CN115023446A

CN115023446A - Process for preparing catalyst and catalyst composition

Info

Publication number: CN115023446A
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: 2022-09-06
Also published as: EP4097153A1; JP2023523494A; WO2021154204A1

Abstract

Support-activators and catalyst compositions including the same for polymerizing olefins are disclosed, wherein the support-activators include clay heteroadducts prepared from colloidal phyllosilicates, such as colloidal montmorillonite clay, chemically modified with a heterocoagulator. By limiting the amount of heterocoagulation agent relative to the colloidal smectite clay described herein, the montmorillonite heteroadduct support-activator is a porous and amorphous solid that can be easily separated from the resulting slurry by conventional filtration processes and can activate metallocenes and related catalysts for olefin polymerization. Related compositions and processes are disclosed.

Description

Process for preparing catalyst and catalyst composition

Cross Reference to Related Applications

None.

Technical Field

The present disclosure relates to catalyst compositions including support-activators for the production of polyethylene and processes for making and using the same.

Background

Compounds such as Methylaluminoxane (MAO) and aryl boranes are commonly used as metallocene catalyst activators or cocatalysts for olefin polymerization. Commercial scale production of polyolefin resins can employ gas phase or slurry reactor platforms rather than solution phase conditions, and therefore heterogeneous catalyst systems are used in 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 a catalyst, it is often necessary to further use cocatalysts or activators such as MAO and aryl boranes, which can be time consuming and expensive. The synthesis of MAO and aryl boranes themselves is atomically inefficient, requiring multiple steps and inert conditions, which may increase the cost of using such activators.

Various support-activators have been investigated in an attempt to reduce the high cost of alumoxanes, aryl boranes, 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 in U.S. patent nos. 6,632,894 and 7,041,753 the use of clay minerals in sol-gel matrices, which can act as support-activators for metallocenes, but which themselves are expensive to produce. Other methods can be seen in the use of chemically modified clay minerals, such as in 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, difficult separation of the modified clay mineral, or stringent preparation conditions under which the clay can be successfully modified and separated.

Thus, there remains a need to improve the 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 would be desirable to develop clay-based support-activators that eliminate the need for alumoxanes and other expensive activators, that are convenient and economical to prepare, that are high in yield, and/or that 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 the catalyst compositions, and processes for polymerizing olefins. In one aspect, chemically modified clay support-activators can readily activate metallocene compounds for olefin polymerization, and they are surprisingly easy to prepare, low in preparation cost, and high in yield. In particular, the process and support-activator of the present disclosure can largely avoid the difficulties of previous isolation of 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 been unexpectedly found that when a colloidal smectite clay, such as a dioctahedral smectite clay, is contacted with a heterocoagulation agent comprising at least one cationic multimetal salt in a liquid carrier (also referred to as a "diluent"), and when the heterocoagulation agent is used in a specific range relative to the amount of the colloidal smectite clay, a carrier-activator comprising an isolated smectite heteroadduct can be synthesized. By limiting the amount of heterocoagulation agent relative to the colloidal smectite clay described herein, the smectite heteroadduct, also referred to as heterocoagulation smectite, can be easily separated from the resulting slurry by conventional filtration processes. Previous separation processes for chemically modified clay support-activators are often difficult, where filtration may require several days, or multiple washing and centrifugation steps may be required. In addition, the montmorillonite heteroadduct support-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 manner can be used in combination with cocatalysts such as alkylaluminum compounds to provide highly active support-activators for metallocene olefin polymerizations, especially when combined with conventional MAO-SiO ₂ Or borane derived support-activator phase. 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 alumoxanes and borane-based activators.

Furthermore, the isolation of the montmorillonite heteroadduct can be achieved using conventional filtration, without centrifugation or high dilution of the reaction mixture, and without extensive washing of the solid thus obtained. This process satisfies the need by providing solid clay heteroadducts that exhibit better activity than the corresponding untreated clay and exhibit comparable or better activity than more difficult to prepare pillared clay supports.

