CN115023446B

CN115023446B - Process for preparing catalyst and catalyst composition

Info

Publication number: CN115023446B
Application number: CN202080094571.XA
Authority: CN
Inventors: 迈克尔·D·詹森; 凯文·钟; 王道永; 施伟春; 许光学; 陈志坚; 查尔斯·R·约翰逊二世; 玛丽·楼·科文
Original assignee: Formosa Plastics Americas Inc
Current assignee: Formosa Plastics Americas Inc
Priority date: 2020-01-27
Filing date: 2020-01-27
Publication date: 2024-08-30
Anticipated expiration: 2040-01-27
Also published as: JP2023523494A; CN115023446A; WO2021154204A1; JP7578702B2; EP4097153A1

Abstract

Carrier-activators for polymerizing olefins and catalyst compositions comprising the same are disclosed, wherein the carrier-activators comprise clay hetero adducts prepared from colloidal phyllosilicates such as colloidal montmorillonite clay chemically modified with a hetero coagulant. By limiting the amount of heterocoagulation reagent relative to the colloidal montmorillonite clay described herein, the montmorillonite heteroadduct carrier-activator is a porous and amorphous solid that can be readily separated from the resulting slurry by conventional filtration processes and can activate the metallocene and related catalyst for olefin polymerization. Related compositions and processes are disclosed.

Description

Process for preparing catalyst and catalyst composition

Cross Reference to Related Applications

And no.

Technical Field

The present disclosure relates to catalyst compositions for producing polyethylene comprising a support-activator and processes for making and using the catalyst compositions.

Background

Compounds such as Methylaluminoxane (MAO) and arylborane are commonly used as metallocene catalyst activators or cocatalysts for olefin polymerization. Industrial scale production of polyolefin resins can employ gas phase or slurry reactor platforms rather than solution phase conditions, and thus heterogeneous catalyst systems are used for these polymerization systems. The preparation and use of these heterogeneous polymerization catalysts can be complex and expensive. For example, when treating inorganic metal oxide supports such as silica or alumina with catalysts, it is often necessary to further use cocatalysts or activators such as MAO and arylboranes, which can be time consuming and expensive. The synthesis of MAO and arylboranes itself is atomically inefficient, requiring 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 in U.S. Pat. Nos. 6,107,230 and 9,670,296 propose the use of amorphous alumina and silica-alumina derivatives as supports and cocatalysts to provide metallocene polymerization activity. McDaniel et al also describe the use of clay minerals in sol-gel matrices in U.S. Pat. Nos. 6,632,894 and 7,041,753, which clay minerals can act as support-activators for metallocenes, but are themselves expensive to produce. Other methods can be seen in the use of chemically modified clay minerals, such as can be seen in the work of Suga et al in U.S. Pat. No. 5,973,084, nikano et al in U.S. Pat. No. 6,531,552, murase et al in U.S. Pat. No. 9,751,961 and McCauley in U.S. Pat. No. 5,202,295. These methods include process limitations such as low catalyst yields, excessive preparation steps, difficulty in isolating the modified clay minerals, or stringent preparation conditions for successfully modifying and isolating the clay.

Thus, there remains a need for improved ease and economy of preparing support-activators. This need is evident when a chemically modified clay support-activator with sufficient activity is desired to produce metallocene-based polyolefins such as high definition film resins. It is desirable to develop clay-based support-activators that eliminate the need for aluminoxanes and other expensive activators, are convenient and economical to prepare, have high yields, and/or exhibit higher activity for polymerization catalysts such as metallocene compounds.

Disclosure of Invention

Aspects of the present disclosure provide novel support-activators and processes for their preparation, novel catalyst compositions comprising the support-activators, methods for producing catalyst compositions, and processes for polymerizing olefins. In one aspect, the chemically modified clay support-activators can readily activate metallocene compounds for olefin polymerization, and they are surprisingly easy to prepare, low in cost, and high in yield. In particular, the processes and support-activators of the present disclosure can largely avoid the previous difficulties of separating chemically modified clay support-activators, e.g., digestion from clay particles and leaching of the octahedral alumina layer of the clay into solution during the activation process, which makes standard filtration extremely difficult as the clay particle size decreases.

It has surprisingly been found that when a colloidal montmorillonite clay, such as a dioctahedral montmorillonite clay, is contacted in a liquid carrier (also referred to as a "diluent") with a heterocoagulation reagent comprising at least one cationic multimetal salt, and when the heterocoagulation reagent is used in an amount within a specific range relative to the amount of the colloidal montmorillonite clay, a carrier-activator comprising an isolated montmorillonite heteroadduct can be synthesized. The montmorillonite heteroadducts, also known as heteroaggregated montmorillonite, can be readily separated from the resulting slurry by conventional filtration processes by limiting the amount of heteroaggregating agent relative to the colloidal montmorillonite clay described herein. Previous separation processes of chemically modified clay support-activators have often been difficult, where filtration may take days, or may require multiple washing and centrifugation steps. In addition, the montmorillonite hetero-adduct carrier-activator isolated according to the present disclosure can be used with little or no washing steps, further improving the usefulness, ease and economy of preparation and use.

The montmorillonite heteroadducts prepared in this way can be used in combination with cocatalysts such as alkylaluminum compounds to provide highly active support-activators for metallocene olefin polymerizations, especially when compared to conventional MAO-SiO ₂ or borane-derived support-activators. The heterocoagulants used in this process can be very inexpensive and can be used with cocatalysts such as alkylaluminum compounds, which can also be very inexpensive compared to aluminoxanes and borane-based activators.

Furthermore, the separation of the smectite heteroadducts can be achieved using conventional filtration, without the need for centrifugation or high-order dilution of the reaction mixture, and without the need for extensive washing of the solid thus obtained. This process provides solid clay heteroadducts that exhibit better activity than the corresponding untreated clay and comparable or better activity than the more difficult to prepare pillared clay supports, thus meeting the need.

Furthermore, unlike pillared clays, the heteroaggregated clay materials of the present disclosure are amorphous solids. The preparation of the heteroaggregated clay provides a three-dimensional structure, but it is non-pillared, amorphous and amorphous. While not intending to be bound by theory, it is believed that the regular crystal structure of the starting montmorillonite not only swells upon contact with the cationic multimetal salt, but rather is broken down upon preparation of the clay hetero-adduct to provide a non-crystalline, non-lamellar amorphous material.

Thus, in one aspect, the present disclosure provides a carrier-activator comprising an isolated montmorillonite heteroadduct comprising the contact product of [1] a colloidal montmorillonite clay and [2] a heteroagglomerating agent in a liquid carrier, the heteroagglomerating agent comprising at least one cationic multimetal salt, and the amount of the heteroagglomerating agent being sufficient to provide a slurry of the montmorillonite heteroadduct having a zeta potential in the range of from about positive 25mV (+25 millivolts) to about negative 25mV (-25 millivolts).

In another aspect, the present disclosure also provides a method of producing a support-activator comprising a montmorillonite hetero adduct, the method comprising:

a) Providing a colloidal montmorillonite clay;

b) Contacting the colloidal montmorillonite clay with a heteroagglomerating agent in a liquid carrier, the heteroagglomerating agent comprising at least one cationic multimetal salt and the heteroagglomerating agent being in an amount sufficient to provide a slurry of montmorillonite heteroadducts having zeta potentials in the range of about positive 25mV (millivolts) to about negative 25 mV; and

C) Separating the montmorillonite hetero adduct from the slurry.

According to another 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 carrier-activator comprising a calcined montmorillonite heteroadduct comprising the contact product of [1] a colloidal montmorillonite clay and [2] a heteroagglomerating agent in a liquid carrier, the heteroagglomerating agent comprising at least one cationic multimetal salt, the heteroagglomerating agent being present in an amount sufficient to provide a slurry of the montmorillonite heteroadduct having a zeta potential in the range of from about positive 25mV (millivolts) to about negative 25 mV.

In another aspect, the present disclosure also provides a process for producing an olefin polymerization catalyst, the process comprising contacting in any order:

a) At least one metallocene compound;

b) Optionally, at least one cocatalyst; and

In one aspect, for example, the optional cocatalyst may be an alkylating agent, which may or may not be necessary for initiating the effective olefin polymerization, depending on the particular metallocene compound used to produce the olefin polymerization catalyst.

In another aspect, a process for polymerizing olefins is provided, the process comprising contacting at least one olefin monomer under polymerization conditions with a catalyst composition to form a polyolefin, wherein the catalyst composition comprises:

a) At least one metallocene compound;

b) Optionally, at least one cocatalyst; and

C) At least one carrier-activator comprising a calcined montmorillonite heteroadduct comprising the contact product of [1] a colloidal montmorillonite clay and [2] a heteroagglomerating agent in a liquid carrier, the heteroagglomerating agent comprising at least one cationic multimetal salt in an amount sufficient to provide a slurry of the montmorillonite heteroadduct having a zeta potential in the range of from about positive 25mV (+25 millivolts) to about negative 25mV (-25 millivolts).

These and other aspects, features and examples of compositions comprising the support-activator and catalyst compositions, methods of producing the compositions, and polymerization processes and related methods are more fully described in the detailed description, figures, examples and claims provided herein.

Drawings

FIG. 1 provides a schematic diagram representing one aspect of the present disclosure illustrating a process for preparing, washing and isolating a support-activator comprising a calcined montmorillonite hetero-adduct of the present disclosure and comparing the process with a process for preparing, washing and isolating pillared clays.

FIG. 2 provides a series of compositions consisting of Aluminum Chlorohydrate (ACH) andPowder XRD (x-ray diffraction) pattern of calcined product of HPM-20 montmorillonite combination. All samples were prepared according to the method of the present invention according to the examples (see examples 18, 20-21 and 23), except for 6.4mmol Al/g clay sample (top), starting clay representing the typically prepared Al ₁₃ -pillared clay (comparative example 5) and itself 0mmol Al/g clay sample (comparative example 3).

FIG. 3 shows the use of the catalyst to give 0.62wt.%Zeta potential titration of 2.5wt.% (wt.%) aqueous aluminum hydroxychloride (ACH; measured density 1.075 g/mL) was added to the aqueous HPM-20 bentonite dispersion by volume and the measured zeta potential was plotted against titrant volume (mL). Titration was set at 0.5mL per titration point and equilibration delay was then 30 seconds. The titrant volume represents the cumulative volume of the aqueous aluminum chlorohydrate solution added. See also table 4.

Fig. 4 shows the conversion of the graph of fig. 3 to a plot of zeta potential versus aluminum-clay mass ratio. Specifically, FIG. 4 illustrates a method for adding 0.62 wt.%sZeta potential titration of 2.5wt.% aqueous aluminum hydroxychloride solution (ACH; measured density 1.075 g/mL) was added to the aqueous HPM-20 bentonite dispersion and the measured zeta potential plotted against Al content (mmol Al/g clay). The amount of titrant indicates the cumulative mmol of aluminum in the added ACH aqueous solution.

FIG. 5 shows the use for the addition of 1wt.%4.58Wt. -% of an aqueous HPM-20 bentonite dispersion was added by volumeZeta potential titration of 290 aqueous polyaluminum chloride solution (empirically Al ₂(OH)_2.5Cl_3.5) was plotted against titrant volume (mL). Titration was set at 1mL per titration point and equilibration was then delayed for 30 seconds. The titrant volume represents the addition of290 Cumulative volume of aqueous polyaluminum chloride solution. See also table 5.

FIG. 6 provides a plot for the addition of 0.75wt.%Volume addition of aqueous HPM-20 Bentonite Dispersion 10wt.%Zeta potential titration (after adjustment) of the AL27 colloidal alumina aqueous dispersion was performed and a graph of measured zeta potential versus titrant volume (mL) was drawn. Titration was set to 0-27mL at 1mL per spot followed by 3mL per spot, with a 60 second delay in equilibration. The titrant volume represents the addition ofCumulative volume of AL27 colloidal alumina aqueous solution. See example 11 and table 6.

FIG. 7 illustrates a method for adding 5wt.%200 Zeta potential titration of aqueous fumed silica dispersion volume with addition of 2.5wt.% aqueous aluminum hydroxychloride (ACH) solution, plotting the measured zeta potential versus titrant volume (mL). Titration was set at 1mL per titration point and equilibration delay was 60 seconds. The titrant volume represents the cumulative volume of ACH aqueous solution added. See example 37.

Fig. 8 shows the conversion of the graph of fig. 7 to a plot of zeta potential versus aluminum-clay mass ratio. Specifically, FIG. 8 provides for the addition of 5 wt.%sZeta potential titration of an aqueous solution of 200 fumed silica with 2.5wt.% aqueous aluminum hydroxychloride (ACH) was performed and a graph of measured zeta potential versus Al content (mmol Al/g clay) was drawn. The amount of titrant indicates the cumulative mmol of aluminum in the added ACH aqueous solution.

FIG. 9 provides for the addition of 1wt.%Aqueous HPM-20 bentonite dispersion containing 5wt.% silica treated with an aqueous solution of aluminum hydroxychloride (ACH)Zeta potential titration (after adjustment) of 200 fumed silica dispersion. Titration was set to 0-1.2mL per titration point 0.2mL, followed by 0.5mL per titration point, with a 30 second equilibration delay. The titrant was a colloidal substance (specie) and therefore the zeta potential was adjusted using the method described in example 11 to provide the chart in figure 9. See example 38.

Fig. 10 shows the results of a nitrogen adsorption/desorption BJH (Barrett, joyner and Halenda) pore volume analysis of the Aluminum Chlorohydrate (ACH) heteroaggregated clay of example 18, providing a pore diameter (angstrom,) Graph of cumulative pore volume (cubic centimeters per gram, cc/g). The formulation for preparing this heteroadduct slurry used 1.76mmol Al/g clay.

FIG. 11 provides comparative shear, then azeotropy, but without further treatment according to comparative example 3The results of the nitrogen adsorption/desorption BJH pore volume analysis of the HPM-20 bentonite sample showed that the value of V _3-10nm was greater than 55% of the cumulative pore volume V _3-30nm.

FIG. 12 shows suspension in water, evaporation and calcination, but without further treatment according to comparative example 1The results of the nitrogen adsorption/desorption BJH pore volume analysis of the untreated sample of HPM-20 bentonite showed that the value of V _3-10nm was greater than 55% of the cumulative pore volume V _3-30nm.

FIG. 13 is a ¹ H NMR spectrum of 7-phenyl-2-methyl-indene in CDCl ₃, wherein a contaminant CH ₂Cl₂ and a water peak are identified, and peak integration values are shown.

FIG. 14 is a ¹ H NMR spectrum of rac-dimethylsilylene bis (2-methyl-4-phenylindenyl) zirconium dichloride in CDCl ₃, wherein the peak integration value is shown.

Detailed Description

To more clearly define the terms and phrases used herein, the following definitions are provided. If any definition or use provided by any document incorporated herein by reference conflicts with the definition or use provided herein, the definition or use provided herein controls.

A. Definition and interpretation of terms

A multi-metal salt. The term "multimetal salt" and similar terms such as "polyoxometalate" are used interchangeably in this disclosure to refer to a water-soluble polyatomic cation that includes two or more metal atoms (e.g., aluminum, silicon, titanium, zirconium, or other metals) and at least one bridging ligand between the metals, such as an oxy, hydroxy, and/or halide ligand. The particular ligand may depend on the precursor and other factors such as the process used to produce the multimetal salt, the pH of the solution, and the like. For example, the multi-metal salts of the present disclosure can be aqueous metal oxides, aqueous metal oxyhydroxides, and the like, including combinations thereof. Bridging ligands such as oxy ligands bridging two or more metals may be present in these materials, however, the multimetal salts may also include terminal oxy, hydroxy, and/or halide ligands.

While many known multi-metal salt species are anionic and the suffix "-ate" is often used to reflect anionic species, the multi-metal salt (polyoxometalate) species used in accordance with the present disclosure are cationic. These materials may be referred to as compounds, substances or compositions, but one of ordinary skill in the art will appreciate that the multi-metal salt composition may contain a variety of substances in a suitable carrier, such as in aqueous solution, depending on, for example, solution pH, concentration, starting precursors to produce the multi-metal salt in aqueous solution, and the like. For clarity and convenience, these various materials are collectively referred to as "polyoxometalates" or "polyoxometalates", whether the composition comprises or consists essentially of a cationic polyoxometalate, a polyhydroxy metal salt, a polyhydroxy metal oxyacid salt, or a material comprising other ligands or mixtures of compounds such as halides. Examples of the polymetallic salts include, but are not limited to, polyaluminum hydroxychloride, aluminum chlorohydrate, polyaluminum chloride, or aluminum sesquichloride hydroxychloride compositions, which may include linear, cyclic, or clustered compounds. These compositions are collectively referred to as multimetal salts, but the term "multimetal salt" or "polyoxometalate" is also used to describe compositions that comprise essentially a single substance.

Both homopolymetallic salts containing a single type of metal and heteropolymetallic salts containing more than one type of metal (or electropositive atom such as phosphorus) are included in the generic term polymetallic salts or polyoxometalates. For example, aluminum polymetallic salts such as provided by Aluminum Chlorohydrate (ACH) or polyaluminum chloride (PAC) are examples of common polymetallic salts. In another example, the multi-metal salts of the present disclosure can be prepared from a first metal oxide that is subsequently treated with a second metal oxide, metal halide, metal oxyhalide, or combination thereof in an amount sufficient to provide a colloidal suspension of the heteropolymetal salt. For example, the first metal oxide may comprise silica, alumina, zirconia, or the like, including fumed silica, alumina, or zirconia, and the second metal oxide, metal halide, or metal oxyhalide may be obtained from an aqueous solution or suspension of a metal oxide, hydroxide, oxyhalide, or halide, such as ZrOCl ₂、ZnO、NbOCl₃、B(OH)₃、AlCl₃, or a combination thereof. Thus, when different metals are employed in this preparation, the resulting material is considered a heteropolymetal salt. Both homopolymetallic and heteropolymetalic salts may be referred to simply as "polymetallic salts".

In another aspect, the multimetal salts according to the present disclosure can be non-alkylated for transition metal compounds such as metallocene compounds. That is, the multimetal salts of the present disclosure may have no direct metal-carbon bonds, as found in aluminoxanes or other organometallic materials.

The size and number of metal ions in the multi-metal salt species can vary widely, and thus, multi-metal salts can be considered to encompass oligomeric or polymeric species. When describing the multimetal salt as "comprising", "consisting of … …", "consisting essentially of … …" or "selected from" particular materials such as polyaluminum chloride or aluminum sesquichloride, it is to be understood that the multimetal salt species formed when these materials are contacted with water or aqueous base (aqueous base) or the like are described in terms of the precursors from which they are produced. Thus, for convenience and for clarity and clarity in accordance with 35 u.s.c. ≡112, the multimetal salt may be described herein in terms of a precursor material or composition from which the cationic multimetal salt is generated to provide the heterocoagulation reagent.

In one aspect, the multimetal salt according to the present disclosure can be at least one aluminum multimetal salt. Examples include, but are not limited to, aluminum Chlorohydrate (ACH), also known as aluminum chlorohydrate, which encompasses a variety of water-soluble aluminum species, generally regarded as having the general formula Al _nCl_3n-m(OH)_m. These multi-metal salt species may be referred to as aluminum oxyhydroxide compounds or compositions. Another multimetal salt that may be used according to the present disclosure is polyaluminum chloride (PAC), which is also not a single substance, but a collection of various aluminum polymeric substances that may include linear, cyclic, or clustered compounds, examples of which may contain 2 to about 30 aluminum atoms, oxy groups, chloro groups, and hydroxyl groups. Other examples of aluminum multimetal salts include, but are not limited to, compounds having the general formula [ Al _mO_n(OH)_xCl_y]·zH₂ O, such as aluminum hydroxychloride, and cluster species, such as Keggin ions, for example [ AlO ₄Al₁₂(OH)₂₄(H₂O)₁₂]⁷⁺·7[Cl]^-, sometimes referred to as "Al ₁₃ -mer" polycations. Polyaluminum chloride (PAC) can be produced, for example, by combining an aqueous hydroxide solution with AlCl ₃, and the resulting mixture of aluminum species has a range of basicity. Aluminum Chlorohydrate (ACH) is generally considered to be the most basic, and aluminum Polychloride (PAC) is the less basic.

The clay heteroadducts or clay heteroagglomerates according to the present disclosure comprise the contact product of [1] a colloidal montmorillonite clay, such as a dioctahedral montmorillonite clay, and [2] a heteroagglomerating agent comprising at least one cationic multimetal salt in a liquid carrier, such as an aqueous carrier, wherein the amount used is sufficient to provide a slurry of the montmorillonite heteroadducts having a zeta potential in the range of from about +25mV to about-25 mV. Once isolated, the montmorillonite hetero-adducts may be heated, dried, and calcined to form the support-activators described herein. Upon calcination, the multimetal salt initially intercalated into or associated with the montmorillonite may undergo additional reactions, e.g., water in the intercalated multimetal salt may distill off and additional oxygen groups may be formed. In this regard, the term "polyoxometalate" may be used particularly to describe the calcined product. Regardless, the terms "polyoxometalate" and "polyoxometalate" are used interchangeably to describe a composition for contacting colloidal montmorillonite.

The multi-metal salts of the present disclosure may also be referred to as "polycations" and may include homo-and hetero-polycations, depending on whether the polycation includes a single type of metal or more than one type of metal. For example, hydrotalcite is [ Mg ₆Al₂(OH)₁₆]CO₃·4H₂ O, which is a heterocation according to the present disclosure.

Other examples of multimetal salts provided by way of example only include the epsilon-Keggin cation [ epsilon-PMo ₁₂O₃₆(OH)₄{Ln(H₂O)₄}₄]⁵⁺, where Ln can be La, ce, nd, or Sm. See, for example, german application chemistry (Angew.Chem., int.Ed.) 2002,41,2398. Other examples include lanthanide-containing cationic heteropolyvanadic clusters having the general formula [ Ln ₂V₁₂O₃₂(H₂O)₈ { Cl } ] Cl, where Ln can be Eu, gd, dy, tb, ho or Er. See, for example, british Royal chemical society of motion (RSC Adv.) 2013,3,6299-6304.

Finally, reference to "at least one" cationic multimetal salt is used to refer to one or more sources of cationic multimetal salts used in the preparation of the heterocoagulation reagent. That is, even when a single source of cationic multimetal salt is used to prepare the heterocoagulation reagent in aqueous solution, and multiple species may be obtained, these multiple species may be collectively referred to as a single or single type of cationic multimetal salt. Thus, reference to one or more than one cationic multimetal salt is intended to refer to one or more precursor compositions or sources of cationic multimetal salts for preparing the heterocoagulation reagent.

And (3) a heterocoagulation reagent. The terms "heterocoagulants", and the like are used herein to describe compositions containing any positively charged oligomeric or polymeric metal oxide-containing material, either in solution or as a colloidal suspension, which when present as a colloidal suspension in combination with a colloidal clay dispersion in an appropriate ratio, forms a solid that is readily filterable (as defined herein). "heterocoagulants" are used interchangeably with the terms "polyoxometalate" or "polyoxometalate" to refer to materials containing any positively charged oligomeric or polymeric metal oxide that are used to form a clay heteroadduct. Thus, "heterocoagulation reagent" emphasizes that when used in an amount sufficient to provide a slurry having a zeta potential in the range of from about +25mV to about-25 mV, a composition comprising one or more cationic polymetallic salt species in a liquid carrier forms a solid that is readily filterable when contacted with a colloidal montmorillonite clay. "heterocondensation" is a term of art described by Lagaly in Ullmann encyclopedia 2012 (Ullmann's Encyclopedia of Chemistry 2012). In the context of the present disclosure, unless otherwise indicated, "heterocoagulation" is defined as the process in which negatively charged colloidal clay particles are combined with positively charged heterocoagulation reagent materials to form a solid that is readily filtered. In the art and herein, heterocoagulation is sometimes also referred to as heteroaggregation, such as Cerbelaud et al, physical progress: x (ADVANCES IN PHYSICS: X), 2017, volume 2, 35-53.

Heteroadducts or heterocoacervates. Similar terms such as "heteroaggregated clay" or "montmorillonite heteroadduct" refer to the contact product obtained by combining a heteroaggregating agent with a colloidal clay. That is, in heterocoagulation reagents, the agglomerates formed by the attraction of negatively charged colloidal clay particles to positively charged species are referred to as "heteroadducts". Reference is made to U.S. patent number 8,642,499 to Wu Cheng et al, which is incorporated herein by reference. In one aspect, as defined herein, these terms refer to the "easy to filter" contact product of the heterocoagulation reagent and the colloidal clay. These terms are used to distinguish the contact product of a heterocoagulum that is readily filtered with a heterocoagulum reagent and a colloidal clay that are combined in a ratio that provides a product that is not readily filtered, e.g., a product that is formed when a pillared clay synthesis formulation is followed. In the case of pillared clay formulations, the contact product is not easily filtered and centrifugation is typically required to separate the pillared clay product.

When the formation of a heteroaggregated clay using an aluminum-containing heteroaggregation reagent is described, and unless otherwise indicated, the ratio of pillaring reagent such as aluminum oxychloride (also referred to as heteroaggregation reagent) to clay is expressed as mm (or mmol or millimole) of Al/g clay, representing the ratio of millimoles of Al to grams of clay in the pillaring reagent or heteroaggregation reagent. Reference is made to Gu et al, clay and Clay minerals (CLAY AND CLAY MINERALS), 1990,38 (5), 493-500, which is incorporated herein by reference. Unless otherwise indicated, when the pillaring agent or aluminum oxychloride heterocoagulation agent is present as a soluble solution, the millimoles of Al are calculated based on the weight percent of Al or the content of Al ₂O₃ (wt.%) provided by the manufacturer. Alternatively, and unless otherwise indicated, the millimoles of Al when starting with the pillared or heterocondensed reagent in solid form, i.e. when dispersed in solution, are determined by the weight used in the formulation and the empirical formula provided by the manufacturer.

Is easy to filter. The terms "easy to filter", "easy to filter or separate", and the like are used herein to describe compositions according to the present disclosure wherein solids in a mixture comprising a liquid phase may be separated from the liquid phase by filtration without resorting to centrifugation, ultracentrifugation or dilute solutions of less than about 2wt.% solids, decanting the liquid from the solids after long settling, and other such techniques. These terms are generally used herein to describe clay heteroadducts which are the contact products of colloidal montmorillonite clay and heteroagglomerating agents according to the present disclosure under certain conditions, without the need for separation by centrifugation, high dilution and sedimentation or settling tanks or ultrafiltration. Thus, by passing the slurry containing the heteroadducts through conventional filter materials, such as sintered glass, metal or ceramic frits, paper, natural or synthetic matt fibers, etc., under gravity or vacuum filtration conditions, the readily filterable clay heteroadducts can be separated from the soluble salts and synthetic byproducts in good yields in a matter of minutes or less, or in less than about one hour.

The present disclosure provides specific experimental and quantitative methods by which filterability can be assessed. For example, specific methods are provided for quantifying filterability of heteroadduct slurries, which demonstrate that the slurries can be considered to be easily filtered or easily filtered when prepared according to the methods of the present disclosure. Lagaly colloids or suspensions described in ullmann encyclopedia 2012 that require long settling or ultrafiltration are not considered "filterable" in the context of the present disclosure. The easy-to-filter suspensions or slurries of the present disclosure can provide a clear filtrate when filtered, while "less-to-filter" suspensions take a much longer time to filter, which can contain particulate matter in the form of a visually observable cloudy or non-clear filtrate, which represents a colloidal clay dispersion. When preparing a support-activator according to the present disclosure to provide a slurry of montmorillonite hetero-adducts having a zeta potential approaching an upper (positive) boundary of about +25mV (millivolts) or approaching a lower (negative) boundary of about-25 mV, some turbidity can be observed in the filtrate when filtering the hetero-adducts, which becomes lighter when preparing montmorillonite hetero-adducts using a ratio of colloidal montmorillonite clay and hetero-agglomerating agent that provides a slurry having a zeta potential closer to or approaching 0 mV.

And (5) colloid. The use of the terms "colloid", "colloidal clay", "colloidal solution", "colloidal suspension" and similar terms are defined in chapter "colloid" of the encyclopedia of Ullman Industrial chemistry published by GERHARD LAGALY at 1 month 15 in 2007. These terms are used interchangeably.

Catalyst composition and catalyst system. Terms such as "catalyst composition," "catalyst mixture," "catalyst system," and the like are used to denote combinations of the listed components that are ultimately formed or used to form an active catalyst according to the present disclosure. The use of these terms does not depend on any particular contacting step, order of contacting, whether any reaction between or among the components is likely to occur, or any product that may be formed by any contacting of any or all of the listed components. The use of these terms also does not depend on the nature of the active catalytic site, or the end of any cocatalyst, metallocene compound, or support-activator after contacting or combining any of these components in any order. Thus, these and similar terms encompass the initially recited components or combinations of starting components of the catalyst composition, as well as any products that may result from contacting these initially recited starting components, whether the catalyst composition is heterogeneous or homogeneous, or includes both soluble and insoluble components. The terms "catalyst" and "catalyst system" or "catalyst composition" may be used interchangeably, such use being apparent to the skilled artisan from the context of the present disclosure.

Catalyst activity. Unless otherwise indicated, the terms "activity", "catalyst composition activity", and the like refer to the polymerization activity of a catalyst composition comprising the dried or calcined clay heteroadducts disclosed herein, which is generally expressed only as the weight of polymer polymerized/weight of catalyst clay support-activator/weight of catalyst polymerized/hour, without the presence of any transition metal catalyst component (such as a metallocene compound), any cocatalyst (such as an organoaluminum compound), or any co-activator (such as an aluminoxane). In other words, the weight of polymer produced per hour divided by the weight of calcined clay heteroadduct is in g/g/h (grams per gram per hour).

The activity of the reference or comparative catalyst composition refers to the polymerization activity of the catalyst composition comprising the comparative catalyst composition and is based on the weight of the comparative ion-exchanged or pillared clay or the weight of the clay component itself used to prepare the clay hetero-adduct. Terms such as "increased activity" or "enhanced activity" describe the activity of a catalyst composition according to the present disclosure that is greater than the activity of a comparative catalyst composition using the same catalyst components such as metallocene compound and cocatalyst, except that the comparative catalyst composition typically uses a different support-activator or activator such as pillared clay, or the clay component used in the catalytic reaction is not a heteroaggregated clay. For example, increased or enhanced activity according to the present disclosure includes greater than or equal to about 300 grams of polyethylene polymer (g/g/h) per gram of calcined heteroaggregated clay per hour based on the activity of the calcined clay heteroadduct, using a standard set of ethylene homopolymerization conditions. In this regard, the standard set of ethylene homopolymerization conditions includes the following. The 2L stainless steel reactor equipped with a marine impeller was set at about 500rpm and slurry polymerization conditions included 1L purified isobutane diluent, a polymerization temperature of 90 ℃, a total ethylene pressure of 450psi, a typical 30 or 60 minute run length, a metallocene catalyst composition comprising (1-Bu-3-MeCp) ₂ZrCl₂ and Triethylaluminum (TEAL) cocatalyst, optionally using a metallocene as a TEAL-containing stock solution, added in an amount to provide a metallocene-clay ratio of about 7X 10 ^-5 mmol metallocene/mg calcined clay. An alkylaluminum cocatalyst is generally used in the polymerization batch and is generally selected from TEAL or Triisobutylaluminum (TIBAL).

Contacting the product. The term "contact product" is used herein to describe a composition in which the components are combined together or "contacted" in any order and for any duration unless the context of the present disclosure states or requires or suggests a particular order. Although "contact product" may include a reaction product, it is not required that the individual components react with each other, and this term is used regardless of any reaction that may or may not occur when contacting the listed components. To form the contact product, the enumerated components may be contacted, for example, by blending or mixing, or the components may be contacted by adding them to the liquid carrier in any order or simultaneously. Furthermore, unless otherwise stated or required or implied by the context in which the term is used, contact of any component may occur in the presence or absence of any other component of the compositions described herein. The combination or contacting of the listed components or any additional materials may be performed by any suitable method. Thus, the term "contact product" includes mixtures, blends, solutions, slurries, reaction products, and the like, or combinations thereof. Similarly, the term "contacting" is used herein to refer to materials that may be blended, mixed, slurried, dissolved, reacted, treated, or contacted in some other manner.

Pore diameter (pore diameter). Nitrogen adsorption/desorption measurements are used to determine pore size and pore volume distribution using the BJH method. Pore size is defined as follows based on the International Union of Pure and Applied Chemistry (IUPAC) porous Material Classification System (see Pure and applied chemistry (chem.)), 1994,66,1739-1758, and Klobes et al, national institute of standards and technology, special publication (National Institute of STANDARDS AND Technology Special Publication), 960-17. As used herein, "microporous" and "microporous" refer to a catalyst or catalyst support produced according to the process of the present disclosure having a diameter present in a catalyst or catalyst support of less thanIs formed by a plurality of holes. As used herein, "mesoporous" and "multi-mesoporous" refer to diameters present in a catalyst or catalyst support produced according to the processes of the present disclosureTo less than(I.e., pores in the range of 2nm to <50 nm). As used herein, "macropores" and "macropores" refer to the presence of a diameter equal to or greater than in a catalyst or catalyst support produced according to the processes of the present disclosure(50 Nm) pores.

Each of the above definitions of micropores, mesopores, and macropores are considered to be different and non-overlapping to ensure that when the percentages or values of the pore size distribution (pore diameter distribution) of any given sample are summed, the same pore is not counted twice.

"D50" means the median pore diameter as measured by porosimetry. Thus, "d50" corresponds to the median pore diameter calculated based on the pore size distribution, and half of the pores have diameters greater than that median. The d50 values reported herein are based on nitrogen desorption using well known calculation methods described by e.p.barrett, l.g. joyner and p.p. halenda ("BJH"), calculation (The Determination of Pore Volume and Area Distributions in Porous Substances.I.Computations from Nitrogen Isotherms)"" of pore volume and area distribution of porous material to determine i.nitrogen isotherms, journal of chemistry (j.am. Chem. Soc.), 1951,73 (1), pages 373-380.

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

Transition metal catalysts. "transition metal catalyst" refers to a transition metal compound or composition that can act as or convert to an active olefin polymerization catalyst when contacted with a support-activator of the present disclosure, either in its current form or when contacted with a cocatalyst capable of transferring or imparting a polymerizable activated ligand to the transition metal catalyst. The use of the term "catalyst" is not intended to reflect any particular mechanism or, when the "transition metal catalyst" is activated or imparted with a polymerizable activated ligand, to reflect that the "transition metal catalyst" itself represents an active site for catalyzing polymerization. The transition metal catalysts are described in terms of one or more transition metal compounds used in the process for preparing the polymerization catalyst and may include metallocene compounds and related compounds as defined herein.

And (3) a cocatalyst. "cocatalyst" is used herein to refer to a chemical agent, compound, or composition that is capable of imparting a ligand to a metallocene that is capable of initiating polymerization when the metallocene is activated by a support-activator. In other words, "cocatalyst" is used herein to refer to a chemical agent, compound or composition capable of providing a polymerizable activated ligand to a metallocene compound. The polymerizable activated ligands include, but are not limited to, hydrocarbyl groups such as alkyl groups such as methyl or ethyl, aryl groups and substituted aryl groups such as phenyl or tolyl, substituted alkyl groups such as benzyl or trimethylsilylmethyl (-CH ₂SiM₃), hydrides, silyl groups and substituted groups such as trimethylsilyl and the like. Thus, in one aspect, the promoter may be an alkylating agent, a hydrogenating agent, a silylating agent, or the like. There is no limitation on the mechanism by which the cocatalyst provides the polymerizable activated ligand to the metallocene compound. For example, the cocatalyst can participate in a metathesis reaction to exchange an exchangeable ligand (such as a halide or alkoxide) on the metallocene compound with a polymerizable activating/initiating ligand (such as methyl or hydride). In one aspect, the cocatalyst is an optional component of the catalyst composition, for example, when the metallocene compound already includes a polymerizable activating/initiating ligand (such as a methyl or hydride). On the other hand, as will be appreciated by those skilled in the art, even when the metallocene compound includes a polymerizable activated ligand, the cocatalyst can be used for other purposes, such as scavenging moisture from the polymerization reactor or process. According to another aspect, the term "cocatalyst" may refer to "activator" or may be used interchangeably with "cocatalyst" as explained herein, as the context requires or allows.

An activator. As used herein, "activator" generally refers to a substance (subtance) capable of converting a metallocene component into an active catalyst system capable of polymerizing olefins, and is intended to be independent of the mechanism by which such activation occurs. "activators" can convert the contact product of a metallocene component and a component that provides an activatable ligand (such as an alkyl or hydride) to a metallocene to a catalyst system that can polymerize olefins, for example, when the metallocene compound has not yet included such a ligand. This term is used regardless of the actual activation mechanism. Exemplary activators may include, but are not limited to, carrier-activators, aluminoxanes, organoboron or organoborate compounds, ionizing compounds (such as ionizing ionic compounds), and the like. The aluminoxane, organoboron or organoborate compound and ionizing compound, when used in a catalyst composition in the presence of a support-activator, may be referred to as an "activator" or "co-activator" but the catalyst composition is supplemented with one or more aluminoxanes, organoboron, organoborates, ionizing compounds or other co-activators.

Carrier-activator. As used herein, the term "support-activator" refers to activators in solid form such as ion-exchanged clays, proton acid treated clays or pillared clays, and similar insoluble supports that also act as activators. When the support-activator is combined with a metallocene having an activatable ligand or alternatively with a metallocene and a cocatalyst which can provide an activatable ligand, a catalyst system for polymerizable olefins is provided.

Ion exchange clay. As used herein, the term "ion-exchanged clay" is understood by those skilled in the art to be a clay (also referred to as a "single ion" or "single cation" clay) in which exchangeable ions of naturally occurring or synthetic clays have been replaced or exchanged with another alternative ion or ions. Ion exchange can be performed by treating naturally occurring or synthetic clays with a selected cation source, typically from a concentrated ionic solution (such as a 2N aqueous cation solution), which treatment includes passing through a plurality of exchange steps, e.g., three exchange steps. The exchanged clay may then be washed several times with deionized water to remove excess ions generated during the treatment process, see for example Sanchez et al, colloid and surface A: physics and engineering (Colloids and Surfaces A: physicochemical AND ENGINEERING ASPECTS), 2013,423,1-10 and Kawamura et al, clay and Clay minerals, 2009,57 (2), 150-160. Typically, centrifugation is used to separate clay from solution between ion treatment and washing.

A metallocene compound. As used herein, the term "metallocene" or "metallocene compound" describes a transition metal or lanthanide metal compound comprising at least one substituted or unsubstituted cycloalkandienyl-type ligand or alkanedienyl-type ligand, including heteroatom analogs thereof, regardless of the particular bonding mode, e.g., whether the cycloalkandienyl-type ligand or alkanedienyl-type ligand is bonded to the metal in the η ⁵-、η³ -or η ¹ -bonding mode, and whether or not more than one of these binding modes is accessible to such ligands. in the present disclosure, the term "metallocene" is also used to refer to compounds comprising at least one pi-bonded allylic ligand wherein eta ³ -allyl is not part of a cycloalkandienyl-or alkanedienyl-type ligand, which compounds are useful as transition metal compound components of the catalyst compositions described herein. Thus, the first and second substrates are bonded together, "metallocene" includes those having substituted or unsubstituted eta ³ to eta ⁵ -cycloalkandienyl types and eta ³ to eta ⁵ -alkanedienyl type ligands, Compounds of eta ³ -allylic ligands, including heteroatom analogs thereof, and include, but are not limited to, cyclopentadienyl ligands, indenyl ligands, fluorenyl ligands, eta ³ -allylic ligands, pentadienyl ligands, boron anion heterophenyl ligands, 1, 2-azaborolidinyl ligands, 1, 2-diaza-3, 5-diboronyl ligands, substituted analogs thereof, and partially saturated analogs thereof. Partially saturated analogs include compounds containing ligands of the eta ⁵ -cycloalkandienyl type containing partial saturation, examples of which include, but are not limited to, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, substituted analogs thereof, and the like. In some cases, the metallocene is simply referred to as a "catalyst", in close agreement with the term "cocatalyst" as used herein to refer to, for example, an organoaluminum compound. Thus, metallocene ligands may be considered in the present disclosure to include at least one substituted or at least one unsubstituted cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, allyl, boron anion heteroaryl, 1, 2-azaborolidinyl, or 1, 2-diaza-3, 5-diboronyl ligand, including substituted analogs thereof. For example, any substituent may be independently selected from the group consisting of a halide, a C ₁-C₂₀ hydrocarbyl, a C ₁-C₂₀ heterohydrocarbyl, a C ₁-C₂₀ organoheteroaryl, a fused C ₄-C₁₂ carbocyclic moiety, or have at least one moiety independently selected from nitrogen, A fused C ₄-C₁₁ heterocyclic moiety of a heteroatom of oxygen, sulfur or phosphorus.

An organoaluminum compound and an organoboron compound. As used herein, the terms "organoaluminum compound" and "organoboron compound" include neutral compounds such as AlMe ₃ and BEt ₃, and also include complex anions such as LiAlMe ₄、LiAlH₄、NaBH₄ and LiBEt ₄, and the like. Thus, unless otherwise indicated, hydride compounds of aluminum and boron are included in the definition of organoaluminum and organoboron compounds, respectively, whether the compound is neutral or anionic.

And (5) pillaring clay. In the present disclosure, "pillared clay" is defined as where the basal spacing of the ordered layers is substantially greater thanTo the point ofClay material of (a) is provided. When analyzing silty clay samples using an X-ray diffraction apparatus capable of scanning 2 ° or greater of 2θ angles, it is generally observed that materials containing such pillared ordering have a significant peak at 2θ values between 2 ° and 9 °. These are generally prepared by introducing a pillaring agent, for example an oxygen-containing inorganic cation, such as an oxygen-containing cation of lanthanum, aluminum or iron. Aluminum pillared clays are often prepared by contacting the pillared clay with a clay in an amount ranging from about 5mmol Al/g clay or 6mmol Al/g clay up to about 30mmol Al/g clay. Typical pillared clay preparations are in contrast to support-activator preparations according to the present disclosure, wherein the support-activators disclosed herein can be prepared using less than or equal to about 2.0mmol Al/g clay, less than or equal to about 1.7mmol Al/g clay, less than or equal to about 1.5mmol Al/g clay, less than or equal to about 1.3mmol Al/g clay, or less than or equal to about 1.2mmol Al/g clay, but greater than about 0.75mmol Al/g clay, or greater than about 1.0mmol Al/g clay. Thus, in one aspect, the pillared clay forming agent may be selected from the same heteroagglomerating agents used to form the heteroagglomerating clay of the present disclosure. As explained herein, some pillared clay species may be formed even during the preparation of the montmorillonite hetero adducts disclosed herein.

And (5) inserting. The term "intercalation" or "intercalation" is a term of art that refers to intercalation of a material into a clay matrix. Unless otherwise indicated, these terms are used herein in a manner understood by those skilled in the art and as described in U.S. patent No. 4,637,992.

Substrate spacing. The terms "basal spacing", "basal d001 spacing" or "d001 spacing" when used in the context of montmorillonite clays such as montmorillonite refer to the distance between similar faces of adjacent layers in the clay structure, typically expressed in angstroms or nanometers. Thus, for example, in a group 2:1 montmorillonite clay comprising montmorillonite, the basal distance is the distance from the top of a tetrahedral sheet to the top of the next tetrahedral sheet of the adjacent 2:1 layer, and includes intermediate octahedral sheets, with or without modification or pillaring. The substrate spacing values were measured using X-ray diffraction analysis (XRD) of the d001 plane. Natural montmorillonite as found in bentonite has aboutTo aboutIs provided. (see, e.g., fifth national clay and clay mineral conference (Fifth National Conference on CLAYS AND CLAY MINERALS), national academy of sciences (National Academy of Sciences), national research committee (National Research Council), publication 566,1958: conference notes: heterogeneity of montmorillonite (Heterogeneity In Montmorillonite), j.l.mcatee, jr., pages 279-88 and table 1 at page 282), XRD test methods for determining substrate spacing are described in: pillared clays and pillared layered Solids (PILLARED CLAYS AND PILLARED LAYERED Solids), R.A. Schooheydt et al, theoretical chemistry and applied chemistry (Pure appl. Chem.), 71 (12), 2367-2371 (1999); and U.S. patent 5,202,295 (McCauley) at column 27, lines 22-43.

