, a fused _C4 - _C12 carbocyclic moiety, or a fused _C4 - _C11 heterocyclic moiety having at least one heteroatom independently selected from nitrogen, oxygen, sulfur, or phosphorus; ,
d) X ¹ and X ² are optionally bridged by at least one linker substituent having 2 to 4 bridging atoms independently selected from C, Si, N, P, or B, each Each available non-bridging valence of a bridging atom is unsubstituted (bonded to H) or substituted, and any substituents are halides, C ₁ -C ₂₀ hydrocarbyls, C ₁ -C ₂₀ heterohydrocarbyls, or C ₁ any hydrocarbyl, heterohydrocarbyl, or organoheteryl substituent independently selected from _—C20 organoheteryl, can form a saturated or unsaturated cyclic structure with the bridging atom or with X ¹ or X ² ;
e) [1] X ³ and X ⁴ are independently selected from halide, hydride, C ₁ -C ₂₀ hydrocarbyl, C ₁ -C ₂₀ heterohydrocarbyl, or C ₁ -C ₂₀ organoheteryl, [2] [GX ^A _k X ^B _4-k ] ⁻ (wherein G is B or Al, k is a number from 1 to 4, and X ^A at each occurrence independently of H or halide selected and X ^B at each occurrence is independently selected from C ₁ -C ₁₂ hydrocarbyl, C ₁ -C ₁₂ heterohydrocarbyl, C ₁ -C ₁₂ organoheteryl), [3] X ³ and X ⁴ are together a C ₄ -C ₂₀ polyene, or [4] X ³ and X ⁴ together with M form an unsubstituted or unsubstituted, saturated or unsaturated C ₃ -C ₆ metallacycle moiety, Optional substituents on said metallacycle moiety are independently selected from halides, C ₁ -C ₂₀ hydrocarbyls, C ₁ -C ₂₀ heterohydrocarbyls, or C ₁ -C ₂₀ organoheteryls. 14. The catalyst composition according to 13. X ¹ and X ² are
a) >EX ⁵ ₂ , -EX ⁵ ₂ EX ⁵ ₂ -, -EX ⁵ ₂ EX ⁵ EX ⁵ ₂ -, or >C=CX ⁵ ₂ where E at each occurrence is independent of C or Si selected),
b) -BX ⁵ -, -NX ⁵ -, or -PX ⁵ , or 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 —],
[-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 ⁵ ₂ (1 , 2-C ₆ H ₄ )CX ⁵ ₂ -]
(wherein X ⁵ at each occurrence is independently selected from H, halide, C ₁ -C ₂₀ hydrocarbyl, C ₁ -C ₂₀ heterohydrocarbyl, or C ₁ -C ₂₀ organoheteryl;
Any ^X5 substituent selected from hydrocarbyl, heterohydrocarbyl, or organoheteryl substituents can form a saturated or unsaturated cyclic structure with a bridging atom, another ^X5 substituent, ^X1 , or ^X2 . 14. The catalyst composition of claim 13, which is crosslinked by linker substituents selected from: 14. The catalyst composition of claim 13, wherein the cocatalyst comprises an alkylating, hydrogenating, or silylating agent. 14. The catalyst composition of claim 13, wherein the cocatalyst comprises an organoaluminum compound, an organoboron compound, an organozinc compound, an organomagnesium compound, an organolithium compound, or any combination thereof. A process for the polymerization of olefins comprising contacting at least one olefin monomer and a catalyst composition under polymerization conditions to form a polyolefin, wherein the catalyst composition comprises:
a) at least one metallocene compound;
b) optionally at least one cocatalyst;
c) at least one supported active agent comprising a calcined smectite heteroadduct, said smectite heteroadduct comprising [1] a colloidal smectite clay; and [2] at least one cationic polymetalate in a liquid carrier. and in an amount sufficient to provide a slurry of the smectite heteroadduct having a zeta potential in the range of about positive 25 (+) mV (millivolts) to about negative (-) 25 mV. and at least one supporting active agent comprising the product. The at least one olefinic monomer is [a] ethylene or propylene, or [b] 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 ethylene combined with at least one comonomer selected from ,3-dimethyl-1,3-butadiene, 1,4-pentadiene, 1,7-hexadiene, vinylcyclohexane, or any combination thereof. 19. The olefin polymerization process of claim 18. The process comprises polymerizing in a gas phase reactor, a slurry loop, double slurry loops in series, multiple slurry tanks in series, a slurry loop combined with a gas phase reactor, a continuously stirred reactor in a batch process, or combinations thereof. 19. The olefin polymerization process of claim 18, comprising: A method of making a support activator, the method comprising:
a) providing a colloidal smectite clay;
b) providing a smectite heteroadduct slurry of said colloidal smectite clay comprising at least one cationic polymetalate and having a zeta potential in the range of about positive (+) 25 mV (millivolts) to about negative (-) 25 mV; contacting the heterocoagulant reagent in the liquid carrier in an amount sufficient to
c) isolating said smectite heteroadduct from said slurry. said colloidal smectite clay and said heterocoagulant reagent in an amount sufficient to provide a smectite heteroadduct slurry having a zeta potential in the range of about positive (+) 20 mV (millivolts) to about negative (−) 20 mV; 22. The method of making a support activator according to claim 21, wherein the contacting. said colloidal smectite clay and said heterocoagulant reagent in amounts sufficient to provide a smectite heteroadduct slurry having a zeta potential in the range of about positive (+) 15 mV (millivolts) to about negative (-) 15 mV; 22. The method of making a support activator according to claim 21, wherein the contacting.

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