Further, unlike pillared clays, the heteroagglomerated clay materials of the present disclosure are amorphous solids. The preparation of the heteroagglomerated 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 is not merely swollen upon contact with the cationic multimetal salt, but is collapsed upon preparation of the clay heteroadduct to provide a non-crystalline, non-lamellar amorphous material.

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

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

a) providing a colloidal montmorillonite clay;

b) contacting the colloidal smectite clay with a heterocoagulation agent in a liquid carrier, the heterocoagulation agent comprising at least one cationic multimetal salt and the heterocoagulation agent in an amount sufficient to provide a slurry of a smectite heteroadduct having a zeta potential in the range of about positive 25mV (millivolts) to about negative 25 mV; and

c) separating the smectite heteroadduct 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 co-catalyst; and

c) at least one support-activator comprising a calcined smectite heteroadduct comprising the contact product of [1] colloidal smectite clay and [2] a heterocoagulating agent comprising at least one cationic multimetal salt in a liquid carrier, the heterocoagulating agent in an amount sufficient to provide a slurry of the smectite heteroadduct having a zeta potential in the range of 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 co-catalyst; and

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

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

a) at least one metallocene compound;

b) optionally, at least one co-catalyst; and

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

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

Drawings

Fig. 1 provides a schematic representation representing an aspect of the present disclosure illustrating a method of preparing, washing, and isolating a support-activator comprising a calcined montmorillonite heteroadduct of the present disclosure and comparing this process to a method of preparing, washing, and isolating a pillared clay.

FIG. 2 provides a series of compositions of Aluminum Chlorohydrate (ACH) and

powder XRD (x-ray diffraction) pattern of the calcined product of HPM-20 montmorillonite combination. All samples were prepared according to the method of the invention according to the examples (see examples 18, 20-21 and 23), except that 6.4mmol Al/g clay sample (top), representing Al typically prepared ₁₃ Pillared Clay (comparative example 5) and the starting Clay as such, i.e.0 mmol Al/g clay sample (comparative example 3).

FIG. 3 shows for 0.62wt. -%)

The zeta potential titration of an aqueous 2.5 wt.% (weight percent) aluminium chlorohydrate solution (ACH; measured density of 1.075g/mL) added volumetrically to an aqueous HPM-20 bentonite dispersion was plotted against titrant volume (mL). Titration was set at 0.5mL per titration point and equilibration was then delayed for 30 seconds. The titrant volume represents the cumulative volume of the aqueous solution of aluminium chlorohydrate added. See also table 4.

Fig. 4 shows the conversion of the graph of fig. 3 into a zeta potential versus aluminum-clay mass ratio. Specifically, FIG. 4 illustrates for milling to 0.62wt. -%)

Zeta potential titration of an aqueous solution of 2.5 wt.% aluminum chlorohydrate (ACH; measured density of 1.075g/mL) was added to an aqueous HPM-20 bentonite dispersion and the measured zeta potential was plotted against Al content (mmol Al/g clay). The amount of titrant represents the cumulative mmol of aluminium in the aqueous ACH added.

FIG. 5 shows for 1wt. -%)

4.58% by volume addition of HPM-20 aqueous bentonite dispersion

290 aqueous solution of polyaluminum chloride (empirically Al) ₂ (OH) _2.5 Cl _3.5 ) Zeta potential titration of (d) and plotting the measured zeta potential against titrant volume (mL). Titration was set at 1mL per titration point and equilibration was delayed for 30 seconds. Titrant volumetric representation of addition

290 cumulative volume of aqueous polyaluminum chloride solution. See also table 5.