Zeta potential. As used herein, the term "zeta potential" refers to the potential difference between the junction of the anchoring layer (STERN LAYER) (a firmly attached layer of counter ions that forms to neutralize the surface charge of the colloidal particles) and the diffusion layer (loosely attached ion clusters that are located farther from the particle surface than the anchoring layer) and the bulk solution or slurry. This property is expressed in voltage units, such as millivolts (mV). Zeta potential can be obtained by quantifying the "electrokinetic acoustic amplitude effect" (ESA) due to the ultrasonic waves generated by the application of an electric potential to a colloidal suspension, as described in us patent number 5,616,872, incorporated herein by reference.

A hydrocarbon group. As used herein, the term "hydrocarbyl" is used in accordance with the IUPAC definition recognized in the art as a monovalent, linear, branched, or cyclic group formed by the removal of a single hydrogen atom from a parent hydrocarbon compound. Unless otherwise indicated, the hydrocarbyl groups may be aliphatic or aromatic; saturated or unsaturated; and may include linear, cyclic, branched, and/or fused ring structures; unless any of these is specifically excluded. See IUPAC general chemical terminology catalogue (Compendium of Chemical Terminology), version 2 (1997) page 190. Examples of hydrocarbyl groups include, but are not limited to, aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, cycloalkyldienyl, alkynyl, aralkyl, aralkenyl, aralkynyl, and the like.

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

Heterohydrocarbyl encompasses heteroaliphatic groups (including saturated and unsaturated groups) and heteroaromatic groups. Thus, heteroatom-substituted vinyl groups, heteroatom-substituted alkenyl groups, heteroatom-substituted dienyl groups, and the like are included in heterohydrocarbon groups.

Organic hetero-radicals (Organoheteryl). The term "organoheterocyclyl" is also used according to the IUPAC definition accepted in the art as a monovalent group containing carbon, and thus is organic, but has a free valence at an atom other than carbon. See IUPAC general catalogue of chemical terminology, 2 nd edition (1997) page 284. The organohetero group may be straight-chain, branched, or cyclic and includes common groups such as alkoxy, aryloxy, organosulfur (or organosulfur), organogermanium (or organogermanium), acetamido, acetoacetamido, alkylamide, dialkylamide, arylamide, diarylamide, trimethylsilyl, and the like. The group (S) is (are) a radical, such as-OMe, -OPh, -S (tolyl), -NHMe, -NMe ₂, -N (aryl )₂、-SiMe₃、-PPh₂、-O₃S(C₆H₄)Me、-OCF₂CF₃、-O₂C( alkyl), -O ₂ C (aryl), -N (alkyl) CO (alkyl), -N (aryl) CO (aryl), -N (alkyl) C (O) N (alkyl) ₂, hexafluoroacetonyl acetate, and the like.

An organic group. An organic group is used in accordance with the definition of IUPAC in the present disclosure to refer to any organic substituent having one free valence on a carbon atom, irrespective of the functional type, e.g. CH ₃CH₂-、ClCH₂C-、CH₃ C (=o) -, 4-pyridylmethyl, etc. The organic group may be linear, branched, or cyclic, and the term "organic group" may be used in combination with other terms, such as in organic thio- (e.g., meS-) and organo-oxy.

A heterocyclic group. The IUPAC general list compares organic groups with other groups such as heterocyclic groups and organic heteroatoms. These terms are stated in IUPAC general catalogue of chemical terms, version 2 (1997), which demonstrates the convention of attaching a "-yl" suffix to a moiety of a molecule or group that carries a valence from a missing hydrogen. Thus, a heterocyclic group is defined as a monovalent group formed by removing a hydrogen atom from any ring atom of a heterocyclic compound. For example, both piperidin-1-yl and piperidin-2-yl shown below are heterocyclyl groups in which the line leading from the nitrogen or carbon atom represents an open valence instead of methyl.

However, piperidin-1-yl is also considered an organic hetero group, whereas piperidin-2-yl is also considered a hetero hydrocarbon group. Thus, the valency of the "heterocyclyl" may be present on any suitable ring atom, while the valency of the "organoheterocyclyl" is present on a heteroatom, and the valency of the heterohydrocarbyl is present on a carbon atom.

Hydrocarbylene and hydrocarbylene radicals. As described in IUPAC general catalog of chemical terms, 2 nd edition (1997), an "alkylene group" is also defined according to its usual and customary meaning as a divalent group formed by removing two hydrogen atoms from a hydrocarbon, the free valences of which do not participate in double bonds. Examples of hydrocarbylene groups include, for example, 1, 2-phenylene, 1, 3-propanediyl (-CH ₂CH₂CH₂ -), cyclopentylene (=cc ₄H₈), or methylene bridging (-CH ₂ -) and not forming a double bond. The hydrocarbylene groups in which the free valences do not participate in a double bond are different from hydrocarbylene groups such as alkylene (alkylidene).

"Hydrocarbylene" is a divalent group formed by removing two hydrogen atoms from the same carbon atom of a hydrocarbon, the free valences of which are a part of a double bond. An alkylene group is an exemplary hydrocarbylene group and is defined as a divalent group formed by removing two hydrogen atoms from the same carbon atom of an alkane, the free valence of which is part of a double bond. Examples of alkylene groups are such as=chme, CHEt, =cme ₂, =chph or methylene in which the methylene carbon forms a double bond (=ch ₂).

Heterohydrocarbylene and heterohydrocarbylene. Like hydrocarbylene, the term "heterohydrocarbylene" refers to a divalent group formed by removing two hydrogen atoms from a parent heterohydrocarbon molecule, the free valences of which do not participate in a double bond. The hydrogen atoms may be removed from two carbon atoms, two heteroatoms, or one carbon and one heteroatom, such that the free valences do not participate in the double bond. Examples of "heterohydrocarbyls" include, but are not limited to -CH₂OCH₂-、-CH₂NPhCH₂-、-SiMe₂(1,2-C₆H₄)SiMe₂-、-CMe₂SiMe₂-、-CH₂NCMe₃-、-CH₂CH₂PMe-、-CH₂[1,2-C₆H₃(4-OMe)]CH₂- and the like.

Similar to hydrocarbylene groups, "heterohydrocarbylene" is a divalent group formed by removing two hydrogen atoms from the same carbon atom of a heterohydrocarbon, the free valency of which is a portion of a double bond. Examples of heterohydrocarbyls include, but are not limited to, groups such as = CHNMe ₂、＝CHOPh、＝CMeNMeCH₂Ph、＝CHSiMe₃、＝CHCH₂ Cl and the like.

Halides and halogens. The terms "halide" and "halogen" refer herein to ions or atoms of fluorine, chlorine, bromine, or iodine, as the context and chemistry permits or dictates, either alone or in any combination. Regardless of the charge or bonding manner of these atoms, these terms may be used interchangeably.

A polymer. The term "polymer" is used generically herein to include olefin homopolymers, copolymers, terpolymers, etc. The copolymer is derived from one olefin monomer and one olefin comonomer, while the terpolymer is derived from one olefin monomer and two olefin comonomers. Thus, "polymer" encompasses copolymers, terpolymers, etc. derived from any of the olefin monomers and comonomers disclosed herein. Similarly, ethylene polymers will include ethylene homopolymers, ethylene copolymers, ethylene terpolymers, and the like. Thus, olefin copolymers such as ethylene copolymers may be derived from ethylene and a comonomer such as propylene, 1-butene, 1-hexene or 1-octene. If the monomer and comonomer are ethylene and 1-hexene, respectively, the resulting polymer will be classified as an ethylene/1-hexene copolymer. Also, the term "polymerization" includes homo-, co-, ter-, and the like. For example, the copolymerization process includes contacting an olefin monomer such as ethylene with an olefin comonomer such as 1-hexene to produce a copolymer. Well known abbreviations of the polyolefin type, such as "HDPE", may be used herein to represent high density polyethylene.

The term "polymer" is used herein to refer to the inorganic composition used in the preparation and formation of pillars in the modified clay, where the context permits or requires. For example, it is known to form columns in montmorillonite clay based on polymeric cationic hydroxy metal complexes using metals such as aluminum, zirconium and/or titanium, such as aluminum chlorohydroxide complexes (also known as "chlorohydrate (chlorhydrate)" or "hydroxychloride (chloroydrol)"). Inorganic copolymers comprising such complexes are also known. See, for example, U.S. patent No.4,176,090 and U.S. patent No.4,248,739. Furthermore, unless explicitly stated otherwise, the term "polymer" is not limited by molecular weight and thus encompasses lower molecular weight polymers (sometimes referred to as oligomers) as well as higher molecular weight polymers.

A main catalyst (Procatalyst). As used herein, the term "procatalyst" means a compound capable of polymerizing, oligomerizing, or hydrogenating olefins when activated by an alumoxane, borane, borate, or other acidic activator (whether lewis acid or bronsted acid) or when activated by a support-activator as disclosed herein.

Additional explanation of terms. The following additional explanation of terms is provided to fully disclosed aspects of the disclosure and claims.

Unless otherwise indicated or the context requires otherwise, the formulas of the multimetal salts disclosed herein for use as heterocoagulants are empirical formulas. Thus, formulas such as (Al, mg) ₂Si₄O₁₀(OH)₂(H₂O)₈ are empirical formulas for multimetal salts that can be considered to encompass oligomeric or polymeric materials, and formulas such as FeO _x(OH)_y(H₂O)_z]ⁿ⁺ can also be considered to encompass oligomers or polymers where the variable subscripts need not be integers.

Several types of numerical ranges are disclosed herein, including, but not limited to, numerical ranges of atomic numbers, substrate spacing, weight ratios, molar ratios, percentages, temperatures, and the like. When disclosing or claiming any type of range, it is the applicant's intention to disclose or claim each possible number that such a range may reasonably cover, consistent with the written description and context, and include the endpoints of the range and any subranges and combinations of subranges covered therein. For example, when applicants disclose or claim a chemical moiety having a certain number of carbon atoms, such as a C1 to C12 (or C ₁ to C ₁₂) alkyl group, or in other words having 1 to 12 carbon atoms, applicants intend to refer to moieties that can be independently selected from alkyl groups having 1,2, 3,4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms, and any range between the two numbers (e.g., a C1 to C6 alkyl group), and also include any combination of ranges between the two numbers (e.g., a C2 to C4 and C6 to C8 alkyl group). If, for any reason, applicants choose to claim less than the full extent of the disclosure, e.g., in view of a reference that the applicant may not know at the time of filing the application, then the applicant reserves the right to limit or exclude any individual member of any such range or group, including any sub-range or combination of sub-ranges within the group, which may be claimed in accordance with the range or in any similar manner.

In another aspect, any numerical range recited in the specification or claims, such as a numerical range representing a particular set of attributes, units of measure, conditions, physical states or percentages, is intended to expressly incorporate by reference or otherwise any number falling within such range, including any subset of numbers within any range so recited. For example, whenever a numerical range having a lower limit RL and an upper limit RU is disclosed, any number R falling within the range is specifically disclosed. Specifically, the following numbers R within this range are specifically disclosed:

R＝RL+k(RU-RL)，

Where k is a variable ranging from 1% to 100% with increments of 1%, e.g., k is 1%, 2%, 3%, 4%, 5% … …%, 51%, 52% … …%, 96%, 97%, 98%, 99% or 100%. Further, any numerical range represented by any two values of R calculated as above is specifically disclosed.

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

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

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

As used in the specification, the terms "comprises," "comprising," and variations thereof, such as "comprises," "comprising," "having," "including," and the like are inclusive and open-ended, and do not exclude additional, unrecited elements or method steps. The transitional phrase "consisting of … …" and variants thereof excludes any element, step, or component not specified in the claims. The transitional phrase "consisting essentially of … …" limits the scope of the claims to specific components or steps as well as those components or steps that do not materially affect the basic and novel characteristics of the claimed invention. Unless otherwise indicated, the description of a compound or composition as "consisting essentially of … …" should not be construed as "comprising" because this phrase is intended to describe the recited components, including materials that do not significantly alter the composition or method in which the term is applied. For example, the precursor or catalyst component may consist essentially of a material that, when prepared by a procedure, may include impurities commonly found in its commercial production samples. When the claims include different features and/or classes of features (e.g., method steps, raw material features, and/or product features, among other possibilities), the transitional terms "comprising," "consisting essentially of … …," and "consisting of … …" apply only to the class of features utilized, and possibly with different transitional terms or phrases utilized with the different features within the claims. For example, a process may comprise several of the recited steps (and other non-recited steps), but is prepared using a catalyst system that "consists" or "consists essentially of" the specific steps, but uses a catalyst system that comprises the recited components and other non-recited components. When the 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" the various components or process steps.

Unless otherwise defined with respect to a particular attribute, feature, or variable, the term "substantially" as applied to any criteria such as an attribute, feature, or variable means that the specified criteria are met to a sufficient degree so that one skilled in the art will understand that the benefit to be achieved, or that the desired condition or attribute value is met. For example, the term "substantially" may be used when describing a metallocene catalyst or catalyst system that is substantially free or substantially free of aluminoxane, borate activator, protonic acid treated clay, or pillared clay. In other words, the terms "substantially" and "subtropically" are used reasonably to describe the subject matter so that its scope will be understood by those of skill in the relevant art and to distinguish the claimed subject matter from any prior art. In one aspect, "substantially free" may be used to describe a composition in which none of the listed components of the composition are added to the composition and only impurity amounts are present, such as amounts derived from purity limits of other components or amounts produced as byproducts. In another aspect, when the composition is referred to as "substantially free of" a particular component, the composition may have less than 20wt.% of the component, less than 15wt.% of the component, less than 10wt.% of the component, less than 5wt.% of the component, less than 3wt.% of the component, less than 2wt.% of the component, less than 1wt.% of the component, less than 0.5wt.% of the component, or less than 0.1wt.% of the component.

The terms "optionally," "optional," and the like with respect to the claim element are intended to mean that the subject element is required, or alternatively, is not required, and that both alternatives are intended to be within the scope of the claim, and that the claim may encompass either or both alternatives.

The periodic table or group of elements in the periodic table refers to the version of the periodic table of elements published on-line at http:// old.iupac.org/reports/periodic_table at IUPAC at month 2 and 19 of 2010. As reflected in the periodic table of elements, reference is made to one or more "groups" of the periodic table, using the IUPAC system for numbering groups of elements from 1 to 18. If any group is identified by Roman numerals of the periodic Table of elements as published, for example, in the Howley's concise chemical dictionary (Hawley's Condensed Chemical Dictionary) (CAS system), it will further identify one or more elements of the group to avoid confusion and provide a cross-reference to the digital IUPAC identifier.

Various patents, publications, and documents are disclosed and cited herein. Each reference, whether patents, publications, or other documents cited in this disclosure are incorporated by reference in their entirety unless otherwise indicated.

References that may provide some background information relevant to the present disclosure include, for example, U.S. patent No. 3,962,135; 4,367,163 th sheet; 5,202,295 th sheet; 5,360,775 th sheet; 5,753,577 th sheet; no. 5,973,084; no. 6,107,230; 6,531,552 th sheet; 6,559,090 th sheet; 6,632,894; 6,943,224 th sheet; 7,041,753 th sheet; 7,220,695 th sheet; 9,751,961 th sheet; U.S. patent application publication nos. 2018/0142047 and 2018/0142048; each of which is incorporated by reference in its entirety. Other publications that may provide some background information relevant to the present disclosure include:

gu, b.; doner, h.e. "clay and clay minerals", 1991,38 (5), 493-500;

Covarrubias et al, application catalysis, section a: general, 347 (2), 9/15/2008, 223-233;

tayano et al, clay science (CLAY SCIENCE), 2016,20,49-58;

Tayano et al, macromolecular reaction engineering (Macromolecular Reaction Engineering), 2017 (11), 201600017;

Journal of molecular catalysis, section a: chemical catalysis (Journal of Molecular CATALYSIS A: chemical), 2016,420,228-236;

Clay science), 2016,20,49-58;

Finevich et al, russian journal of general chemistry (Russian Journal of GENERAL CHEMISTRY), 2007,77 (12), 2265-2271;

Bibi, singh and SILVESTER, applied geochemistry (Applied Geochemistry), 2014,51,170-183;

Shalma et al, journal of materials science (MATERIAL SCIENCE), 2018,53,10095-10110;

Okada et al, clay science 2003,12,159-163;

sucha et al, clay minerals (CLAY MINERALS), 1996,31,333-335;

Vlasova et al, sintering science (Science of Sintering), 2003,35,155-166;

Kline and Fogler, industrial & engineering chemistry foundation (Industrial & ENGINEERING CHEMISTRY Fundamentals), 1981,20 (2), 155-161;

Ocelli, clay and Clay minerals, 2000,48 (2), 304-308;

Kooli microporous and mesoporous materials (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 by reference in its entirety.

B. Summary of the invention

The support-activators of the present disclosure can be formed by: starting from a slurry of swelling clay in a liquid carrier such as montmorillonite or dioctahedral montmorillonite clay, and contacting the clay in the slurry with a heterocoagulation reagent comprising at least one cationic multimetal salt produced under the conditions specified herein. Heteroaggregated clays are formed which can be very conveniently isolated by filtration and subsequently dried and calcined to provide a support-activator for supporting and activating metallocene catalysts for olefin polymerization. The formation of a clay heteroadduct in good yields can be achieved by controlling the proportion or amount of heteroagglomerating agent used relative to the clay, as measured by the zeta potential of the slurry forming the clay heteroadduct. Thus, the clay heteroadduct comprises the contact product of [1] a montmorillonite clay such as a colloidal montmorillonite clay and [2] a heteroagglomerating agent in a liquid carrier, the heteroagglomerating agent comprising at least one cationic multimetal salt, and the amount of the heteroagglomerating agent being sufficient to provide a slurry of the resulting clay heteroadduct having a zeta potential in the range of from about positive 25mV (millivolts) to about negative 25 mV.

When montmorillonite clay is contacted with a heteroagglomerating agent in a liquid carrier using a mole number of cationic polymetallic salts per gram of clay greater than the mole number specified immediately above, such that the resulting slurry has a zeta potential of greater than about +25mV, which may occur with formulations such as Aluminum Chlorohydrate (ACH) and colloidal montmorillonite clay using greater than about 2.3mmol Al/g clay, greater than about 2.5mmol Al/g clay, greater than about 2.7mmol Al/g clay, or greater than about 3.0mmol Al/g clay (millimoles of aluminum per gram of clay), a large amount of the corresponding pillared clay may be formed. Although the desired slurry of montmorillonite heteroadduct may include some of the corresponding pillared clay and some of the pillared clay formation is secondary or incidental to the carrier-activator formation as observed by powder X-ray diffraction (XRD), a carrier-activator having too high a concentration of pillared clay results in a loss of ready filterability of the slurry compared to the clay heteroadduct, such that the ease of carrier-activator separation is compromised. When the montmorillonite clay is contacted with the heterocoagulation reagent in a liquid carrier using a small molar amount of cationic polymetallic salt per gram of clay such that the resulting slurry has a zeta potential of less than about-25 mV (which may occur when less than about 0.5mmol Al/g clay, less than about 0.6mmol Al/g clay, or less than about 0.8mmol Al/g clay, or in some cases less than about 1.0mmol Al/g clay (millimoles aluminum/g clay) is used) of aluminum chlorohydrate and colloidal montmorillonite clay, a small amount of clay heteroadducts is formed and a large amount of colloidal montmorillonite clay remains.

It has also been unexpectedly found that the clay heteroadduct carrier-activators of the present disclosure can be used with little or no subsequent washing steps after separation by filtration, as compared to pillared clay carrier-activators and similar clay-based activators used to support and activate metallocene catalysts. That is, the isolated heteroadduct support-activator can be used directly with a metallocene and a cocatalyst such as an aluminum alkyl (if desired) to form a catalyst without the need for extensive or time-consuming purification, washing or other purification stages commonly used in clay-based supports. This advantage can lead to great economic advantages and greater ease of use when preparing olefin polymerization catalysts.

Thus, in one aspect, the present disclosure provides a carrier-activator comprising an isolated montmorillonite heteroadduct comprising the contact product of [1] a colloidal montmorillonite clay and [2] a heteroagglomerating agent in a liquid carrier, the heteroagglomerating agent comprising at least one cationic multimetal salt, and the amount of the heteroagglomerating agent being sufficient to provide a slurry of the montmorillonite heteroadduct having a zeta potential in the range of from about positive 25mV (millivolts) to about negative 25 mV.

a) Providing a colloidal montmorillonite clay;

b) Contacting the colloidal montmorillonite clay with a heteroagglomerating agent in a liquid carrier, the heteroagglomerating agent comprising at least one cationic multimetal salt, and the amount of heteroagglomerating agent being sufficient to provide a slurry of montmorillonite heteroadducts having zeta potentials in the range of about positive 25mV (millivolts) to about negative 25 mV.

The process may further comprise the step of c) separating the montmorillonite hetero adduct from the slurry.

a) At least one transition metal catalyst, such as a metallocene compound;

b) Optionally, at least one cocatalyst; and

In another aspect, a method of preparing an olefin polymerization catalyst is provided, the method comprising contacting in any order:

a) At least one transition metal catalyst, such as a metallocene compound;

b) Optionally, at least one cocatalyst; and

C) At least one carrier-activator comprising a calcined montmorillonite heteroadduct according to the present disclosure.

Another aspect of the present disclosure is a process for polymerizing olefins comprising contacting at least one olefin monomer under polymerization conditions with a catalyst composition 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; and

C) At least one support-activator comprising a calcined montmorillonite hetero adduct as described herein.

Reference is made to the examples, data, and aspects of this disclosure section of this written description, wherein is listed the detailed information for making and using the various aspects and embodiments of the support-activator and catalyst compositions described herein. Some specific details of the components used to prepare the catalyst composition and polymerize olefins using the catalyst composition are set forth in the following sections.

C. colloidal montmorillonite clay

In addition to the definition section, the following disclosure provides additional information related to montmorillonite clay.

Swelling clays (such as montmorillonite or 2:1 dioctahedral montmorillonite clays) or combinations of swelling clays can be used to prepare the support-activators described herein. These swelling clays can be described as phyllosilicates or phyllosilicate clays, as certain members of the clay mineral family of phyllosilicates can be used. Suitable starting clays may include layered, naturally occurring or synthetic montmorillonite. The starting clay may also include a dioctahedral montmorillonite clay. In addition, suitable starting clays may also include clays such as montmorillonite, sauconite, nontronite, hectorite, beidellite, saponite, bentonite, or any combination thereof. Montmorillonite is a 2:1 layered clay mineral with a lattice charge that swells when dissolved in water and ethanol. Thus, suitable starting clays may include, for example, single cation exchanged dioctahedral smectites, such as lithium exchanged clays, sodium exchanged clays, or potassium exchanged clays, or combinations thereof.

The water may also be coordinated to the lamellar clay structural units, either in combination with the clay structure itself, or as a hydrated layer with cations. When dehydrated, in powder X-ray diffraction (XRD), the repeat distance or d001 substrate spacing of the 2:1 layered clay is about(Angstrom) to about(Angstrom); or alternatively in about powder X-ray diffraction (XRD)(Angstrom) to about(Angstrom) range.

Layered montmorillonite clays are known as 2:1 clays because their structure is a "sandwich" structure, comprising two outer layers of tetrahedral silicate and an inner layer of octahedral alumina sandwiched between layers of silica platelets. Thus, these structures are also known as "TOT" (tetrahedron-octahedron-tetrahedron) structures. These sandwich structures are stacked one on top of the other to produce clay particles. This arrangement can provide about five angstroms per nine points, as compared to pillared or intercalated clays created by inserting "pillars" of inorganic oxide material between the layers to provide more space between the natural clay layersIs a repeating structure of (a).

In one aspect, the clay used to prepare the support-activator may be a colloidal montmorillonite clay. Accordingly, the montmorillonite clay may have an average particle size of less than about 10 μm (microns), less than about 5 μm, less than about 3 μm, less than 2 μm, or less than 1 μm, wherein the average particle size is greater than about 15nm, greater than about 25nm, greater than about 50nm, or greater than about 75nm. That is, any range of clay particle sizes between these reference numbers is disclosed. While clays that are incapable of producing colloidal suspensions may be used, they are not preferred over colloidal clays.

In one aspect, the clay used to prepare the support-activator may be free of divalent or trivalent ion-exchanged montmorillonite, such as Mg-exchanged or Al ion-exchanged montmorillonite described in U.S. patent No. 6,531,552. In another aspect, the clay used to prepare the carrier-activator may be free of mica or laponite, as described in U.S. Pat. nos. 6,531,552 and 5,973,084. In yet another aspect, the clay used to prepare the support-activator may be free of octahedral montmorillonite or may be free of vermiculite.

In one aspect, the montmorillonite clay may further comprise structural units characterized by the formula:

(M ^AIV)₈(M^BVI)_pO₂₀(OH)₄; therein

A) M ^A IV is tetra-coordinated Si ⁴⁺, wherein the tetra-coordinated cation of non-Si ⁴⁺ optionally partially replaces Si ⁴⁺ (e.g., the cation of non-Si ⁴⁺ may be independently selected from Al ³⁺、Fe³⁺、P⁵⁺、B³⁺、Ge⁴⁺、Be²⁺、Sn⁴⁺, etc.);

b) M ^B VI is hexacoordinated Al ³⁺ or Mg ²⁺, wherein the hexacoordinated cation other than Al ³⁺ or Mg ²⁺ optionally partially replaces Al ³⁺ or Mg ²⁺ (e.g., the cation other than Al ³⁺ or Mg ²⁺ may be independently selected from Fe³⁺、Fe²⁺、Ni²⁺、Co²⁺、Li⁺、Zn²⁺、Mn²⁺、Ca²⁺、Be²⁺, etc.);

c) P is four for cations with +3 formal charge or 6 for cations with +2 formal charge; and

D) Any charge deficiency resulting from partial substitution of cations other than Si ⁴⁺ at M ^A IV and/or from cations other than Al ³⁺ or Mg ²⁺ at M ^B VI is balanced by cations interposed between the building blocks (e.g., the cations interposed between the building blocks may be selected from mono-cations, di-cations, tri-cations, other multi-cations, or any combination thereof).

Examples, data, and aspects of the present disclosure provide additional detailed information on various aspects and embodiments of montmorillonite clay.

D. Cationic polymetallic salts for heterocoagulation reagents

In addition to the definitions and aspects of the present disclosure, the following additional information further describes the cationic multimetal salts.

As explained in the definition section, the term "multimetal salt" and similar terms such as "polyoxometalate" refer to a polyatomic cation comprising two or more metals (e.g., aluminum, silicon, titanium, zirconium, or other metals) and at least one bridging ligand (such as an oxy, hydroxy, and/or halide ligand) between the metals. For example, the multimetal salt can be a hydrated metal oxide, a hydrated metal oxyhydroxide, and the like, and can include bridging ligands (such as oxyligands bridging two or more metals can be present in these materials), and can also include terminal oxygens, hydroxyl groups, and/or halide ligands. While many multimetal salt species are anionic and the suffix "-ate" is often used to reflect anionic species, the multimetal salt (polyoxometalate) complex used in accordance with the present disclosure is cationic.

The heterocoagulants of the present disclosure may be positively charged species that, when combined with a colloidal suspension of clay in an appropriate ratio, form a coagulum that is easy to filter and wash. Positively charged species include soluble polyoxometalates, polyhydroxy metal salts and polyhydroxy metal oxyacid salt cations, as well as related cations that are partially halide substituted, such as polyaluminum chloride species of polyhydroxy aluminum oxychloride or aluminum chlorohydrate or linear, cyclic or clustered compounds. These compounds are collectively referred to as multimetal salts. The latter aluminum compound may contain from about 2 to about 30 aluminum atoms.

Useful heterocoagulation reagents also include any colloidal substance characterized by a positive zeta potential when dispersed in an aqueous solvent or a mixture of aqueous and organic (e.g., alcohol) solvents. For example, useful heterocoagulation reagent dispersions may exhibit zeta potentials greater than (>) +20mV (positive 20 mV), greater than +25mV, or greater than +30 mV. Although the starting colloidal clay may include monovalent ions or species, such as protons, lithium ions, sodium ions, or potassium ions, at least a portion, some, most, substantially all, or all of these ions are replaced by the heterocoagulation reagent during formation of the readily filterable clay heteroadduct. As discussed below, protons, lithium ions, sodium ions, potassium ions, or the like do not provide the filterability provided by the cationic multimetal salts of the present disclosure. This feature can be observed by the resulting long filtration times when preparing and attempting to isolate the hydrochloric acid treated carrier-activator, such as in examples 40 and 41.

Furthermore, unlike treatments that use strong acids to leach Al ions from montmorillonite, the formation of clay heteroadducts does not leach Al ions from clay. When an aluminum-containing heterocoagulation reagent such as ACH or PAC is used, the aluminum content of the support-activator is actually higher than that of the starting clay, although the aluminum content is much lower than that of the corresponding pillared clay.

In one aspect, the heterocoagulation reagent may comprise a colloidal suspension of boehmite (alumina hydroxide) or a metal oxide such as a gas phase metal oxide (e.g., gas phase alumina) that provides a positive zeta potential. In another aspect, the heterocoagulation reagent may comprise a chemically modified or chemically treated metal oxide, such as aluminum chlorohydrate treated fumed silica, such that the chemically treated metal oxide provides a positive zeta potential when in suspension, as described below. In another aspect, the heterocoagulation reagent may be produced by treating a metal oxide or metal oxide hydroxide or the like with a reagent in a fluidized bed that will provide a positive zeta potential when the reagent is dispersed in the suspension. The heterocoagulants may exhibit positive values of greater than +20mV prior to combining with the phyllosilicate clay component.

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

In another aspect, the cationic polymetallic salt composition may comprise or be selected from the group consisting of [1] fumed silica, fumed alumina, fumed silica-alumina, fumed magnesia, fumed zinc oxide, fumed titania, fumed zirconia, fumed ceria, or any combination thereof, which is chemically treated with [2] polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichloride, polyhydroxy aluminum oxychloride, or any combination thereof. For example, the cationic multi-metal salt composition may comprise or be selected from aluminum chlorohydrate treated fumed silica, aluminum chlorohydrate treated fumed alumina, aluminum chlorohydrate treated fumed silica-alumina, or any combination thereof.

While not intending to be bound by theory, it is believed that the treated metal oxide may form a core-shell structure of a positively charged shell and a negatively charged core, or a continuous structure of mixed positive and negative regions or atoms, such that the surface exhibits a positive zeta potential of greater than about +20 mV. Some vapor phase metal oxides, such as vapor phase alumina, may already exhibit a positive zeta potential prior to chemical treatment. However, gas phase metal oxides having no zeta potential or a positive zeta potential of less than about +20mV may also be chemically treated with a material such as aluminum chlorohydrate, and after treatment, a colloidal suspension having a zeta potential of greater than about +20mV may be obtained.

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

In another embodiment, the heterocoagulation reagent can comprise any colloidal inorganic oxide particles, such as those described in U.S. patent No. 4,637,992 to Lewis et al (such as colloidal ceria or colloidal zirconia or any of the positively charged colloidal metal oxides disclosed therein), which is incorporated herein by reference. In another aspect, the heterocoagulation reagent may comprise magnetite or ferrierite. For example, the cationic multimetal salt can comprise or be selected from boehmite, fumed silica-alumina, colloidal ceria, colloidal zirconia, magnetite, ferrihydrite, any positively charged colloidal metal oxide, or any combination thereof.

In another aspect, the heterocoagulation reagent may include a cationic oligomeric or polymeric aluminum species in solution, such as aluminum hydroxychloride, also known as Aluminum Chlorohydrate (ACH), aluminum Polychloride (PAC), aluminum hydroxychloride, or any combination or mixture thereof. For example, the cationic polymetallic salt heterocoagulants may include or be selected from aluminum species or any combination of species having the empirical formula:

Al₂(OH)_nCl_m(H₂O)_x，

Where n+m=6 and x is a number from 0 to about 4.

In one aspect, the cationic multimetal salt can comprise or can be selected from aluminum species having the formula [ AlO ₄(Al₁₂(OH)₂₄(H₂O)₂₀]⁷⁺, which is a so-called "Al ₁₃ -mer" polycation, and is considered a precursor of Al ₁₃ pillared clay.

When aluminum chlorohydrate is used as a heterocoagulation reagent or chemical treatment reagent for treating other metal oxides, aluminum Chlorohydrate (ACH) solutions or solid powders from commercial sources may be used. The aluminum chlorohydrate solution may be referred to as a polymeric cationic aluminum hydroxy complex or aluminum chlorohydrate, which refers to a polymer formed from a monomer precursor having the general empirical formula 0.5[ Al ₂(OH)₅Cl(H₂O)₂ ]. The preparation of aluminum chlorohydrate solutions is described in U.S. patent nos. 2,196,016 and 4,176,090, which are incorporated herein by reference, and may involve treating aluminum metal with hydrochloric acid in an amount that produces a composition having the formula described above.

Alternatively, various aluminum sources such as aluminum oxide (Al ₂O₃), aluminum nitrate, aluminum chloride, or other aluminum salts may be used and treated with an acid or base to obtain an aluminum chlorohydrate solution. Many species that may be present in such solutions, including the decatrimeric [ AlO ₄(Al₁₂(OH)₂₄(H₂O)₂₀]⁷⁺(Al₁₃ -mer ] polycations, are described in Perry and Shafran, journal of inorganic biochemistry (Journal of Inorganic Biochemistry) 2001,87,115-124, which is incorporated herein by reference. The materials disclosed in this study as being present in such solutions, either alone or in combination, can be used as cationic polymetallic salts of montmorillonite clay heterocoagulation.

In one aspect, the aqueous aluminum chlorohydrate solution used in accordance with the present disclosure may have an aluminum content calculated or expressed as a weight percent of Al ₂O₃, which may range from about 15wt.% to about 55wt.%, although more dilute concentrations may be used. As will be appreciated by those of ordinary skill in the art, other reaction conditions, such as time and temperature, may be adjusted simultaneously using a more dilute solution. Alternative aluminum concentrations in aqueous solutions of multi-metal salts such as aqueous aluminum chlorohydrate expressed as weight percent of Al ₂O₃ may include: about 0.1wt.% to about 55wt.% Al ₂O₃; About 0.5wt.% to about 50wt.% Al ₂O₃; about 1wt.% to about 45wt.% Al ₂O₃; about 2wt.% to about 40wt.% Al ₂O₃; about 3wt.% to about 37wt.% Al ₂O₃; About 4wt.% to about 35wt.% Al ₂O₃; about 5wt.% to about 30wt.% Al ₂O₃; or about 8wt.% to about 25wt.% Al ₂O₃; each range includes each individual concentration expressed in tenth (0.1) of the weight percent covered therein, and includes any subrange therein. For example, references to about 0.1wt.% to about 30wt.% Al ₂O₃ include references to 10.1wt.% to about 26.5wt.% Al ₂O₃. When convenient, solid multimetal salts, such as solid aluminum chlorohydrate, can be used and added to the slurry of colloidal clay in the preparation of the heterocondensate. Thus, the concentrations disclosed above are not limiting, but are exemplary.

In one aspect, the cationic multimetal salt can comprise or can be selected from oligomers prepared by copolymerizing (co-oligomerizing) a soluble rare earth salt with a cationic metal complex of at least one additional metal selected from aluminum, zirconium, chromium, iron, or a combination thereof according to U.S. patent No. 5,059,568, which is incorporated herein by reference, for example, wherein the at least one rare earth metal can be cerium, lanthanum, or a combination thereof. In one aspect, the heterocoagulation reagent may comprise an aqueous solution of a lanthanide and Al ₁₃ Keggin ions, such as described in us patent No. 5,059,568 to McCauley. However, the calcined clay heteroadducts of the present disclosure prepared using McCauley multi-metal salts do not provide substrate spacing greater than(Angstrom) uniform intercalation structure. While not wishing to be bound by theory, it is believed that this observation may be due to the much smaller ratio of Ce-Al heterocoagulation reagent to colloidal clay used in accordance with the present disclosure. This lesser amount results from the contacting conditions of the montmorillonite clay and the heteroagglomerating agent in an amount sufficient to provide a slurry of the montmorillonite heteroadduct having a zeta potential in the range of about +25mV (millivolts) to about-25 mV.

In further aspects, exemplary multimetal salts of the present disclosure can include: [1] epsilon-Keggin cation [ epsilon-PMo ₁₂O₃₆(OH)₄{Ln(H₂O)₄}₄]⁵⁺, wherein Ln can be La, ce, nd or Sm; and [2] a lanthanide-containing cationic vanadic oxygen cluster having the general formula [ Ln ₂V₁₂O₃₂(H₂O)₈ { Cl } ] Cl, where Ln can be Eu, gd, dy, tb, ho or Er.

In another aspect, the heterocoagulants may be layered double hydroxides, such as those described in Abend et al, "Colloid and Polymer science (sci.)" 1998,276,730-731, or synthetic hematite, hydrotalcite, or other positively charged layered double hydroxides, including but not limited to those described in U.S. Pat. No. 9,616,412, incorporated herein by reference. Thus, the cationic multimetal salt used as the heterocoagulation reagent can be a layered double hydroxide or a mixed metal layered hydroxide. For example, the mixed metal layered hydroxide may be selected from Ni-Al, mg-Al or Zn-Cr-Al types having a positively charged layer. In another aspect, the layered double hydroxide or mixed metal layered hydroxide may comprise or may be selected from aluminum magnesium nitrate, aluminum magnesium sulfate, aluminum magnesium chloride, mg _x(Mg,Fe)₃(Si,Al)₄O₁₀(OH)₂(H₂O)₄ (x is a number from 0 to 1, e.g., about 0.33 for saponite), (Al, mg) ₂Si₄O₁₀(OH)₂(H₂O)₈, synthetic hematite, hydrozincite (basic zinc carbonate) Zn ₅(OH)₆(CO₃)₂, hydrotalcite [ Mg ₆Al₂(OH)₁₆]CO₃·4H₂ O, hydrohalite [ Ni ₆Al₂(OH)₆]CO₃·4H₂ O, hydrocalumite [ Ca ₂Al(OH)₆]OH·6H₂ O, magnesium plus aluminum [ Mg ₁₀Al₅(OH)₃₁](SO₄)₂·mH₂ O, lepidomagnesium [ Mg ₆Fe₂(OH)₁₆]CO₃·4.5H₂ O, ettringite [ Ca ₆Al₂(OH)₁₂](SO₄)₃·26H₂ O, or any combination thereof.

In yet another aspect, the heterocoagulation reagent may comprise an aqueous solution of Fe polycations, such as Oades, clay and clay minerals, 1984,32 (1), 49-57, or Cornell and SCHWERTMANN in iron oxides: structure, properties, reactions, events and uses (The Iron Oxides: structures, properties, reactions, occurrences and Uses), second edition, 2003, described by Wiley VCH. The cationic polymetallic salts may contain or may be selected from iron polycations having the empirical formula FeO _x(OH)_y(H₂O)_z]ⁿ⁺, wherein 2x+y is less than (<) 3, z is a number from 0 to about 4, and n is a number from 1 to 3.

The use of cations such as protons, lithium ions, sodium ions, or potassium ions, such as described in examples 40 and 41, does not provide a clay hetero-adduct as provided by the cationic multimetal salts of the present disclosure, e.g., these acid treated clays are generally not easily filterable. While not wishing to be bound by theory, it is believed that monovalent ions, such as protons from HCl or H ₂SO₄ in aqueous solution, such as described in U.S. patent No. 6,531,552 and references thereto by Nakano et al, which are incorporated herein by reference, do not form stable, easily filterable heteroaggregated clay adducts, whether dilute or concentrated acids are used. Colloidal dispersions of montmorillonite, such as bentonite or montmorillonite, have a permanent negative charge and therefore exhibit a permanent negative zeta potential even at low pH. Also, while not intending to be bound by theory, at high acid concentrations at low pH (< 3), the potential of the colloidal dispersion of montmorillonite becomes less negative, possibly even approaching a zeta potential of about minus 30mV (-30 mV). (see Duran et al, journal of colloid and interface science (Journal of Colloid AND INTERFACE SCIENCE), 2000,229, pages 107-117, incorporated herein by reference. ) However, before the colloidal clay is able to approach or reach a neutralized or near neutralized surface charge, the clay structure itself is believed to be destroyed by peptization of the octahedral alumina layer. (see Tayano et al; macromolecular reaction engineering, 2017,11,201600017 and clay science, 2016,20,49-58, all of which are incorporated herein by reference.) leaching of octahedral alumina layers from the TOT structure and dissolution of clay into strongly acidic solutions is described, for example, in the following documents: U.S. patent No. 3,962,135; bi, singh and SILVESTER, "dissolution kinetics of kaolinite, illite and montmorillonite under acid-sulfate conditions: a comparative study (Dissolution kinetics of kaolinite,illite and montmorillonite under acid-sulfate conditions:a comparative study)", was written in clay mineral chapter 4 (manuscript available from https://ses.library.usyd.edu.au/bitstream/handle/2123/8647/Chapter％204_Dissolution％20of％20illite,％20kaolinite,％20montmorillonite.pdfsequence＝5) and also from https:// pdfs.semaniischolar. Org/6836/3c9c293dfd4255f9 d 8867881770c 384d3.Pdf, And Dudkin et al, chemistry facilitation sustainable development (CHEMISTRY FOR SUSTAINABLE DEVELOPMENT), 2004,12,327-330; And Okada et al, clay science, 2003,12,159-165, which are incorporated herein by reference.

While not wishing to be bound by theory, it has been observed that the addition of other aprotic monovalent cations such as lithium, sodium or potassium ions in the form of their respective salts to the colloidal montmorillonite particles at the point where flocculation may occur is believed to be due to shielding and reduction of the niobium repulsive forces between the montmorillonite particles. The concentration of single cations at which coagulation occurs is referred to as the critical coagulation concentration, and the concentration of monovalent cations required to effect coagulation is typically significantly greater than that required when divalent or trivalent cations are used. Also, while not wishing to be bound by theory, monovalent cation-clay products remain difficult to filter and may need to be separated by centrifugation or high dilution and settling tanks. If the monovalent ion salt is not washed and removed, the flocculated clay will not produce a metallocene support-activator catalyst with sufficient practical activity. Furthermore, for simple ion intercalation, such as in sodium-exchanged montmorillonite or aluminum-exchanged montmorillonite, which may be evident in powder XRD of calcined clay heteroadducts, these materials are considered to occur as unwanted byproducts or result from incomplete reaction of the colloidal clay with the polymetallic salt.

In another aspect, the colloidal montmorillonite clay may comprise or be selected from colloidal montmorillonite clay, such asHPM-20 bentonite. The heterocoagulation reagent may comprise or be selected from aluminum chlorohydrate, polyaluminum chloride, or aluminum sesquichloride.

According to one aspect, the cationic multimetal salt can comprise or be selected from a complex of formula I or formula II or any combination of complexes of formula I or formula II according to the following formula:

[M(II)_1-xM(III)_x(OH)₂]A_x/n·m L (I)

[LiAl₂(OH)₆]A_1/n·m L (II)

Wherein:

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

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

A is at least one inorganic anion;

L is an organic solvent or water;

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

X is a number from 0.1 to 1; and

M is a number from 0 to 10.

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

In one aspect, the cationic polymetallic salt may comprise polyaluminum chloride, aluminum chlorohydrate, aluminum hydroxychloride or aluminum polyhydroxyoxychloride, or a combination thereof. In yet another aspect, the cationic multimetal salt can comprise linear, cyclic or clustered aluminum compounds containing, for example, 2 to 30 aluminum atoms. In the formulation used to prepare the montmorillonite heteroadduct, the ratio of millimoles (mmol) of aluminum (Al) to grams (g) of colloidal montmorillonite clay in polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichloride, or aluminum chlorohydrate can be in the range of, for example, about 0.75mmol Al/g clay to about 2.0mmol Al/g clay, about 0.8mmol Al/g clay to about 1.9mmol Al/g clay, about 1.0mmol Al/g clay to about 1.8mmol Al/g clay, about 1.1mmol Al/g clay to about 1.8mmol Al/g clay, or about 1.1mmol Al/g clay to about 1.7mmol Al/g clay. Alternatively, in the formulation used to prepare the montmorillonite heteroadduct, millimoles (mmol) of aluminum (Al) per gram (g) of polyaluminum chloride, aluminum chlorohydrate, aluminum hydroxychloride, or aluminum polyhydroxyoxychloride of the colloidal montmorillonite clay may be, for example, about 0.75mmol Al/g clay, about 0.8mmol Al/g clay, about 0.9mmol Al/g clay, about 1.0mmol Al/g clay, about 1.1mmol Al/g clay, about 1.2mmol Al/g, about 1.3mmol Al/g clay, about 1.4mmol Al/g clay, about 1.5mmol Al/g clay, about 1.6mmol Al/g clay, about 1.7mmol Al/g clay, about 1.8mmol Al/g clay, about 1.9mmol Al/g clay, or about 2.0mmol Al/g clay, including any range between any of these ratios or combinations of subranges therebetween.

In another aspect, in a formulation for preparing an isolated or calcined montmorillonite heteroadduct, the ratio of millimoles (mmol) of aluminum (Al) to grams (g) of colloidal clay in polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichlorohydrate, or aluminum polyhydroxyoxychloride can be about 90% or less, about 80% or less, about 70% or less, about 60% or less, about 50% or less, about 45% or less, about 40% or less, or about 35% or less of the ratio of millimoles of aluminum to grams of colloidal clay used in preparing a pillared clay using the same colloidal gelatin clay and heterocoagulation reagent.

In this regard, in the pillared formulation, the ratio of aluminum reagent to clay is expressed in mmol Al/g clay, representing the millimoles of Al in the chlorine hydrated aluminum reagent relative to the grams of clay in the formulation. In particular, this ratio reflects the ratio employed in the synthetic formulation, rather than the ratio in the final pillared clay product. As an example, considering Ocelli, clay and clay minerals, 2000,48 (2), model Al ₁₃ Keggin ions described in 304-308, the amount of Al used in pillared clay preparation far exceeds the amount of Al eventually intercalated between the final pillared clay solids layers. The use of an excess of aluminum reagent is employed to provide the maximum column content in the final product and to achieve the desired porosity and surface area of the final calcined material. Kooli in microporous and mesoporous materials; 2013,167,228-236 discloses that about 6mmol Al/g clay is typically required in the formulation to optimize pillaring. In recent scale-up studies and optimization of Al ₁₃ Keggin ion pillared clays, pergher and Bertella in Materials, 2017,10,712 disclose that a dilute dispersion of 15mmol Al/g clay and about 1wt.% clay is required in order to obtain a pillared with the desired substrate spacing and surface area.

E. preparation and Properties of Clay heteroadducts (heteroaggregated Clays)

Unlike pillared clays, the heteroaggregated clays of the present disclosure are amorphous solids. Thus, the preparation of the heteroaggregated clay provides a three-dimensional structure, but it is non-pillared, amorphous and amorphous. While not intending to be bound by theory, it is believed that the regular crystal structure of the starting montmorillonite not only swells upon contact with the cationic multimetal salt, but rather is broken down upon preparation of the clay hetero-adduct to provide a non-crystalline, irregular, non-lamellar amorphous material. Factors that can affect the formation of the amorphous three-dimensional structure include reaction time, reaction temperature, purity of the starting clay and clay particle size, drying method, etc., as described herein, these factors are readily determinable for each heterocoagulation reagent and clay system.

During the preparation of the clay heteroadducts, the heterocoagulants may be added to the slurry of colloidal clay, the colloidal clay may be added to the slurry or solution of the heterocoagulants, or the heterocoagulants and the colloidal clay may be added to the liquid carrier simultaneously or over overlapping time periods. Alternatively, the heterocoagulants and the colloidal clay may be added simultaneously to the residue of the heteroaddition product, such as by adding the heterocoagulants and clay as solids or suspensions to a vessel or reactor containing water or an aqueous residue.

In one aspect, the liquid vehicle for preparing the clay hetero-adduct may be aqueous or water-based, wherein additional components, such as ethanol and/or at least one surfactant, may 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 aspects of the disclosure section.

As described above, the ratio of heterocoagulation reagent to clay used in the formulation is defined as the ratio of slurries that provide a coagulated product mixture, such as zeta potential, in the range of about plus (+) 25mV (millivolts) to about minus (-) 25 mV. Thus, the amount of heterocoagulants added to a known clay sample, i.e., the ratio of cationic polymetallic salt (heterocoagulants) to clay, is determined by titration of the clay with the heterocoagulants. For example, when the heterocoagulation reagent comprises a cationic multimetal salt of aluminum, the ratio of millimoles (mmol) of aluminum (Al) to grams (g) of clay in the cationic aluminum multimetal salt can be used to report the heterocoagulation reagent to clay ratio. The actual amount of cationic multimetal salt used to form the clay heteroadduct, i.e., the ratio of heteroagglomerating agent to clay, may depend on factors such as the degree of positive charge of the cationic multimetal salt, the zeta potential of the clay, and the like. The heterocoagulation reagent and clay are mixed in a ratio such that the resulting slurry (dispersion) of the heterocoagulation clay formed exhibits a zeta potential in the range of about +25mV to about-25 mV. Alternatively, the heterocoagulation reagent and clay are mixed in a ratio such that the resulting dispersion of the heterocoagulation clay formed exhibits a zeta potential of from about +22mV to about-22 mV, from about +20mV to about-20 mV, from about +18mV to about-18 mV, from about +15mV to about-15 mV, from about +10mV to about-10 mV, from about +5mV to about-5 mV, or about 0 mV.

As described in the examples, the colloidal dynamic Zetaprobe analyzer ^TM is used to measure zeta potential, including dynamically tracking changes in zeta potential during titration of colloidal clay dispersions with cationic polymetallic salt titrant. Exemplary results of zeta potential titration are shown in the figures and described in the examples, e.g., the data presented in tables 4-6. For example, FIG. 3 depicts an Aluminum Chlorohydrate (ACH) pair in useThe zeta potential of a series of dispersions formed during titration of HPM-20 montmorillonite plots the cumulative titrant volume (x) of the added ACH aqueous solution against the zeta potential (mV, (y)) of the dispersion. Similarly, FIG. 4 plots cumulative mmol Al/g clay versus zeta potential (mV) of the dispersion for the same titration. Samples of some of the solid products formed during zeta potential titration of HPM-20 clay with ACH were collected and FIG. 2 provides a powder XRD pattern of the series of calcined products collected during zeta potential titration of HPM-20 clay with ACH. Thus, a comparison and correlation of the filterability of mmol Al/g clay with zeta potential and the resulting product was examined, and from this analysis, it was unexpectedly found that when clay and heterocoagulation reagent comprising at least one cationic multimetal salt were contacted with each other in a liquid carrier in an amount or ratio providing a slurry of montmorillonite heteroadducts having zeta potential in the range of about positive 25mV (millivolts) to about negative 25mV, the resulting product was easy to filter, was useful as a support-activator without washing or with minimal washing, and gave high polymerization activity to the supported metallocene catalyst.

In a synthesis reaction or titration using cationic multimetal salts, calculating the ratio of millimoles of metal atoms in the multimetal salt per lump clay provides a useful metric for comparing the multimetal salts. For example, in zeta potential titration using an aluminum cation multimetal salt as the heterocoagulation reagent, the ratio of millimoles of aluminum per clay allows for a more direct comparison of different Al-containing heterocoagulation reagents, as shown in the titration curve of fig. 4. The derivation of this value is done by obtaining the aluminum weight percent of the heterocoagulants, which is typically provided directly by the manufacturer or as an equivalent weight percent of aluminum oxide (e.g., al ₂O₃). In the latter case, the weight percent of aluminum may be derived from the product of the weight percent of aluminum oxide and the weight ratio of aluminum in the empirical formula. From this aluminum weight percentage, the molar amount of aluminum heterocoagulation reagent can be determined and the molar mass ratio of aluminum/clay can be obtained.

For example, FIG. 4 shows aluminum hydroxychloride (ACH) expressed in mmol Al/g clay over a desired zeta potential rangeOne ratio of HPM-20 was 1.76mmol Al/g clay. The actual ratio may vary somewhat depending on the batch of aluminum chlorohydrate, the method of preparation, the degree of contamination or aging, and/or the particular batchHPM-20. FIG. 2 shows the United states colloid companyZeta potential titration of HPM-20 (with 22wt.% aluminum chlorohydrate from GEO SPECIALTY CHEMICALS). Thus, mmol Al/g clay can be determined as a point at which the zeta potential of the colloidal material in the mixture drops below +25mV and above-25 mV, for example between about +10mV and-10 mV, thereby providing a heteroaggregated solid that is readily separated by conventional filtration methods, such as using filter paper, as described in detail below. Thus, rapid filtration of the resulting clay heteroadducts can be performed with or without vacuum assistance, belt filters, and the like.

The resulting dispersion of the heteroaggregated clay formed exhibits a zeta potential centered at about zero within the disclosed range, providing an easily separable (easily filterable) heteroadduct. While not limiting the zeta potential range disclosed and claimed herein, and not wishing to be bound by theory, excellent yields and filterability of clay heteroadducts may be obtained when the amount of heteroagglomerating agent combined with colloidal montmorillonite (such as dioctahedral montmorillonite herein) provides a dispersion of particles having a zeta potential near zero such that the particles in the dispersion have little or no electrophoretic mobility. This zero zeta potential point can be considered the nominal target ratio of cationic polymetallic salt to colloidal clay. For example, aspects of electrophoretic mobility are described in Gu et al, clay and Clay minerals, 1990,38, 493-500.

The ratio of the experimentally obtained heterocoagulation reagent (cationic polymetallic salt) to the colloidal clay can be determined by providing a dispersion of the colloidal clay in water, adding the dispersion to a zeta potential measurement vessel, and measuring the initial zeta potential of the clay dispersion. Solutions of the selected heterocoagulants were prepared and added to the dispersion in portions, the zeta potential of the dispersion being measured after each addition. The ratio of cationic polymetallic salt to colloidal clay used to prepare the filterable clay hetero-adducts is calculated by determining from the resulting zeta potential titration curve the ratio of heterocoagulation reagent required to reach zero zeta potential or substantially zero zeta potential.

In another aspect, when the zeta potential titration curve is ambiguous or discontinuous at or near zero potential (mV), extrapolation of the point closest to the zero zeta potential may be used to estimate the crossing point of the zeta potential curve from negative zeta potential to positive zeta potential, describing the nominal target ratio. In another aspect, when the zeta potential titration curve is discontinuous near zero and remains discontinuous at or near the limits of the zeta potential (e.g., ±20mV or ±25 mV), the linear extrapolation between points on the titration curve just before and after the discontinuity can be used to estimate the heterocoagulation reagent to clay ratio to help achieve the desired zeta potential. Examples of zeta probe (zeta potential) titration and determination of nominal target ratios of heterocoagulation reagents to clay are provided in the figures and examples section of this disclosure. See, for example, fig. 2-8, examples 8-12, and example 38.

Aluminum mmol (mmol Al) of aluminum hydroxychloride for preparing clay hetero adducts andThe ratio of grams of HPM-20 colloidal montmorillonite can be significantly less than the ratio of mmol Al/g clay used to prepare pillared HPM-20 clay with aluminum chlorohydrate, sometimes less than an order of magnitude. That is, the same cationic polymetallic salt and colloidal clay are used, but using a mmol Al/g clay ratio in excess of the range of about +25mV to about-25 mV, as determined by the zeta potential of the clay hetero-adduct dispersion, will form a pillared clay. Thus, the ratio of cationic multimetal salt to colloidal clay forming the clay hetero-adducts of the present disclosure is different from the ratios in, for example, U.S. patent application publication nos. 2018/0142047 and 2018/0142048 to w.r.Grace, which employ lanthanide-containing aluminum pillared clay as the carrier-activator.

In contrast, when too low a heterocoagulation reagent to clay ratio is used in the formulation in an attempt to prepare a clay heteroadduct, it is not possible to rapidly filter the resulting contact product by conventional filtration methods. This feature is shown in example 19, where a clay heteroadduct of 0.30mmol Al/g clay formulation was prepared using Aluminum Chlorohydrate (ACH) and HPM-20 clay, when deduced from the zeta potential titration in FIG. 2, the predicted zeta potential was-44 mV. Filtration of the resulting contact product is difficult and separation and preparation of the sample requires centrifugation to isolate the product. For convenience, such products may be referred to herein as "heteroadducts" that are readily filtered even outside the zeta potential range. Similarly, in example 26, a powder was usedThe formulation of 0.30mmol Al/g clay of 51P chlorine hydrate aluminum (PARCHEM FINE AND SPECIALTY CHEMICALS) provides a contact product heteroadduct that is difficult to handle and isolate and requires centrifugation to isolate the product.

Since ions isomorphously displace to one of the "TOT" layers, e.g., al ³⁺ in the octahedral alumina layer is replaced with Mg ²⁺, imparting a negative charge, the starting clay particles, such as montmorillonite, carry a permanent negative charge. Thus, when negatively charged clay particles repel each other and stabilize in a polar aqueous environment, the starting clay forms a dispersion or suspension in the water. While not wishing to be bound by theory, it is believed that contact of cations, such as the cationic polymetallic salts disclosed herein, with negatively charged colloidal clay initially promotes agglomeration of the colloidal clay by coulombic, heterocharge type interactions and neutralization of the clay surface. This neutralization causes precipitation of the clay hetero-adducts from the polar aqueous carrier as large agglomerated or coacervated particles that are readily filtered. When additional cationic multimetal salts are added in excess to the coalescing composition, such as when preparing ion-exchanged, protonic acid-treated, or pillared clays, some or all of the coalescing surfaces may be "reloaded" as positively charged species, thereby being resuspended in a polar carrier such as water. This re-suspension provides a dispersion of highly charged materials that are difficult or impossible to filter out and can clog the filter media. The clay hetero adducts of the present disclosure are formed at ratios below these high ratios, and thus it is believed that reloading and re-suspension of the clay hetero adducts is avoided. Thus, the near zero zeta potential surface of the clay heteroadducts provides a product that is easy to filter and at the same time substantially avoids pillaring of the clay and further avoids a homogeneously intercalated clay structure of the pillared clay and the starting clay. Surprisingly, these structures, even without pillaring, form thermally stable, strong structures that can be used as very active support-activators for metallocenes.

In one aspect, fig. 1 provides a schematic of the practical and desirable aspects of preparing neutral or weakly charged dispersions having low magnitude, near zero or zero zeta potential. Filtration of the clay heteroadducts with these properties proceeds very rapidly and typically requires little continuous filtration to produce a support with the desired surface area, porosity and polymerization activity. In contrast, highly charged dispersions, such as the type obtained from the preparation of pillared clays, are not easy to filter and must be processed using relatively more expensive and cumbersome methods to obtain useful carrier-activators.

Also in comparison to other materials such as those described in U.S. patent application publication nos. 2018/0142047 and 2018/0142048 to Jensen et al, assigned to w.r.Grace, the clay heteroadducts of the present disclosure, after filtration and calcination at 300 ℃ or higher, may exhibit no or substantially no d001 peak of 2θ (2θ) of less than 10 degrees in a powder XRD scan. This characteristic is illustrated by the example in FIG. 2, which shows a powder XRD (x-ray diffraction) pattern of a series of calcined products from the group consisting of Aluminum Chlorohydrate (ACH) andHPM-20 montmorillonite was combined, each sample differing in the amount of cationic polymetallic salt used to prepare the heteroaggregated clay. These samples were prepared according to examples 18, 20-21, 23 and 25, except for the following samples. The sample labeled as derived from a 6.4mmol Al/g clay sample (upper panel) represents a typical preparation of Al ₁₃ pillared clay (see example 5). XRD of the starting clay itself (bottom) was marked as coming from a 0mmol Al/g clay sample (see example 3).

Sample preparation referring again to fig. 2 and examples, examples 12-30 provide the preparation of ACH-clay heteroadducts from 0mmol Al/g clay to 6.4mmol Al/g clay examined in this figure, including some comparative examples. The XRD pattern below about 10 degrees 2 theta in fig. 2 shows that there are two main peaks that vary as the proportion of cationic polymetallic salt in the preparation formulation increases. First, the XRD peak at about 9 degrees 2θ (2θ) corresponding to the starting clay disappears, and as the proportion of cationic polymetallic salt increases, one peak gradually increases from about 9 degrees (2θ) to about 10 degrees (2θ). The disappearance of the 9 degree (2θ) peak appears to indicate the reaction process to form a largely amorphous heteroaggregated clay, and the subsequent 9-10 degree (2θ) peak may represent a simple ion intercalation, such as Al ³⁺ ion intercalation, characterized by a smaller substrate spacing than the original ion-exchanged clay. As more multimetal salt is added to the slurry, a peak grows from about 4 degrees (2θ) to about 6 degrees (2θ), and this peak represents the major product of 6.4mmol Al/g clay. This 4-6 degree (2 theta) peak may correspond to a Keggin ion intercalation pillared structure that forms as the concentration of added multimetal salt increases. At concentrations where the clay of these experiments was not highly diluted (i.e., not less than 1wt.% clay), 6.4mmol Al/g clay product was not easily separated by simple filtration, but had to be separated and washed with multiple centrifugation and decantation steps. In addition, the starting clay colloidal clay as a comparative sample was also not easily filtered.

In one aspect, when Aluminum Chlorohydrate (ACH) is the heterocoagulation reagent and Volclay HPM-20 montmorillonite is the colloidal clay, zeta potential data and XRD data indicate that the zeta potential range of ± 25mV corresponds to a range of about 1mmol Al/g clay to 1.8mmol Al/g clay. Similarly, a zeta potential range of + -15 mV for the less charged clay hetero-adducts corresponds to a range of about 1.3mmol Al/g clay to 1.7mmol Al/g clay. These data also indicate that a zeta potential of 0 (zero) mV, where the clay hetero-adduct is near zero charge, corresponds to about 1.5mmol Al/g clay. FIG. 2 demonstrates that at 1.52mmol Al/g clay, powder XRD shows little or virtually no pillaring (XRD pattern between 4.8 degrees (2. Theta.) and 5.2 degrees (2. Theta.) and little or virtually no simple ion-exchanged clay (XRD pattern between 9 degrees (2. Theta.) and 10 degrees (2. Theta.) relative to the mineral impurities present in the starting colloidal clay in the 2. Theta.) range between 20 and 30 degrees 2. Theta.).

While not wishing to be bound by theory, when using aluminum chlorohydrate and colloidal montmorillonite, the near zero charge of the hetero-adduct provided by the 1.5mmol Al/g clay formulation corresponds to less than half the amount (ratio) of aluminum that may actually be incorporated into the Al ₁₃ -pillared montmorillonite, as well as to a smaller portion of the aluminum used in the pillared formulation. See, e.g., schoonheydt et Al, clay and clay minerals, 1994,42 (5), 518-525, which describe this amount as being about 3-4mmol Al/g clay actually incorporated. As described above, the amount of heterocoagulation reagent providing a zeta potential of 0 (zero) mV heteroadduct (which can be considered a preferred amount of about 1.5mmol Al/g clay) is an order of magnitude less than the amount used for the optimized pillared formulation of 15mmol Al/g clay. Surprisingly, the clay heteroadducts of the present disclosure are characterized by the absence or substantial absence of regularly intercalated pillared structures, however, the clay heteroadducts provide comparable and generally higher activity as metallocene support-activators.

The clay hetero adducts of the present disclosure are not regularly intercalated pillared structures such as those described in U.S. patent application publication nos. 2018/0142047 and 2018/0142048 to Jensen et al. In particular, the clay heteroadducts of the present disclosure are not or substantially not intercalated with regular complex ions ("irregular intercalation"), and the microporous catalytic component comprises a layered colloidal clay having a plurality of pillars intercalated between the swelling molecular layers of the clay. Thus, the clay heteroadducts of the present disclosure are not regularly ordered and there is no evidence of consistent regularity imparted by consistent columns and/or intercalation of consistent aluminum oxides or hydroxides, such as poly-Al ₁₃ columns derived from Al ₁₃ Keggin ions or lanthanide centers in U.S. patent application publication nos. 2018/0142047 and 2018/0142048. However, particularly in some examples of multiple washes and filters, powder XRD peaks may be detected that indicate some pillariing. For example, an XRD pattern for a 1.76mmol Al/g clay sample corresponds approximately to +23mV zeta potential, but the intensity of the peaks is significantly less than for a pillared formulation, for example, using 6.4mmol Al/g and higher clay.

Thus, in another aspect, the calcined clay heteroadducts of the present disclosure are free of ordered domains, as evidenced by the lack of XRD peaks between 0-12 degrees 2θ. This observation emphasizes one difference from simple single-atom ion exchange processes or complex polyatomic ion exchange processes by which sodium ions (e.g., in the starting sodium montmorillonite) are exchanged for divalent, trivalent, or multivalent ions, which upon drying provide ordered and lamellar structures reflecting the simple single-atom ion size or polyatomic ion (such as Al ₁₃ Keggin ions or other pillared species demonstrated by the associated d001 radical spacing in XRD).

In one aspect, the isolated clay heteroadduct is collected, e.g., by filtration, and not washed. In another aspect, the isolated clay heteroadducts are minimally washed, e.g., one or two times with a suitable wash liquid such as water, e.g., just enough to provide some purification benefits. While not wishing to be bound by theory, as described by Schoonheydt et al in clay and clay minerals 1994,42 (5), 518-525, which is incorporated herein by reference, it has been observed that washing promotes pillaring. Thus, washing to the point where pillaring occurs appears to sacrifice the desired clay heteroadduct that separates, forming the undesirable by-product pillared clay.

In another aspect of the present disclosure, and in further contrast to regularly intercalated ion-exchange clays such as those disclosed in U.S. patent application publication nos. 2018/0142047 and 2018/0142048 to Jensen et al, extensive washing of the solid clay heteroadducts of the present disclosure until the resulting wash water exhibits a negative AgNO ₃ test (chloride test) is not necessary to impart high polymerization activity to the clay heteroadducts. In contrast, a single filtration of the direct heteroadduct mixture containing about 5wt.% solids provides good polymerization activity in the final catalyst mixture without the use of a dilute solution. This feature is demonstrated in examples 22, 24, 29-31, 33 and 35-36, etc. For example, examples 22 and 23 differ in the preparation of ACH-clay heteroadducts in whether the product was prepared using one filtration or two filtration, the latter comprising one wash between each filtration. Thus, in example 22, where a clay hetero adduct was prepared using a single filtration, the filtrate obtained from the filtered slurry was characterized by a conductivity of 1988. Mu.S/cm. In contrast, example 23 uses two filtrations and a wash between the two filtrations to prepare a clay hetero-adduct, the filtrate provided is characterized by a conductivity of 87 μs/cm, almost 23 times different. However, the polymerization activity of the catalysts prepared using these support-activators varies by only 10%, which the skilled artisan would consider to be within the variability of laboratory scale polymerization experiments.

Similarly, the polymerization batches using the support-activators of examples 24 and 25 further indicate the economic benefits of the support-activators, wherein once filtration and twice filtration of the clay hetero-adducts again provide substantially the same polymerization activity. Specifically, the catalyst formed from the single filtration support-activator exhibited an activity of 3581g/g/h, while the catalyst formed from the double filtration support-activator exhibited an activity of 3547g/g/h. The conductivity of the slurry of the single filtered product (example 24) was 1500. Mu.S/cm and the conductivity of the final slurry of the two filtered products (example 25) was 180. Mu.S/cm. Thus, it was unexpectedly found that extensive washing of the clay hetero-adducts is not necessary for good polymerization activity (again in contrast to U.S. patent application publication nos. 2018/0142047 and 2018/0142048).

Samples produced according to example 28 (additional washing step) and example 29 (single filtration) using 1.52mmol Al/g clay provided 1404g/g/h and 1513g/g/h of catalyst activity, respectively. In this comparison, a single filtration of the heteroadduct slurry of example 29 at a conductivity of 1750 μS/cm actually provided higher activity than the sample of example 28, where the sample of example 28 was washed and filtered twice after the initial filtration, with a slurry conductivity of 169 μS/cm. In another aspect, and in further contrast to the support-activators of U.S. patent application publication nos. 2018/0142047 and 2018/0142048, it is not necessary to age the clay hetero-adduct slurry of the present disclosure at room temperature or elevated temperature for at least 10 days prior to isolation and use. Instead, the clay hetero-adduct slurry of the present disclosure may be immediately filtered and then dried or calcined to provide a more efficient carrier-activator synthesis.

The formation of heterocoagulants has not been found to be very temperature sensitive because clays form heteroadducts with heterocoagulants over a wide temperature range. For example, the formation of the clay heteroadduct is carried out in the range of about 20 ℃ to about 30 ℃, although a temperature range from almost 0 ℃ to the boiling point of the clay heteroadduct-containing slurry may be used.

The pH of the solution containing the heterocoagulants can be adjusted to provide a minimum zeta potential of the heterocoagulants, which can be readily determined by the experiments described by Goldberg et al in Clay and Clay minerals, 1987,35,220-270. The resulting heteroadducts isolated by this process can also be used with metallocenes for the polymerization of olefins. In addition, this method of adjusting zeta potential can be used where the ratio of heterocoagulants to clay itself does not provide a zeta potential within the range of + -25 mV (or alternatively, + -22 mV, + -20 mV, etc.) disclosed herein and including the range. However, this pH adjustment method requires additional steps in the synthesis and isolation of the clay hetero-adducts, and it has been observed that this method does not guarantee ready filterability or optimal final polymerization activity. While not wishing to be bound by theory, it is believed that in such cases pH adjustment may result in protonated or hydroxylated clays, heterocoagulants, and/or clay heteroadducts, which may affect the properties and final catalytic activity of the clay heteroadducts.

In another aspect, the present disclosure provides for the removal of salts and small amounts of unagglomerated colloidal species formed in the preparation of heterocoagulation products. For example, by washing with water and then simply filtering the heterocondensed product, soluble byproducts such as sodium chloride and the like can be easily removed from the heterocondensed product in addition to a small amount of colloidal material. Washing may be accomplished by re-suspending the isolated heterocoagulated product in water with mechanical agitation or shaking to form a slurry and then filtering again. This process is in contrast to the pillaring process, which typically requires multiple washing and separation steps using high speed centrifugation, decantation, changing the pH of the pillared-clay solution, or large dilution and settling tanks for separating the pillared clay product. Such additional steps increase the time and cost of separating and washing the pillared or chemically treated clay mineral adducts from impurities including their starting components, nano-or micro-sized quartz and other inorganic metal oxides, and the like. Instead, filtration of the clay heteroadducts may be carried out batchwise by sintering glass frit, metal frit, plain filter paper, felt or other filter media, or continuously using a moving belt filter. Filtration is practical because it can be rapid, for example, the time to complete filtration can be as little as one minute or even less, less than or equal to about 5 minutes, less than or equal to about 10 minutes, less than or equal to about 15 minutes, less than or equal to about 30 minutes, less than or equal to about 1 hour, less than or equal to about 2 hours, less than or equal to about 5 hours, less than or equal to about 8 hours, or less than or equal to about 24 hours.

The conductivity of the filtrate or slurry of the clay hetero-adduct can be monitored using a commercially available conductivity meter. In one aspect, when the concentration of the slurry ranges from about 1wt.% to about 10wt.% solids, from about 2.5wt.% to about 10wt.% solids, or from about 5wt.% to about 10wt.% solids, the clay hetero-adduct slurry may be characterized by a conductivity in the range of from about 100 μS/cm (0.1 mS/cm) to about 50,000 μS/cm (50 mS/cm), from about 250 μS/cm to about 25,000 μS/cm, or from about 500 μS/cm to about 15,000 μS/cm, or from about 1,000 μS/cm (1 mS/cm) to about 10,000 μS/cm (10 mS/cm).

If desired, the heterocoagulated solids can be dried via azeotropic methods, as is done in some examples. It is believed that azeotropic drying maintains pore volume and surface area during drying, as compared to simply heating the heterocondensed solid. For example, the filtered montmorillonite heteroadduct may be resuspended in a slurry with a solvent that will lower the boiling point of water in the heterocondensation product. This water lost during drying is characterized by free or chemically bound water. That is, the water lost during drying may result from free water in or on the outer surface of the heteroadduct pores, as well as chemically bound water generated by dehydration of the surface hydroxyl groups during the drying and calcining processes. Various alcohols are used as azeotroping agents including, but not limited to, n-butanol, n-hexanol, isoamyl alcohol, ethanol, and the like, including any combination thereof.

Freeze drying, flash drying, fluid bed drying, or any combination thereof may also be used to remove water from the clay heteroadduct. These methods, whether used alone or in combination, help to maintain pore volume and surface area during the drying process. In another aspect, spray drying of the clay heteroadduct suspension can be used to control the morphology of the support-activator and supported catalyst particles. For example, suspensions of the clay heteroadducts in aqueous or organic solvents or combinations of water and organic solvents may be spray dried. Dry or wet milling and sieving can be used to refine the morphology, particle size and particle size distribution of the heteroaggregated clay. These methods may be employed alone or in combination to obtain the desired carrier-activator particle morphology, particle size, and particle size distribution of the clay heteroadduct. Spray drying and/or sieving of the clay heteroadducts may be used, as may other methods known to those skilled in the art to remove fines or larger particles that may be problematic in transporting or using the heteroadducts as carrier-activators.

The heterocondensed solids may be calcined or heated in a fluidized bed, for example, at a temperature in the range of about 100 ℃ to about 900 ℃. For example, the heteroaggregated montmorillonite clay may be calcined or heated in a fluidized bed at a temperature of from about 100 ℃ to about 900 ℃, from about 200 ℃ to about 800 ℃, from about 250 ℃ to about 600 ℃, or from about 300 ℃ to about 500 ℃. Calcination may be carried out in an atmospheric environment (air), e.g., calcination may be carried out in dry air at a temperature in the range of at least 110 ℃, e.g., the temperature may be in the range of about 200 ℃ to about 800 ℃ for a time in the range of about 1 minute to about 100 hours. For example, the montmorillonite heteroadduct may be calcined using any of the following conditions: a) A temperature in the range of about 110 ℃ to about 600 ℃ for a time in the range of about 1 hour to about 10 hours; b) A temperature in the range of about 150 ℃ to about 500 ℃ for a time in the range of about 1.5 hours to about 8 hours; c) The temperature ranges from about 200 ℃ to about 450 ℃ and the time ranges from about 2 hours to about 7 hours.

The clay heteroadducts may also be calcined at a temperature of about 225 ℃ to about 700 ℃ for a period of time in the range of about 1 hour to about 10 hours, most preferably at a temperature of about 250 ℃ to about 500 ℃ for a period of time in the range of about 1 hour to about 10 hours. Alternatively, the temperature range of calcination in air may be 200 ℃ to 750 ℃, 225 ℃ to 700 ℃, 250 ℃ to 650 ℃, 225 ℃ to 600 ℃, 250 ℃ to 500 ℃, 225 ℃ to 450 ℃, or 200 ℃ to 400 ℃. As mentioned above, the calcination temperature is selected from any single temperature or range between two temperatures, for example, temperatures in the range of 110 ℃ to 800 ℃ separated by at least 10 ℃ (i.e., 10 degrees celsius) can be used to develop the final catalytic activity.

The heat treatment (such as calcination) may be performed in an ambient atmosphere or under other conditions conducive to removal of water, for example, calcination may be performed in a carbon monoxide atmosphere. The use of such an atmosphere allows for more efficient removal of surface hydroxyl groups at lower temperatures than those used in ambient air calcination processes, thereby maintaining a larger pore volume and surface area during surface dehydration. After calcination, the heteroaggregated product may be described as a continuous, amorphous combination of clay and inorganic oxide particles, which we refer to herein as an activator-support or support-activator.

Determination of the total porosity, pore volume distribution, and surface area of the activator-support of the present disclosure can be accomplished by any method known in the art, for example, analysis using nitrogen adsorption-desorption measurements. The adsorption isotherm or desorption isotherm, respectively, depicts the volume of gas (nitrogen in this case) adsorbed to or desorbed from the surface of the analyte (clay heteroadduct) as the pressure increases or decreases at a constant temperature. The isotherm data can be analyzed using the BJH method to determine the total pore volume and produce a pore size distribution as follows, and the BET method can be used to analyze the isotherm data to determine the surface area.

Heterocondensation of montmorillonite clay can provide an activator support that has substantial porosity and exhibits catalyst activation properties when combined with a metallocene or other organic transition metal compound capable of polymerizing olefins. In one aspect, the calcined clay heteroadduct may exhibit a BJH porosity in the range of about 0.2cc/g to about 3.0cc/g, about 0.3cc/g to about 2.5cc/g, or about 0.5cc/g to about 1.8 cc/g. The calcined clay heteroadducts may also exhibit BJH porosities greater than or equal to 0.5cc/g. Calcined clay heteroadducts having porosities as low as about 0.2cc/g may be used, e.g., BJH porosities exhibit heteroadducts in the range of about 0.2cc/g to about 0.5cc/g, but clay heteroadducts having porosities less than about 0.2cc/g may exhibit lower polymerization activities, e.g., <200g PE/g support-activator/hour, when combined with a metallocene such as bis (1-butyl-3-methylcyclopentadienyl) zirconium dichloride to prepare a catalyst system. In the present disclosure, the term "g support-activator" refers to the grams of calcined clay heteroadduct used to prepare the catalyst.

A comparison of BJH porosities for clay and clay hetero-adducts is presented in fig. 10, 11 and 12. The BJH pore volume analysis of the calcined but not azeotroped and untreated starting montmorillonite with the heterocoagulant is presented in fig. 11 (example 1). Pore volume analysis of the sheared, then azeotroped and calcined starting montmorillonite without treatment with the heterocoagulant is presented in fig. 12 (example 3). Finally, pore volume analysis of the Aluminum Chlorohydrate (ACH) heteroaggregated clay of example 18 (1.76 mmol Al/g clay) is presented in fig. 10. Thus, calcined montmorillonite (such as bentonite) BJH can have a BJH porosity of about 0cc/g to about 0.2cc/g without the heterocoagulation reagent.

The cumulative pore volume between specific pore size boundaries can be determined using a BJH method derived pore volume distribution. Method for determining cumulative pore volume between pore size X nm (nanometers) and Y nm (V _X-Ynm), where X nm is the lower limit of pore size and Y is the upper limit of pore size: the total cumulative pore volume of pore diameters 0nm to Y nm was subtracted from the total cumulative pore volume of pore diameters 0nm to X nm. In the event that the total cumulative pore volume of either the upper or lower pore size limit is not available, the pore volume is estimated by linear interpolation between the two closest pore size points used to obtain the cumulative pore volume data.

In one aspect of the calcined clay heteroadduct, the total or cumulative pore volume (V _3-10nm, or "small mesopores") of the pores having a diameter of 3-10nm can comprise <55% of the cumulative pore volume (V _3-30nm) of the pores of 3-30 nm. In another aspect, V _3-10nm can comprise <50% of the cumulative pore volume V _3-30nm, or alternatively, V _3-10nm can comprise <40% of the cumulative pore volume V _3-30nm. This feature is shown in the data of fig. 10, which shows a BJH pore volume analysis of the montmorillonite heteroadduct of example 18, where V _3-10nm has a value of about 0.33 (V _3-30nm). This pore volume analysis is in contrast to the BJH pore volume analysis of untreated zeotropic clay (example 1, fig. 11) and the BJH pore volume analysis of azeotropic clay (example 3, fig. 12), both characterized by V _3-10nm of greater than 0.55 (V _3-30nm).

These pore volume characteristics of the clay hetero adducts of fig. 10 of the present disclosure are in contrast to those of the acid treated clay of us patent 9,751,961 to Murase et al, which discloses that the sum of the pore volumes of pores having diameters of 2nm to 10nm (V _2-10nm) is 60% -100% of the total volume of the mesopores (i.e., all 2nm to 50nm pores). (see FIG. 1 and Table 1 of U.S. Pat. No. 9,751,961). In particular, murase et al disclose that the smaller mesopores of 2nm to 10nm account for a majority of the total mesopore volume (2 nm to 50 nm), which can be calculated by, for example, V _2-10nm+V_10-30nm+V_30-50nm. In contrast, the clay hetero-adducts of the present disclosure are characterized by V _10-30nm alone exceeding the smaller mesopore volume V _3-10nm. While not wishing to be bound by theory, it is believed that in the present disclosure, the increased proportion of larger mesopores to total porosity facilitates diffusion of the metallocene compound and proximity to ionization sites on the clay hetero-adduct surface. This is believed to be in contrast to smaller mesopores which may hinder or even preclude diffusion of the metallocene to the surface containing the ionization sites, especially for metallocenes having a radius of gyration exceeding the minimum end of the mesopore diameter.

In addition, as shown, for example, in U.S. patent No. 6,677,411, the pore size distribution determined by the BJH method can be depicted by plotting dV (log D) versus pore size. The diameter showing the highest value of this function can be denoted by D _M and is considered the most commonly occurring pore size. That is, D _M is the one corresponding toAndThe diameter of the point with the highest DV value (log D) in the region between the apertures. The ordinate value of D _M is the maximum value, denoted by the term D _VM. In one aspect, this log differential pore volume distribution generally has aboutTo about(Angstrom) local maxima. This local maximum density may also be the global maximum density D _VM. In one aspect, the intensity at D _VM may be at most betweenAndAbout 200% of the intensity of the dV (log D) maximum between. Alternatively, the intensity at D _VM may be at most betweenAndAbout 120% of the intensity of the dV (log D) maximum between. Alternatively, the intensity at D _VM may still be at most betweenAndAbout 100% of the intensity of the dV (log D) maximum between. On the other hand betweenAndThe maximum value of dV (log D) in between exceeds the value in betweenAndAll dV (log D) values in between. This is in contrast to, for example, the acid treated clay of U.S. patent number 6,677,411 to Uchino et al, which is incorporated herein by reference, wherein the maximum D _VM value observed in the log differential pore size distribution of the ideal embodiment has a value betweenAndRelated diameter D _M therebetween.

Similarly, casty et al describe in U.S. Pat. No. 7,220,695 a preferred embodiment of the treated clay activator in which the diameter D _M, which exhibits the maximum D _VM value, is betweenAnd(Angstrom) between. In contrast, the most commonly occurring pore diameters D _M of the clay hetero adducts of the present disclosure are inTo the point ofWithin (2) or within (2)To the point ofWithin a range of (2).

Furthermore, the differential logarithmic pore volume distribution in U.S. patent number 6,677,411 demonstrates thatTo the point ofIn contrast to the range of the present invention,AndThe intensity in the range is significantly lower.AndThe maximum value of dV (log D) in the range is usually less thanAnd10% Of the maximum value of dV (log D) in the range. In contrast, the clay hetero adducts of the present disclosure may provideAndMaximum in-range dV (log D), which is generally greater thanAnd100% Of the maximum value of dV (log D) in the range. While not wishing to be bound by theory, it is desirable that a greater proportion of larger mesopores be present in the clay hetero-adducts of the present disclosure, as the metallocene diffuses more readily to the ionization sites of the support-activator.

F. filterability of montmorillonite heteroadducts

The clay heteroadducts prepared in slurry form in accordance with the present disclosure exhibit unexpectedly improved ease of separation over similar pillared clays prepared using the same montmorillonite clay and heteroagglomerating agent over the zeta potential range. In particular, unlike pillared clays, the clay heteroadducts can be rapidly isolated by filtration. This enhanced filterability is observed and quantified, for example, by comparing the settling rate of a slurry of a clay heteroadduct to the settling rate of a similar pillared clay prepared using the same clay and a slurry containing the same amount of clay.

Table 1 sets forth a comparison of slurry settling rates between pillared clay and heteroaggregated clay (each prepared with 5wt.% of an aqueous HPM-20 clay dispersion). Each slurry was prepared as in the reference example and added to a graduated cylinder and the sedimentation rate was measured as a function of time based on the observed volume of the substantially transparent layer (no turbidity of the visible colloidal particles on top of the slurry). In this comparison, the settling rate of the heteroaggregated clay is significantly faster, e.g., 5 times faster by volume. While not wishing to be bound by theory, it is believed that "increasing the particle size of the heteroaggregated clay dispersion, which increases the zeta potential by a relatively narrow range of about 0mV, e.g., in the range of about ±10mv, relative to the pillared clay particles facilitates flocculation, whereas the pillared clay particles tend to remain dispersed.

TABLE 1 comparison of slurry settling rates between pillared and heteroaggregated clays (each prepared with 2.5wt.% of an aqueous HPM-20 clay dispersion)

Thus, one method employed to evaluate filterability of a heteroaggregated clay slurry as "easy to filter" is to examine the settling rate of the slurry as compared to the settling rate of a pillared clay slurry. In one aspect, if the settling rate of 2.5wt.% of the water-based heteroadduct slurry (as explained in the present disclosure) is 3 times, 3.5 times, 4 times, 4.5 times, 5 times, 6 times, 7 times, 8 times, 9 times, or 10 times or more the settling rate of 2.5wt.% of the water-based pillared clay slurry (prepared using the same colloidal montmorillonite clay, the same heteroagglomerating agent, and the same liquid carrier), then the composition (such as the clay heteroadduct) is easy or easy to filter, wherein the settling rates of 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 after the initiation of the settling test are compared.

As shown in table 2, additional evidence of filterability was observed by quantifying the filtration rate or filtration speed of the clay slurry. When the pillared clay slurry and the heteroaggregated clay slurry (each using 5g of clay) were prepared to have a total mass of 250g and filtered, the heteroaggregated clay slurry was rapidly filtered, the filtrate water was rapidly separated, and the filtration rate of the pillared clay slurry was slow exceeding 80%. Also, while not wishing to be bound by theory, it is believed that the increased particle size of the flocculated heterocohesive clay allows for easy separation of the heterocohesive clay particles from the water, while the smaller particle size of the pillared clay results in a slow filter paper plugging and separation, as the plugged filter needs to be replaced, thus requiring longer filtration times and continuous filtration to effect preparative scale separation of the pillared clay.

TABLE 2 comparison of filtration rates between pillared and heterocoagulated clay slurries (each prepared with 2.0wt.% of HPM-20 clay aqueous dispersion)

Thus, in one aspect, the present disclosure provides other methods of quantifying filterability of a heteroadduct slurry, indicating that the slurry can be considered to be easy to filter and easy to filter. In one aspect, the composition (such as a clay heteroadduct) is easy or easy to filter if the slurry is characterized by the following filtration behavior:

[a] when 2.0wt.% of the water-based heteroadduct slurry is filtered over a period of 0 to 2 hours after contacting step b) (i.e., after initial formation of the heteroadduct slurry), the proportion of filtrate obtained using vacuum filtration or gravity filtration over a filtration time of 10 minutes (based on the weight of liquid carrier in the montmorillonite heteroadduct slurry) is within the following range: (1) From about 50% to about 100% by weight of the liquid carrier in the pre-filtration slurry, i.e., the initial slurry water weight; (2) about 60% to about 100% by weight of the liquid carrier in the slurry; (3) About 70% to about 100% by weight of the liquid carrier in the slurry, or (4) about 80% to about 100% by weight of the liquid carrier in the slurry prior to filtration; and

[B] Upon evaporation, the filtrate in the heteroadduct slurry yields a solid comprising <20%, <15% or <10% of the initial total weight of clay and heterocoagulants.