FIG. 6 provides for%

10% by volume addition of HPM-20 aqueous bentonite dispersion

Zeta potential titration of aqueous AL27 colloidal alumina dispersion (after adjustment) was performed and the measured zeta potential was plotted against titrant volume (mL). Titration was set at 1mL per titration point from 0-27mL, followed by 3mL per titration point, with equilibration delay of 60 seconds. Titrant volumetric representation of addition

Cumulative volume of AL27 colloidal alumina aqueous solution. See example 11 and table 6.

FIG. 7 illustrates for 5wt. -%)

Zeta potential titration of a 200 aqueous fumed silica dispersion with a 2.5 wt.% aqueous solution of Aluminum Chlorohydrate (ACH) added volumetrically, plotting the measured zeta potential against titrant volume (mL). Titration was set at 1mL per titration point and equilibration delayed for 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 zeta potential versus aluminum-clay mass ratio. Specifically, fig. 8 provides for a 5wt. -%)

Zeta potential titration of 200 aqueous fumed silica dispersion with addition of 2.5 wt.% aqueous Aluminum Chlorohydrate (ACH) was performed and the measured zeta potential was plotted against Al content (mmol Al/g clay). The amount of titrant represents the cumulative mmol of aluminium in the aqueous ACH added.

FIG. 9 provides for converting to 1wt. -%)

HPM-20 aqueous bentonite dispersion volumetrically added Aluminum Chlorohydrate (ACH) solution treated silica-containing 5 wt.%

Zeta potential titration of 200 fumed silica dispersion (after conditioning). Titration was set at 0-1.2mL per titration point 0.2mL followed by 0.5mL per titration point with a 30 second delay in equilibration. The titrant was a colloidal substance (species) and therefore the zeta potential was adjusted using the method described in example 11 to provide the graph in figure 9. See example 38.

FIG. 10 shows the nodes of the nitrogen adsorption/desorption BJH (Barrett, Joyner and Halenda) pore volume analysis of the Aluminum Chlorohydrate (ACH) heterocoagulation clay of example 18As a result, the pore diameters (angstroms,

) Graph relating 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 followed by azeotropy, but without further treatment according to comparative example 3

Results of nitrogen adsorption/desorption BJH pore volume analysis of HPM-20 bentonite sample, showing V _3-10nm A value of greater than the cumulative pore volume V _3-30nm 55% of the total.

FIG. 12 shows suspension in water, evaporation and calcination, but without further treatment according to comparative example 1

Nitrogen adsorption/desorption BJH pore volume analysis results of HPM-20 bentonite-untreated sample, showing V _3-10nm A value of greater than the cumulative pore volume V _3-30nm 55% of the total.

FIG. 13 is CDCl ₃ Process for preparation of 7-phenyl-2-methyl-indene ¹ H NMR spectrum of contaminant CH ₂ Cl ₂ And a water peak is identified and a peak integration value is shown.

FIG. 14 is CDCl ₃ Process for preparing rac-dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride ¹ H NMR spectrum, where peak integration values are shown.

Detailed Description

In order to more clearly define the terms and phrases used herein, the following definitions are provided. To the extent that any definition or use provided by any document incorporated 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 "polyoxometallate" 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, hydroxyl, and/or halide ligand. The specific ligand may depend on the precursor and other factors such as the process used to generate the multimetal salt, the solution pH, etc. For example, the multimetal salts of the present disclosure can be aqueous metal oxides, aqueous metal oxyhydroxides, and the like, including combinations thereof. Bridging ligands such as oxo ligands that bridge two or more metals may be present in these materials, however, the multimetal salts may also include terminal oxo, hydroxy, and/or halide ligands.