The feature of filtering from 0 to 2 hours after initial formation is specified, as some non-heteroadduct slurries (including some pillared clay slurry compositions) can be filtered more quickly after the slurry has passed through an initial settling period of several days.

In the example used to generate the data of table 2, the heteroadduct slurry and pillared clay slurry were filtered using a 20 micron filter within minutes after the contacting step between the colloidal clay and the multimetal salt. At 10 minutes after the start of vacuum filtration, substantially all of the water in the heteroadduct slurry has been filtered out, while at 10 minutes after the start of vacuum filtration, substantially no water in the pillared clay slurry has been filtered out. By using a combination of the above two features to evaluate "easy filtration", it is not necessary to specify a filter pitch (e.g., 20 μm), nor is it necessary to specify filtration or use gravity filtration or vacuum filtration. That is, one of ordinary skill can readily identify a filter having a particular opening size, such as the 20 μm filter used in the examples, that meets both criteria for the clay heteroadduct, but no filter size that meets both criteria for the pillared clay.

As an example of applying this "easy-to-filter" test, if a filter with too large an opening between the filter media is used so that the pillared clay filtration meets the requirements of part [ a ] of the above criteria, it will not meet the requirements of part [ b ] and is not considered easy-to-filter. With such larger filter sizes, the clay hetero-adducts also do not meet the requirements of part [ b ], but reducing the filter size (e.g., to about 20 μm) would allow the clay hetero-adducts to meet both criteria [ a ] and [ b ], while the pillared clay does not meet the requirements of part [ a ] when the filter size is reduced, because the filter would plug and hardly filter the liquid vehicle.

Also, gravity filtration or vacuum filtration can be used for the "easy-to-filter" test, since at the point in time at which the filtrate is measured (10 minutes after the start of filtration), the ordinarily skilled artisan can readily determine the appropriate filter size, which will cause the clay heteroadduct to meet criteria [ a ] and [ b ], while the pillared clay will not meet at least one of criteria [ a ] and [ b ].

In another aspect, another method of quantifying filterability is as follows. A composition (such as a clay heteroadduct) may be considered to be easy to filter or easy to filter if the slurry is characterized by the following filtering behavior:

[a] Filtering the 2.0wt.% aqueous heteroadduct slurry over a period of 0 to 2 hours after contacting step b) to provide a first filtrate, the weight ratio of the second filtrate to the first filtrate being 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, wherein the second filtrate is a 2.0wt.% pillared clay slurry prepared by filtering using colloidal montmorillonite clay, heteroagglomerating agent, and liquid carrier, and measuring the weight of the first filtrate and the weight of the second filtrate after the same filtration time (5 minutes, 10 minutes, or 15 minutes); and

Thus, this test compares the filtrate collected from the slurry of the heteroadduct with the pillared clay, while the previous test compared the filtrate collected from the slurry of the heteroadduct with the aqueous carrier in the initial slurry.

G. metallocene compound

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

The support-activators of the present disclosure can be used with a metallocene compound (also referred to herein as a metallocene catalyst) and a cocatalyst (such as an organoaluminum compound), with the resulting composition exhibiting catalytic polymerization activity in the absence or substantial absence of ion-exchange, protonic acid treatment or pillared clay, or aluminoxane or borate activators. Previously, activators such as aluminoxane or borate activators have been considered necessary to achieve polymerization catalytic activity with metallocene or single site or coordination catalyst systems. However, if it is desired to impart a metallocene-activatable alkyl ligand, the combination of the heteroadduct carrier-activator, the metallocene, and the cocatalyst (e.g., an alkylaluminum compound) creates the need for an active catalyst requiring additional activators (e.g., aluminoxane or borate activators).

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

In one aspect, the metallocene may be a group 3 to group 6 transition metal containing metallocene or a lanthanide metal containing metallocene or a combination of more than one metallocene. For example, the metallocene may comprise a group 4 transition metal (titanium, zirconium or hafnium). In another aspect, the metallocene compound may comprise, consist essentially of, or may be of one compound or a combination of compounds, each independently having the formula:

(X ¹)(X²)(X³)(X⁴) M in which

A) M is selected from titanium, zirconium or hafnium;

b) X ¹ is selected from the group consisting of substituted or unsubstituted cyclopentadienyl, indenyl, fluorenyl, pentadienyl, allyl, boro-negative heteroaryl, 1, 2-azaborolidienyl, or 1, 2-diaza-3, 5-diboronyl, wherein any substituent is independently selected from the group consisting of halide, C ₁-C₂₀ hydrocarbyl, C ₁-C₂₀ heterohydrocarbyl, C ₁-C₂₀ organoheteroaryl, fused C ₄-C₁₂ carbocyclic moiety, or fused C ₄-C₁₁ heterocyclic moiety having at least one heteroatom independently selected from the group consisting of: nitrogen, oxygen, sulfur or phosphorus;

c) X ² is selected from: [1] a substituted or unsubstituted cyclopentadienyl, indenyl, fluorenyl, pentadienyl, or allyl group, wherein any substituent is independently selected from the group consisting of a halide, a C ₁-C₂₀ hydrocarbon group, a C ₁-C₂₀ heterohydrocarbon group, or a C ₁-C₂₀ organoheteroaryl group; or [2] a halide, hydride, C ₁-C₂₀ hydrocarbyl, C ₁-C₂₀ heterohydrocarbyl, C ₁-C₂₀ organoheteroaryl, fused C ₄-C₁₂ carbocyclic moiety, or fused C ₄-C₁₁ heterocyclic moiety having at least one heteroatom independently selected from: nitrogen, oxygen, sulfur or phosphorus;

d) Wherein at least one linker substituent having 2 to 4 bridging atoms independently selected from C, si, N, P or B optionally bridges X ¹ and X ², wherein each of the bridging atoms may be unsubstituted (bonded to H) or substituted with a non-bridge ad valorem, wherein any substituent is independently selected from a halide, a C ₁-C₂₀ hydrocarbyl, a C ₁-C₂₀ heterohydrocarbyl, or a C ₁-C₂₀ organoheteroatom, and wherein any hydrocarbyl, heterohydrocarbyl, or organoheteroatom substituent may form a saturated or unsaturated cyclic structure with bridging atoms or X ¹ or X ²;

e) [1] X ³ and X ⁴ are independently selected from the group consisting of halides, hydrides, C ₁-C₂₀ hydrocarbyl, C ₁-C₂₀ heterohydrocarbyl or C ₁-C₂₀ organoheteroaryl; [2] [ GX ^A _kX^B _4-k ] -, where G is B or Al, k is a number from 1 to 4, and X ^A is independently selected at each occurrence from H or a halide, and X ^B is independently selected at each occurrence from C ₁-C₁₂ hydrocarbyl, C ₁-C₁₂ heterocarbyl, C ₁-C₁₂ organoheterocarbyl; [3] X ³ and X ⁴ together are a C ₄-C₂₀ polyene; Or [4] X ³ and X ⁴ together with M form a substituted or unsubstituted, saturated or unsaturated C ₃-C₆ metallocycle moiety, wherein any substituent on said metallocycle moiety is independently selected from the group consisting of a halide, a C ₁-C₂₀ hydrocarbyl group, c ₁-C₂₀ heterocarbyl or C ₁-C₂₀ organoheterocarbyl.

According to another aspect, if desired, X ¹ and X ² may be bridged by a linker substituent selected from the group consisting of:

a)>EX⁵ ₂、-EX⁵ ₂EX⁵ ₂-、-EX⁵ ₂EX⁵EX⁵ ₂- Or > c=cx ⁵ ₂, wherein E is independently selected at each occurrence from C or Si;

b) -BX ⁵-、-NX⁵ -or-PX ⁵ -; or (b)

c)[-SiX⁵ ₂(1,2-C₆H₄)SiX⁵ ₂-]、[-CX⁵ ₂(1,2-C₆H₄)CX⁵ ₂-]、[-SiX⁵ ₂(1,2-C₆H₄)CX⁵ ₂-]、[-SiX⁵ ₂(1,2-C₂H₂)SiX⁵ ₂-]、[-CX⁵ ₂(1,2-C₆H₄)CX⁵ ₂-] Or [ -SiX ⁵ ₂(1,2-C₆H₄)CX⁵ ₂ - ];

Wherein X ⁵ is independently at each occurrence selected from H, a halide, a C ₁-C₂₀ hydrocarbyl, a C ₁-C₂₀ heterohydrocarbyl, or a C ₁-C₂₀ organoheteroaryl;

And wherein any of the substituents X ⁵ selected from hydrocarbyl, heterohydrocarbyl or organoheteroaryl substituents may form a saturated or unsaturated cyclic structure with the bridging atom, another X ⁵ substituent, X ¹ or X ².

Examples of suitable linker substituents that may bridge X ¹ and X ² include C ₁-C₂₀ hydrocarbylene, C ₁-C₂₀ hydrocarbylene, C ₁-C₂₀ heterohydrocarbylene, C ₁-C₂₀ heterohydrocarbylene, C ₁-C₂₀ heterohydrocarbylene, or C ₁-C₂₀ heterohydrocarbylene. For example, X ¹ and X ² may be bridged by at least one substituent having the formula: EX ⁵ ₂,-EX⁵ ₂EX⁵ ₂ -, or-BX ⁵ -, wherein E is independently C or Si, X ⁵ is independently at each occurrence selected from the group consisting of a halide, a C ₁-C₂₀ aliphatic, a C ₆-C₂₀ aromatic, a C ₁-C₂₀ heteroaliphatic, a C ₄-C₂₀ heteroaromatic, or a C ₁-C₂₀ organohetero group.

Aspects of the disclosure list in part additional descriptions and choices regarding the linking moiety between X ¹ and X ², regarding X ⁵, and regarding particular linker substituents or X ⁵ substituents.

Additional descriptions and choices of X ¹ and X ² are also set forth in the aspects of the disclosure, including the particular substituents on X ¹ and X ².

Additional descriptions and choices of X ³ and X ⁴ are also set forth in the aspects of the disclosure, including the particular substituents on X ³ and X ⁴.

Aspects of the present disclosure also provide, in part, some specific examples of metallocene compounds for use in combination with the support-activators of the present disclosure.

Those skilled in the art are aware of metallocene compounds and will recognize and understand the methods of making and using metallocenes in olefin polymerization catalyst systems. Many metallocene and organic transition metal compound fabrication processes are known in the art, such as the following disclosures: U.S. Pat. nos. 4,939,217; 5,210,352 th sheet; 5,436,305 th sheet; 5,401,817 th sheet; 5,631,335, 5,571,880; 5,191,132 th sheet; 5,480,848 th sheet; 5,399,636; 5,565,592; 5,347,026 th sheet; 5,594,078 th sheet; 5,498,581 th sheet; 5,496,781; 5,563,284 th sheet; 5,554,795 th sheet; 5,420,320 th sheet; 5,451,649; 5,541,272 th sheet; 5,705,478 th sheet; 5,631,203 th sheet; 5,654,454; 5,705,579 th sheet; 5,668,230 th sheet; 9,045,504 and 9,163,100 and U.S. patent application publication 2017/0342175, the entire disclosures of which are incorporated herein by reference.

H. Co-catalyst

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 carrier-activator as described herein. Cocatalysts include compounds such as trialkylaluminum, which are believed to impart a ligand to the metallocene that can initiate polymerization when the metallocene is otherwise activated with a support-activator. Cocatalysts may be considered optional, for example, where the metallocene may already include a polymerizable activating/priming ligand (such as methyl or hydride). It will be appreciated that even when the metallocene compound includes, for example, a polymerizable activating/priming ligand, the cocatalyst can be used for other purposes, such as scavenging moisture from the polymerization reactor or process. Thus, the cocatalyst may comprise or be selected from, for example, alkylating, hydrogenating or silylating agents. The metallocene compound, the support-activator and the cocatalyst may be contacted in any order.

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

Aspects of the present disclosure list, in part, additional descriptions and choices of organoaluminium compounds, organoboron compounds, organozinc compounds, organomagnesium compounds, and organolithium compounds.

In one aspect, for example, the cocatalyst can comprise, consist essentially of, or consist of at least one organoaluminum compound, which can independently have the formula Al(X^A)_n(X^B)_m、M^x[AlX^A ₄]、Al(X^C)_n(X^D)_3-n、M^x[AlX^C ₄],, i.e., can be a neutral molecular compound or an ionic compound/salt of aluminum, wherein each variable of these formulas is defined in the aspects of this disclosure. For example, the cocatalyst can comprise, consist essentially of, or consist of trimethylaluminum, triethylaluminum (TEA), tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, ethyl- (3-alkylcyclopentadiyl) aluminum, ethoxydiethylaluminum, diisobutylaluminum hydride, triisobutylaluminum (TIBAL), diethylaluminum chloride, ethyl- (3-alkylcyclopentadiyl) aluminum, and the like, including any combination thereof.

In another aspect, for example, the promoter may comprise, consist essentially of, or consist of at least one organoboron compound, which may independently have the formula B (X ^E)_q(X^F)_3-q or M ^y[BX^E ₄), i.e., may be a neutral molecular compound or ionic compound/salt of boron, wherein each of these formulas is defined in the aspects of the disclosure, e.g., the promoter may comprise trimethylboron, triethylboron, tripropylboron, tributylboron, trihexylboron, trioctylboron, diethylethoxyboron, diisobutylboron hydride, triisobutylboron, diethylboron chloride, di-3-pinan-ylborane, pinacolborane, catecholborane, lithium borohydride, lithium triethylborohydride, and the like, in another aspect, the promoter may comprise or may be a halogenated organoboron compound, such as a fluorinated organoboron compound, examples of which include tris (pentafluorophenyl) boron, tris [3, 5-bis (trifluoromethyl) phenyl ] boron, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate, lithium tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis [3, 5-bis (trifluoromethyl) phenyl ] borate, triphenylcarbonium tetrakis [3, 5-bis (trifluoromethyl) phenyl ] borate, and any combination or mixture thereof.

In another aspect, for example, the cocatalyst can comprise, consist essentially of, or consist of at least one organozinc or organomagnesium compound that can independently have the formula M ^C(X^G)_r(X^H)_2-r, wherein each variable of this formula is defined in the aspects of the disclosure. For example, the promoter may comprise, consist essentially of, or be selected from the group consisting of dimethyl zinc, diethyl zinc, diisopropyl zinc, dicyclohexyl zinc, diphenyl zinc, butylethylmagnesium, dibutylmagnesium, n-butyl-sec-butylmagnesium, dicyclopentadiene-based magnesium, ethylmagnesium chloride, butylmagnesium chloride, and the like, including any combination thereof.

In another aspect, for example, the promoter may comprise, consist essentially of, or consist of at least one organolithium compound, which may independently have the formula Li (X ^J), wherein each variable of the formula is defined in the aspects of the disclosure. For example, the promoter may comprise, consist essentially of, or be selected from methyl lithium, ethyl lithium, propyl lithium, butyl lithium (including n-butyl lithium and t-butyl lithium), hexyl lithium, isobutyl lithium, and the like, or any combination thereof.

I. Optional co-activator

In one aspect, if desired, other activators may be used in the catalyst compositions of the present disclosure in addition to the calcined montmorillonite hetero adduct activator support. These are referred to as co-activators, examples of which include, but are not limited to, ion-exchanged clays, proton acid treated clays, pillared clays, alumoxanes, borate activators, aluminate activators, ionizing ionic compounds, solid oxides treated with electron withdrawing anions, or any combination thereof.

Aspects of the present disclosure detail additional descriptions and options for each optional co-activator.

Aluminoxane. Aluminoxanes (also known as poly (hydrocarbylaluminum oxides) or organoaluminoxanes) can be used in contact with other catalyst components, for example, in any solvent that is substantially inert to the reactants, intermediates, and products of the activation step, such as saturated hydrocarbon solvents or solvents, such as toluene. The catalyst composition formed in this way may be isolated if desired or introduced into the polymerization reactor without isolation.

As understood by those skilled in the art, aluminoxanes are oligomers in which the aluminoxane compounds can comprise linear structures, cyclic or cage structures, or mixtures thereof. For example, the cyclic aluminoxane compound has the formula (R-Al-O) _n, where R can be a straight or branched alkyl group having from 1 to about 12 carbon atoms and n can be an integer from 3 to about 12. The (AlRO) _n moiety also constitutes a repeating unit of a linear aluminoxane, for example having the formula: r (R-Al-O) _nAlR₂, wherein R may be a straight or branched alkyl group having from 1 to about 12 carbon atoms and n may be an integer from 1 to about 75. For example, the R group may be a straight or branched C ₁-C₈ alkyl group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl, where n may represent an integer from 1 to about 50. Depending on how the organoaluminoxane is prepared, stored, and used, the value of n can vary in a single sample of aluminoxane, and combinations or populations of such organoaluminoxane species are typically present in any sample.

The organoaluminoxanes can be prepared by various procedures known in the art, for example, those disclosed in U.S. Pat. nos. 3,242,099 and 4,808,561, each of which is incorporated herein by reference in its entirety. In one aspect, the aluminoxane can be prepared by reacting water in an inert organic solvent with an alkylaluminum compound such as AlR ₃ to form the desired organoaluminoxane compound. Alternatively, the organoaluminoxane can be prepared by reacting an alkylaluminum compound such as AlR ₃ with a hydrated salt such as hydrated copper sulfate in an inert organic solvent.

In one embodiment, the aluminoxane compound can be methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, isopropylluminoxane, n-butylaluminoxane, tert-butylaluminoxane, sec-butylaluminoxane, isobutylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane, neopentylaluminoxane, or a combination thereof. In one aspect, methylaluminoxane (MAO), ethylaluminoxane (EAO) or Isobutylaluminoxane (IBAO) may be used as optional cocatalyst, and these aluminoxanes may be prepared from trimethylaluminum, triethylaluminum or triisobutylaluminum, respectively. These compounds may be complex compositions sometimes referred to as poly (methyl alumina), poly (ethyl alumina) and poly (isobutyl alumina), respectively. In another aspect, the aluminoxane can be used in combination with a trialkylaluminum, as disclosed in U.S. Pat. No. 4,794,096, which is incorporated herein by reference in its entirety.

In preparing a catalyst composition comprising an optional aluminoxane, the molar ratio of aluminum present in the aluminoxane to the metallocene compound in the composition can be lower than the typical molar ratio used in the absence of the support-activator of the present disclosure. In the absence of the support-activator of the present disclosure, the amount of aluminoxane can be, for example, from about 1:10 mole Al/mole metallocene (mole Al/mole metallocene) to about 100,000:1 mole Al/mole metallocene or from about 5:1 mole Al/mole metallocene to about 15,000:1 mole Al/mole metallocene. When used in combination with the disclosed support-activators, the relative amounts of aluminoxanes can be reduced. For example, the optional aluminoxane amount added to the polymerization zone can be less than the typical amount previously in the range of from about 0.01mg/L to about 1000mg/L, from about 0.1mg/L to about 100mg/L, or from about 1mg/L to about 50 mg/L. Alternatively, the aluminoxane may be used in the amounts typically used in the prior art, but the support-activators of the present disclosure are additionally used to obtain further advantages of such combinations.

An organoboron compound. In addition to the components detailed (support-activator, metallocene, and optional cocatalyst), the catalyst compositions of the present disclosure may also comprise an optional organoboron co-activator, if desired. In one aspect, the organoboron compound may comprise or be selected from a neutral boron compound, a borate, or a combination thereof. For example, the organoboron compound may comprise or be selected from fluoroorganoboron compounds, fluoroorganoborate compounds, or combinations thereof, and any such fluorine compounds known in the art may be used.

Thus, the term fluoroorganoboron compound is used herein to refer to neutral compounds in the form of BY ₃ and the term fluoroorganoborate compound is used herein to refer to monoanionic salts of fluoroorganoboron compounds in the form of [ cation ] ⁺[BY₄]^-, wherein Y represents a fluorinated organic group. For convenience, fluoroorganoboron and fluoroorganoborate compounds are commonly referred to collectively as organoboron compounds, or any of these designations will be used as the context requires.

In one aspect, examples of fluoroorganoboron compounds useful as co-activators include, but are not limited to, tris (pentafluorophenyl) boron, tris [3, 5-bis (trifluoromethyl) phenyl ] boron, and the like, including mixtures thereof. Examples of fluoroorganoborate compounds useful as optional co-activators include, but are not limited to, fluorinated arylborates such as N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate, lithium tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis [3, 5-bis (trifluoromethyl) phenyl ] borate, triphenylcarbonium tetrakis [3, 5-bis (trifluoromethyl) phenyl ] borate, and the like, including mixtures thereof.

Additional description and options for optional fluoroorganoboron and fluoroorganoborate compound co-activators are detailed in the aspects of this disclosure.

While not intending to be bound by theory, it is believed that these fluoroorganoborates and fluoroorganoboron compounds form weakly coordinating anions when combined with metallocene compounds, as disclosed in U.S. Pat. No. 5,919,983, which is incorporated herein by reference in its entirety.

In general, any amount of organoboron compound may be used as an optional co-activator. For example, in one aspect, the molar ratio of organoboron compound to metallocene compound in the composition can be from about 0.1:1 moles of organoboron or organoborate compound (mol/mol) to about 10:1mol/mol, or from about 0.5mol/mol to about 10mol/mol (moles of organoboron or organoborate compound per mole of metallocene), or alternatively in the range of from about 0.8mol/mol to about 5mol/mol (moles of organoboron or organoborate compound per mole of metallocene). However, it should be understood that the amount of clay hetero-adduct carrier-activator, if present, may be reduced or adjusted downwardly.

An ionizing compound. In another aspect, optional co-activators that may be used in addition to the enumerated components of the catalyst composition of the present disclosure may comprise or may be selected from ionizing compounds. Examples of ionizing compounds are disclosed in U.S. patent nos. 5,576,259 and 5,807,938, each of which is incorporated herein by reference in its entirety.

Aspects of the present disclosure detail additional descriptions and options for optional ionizing compound co-activators.

The term ionizing compound is a term of art and refers to a compound, particularly an ionizing compound, that can function to enhance the activity of a catalyst composition. In one aspect, fluoroorganoborate compounds described herein as optional organoboron co-activators are also contemplated and used as ionizing compound co-activators. However, the range of ionizing compounds is broader than fluoroorganoborate compounds, such as compounds encompassed by ionizing compounds, such as fluoroorganoaluminates.

While not intending to be bound by theory, it is believed that the ionizing compound may be capable of interacting or reacting with the metallocene compound and converting the metallocene into a cationic or initial cationic metallocene compound, which activates the polymerization activity of the metallocene. Also, while not intending to be bound by theory, it is believed that the ionizing compound may function by extracting the anionic ligand, in particular a non-cycloalkandienyl ligand or a non-dienyl ligand, from the metallocene, either fully or partially, such as (X ³) or (X ⁴) of the metallocene formula (X ¹)(X²)(X³)(X⁴) M disclosed herein, to form a cationic or initial cationic metallocene. However, the ionizing compound may act as an activator (co-activator) regardless of the mechanism by which it acts. For example, the ionizing compound may ionize the metallocene, abstract the X ³ or X ⁴ ligand in a manner that forms an ion pair, weaken the metal-X ³ or metal-X ⁴ bond, or simply coordinate to the X ³ or X ⁴ ligand, or any other mechanism by which activation may occur. Furthermore, the ionizing compound does not have to activate (co-activate) only the metallocene, because the activating function of the ionizing compound is more pronounced for the enhanced activity of the catalyst composition as a whole, compared to a catalyst composition comprising a catalyst composition not comprising any ionizing compound.

Examples of ionizing compounds include, but are not limited to, the list of compounds presented in the aspects of the present disclosure.

Optionally a carrier-activator. In another aspect, in addition to the recited components of the catalyst compositions of the present disclosure, optional co-activators that may be used may comprise or may be selected from other support-activators, sometimes referred to as activator-supports, when used in the catalyst compositions described herein. Examples of alternative co-activator-supports are disclosed in U.S. Pat. nos. 6,107,230, 6,653,416, 6,992,032, 6,984,603, 6,833,338, and 9,670,296, each of which is incorporated herein by reference in its entirety.

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

In one aspect, the optional co-activator-support may be selected from, for example, fluorided alumina, chlorided alumina, brominated alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, brominated silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, and the like, any one or any combination thereof may be used in the catalyst compositions disclosed herein. Alternatively or additionally, the co-activator-support may comprise or be selected from solid oxides treated with electron-withdrawing anions such as fluorided silica-alumina or sulfated alumina, and the like.

Examples of co-activator-supports may include, but are not limited to, the examples listed in the aspects of the disclosure.

J. Preparation of the catalyst composition

The relative concentration or ratio of the metallocene, e.g., the group 4 metallocene of formula (X ¹)(X²)(X³)(X⁴) M, to the calcined clay heteroadduct in the catalyst system can be expressed as moles of M (metal) per gram of calcined clay heteroadduct (mol M/g heteroadduct). In one aspect, it has been found that the molar ratio of M per gram of calcined clay heteroadduct can range from about 0.025 moles of M per gram of heteroadduct to about 0.000000005 moles of M per gram of heteroadduct. In another aspect, the number of M moles per gram of calcined clay heteroadduct may be used in the range of about 0.0005 mole of M/g heteroadduct to about 0.00000005 mole of M/g heteroadduct, or alternatively, in the range of about 0.0001 mole of M/g heteroadduct to 0.000001 mole of M/g heteroadduct. As in all ranges disclosed herein, the recited ranges include the endpoints and intermediate values and subranges within the recited ranges. These ratios reflect the catalyst formulation, i.e., the ratios are based on the number of combined components that result in the catalyst composition, regardless of the ratio in the final catalyst.

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

The catalyst composition may be produced by contacting a transition metal compound (e.g., metallocene, calcined clay heteroadduct) and a cocatalyst (e.g., an organoaluminum compound) under suitable conditions. The contacting may be performed in a variety of ways, such as by blending, by contacting in a carrier liquid, by adding the components to the reactor separately or in any order or combination. For example, the components or various combinations of compounds may be contacted with each other before further contact with the remaining compounds or components in the reactor. Alternatively, all three components or compounds may be contacted together prior to introduction into the reactor. With respect to additional optional components, such as co-activators, ionizing ionic compounds, and the like, that may be employed in the catalyst systems disclosed herein, the step of contacting with these optional components may be performed in any manner and in any order.

In one aspect, the catalyst composition can be prepared by first contacting a transition metal compound (e.g., a metallocene) with a cocatalyst (e.g., an organoaluminum compound) for about 1 minute to about 24 hours, or alternatively for about 1 minute to about 1 hour, at a temperature ranging from about 10 ℃ to about 200 ℃, or alternatively from about 12 ℃ to about 100 ℃, alternatively from about 15 ℃ to about 80 ℃, or alternatively from about 20 ℃ to about 80 ℃, to form a first mixture, and then the mixture can be contacted with a calcined clay heteroadduct to form the catalyst composition.

In another aspect, the metallocene, cocatalyst (e.g., organoaluminum compound), and calcined clay heteroadduct may be precontacted prior to introduction into the reactor. For example, the precontacting step may be performed over a period of about 1 minute to about 6 months. In one aspect, for example, the precontacting step can be conducted at a temperature of about 10 ℃ to about 200 ℃ or about 20 ℃ to about 80 ℃ for a time of about 1 minute to about 1 week to provide an active catalyst composition. Furthermore, any subset of the final catalyst components may also be precontacted in one or more precontacting steps, each step having its own precontacting time.

After any or all of the catalyst system components have been precontacted, the catalyst composition can be said to comprise the contacted components. For example, the catalyst composition may comprise a post-contact metallocene, a post-contact cocatalyst (e.g., an organoaluminum compound), and a post-contact calcined clay heteroadduct component. In the field of catalyst technology, it is not uncommon for the specific and detailed nature of the active catalytic sites, as well as the specific nature and results of each component used to prepare the active catalyst, to be not precisely known. While not intending to be bound by theory, the majority of the weight of the catalyst composition, based on the relative weights of the individual components, may be considered to comprise the calcined clay heteroadduct after contact. Because the nature of the active site and the post-contact component are not precisely known, the catalyst composition may be described simply in terms of its components, or as comprising the post-contact compound or component.

The polymerization activity of the catalyst composition can be expressed as the weight of carrier-activator comprising calcined montmorillonite hetero-adduct per unit time per weight of polymer polymerized, e.g., g polymer/g (calcined) carrier-activator/h (g/g/h). That is, the activity may be calculated based solely on the support-activator, without the presence of any metallocene or cocatalyst components. This measurement allows comparison of various activator supports, including comparison with other activators, wherein the metallocene, cocatalyst, and other conditions are the same or substantially the same. Unless otherwise indicated, the activity values disclosed in the examples are measured under slurry polymerization conditions using isobutane as the diluent at a polymerization temperature of about 50 ℃ to about 150 ℃ (e.g., at a temperature of 90 ℃), using a combined ethylene and isobutane pressure in the range of about 300psi to about 800psi, e.g., a combined ethylene and isobutane total pressure of 450psi. The activity data are reported as the weight of polymer produced per hour divided by the weight of calcined clay heteroadduct.

The catalyst activity may be a function of metallocene and calcined clay heteroadducts, as well as other components and conditions. Under the conditions described above, the activity based on the weight of the calcined clay heteroadduct may be greater than about 1,000 grams of polyethylene polymer per gram of calcined clay heteroadduct per hour (g PE/g heteroadduct/h, or simply g/g/h). In another aspect, the activity based on the weight of the calcined clay heteroadduct may be greater than about 2000g/g/h, greater than about 4,000g/g/h, greater than about 6,000g/g/h, greater than about 8,000g/g/h, greater than about 10,000g/g/h, greater than about 15,000g/g/h, greater than about 25,000g/g/h, or greater than about 50,000g/g/h. Each of these activities may be up to about 70,000g/g/h, such that the activities may range from greater than these disclosed values to less than about 75,000g/g/h.

For example, in one aspect and using the conditions described herein, the activator-support can have a polymerization activity of about 500g/g/h, about 750g/g/h, about 1,000g/g/h, about 1,250g/g/h, about 1,500g/g/h, 1,750g/g/h, about 2,000g/g/h, about 2,500g/g/h, about 3,500g/g/h, about 5,000g/g/h, about 7,500g/g/h, about 10,000g/g/h, about 12,500g/g/h, about 15,000g/g/h, about 17,500g/g/h, about 20,000g/g/h, about 25,000g/g/h, about 30,000g/g/h, about 35,000g/g/h, about 40,000g/g/h, about 50,000g/g/h, about 60,000g/g/h, or about 75,000g/g/h, including any range therebetween. Higher polymerization activity values may be associated with clay supports having extremely high site densities, and these activity values may also be dependent on metallocene. Thus, by applying the teachings herein, activity levels in the range between the two values recited can be obtained, for example, activity levels in the range of 500-75,000g/g/h can be obtained, as well as intermediate values and ranges, such as 1,000-50,000g/g/h, 2,000-40,000g/g/h, or 2,500-20,000g/g/h. The activities in the examples and tables are measured under slurry homopolymerization conditions, using isobutane as the diluent, a polymerization temperature of 90 ℃, a combined ethylene and isobutane total pressure of 450psi, and (1-n-butyl-3-methyl-cyclopentadienyl) ₂ZrCl₂ and triethylaluminum catalyst compositions, unless otherwise specified.

In one aspect, alumoxane (e.g., methylalumoxane) is not required to activate the metallocene and form the catalyst composition. Methylaluminoxane (MAO) is an expensive activator compound and adds significantly to the cost of producing the polymer. Furthermore, in another aspect, organoboron compounds or ionizing compounds (e.g., borate compounds) are not required to activate the metallocene and form the catalyst composition. In addition, ion exchange, protonic acid treatment or pillared clays, which require similar multi-step preparations at increased cost, are also not required to activate the metallocene and form the catalyst composition. Thus, the active heterogeneous catalyst composition can also be produced easily and inexpensively and used to polymerize olefin monomers, and comonomers if desired, without the presence of any aluminoxane compounds, boron compounds or borate compounds, ion exchange, protonic acid treatment, or pillared clays. Although MAO or other aluminoxane, boron or borate compounds, ion exchange clays, proton acid treated clays or pillared clays are not necessary in the disclosed catalyst system, these compounds can be used in reduced or typical amounts according to other aspects of the present disclosure.

K. Polyolefin and polymerization process

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

In one aspect, the homopolymer comprises monomer residues having from 2 to about 20 carbon atoms per molecule, preferably from 2 to about 10 carbon atoms per molecule. The olefin monomer may comprise or be selected from ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 3-ethyl-1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and mixtures thereof. In one aspect, homopolymers of ethylene, homopolymers of propylene, and homopolymers of other olefins are encompassed within the present disclosure. In another aspect, copolymers of ethylene and at least one comonomer, as well as less common copolymers of two non-ethylene copolymers, are also encompassed in the present disclosure.

When copolymers are desired, each monomer may have from about 2 to about 20 carbon atoms per molecule. Ethylene comonomers may include, but are not limited to, aliphatic 1-olefins having 3 to 20 carbon atoms per molecule such as, for example, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, styrene, vinylcyclohexane, and other olefins, as well as conjugated or non-conjugated dienes such as 1, 3-butadiene, isoprene, piperylene, 2, 3-dimethyl-1, 3-butadiene, 1, 4-pentadiene, 1, 7-hexadiene, and other such dienes, and mixtures thereof. In another aspect, ethylene may 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 may be introduced into the reactor zone sufficient to produce a copolymer, which may comprise from about 0.01wt.% to about 10wt.% or even more than this range of comonomer, based on the total weight of monomer and comonomer in the copolymer; alternatively, about 0.01wt.% to about 5wt.% comonomer; still alternatively, about 0.1wt.% to about 4wt.% comonomer; still alternatively, any amount of comonomer can be introduced into the reactor zone to provide the desired copolymer. In general, the catalyst composition may be used to homo-polyethylene or propylene, or to co-polymerize ethylene with a comonomer, or to co-polymerize ethylene and propylene. In another aspect, several comonomers may be polymerized with the monomer in the same or different reactor zones to obtain desired polymer properties.

Other useful comonomers may include polar vinyl, conjugated and non-conjugated dienes, acetylene and acetaldehyde monomers, which may be included in minor amounts in terpolymer compositions, for example. For example, the non-conjugated diene that may be used as a comonomer may be a linear hydrocarbon diene or cycloalkenyl-substituted olefin having from 6 to 15 carbon atoms. Suitable non-conjugated dienes may include, for example: (a) Linear acyclic dienes such as 1, 4-hexadiene and 1, 6-octadiene; (b) Branched acyclic dienes such as 5-methyl-1, 4-hexadiene; 3, 7-dimethyl-1, 6-octadiene; and 3, 7-dimethyl-1, 7-octadiene; (c) a monocyclic cycloaliphatic diene, such as 1, 4-cyclohexadiene; 1, 5-cyclooctadiene and 1, 7-cyclododecadiene; (d) Polycyclic alicyclic fused rings and bridged ring dienes, such as tetrahydroindene; norbornadiene; methyl tetrahydroindene; dicyclopentadiene (DCPD); bicyclo- (2.2.1) -hepta-2, 5-diene; alkenyl, alkylene, cycloalkenyl, and cycloalkylene norbornenes, such as 5-methylene-2-norbornene (MNB), 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5- (4-cyclopentenyl) -2-norbornene, 5-cyclohexylidene-2-norbornene, and 5-vinyl-2-norbornene (VNB); and (e) cycloalkenyl-substituted olefins such as vinylcyclohexene, allylcyclohexene, vinylcyclooctene, 4-vinylcyclohexene, allylcyclodecene, and vinylcyclododecene. Particularly useful non-conjugated dienes include dicyclopentadiene, 1, 4-hexadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene and tetracyclic (. DELTA. -11, 12) -5, 8-dodecene. Particularly useful dienes include 5-ethylidene-2-norbornene (ENB), 1, 4-hexadiene, dicyclopentadiene (DCPD), norbornadiene and 5-vinyl-2-norbornene (VNB). Note that throughout this disclosure, the terms "non-conjugated diene" and "diene" are used interchangeably.

The catalyst composition can be used to polymerize olefins to produce oligomers and polymeric materials having a wide range of densities, for example, in the range of about 0.66g/mL (also referred to as g/cc) to about 0.96g/mL, which is used in many applications. The catalyst compositions disclosed herein are particularly useful for producing copolymers. For example, the copolymer resin may have a density of 0.960g/cc or less, preferably 0.952g/cc or less, or more preferably 0.940g/cc or less. Densities of less than 0.91g/cc, even as low as 0.860g/cc, may be achieved in accordance with certain aspects of the present disclosure. When describing a density as being less than a particular density, a lower limit for such a density may be about 0.860g/cc. The copolymer resin may contain at least about 65wt.% (weight percent) of ethylene units, that is, the weight percent of ethylene monomers that are actually incorporated into the copolymer resin. In another aspect, the copolymer resins of the present disclosure may contain at least about 0.5wt.%, e.g., 0.5wt.% to 35wt.% of alpha-olefins (alpha-olefins), which refers to the weight percent of alpha-olefin comonomer actually incorporated into the copolymer resin.

Catalyst compositions prepared according to the present disclosure may also be used to prepare: (a) Ethylene/propylene copolymers, including "random copolymers" wherein the copolymer is randomly distributed along the polymer backbone or chain; (b) "propylene random copolymer" wherein the random copolymer of propylene and ethylene comprises about 60wt.% derived from propylene unit polymers; and (c) "impact copolymer" refers to two or more polymers, one of which is dispersed in the other, typically one polymer comprising a matrix phase and the other polymer comprising an elastomeric phase. The catalyst compositions described herein may be further used to prepare polyalphaolefins having monomers containing more than three carbons. Such oligomers and polymers are particularly useful, for example, in lubricants.

Any number of polymerization methods or processes may be used with the catalyst compositions of the present disclosure. For example, slurry polymerization, gas phase polymerization, solution polymerization, and the like, including multi-reactor combinations thereof, may be used. The multiple reactor combination may be configured in series or parallel, or a combination thereof, depending on the desired polymerization sequence. Examples of reactor systems and combinations may include, for example, tandem dual slurry loop, tandem multiple slurry tanks, or slurry loop combined with a gas phase, or various combinations of these processes, wherein polymerization of ethylene, propylene, and alpha-olefins may be performed alone or together. In another aspect, the gas phase reactor may comprise a fluidized bed reactor or a tubular reactor, the slurry reactor may comprise a vertical loop or a horizontal loop or a stirred tank, and the solution reactor may comprise a stirred tank or an autoclave reactor. Thus, any polymerization zone known in the art may be used that can produce polyolefins, such as ethylene and alpha-olefin containing polymers, including polyethylene, polypropylene, ethylene alpha-olefin copolymers, and more generally substituted olefins, such as vinylcyclohexane. In one aspect, for example, a stirred reactor may be used for a batch process, and then the reaction may be carried out continuously in a loop reactor or a continuously stirred reactor or a gas phase reactor.

The catalyst composition comprising the recited components may polymerize olefins in the presence of a diluent or liquid carrier, and the two terms are used interchangeably herein even though the catalyst components are insoluble in the diluent or liquid carrier. Suitable diluents for 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 mean that the material is inert, as the diluent may aid in polymerization, such as in bulk polymerization with propylene.

Suitable hydrocarbon diluents may include, but are not limited to, cyclohexane, isobutane, n-butane, propane, n-pentane, isopentane, neopentane, and n-hexane, as well as higher boiling solvents such as ISOPAR ^TM, and the like. 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, 4,737,280 and 5,597,892; these patents are incorporated by reference in their entirety. When polymerizing propylene or other alpha-olefins, the propylene or alpha-olefin may itself comprise a solvent, which is known in the art as bulk polymerization.

In various aspects and embodiments, a polymerization reactor suitable for use with a catalyst system may comprise at least one raw material feed system, at least one catalyst or catalyst component feed system, at least one reactor system, at least one polymer recovery system, or any suitable combination thereof. Suitable reactors may further comprise any one or combination of a catalyst storage system, an extrusion system, a cooling system, a diluent recycle system, a monomer recycle system, and a comonomer recycle system or control system. Such reactors may contain continuous withdrawal and direct recycle of catalyst, diluent, monomer, comonomer, inert gas and polymer as desired. In one aspect, a continuous process may comprise continuously introducing monomer, comonomer, catalyst, cocatalyst (if desired) and diluent into a polymerization reactor, and continuously removing a suspension comprising polymer particles and diluent from the reactor.

In one aspect, the polymerization process can be conducted over a wide temperature range, for example, the polymerization temperature can be in the range of about 50 ℃ to about 280 ℃, and in another aspect, the polymerization temperature can be in the range of about 70 ℃ to about 110 ℃. The polymerization pressure may be any pressure at which the polymerization is not terminated. In one aspect, the polymerization pressure can be from about atmospheric to about 30000psig. In another aspect, the polymerization pressure can be from about 50psig to about 800psig.

The polymerization reaction may be carried out in an inert atmosphere, that is, in an atmosphere substantially free of molecular oxygen and under substantially anhydrous conditions; therefore, there is no water present at the beginning of the reaction. Thus, a dry inert atmosphere, such as dry nitrogen or dry argon, is typically used in the polymerization reactor.

In one aspect, hydrogen may be used in the polymerization process to control the polymer molecular weight. In another aspect, a method of deactivating a catalyst by adding carbon monoxide to a polymerization zone, as described in U.S. patent No. 9,447,204, incorporated herein by reference, can be used to mitigate or stop uncontrolled or uncontrolled polymerization.

For the catalyst systems of the present disclosure, the polymerizations disclosed herein are typically conducted in a loop reaction zone or batch process using a slurry polymerization process or in a gas phase zone using a fluidized or stirred bed.

Slurry loop. In one aspect, a typical polymerization process is a slurry polymerization process (also referred to as a "particle formation process"), which is disclosed, for example, in U.S. Pat. No. 3,248,179, incorporated herein by reference. Other polymerization processes for slurry processes may employ loop reactors of the type disclosed in U.S. Pat. No. 3,248,179, as well as reactors used in multiple stirred reactors in series, parallel, or a combination thereof.

The polymerization reactor system may comprise at least one loop slurry reactor and may comprise vertical or horizontal loops or a combination thereof, which may be independently selected from a single loop or a series of loops. The multiple loop reactor may comprise vertical and horizontal loops. Slurry polymerization may be carried out in an organic solvent as a carrier or diluent. Examples of suitable solvents include propane, hexane, cyclohexane, octane, isobutane, or combinations thereof. The olefin monomer, carrier, catalyst system components and any comonomer may be fed continuously to the loop reactor where polymerization takes place. The reactor effluent may be flashed to separate the solid polymer particles.

A gas phase. In one aspect, the method of producing polyolefin polymers according to the present disclosure is a gas phase polymerization process using, for example, a fluidized bed reactor. Such reactors and means of operating the reactors are described, for example, in U.S. Pat. Nos. 3,709,853, 4,003,712, 4,011,382, 4,302,566, 4,543,399, 4,882,400, 5,352,749, 5,541,270, EP-A-0 802 202, belgium patent 839,380, each of which is incorporated herein by reference. These patents disclose gas phase polymerization processes wherein the polymerization medium is mechanically agitated or fluidized by the continuous flow of gaseous monomer and diluent.

The gas phase polymerization system may employ a continuous recycle stream containing one or more monomers that is continuously circulated through a fluidized bed in the presence of a catalyst. The recycle stream may be withdrawn from the fluidised bed and recycled back to the reactor. At the same time, the polymer product can be withdrawn from the reactor and fresh monomer can be added instead of polymerized monomer. Such gas phase reactors may comprise a multi-step gas phase polymerization process of olefins in which the olefins are gas phase polymerized in at least two separate gas phase polymerization zones while feeding the catalyst-containing polymer formed in the first polymerization zone to the second polymerization zone.

Other gas phase processes contemplated by the disclosed polymerization processes include tandem or multistage polymerization processes. In one aspect, gas phase processes that may be used in accordance with the present disclosure include those described in U.S. Pat. Nos. 5,627,242, 5,665,818, and 5,677,375, and European publications EP-A-0 794 200, EP-B1-0 649 992, EP-A-0 802 202, and EP-B-634 421, all of which are incorporated herein by reference.

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

According to other aspects, in a fluidized bed process for producing a polymer, a gas stream containing one or more monomers may be continuously circulated through the fluidized bed in the presence of a catalyst under reaction conditions. The gas stream may be withdrawn from the fluidised bed and recycled to the reactor, whilst the polymer product may be withdrawn from the fluidised bed and withdrawn from the reactor, whilst fresh monomer may be added in place of polymerised monomer. See, for example, U.S. Pat. nos. 4,543,399, 4,588,790, 5,028,670, 5,317,036, 5,352,749, 5,405,922, 5,436,304, 5,543,471, 5,462,999, 5,616,661, and 5,668,228; each of which is incorporated by reference in its entirety.

In another aspect, the antistatic compound may be fed to the polymerization zone simultaneously with the finished catalyst. Alternatively, antistatic compounds such as those described in U.S. patent nos. 7,919,569, 6,271,325, 6,281,306, 6,140,432, and 6,117,955, each of which is incorporated herein by reference in its entirety, may be used. For example, the clay heteroadducts may be contacted or impregnated with one or more antistatic compounds. The antistatic compounds may be added at any point, for example, they may be added at any time after calcination, such as until (including) the final post-contact catalyst preparation.

In another aspect, so-called "self-limiting" compositions may be added to the clay heteroadducts to inhibit caking, fouling, or uncontrolled reactions in the polymerization zone. For example, U.S. Pat. nos. 6,632,769, 6,346,584, and 6,713,573, each of which is incorporated herein by reference, disclose additives that release a catalyst poison above a threshold temperature. In general, such compositions may be added at any time after calcination in order to limit or stop polymerization activity above the desired temperature.

A solution. The polymerization reactor may also comprise a solution polymerization reactor in which the monomers are contacted with the catalyst composition by suitable agitation or other means. The solution polymerization may be carried out in a batch manner or in a continuous manner. A support comprising an inert organic diluent or excess monomer may be employed and the polymerization zone maintained at a temperature and pressure that will result in the formation of a polymer solution in the reaction medium. Agitation may be employed during the polymerization to achieve better temperature control and to maintain a uniform polymerization mixture throughout the polymerization zone and to dissipate the polymerization exotherm using appropriate means. The reactor may also comprise a series of at least one separator employing high and low pressures to separate the desired polymer.

Tubular reactor and high pressure LDPE. In yet another aspect, the polymerization reactor may comprise a tubular reactor that may produce the polymer by free radical initiation or alternatively by employing the disclosed catalysts. The tubular reactor may have several zones where fresh monomer, initiator or catalyst and cocatalyst are added. For example, the monomer may be entrained in an inert gas stream and introduced in one zone of the reactor, and the initiator, catalyst composition and/or catalyst components may be entrained in the gas stream and introduced in another zone of the reactor. These streams can then be mixed for polymerization, wherein the heat and pressure can be appropriately adjusted to obtain optimal polymerization conditions.

A combination or multiple reactors. In another aspect, the catalysts and processes of the present disclosure are not limited by the type of reactor or combination of reactor types possible. For example, the disclosed catalysts and processes can be used in a multi-reactor system that can include a combination or connected reactor to perform polymerization, or multiple reactors that are not connected. The polymer may be polymerized in one reactor under one set of conditions, and then the polymer may be transferred to a second reactor for polymerization under a different set of conditions.

In this regard, the polymerization reactor system may comprise a combination of two or more reactors. The production of the polymer in a plurality of reactors may comprise several stages in at least two separate polymerization reactors which are connected to each other by transfer means for transferring the polymer produced by the first polymerization reactor to the second reactor, wherein the polymerization conditions in the respective reactors are different. Alternatively, polymerization in multiple reactors may include manual transfer of polymer from one reactor to a subsequent reactor to continue polymerization. Such reactors may include any combination including, but not limited to, multi-loop reactors, multi-gas reactors, combinations of loop and gas reactors, combinations of autoclave or solution reactors with gas or loop reactors, multi-solution or multi-autoclave reactors, and the like.

Polymers produced using the disclosed catalysts and processes. The catalyst composition used in the process can produce high quality polymer particles without substantially contaminating the reactor. When the catalyst composition is used in a loop reactor zone under slurry polymerization conditions, the particle size of the calcined heterocoagulation product can be in the range of from about 10 micrometers (μm) to about 1000 micrometers, from about 25 micrometers to about 500 micrometers, from about 50 micrometers to about 200 micrometers, or from about 30 micrometers to about 100 micrometers to provide good control over polymer particle production during polymerization.

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

In other polymerization reactor systems, whether single or multiple systems in series, the suitable particle size 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 may be determined by the polymerization reactor system, such as whether the particles are easily fluidized in a gas phase system, but the particles are large enough that they are not entrained with the fluidizing gas, which entrainment may cause plugging of downstream filters. Likewise, when the catalyst-polymer composite particles are melted and extruded into pellets, the optimal size and size distribution in the polymerization system may be balanced with the ease of transporting or handling them in a storage silo or extrusion facility.

The polymers produced using the catalyst compositions of the present disclosure may be formed into a variety of articles such as household containers and appliances, film products, automotive bumper components, drums, fuel tanks, pipes, geomembranes, and gaskets. In one aspect, additives and modifiers may be added to the polymer to provide a desired effect, such as a desired combination of physical, structural, and flow properties. It is believed that by using the methods and materials described herein, articles can be produced at lower cost while maintaining the desired polymer properties obtained from polymers produced using the transition metal or metallocene catalyst compositions disclosed herein.

Specific embodiments. In a more specific embodiment of the present disclosure, there is provided a process for producing a catalyst composition, the process comprising (optionally, "consisting essentially of … …" or "consisting of … …"):

(1) Contacting a suitable dioctahedral phyllosilicate clay with a heterocoagulant to form a solid that is readily filtered and washed to a conductivity of less than 10mS/cm, or less than 5mS/cm, or between 1mS/cm and 50 μS/cm, or between 500 μS/cm and 50 μS/cm;

(2) Dehydrating and dehydroxylating the washed clay heteroadduct at one or more temperatures in the range of from about-10 ℃ to about 500 ℃ to produce a calcined heterocohesive clay adduct composition that does not or substantially not exhibit a2Θd001 peak at less than 8 degrees, preferably does not or substantially not exhibit a2Θd001 peak at less than 10 degrees. If peaks exist in the region of less than 10 degrees 2 theta, the main peak thereof is not less than 4 degrees 2 theta, or the intensity is greater than the peak of the intensity exhibited by the clay mineral itself after calcination at 300 ℃, such as from 8 degrees 2 theta to 12 degrees 2 theta;

(3) Combining the calcined heteroaggregated clay adduct composition with a metallocene, such as bis (1-butyl-3-methylcyclopentadienyl) zirconium dichloride, at a temperature in the range of 15 ℃ to 100 ℃ to produce a mixture; and

(4) After 1 minute and 1 hour, the mixture in part (3) is combined with a trialkylaluminum, such as triethylaluminum, trioctylaluminum, or triisobutylaluminum, to prepare a catalyst composition.

An alternative embodiment is to reverse the order of addition of metallocene and trialkylaluminum in steps (1) to (4) above.

Examples

The foregoing description is intended to illustrate, but not limit the scope of the disclosure, which is further illustrated by the following examples. The examples should not be construed as imposing limitations upon the scope of the present disclosure. On the contrary, it is to be understood that resort may be had to various other embodiments, aspects, modifications, and equivalents thereof, which, from the written description, suggest themselves to those of ordinary skill in the art without departing from the spirit of the present invention or the scope of the appended claims. Accordingly, the following examples are put forth so as to provide those of ordinary skill in the art with a more detailed disclosure and description.

Reagents and general procedure

All reagents used to prepare the clay-hetero adducts of the present disclosure were obtained from the commercial sources shown and used "as received" unless otherwise indicated.

Produced by American colloid Co LtdHPM-20 bentonite aqueous dispersion (montmorillonite), also referred to as HPM-20 or HPM-20 clay, is obtained from McCullough & Associates. 50% aqueous solution of polyaluminum chloride (abbreviated as "ACH") obtained from GEO SPECIALTY CHEMICALS and290 (Polyaluminum chloride, commonly known as Al ₂(OH)_2.5Cl_3.5). Obtaining chlorine hydration aluminium powder from PARCHEM FINE AND SPECIALTY CHEMICALS51P, commonly known as Al ₂Cl(OH)₅) and aluminum sesquichloride solution31L). Obtaining fumed silica from Evonik Industries AG200 Air-phase alumina aqueous dispersionW400). From Nano Technologies, inc. colloidal alumina is obtainedAL 27).

Unless otherwise indicated, in the specification and examples, clay dispersions, clay heteroadducts, pillared clays and other compositions can be prepared using a double speed Conair ^TM Waring^TM commercial laboratory blender 7010G equipped with a timer. The "low" speed versus "high" speed blending of the blender speed is compared to: the 7010G type blender was connected to a Staco energy variable transformer (model 3PN 1010B) and the speed of the blender was adjusted by changing the settings on the transformer. In the examples and description, "low speed" blending is achieved by setting the transformer between 0 and 50, while "high speed" blending is achieved by setting the transformer between 50 and 100.

Conductivity was measured using Eutech PCSTestr or a radiometer analysis conductivity meter, according to the instruction manual and the references provided by each instrument. The pH of the solution or slurry was measured using Eutech PCSTestr or Beckmann phi 265 laboratory acidometer.

Preliminary pretreatment of water by using Prepak A pretreatment package followed by Millipore Milli-ADVANTAGE A10A water purification System further purifies the water to obtain deionized water, referred to herein as Milli-And (3) water. This water is typically used within 2 hours after collection.

Hexane, heptane, toluene and methylene chloride were dried over activated molecular sieves and degassed with nitrogen prior to use. Instrument grade isobutane used as a solvent for ethylene homo-polymerization was purchased from Airgas and purified by activated carbon column, alumina column, 13X molecular sieve column, and finally purified by a OxyClear ^TM gas purifier model RGP-R1-500 from Diamond Tool and Die, inc. Ultra-high purity grade ethylene and hydrogen were obtained from Airgas. UHP (ultra high purity) ethylene is further purified by activated carbon column, alumina column, 13X molecular sieve column and OxyClear ^TM gas purifier model RGP-R1-500. UHP hydrogen is purified by a OxyClear ^TM gas purifier model RGP-R1-500. Purified propylene was obtained as a slip stream from a commercial polypropylene plant.

All preparations involving treatment with organometallic compounds were carried out under nitrogen (N ₂) atmosphere using Schlenk techniques or in a glove box.

Zeta potential measurement

The zeta potential of the colloidal suspensions disclosed herein is obtained by measuring the electroacoustic effect upon application of an electric field across the suspension. The device used to make these measurements is Colloidal DynamicsZetaprobe Analyzer ^TM. For example, zeta potential measurements are used to determine dispersion at 0.5wt.% to 1wt.%HPM-20/aqueous dispersion is as follows. A 250g to 300g sample of the dispersion to be measured is transferred to a measuring vessel containing an axial bottom stirrer. The agitation speed is set fast enough to prevent sedimentation or substantial sedimentation of the dispersion, but slow enough to allow the electroacoustic probe to be fully immersed in the mixture when fully lowered. Typically the stirring speed is set between 250rpm and 350rpm, most typically 300rpm.

The Colloidal DynamicZetaprobe Analyzer ^TM measurement parameters used were as follows: reading 5 times at a rate of 1 reading/min; particle density of 2.6g/cc; the dielectric constant was 4.5. The initial estimated colloidal weight percentage is 0.7wt.% to 1.0wt.% (concentration _{Estimated value}), typically entered into Zetaprobe Analyzer ^TM software. Measurement of 5wt.%HPM-20/aqueous dispersion gives a zeta potential of-46 mV. If the final dispersed clay concentration is referred to as "concentration" in the following equation, the final dispersed clay concentration may be calculated from the initial estimated concentration according to the following equation.

Concentration = concentration _{Estimated value} x (measured zeta potential/(-46))

Zetaprobe Analyzer ^TM are also used to dynamically track the zeta potential evolved during titration of clay dispersions, whether colloidal dispersions or non-colloidal solutions. Typically, a cationic polymetallic salt titrant (or other cationic titrant) is added to 0.5wt.% to 5.0wt.%HPM-20/aqueous dispersion with a concentration of 0.25mL to 2.0mL per titration point and an equilibration delay time of 30 seconds to 120 seconds.

Zetaprobe software uses the weight percent of colloidal particles not counted in the colloidal titrant to calculate the zeta potential. Thus, where the titrant is a colloidal substance, the measured zeta potential is adjusted to reflect the additional colloidal content of the measurement solution by the following method. Initially, the weight of the titrand clay and titrant cationic species is determined by the following equation (where x represents multiplication, W is weight, V is volume).

W _{titration agent}＝V_{titration agent} density _{titration agent} solids% _{titration agent}

W _Clay＝V_{Total amount of} x density _{Dripped article} x particle concentration _{Measurement value}

Determination of 5%The density of the HPM-20 aqueous dispersion (the substrate) was about 1.03g/mL. According to particle density of titrant relative to object to be drippedThe particle density of HPM-20 (montmorillonite) was scaled to the titrant weight to provide an effective titrant weight (W _{effective titrant}), which was calculated in this example as follows.

W _{effective titrant}＝W_{titration agent} particle density _{titration agent}/particle density _{Dripped article}

The effective colloidal particle weight percent (wt.% _{Effective and effective}) was then calculated to provide an estimate of the relative increase in colloidal content relative to an equivalent titration using a non-colloidal titrant. The inverse of this value is then multiplied by the measured zeta potential to determine the adjusted zeta potential as follows.

wt.％_{Effective and effective}＝(W_{effective titrant}+W_Clay)/V_t

A＝wt.％_{Measurement value}/wt.％_{Effective and effective}

ZP_{Adjustment value}＝ZP_{Measurement value}*A

In zeta potential titration of clay dispersions using cationic multimetal salts, e.g. using Aluminum Chlorohydrate (ACH) pairsHPM-20 montmorillonite was titrated and zeta potential measured before and during titration as a function of titrant volume and mmol Al/g clay. Samples of solid material formed at various points during titration (e.g., at 0mmol Al/g clay, 1.17mmol Al/g clay, 1.52mmol Al/g clay, etc.) were collected, each sample dried, calcined, and analyzed by powder XRD (x-ray diffraction). As an example of zeta potential titration, FIG. 3 depicts a graph obtained by titrating with Aluminum Chlorohydrate (ACH)The zeta potential of a series of dispersions provided by titration of HPM-20 montmorillonite plotted against the titrant volume versus the zeta potential (mV) of the dispersion and FIG. 4 plotted against the zeta potential (mV) of the same titrated mmol Al/g clay versus the dispersion. Figure 2 provides the powder XRD patterns of the series of calcined products collected during this zeta potential titration of HPM-20 clay with ACH.

Powder X-ray diffraction (XRD) study

Powder X-ray patterns of clay and clay heteroadducts were obtained on a Bruker D8 daVinci instrument having a Bragg Brentano geometry of the "theta-theta" scan type using standard X-ray powder diffraction techniques, and using a afterloaded stent with zero background silicon chips. The detector used was a linear silicon strip (LynxEYE) PSD detector. The test sample is placed in a sample holder of a two-circle goniometer enclosed in a radiation-safe housing. The X-ray source was a 2.0kW Cu X-ray tube, and the operating current was maintained at 40kV and 25mA. The X-ray optical system is a standard Bragg-Bretano Zhong Jiao mode, with X-rays emanating from a DS slit (0.6 mm) on the tube to strike the sample and then converging on a position sensitive X-ray detector (Lynx-Eye, bruker-AXS). The double-circle 250mm diameter goniometer is computer controlled by an independent stepper motor and optical encoder. The flat compressed powder sample was scanned at a speed of 0.8 ° (2θ) per minute (2-30 ° 2θ in 35 minutes). The software suite for data collection and evaluation is based on Windows (Windows). Data was collected automatically using COMMANDER program by using BSML file and analyzed by program diffrac.

For example, mcCauley describes XRD test methods applied to calcined clay heteroadducts disclosed herein to determine substrate spacing in U.S. Pat. No. 5,202,295 (e.g., column 27, lines 22-43). The bragg equation or law applied to clay is: nλ=2dsin θ, where n is the repetition number, λ is 1.5418, d is the d001 pitch, θ is the angle of incidence.

Pore volume and pore volume distribution

The pore volume of the clay hetero-adducts is reported as the cumulative volume of all pores discernable by the nitrogen desorption method in cc/g (cm ³/g, cubic centimeters per gram). For catalyst supports or support particles such as alumina powders, and for clay and clay heteroadducts of the present disclosure, pore size distribution and pore volume are calculated by b.e.t. (or BET) technique with reference to nitrogen desorption isotherms (assuming cylindrical pores), as described in s.brunauer, p.emmett, and e.teller, journal of chemistry, 1939,60,309; see also ASTM D3037, which determines the procedure for determining surface area using the nitrogen BET method.

The pore volume distribution is helpful in understanding catalyst performance, and various properties of the pore volume (total pore volume), pore volume distribution, such as Kong Bai percent over various size ranges, and "pore mode", describe pore diameters corresponding to dV (log D) and local maxima of pore size distribution, obtained from nitrogen adsorption-desorption isotherms according to the method described in e.p.barrett, l.g. joyner, and p.p.halenda ("BJH") in calculation (The Determination of Pore Volume and Area Distributions in Porous Substances.I.Computations from Nitrogen Isotherms)" of pore volume and area distribution determination of i. U.S. chemical society, 1951,73 (1), pages 373-380.

Surface area

Surface area was determined by a nitrogen adsorption method using a nitrogen adsorption-desorption isotherm using b.e.t. (or BET) technique as described in s.brunauer, p.emmett, and e.teller, journal of american chemical society, 1939,60,309; see also ASTM D3037, which determines the procedure for determining surface area using the nitrogen BET method. All morphological properties related to weight, such as Pore Volume (PV) (cc/g, cubic centimeter per gram) or Surface Area (SA) (m ²/g, square meter per gram), are normalized to a "metal-free basis" according to procedures well known in the art. However, unless otherwise indicated, the morphological properties reported herein are based on "measurements" and no correction is made for metal content.

Polymerization reaction

The ethylene homo-polymerization was carried out in a dry 2L stainless steel Parr autoclave reactor using 1L isobutane diluent. Table 3A reports the performance and polymerization data of comparative supports and the heteroaggregated clay supports of the invention using (1-n-butyl-3-methyl-cyclopentadienyl) ₂ZrCl₂ and triethylaluminum (AlEt ₃) as metallocene and cocatalyst. The selected pressure in the reactor used to calculate the activity reported in table 3A was 450 total psi, the temperature was 90 ℃, either maintained electronically by an ethylene mass flow controller, or manually using a jacket temperature controller. Table 3B reports the surface area and porosity properties of the comparative support and the heteroaggregated clay support of the invention.

Polymerization data using the support-activators of the present disclosure and polymerization data using the comparative catalyst system are presented in table 3A. Polymerization batches are labeled P1 through P39 and specific example numbers of carriers used in each polymerization batch are listed.

When hydrogen is used, a pre-mixed gas feed tank of purified hydrogen and ethylene is used to maintain the desired total reactor pressure, the pressure in the feed tank being sufficiently high so as not to significantly alter the ethylene to hydrogen ratio in the reactor feed. The addition of hydrogen affects the melt index of the polymer obtained with any given catalyst.

The water inside the reactor was first removed by preheating the reactor to at least 115 ℃ under a dry nitrogen flow for at least 15 minutes before the polymerization batch was carried out. Agitation is provided by the impeller and Magnadrive ^TM, set point is, for example, 600rpm. The metallocene catalyst used in the polymerization batch of Table 3A was (1-n-butyl-3-methyl-cyclopentadienyl) ₂ZrCl₂ and triethylaluminum (AlEt ₃ or TEA) was used as cocatalyst or alkylating agent, of which 1.8mmol of AlEt ₃ (3 mL of 0.6m TEA in hexane) was generally used in the polymerization batch in this table. The contacted catalyst components, that is, the composition containing all of the listed catalyst system components previously contacted to form the composition, are prepared in an inert atmosphere glove box and transferred to a catalyst loading tube or vessel. The catalyst addition vessel contents were then charged to the reactor by flushing with 1L of isobutane. The reactor temperature control system is then opened to a temperature a few degrees below the temperature set point, which typically takes about 7 minutes. The reactor was brought to batch pressure by opening a manual feed valve for ethylene and the polymerization batch was run for the time reported in table 3A, for example 30 minutes or 60 minutes.

Table 3A compares the attributes and polymerization data of the support and the heteroaggregated clay support of the invention. Polymerization was carried out using (1-n-butyl-3-methyl-cyclopentadienyl) ₂ZrCl₂ and triethylaluminum (AlEt ₃) as metallocene and cocatalyst at 450psi reactor pressure and 90 ℃. ^A

^A Abbreviations: MCN, metallocenes; PE, polyethylene.

Table 3B. Surface area and porosity properties of the carrier and the heteroaggregated clay carrier of the invention are compared. ^A

^A Abbreviations: NA, unavailable; DVlogDmax 30-40max/DvlogD200-500max, also abbreviated as D _VM(30-40)/D_VM(200-500), areAndMaximum value of dV (log D) andAndA ratio of dV (log D) maxima therebetween; and DVlogDmax200-500max/DvlogD60-200max, also abbreviated as D _VM(200-500)/D_VM(60-200), areAndMaximum value of dV (log D) andAndThe ratio of the maximum values of dV (log D) between.

Alternatively, the contents of the catalyst feed tube may be pushed into the reaction vessel with ethylene at a temperature several degrees below the batch set point temperature, for example about 10 degrees celsius below the set point temperature. In this method, two feed tubes are used. When the batch pressure is reached, the reactor pressure is controlled by a mass flow controller. Ethylene consumption and temperature were monitored electronically. During the polymerization, the reactor temperature was maintained within ±2 ℃ of the set temperature except for the initial charge of catalyst during the first few minutes of the batch. After 60 minutes or after a specified batch time, the polymerization was stopped by closing the ethylene inlet valve and venting isobutane. The reactor was returned to ambient temperature. The polymer produced in the reaction is then withdrawn from the reactor and dried, and the polymer weight is used to calculate the activity of the particular polymerization. Following stabilization of the polymer with Butylated Hydroxytoluene (BHT) according to ASTM procedures D618-05 and D1238-04C, the polymer melt index, specifically, the Melt Index (MI) and the High Load Melt Index (HLMI) were obtained. The polymer density was measured according to ASTM D1505-03.

Catalyst and polymer characterization

The ¹ H NMR spectrum of the metallocene compound was collected at room temperature by placing 20mg of the metallocene sample into a 10mm NMR tube, to which 3.0mL of CDCl ₃ was added. ¹ H NMR spectra were obtained on a Bruker AVANCE ^TM NMR (400.13 MHz). Chemical shifts are reported in ppm (δ) relative to TMS, or chemical shifts referenced to residual solvent proton resonance. Coupling constants are reported in hertz (Hz).

NMR determination of the isotactic pentad content in polypropylene was obtained by placing 400mg of a polymer sample into a 10mm NMR tube, to which were added 1.7g of tetrachloroethane-d 2 and 1.7g of o-dichlorobenzene. ¹³ The C NMR spectrum was obtained on a Bruker AVANCE ^TM NMR (100.61 MHz,90℃pulse, 12 seconds pulse-to-pulse delay). Each spectrum stores approximately 5000 transients, mmmm pentad peak (21.09 ppm) for reference. Microstructure analysis was performed as described in Busico et al, macromolecules, 1994,27,4521-4524.

The polypropylene Melt Flow Rate (MFR) was determined according to ASTM D-1238 procedure at 230℃under a load of 2.16 kg.

The melting temperature Tm of the polypropylene was obtained according to ASTM D-3417 procedure using DSC and TA Instrument, inc. DSC Q1000.

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

Example 1 comparative example of calcined clay preparation

700Mg of the powder as suchHPM-20 clay samples were combined with 60mL deionized water. The mixture was stirred vigorously and rotary evaporated at 55 ℃ for 20-30 minutes. The resulting sample was then calcined at 300℃for 6 hours to give 620mg of a gray powder. The nitrogen adsorption/desorption BJH pore volume analysis is plotted in fig. 12.

Example 2 comparative example of azeotropic Clay preparation

Will be 5.16gA sample of HPM-20 clay powder was placed in a round bottom flask and combined with 40mL to 60mL of n-butanol. The mixture was stirred vigorously and then rotary evaporated to dryness at 45 ℃. This drying step is stopped shortly after the alcohol has evaporated significantly. After this process, the odor of the n-butanol of the sample is generally clearly audible. A sample of 5.39g of wet clay was obtained, and 4.46g of this material was calcined at 300℃for 6 hours to obtain 3.3g of black powder.

Example 3 comparative example of preparation of sheared then azeotroped clay

A sample of 133g of 5wt.% HPM-20/aqueous dispersion was prepared by mixing atThe HPM-20 clay was slowly added to deionized water in a blender and stirred to prepare, initially rotary evaporated at 45℃to 55℃to remove most of the water, followed by 50mL of n-butanol. The rotary evaporation was continued at 45℃and the drying was stopped shortly after the apparent evaporation of ethanol. A3.2 g sample of this material was then calcined at 300℃for 6 hours to give 2.6g of a gray powder. The BJH pore volume analysis of this material is provided in fig. 11.

EXAMPLE 4 preparation of colloidal clay Dispersion

To the direction of570G deionized water was added to the blender and 30.0 g HPM-20 was added in portions with stirring. This mixture was stirred at a high rate (revolutions per minute, rpm) to give a dispersion that was substantially free of lumps or lumps-5 wt.% of the HPM-20 suspension. When prepared using 20g HPM-20 and 394g water4.8Wt.% dispersion of HPM-20 clay and useWhen the blender was stirred at high rpm to give a non-caking dispersion, the dispersion was characterized by a conductivity of 908. Mu.S/cm and a pH of 9.39.

EXAMPLE 5 preparation of aluminum chlorohydrate (Al ₁₃ Keggin-ion) -pillared Clay Using aluminum chlorohydrate solution (6.4 mmol Al/g Clay)

100G of the colloidal clay dispersion prepared according to example 4 was chargedThe blender was then charged with 6.9g of a 50% GEO aluminum chlorohydrate solution with stirring, which was reported to have an alkalinity of 83.47%. After the addition of aluminum chlorohydrate, the mixture was stirred at a high rate (rpm) for an additional 3 minutes. The pH of the mixture was measured to be pH 4.23. Filtration of the resulting mixture through Fisherbrand ^TM P8 filter paper was attempted, but was unsuccessful. Thus, two aliquots of the mixture were transferred to 50 ml plastic centrifuge tubes and the samples were centrifuged at 3600rpm for a total of 140 minutes on a beckmann coulter Allegra 6 centrifuge. The resulting clear supernatant was decanted from each tube and replaced with deionized water. The sample was shaken to re-suspend the solids and centrifuged again. This process is repeated multiple times (typically 4 to 8 times) until the supernatant of the centrifuged sample reaches a conductivity of 67 mus/cm and a pH of 6.0. The supernatant was then decanted and the solid was transferred to an erlenmeyer flask with a minimum of deionized water along with approximately 70mL of n-butanol. Rotary evaporation gave 2.11g of an off-white powder. A437 mg sample of this powder was loaded into a ceramic bowl and placed in an oven at 300℃for 6 hours, yielding 0.301 g of a dark gray powder.

Example 6 reproducibility of aluminum chlorohydrate (Al ₁₃ Keggin-ion) -pillared Clay Using an aluminum chlorohydrate solution (6.4 mmol Al/g Clay)

30G of HPM-20 clay was slowly added over 1 to 2 minutes with stirring to a solution containing 570g of deionized Milli-Of waterIn the blender, while stirring at low speed, a gray colloidal dispersion is obtained that is free or substantially free of visible lumps or clumps. After the addition was complete, the resulting dispersion was blended at high speed for 5 to 10 minutes to give a slightly viscous mixture of 5wt.% aqueous dispersion of HPM-20 clay.

150G of a 5wt.% aqueous dispersion of this HPM-20 was transferred toIn the blender, 9.35g of a 50wt.% aqueous solution of GEO aluminum hydroxychloride was pipetted into a vial and added to the dispersion in one portion. The mixture was blended at high speed for 5 minutes and then sub-packaged into four 50mL centrifuge tubes and centrifuged at 3000rpm to 3500rpm for 30 minutes to 60 minutes. The pH and conductivity of the supernatant were measured (Eutech PCSTestr). The supernatant was decanted and the remaining wet solids resuspended in deionized Milli-In water. The centrifugation process (centrifugation, supernatant pH/conductivity measurement, supernatant removal, re-suspension in deionized Milli-In water) until the conductivity of the supernatant reaches 100 to 300. Mu.S/cm. A total of six centrifuges were performed, at which time the supernatant was discarded last time. 200mL of 1-butanol was added to the remaining wet solid, and after rotary evaporation at 45℃9.75g of wet solid was obtained. The wet solid was then ground with a pestle and mortar, 4.28g of the solid was transferred to a ceramic crucible and calcined at 300 ℃ for 6 hours to give 1.65g of a gray black powder.

EXAMPLE 7 preparation of aluminum chlorohydrate (Al ₁₃ Keggin-ion) -pillared Clay Using powdered aluminum chlorohydrate (6.4 mg Al/g Clay)

A30 g sample of HPM-20 clay was slowly added over 1 to 2 minutes with stirring to a solution containing 570g of deionized Milli-Of waterIn the blender, while stirring at low speed, a gray colloidal dispersion is obtained that is free or substantially free of visible lumps or clumps. After the addition was complete, the dispersion was blended at high speed for 5 to 10 minutes to give a slightly viscous mixture of 5wt.% aqueous dispersion of HPM-20 clay.

100G samples of this 5wt.% aqueous HPM-20 dispersion were transferred toIn the blender, weigh 3.42g Parchem51P powder into vials, deionized Milli-Diluted with water and then added to the dispersion in one portion. The mixture was blended at high speed for 5 minutes, then split into four 50mL centrifuge tubes, and centrifuged at 3000rpm to 3500rpm for 30 minutes to 60 minutes. The pH and conductivity of the supernatant were measured (Eutech PCSTestr). The supernatant was decanted and the remaining wet solids resuspended in deionized Milli-In water. The centrifugation process (centrifugation, supernatant pH/conductivity measurement, supernatant removal, re-suspension in deionized Milli-In water) until the conductivity of the supernatant reached 100 μs/cm to 300 μs/cm (six total centrifuges were performed, the final supernatant pH was 4.25, and the conductivity was 225 μs/cm), at which time the supernatant was discarded last time. The remaining wet solid was combined with 100mL to 200mL of 1-butanol in a round bottom flask and rotary evaporated at 45 ℃ to give 5.54g of wet solid, which was then ground with a pestle and mortar. A portion of 1.8g of this solid was transferred to a ceramic crucible and calcined at 300℃for 6 hours to give 1.2g of a gray-black powder.

EXAMPLE 8.1%Gravimetric determination of the colloidal clay content in the aqueous HPM-20 dispersion

A60 g sample of a 5wt.% dispersion of HPM-20 clay in water was mixed with 240g Milli-Deionized water was combined to give 300g of a 1wt.% aqueous dispersion of HPM-20. After standing for a period of time (30 minutes to one hour), a large amount of settled clay was observed in this diluted dispersion. The colloidal fraction was decanted and the precipitated fraction was collected, dried and weighed. This procedure resulted in 900mg of collected HPM-20 clay, corresponding to a colloid content of 0.7% of the diluted dispersion. During multiple iterations of this experiment using 280g to 290g of this 1% hpm-20 dispersion, 630mg and 910mg of solid clay were isolated, respectively, resulting in diluted dispersions with colloid content values of 0.77wt.% and 0.69wt.%.

EXAMPLE 9 Chloroaluminum in Clay heteroadduct +.Zeta potential measurement of HPM-20 ratio

30G of HPM-20 clay was slowly added over several minutes with stirring to a solution containing 570g Milli-Deionized waterIn the blender, a gray colloidal dispersion is obtained that is free or substantially free of visible lumps or clumps. After the addition was complete, the dispersion was stirred at high speed for 5 to 10 minutes to give a slightly viscous mixture of 5wt.% aqueous dispersion of HPM-20 clay. 42g of a portion of this 5wt.% aqueous HPM-20 dispersion was mixed with 258g of Milli-Deionized water was combined to give 0.7wt.% of an aqueous HPM-20 dispersion. Then 280g of this 0.7wt.% colloidal dispersion are transferred to a measuring vessel containing Colloidal DynamicsZetaprobe Analyzer ^TM an axial bottom stirrer. The stirring speed was set between 250rpm and 350 rpm.

The zeta potential measurement was performed on the diluted aqueous HPM-20 dispersion using an initial colloid content estimate of 0.7wt.% to determine the actual colloid content of the clay dispersion according to the procedure outlined in the instrument attached Colloidal DynamicsZetaprobe Analyzer ^TM handbook. 5wt.% of the aqueous HPM-20 dispersion was measured, resulting in a zeta potential measurement of-46 mV (minus 46 mV). The initial colloid content estimate was adjusted to match this zeta potential. In this case, the HPM-20 colloid content of the dispersion was determined to be 0.62%. Colloidal DynamicZetaprobe the measurement parameters are as follows: reading 5 times at a rate of 1 reading/min; particle density of 2.6g/cc; the dielectric constant was 4.5.

By diluting 50wt.% of an aluminum hydroxychloride solution (GEO), 2.5wt.% of an aqueous aluminum hydroxychloride (ACH) solution was obtained. This 2.5wt.% ACH solution was then volume titrated into a 0.7wt.% HPM-20 aqueous dispersion. Titration was set at 0.5mL per titration point, with a 30 second delay in equilibration, that is, 30 seconds after addition of 0.5mL of ACH aqueous solution before zeta potential measurement to allow equilibration.

Fig. 3 and table 4 report the zeta potential titration results of 2.5wt.% aqueous aluminum hydroxychloride (ACH) added to 0.7wt.% aqueous HPM-20 dispersion, plotting the measured zeta potential versus titrant volume (mL). The titrant volume represents the cumulative volume of the aqueous aluminum chlorohydrate solution added. The ACH mole aluminum/clay mass ratios for achieving zeta potentials of-20 mV, neutral, and +20mV are summarized in table 4, based on the amount of ACH solution and the measured density of ACH solution of 1.075 g/mL.

TABLE 4 ACH addition toZeta potential titration results of aqueous HPM-20 dispersions

EXAMPLE 10 polyaluminum chloride in Clay heteroadducts290/Zeta potential determination of HPM-20 ratio

30G of HPM-20 clay was slowly added over 1 to 2 minutes to a slurry containing 570g Milli-Deionized waterIn the blender, while stirring at low speed, a gray colloidal dispersion is obtained that is free or substantially free of visible lumps or clumps. After the addition was complete, the dispersion was stirred by high speed blending for 5 to 10 minutes to give a slightly viscous mixture of 5wt.% aqueous dispersion of HPM-20 clay.

60G of a portion of this 5wt.% aqueous HPM-20 dispersion was mixed with 240g of Milli-Deionized water was combined to give 1wt.% of an aqueous HPM-20 dispersion. About 280g of this 1wt.% colloidal dispersion was transferred to a measuring vessel containing Colloidal DynamicsZetaprobe Analyzer ^TM an axial bottom stirrer. The stirring speed was set as described above.

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

Using Milli-Deionized water A4.58 g sample of polyaluminum chloride (abbreviated as "PAC")290 (Al ₂O₃ content 17.1%) was diluted into a 100mL volumetric flask. This 4.58wt. -% was then added290 Solution volume titrated into the above 1wt.% HPM-20 clay dispersion. Titration was set at 1mL per titration point and equilibration delay was 30 seconds.

These zeta potential measurements are reported in fig. 5 and table 5, where titrant volume represents 4.58wt.% aqueous added290 Cumulative volume of solution, and plotting measured zeta potential versus titrant volume (mL). Table 5 summarizes the values used to achieve-20 mV, neutral and +20mV zeta potentials290 Amount of dispersion.

TABLE 5 will290 ToResults of zeta potential titration of aqueous HPM-20 dispersion

EXAMPLE 11 Clay heteroadductsAL27 colloidal alumina-Zeta potential determination of HPM-20 ratio

By adding about 60g of a 5wt.% aqueous dispersion of HPM-20 clay to 240g of Milli-In water, 1wt.% of an HPM-20 clay dispersion was prepared. 285g to 300g of a portion of 1wt.% dispersion was transferred to a Zetaprobe 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 aqueous HPM-20 dispersion to determine the actual colloidal content of the clay dispersion. 5wt.% of the aqueous HPM-20 dispersion was measured to give a zeta potential of-44.2 mV. The initial colloid content estimate was adjusted to match this zeta potential. In this case, the HPM-20 clay colloid content of the dispersion was determined to be 0.92%. Colloidal DynamicZetaprobe the measurement parameters are as follows: reading 5 times at a rate of 1 reading/min; particle density of 2.6g/cc; the dielectric constant was 4.5.

Will be commercially available100G sample of AL27 colloidal alumina Dispersion (20 wt.% Al ₂O₃) and 100g Milli-Deionized water is combined to obtain10Wt.% AL ₂O₃ dispersion of AL 27. This 10wt.% dispersion was then titrated into the 1wt.% HPM-20 clay dispersion described above. (1 wt.% HPM-20 concentration designation is based on formulation, rather than an estimate of zeta potential, which is determined to be about 0.92wt.%, since not all clays are colloidal at dilution.) titration settings are as follows: from 0mL to 27mL, 1mL at each drop point, followed by 3mL at each drop point, the equilibration delay was 60 seconds.

These measurements are reported in FIG. 6 and Table 6, where titrant volume represents additionCumulative volume of AL27 alumina dispersion. In this example, the titrant is also a colloidal substance. Zeta potential was adjusted using the methods described previously to provide the data in fig. 6. . For achieving zeta potentials of-20 mV, neutral and +20mVThe amounts of AL27 dispersion are summarized in table 6.

TABLE 6 willAL27 colloidal alumina addition toResults of zeta potential titration in HPM-20

EXAMPLE 12 preparation of Chlorohydrated aluminum Clay heteroadducts (1.76 mmol Al/g Clay)

At the position of475.22 Grams of deionized water was added to the blender. With stirring, 25.09 grams of HPM-20 clay from American colloid company was slowly added. After the clay addition was completed, the mixture was stirred at high speed for 5 minutes to give a uniform suspension without lumps, after which 9.53 g of aluminum chlorohydrate 50wt.% aqueous solution was added with stirring and stirring was continued for 9 minutes. The mixture was poured into high density polyethylene bottles. With 42.5 g of deionized Milli-Water flushingFlask and transfer rinse water into the flask. The flask was shaken to thoroughly mix the contents and the conductivity of the slurry was measured to be 4.03mS/cm and pH 5.89.

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

EXAMPLE 13 comparative example of preparation of a aluminum sesquichloride-Clay heteroadduct Using powdered aluminum sesquichloride (ASCH, 6.4mmol Al/g Clay)

In this comparative example, powdered Aluminum Sesquichloride (ASCH) was used to synthesize an aluminum sesquichloride-hydroxyaluminum clay heteroadduct, which suggests that multiple washes and centrifuges were required to isolate the product as compared to the procedure and product of examples 31 and 32.

30G of HPM-20 clay was slowly added over 1 to 2 minutes with stirring to a solution containing 570g of deionized Milli-Of waterIn the blender, while stirring at low speed, a gray colloidal dispersion is obtained that is free or substantially free of visible lumps or clumps. After the addition was complete, the dispersion was blended at high speed for 5 to 10 minutes to give a slightly viscous mixture of 5wt.% aqueous dispersion of HPM-20 clay.

100G of a portion of this 5wt.% aqueous HPM-20 clay dispersion was transferred toIn a blender. Into a separate vial was added 3.53g31P powder and 35mL to 40mL deionized Milli-Water and this mixture was poured into the stirred dispersion in one portion. The mixture was blended at high speed for 5 minutes and then sub-packaged into four 50mL centrifuge tubes and centrifuged at 3000rpm to 3500rpm for 30 minutes to 60 minutes. The pH and conductivity (Eutech PCSTestr) of the supernatant were measured, the pH being 4.0 and the conductivity being 7300. Mu.S/cm. The supernatant was decanted and the remaining wet solids resuspended in deionized Milli-In water. The centrifugation process (centrifugation, supernatant pH/conductivity measurement, supernatant removal, re-suspension in deionized Milli-In water) until the conductivity of the supernatant reaches 100 to 300. Mu.S/cm. Six total centrifuges were required to achieve this conductivity, the final supernatant pH was found to be 4.3 and the conductivity was found to be 286. Mu.S/cm. At this time, the supernatant was discarded last time, the remaining wet solid was combined with 100 to 200mL of 1-butanol in a round bottom flask and rotary evaporated at 45 ℃ to give 5.82g of wet solid, which was then ground with a pestle and mortar. 2.1g of this solid sample was transferred to a ceramic crucible and calcined at 300℃for 6 hours to give 1.1g of a gray-black powder.

EXAMPLE 14 spray drying, sieving and calcining unwashed chlorine hydrated aluminum clay heteroadduct (1.76 mmol Al/g Clay) retained on a 325 mesh screen

A portion of the aluminum chlorohydrate clay heteroadduct (1.76 mmol Al/g clay) mixture (slurry) prepared according to example 12 was spray dried using a Buchi B290 laboratory spray dryer. Some of the spray-dried clay heteroadducts were sieved through a 325 mesh screen. Two grams of material remaining on a 325 mesh screen were loaded into a 300 ℃ oven and heated in air for 6 hours. While hot, the material was transferred to a vacuum chamber and cooled to room temperature under vacuum.

EXAMPLE 15 spray drying, sieving and calcining unwashed chlorine hydrated aluminum clay heteroadduct (1.76 mmol Al/g Clay) on a 325 mesh screen

A portion of the aluminum chlorohydrate clay heteroadduct (1.76 mmol Al/g clay) mixture (slurry) prepared according to example 12 was spray dried using a Buchi B290 laboratory spray dryer. Some of the spray-dried clay heteroadducts were sieved through a 325 mesh screen. Two grams of the sieve material were placed in an oven at 300 c and heated in air for 6 hours. While hot, the material was transferred to a vacuum chamber and cooled to room temperature under vacuum.

EXAMPLE 16 spray drying and calcination of washed chloro-hydrated aluminum Clay heteroadducts (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 Fisher brand ^TM P8 filter paper using a Buchner funnel and vacuum. 158g of the filter cake was then transferred to HDPE bottles, which were resuspended in about 1.2L of deionized water by shaking. The slurry thus obtained had a conductivity of 114. Mu.S/cm and a pH of 6.25. The slurry was filtered through Fisher brand ^TM P8 filter paper again and left on the filter under vacuum overnight to give 109.03 g of a gray solid. A97.07 g sample of this solid was charged into HDPE bottles with 452g deionized water and shaken until no lumps were visible in the slurry. The conductivity of this slurry was 112. Mu.S/cm and the pH was 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 was loaded into a 300 ℃ oven and calcined in air for 6 hours. The material was then transferred to a vacuum chamber while hot and cooled to room temperature under vacuum.