While many known multimetal salt species are anionic, and the suffix "-ate" is often used to reflect anionic species, the multimetal salt (polyoxometalate) species used in accordance with the present disclosure are cationic. These materials may be referred to as compounds, species, or compositions, but one of ordinary skill in the art will appreciate that the multimetallic salt compositions can contain a variety of species in a suitable carrier, such as in an aqueous solution, depending on, for example, solution pH, concentration, starting precursors to produce multimetallic salts in aqueous solution, and the like. For the sake of clarity and convenience, these various materials are collectively referred to as "multimetal salts" or "polyoxometalates," regardless of whether the composition includes or consists essentially of a cationic polyoxometalate, a multihydroxy metal salt, a multihydroxy oxometallate, or a material that includes or consists of a mixture of other ligands or compounds, such as halides. Examples of multimetal salts include, but are not limited to, aluminum chlorohydrate, polyaluminum chloride, or aluminum chlorohydrate compositions, which may include linear, cyclic, or cluster 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 species.

Both isopolymetal salts containing a single type of metal and heteropolymetal salts containing more than one type of metal (or electropositive atom such as phosphorus) are included in the generic term polymetallic salts or polyoxometallates. For example, such asAluminum multimetal salts provided by Aluminum Chlorohydrate (ACH) or polyaluminum chloride (PAC) are examples of isopoly metal salts. In another example, the multimetal salts of the present disclosure can be prepared from a first metal oxide that is subsequently 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 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 the metal oxide, hydroxide, oxyhalide, or halide, such as ZrOCl ₂ 、ZnO、NbOCl ₃ 、B(OH) ₃ 、AlCl ₃ Or a combination thereof. Thus, when different metals are employed in this preparation, the resulting material is considered to be a heteropolymetal salt. Both isopoly and heteropoly metal salts may be referred to as "multimetal salts" for short.

In another aspect, the multimetallic salts according to the present disclosure can be non-alkylated with transition metal compounds such as metallocene compounds. That is, the multimetal salts of the present disclosure can be free of direct metal-carbon bonds, as found in aluminoxanes or other organometallic species.

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

In one aspect, the multimetallic salt according to the present disclosure can beAt 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, commonly considered to be of the general formula Al _n Cl _3n-m (OH) _m . These multimetallic salt species may be referred to as aluminum hydroxychloride compounds or compositions. Another multimetal salt that can be used in accordance with the present disclosure is polyaluminum chloride (PAC), which is also not a single species, but rather a collection of multiple aluminum polymeric species that can include linear, cyclic, or cluster compounds, examples of which can contain from 2 to about 30 aluminum atoms, oxy groups, chlorine, and hydroxyl groups. Other examples of aluminum multimetal salts include, but are not limited to, those having the formula [ Al _m O _n (OH) _x Cl _y ]·zH ₂ O compounds such as aluminum sesquichloride, and cluster-type species such as Keggin ions, e.g., [ AlO ] ₄ Al ₁₂ (OH) ₂₄ (H ₂ O) ₁₂ ] ⁷⁺ ·7[Cl] ^- Sometimes referred to as "Al ₁₃ Mer "polycations. Polyaluminum chlorides (PACs) can be prepared, for example, by reacting aqueous hydroxides with AlCl ₃ Are produced in combination and the resulting mixture of aluminum species has a range of basicities. Aluminum Chlorohydrate (ACH) is generally considered to be the most basic, and polyaluminum chloride (PAC) is the less basic.

A clay heteroadduct or clay heterocoacervate according to the present disclosure includes the contact product of [1] a colloidal montmorillonite clay, such as a dioctahedral montmorillonite clay, and [2] a heterocoacervating agent comprising at least one cationic multimetal salt in a liquid vehicle, such as an aqueous carrier, wherein the amount used is sufficient to provide a slurry of the montmorillonite heteroadduct having a zeta potential in the range of about +25mV to about-25 mV. Once isolated, the montmorillonite heteroadduct can be heated, dried, and calcined to form the support-activator described herein. Upon calcination, additional reactions may occur with the multimetallic salt initially intercalated or bound to the montmorillonite, for example, water in the intercalated multimetallic salt may distill off and additional oxygen radicals may be formed. In this respect, the term "polyoxometallate" may be used in particular to describe the calcination product. In any event, the terms "multimetal salt" and "polyoxometalate" are used interchangeably to describe a composition for contacting colloidal montmorillonite.