EXAMPLE 17 Single filtration, azeotroping and calcination of aluminum chlorohydrate Clay heteroadducts (1.76 mmol Al/g Clay)

543G of a slurry of a chlorohydrate aluminum clay heteroadduct (1.76 mmol Al/g clay) prepared according to example 12 was vacuum filtered through Fisher brand ^TM brand P8 filter paper. The resulting filter cake was then resuspended in approximately 1L of deionized water to give a slurry with a conductivity of 114. Mu.S and a pH of 6.25. The slurry was then vacuum filtered through Fisher brand ^TM brand P8 paper and 11.5 grams of filter cake derived from the clay heteroadduct remaining on the filter paper was charged to a conical flask equipped with a stir bar. 200mL of n-butanol was then added and the mixture stirred until a slurry was obtained without visible lumps or clumps. The stirrer bar was removed and the flask was rotary evaporated in a 45 ℃ bath. The off-white powder containing some flakes and chunks was lightly ground to a uniform powder and 1.04g of the powder was charged into a ceramic crucible which was calcined in air at 300 ℃ for 6 hours. The calcined material was cooled under vacuum and 0.867g of the material was transferred into an inert atmosphere glove box.

EXAMPLE 18 reproducibility of the one-time filtration, azeotroping and calcination of aluminum chlorohydrate Clay heteroadduct (1.76 mmol Al/g Clay) according to example 17

Transferring 100g of this 5wt.% aqueous dispersion of a portion of HPM-20 clay toIn the blender, 1.91g of a 50wt.% aqueous solution of GEO aluminum hydroxychloride was pipetted into a vial and added to the dispersion in one portion. The mixture rapidly coagulated and 70mL of deionized Milli-Water to promote agitation. The mixture was then blended at high speed for 5 minutes, followed by vacuum filtration through Fisher P8 qualitative grade filter paper (coarse porosity). After allowing to filter for 15 to 30 minutes, the pH and conductivity of the filtrate were measured (Eutech PCSTestr), resulting in a pH of 6.1 and a conductivity of 1516. Mu.S/cm. The filtrate is discarded and the remaining wet solids are resuspended in 50mL to 100mL deionized Milli-In water.

The filtration process was repeated again (suspension of wet solids in deionized Milli-In water, vacuum filtration, filtrate pH/conductivity measurement). The remaining wet solids were resuspended in 150mL to 200mL 1-butanol and rotary evaporated at 45 ℃. The resulting solid was then ground with a pestle and mortar to give 5.18g of a light gray powder. A portion of 1.90g of this solid was transferred to a ceramic crucible and calcined at 300℃for 6 hours to give 0.9g of a gray-black powder. The powder XRD (x-ray diffraction) pattern of this sample is shown in fig. 2, and the BJH pore volume analysis of this sample is plotted in fig. 10.

EXAMPLE 19 comparative example of preparation of Aluminum Chlorohydrate (ACH) ion-exchanged clay (0.3 mmol Al/g Clay)

100G of a portion of this 5wt.% aqueous HPM-20 clay dispersion was transferred toIn a blender. A0.325 g sample (50 wt.%) of the aqueous GEO ACH dispersion was pipetted into a vial and combined with 20mL of deionized Milli-The water was combined and then poured into the clay dispersion at one time. 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/second). After a filtration process which allowed 15 to 30 minutes, the pH and conductivity of the filtrate (Eutech PCSTestr) were measured, resulting in a pH of 7.3 and a conductivity of 487. Mu.S/cm. The filtrate was discarded and the remaining wet solids were resuspended in 50mL of deionized Milli-In water, and one centrifugation is performed at 3000rpm to 3500rpm for 30 minutes to 60 minutes. After removal of the supernatant (180. Mu.S/cm measured conductivity), the remaining wet solid was resuspended in 50mL to 100mL 1-butanol and rotary evaporated at 45 ℃. The resulting solid was then ground with a pestle and mortar, and then 1.7g of the ground solid was transferred to a ceramic crucible and calcined at 300 ℃ for 6 hours to give 0.8g of a gray black powder.

EXAMPLE 20 preparation of Aluminum Chlorohydrate (ACH) -Clay heteroadducts (1.17 mmol Al/g Clay)

30G are stirred for 1 to 2 minutesHPM-20 clay was slowly added to a solution containing 570g of deionized Milli-Of waterIn the blender, while stirring at low speed, a gray colloidal dispersion is obtained that is free or substantially free of visible lumps or clumps. After the addition was complete, the dispersion was blended at high speed for 5 to 10 minutes to give a slightly viscous mixture of 5wt.% aqueous dispersion of HPM-20 clay.

100G of a portion of this 5wt.% aqueous HPM-20 clay dispersion was transferred toIn a blender. Then, 1.27g of a 50wt.% aqueous solution of GEO aluminum hydroxychloride was pipetted into a vial and added to the dispersion in one portion. The mixture rapidly coagulated and 70mL of deionized Milli-Water to promote agitation. The mixture was then blended at high speed for 5 minutes, followed by vacuum filtration through Fisher P8 qualitative grade filter paper (coarse porosity). After filtration for 15 to 30 minutes, the pH and conductivity of the filtrate were measured (Eutech PCSTestr) to give a pH of 6.25 and a conductivity of 1166. Mu.S/cm. The filtrate is discarded and the remaining wet solids are resuspended in 50mL to 100mL deionized Milli-In water.

The filtration process was repeated (suspension of wet solids in deionized Milli-In water, vacuum filtration, filtrate pH/conductivity measurement) until the conductivity of the resuspended slurry reaches 100 μs/cm to 300 μs/cm. In this case, one additional filtration was performed to obtain a slurry having a pH of 6.2 and a conductivity of 188. Mu.S/cm. The remaining wet solids were resuspended in 150mL to 200mL 1-butanol and rotary evaporated at 45 ℃. The solid was then ground with a pestle and mortar to give 2.97g of a light gray powder. A portion of 1.7g of this solid was transferred to a ceramic crucible and calcined at 300℃for 6 hours to give 1.0g of a gray-black powder. The powder XRD (x-ray diffraction) pattern of this sample is shown in figure 2.

EXAMPLE 21 preparation of Aluminum Chlorohydrate (ACH) -Clay heteroadducts (1.52 mmol Al/g Clay)

100G of a portion of this 5wt.% aqueous HPM-20 clay dispersion was transferred toIn a blender. A sample of a50 wt.% aqueous solution of 1.66g GEO aluminum hydroxychloride was pipetted into a vial and added to the dispersion in one portion. The resulting mixture rapidly coagulated and 80mL of deionized Milli-Water to promote agitation. The mixture was then blended at high speed for 5 minutes, followed by vacuum filtration through Fisher P8 qualitative grade filter paper (coarse porosity). After allowing to filter for 15 to 30 minutes, the pH and conductivity of the filtrate were measured (Eutech PCSTestr), resulting in a pH of 6.2 and a conductivity of 1518. Mu.S/cm. The filtrate is discarded and the remaining wet solids are resuspended in 50mL to 100mL deionized Milli-In water.

The filtration process was repeated (suspension of wet solids in deionized Milli-In water, vacuum filtration, measurement of filtrate pH/conductivity) until the conductivity of the resuspended slurry reaches 100 μs/cm to 300 μs/cm. In this case, one additional filtration was performed to obtain a slurry having a pH of 6.1 and a conductivity of 199. Mu.S/cm. The remaining wet solids were resuspended in 150mL to 200mL 1-butanol and rotary evaporated at 45 ℃. The resulting solid was then ground with a pestle and mortar to give 3.19g of a light gray powder. 1.65g of this solid sample was transferred to a ceramic crucible and calcined at 300℃for 6 hours to give 0.9g of a gray-black powder. The powder XRD pattern of this sample is shown in figure 2.

EXAMPLE 22 comparative example of preparation of Aluminum Chlorohydrate (ACH) -Clay heteroadduct (2.5 mmol Al/g Clay) and Single filtration

100G of this 5wt.% aqueous dispersion of a portion of HPM-20 clay was transferred toIn a blender. A sample of a 50wt.% aqueous solution of 2.71g GEO aluminum hydroxychloride was pipetted into a vial and added to the dispersion in one portion. The mixture became viscous rapidly, 100mL of deionized Milli-Water to promote agitation. The mixture was then blended at high speed for 5 minutes and then vacuum filtered through Fisher P8 qualitative grade filter paper (coarse porosity). After allowing to filter for 15 to 30 minutes, the pH and conductivity of the filtrate were measured (Eutech PCSTestr), resulting in a pH of 4.72 and a conductivity of 1988. Mu.S/cm. A portion of the wet solid filter cake was resuspended in 50mL to 100mL 1-butanol and rotary evaporated at 45 ℃. The dry solid was then ground with a pestle and mortar to yield 0.66g of a light gray powder. A portion of 0.64g of this solid was transferred to a ceramic crucible and calcined at 300℃for 6 hours to give 0.5g of a gray-black powder.

EXAMPLE 23 preparation of Aluminum Chlorohydrate (ACH) -Clay heteroadduct and comparative example of additional washing/filtration compared to example 22 (2.5 mmol Al/g Clay)

100G of this 5wt.% aqueous dispersion of a portion of HPM-20 clay was transferred toIn a blender. A sample of a 50wt.% aqueous solution of 2.71g GEO aluminum hydroxychloride was pipetted into a vial and added to the dispersion in one portion. The mixture became viscous rapidly, 100mL of deionized Milli-Water to promote agitation. The mixture was then blended at high speed for 5 minutes and then vacuum filtered through Fisher P8 qualitative grade filter paper (coarse porosity). After allowing to filter for 15 to 30 minutes, the pH and conductivity of the filtrate were measured (Eutech PCSTestr). The filtrate is discarded and the remaining wet solids are resuspended in 50mL to 100mL deionized Milli-In water.

The filtration process was repeated (suspension of wet solids in deionized Milli-In water, vacuum filtration, measurement of filtrate pH/conductivity) until the conductivity of the resuspended slurry reaches 100 μs/cm to 300 μs/cm. In this case, one additional filtration was performed to obtain a slurry having a pH of 4.67 and a conductivity of 87. Mu.S/cm. The remaining wet solid was resuspended in 50mL to 100mL 1-butanol and rotary evaporated at 45 ℃. The dry solid was then ground with a pestle and mortar to give 3.73g of a light gray powder. A portion of 1.37g of this solid was transferred to a ceramic crucible and calcined at 300℃for 6 hours to give 0.6g of a gray-black powder. The powder XRD pattern of this sample is shown in figure 2.

EXAMPLE 24 comparative example of preparation of Aluminum Chlorohydrate (ACH) -Clay heteroadduct (3.5 mmol Al/g Clay) and Single filtration

100G of this 5wt.% aqueous dispersion of a portion of HPM-20 clay was transferred toIn a blender. A sample of 3.80g GEO aluminum hydroxychloride in 50wt.% aqueous solution was pipetted into a vial and added to the dispersion in one portion, and 20mL of deionized Milli-Water to promote agitation. The mixture was then blended at high speed for 5 minutes and then vacuum filtered through Fisher P8 qualitative grade filter paper (coarse porosity). After allowing to filter for 15 to 30 minutes, the pH and conductivity of the filtrate were measured (Eutech PCSTestr) to give a pH of 4.34 and a conductivity of 1500. Mu.S/cm. A portion of the wet solid was resuspended in 50mL to 100mL 1-butanol and rotary evaporated at 45 ℃. The dry solid was then ground with a pestle and mortar to yield 0.74g of a light gray powder. A portion of 0.62g of this solid was transferred to a ceramic crucible and calcined at 300℃for 6 hours to give 0.5g of a gray-black powder.

EXAMPLE 25 preparation of Aluminum Chlorohydrate (ACH) -Clay heteroadduct and comparative example of additional washing/filtration compared to example 24 (3.5 mmol Al/g Clay)

100G of this 5wt.% aqueous dispersion of a portion of HPM-20 clay was transferred toIn a blender. A sample of a 50wt.% aqueous solution of 3.80g GEO aluminum hydroxychloride was pipetted into a vial and added to the dispersion in one portion. The mixture became viscous rapidly and 20mL of deionized Milli-Water to promote agitation. The mixture was then blended at high speed for 5 minutes and then vacuum filtered through Fisher P8 qualitative grade filter paper (coarse porosity). After allowing to filter for 15 to 30 minutes, the pH and conductivity of the filtrate were measured (Eutech PCSTestr). The filtrate is discarded and the remaining wet solids are resuspended in 50mL to 100mL deionized Milli-In water.

The filtration process was repeated (suspension of wet solids in deionized Milli-In water, vacuum filtration, measurement of filtrate pH/conductivity) until the conductivity of the resuspended slurry reaches 100 μs/cm to 300 μs/cm. In this case, one additional filtration was performed to obtain a slurry having a pH of 4.5 and a conductivity of 180. Mu.S/cm. The remaining slurry was resuspended in 50mL to 100mL 1-butanol and rotary evaporated at 45 ℃. The dry solid was then ground with a pestle and mortar to give 4.33g of a light gray powder. A portion of 1.36g of this solid was transferred to a ceramic crucible and calcined at 300℃for 6 hours to give 0.6g of a gray-black powder. The powder XRD pattern of this sample is shown in figure 2.

EXAMPLE 26 comparative example of preparation of Aluminum Chlorohydrate (ACH) -Clay heteroadduct Using powdered ACH reagent (0.3 mmol Al/g Clay)

100G of this 5wt.% aqueous dispersion of a portion of HPM-20 clay was transferred toIn a blender. Into a separate vial was added 0.160g51P powder and 20mL deionized Milli-And (3) water. The mixture was poured into the stirred dispersion in one portion and 40mL of deionized Milli-Water to promote agitation. The mixture was then high speed blended for 5 minutes and then vacuum filtered through Fisherbrand ^TM P8 qualitative grade filter paper (coarse porosity). Filtration was slow (< 1 drop/second). After allowing to filter for 15 to 30 minutes, the pH and conductivity of the filtrate (Eutech PCSTestr) were measured, resulting in a pH of 6.5 and a conductivity of 780. Mu.S/cm. The filtrate was discarded and the remaining wet solids were resuspended in 50mL of deionized Milli-In water, and one centrifugation is performed at 3000rpm to 3500rpm for 30 minutes to 60 minutes. After removal of the supernatant (conductivity 180. Mu.S/cm), the remaining wet solid was resuspended in 50mL to 100mL 1-butanol and rotary evaporated. The resulting solid was then ground with a pestle and mortar, then transferred to a ceramic crucible, and calcined at 300 ℃ for 6 hours to give a gray black powder.

EXAMPLE 27 comparative example of preparation of Aluminum Chlorohydrate (ACH) -Clay heteroadduct Using powdered ACH reagent (0.6 mmol Al/g Clay)

100G of this 5wt.% aqueous dispersion of a portion of HPM-20 clay was transferred toIn a blender. Into a separate vial was added 0.4g51P powder and 20mL deionized Milli-And (3) water. This mixture was poured into the stirred dispersion in one portion. 40mL of deionized Milli was addedWater to promote agitation. The mixture was then blended at high speed for 5 minutes and then vacuum filtered through Fisher P8 qualitative grade filter paper (coarse porosity). After allowing to filter for 15 to 30 minutes, the pH and conductivity of the filtrate were measured (Eutech PCSTestr) to give a pH of 7.2 and a conductivity of 180. Mu.S/cm. The filtrate was discarded and the remaining wet solids were resuspended in 50mL of deionized Milli-In water, and one centrifugation is performed at 3000rpm to 3500rpm for 30 minutes to 60 minutes. After removal of the supernatant (conductivity 180. Mu.S/cm), the remaining wet solid was resuspended in 50mL to 100mL 1-butanol and rotary evaporated at 45 ℃. The resulting solid was then ground with a pestle and mortar to give 2g of gray powder, which was then transferred to a ceramic crucible and calcined at 300 ℃ for 6 hours to give a gray black powder.

EXAMPLE 28 preparation and additional washing of Aluminum Chlorohydrate (ACH) -Clay heteroadducts Using powdered ACH reagent compared to EXAMPLE 29 (1.52 mmol Al/g Clay)

100G of this 5wt.% aqueous dispersion of a portion of HPM-20 clay was transferred toIn a blender. Into a separate vial was added 0.812g51P powder and 20mL deionized Milli-And (3) water. This mixture was poured into the stirred dispersion in one portion. Adding 20-40mL deionized Milli-Water to promote agitation. The mixture was then blended at high speed for 5 minutes and then vacuum filtered through Fisher P8 qualitative grade filter paper (coarse porosity). After allowing to filter for 15 to 30 minutes, the pH and conductivity of the filtrate were measured (Eutech PCSTestr). Resuspending the remaining wet solids in 50mL to 100mL deionized MilliIn water.

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

EXAMPLE 29 preparation and Single filtration of Aluminum Chlorohydrate (ACH) -Clay heteroadducts Using powdered ACH reagent compared to EXAMPLE 28 (1.52 mmol Al/g Clay)

100G of this 5wt.% aqueous dispersion of a portion of HPM-20 clay was transferred toIn a blender. Into a separate vial was added 0.812g51P powder and 20mL deionized Milli-And (3) water. The mixture is poured into the stirred dispersion in one portion and 20-40mL of deionized Milli-Water to promote agitation. The resulting mixture was then blended at high speed for 5 minutes and then vacuum filtered through Fisher ^TM P8 qualitative grade filter paper. After allowing to filter for 15 to 30 minutes, the pH and conductivity of the filtrate were measured (Eutech PCSTestr) to give a pH of 5.8 and a conductivity of 1750. Mu.S/cm. A portion of the remaining wet solids was resuspended in 50mL to 100mL 1-butanol and rotary evaporated at 45 ℃. The solid was then ground with a pestle and mortar to give 1g of gray powder, which was then transferred to a ceramic crucible and calcined at 300 ℃ for 6 hours to give 0.6g of gray black powder.

EXAMPLE 30 preparation of Aluminum Chlorohydrate (ACH) -Clay heteroadducts Using powdered ACH reagent (1.76 mmol Al/g Clay)

100G of this 5wt.% aqueous dispersion of a portion of HPM-20 clay was transferred toIn a blender. Into a separate vial was added 0.940g51P powder and 20mL deionized Milli-And (3) water. This mixture was poured into the stirred dispersion in one portion. Adding 20mL to 40mL of deionized Milli-Water to promote agitation. The mixture was then blended at high speed for 5 minutes and vacuum filtered through Fisher brand ^TM P8 qualitative grade filter paper and deionized Milli- -Washing with water. After allowing to filter for 15 to 30 minutes, the pH and conductivity of the filtrate were measured (Eutech PCSTestr) to give a pH of 6.1 and a conductivity of 1799. Mu.S/cm. A portion of the remaining wet solids was resuspended in 50mL to 100mL 1-butanol and rotary evaporated at 45 ℃. The solid was then ground with a pestle and mortar to give 1.07g of gray powder, which was then transferred to a ceramic crucible and calcined at 300 ℃ for 6 hours to give 0.9g of gray black powder.

EXAMPLE 31 preparation of aluminum sesquichloride-Clay heteroadducts (1.52 mmol Al/g Clay)

100G of this 5wt.% aqueous dispersion of a portion of HPM-20 clay was transferred toIn a blender. Weigh 1.30gA31L sample of the solution was placed in a vial and mixed with sufficient deionized Milli-Water is added to the dispersion together to promote agitation. The mixture was then blended at high speed for 5 minutes and the conductivity measured (Eutech PCSTestr) to give a conductivity of 2600. Mu.S/cm. The mixture was then vacuum filtered through Fisher brand ^TM P8 qualitative grade filter paper and 100mL deionized Milli-The water is simply washed. After allowing to filter for 15 to 30 minutes, a portion of the remaining wet solids is resuspended in 50 to 100mL of water and the conductivity is measured again, typically in the range of 100 μS/cm to 500 μS/cm (in this case, 70 μS/cm). The suspension was then combined with 100 to 200ml 1-butanol and rotary evaporated at 45 ℃. The solid was then ground with a pestle and mortar to give 6.2g of gray powder, and then 1.8g of this solid was transferred to a ceramic crucible and calcined at 300 ℃ for 6 hours to give 0.9g of gray black powder.

EXAMPLE 32 comparative example of preparation of aluminum sesquichloride-Clay heteroadduct (2.5 mmol aluminum/g Clay)

100G of this 5wt.% aqueous dispersion of a portion of HPM-20 clay was transferred toIn a blender. Weigh 2.79gA31L sample of the solution was placed in a vial and mixed with sufficient deionized Milli-Water is added to the dispersion together to promote agitation. The mixture was then blended at high speed for 5 minutes and the conductivity measured (Eutech PCSTestr) to give a conductivity of 2800. Mu.S/cm. The mixture was then vacuum filtered through Fisher brand ^TM P8 qualitative grade filter paper and 100mL deionized Milli-The water is simply washed. After allowing to filter for 15 to 30 minutes, a portion of the remaining wet solids is resuspended in 50 to 100mL of water and the conductivity (320 μS/cm) is again measured, typically between 100 μS/cm and 500 μS/cm. This suspension was then combined with 100mL to 200mL of 1-butanol and rotary evaporated at 45 ℃. The solid was then ground with a pestle and mortar to give 5.57g of gray powder, and then 1.7g of this solid was transferred to a porcelain crucible and calcined at 300 ℃ for 6 hours to give 1g of gray black powder.

EXAMPLE 33 comparative example of preparation of polyaluminum chloride (PAC) -Clay heteroadduct (0.5 mmol Al/g Clay)

5.0Wt. -% to be prepared according to the procedure in example 4177.28 G sample charge of HPM-20 suspensionIn a blender. 1.32g ofThe 290 solution (GEO) was added to the HPM-20 clay slurry, after which it was stirred at high speed for 9 minutes. The gray heteroadduct viscous material was then transferred in 2 portions with 210g deionized water into HDPE polyethylene bottles. The gray heteroadduct slurry was then shaken by hand for about 1 minute to give a pH of 4.31 and a conductivity of 1672. Mu.S/cm. The slurry was filtered through Fisher brand ^TM P8 straining paper to give 28.03g of wet cake, which was transferred to HDPE bottles, to which 308g of deionized water was also added. The flask was shaken to leave the slurry free of lumps, pH 4.76, conductivity 200. Mu.S/cm. The slurry was filtered through Fisher brand ^TM P8 filter paper to give 22.30g of wet cake, which was transferred to a conical flask equipped with a stirring bar along with 200mL of n-butanol and stirred until no lumps were visible. The stirring bar was removed and the mixture was rotary evaporated in a 45 ℃ bath to give 9.49g of an off-white powder which was lightly ground to a fine powder using a mortar and pestle. 1.10 g of an off-white powder was charged into a ceramic crucible, then into an oven at 300℃and calcined for 6 hours, giving 0.8960g of a dark gray powder. The powder was cooled to ambient temperature under vacuum and then transferred to an inert atmosphere glove box.

EXAMPLE 34 preparation of polyaluminum chloride (PAC) -Clay heteroadducts (1.01 mmol Al/g Clay)

A sample of 201.23.0 wt.% HPM-20 clay suspension as prepared in example 4 was loadedIn a blender. 3.036g under stirringThe 290 solution (GEO) was added to the HPM-20 slurry. The obtained thick matter can not be usedThe blender was stirred but transferred to HDPE bottles, ground twice with deionized water, and 185g total were shaken by hand until no lumps or clumps were visible. The pH of the resulting slurry was 3.8 and the conductivity was 26mS/cm. The slurry was filtered through Fisher brand ^TM coarse filter paper No. 8, and the clear filtrate had a conductivity of 5.2mS/cm. 61g of the filter cake was then transferred to the original polymer bottle and resuspended by shaking in 328g of deionized water until no lumps were visible. The conductivity obtained was 1116. Mu.S/cm, and the pH was 3.93. The slurry was then filtered through Fisher brand ^TM P8 filter paper. The conductivity of the clear filtrate was 1200. Mu.S/cm. A 9.95g sample of the filter cake was transferred to the conical flask. The remaining filter cake was resuspended in fresh HDPE bottles in 281g of deionized water while shaking to give a slurry with a pH of 4.11 and a conductivity of 150. Mu.S/cm. After standing overnight, the slurry was filtered through Fisher brand ^TM P8 filter paper and 18.25g of filter cake was transferred to an Erlenmeyer flask with 100mL of n-butanol. The flask was shaken to break up the large pieces, and then rotary evaporated in a 40℃bath to give 9.08g of an off-white powder. 2.384g of an off-white powder sample were charged into a ceramic crucible and placed in an oven at 300℃for 6 hours to give 1.72g of a gray powder, which was cooled to ambient temperature under vacuum 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)

199.31G of a 5.0wt.% HPM-20 clay suspension prepared according to example 4 was loaded with a sampleIn a blender. 4.36g of the extract from GEO SPECIALTY CHEMICALS are stirredThe 290 solution was added to the HPM-20 clay slurry. The flask was removed from the stirrer and swirled until the viscous gray material could be stirred using the stirrer, after which it was stirred at high speed for 9 minutes. The viscous material was then poured into HDPE polymer bottles with 2 parts of a total of 85g deionized water to give a total of 275g gray heteroadduct slurry, which was then shaken by hand for about 1 minute to give a slurry having a pH of 3.73 and a conductivity of 6.79 mS/cm. The slurry was filtered through Fisher brand ^TM P8 straining paper, and the filter cake was resuspended in approximately 200mL deionized water to give a slurry with a conductivity of 1 mS/cm. The slurry was filtered and 34g of the partial cake was transferred to a 500mL Erlenmeyer flask equipped with a stir bar along with 200mL of n-butanol. The mixture was stirred overnight to break up the solid chunks. The stirring bar was then removed and the mixture was rotary evaporated in a 45 ℃ bath to give 10.78g of an off-white powder which was lightly ground to a fine powder using a mortar and pestle. 1.07g of an off-white powder was charged into a ceramic crucible and then calcined at 300℃for 6 hours to obtain 0.8800 g of a dark gray powder. The powder was cooled to ambient temperature under vacuum and then transferred into an inert atmosphere glove box.

EXAMPLE 36 preparation of nano alumina clay-hetero adduct (0.49 g alumina/g clay, 4.8mmol Al/g clay)

Then, 80g of 5wt.% colloidal suspension of HPM-20 clay was added to a graduated addition funnel. 9.7g ofThe AL-27 dispersion (20% Al ₂O ₃) was added to a separate addition funnel and the suspension was diluted to a 80mL capacity level. The solution was added simultaneously to a solution containing 137g Milli- -Of waterIn a blender. The resulting mixture was then blended at high speed for about 5 minutes, followed by vacuum filtration through Fisher P8 qualitative grade filter paper. After allowing to filter for 15 to 30 minutes, the pH and conductivity of the filtrate (Eutech PCSTestr) were measured, resulting in a pH of 9.1 and a conductivity of 451. Mu.S/cm. A portion of the remaining wet solids was resuspended in 50mL to 100mL 1-butanol and rotary evaporated at 45 ℃. The resulting solid was then ground with a pestle and mortar to give 1.79g of a light gray powder, 0.65g of this powder was transferred to a ceramic crucible and calcined at 300℃for 6 hours to give 0.53g of a gray powder.

EXAMPLE 37 zeta potential titration of fumed silica with aluminum chlorohydrate

This and the following examples demonstrate that "stand-alone" cationic multimetal salts (such as ACH) can be combined with fumed silica to produce new cationic colloidal multimetal salt systems that can be used as heteroagglomerating agents so that when contacted with colloidal clay, heteroagglomerating clay can be formed.

15G in a beaker200 Fumed silica sample with 277g deionized Milli-And (5) mixing water. Using ULTRA-The dispersion tool dispersed the mixture at 5400rpm for 10 minutes and further redispersed at 7000rpm for 5 minutes, yielding a 5wt.% (calculated as silica) dispersion. 270g of this dispersion were transferred to a Colloidal DynamicsZetaprobe Analyzer ^TM measuring vessel which contained an axial bottom stirrer. The stirring speed is set fast enough to prevent substantial settling of the dispersion, but slow enough to allow the electroacoustic probe to be fully immersed in the mixture when fully lowered. The stirring speed is typically set between 250rpm and 350rpm, most often 300rpm.

A2.5 wt.% solution of aluminum chlorohydrate was prepared by diluting 6.16g of aqueous ACH (50 wt.% aluminum chlorohydrate; GEO SPECIALTY CHEMICALS) in 117g of water. This 2.5wt.% ACH solution was then added to the aforementioned 5wt.%Volumetric zeta potential titration of 200 dispersions. Titration was set at 1mL per titration point and equilibration delay was 60 seconds. The data obtained are depicted in FIG. 7ACH-200。

The comparison of zeta potential to titrant volume data in FIG. 7 was converted to zeta potential and titrant volume dataA comparison of 200 fumed silica masses is plotted in figure 8. From FIG. 8, any point is selected with a ratio higher than 0.04g ACH/g200, Corresponding to a zeta potential of about +30mV and below a ratio of about a monolayer, to produce a heterocoagulation reagent. The ratio of heterocoagulants to clay was then determined in the conventional manner described in examples 8 to 11, in particular by zeta potential titration of clay with such ACH-fumed silica heterocoagulants.

EXAMPLE 38 zeta potential titration of clay with ACH-fumed silica and determination of ACH-SiO ₂/clay ratio

Will 15g200 Fumed silica sample with 277g deionized Milli-The water was combined in a beaker. Using ULTRA-The dispersing means disperses the mixture at 6000rpm to 7000rpm for 10 minutes, after which 7.86g of GEO aluminum hydroxychloride (ACH) solution is added. The mixture was then redispersed at 7000rpm for 5 minutes to give 5wt.% (calculated as silica) ACH-200 Fumed silica dispersion.

Separately, 30g of HPM-20 clay was slowly added over 1 to 2 minutes to a solution containing 570g of deionized Milli-Of waterIn the blender, while stirring at low speed, a gray colloidal dispersion is obtained that is free or substantially free of visible lumps or clumps. After the addition was complete, the dispersion was stirred at high speed for 5 to 10 minutes, yielding a slightly viscous mixture of 5wt.% aqueous dispersion of Volclay.

60G of a sample of this 5wt.% aqueous HPM-20 dispersion was mixed with 240g of deionized Milli-The water was combined and shaken to give 1wt.% of an aqueous HPM-20 dispersion. About 280g of this colloidal dispersion was transferred to a measuring vessel containing Colloidal DynamicsZetaprobe Analyzer ^TM an axial bottom stirrer. The stirring speed was set as described above. Zeta potential measurements were performed on diluted HPM-20/water dispersions according to Zetaprobe Analyzer ^TM handbook to determine the actual colloidal content of the clay dispersion. 5wt.% of the aqueous HPM-20 dispersion was measured to give a zeta potential of-43 mV. The initial colloid content estimate was adjusted to match this zeta potential. In this case, the HPM-20 clay colloid content of the dispersion was estimated to be 0.86%. Colloidal DynamicZetaprobe the measurement parameters are as follows: reading 5 times at a rate of 1 reading/min; particle density of 2.6g/cc; the dielectric constant was 4.5.

Then ACH-Volume titration of 200 fumed silica dispersion to clay dispersion. Titration was set from 0 to 1.2mL, 0.2mL per titration point, 0.5mL per titration point up, equilibration delay 30 seconds, resulting in the data shown in fig. 9. In this example, the titrant is also a colloidal substance. Thus, the zeta potential was adjusted using the method described previously in example 11 to give the graph in fig. 9. ACH-A-II for achieving zeta potentials of-20 mV, neutral and +20mVAEROSIL in 200 fumed silica DispersionThe amount of fumed silica is summarized in table 7.

Table 7.Zeta potential titration results of 200 and ACH versus HPM-20

EXAMPLE 39 preparation of ACH-fumed silica/Clay heteroadducts (3.31 mmol Al/g Clay)

Will 15g200 Fumed silica sample with 277g deionized Milli-The water was combined in a beaker and ULTRA was usedThe dispersing tool disperses the mixture at 6000-7000rpm for 10 minutes. A sample of 7.86g GEO aluminum hydroxychloride solution was then added followed by redispersion at 7000rpm for 5 minutes.

Will be 57mLA 200 dispersion sample was loaded into a graduated addition funnel and 80gHPM-20 clay dispersion was transferred to a separate graduated addition funnel. Stirring while going to135G of deionized Milli in a stirrerThe contents of the addition funnel were added dropwise to the water. After the addition was complete, the mixture was mixed at high speed for 5 to 10 minutes and then vacuum filtered through Fisher brand ^TM P8 qualitative grade filter paper. After allowing to filter for 15 to 30 minutes, the pH and conductivity of the filtrate were measured (Eutech PCSTestr). Resuspending the remaining wet solids in 50mL to 100mL deionized Milli-In water.

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

EXAMPLE 40 preparation of hydrochloric acid treated Clay (5.28 mmol H+/g Clay)

This 5wt.% aqueous dispersion of 80g of HPM-20 clay sample was transferred toIn a blender. 42.2mL aliquots of 0.5M aqueous HCl were metered into graduated cylinders and then added to the clay dispersion in one portion. The mixture was blended at high speed for 5 minutes and then vacuum filtered through Fisher P8 qualitative grade filter paper (coarse porosity). After allowing to filter for 2 to 3 hours, the filtrate was discarded and the remaining wet solids were resuspended in 80mL deionized Milli-In water. The pH and conductivity (Eutech PCSTestr) of the resulting suspension were measured, resulting in a pH of 2.27 and a conductivity of 1560. Mu.S/cm.

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

EXAMPLE 41 preparation of hydrochloric acid treated Clay (1.5 mmol H ⁺/g Clay)

This 5wt.% aqueous dispersion of 80g of HPM-20 clay sample was transferred toIn a blender. 12mL aliquots of 0.5M aqueous HCl were metered into a graduated cylinder and then added to the clay dispersion in one portion, followed by 30mL of deionized Milli-Water to promote agitation. The mixture was then blended at high speed for 5 minutes and then vacuum filtered through Fisher P8 qualitative grade filter paper (coarse porosity). After allowing to filter for 2 to 3 hours, the filtrate was discarded and the remaining wet solids were resuspended in 80mL deionized Milli-In water. The pH and conductivity (Eutech PCSTestr) of the resulting suspension were measured, resulting in a pH of 2.56 and a conductivity of 4100. Mu.S/cm.

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

EXAMPLE 42 slurry sedimentation test of heteroaggregated Clay (1.52 mmol Al/g Clay)

40G of HPM-20 clay was slowly added over 1 to 2 minutes with stirring to a solution containing 760g of deionized Milli-Of waterIn the blender, while stirring at low speed, a gray colloidal dispersion is obtained that is free or substantially free of visible lumps or clumps. After the addition was complete, the dispersion was blended at high speed for 5 to 10 minutes to give a slightly viscous mixture of 5wt.% aqueous dispersion of HPM-20 clay.

100G of a portion of this 5wt.% aqueous HPM-20 clay dispersion was transferred toIn a blender. Then, 1.66g of a 50wt.% aqueous solution of GEO aluminum hydroxychloride was pipetted into a vial and added to the dispersion in one portion. An additional 28mL of deionized Milli-Water to promote agitation. The mixture was blended at high speed for 5 minutes and then transferred to a bottle. With an additional 70g of deionized Milli-The stirrer was washed with water, and 184g of slurry was obtained.

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

EXAMPLE 43 comparative example of slurry sedimentation test of ACH-pillared Clay (5.7 mmol Al/g Clay)

5Wt.% aqueous dispersion of HPM-20 clay was prepared by slowly adding 40g of HPM-20 clay to a solution containing 760g of deionized Milli-Of waterIn the blender, while stirring at low speed, a gray colloidal dispersion is produced that is free or substantially free of visible lumps or clumps. After the addition was complete, the dispersion was blended at high speed for 5 to 10 minutes to give a slightly viscous 5wt.% aqueous dispersion of HPM-20 clay.

100G of a portion of this 5wt.% aqueous HPM-20 clay dispersion was transferred toIn a blender. A sample of a 50wt.% aqueous solution of 6.18g GEO aluminum hydroxychloride was pipetted into a vial and added to the dispersion in one portion. An additional 13.8mL of deionized Milli-The water was then blended at high speed for 5 minutes and subsequently transferred to a bottle. With an additional 30g of deionized Milli-The stirrer was washed with water. Then 50g of the fraction Milli-Deionized water was added to the mixture to give 194g of slurry.

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

EXAMPLE 44 quantitative measurement of filtrate from heteroaggregated Clay (1.52 mmol Al/g Clay)

The preparation of a 5wt.% aqueous dispersion of HPM-20 clay is described in example 42.

100G of a portion of this 5wt.% aqueous HPM-20 clay dispersion was transferred toIn a blender. Then, 1.66g of a 50wt.% aqueous solution of GEO aluminum hydroxychloride was pipetted into a vial and added to the dispersion in one portion. An additional 38mL of deionized Milli-Water to facilitate agitation. The mixture was blended at high speed for 5 minutes and then transferred to a bottle. A total of 110g of deionized Milli-Water gave a slurry of total mass 250 g.

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

EXAMPLE 45 comparative example of filtrate quantification test of ACH-pillared Clay (5.7 mmol Al/g Clay)

The preparation of a 5wt.% aqueous dispersion of HPM-20 clay is described in example 43. Transferring a 100g portion of a 5wt.% aqueous dispersion of HPM-20 clay toIn a blender. A sample of a 50wt.% aqueous solution of 6.18g GEO aluminum hydroxychloride was pipetted into a vial and added to the dispersion in one portion. An additional 44g of deionized Milli-Water, then high speed blended for 5 minutes, then transferred to a bottle, then 100g Milli-Deionized water to give a slurry of total mass 250 g.

The resulting mixture was then vacuum filtered through a 11cm Fisher P8 qualitative grade filter paper in a 550mL Buchner funnel using a Welch 2034DryFast ^TM diaphragm pump. After 20 minutes of filtration, 39g of a filtrate was obtained. The unfiltered mixture was allowed to stand for 96 hours, after which time it was vacuum filtered using the same grade filter paper and pump to give an additional 172g of filtrate, leaving 40g of wet cake. The resulting filtrate was rotary evaporated at 55℃to give 1.4g of a solid residue.

Example 46.7 preparation of phenyl-2-methyl-indene

To a solution of phenylboronic acid (3.05 g,25.0 mmol), pd ₂(dba)₃ (229 mg,0.25 mmole, dba is dibenzylideneacetone) and K ₃PO₄ (15.9 g,75.0 mmol) in toluene (50 mL) under a nitrogen atmosphere were added P (t-Bu) ₃ (202 mg,1.00 mmole) and 7-bromo-2-methyl-1H-indene (5.23 g,25.0 mmol) and the reaction mixture was vigorously stirred at 110℃for about 18 hours, after which the mixture was cooled to room temperature and the solution was passed through a silica gel, washed with dichloromethane. After removing volatiles from the filtrate by rotary evaporation, the resulting crude 7-phenyl-2-methyl-1H-indene product was purified by column chromatography (hexane) to give a colorless oil (4.41 g, 86%). The product in CDCl ₃, which contains traces of dichloromethane and water, has an NMR spectrum shown in fig. 13.

EXAMPLE 47 preparation of the ansa-metallocene ligand dimethylsilylene bis (2-methyl-4-phenylindenyl)

N-BuLi (8.56 mL, 2.5M in hexane, 21.4 mmol) was added to 60mL of anhydrous toluene under N ₂, then added to a solution of 7-phenyl-2-methyl-1H-indene (4.41 g,21.4 mmol) with stirring at room temperature. After stirring at room temperature for a period of 6 hours, the reaction mixture was cooled to-35℃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 ℃ for about 18 hours. The resulting mixture was cooled to ambient temperature and the solution was passed through a silica gel, washed with dichloromethane, and volatiles were removed from the filtrate by rotary evaporation. The resulting crude product was purified by column chromatography (200:1 (vol: vol)) to give a yellow solid (2.65 g,53% yield).

EXAMPLE 48 Synthesis of rac-dimethylsilylene bis (2-methyl-4-phenylindenyl) zirconium dichloride

A portion of the yellow solid dimethylsilylene bis (2-methyl-4-phenylindenyl) ligand (410 mg,0.875 mmol) from the previous example was dissolved in methyl tert-butyl ether (2 mL) and diluted with diethyl ether (2 mL). The solution was cooled to-35℃and a portion of n-butyllithium (0.7 mL,2.5M in hexanes) was added dropwise with stirring. The resulting red solution was warmed to room temperature, stirred overnight, and cooled again to-35 ℃. The cold ligand solution was then added to a hexane (10 mL) slurry containing ZrCl ₄(THF)₂ (333 mg,0.875 mmol) pre-cooled to-35 ℃. The resulting orange slurry was warmed to room temperature and stirred overnight, after which the volatile components were removed in vacuo and the residual solid 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 from Dichloromethane (DCM)/hexane (1/1 (v: v)) to give 145mg of crystals and once more from DCM to give 60mg of substantially isomerically pure rac-dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride. The recrystallized product in CDCl ₃ contains trace amounts of dichloromethane and the ¹ H NMR spectrum of this product is shown in fig. 14.

EXAMPLE 49 propylene polymerization catalyzed by rac-dimethylsilylene bis (2-methyl-4-phenylindenyl) zirconium dichloride, the calcined clay heteroadduct of example 17, and trialkylaluminum

To a solution of 6.0. Mu. Mol of rac-dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride from example 45 in 2mL of toluene was added 1.3mL of tri-n-octylaluminum (TnOA, 1.2 mmol). The resulting solution was mixed with 75mg of a single filtered, azeotroped and calcined chlorine hydrated aluminum 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 polymerization was carried out in a laboratory-scale 2L reactor according to the following procedure. The reactor was first preheated to at least 100 ℃ with a nitrogen sweep to remove residual moisture and oxygen, and then cooled to 50 ℃.1 liter (L) of dry heptane was introduced into the reactor under nitrogen. When the reactor temperature was about 50 ℃, 2.0mL of tri-n-octylaluminum (0.92M in hexane) and the catalyst slurry prepared as above were added to the reactor. The pressure in the reactor was raised to 28.5psig at 50 ℃ by introducing nitrogen.

The reactor temperature was then raised to 70 ℃, the total reactor pressure was raised to and controlled at 90psig by continuously introducing propylene into the reactor, and the polymerization was allowed to continue for 1 hour. After this time, the reactor was vented to reduce the pressure to 0psig and the reactor temperature was cooled to 50 ℃. The reactor was opened, 500mL of methanol was added to the reactor content, and the resulting mixture was stirred for 5 minutes, followed by filtration to obtain a polymer product. The polymer obtained was dried in vacuo at 80℃for 6 hours. The Melt Flow Rate (MFR) and isotacticity of the polymer were evaluated and the activity of the catalyst was also determined. Table 8 below summarizes the propylene polymerization results of this example.

TABLE 8 propylene polymerization batches catalyzed by rac-dimethylsilylene bis (2-methyl-4-phenylindenyl) zirconium dichloride, calcined clay hetero adducts and trialkylaluminum according to examples 46 and 47

EXAMPLE 50 propylene polymerization catalyzed by rac-dimethylsilylene bis (2-methyl-4-phenylindenyl) zirconium dichloride, the calcined clay hetero adduct of example 16 and trialkylaluminum

The procedure in example 49 was repeated using the spray-dried and calcined washed clay heteroadduct of example 16 and polymerization was carried out at a temperature of 80 ℃ instead of 70 ℃ (as in example 49). Table 8 summarizes the propylene polymerization results of this example.

EXAMPLE 51 ethylene homo-polymerization catalysis of the inventive and comparative support and metallocene catalyst

Using the reaction procedure and conditions described previously, homopolymerization of ethylene was performed at 450 total psi and 90 ℃. The 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 present invention. These and other descriptions in accordance with the present disclosure may further include various embodiments and aspects presented below.

Other examples

Table 9 illustrates some practical and constructive examples of components that may be selected and used to prepare the heteroaggregated clay activator support, and additional components that may be selected and used in combination with the activator support to produce an olefin polymerization catalyst. Any one or more compounds or compositions listed in each component list may be selected independently of any other compound or composition listed in any other component list. For example, this table discloses that any one or more of component 1, any one or more of component 2, optionally any one or more of component a, and optionally any one or more of component B, can be selected independently of each other and combined or contacted in any order to provide a heterocohesive clay activator support as disclosed herein. Any one or more of component 3 (metallocene), optionally any one or more of component C, and optionally any one or more of component D, may be selected independently of each other and combined or contacted with each other and with the heteroaggregated clay activator support in any order to obtain an olefin polymerization catalyst as disclosed herein.

Table 9. Practical and constructive examples of components that can be independently selected and used to prepare the heteroaggregated clay activator support and olefin polymerization catalyst.

In table 9, certain abbreviations, such as TEA (triethylaluminum), tnOA (tri-n-octylaluminum), tiBA (triisobutylaluminum), MAO (methylaluminoxane), EAO (ethylaluminoxane), etc., as would be understood by a person of ordinary skill in the art are used. Unless otherwise indicated, a group such as "hydrocarbyl" or "siliceous hydrocarbyl" may be considered to have from 1 to about 12 carbons, such as, for example, methyl, n-propyl, phenyl, trimethylsilylmethyl, neopentyl, and the like. In table 9, each group or substituent is selected independently of any other substituent. Thus, each "R" substituent is selected independently of any other R substituent, each "Q" group is selected independently of any other Q group, etc.

Also with respect to Table 9, the promoter component is referred to as optional (optional component C) and includes alkylating agents, hydrogenating agents, and the like. Cocatalyst components, such as those listed, are typically used in the formation of polymerization catalysts because metallocenes are typically substituted with halides and cocatalysts may provide polymerizable activating/initiating ligands such as methyl or hydrides.

Aspects of the present disclosure

Aspect 1. A catalyst composition for olefin polymerization, the catalyst composition comprising:

a) At least one metallocene compound;

b) Optionally, at least one cocatalyst; and

Aspect 2. A process for polymerizing olefins comprising contacting at least one olefin monomer under polymerization conditions with a catalyst composition to form a polyolefin, wherein the catalyst composition comprises:

a) At least one metallocene compound;

b) Optionally, at least one cocatalyst; and

Aspect 3. A process for preparing an olefin polymerization catalyst, the process comprising contacting in any order:

a) At least one metallocene compound;

b) Optionally, at least one cocatalyst; and

Aspect 4. A support-activator comprising an isolated montmorillonite heteroadduct comprising the contact product of [1] a colloidal montmorillonite clay and [2] a heteroagglomerating agent in a liquid carrier, the heteroagglomerating agent comprising at least one cationic multimetal salt, the heteroagglomerating agent being present in an amount sufficient to provide a slurry of the montmorillonite heteroadduct having a zeta potential in the range of from about plus 25mV (millivolts) to about minus 25 mV.

Aspect 5. A method of producing a carrier-activator, the method comprising:

a) Providing a colloidal montmorillonite clay;

C) Separating the montmorillonite hetero adduct from the slurry.

Aspect 6. The catalyst composition, process for polymerizing olefins, process for preparing olefin polymerization catalyst, support-activator, or process for preparing support-activator according to any of aspects 1 to 5, wherein the liquid carrier comprises, consists essentially of, or is selected from the group consisting of:

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; or any combination thereof; and

Optionally further comprising, consisting essentially of, or selected from the group consisting of:

Anionic surfactants such as sulfates, sulfonates, phosphates, carboxylates, or other anionic surfactants, examples of which include, but are not limited to, dialkyl sulfocarboxylates, alkylaryl sulfonates, alkyl sulfonates, sulfosuccinates, fatty acid base salts, polycarboxylates, polyoxyethylene alkyl ether phosphate salts, alkyl naphthalene sulfonates, wherein the salts may be selected from alkali metals (such as lithium, sodium, or potassium), alkaline earth metals (such as calcium or magnesium), or ammonium, or hydrocarbon ammonium salts;

Cationic surfactants such as primary, secondary or tertiary amines, ammonium compounds or quaternary ammonium compounds, and the like, examples of which include, but are not limited to, tetrabutylammonium bromide, dioctadecyl dimethyl ammonium chloride, cetyl trimethyl ammonium chloride, stearyl ammonium chloride, trimethyl stearyl ammonium chloride or cetyl trimethyl ammonium bromide;

Nonionic surfactants such as ethoxylates, glycol ethers, fatty alcohol polyoxyethylene ethers, combinations thereof, or other nonionic surfactants, examples of which include, but are not limited to, octylphenol ethoxylates, polyethylene glycol tertiary octylphenyl ether, polymers of methyl ethylene oxide with 1,2, -ethylenediamine and ethylene oxide, or polymers of 1, 2-ethylenediazo tetrapropanol with ethylene oxide and methyl propylene oxide; or (b)

An amphoteric surfactant comprising an anionic surfactant moiety and a cationic surfactant on the same molecule.

Aspect 7. The support-activator or the process for producing a support-activator according to any one of aspects 4 to 5, wherein the isolated montmorillonite hetero adduct is [1] washed with water, [2] heated, dried and/or calcined, or [3] washed with water and heated, dried and/or calcined.

Aspect 8. The support-activator or the method of producing a support-activator according to any one of aspects 4 to 5, wherein the montmorillonite hetero adduct:

a) Separating from the slurry by filtration or by azeotropic processes; and/or

B) No ultrafiltration, centrifugation or settling tanks are used for separation from the slurry.

Aspect 9. The support-activator or the process for producing a support-activator according to any one of aspects 4 to 5, wherein the montmorillonite hetero adduct is separated from the slurry by ultrafiltration, centrifugation or a settling tank.

Aspect 10. The support-activator or the process for producing a support-activator according to any one of aspects 4 to 5 or 7 to 9, wherein the montmorillonite hetero adduct is isolated by heating in air, in an inert atmosphere or under vacuum, further drying or calcining.

Aspect 11. The support-activator or the method of producing a support-activator of aspect 10, wherein the heating is to a temperature of at least about 100 ℃.

Aspect 12. The catalyst composition, process for polymerizing olefins, process for preparing olefin polymerization catalyst, support-activator, or process for preparing support-activator according to any of aspects 1 to 11, wherein the montmorillonite clay is [1] natural or synthetic, and/or [2] dioctahedral montmorillonite clay.

Aspect 13. The catalyst composition, process for polymerizing olefins, process for preparing olefin polymerization catalyst, support-activator or process for preparing support-activator according to any of aspects 1 to 12, wherein:

a) The montmorillonite clay is colloidal; and/or

B) The montmorillonite clay has an average particle size of less than about 10 μm (microns), less than about 5 μm, less than about 3 μm, less than 2 μm, or less than 1 μm, wherein the average particle size is greater than about 15nm, greater than about 25nm, greater than about 50nm, or greater than about 75nm.

Aspect 14. The catalyst composition, process for polymerizing olefins, process for preparing olefin polymerization catalyst, support-activator, or process for preparing support-activator according to any of aspects 1 to 13, wherein the montmorillonite clay comprises, consists essentially of, or is selected from the group consisting of: montmorillonite, sauconite, nontronite, hectorite, beidellite, saponite, bentonite, or any combination thereof.

Aspect 15. The catalyst composition, process for polymerizing olefins, process for preparing olefin polymerization catalyst, support-activator, or process for preparing support-activator according to any of the preceding aspects such as aspects 1 to 13, wherein the montmorillonite clay comprises structural units characterized by the formula:

(M ^AIV)₈(M^BVI)_pO₂₀(OH)₄; therein

A) M ^A IV is tetra-coordinated Si ⁴⁺, wherein Si ⁴⁺ is optionally partially substituted with a tetra-coordinated cation other than Si ⁴⁺;

b) M ^B VI is hexacoordinated Al ³⁺ or Mg ²⁺, wherein Al ³⁺ or Mg ²⁺ is optionally partially substituted with a hexacoordinated cation other than Al ³⁺ or Mg ²⁺;

D) Any charge starvation in M ^A IV by partial substitution of cations other than Si ⁴⁺ and/or in M ^B VI by partial substitution of cations other than Al ³⁺ or Mg ²⁺ is balanced by cations interposed between the building blocks.

Aspect 16. The catalyst composition, process for polymerizing olefins, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator according to aspect 15, wherein:

a) The cations of non-Si ⁴⁺ are independently selected in each case from Al ³⁺、Fe³⁺、P⁵⁺、B³⁺、Ge⁴⁺、Be²⁺、Sn⁴⁺ and the like;

b) In each case, the cation other than Al ³⁺ or Mg ²⁺ is independently selected from Fe³⁺、Fe²⁺、Ni²⁺、Co²⁺、Li⁺、Zn²⁺、Mn²⁺、Ca²⁺、Be²⁺ and the like; and/or

C) The cations inserted between the building blocks are selected from mono-cations, di-cations, tri-cations, other multi-cations, or any combination thereof.

Aspect 17. The catalyst composition, process for polymerizing olefins, method of preparing olefin polymerization catalyst, support-activator, or method of preparing support-activator according to aspect 15, wherein:

a) The cations of non-Si ⁴⁺ are independently selected in each case from Al ³⁺ or Fe ³⁺; and

B) In each case, the cation other than Al ³⁺ or Mg ²⁺ is independently selected from Fe ³⁺、Fe²⁺、Ni²⁺ or Co ²⁺.

C) The cations inserted between the building blocks are selected from single cations.

Aspect 18. The catalyst composition, process for polymerizing olefins, process for preparing olefin polymerization catalyst, support-activator, or process for preparing support-activator according to any of aspects 1 to 17, wherein montmorillonite clay is single cation exchanged with at least one of lithium, sodium, or potassium.

Aspect 19. The catalyst composition, process for polymerizing olefins, process for preparing olefin polymerization catalyst, support-activator, or process for preparing support-activator according to any of aspects 1 to 18, wherein the cationic polymetallic salt comprises, consists essentially of, or is selected from cationic oligomeric aluminum species or cationic polymeric aluminum species.

Aspect 20. The catalyst composition, process for polymerizing olefins, process for preparing olefin polymerization catalyst, support-activator, or process for preparing support-activator according to any of aspects 1 to 18, wherein the cationic polymetallic salt comprises, consists essentially of, or is selected from the group consisting of: polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichloride or polyaluminum hydroxychloroxide.

Aspect 21. The catalyst composition, process for polymerizing olefins, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator of aspect 20, wherein the ratio of millimoles (mmol) of aluminum (Al) in polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichloride, or polyhydroxy aluminum oxychloride to grams (g) of colloidal montmorillonite clay is in the range of: about 0.2mmol Al/g clay to about 2.5mmol Al/g clay, about 0.5mmol Al/g clay to about 2.2mmol Al/g clay, about 0.75mmol Al/g clay to about 2.0mmol Al/g clay, or about 1.0mmol Al/g clay to about 1.8mmol Al/g clay.

Aspect 22. The catalyst composition, process for polymerizing olefins, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator of aspect 20, wherein the ratio of millimoles (mmol) of aluminum (Al) in polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichloride, or polyhydroxy aluminum oxychloride to grams (g) of isolated colloidal montmorillonite clay or calcined montmorillonite heteroadduct is about 70% or less, about 60% or less, about 50% or less, about 45% or less, about 40% or less, or about 35% or less of the ratio of millimoles of aluminum to grams of colloidal clay used in preparing a pillared clay using the same colloidal montmorillonite clay and heterocoagulation reagent.

Aspect 23. The catalyst composition, process for polymerizing olefins, process for preparing olefin polymerization catalyst, support-activator, or process for preparing support-activator according to any of aspects 1 to 18, wherein the cationic polymetallic salt comprises a linear, cyclic, or clustered aluminum compound containing 2 to 30 aluminum atoms.

Aspect 24. The catalyst composition, process for polymerizing olefins, process for preparing olefin polymerization catalyst, support-activator, or process for preparing support-activator according to any of aspects 1 to 19, wherein the cationic polymetallic salt comprises, consists essentially of, or is selected from the group consisting of: the chemically-treated first metal oxide is chemically-treated with a second metal oxide, a metal halide, a metal oxyhalide, or a combination thereof in an amount sufficient to provide a colloidal suspension of the chemically-treated first metal oxide having a zeta potential greater than positive 20mV (millivolts).

Aspect 25. The catalyst composition, process for polymerizing olefins, process for preparing olefin polymerization catalyst, support-activator, or process for preparing support-activator according to aspect 24, wherein the first metal oxide comprises, consists essentially of, or is selected from the group consisting of: fumed silica, fumed alumina, fumed silica-alumina, fumed magnesia, fumed zinc oxide, fumed titania, fumed zirconia, fumed ceria, or any combination thereof.

Aspect 26. The catalyst composition of aspect 24, a process for polymerizing olefins, a method of preparing an olefin polymerization catalyst, a support-activator, or a method of preparing a support-activator, wherein:

the first metal oxide comprises SiO ₂ or Al ₂O₃, and wherein the second metal oxide, metal halide, or metal oxyhalide is obtained from an aqueous solution or suspension of a metal oxide, hydroxide, oxyhalide, or halide (such as ZrOCl ₂、ZnO、NbOCl₃、B(OH)₃、AlCl₃, or a combination thereof); or alternatively

The first metal oxide comprises SiO ₂, wherein the second metal oxide, metal halide, or metal oxyhalide comprises Al ₂O₃、ZnO、AlCl₃, or a combination thereof.

Aspect 27. The catalyst composition, process for polymerizing olefins, process for preparing olefin polymerization catalyst, support-activator, or process for preparing support-activator according to any of aspects 1 to 18, wherein the cationic polymetallic salt composition comprises, consists essentially of, or is selected from the group consisting of:

Fumed silica, fumed alumina, fumed silica-alumina, fumed magnesia, fumed zinc oxide, fumed titania, fumed zirconia, fumed ceria, or any combination thereof; which is a kind of

The chemical treatment is performed with polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichloride, polyhydroxy aluminum oxychloride, or any combination thereof.

Aspect 28. The catalyst composition, process for polymerizing olefins, process for preparing olefin polymerization catalyst, support-activator, or process for preparing support-activator according to any of aspects 1 to 18, wherein:

a) The colloidal montmorillonite clay comprises a colloidal montmorillonite such as HPM-20Volclay; and

B) The heterocoagulation reagent comprises aluminum chlorohydrate, polyaluminum chloride or aluminum sesquichloride.

Aspect 29. The catalyst composition, process for polymerizing olefins, process for preparing olefin polymerization catalyst, support-activator, or process for preparing support-activator according to any of aspects 1 to 18, wherein the cationic polymetallic salt comprises, consists essentially of, or is selected from the group consisting of: boehmite, fumed silica-alumina, colloidal ceria, colloidal zirconia, magnetite, ferrierite, any positively charged colloidal metal oxide, or any combination thereof.

Aspect 30 the catalyst composition, process for polymerizing olefins, process for preparing olefin polymerization catalyst, support-activator, or process for preparing support-activator according to any of aspects 1 to 18, wherein the cationic polymetallic salt comprises, consists essentially of, or is selected from the group consisting of: aluminum chlorohydrate treated fumed silica, aluminum chlorohydrate treated fumed alumina, aluminum chlorohydrate treated fumed silica-alumina, or any combination thereof.

Aspect 31. The catalyst composition, process for polymerizing olefins, process for preparing olefin polymerization catalyst, support-activator, or process for preparing support-activator according to any of aspects 1 to 18, wherein the cationic polymetallic salt comprises, consists essentially of, or is selected from the group consisting of: an aluminum species or any combination of species having the empirical formula:

Al₂(OH)_nCl_m(H₂O)_x，

Where n+m=6 and x is a number from 0 to about 4.

Aspect 32. The catalyst composition, process for polymerizing olefins, process for preparing olefin polymerization catalyst, support-activator, or process for preparing support-activator according to any of aspects 1 to 18, wherein the cationic polymetallic salt comprises, consists essentially of, or is selected from the group consisting of: an aluminum species having the empirical formula 0.5[ Al ₂(OH)₅Cl(H₂O)₂ ] or [ AlO ₄(Al₁₂(OH)₂₄(H₂O)₂₀]⁷⁺("Al₁₃ -mer ") polycation.

Aspect 33. The catalyst composition, process for polymerizing olefins, process for preparing an olefin polymerization catalyst, support-activator, or process for preparing a support-activator according to any of aspects 1 to 18, wherein the cationic multimetal salt comprises, consists essentially of, or is selected from oligomers prepared by copolymerizing a soluble rare earth salt with a cationic metal complex of at least one additional metal selected from aluminum, zirconium, chromium, iron, or a combination thereof according to U.S. patent No. 5,059,568.

Aspect 34. The catalyst composition, process for polymerizing olefins, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator according to aspect 33, wherein the at least one rare earth metal is selected from cerium, lanthanum, or a combination thereof.

Aspect 35. The catalyst composition, process for polymerizing olefins, process for preparing olefin polymerization catalyst, support-activator, or process for preparing support-activator according to any of aspects 1 to 18, wherein the cationic polymetallic salt comprises, consists essentially of, or is selected from the group consisting of: a complex of formula I or formula II or any combination of complexes of formula I or formula II according to the following formula:

[M(II)_1-xM(III)_x(OH)₂]A_x/n·m L (I)

[LiAl₂(OH)₆]A_1/n·m L (II)

Wherein:

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

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

A is at least one inorganic anion;

L is an organic solvent or water;

X is a number from 0.1 to 1; and

M is a number from 0 to 10.

Aspect 36. The catalyst composition, process for polymerizing olefins, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator according to aspect 35, wherein:

m (II) comprises, consists of, consists essentially of, or is selected from the group consisting of: zinc, calcium, strontium, barium, iron, cobalt, nickel, cadmium, manganese, copper or magnesium;

m (III) comprises, consists of, consists essentially of, or is selected from the following: iron, chromium, manganese, bismuth, cerium or aluminum;

A comprises, consists of, consists essentially of, or is selected from the following: bicarbonate (bicarbonate), sulfate, nitrate, nitrite, phosphate, chloride, bromide, fluoride, hydroxide or carbonate.

N is a number from 1 to 3; and

L comprises, consists of, consists essentially of, or is selected from the following: methanol, ethanol or isopropanol or water.

Aspect 37. The catalyst composition, process for polymerizing olefins, process for preparing olefin polymerization catalyst, support-activator, or process for preparing support-activator according to aspect 35 wherein the cationic polymetallic salt is selected from the complex of formula I wherein M (II) is magnesium, M (III) is aluminum, and a is carbonate.

Aspect 38. The catalyst composition, process for polymerizing olefins, process for preparing olefin polymerization catalyst, support-activator, or process for preparing support-activator according to any of aspects 1 to 18, wherein the cationic polymetallic salt comprises, consists essentially of, or is selected from the group consisting of: layered double hydroxides or mixed metal layered hydroxides.

Aspect 39. The catalyst composition, process for polymerizing olefins, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator according to aspect 38, wherein the mixed metal layered hydroxide is selected from the group consisting of Ni-Al, mg-Al, or Zn-Cr-Al types having a positive layer charge.

Aspect 40. The catalyst composition, process for polymerizing olefins, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator according to aspect 39, wherein the layered double hydroxide or mixed metal layered hydroxide comprises, consists essentially of, or is selected from the group consisting of: aluminum magnesium nitrate, aluminum magnesium sulfate, aluminum magnesium chloride, mg _x(Mg,Fe)₃(Si,Al)₄O₁₀(OH)₂(H₂O)₄ (x is a number from 0 to 1, for example, iron soap Dan Yaowei 0.33.33), (Al, mg) ₂Si₄O₁₀(OH)₂(H₂O)₈, synthetic hematite, hydrozincite (basic zinc carbonate) Zn ₅(OH)₆(CO₃)₂, hydrotalcite [ Mg ₆Al₂(OH)₁₆]CO₃·4H₂ O, hydrobauxite [ Ni ₆Al₂(OH)₆]CO₃·4H₂ O, hydrocalumite [ Ca ₂Al(OH)₆]OH·₆H₂ O, magnesium aluminum [ Mg ₁₀Al₅(OH)₃₁](SO₄)₂·mH₂ O ], lepidomagnesium iron ore [ Mg ₆Fe₂(OH)₁₆]CO₃·4.5H₂ O, ettringite [ Ca ₆Al₂(OH)₁₂](SO₄)₃·26H₂ O, or any combination thereof.

Aspect 41. The catalyst composition, process for polymerizing olefins, process for preparing olefin polymerization catalyst, support-activator, or process for preparing support-activator according to any of aspects 1 to 18, wherein the cationic polymetallic salt comprises, consists essentially of, or is selected from the group consisting of: an iron polycation having the empirical formula FeO _x(OH)_y(H₂O)_z]ⁿ⁺, wherein 2x+y is less than (<) 3, z is a number from 0 to about 4, and n is a number from 1 to 3.

Aspect 42. The catalyst composition, process for polymerizing olefins, process for preparing olefin polymerization catalyst, support-activator or process for preparing support-activator according to any of aspects 1 to 41, wherein the slurry of montmorillonite hetero adducts is characterized by a range of electrical conductivities: about 20,000 to about 100, about 10,000 to about 200, or about 1000 to about 300 μs/cm, wherein the slurry concentration is greater than or equal to about 1wt.%, or greater than or equal to about 2.5wt.%, or the slurry concentration range is: about 1wt.% to about 10wt.% solids, about 2.5wt.% to about 10wt.% solids, about 5wt.% to about 10wt.% solids.

Aspect 43. The catalyst composition, process for polymerizing olefins, process for preparing an olefin polymerization catalyst, support-activator, or process for preparing a support-activator according to any of aspects 1 to 41, wherein the slurry of montmorillonite hetero adducts is characterized by a conductivity of less than 10mS/cm, less than 5mS/cm, or less than 1mS/cm, or wherein the slurry of montmorillonite hetero adducts is characterized by a conductivity in the range of about: 2mS/cm to 10 mus/cm, 1mS/cm to 50 mus/cm, 500 mus/cm to 100 mus/cm, wherein the slurry concentration is greater than or equal to about 1wt.% solids, or greater than or equal to about 2.5wt.%, or the slurry concentration range is: about 1wt.% to about 10wt.% solids, about 2.5wt.% to about 10wt.% solids, about 5wt.% to about 10wt.% solids.

Aspect 44. The catalyst composition, process for polymerizing olefins, process for preparing olefin polymerization catalyst, support-activator, or process for preparing support-activator according to any of aspects 1 to 43, wherein the montmorillonite heteroadduct is calcined using any of the following conditions:

a) A temperature in the range of about 110 ℃ to about 600 ℃ and a period of time in the range of about 1 hour to about 10 hours;

b) A temperature in the range of about 150 ℃ to about 500 ℃ and a time in the range of about 1.5 hours to about 8 hours; or alternatively

C) A temperature in the range of about 200 ℃ to about 450 ℃ and a time in the range of about 2 hours to about 7 hours;

Aspect 45. The catalyst composition, process for polymerizing olefins, process for preparing olefin polymerization catalyst, support-activator, or process for preparing support-activator according to any of aspects 1 to 43, wherein the montmorillonite hetero adduct is calcined in air in the following temperature range: 200 ℃ to 750 ℃, 225 ℃ to 700 ℃, 250 ℃ to 650 ℃, 225 ℃ to 600 ℃, 250 ℃ to 500 ℃, 225 ℃ to 450 ℃, or 200 ℃ to 400 ℃.

Aspect 46. The catalyst composition, process for polymerizing olefins, process for preparing an olefin polymerization catalyst, support-activator, or process for preparing a support-activator according to any of aspects 1 to 45, wherein the montmorillonite heteroadduct is calcined in an atmosphere comprising air or carbon monoxide, or in an inert atmosphere such as nitrogen.

Aspect 47. The catalyst composition, process for polymerizing olefins, process for preparing an olefin polymerization catalyst, support-activator, or process for preparing a support-activator according to any of aspects 1 to 45, wherein the montmorillonite hetero adduct is calcined in air or carbon monoxide in a fluidized bed.

Aspect 48. The catalyst composition, process for polymerizing olefins, process for preparing an olefin polymerization catalyst, support-activator, or process for preparing a support-activator according to any of aspects 1 to 43, wherein the montmorillonite hetero adduct is calcined in a fluidized bed air atmosphere or an atmosphere comprising carbon monoxide at a temperature in the range of 100 ℃ to 900 ℃, 200 ℃ to 800 ℃, 250 ℃ to 600 ℃, or 300 ℃ to 500 ℃.

Aspect 49. The catalyst composition, process for polymerizing olefins, process for preparing olefin polymerization catalyst, support-activator or process for preparing support-activator according to any of aspects 1 to 43, wherein the calcined montmorillonite hetero adduct is calcined at a temperature of 250 ℃ or higher.

Aspect 50. The catalyst composition, process for polymerizing olefins, process for preparing olefin polymerization catalyst, support-activator or process for preparing support-activator according to any of aspects 1 to 43, wherein the calcined montmorillonite hetero adduct is calcined at a temperature of 300 ℃ or more.

Aspect 51. The catalyst composition, process for polymerizing olefins, process for preparing olefin polymerization catalyst, support-activator or process for preparing support-activator according to any of aspects 1 to 43, wherein the calcined montmorillonite hetero adduct is calcined at a temperature of 350 ℃ or more.

Aspect 52. The catalyst composition, process for polymerizing olefins, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator according to any of aspects 1 to 51, wherein the calcined montmorillonite hetero-adduct is absent or substantially absent of ordered domains characterized by powder X-ray diffraction (XRD) peaks in the range of 0 degrees 2 theta (2 theta) to 13 degrees 2 theta.

Aspect 53. The catalyst composition, process for polymerizing olefins, process for preparing olefin polymerization catalyst, support-activator or process for preparing support-activator according to any of aspects 1 to 51, wherein the calcined montmorillonite hetero adduct is characterized by any of the following features:

a) The presence or substantial absence of d001 substrate spacing in powder X-ray diffraction (XRD) is greater than or equal to about (Angstrom) uniform intercalation structure;

b) The presence or substantial absence of d001 substrate spacing in powder X-ray diffraction (XRD) ranges from about (Angstrom) to aboutIn the (angstrom) range, or alternatively in powder X-ray diffraction (XRD) at about(Angstrom) to aboutA uniform intercalation structure within the range of (angstroms); or (b)

C) a) and b).

Aspect 54. The catalyst composition, process for polymerizing olefins, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator according to any of aspects 1 to 51, wherein the calcined montmorillonite hetero-adduct sample is characterized by a non-montmorillonite hetero-adduct intercalation structure characterized by powder X-ray diffraction (XRD) peaks in the range of about 4 degrees 2Θ (2Θ) to about 5 degrees 2Θ, wherein the non-montmorillonite hetero-adduct intercalation structure is present in the calcined montmorillonite hetero-adduct sample at a concentration of less than 60wt.%, less than 50wt.%, less than 40wt.%, less than 30wt.%, less than 20wt.%, less than 10wt.%, or less than 5 wt.%.

Aspect 55. The catalyst composition, process for polymerizing olefins, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator according to any of aspects 1 to 54, wherein the calcined montmorillonite hetero-adduct exhibits a BJH porosity of about 0.2cc/g to about 3.0cc/g, about 0.3cc/g to about 2.5cc/g, or about 0.5cc/g to about 1.8cc/g.

Aspect 56. The catalyst composition, process for polymerizing olefins, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator according to any of aspects 1 to 55, wherein the calcined montmorillonite hetero adduct exhibits a total cumulative pore volume of pores having a diameter of 3-10nm (V _3-10nm) that is less than 55%, 50%, 45%, or 40% of the total cumulative pore volume of pores having a diameter of 3-30nm (V _3-30nm).

Aspect 57. The catalyst composition, process for polymerizing olefins, method of preparing olefin polymerization catalyst, support-activator, or method of preparing support-activator according to any of aspects 1 to 56, wherein the calcined montmorillonite hetero adduct exhibits a log differential pore volume distribution (dV (log D) versus pore size) with a ratio of(Angstrom) to (D _VM(30-40)) local maxima within the range.

Aspect 58 the catalyst composition, process for polymerizing olefins, method of preparing olefin polymerization catalyst, support-activator, or method of preparing support-activator according to any of aspects 1 to 57, wherein the calcined montmorillonite hetero adduct is characterized by a log differential pore volume distribution (dV (log D) versus pore size) having a ratio of(Angstrom) toWithin (D _VM(30-40)) or from(Angstrom) to(D _VM(200-500)) the highest value in the range (D _M, representing the most frequently occurring pore size).

Aspect 59. The catalyst composition, process for polymerizing olefins, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator of aspect 58, wherein the local maximum D _VM(30-40) is a global maximum.

Aspect 60 the catalyst composition, process for polymerizing olefins, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator of aspect 58, wherein the local maximum D _VM(30-40) is less than(Angstrom) and(D _VM(200-500)) 210%, 150%, 120% or 100% of the local maxima between.

Aspect 61, the catalyst composition, the process for polymerizing olefins, the method of preparing an olefin polymerization catalyst, the support-activator, or the method of preparing a support-activator according to aspect 58, wherein the log differential pore volume distribution (dV (log D) versus pore size) is exhibited by(Angstrom) and(D _VM(200-500)) local maxima between which are exceeded(Angstrom) andAll dV (log D) values in between.

Aspect 62. The catalyst composition of any one of aspects 1 to 61, the process for polymerizing olefins, the method of preparing an olefin polymerization catalyst, the support-activator, or the method of preparing a support-activator, wherein the heterocoagulation reagent comprises an aluminum concentration within the range of:

a) About 1wt.% to about 60wt.% calculated on Al ₂O₃;

a) About 5wt.% to about 50wt.% calculated on Al ₂O₃;

b) About 10wt.% to about 45wt.% calculated on Al ₂O₃; or (b)

C) About 15wt.% to about 35wt.% calculated on Al ₂O₃.

Aspect 63. The catalyst composition, process for polymerizing olefins, process for preparing an olefin polymerization catalyst, support-activator, or process for preparing a support-activator according to any of aspects 1 to 62, wherein [1] the colloidal montmorillonite clay and the [2] the heteroagglomerating agent are contacted in an amount sufficient to provide a montmorillonite heteroadduct slurry having a zeta potential in the range of:

a) About plus (+) 22mV (millivolts) to about minus (-) 22mV;

b) About plus (+) 20mV (millivolts) to about minus (-) 20mV;

c) About plus (+) 18mV (millivolts) to about minus (-) 18mV;

d) About plus (+) 15mV (millivolts) to about minus (-) 15mV;

e) About plus (+) 12mV (millivolts) to about minus (-) 12mV;

f) About plus (+) 10mV (millivolts) to about minus (-) 10mV;

g) About positive (+) 8mV (millivolts) to about negative (-) 8mV; or (b)

H) About plus (+) 5mV (millivolts) to about minus (-) 5mV.

Aspect 64. The catalyst composition, process for polymerizing olefins, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator of any of aspects 1 to 63, wherein [1] the colloidal montmorillonite clay and the [2] heterocoagulation reagent are contacted at 25 ℃ ± 5 ℃ for a period of time of 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.

Aspect 65. The catalyst composition, process for polymerizing olefins, process for preparing an olefin polymerization catalyst, support-activator, or process for preparing a support-activator according to any of aspects 1 to 64, wherein after contacting the colloidal montmorillonite clay of [1] with the [2] heteroagglomerating agent, the montmorillonite heteroadduct is separated from the slurry by filtration without the use of ultrafiltration, centrifugation, or a settling tank.

Aspect 66. The catalyst composition, process for polymerizing olefins, process for preparing olefin polymerization catalyst, support-activator, or process for preparing support-activator according to any of aspects 1 to 65, wherein the montmorillonite hetero adduct is amorphous.

Aspect 67. The catalyst composition, process for polymerizing olefins, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator of any of aspects 1 to 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 borate co-activator, or any combination thereof.

Aspect 68. The catalyst composition, process for polymerizing olefins, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator of any of aspects 1 to 66, wherein the catalyst composition or support-activator is substantially free of ion-exchange clay, protonic acid treated clay, pillared clay, aluminoxane, borate co-activator, or any combination thereof.

Aspect 69. The method of preparing a support-activator according to any one of aspects 5 to 68, wherein the montmorillonite hetero adduct is subsequently dried and/or calcined.

Aspect 70. The method of preparing a support-activator according to any one of aspects 5 to 69, wherein the montmorillonite hetero adduct is subsequently dried by heating, azeotropic drying, freeze drying, flash drying, fluidized bed drying, spray drying, or any combination thereof.

Aspect 71. The method for preparing a support-activator according to any one of aspects 5 to 70, wherein the montmorillonite hetero adduct is subjected to wet milling or dry milling after separation.

Aspect 72. The process for preparing a support-activator according to any one of aspects 5 to 71, wherein the isolated montmorillonite hetero adduct is dried to constant weight to obtain a dried montmorillonite hetero adduct.

Aspect 73. The method of preparing a support-activator according to any one of aspects 5 to 71, wherein the montmorillonite hetero adduct is calcined at a temperature in the range of about 110 ℃ to about 900 ℃ for a period of time in the range of about 1 hour to about 12 hours.

Aspect 74. The method of preparing a support-activator according to any one of aspects 5 to 71, wherein the montmorillonite hetero adduct is calcined for a time and at a temperature sufficient to achieve a catalyst productivity of at least about 1,500g polymer/g support-activator, or a catalyst productivity of from about 1,500g polymer/g support-activator to about 30,000g polymer/g support-activator.

Aspect 75. The process for preparing a support-activator according to any one of aspects 5 to 71, further comprising the step of removing entrained air from the dried or calcined montmorillonite hetero adduct by: [1] placing the dried or calcined montmorillonite hetero-adduct in a vacuum, followed by an inert atmosphere such as nitrogen or argon, and optionally repeating one or more vacuum and inert gas cycles; or [2] when the montmorillonite hetero adduct is calcined in a fluidizing gas of air or carbon monoxide, the fluidizing gas is changed to an inert gas such as nitrogen or argon.

Aspect 76. The method of preparing a support-activator according to any one of aspects 5 to 75, wherein the concentration of the montmorillonite hetero adduct solid in the slurry is at least about 5wt.%.

Aspect 77. The method of making a support-activator of any of aspects 5-76, wherein the concentration of the montmorillonite hetero-adduct solids in the slurry is up to about 30wt.%, up to about 25wt.%, up to about 20wt.%, up to about 15wt.%, up to about 10wt.%, up to about 5wt.%, or wherein the concentration of the montmorillonite hetero-adduct solids in the slurry is in the range of about 2wt.% to about 30wt.%, about 3wt.% to about 20wt.%, or about 5wt.% to about 15wt.%.

Aspect 78. The method of preparing a support-activator according to any one of aspects 5 to 77, wherein the contacting step is performed in the substantial absence of ion-exchanged clay, protonic acid-treated clay, aluminoxane, borate co-activator, or any combination thereof.

Aspect 79. The method of preparing a support-activator according to any one of aspects 5 to 78, wherein the contacting step is performed at a temperature ranging from about 20 ℃ to about 100 ℃.

Aspect 80. The support-activator or the method of preparing a support-activator according to any one of aspects 4 to 79, wherein the slurry of the montmorillonite hetero adduct is characterized by the following filtration behavior:

[a] When the heteroadduct slurry having a water-based heteroadduct concentration of 2.0wt.% is filtered over a period of 0 to 2 hours after contacting step b), the proportion of filtrate obtained using vacuum filtration or gravity filtration over a filtration time of 10 minutes, based on the weight of liquid carrier in the montmorillonite heteroadduct slurry, is within the following range: (1) about 50% to about 100% by weight of the liquid carrier in the slurry prior to filtration, (2) about 60% to about 100% by weight of the liquid carrier in the slurry prior to filtration, (3) about 70% to about 100% by weight of the liquid carrier in the slurry prior to filtration, or (4) about 80% to about 100% by weight of the liquid carrier in the slurry prior to filtration; and

Aspect 81. The support-activator or the method of preparing a support-activator according to any one of aspects 4 to 79, wherein the slurry of the montmorillonite hetero adduct is characterized by the following filtration behavior:

[a] When the heteroadduct slurry having a water-based heteroadduct concentration of 2.0wt.% is filtered over a period of 0 hours to 2 hours after contacting step b) to provide a first filtrate, the weight ratio of the second filtrate 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, wherein the second filtrate is a 2.0wt.% pillared clay slurry prepared by filtration using colloidal montmorillonite clay, heteroagglomerating agent and liquid carrier, and the weight of the first filtrate and the weight of the second filtrate are measured after the same filtration time (5 minutes, 10 minutes or 15 minutes); and

Aspect 82. The support-activator or the method of preparing a support-activator of any of aspects 4 to 79, wherein the montmorillonite hetero-adduct slurry is characterized by a settling rate of 2.5wt.% aqueous hetero-adduct slurry composition that is 3, 3.5, 4, 4.5, 5,6,7,8, 9, or 10 times greater than a settling rate of a 2.5wt.% aqueous pillared clay slurry prepared using colloidal montmorillonite clay, hetero-agglomeration reagent, and liquid carrier, wherein the settling rates are compared 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 after initiation of the settling test.

Aspect 83. The catalyst composition, process for polymerizing olefins, or process for preparing olefin polymerization catalysts according to any of aspects 1 to 3 and 6 to 68, wherein the metallocene compound is selected from at least one metallocene compound that has olefin polymerization activity when activated using ion-exchange clay, protonic acid treated clay, pillared clay, aluminoxane, borate co-activator, or any combination thereof.

Aspect 84. The catalyst composition, process for polymerizing olefins, or process for preparing olefin polymerization catalysts according to any of aspects 1 to 3, 6 to 68 and 83, wherein the metallocene compound comprises, consists essentially of, or is selected from the group consisting of: non-bridged (non-ansa) metallocene compounds or bridged (ansa) metallocene compounds.

Aspect 85 the catalyst composition, process for polymerizing olefins, or process for preparing olefin polymerization catalysts of any of aspects 1 to 3, 6 to 68, and 83, wherein the metallocene compound comprises, consists essentially of, or is selected from the group consisting of: a compound or combination of compounds, each independently having the formula:

(X ¹)(X²)(X³)(X⁴) M in which

A) M is selected from titanium, zirconium or hafnium;

Aspect 86. The catalyst composition, process for polymerizing olefins, or method of preparing an olefin polymerization catalyst according to aspect 85, wherein X ¹ and X ² are bridged by a linker substituent selected from the group consisting of:

b) -BX ⁵-、-NX⁵ -or-PX ⁵ -; or (b)

Aspect 87. The catalyst composition, process for polymerizing olefins, or method for preparing an olefin polymerization catalyst according to aspect 85, wherein X ¹ and X ² are bridged by a linker substituent selected from the group consisting of a C ₁-C₂₀ alkylene group, a C ₁-C₂₀ alkylene group, a C ₁-C₂₀ heterohydrocarbon group, a C ₁-C₂₀ heterohydrocarbon group, a C ₁-C₂₀ heteroalkylene group, or a C ₁-C₂₀ heterohydrocarbon group.

Aspect 88. The catalyst composition, process for polymerizing olefins, or process for preparing an olefin polymerization catalyst according to aspect 85, wherein X ¹ and X ² are bridged by at least one substituent having the formula > EX ⁵ ₂、-EX⁵ ₂EX⁵ ₂ -or-BX ⁵ -, wherein E is independently C or Si, and X ⁵ is independently selected in each instance from the group consisting of a halide, a C ₁-C₂₀ aliphatic, a C ₆-C₂₀ aromatic, a C ₁-C₂₀ heteroaliphatic, a C ₄-C₂₀ heteroaromatic, or a C ₁-C₂₀ organohybrid.

Aspect 89 the catalyst composition, process for polymerizing olefins, or process for preparing an olefin polymerization catalyst according to any of aspects 86 to 88, wherein X ⁵ is independently selected in each occurrence from the group consisting of a halide, C ₁-C₁₈ or C ₁-C₁₂ alkyl, C ₂-C₁₈ or C ₂-C₁₂ alkenyl, C ₆-C₁₈ or C ₆-C₁₂ aromatic, C ₄-C₁₈ or C ₄-C₁₂ heteroaromatic, C ₁-C₁₈ or C ₁-C₁₂ heterocarbyl, C ₁-C₂₁ or C ₁-C₁₅ organosilicon radical, C ₁-C₁₈ or C ₁-C₁₂ haloalkane (haloalkyl) radical, C ₁-C₁₈ or C ₁-C₁₂ organophosphorus radical, or C ₁-C₁₈ or C ₁-C₁₂ organonitrogen radical.

Aspect 90. The catalyst composition, process for polymerizing olefins, or method for preparing an olefin polymerization catalyst according to aspect 85, wherein X ¹ and X ² are bridged by a linker substituent selected from the group consisting of silylene, methylsilylene, dimethylsilylene, diisopropylsilylene, dibutylsilylene, methylbutylsilylene, methyl-t-butylsilylene, dicyclohexylsilylene, methylcyclohexylsilylene, methylphenylsilylene, diphenylsilylene, xylylylene, methylnaphthylsilylene, dinaphthylsilylene, cyclodimethylsilylene, cyclotrimethylsilylene, cyclotetramethylsilylene, cyclopentamethylsilylene, cyclohexamethylsilylene, or cycloheptylmethylsilylene.

Aspect 91 the catalyst composition, process for polymerizing olefins, or process for preparing an olefin polymerization catalyst according to any of aspects 85 to 90, wherein X ¹ is selected from the group consisting of substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl, wherein any substituent is independently selected from the group consisting of halide, C ₁-C₂₀ aliphatic, C ₆-C₂₀ aromatic, C ₁-C₂₀ heteroaliphatic, C ₄-C₂₀ heteroaromatic, or C ₁-C₂₀ organohetero.

Aspect 92. The catalyst composition, process for polymerizing olefins, or process for preparing an olefin polymerization catalyst according to any of aspects 85 to 90, wherein X ¹ is selected from substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl, wherein any substituent is independently selected from halide, C ₁-C₁₈ or C ₁-C₁₂ alkyl, C ₂-C₁₈ or C ₂-C₁₂ alkenyl, C ₆-C₁₈ or C ₆-C₁₂ aromatic, C ₄-C₁₈ or C ₄-C₁₂ heteroaromatic, C ₁-C₂₁ or C ₁-C₁₅ organosilicon group, C ₁-C₁₈ or C ₁-C₁₂ haloalkane (haloalkyl) group, C ₁-C₁₈ or C ₁-C₁₂ organophosphorus group, or C ₁-C₁₈ or C ₁-C₁₂ organonitrogen group.

Aspect 93 the catalyst composition, process for polymerizing olefins, or process for preparing olefin polymerization catalysts according to any of aspects 85 to 90, wherein X ¹、X² or X ¹ and X ² are independently selected from substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl, wherein any substituent is independently selected from:

a) Silicon groups having the formula-SiH ₃、-SiH₂R、-SiHR₂、-SiR₃、-SiR₂(OR)、-SiR(OR)₂ OR-Si (OR) ₃;

b) Has the formula-PHR, -PR ₂、-P(O)R₂、-P(OR)₂、-P(O)(OR)₂、-P(NR₂)₂, or-P (O) (NR ₂)₂;

c) Boron groups having the formula-BH ₂、-BHR、-BR₂, -BR (OR) OR-B (OR) ₂;

d) Germanium groups having the formula-GeH ₃、-GeH₂R、-GeHR₂、-GeR₃、-GeR₂(OR)、-GeR(OR)₂ OR-Ge (OR) ₃; or (b)

E) Any combination thereof;

Wherein R is independently selected in each occurrence from a C ₁-C₂₀ hydrocarbon group.