The multimetal salts of the present disclosure can also be referred to as "polycations" and can include both homopolycations and heteropolycations depending on whether the polycation includes a single type of metal or more than one type of metal. For example, the hydrotalcite is [ Mg ] ₆ Al ₂ (OH) ₁₆ ]CO ₃ ·4H ₂ O, which is a heteropolycation according to the present disclosure.

Other examples of multimetallic salts provided by way of example only include the epsilon-Keggin cation [ epsilon-PMo ] ₁₂ O ₃₆ (OH) ₄ {Ln(H ₂ O) ₄ } ₄ ] ⁵⁺ In the formula, Ln can be La, Ce, Nd or Sm. See, e.g., german applied chemistry (angelw.chem., int.ed.) 2002,41, 2398. Other examples include those having the formula [ Ln ₂ V ₁₂ O ₃₂ (H ₂ O) ₈ {Cl}]A lanthanide-containing cationic heteropolyoxovanadium cluster of Cl, wherein Ln can be Eu, Gd, Dy, Tb, Ho or Er. See, e.g., the Bureau of chemistry in England (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 salt 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 an aqueous solution, and multiple species are possible, 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 use in preparing the heterocoagulation reagent.

A heterocoagulation reagent. The terms "heterocoagulant", and the like are used herein to describe compositions containing any positively charged oligomeric or polymeric metal oxide-containing material that are present 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 readily filterable solid (as defined herein). "heterocoagulation reagent" is used interchangeably with the terms "multimetallic salt" or "polyoxometallate" to refer to a material containing any positively charged oligomeric or polymeric metal oxide that is used to form clay heteroadducts. Thus, "heterocoacervation agents" emphasize that when used in an amount sufficient to provide a slurry having a zeta potential in the range of about +25mV to about-25 mV, a composition comprising one or more cationic multimetal salt materials in a liquid carrier forms an easily filterable solid when contacted with a colloidal montmorillonite clay. "heterocoagulation" is a term of art described by Lagaly in Ullmann's Encyclopedia of Chemistry 2012. In the context of the present disclosure, "heterocoagulation" is defined as a process in which negatively charged colloidal clay particles are combined with positively charged heterocoagulation reagent species to form a readily filterable solid, unless otherwise specified. Heteroagglomerations are also sometimes referred to in the art and herein as heteroagglomerations, such as Cerberlaud et al "advances in physics: x (Advances in Physics: X), 2017, Vol.2, 35-53.

Heteroadducts or heterocoagulates. Clay heteroadducts or clay heteroadducts and similar terms such as "heteroagglomerated clay" or "montmorillonite heteroadduct" and the like refer to contact products obtained by combining a heteroagglomerating agent and a colloidal clay. That is, in the heterocoagulation reagent, 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 No. 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 "easily filterable" contact product of a heterocoagulation reagent and a colloidal clay. These terms are used to distinguish the contact products of a heterocoacervate that is easily filterable from a heterocoacervating agent and colloidal clay that are combined in a ratio that provides a product that is not easily filterable, e.g., a product formed when following a pillared clay synthesis recipe. In the case of pillared clay formulations, the contact product is not easily filtered and centrifugation is usually required to isolate the pillared clay product.

When tracingWhen the aluminum-containing heterocoagulation reagent is used to form the heterocoagulation clay, and unless otherwise specified, the ratio of the pillaring reagent (also referred to as the heterocoagulation reagent) such as aluminum oxychloride to the clay is expressed as mm (or mmol or millimole) Al/g of clay, which is the ratio of millimoles of Al in the pillaring reagent or heterocoagulation reagent to grams of clay. 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 reagent or the alundum heterocoagulation reagent is present in a soluble solution, the millimoles of Al are based on the weight percent Al or the Al provided by the manufacturer ₂ O ₃ Content (wt.%). Alternatively, and unless otherwise specified, the number of millimoles of Al when starting with a pillaring or heterocoagulating agent in solid form, i.e. dispersed in solution, is determined by the weight used in the formulation and the empirical formula provided by the manufacturer.