Aspect 94. The catalyst composition, process for polymerizing olefins, or method of preparing olefin polymerization catalysts according to any of aspects 85 to 90, wherein X ¹、X² or X ¹ and X ² are substituted with a fused carbocyclic or heterocyclic moiety selected from pyrrole, furan, thiophene, phosphole, imidazole, imidazoline, pyrazole, pyrazoline, oxazole, oxazoline, isoxazole, isoxazoline, thiazole, thiazoline, isothiazoline, or partially saturated analogs thereof.

Aspect 95. The catalyst composition, process for polymerizing olefins, or process for preparing olefin polymerization catalysts according to any of aspects 85 to 92, wherein X ² is selected from: [1] a substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl group, wherein any substituent is independently selected from the group consisting of a halide, a C ₁-C₂₀ aliphatic group, a C ₆-C₂₀ aromatic group, a C ₁-C₂₀ heteroaliphatic group, a C ₄-C₂₀ heteroaromatic group, or a C ₁-C₂₀ organoheteroaryl group; or [2] halides, C ₁-C₂₀ aliphatic groups, C ₆-C₂₀ aromatic groups, C ₁-C₂₀ heteroaliphatic groups, C ₄-C₂₀ heteroaromatic groups or C ₁-C₂₀ organoheteroatoms.

Aspect 96 the catalyst composition, process for polymerizing olefins, or process for preparing olefin polymerization catalysts according to any of aspects 85 to 92, wherein X ² is selected from: [1] a substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl group, wherein any substituent is independently selected from the group consisting of halides, C ₁-C₁₈ or C ₁-C₁₂ alkyl groups, C ₂-C₁₈ or C ₂-C₁₂ alkenyl, C ₆-C₁₈ or C ₆-C₁₂ aromatic, C ₄-C₁₈ or C ₄-C₁₂ heteroaromatic, C ₁-C₂₁ or C ₁-C₁₅ organosilicon radical, C ₁-C₁₈ or C ₁-C₁₂ haloalkane (haloalkyl) radical, C ₁-C₁₈ or C ₁-C₁₂ organophosphorus radical, and, C ₁-C₁₈ or C ₁-C₁₂ organic nitrogen group; Or [2] halides, C ₁-C₁₈ or C ₁-C₁₂ alkyl, C ₂-C₁₈ or C ₂-C₁₂ alkenyl, C ₆-C₁₈ or C ₆-C₁₂ aromatic groups, C ₄-C₁₈ or C ₄-C₁₂ heteroaromatic radical, C ₁-C₂₁ or C ₁-C₁₅ organosilicon radical, C ₁-C₁₈ or C ₁-C₁₂ haloalkane (haloalkyl) radical, C ₁-C₁₈ or C ₁-C₁₂ organophosphorus group, or C ₁-C₁₈ or C ₁-C₁₂ organic nitrogen group.

Aspect 97. The catalyst composition, process for polymerizing olefins, or method of preparing an olefin polymerization catalyst according to any of aspects 85 to 96, wherein at least one of the linking substituents between X ¹、X² or X ¹ and X ² is substituted with a C ₃-C₁₂ alkenyl group having the formula- (CH ₂)_nCH＝CH₂), wherein n is 1-10.

Aspect 98. The catalyst composition, process for polymerizing olefins, or process for preparing olefin polymerization catalyst according to any of aspects 85 to 97, wherein: [1] x ³ and X ⁴ are independently selected from the group consisting of halides, hydrides, C ₁-C₂₀ aliphatic, C ₆-C₂₀ aromatic, C ₁-C₂₀ heteroaliphatic, C ₄-C₂₀ heteroaromatic, or C ₁-C₂₀ organohybrid; [2] x ³ and X ⁴ together are substituted or unsubstituted 1, 3-butadiene having 4 to 20 carbon atoms; or [3] X ³ and X ⁴ together with M form a substituted or unsubstituted, saturated or unsaturated C ₄-C₅ metallocycle moiety, wherein any substituent on the metallocycle moiety is independently selected from the group consisting of a halide, a C ₁-C₂₀ aliphatic group, a C ₆-C₂₀ aromatic group, a C ₁-C₂₀ heteroaliphatic group, a C ₄-C₂₀ heteroaromatic group, or a C ₁-C₂₀ organoheteroatom.

Aspect 99. The catalyst composition, process for polymerizing olefins, or process for preparing olefin polymerization catalyst according to any of aspects 85 to 97, wherein: [1] x ³ and X ⁴ are independently selected from the group consisting of halides, hydrides, C ₁-C₁₈ or C ₁-C₁₂ alkyl groups, C ₂-C₁₈ or C ₂-C₁₂ alkenyl, C ₆-C₁₈ or C ₆-C₁₂ aromatic, C ₄-C₁₈ or C ₄-C₁₂ heteroaromatic, C ₁-C₂₁ or C ₁-C₁₅ organosilicon radical, C ₁-C₁₈ or C ₁-C₁₂ haloalkane (haloalkyl) radical, C ₁-C₁₈ or C ₁-C₁₂ organophosphorus radical, and, C ₁-C₁₈ or C ₁-C₁₂ organic nitrogen group; Or [2] X ³ and X ⁴ together are a substituted or unsubstituted 1, 3-butadiene having from 4 to 18 carbon atoms; Or [3] X ³ and X ⁴ together with M form a substituted or unsubstituted, saturated or unsaturated C ₄-C₅ metallocycle moiety, wherein any substituent on the metallocycle moiety is independently selected from the group consisting of a halide, C ₁-C₁₈ or C ₁-C₁₂ alkyl, C ₂-C₁₈ or C ₂-C₁₂ alkenyl, C ₆-C₁₈ or C ₆-C₁₂ aromatic, C ₄-C₁₈ or C ₄-C₁₂ heteroaromatic, C ₁-C₂₁ or C ₁-C₁₅ organosilicon radical, C ₁-C₁₈ or C ₁-C₁₂ haloalkane (haloalkyl) radical, C ₁-C₁₈ or C ₁-C₁₂ organophosphorus radical, and, or C ₁-C₁₈ or C ₁-C₁₂ organic nitrogen group.

Aspect 100. The catalyst composition, process for polymerizing olefins, or process for preparing olefin polymerization catalysts according to any of aspects 85 to 97, wherein X ³ and X ⁴ are independently selected from the group consisting of [1] halides, hydrides, borohydrides, aluminum hydrides; or [2] a substituted or unsubstituted C ₁-C₁₈ aliphatic group, C ₁-C₁₂ alkoxy, C ₆-C₁₀ aryloxy, C ₁-C₁₂ alkylthio, C ₆-C₁₀ arylthio, wherein any substituent is independently selected from the group consisting of halide, C ₁-C₁₀ alkyl, or C ₆-C₁₀ aryl; or [3] amido or phosphide groups, wherein any substituent is independently selected from C ₁-C₁₀ alkyl or C ₆-C₁₀ aryl.

Aspect 101. The catalyst composition, process for polymerizing olefins, or process for preparing olefin polymerization catalyst of any of aspects 1 to 3,6 to 68, or 83, wherein the metallocene compound comprises, consists essentially of, or is selected from the group consisting of: bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (1, 2-dimethylcyclopentadienyl) zirconium dichloride, bis (1, 3-dimethylcyclopentadienyl) zirconium dichloride, bis (1-butyl-3-methylcyclopentadienyl) zirconium dichloride, bis (1, 2, 3-trimethylcyclopentadienyl) zirconium dichloride, Bis (1, 2, 4-trimethylcyclopentadienyl) 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 (phenylpropylcyclopentadienyl) zirconium dichloride, bis (tert-butylcyclopentadienyl) zirconium dichloride, bis (indenyl) -zirconium dichloride, bis (4-methyl-1-indenyl) zirconium dichloride, bis (5-methyl-1-indenyl) 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-dimethoxy-1-indenyl) zirconium dichloride, (indenyl) (fluorenyl) zirconium dichloride, bis (trimethylsilyl) zirconium dichloride, bis (trimethylgermyl) cyclopentadienyl zirconium dichloride, bis (trimethylstannyl) cyclopentadienyl zirconium dichloride, bis (trifluoromethylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) - (methylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (dimethylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (ethylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (diethylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (triethylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (tetraethylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (pentacyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (fluorenyl) zirconium dichloride, (cyclopentadienyl) (2, 7-di-tert-butylfluorenyl) zirconium dichloride, (cyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (cyclopentadienyl) (4-methoxyfluorenyl) zirconium dichloride, (methylcyclopentadienyl) (tert-butylcyclopentadienyl) zirconium dichloride, (methylcyclopentadienyl) (fluorenyl) zirconium dichloride, (methylcyclopentadienyl) (2, 7-di-tert-butylfluorenyl) zirconium dichloride, (methylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (methylcyclopentadienyl) (4-methoxyfluorenyl) -zirconium dichloride, (dimethylcyclopentadienyl) (fluorenyl) -zirconium dichloride, (dimethylcyclopentadienyl) (2, 7-di-t-butylfluorenyl) zirconium dichloride, (dimethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (dimethylcyclopentadienyl) (4-methoxyfluorenyl) 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.

Aspect 102 the catalyst composition or process for polymerizing olefins according to any of aspects 1 to 3, 6 to 68 or 83 to 101, wherein the catalyst composition further comprises a cocatalyst.

Aspect 103. The method of preparing an olefin polymerization catalyst according to any one of aspects 1 to 3, 6 to 68 or 83 to 102, wherein the contacting step further comprises contacting the metallocene compound and the support-activator with a cocatalyst in any order.

Aspect 104. The catalyst composition, process for polymerizing olefins, or process for preparing an olefin polymerization catalyst according to any of aspects 1 to 3, 6 to 68, or 83 to 103, wherein the cocatalyst comprises an alkylating agent, a hydrogenating agent, or a silylating agent.

Aspect 105 the catalyst composition, process for polymerizing olefins, or process for preparing an olefin polymerization catalyst of any of aspects 1 to 3, 6 to 68, or 83 to 104, wherein the cocatalyst comprises, consists essentially of, or is selected from the group consisting of: an organoaluminum compound, an organoboron compound, an organozinc compound, an organomagnesium compound, an organolithium compound, or any combination thereof.

Aspect 106. The catalyst composition, process for polymerizing olefins, or process for preparing an olefin polymerization catalyst according to any of aspects 1 to 3,6 to 68, or 83 to 104, wherein the cocatalyst comprises, consists essentially of, or is selected from the group consisting of: 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, wherein n and m are not limited to integers;

b) X ^A is independently selected from: [1] a hydride, a C ₁-C₂₀ hydrocarbon group, or a C ₁-C₂₀ heterohydrocarbon group; [2] a hydride, a C ₁-C₂₀ aliphatic, a C ₆-C₂₀ aromatic, a C ₁-C₂₀ heteroaliphatic, or a C ₄-C₂₀ heteroaromatic; or [3] two X ^A together comprise a C ₄-C₅ hydrocarbylene group, the remaining X ^A being independently selected from the group consisting of a hydride, a C ₁-C₂₀ hydrocarbyl group, or a C ₁-C₂₀ heterohydrocarbyl group;

c) X ^B is independently selected from: [1] a halide or C ₁-C₂₀ organoheteroaryl; or [2] a halide, C ₁-C₁₂ alkoxy or C ₆-C₁₀ aryloxy ether group; and

D) M ^x is selected from Li, na, or K.

Aspect 107. The catalyst composition, process for polymerizing olefins, or process for preparing an olefin polymerization catalyst according to any of aspects 102 to 103, wherein the cocatalyst comprises, consists essentially of, or is selected from the group consisting of: 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, inclusive;

b) X ^C is independently selected from hydride or C ₁-C₂₀ hydrocarbyl;

c) X ^D is a form of anionic species independently selected from: a fluoride; a chloride; a bromide; iodide; bromate; chlorate; perchlorate; hydrocarbyl sulfate; hydrocarbyl sulfites; sulfamate; hydrocarbon sulfides, hydrocarbon carbonates; bicarbonate (bicarbonate); a carbamate; a nitrite salt; nitrate salts; hydrocarbyl oxalates; a dihydrocarbyl phosphate; hydrocarbylselenite; a sulfate; a sulfite; a carbonate salt; an oxalate salt; phosphate; a phosphite; selenite; a selenide; a sulfide; an oxide; sulfamate; an azide; an alkoxide; an amido group; hydrocarbyl amide groups; a dihydrocarbyl amide group; r ^A[CON(R)]_q; wherein R ^A is independently at each occurrence H or a substituted or unsubstituted C ₁-C₂₀ hydrocarbyl group, q is an integer from 1 to 4, inclusive; and R ^B[CO₂ ] R, wherein R ^B is independently at each occurrence H or a substituted or unsubstituted C ₁-C₂₀ hydrocarbyl group, R is an integer from 1 to 3, inclusive; and

D) M ^x is selected from Li, na, or K.

Aspect 108 the catalyst composition, process for polymerizing olefins, or process for preparing an olefin polymerization catalyst of any of aspects 1 to 3, 6 to 68, or 83 to 104, wherein the cocatalyst comprises, consists essentially of, or is selected from the group consisting of: [1] trimethylaluminum, triethylaluminum (TEA), tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, ethyl- (3-alkylcyclopentanediyl) aluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, triisobutylaluminum (TIBAL), diethylaluminum chloride, or any combination or mixture thereof; or [2] ethyl- (3-alkylcyclopentanediyl) aluminum, triisobutylaluminum (TIBAL), trioctylaluminum, or any combination or mixture thereof; or [3] any combination of any one or more cocatalysts [1] and any one or more mixtures of cocatalysts [2 ].

Aspect 109. The catalyst composition, process for polymerizing olefins, or process for preparing an olefin polymerization catalyst according to any of aspects 1 to 3, 6 to 68, or 83 to 104, wherein the cocatalyst or co-activator comprises, consists essentially of, or is selected from the group consisting of: 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 1 to 3, inclusive;

b) X ^E is independently selected from: [1] a hydride, a C ₁-C₂₀ hydrocarbon group, or a C ₁-C₂₀ heterohydrocarbon group; [2] a hydride, a C ₁-C₂₀ aliphatic, a C ₆-C₂₀ aromatic, a C ₁-C₂₀ heteroaliphatic, or a C ₄-C₂₀ heteroaromatic; [3] fluorinated C ₁-C₂₀ hydrocarbyl, or fluorinated C ₁-C₂₀ heterohydrocarbyl; or [4] fluorinated C ₁-C₂₀ aliphatic, fluorinated C ₆-C₂₀ aromatic, fluorinated C ₁-C₂₀ heteroaliphatic or fluorinated C ₄-C₂₀ heteroaromatic;

c) X ^F is independently selected from: [1] a halide or C ₁-C₂₀ organoheteroaryl; or [2] a halide, C ₁-C₁₂ alkoxy or C ₆-C₁₀ aryloxy ether group; and

D) M ^y is selected from Li, na, or K.

Aspect 110. The catalyst composition, process for polymerizing olefins, or process for preparing an olefin polymerization catalyst according to any of aspects 1 to 3, 6 to 68, or 83 to 104, wherein the cocatalyst or co-activator comprises, consists essentially of, or is selected from the group consisting of: [1] trimethylboron, triethylboron, tripropylboron, tributylboron, trihexylboron, trioctylboron, diethylethanolborohydride, diisobutylboron, diethylborochloride, di-3-pinanyl borane, pinacol borane, catechol borane, lithium borohydride, lithium triethylborohydride, lewis base adducts thereof, or any combination or mixture thereof; or [2] tris (pentafluorophenyl) boron, tris [3, 5-bis (trifluoromethyl) phenyl ] boron, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate, lithium tetrakis- (pentafluorophenyl) borate, N-dimethylanilinium tetrakis [3, 5-bis (trifluoromethyl) phenyl ] borate, triphenylcarbonium tetrakis [3, 5-bis (trifluoromethyl) -phenyl ] borate, and any combination or mixture thereof.

Aspect 111 the catalyst composition, process for polymerizing olefins, or process for preparing an olefin polymerization catalyst according to any of aspects 1 to 3, 6 to 68, and 83 to 104, wherein the cocatalyst comprises, consists essentially of, or is selected from the group consisting of: an organozinc or organomagnesium compound, or a combination of organozinc and/or organomagnesium compounds, each independently having the formula:

m ^C(X^G)_r(X^H)_2-r, wherein

A) M ^C is zinc or magnesium;

a) r is a number from 1 to 2, inclusive;

b) X ^G is independently selected from: [1] a hydride, a C ₁-C₂₀ hydrocarbon group, or a C ₁-C₂₀ heterohydrocarbon group; or [2] a hydride, a C ₁-C₂₀ aliphatic, a C ₆-C₂₀ aromatic, a C ₁-C₂₀ heteroaliphatic, or a C ₄-C₂₀ heteroaromatic; and

C) X ^H is independently selected from: [1] a halide or C ₁-C₂₀ organoheteroaryl; or [2] a halide, a C ₁-C₁₂ alkoxy group, or a C ₆-C₁₀ aryloxy ether group.

Aspect 112 the catalyst composition, process for polymerizing olefins, or process for preparing an olefin polymerization catalyst of any of aspects 1 to 3, 6 to 68, or 83 to 104, wherein the cocatalyst comprises, consists essentially of, or is selected from the group consisting of: [1] dimethyl zinc, diethyl zinc, diisopropyl zinc, dicyclohexyl zinc, diphenyl zinc, or any combination thereof; [2] butyl ethyl magnesium, dibutyl magnesium, n-butyl-sec-butyl magnesium, dicyclopentadiene magnesium, or any combination thereof; or [3] any combination of any organozinc promoter from group [1] and any organomagnesium promoter from group [2 ].

Aspect 113. The catalyst composition, process for polymerizing olefins, or process for preparing an olefin polymerization catalyst according to any of aspects 1 to 3, 6 to 68, or 83 to 104, wherein the cocatalyst comprises, consists essentially of, or is selected from the group consisting of: an organolithium compound having the formula

Li (X ^J) in which

X ^J is independently selected from: [1] a hydride, a C ₁-C₂₀ hydrocarbon group, or a C ₁-C₂₀ heterohydrocarbon group; or [2] a hydride, a C ₁-C₂₀ aliphatic, a C ₆-C₂₀ aromatic, a C ₁-C₂₀ heteroaliphatic, or a C ₄-C₂₀ heteroaromatic.

Aspect 114. The catalyst composition, process for polymerizing olefins, process for preparing olefin polymerization catalyst according to any of aspects 1 to 3, 6 to 68 or 83 to 104, wherein the cocatalyst comprises, consists essentially of, or is selected from the group consisting of: methyl lithium, ethyl lithium, propyl lithium, butyl lithium (including n-butyl lithium and t-butyl lithium), hexyl lithium, isobutyl lithium, or any combination thereof.

Aspect 115. The catalyst composition, process for polymerizing olefins, or method of preparing an olefin polymerization catalyst of any of aspects 1-3, 6-68, or 83-104, wherein the catalyst composition further comprises a catalyst selected from the group consisting of ion-exchanged clay, protonic acid treated clay, pillared clay, alumoxane, borate co-activator, aluminate co-activator, ionizing ionic compound, solid oxide treated with an electron withdrawing anion, or any combination thereof.

Aspect 116 the catalyst composition, process for polymerizing olefins, or method of preparing an olefin polymerization catalyst of any of aspects 1 to 3, 6 to 68, or 83 to 104, wherein the catalyst composition further comprises an ionizing compound.

Aspect 117. The catalyst composition, process for polymerizing olefins, or method of preparing an olefin polymerization catalyst according to aspect 116, wherein the ionizing compound comprises, consists essentially of, or is selected from the group consisting of: 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-dimethylanilinium tetraphenylborate, N-diethylanilinium tetraphenylborate, N-dimethyl- (2, 4, 6-trimethylanilinium) tetraphenylborate, A tall-onium tetraphenyl borate, a triphenylcarbonium tetraphenyl borate, a triphenylphosphonium tetraphenyl borate triethylsilyltetraphenyl borate, a benzene (diazonium) tetraphenyl borate, a trimethylammonium tetrakis (pentafluorophenyl) borate, a triethylammonium tetrakis (pentafluorophenyl) borate, a tripropylammonium tetrakis (pentafluorophenyl) borate, a tri (N-butyl) ammonium tetrakis (pentafluorophenyl) borate, a tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate, an N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, an N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, an N, N-dimethyl- (2, 4, 6-trimethylanilinium) tetrakis (pentafluorophenyl) borate, A tall-round onium tetrakis (pentafluorophenyl) borate, a triphenylcarbenium tetrakis (pentafluorophenyl) borate, a triphenylphosphonium tetrakis (pentafluorophenyl) borate, a triethylsilicon tetrakis (pentafluorophenyl) borate, a benzene (diazonium) tetrakis (pentafluorophenyl) borate, a trimethylammonium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate, a triethylammonium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate, a tripropylammonium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate, a tri (N-butyl) ammonium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate, a 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-dimethyl- (2, 4, 6-trimethylanilinium) tetrakis- (2, 3,4, 6-tetrafluorophenyl) borate, zettainium tetrakis- (2, 3,4, 6-tetrafluorophenyl) borate, triphenylcarbonium tetrakis- (2, 3,4, 6-tetrafluorophenyl) borate, triphenylphosphonium tetrakis- (2, 3,4, 6-tetrafluorophenyl) borate, triethylsilatetrakis (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-dimethylanilinium tetrakis (perfluoronaphthyl) borate, N-diethylanilinium tetrakis (perfluoronaphthyl) borate, N-dimethyl- (2, 4, 6-trimethylanilin) tetrakis (perfluoronaphthyl) borate, zebra-onium tetrakis (perfluoronaphthyl) borate, triphenylcarbonium tetrakis (perfluoronaphthyl) borate, triphenylphosphonium tetrakis (perfluoronaphthyl) borate, triethylsilatetrakis (perfluoronaphthyl) borate, benzene (diazo) tetrakis (perfluoronaphthyl) borate, Trimethyl ammonium tetrakis (perfluorobiphenyl) borate, triethyl ammonium tetrakis (perfluorobiphenyl) borate, tripropyl ammonium tetrakis (perfluorobiphenyl) borate, tri (N-butyl) ammonium tetrakis (perfluorobiphenyl) borate, tri (t-butyl) ammonium tetrakis (perfluorobiphenyl) borate, N-dimethylanilinium tetrakis (perfluorobiphenyl) borate, N-diethylanilinium tetrakis (perfluorobiphenyl) borate, N-dimethyl- (2, 4, 6-trimethylanilinium) tetrakis (perfluorobiphenyl) borate, altronium tetrakis (perfluorobiphenyl) borate, triphenylcarbonium tetrakis (perfluorobiphenyl) borate, triphenylphosphonium tetrakis (perfluorobiphenyl) borate, triethylsilatetrakis (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-dimethylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, N-diethylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, N-dimethyl- (2, 4, 6-trimethylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, A zebra onium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, a triphenylcarbonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, a triphenylphosphonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, triethylsilatetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, a benzene (diazonium) tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, and dialkylammonium salts such as: di- (isopropyl) ammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetrakis (pentafluorophenyl) borate; and additional trisubstituted phosphonium salts such as tris (o-tolyl) phosphonium tetrakis (pentafluorophenyl) borate, tris (2, 6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, or any combination thereof.

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

Aspect 119. The catalyst composition of aspect 118, a process for polymerizing olefins, or a method of preparing an olefin polymerization catalyst, wherein:

a) The solid oxide comprises, consists of, consists essentially of, or is selected from the group consisting of: silica, alumina, silica-coated alumina, silica-zirconia, silica-titania, aluminum phosphate, heteropolytungstates, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or any combination thereof; and

B) The electron withdrawing anion comprises, consists essentially of, or is selected from the group consisting of: fluoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate, fluorophosphate, fluorosulfate, or any combination thereof.

Aspect 120. The catalyst composition, process for polymerizing olefins, or method of preparing an olefin polymerization catalyst according to aspect 118, wherein the co-activator comprises, consists essentially of, or is selected from the group consisting of: fluorided alumina, chlorided alumina, brominated alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, brominated silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, or any combination thereof.

Aspect 121. The catalyst composition, process for polymerizing olefins, or method of preparing an olefin polymerization catalyst of any of aspects 1 to 3, 6 to 68, or 83 to 120, wherein the catalyst composition further comprises a carrier or diluent, or the contacting occurs in any order in the carrier or diluent.

Aspect 122. The catalyst composition, process for polymerizing olefins, or method of preparing an olefin polymerization catalyst according to aspect 121, wherein the carrier or diluent comprises, consists essentially of, or is selected from the group consisting of: hydrocarbons, ethers, or combinations thereof, each having from 1 to 20 carbon atoms.

Aspect 123. The catalyst composition, process for polymerizing olefins, or method of preparing an olefin polymerization catalyst according to aspect 121, wherein the carrier or diluent comprises, consists essentially of, or is selected from the group consisting of: cyclohexane, isobutane, n-butane, propane, n-pentane, isopentane, neopentane, n-hexane, isopar ^TM, at least one olefin, or any combination thereof.

Aspect 124. The catalyst composition, process for polymerizing olefins, or method of preparing an olefin polymerization catalyst according to aspect 121, wherein the carrier or diluent comprises, consists essentially of, or is selected from the group consisting of: at least one olefin.

Aspect 125. The catalyst composition, process for polymerizing olefins, or process for preparing olefin polymerization catalysts of any of aspects 1 to 3, 6 to 68, or 83 to 124, wherein the activity of the catalyst is greater than or equal to about 300 grams of polyolefin per hour (g/g/h) per gram of carrier-activator comprising calcined montmorillonite heteroadduct under polymerization conditions comprising a ratio of metallocene compound to calcined montmorillonite heteroadduct [1] of about 7 x 10 ^-5 mmol of metallocene compound per mg of calcined montmorillonite heteroadduct, and other standard conditions described in the specification.

Aspect 126. The catalyst composition, process for polymerizing olefins, or process for preparing an olefin polymerization catalyst according to any of aspects 1 to 3, 6 to 68, or 83 to 125, wherein the catalyst composition comprises an organoaluminum compound and a calcined montmorillonite heteroadduct in a relative concentration in moles of organoaluminum compound per gram of calcined montmorillonite heteroadduct in the range of about 0.5 to about 0.000005, about 0.1 to about 0.00001, or about 0.01 to about 0.0001.

Aspect 127. The process for polymerizing olefins according to any of aspects 1 to 3, 6 to 68 or 83 to 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.

Aspect 128. The process for polymerizing olefins according to any of aspects 1 to 3, 6 to 68 or 83 to 127, wherein the process comprises polymerization in a gas phase reactor, a slurry loop, a dual slurry loop in series, a plurality of slurry tanks in series, a slurry loop in combination with a gas phase reactor, a continuously stirred reactor in a batch process, or a combination thereof.

Aspect 129 the process for polymerizing an olefin according to any of aspects 1 to 3, 6 to 68 or 83 to 128, wherein the polyolefin comprises, consists essentially of, or is selected from the group consisting of: olefin homopolymers or olefin copolymers.

Aspect 130 the process for polymerizing olefins according to any of aspects 1 to 3, 6 to 68 or 83 to 129, wherein the polyolefin comprises, consists essentially of, or is selected from the group consisting of: an olefin homopolymer comprising residues of olefin monomers having from 2 to about 20 carbon atoms per monomer molecule.

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

Aspect 132. The process for polymerizing olefins according to any of aspects 2, 6 to 68 or 83 to 129, wherein the polyolefin comprises, consists essentially of, or is selected from the group consisting of: an ethylene-olefin comonomer copolymer comprising alpha olefin comonomer residues having from 3 to about 20 carbon atoms per monomer molecule.

Aspect 133. The process for polymerizing olefins according to aspect 132, wherein the olefin comonomer is selected from aliphatic C ₃ to C ₂₀ olefins, conjugated or unconjugated C ₃ to C ₂₀ dienes, or any mixture thereof.

Aspect 134. The process for polymerizing olefins according to aspect 132, wherein the olefin comonomer is selected from propylene, 1-butene, 2-butene, 3-methyl-1-butene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 3-ethyl-1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1, 3-butadiene, isoprene, piperylene, 2, 3-dimethyl-1, 3-butadiene, 1, 4-pentadiene, 1, 7-hexadiene, vinylcyclohexane, or any combination thereof.

Aspect 135. The process for producing an olefin polymerization catalyst according to any one of aspects 3, 6 to 68 or 83 to 126, wherein:

a) Contacting the metallocene compound with the cocatalyst for a period of time of [1] from about 1 minute to about 24 hours or from about 1 minute to about 1 hour, and [2] at a temperature of from about 10 ℃ to about 200 ℃ or from about 15 ℃ to about 80 ℃ to form a first mixture; then

B) The first mixture is contacted with a support-activator comprising a calcined montmorillonite hetero-adduct to form the catalyst composition.

Aspect 136. The process for preparing an olefin polymerization catalyst according to any one of aspects 3,6 to 68 or 83 to 126, wherein the metallocene compound, the cocatalyst, and the support-activator comprising a calcined montmorillonite hetero adduct are contacted [1] for a period of time of from about 1 minute to about 6 months or from about 1 minute to about 1 week, and [2] at a temperature of from about 10 ℃ to about 200 ℃ or from about 15 ℃ to about 80 ℃ to form the olefin polymerization catalyst.

Aspect 137 the catalyst composition prepared according to any one of aspects 3, 6 to 68, 83 to 126 or 135 to 136.

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

Aspect 139. The catalyst composition, process for polymerizing olefins, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator according to any of aspects 1 to 138, wherein the catalyst composition, process, method, and support-activator are any of the catalyst compositions, processes, methods, and support-activators disclosed herein.

Claims

1. A carrier-activator comprising an isolated montmorillonite heteroadduct comprising the contact product of [1] a colloidal montmorillonite clay and [2] a heteroagglomerating agent in a liquid carrier, the heteroagglomerating agent comprising at least one cationic multimetal salt in an amount sufficient to provide the slurry of the montmorillonite heteroadduct having a zeta potential in the range of positive (+) 25mV (millivolts) to negative (-) 25mV quantified according to the electro-acoustic amplitude (ESA) effect prior to separating the montmorillonite heteroadduct from the slurry, wherein the montmorillonite clay comprises montmorillonite, sauconite, nontronite, hectorite, beidellite, saponite, bentonite, or any combination thereof, and wherein the cationic multimetal salt comprises a cationic polyaluminate selected from polyaluminum chloride, aluminum chlorohydrate, aluminum hydroxychloride, or polyaluminum hydroxychloroxide, or any combination thereof.

2. The support-activator of claim 1, wherein the ratio of millimoles (mmol) of aluminum (Al) to grams (g) of colloidal montmorillonite clay in the cationic polymeric aluminate is in the range of 0.2 mmole Al/g clay to 2.5 mmole Al/g clay.

3. The carrier-activator of claim 1, wherein the cationic multimetal salt further comprises a first metal oxide chemically treated with a second metal oxide, a metal halide, a metal oxyhalide, or a combination thereof, the amount of the first metal oxide being sufficient to provide a colloidal suspension of the chemically treated first metal oxide having a zeta potential greater than positive (+) 20mV (millivolts).

4. The carrier-activator of claim 1, wherein the cationic multimetal salt further comprises fumed silica, fumed alumina, fumed silica-alumina, fumed magnesia, fumed zinc oxide, fumed titania, fumed zirconia, fumed ceria, or any combination thereof, chemically treated with polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichloride, polyhydroxy aluminum chloroxide, or any combination thereof.

5. The support-activator of claim 1, wherein the slurry of the montmorillonite hetero-adduct is characterized by a conductivity in the range of 2mS/cm to 10 μs/cm when measured using Eutech PCSTestr when the concentration of the slurry is in the range of 1wt.% to 10wt.% solids, and wherein the isolated montmorillonite hetero-adduct is calcined.

6. The support-activator of claim 1, wherein the montmorillonite hetero-adduct is calcined and the calcined montmorillonite hetero-adduct exhibits a BJH porosity of 0.2cc/g to 3.0cc/g and a total cumulative pore volume of pores with a diameter of 3-10nm (V _3-10nm) of less than 55% of a total cumulative pore volume of pores with a diameter of 3-30nm (V _3-30nm) as measured by BJH analysis of nitrogen adsorption-desorption isotherm curve data.

7. The carrier-activator of claim 1, wherein the colloidal montmorillonite clay and the heteroagglomerating agent are contacted in an amount sufficient to provide a slurry of the montmorillonite heteroadduct having a zeta potential in the range of plus (+) 20mV (millivolts) to minus (-) 20 mV.

8. The carrier-activator of claim 1, wherein the colloidal montmorillonite clay and the heteroagglomerating agent are contacted in an amount sufficient to provide a slurry of the montmorillonite heteroadduct having a zeta potential in the range of plus (+) 15mV (millivolts) to minus (-) 15 mV.

9. The support-activator of claim 1, wherein the montmorillonite hetero-adduct is separated from the slurry by filtration without the use of ultrafiltration, centrifugation or a settling tank, and wherein the separated montmorillonite hetero-adduct [1] is optionally washed with water and [2] dried and/or calcined.

10. The support-activator of claim 1, wherein the slurry of the montmorillonite hetero adduct is characterized by the following filtration behavior:

(a) When 2.0wt.% of the aqueous slurry of the montmorillonite hetero adduct is filtered over a period of 0to 2 hours after contacting step b), the proportion of filtrate obtained using vacuum filtration or gravity filtration over a filtration time of 10 minutes is in the range of 50 to 100% by weight of the liquid carrier in the slurry before filtration, based on the weight of the liquid carrier in the slurry of the montmorillonite hetero adduct; and

(B) When evaporated, the filtrate from the slurry of the montmorillonite heteroadduct produces a solid comprising less than 20% of the initial total weight of clay and heterocoagulants.

11. The carrier-activator of claim 1, wherein the liquid carrier comprises water, an alcohol, an ether, a ketone, or an ester, or any combination thereof.

12. The carrier-activator of claim 1, wherein the liquid carrier comprises a surfactant.

13. The carrier-activator of claim 1, wherein the liquid carrier comprises an anionic surfactant, a cationic surfactant, or a nonionic surfactant.

14. The carrier-activator of claim 13, wherein the anionic surfactant is selected from the group consisting of sulfates, sulfonates, phosphates, carboxylates, dialkyl sulfocarboxylates, alkylaryl sulfonates, alkyl sulfonates, sulfosuccinates, fatty acid alkali metal salts, polycarboxylates, polyoxyethylene alkyl ether phosphate salts, or alkyl naphthalene sulfonates, wherein each salt comprises a cation selected from the group consisting of alkali metals, alkaline earth metals, ammonium, or hydrocarbyl ammonium.

15. The carrier-activator of claim 13, wherein the cationic surfactant is selected from the group consisting of:

Primary, secondary or tertiary amines; or alternatively

Primary, secondary, tertiary or quaternary ammonium compounds.

16. The carrier-activator of claim 13, wherein the nonionic surfactant is selected from ethoxylates, glycol ethers, fatty alcohol-polyoxyethylene ethers, or combinations thereof.

17. A catalyst composition for the polymerization of olefins, the catalyst composition comprising:

a) At least one metallocene compound;

b) Optionally, at least one cocatalyst; and

C) At least one carrier-activator comprising a calcined montmorillonite heteroadduct comprising the contact product of [1] a colloidal montmorillonite clay and [2] a heteroagglomerating agent in a liquid carrier, the heteroagglomerating agent comprising at least one cationic multimetal salt in an amount sufficient to provide the slurry of the montmorillonite heteroadduct having a zeta potential in the range of positive (+) 25mV (millivolts) to negative (-) 25mV, quantified according to the electro-acoustic amplitude (ESA) effect, prior to separating the montmorillonite heteroadduct from the slurry, wherein the montmorillonite clay comprises montmorillonite, sauconite, nontronite, hectorite, bedtime, saponite, bentonite, or any combination thereof, and wherein the cationic multimetal salt comprises a cationic polyaluminate selected from polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichloride, or polyaluminum hydroxychloroxide, or any combination thereof.

18. The catalyst composition of claim 17, wherein the at least one metallocene compound has the formula:

(X ¹)(X²)(X³)(X⁴) M in which

A) M is selected from titanium, zirconium or hafnium;

c) X ² is selected from: [1] a substituted or unsubstituted cyclopentadienyl, indenyl, fluorenyl, pentadienyl, or allyl group, wherein any substituent is independently selected from the group consisting of a halide, a C ₁-C₂₀ hydrocarbon group, a C ₁-C₂₀ heterohydrocarbon group, or a C ₁-C₂₀ organoheteroaryl group;

Or [2] a halide, hydride, C ₁-C₂₀ hydrocarbyl, C ₁-C₂₀ heterohydrocarbyl, C ₁-C₂₀ organoheteroaryl, fused C ₄-C₁₂ carbocyclic moiety, or fused C ₄-C₁₁ heterocyclic moiety having at least one heteroatom independently selected from: nitrogen, oxygen, sulfur or phosphorus;

19. The catalyst composition of claim 18, wherein X ¹ and X ² are bridged by a linker substituent selected from the group consisting of:

b) -BX ⁵-、-NX⁵ -or-PX ⁵ -; or (b)

c)[-SiX⁵ ₂(1,2-C₆H₄)SiX⁵ ₂-]、[-CX⁵ ₂(1,2-C₆H₄)CX⁵ ₂-]、[-SiX⁵ ₂(1,2-C₆H₄)CX⁵ ₂-]、

[-SiX⁵ ₂(1,2-C₂H₂)SiX⁵ ₂-]、[-CX⁵ ₂(1,2-C₆H₄)CX⁵ ₂-] Or [ -SiX ⁵ ₂(1,2-C₆H₄)CX⁵ ₂ - ];

20. The catalyst composition of claim 17, wherein the cocatalyst comprises an alkylating, hydrogenating, or silylating agent.

21. The catalyst composition of claim 17, wherein the cocatalyst comprises an organoaluminum compound, an organoboron compound, an organozinc compound, an organomagnesium compound, an organolithium compound, or any combination thereof.

22. The catalyst composition of claim 17, wherein the liquid carrier comprises water, an alcohol, an ether, a ketone, or an ester, or any combination thereof.

23. The catalyst composition of claim 17, wherein the liquid carrier comprises a surfactant.

24. The catalyst composition of claim 17, wherein the liquid carrier comprises an anionic surfactant, a cationic surfactant, or a nonionic surfactant.

25. The catalyst composition of claim 24, wherein the anionic surfactant is selected from the group consisting of sulfate, sulfonate, phosphate, carboxylate, dialkyl sulfocarboxylate, alkylaryl sulfonate, alkyl sulfonate, sulfosuccinate, fatty acid alkali metal salt, polycarboxylate, polyoxyethylene alkyl ether phosphate salt, or alkyl naphthalene sulfonate, wherein each salt comprises a cation selected from the group consisting of alkali metal, alkaline earth metal, ammonium, or hydrocarbyl ammonium.

26. The catalyst composition of claim 24, wherein the cationic surfactant is selected from the group consisting of:

Primary, secondary or tertiary amines; or alternatively

Primary, secondary, tertiary or quaternary ammonium compounds.

27. The catalyst composition of claim 24, wherein the nonionic surfactant is selected from ethoxylates, glycol ethers, fatty alcohol-polyoxyethylene ethers, or combinations thereof.

28. A process for polymerizing 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; and

C) At least one carrier-activator comprising a calcined montmorillonite heteroadduct comprising the contact product of [1] a colloidal montmorillonite clay and [2] a heteroagglomerating agent in a liquid carrier, the heteroagglomerating agent comprising at least one cationic multimetal salt in an amount sufficient to provide the slurry of the montmorillonite heteroadduct having a zeta potential in the range of positive 25 (+) mV (millivolts) to negative (-) 25mV, quantified according to the electro-acoustic amplitude (ESA) effect, prior to separating the montmorillonite heteroadduct from the slurry, wherein the montmorillonite clay comprises montmorillonite, sauconite, nontronite, hectorite, bedtime, saponite, bentonite, or any combination thereof, and wherein the cationic multimetal salt comprises a cationic polyaluminate selected from polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichloride, or polyaluminum hydroxychloroxide, or any combination thereof.

29. The process for polymerizing olefins according to claim 28, wherein the at least one olefin monomer is selected from [ a ] ethylene or propylene, or [ b ] ethylene combined with at least one comonomer selected from the group consisting of: propylene, 1-butene, 2-butene, 3-methyl-1-butene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 3-ethyl-1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1, 3-butadiene, isoprene, piperylene, 2, 3-dimethyl-1, 3-butadiene, 1, 4-pentadiene, 1, 7-hexadiene, vinylcyclohexane, or any combination thereof.

30. The process for polymerizing olefins according to claim 28, wherein the process comprises polymerization in a gas phase reactor, a slurry loop, a dual slurry loop in series, a plurality of slurry tanks in series, a slurry loop in combination with a gas phase reactor, a continuously stirred reactor in a batch process, or a combination thereof.

31. The process for polymerizing olefins according to claim 28, wherein the liquid carrier comprises water, an alcohol, an ether, a ketone, or an ester, or any combination thereof.

32. The process for polymerizing olefins according to claim 28, wherein the liquid carrier comprises a surfactant.

33. The process for polymerizing olefins according to claim 28, wherein the liquid carrier comprises an anionic surfactant, a cationic surfactant, or a nonionic surfactant.

34. The process for polymerizing olefins according to claim 33, wherein the anionic surfactant is selected from the group consisting of sulfate, sulfonate, phosphate, carboxylate, dialkyl sulfocarboxylate, alkylaryl sulfonate, alkyl sulfonate, sulfosuccinate, fatty acid alkali metal salt, polycarboxylate, polyoxyethylene alkyl ether phosphate salt, or alkyl naphthalene sulfonate, wherein each salt comprises a cation selected from the group consisting of alkali metal, alkaline earth metal, ammonium, or hydrocarbyl ammonium.

35. The process for polymerizing olefins according to claim 33, wherein the cationic surfactant is selected from the group consisting of:

Primary, secondary or tertiary amines; or alternatively

Primary, secondary, tertiary or quaternary ammonium compounds.

36. The process for polymerizing olefins according to claim 33, wherein the nonionic surfactant is selected from ethoxylates, glycol ethers, fatty alcohol-polyoxyethylene ethers, or combinations thereof.

37. A method of producing a carrier-activator, the method comprising:

a) Providing a colloidal montmorillonite clay;

b) Contacting the colloidal montmorillonite clay with a heteroagglomerating agent in a liquid carrier, the heteroagglomerating agent comprising at least one cationic multimetal salt in an amount sufficient to provide a slurry of montmorillonite heteroadducts having a zeta potential in the range of positive (+) 25mV (millivolts) to negative (-) 25mV quantified according to the electro-acoustic amplitude (ESA) effect prior to separating the montmorillonite heteroadducts from the slurry, wherein the montmorillonite clay comprises montmorillonite, sauconite, nontronite, hectorite, beidellite, saponite, bentonite, or any combination thereof, and wherein the cationic multimetal salt comprises a cationic polyaluminate selected from polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichloride, or aluminum polyhydroxyl oxychloride, or any combination thereof; and

C) Separating the montmorillonite hetero adduct from the slurry.

38. The method of producing a carrier-activator of claim 37, wherein the colloidal montmorillonite clay and the heteroagglomerating agent are contacted in an amount sufficient to provide a slurry of montmorillonite heteroadducts having zeta potentials in the range of plus (+) 20mV (millivolts) to minus (-) 20 mV.

39. The method of producing a carrier-activator of claim 37, wherein the colloidal montmorillonite clay and the heteroagglomerating agent are contacted in an amount sufficient to provide a slurry of montmorillonite heteroadducts having zeta potentials in the range of plus (+) 15mV (millivolts) to minus (-) 15 mV.