Easy to filter. The terms "readily filterable", "readily filterable or separable", and the like, are used herein to describe compositions according to the present disclosure in which solids in a mixture containing a liquid phase can be separated from the liquid phase by filtration without resorting to centrifugation, ultracentrifugation, or dilute solutions of less than about 2 wt.% solids, decantation of liquids from solids after long settling times, and other such techniques. These terms are used generally herein to describe clay heteroadducts, which are the contact products of colloidal montmorillonite clay according to the present disclosure and a heterocoagulation reagent under certain conditions, without the need for separation by centrifugation, high dilution and settling or settling tanks or ultrafiltration. Thus, clay heteroadducts that are easily filterable can be separated from soluble salts and synthetic byproducts in good yield under gravity or vacuum filtration conditions by passing the slurry containing the heteroadduct through conventional filter materials such as sintered glass, metal or ceramic frits, paper, natural or synthetic matte fibers, and the like, in minutes or less, or in less than about an hour.

The present disclosure provides specific experimental and quantitative methods by which filterability can be assessed. For example, specific methods of quantifying filterability of heteroadduct slurries are provided that demonstrate that the slurries can be considered easy to filter or filterable when prepared according to the methods of the present disclosure. Colloids or suspensions described by Lagaly in the encyclopedia 2012 of ullmann chemistry, which require long settling or ultrafiltration, are not considered "filterable" in the context of the present disclosure. The readily filterable suspensions or slurries of the present disclosure can provide clear filtrates upon filtration, while "less readily filterable" suspensions take much longer to filter, which can contain particulate matter in the form of cloudy or non-clear filtrates that are observable to the naked eye, which is indicative of colloidal clay dispersions. When a slurry of the smectite heteroadduct according to the present disclosure is prepared to provide a zeta potential near the upper (positive) boundary of about +25mV (millivolts) or near the lower (negative) boundary of about-25 mV, some turbidity can be observed in the filtrate when the heteroadduct is filtered, which is reduced when the smectite heteroadduct is prepared using a ratio of colloidal smectite clay and heterocoagulating agent that provides a slurry with a zeta potential closer to or near 0 mV.

And (3) colloid. The use of the terms "colloid", "colloidal clay", "colloidal solution", "colloidal suspension" and similar terms are defined in the chapter "colloid" of the Ullmann encyclopedia of Industrial chemistry, 2007, 1, 15, by Gerhard Lagaly. These terms may be used interchangeably.

Catalyst compositions and catalyst systems. Terms such as "catalyst composition," "catalyst mixture," "catalyst system," and the like are used to denote the combination of the listed components that ultimately form or are used to form an active catalyst according to the present disclosure. The use of these terms is not dependent upon whether any particular contacting step, order of contacting, between or among the components, any reaction may occur, or any product that may result from 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 fate of any cocatalyst, metallocene compound or support-activator after contacting or combining any of these components in any order. Thus, these and similar terms encompass the initially recited components or combinations of starting components of the catalyst composition, as well as any products that may result from contacting such 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, and such use will be apparent to the skilled artisan from the context of the present disclosure.

And (4) 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 heteroadduct disclosed herein, which is typically expressed only as the weight of polymer polymerized/weight of catalyst clay support-activator/hour of polymerization, in the absence of any transition metal catalyst component (such as a metallocene compound), any cocatalyst (such as an organoaluminum compound), or any 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 given 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-exchange or pillared clay or the weight of the clay component itself used to prepare the clay heteroadduct. Terms such as "increased activity" or "increased activity" describe the activity of a catalyst composition according to the present disclosure that is greater than the activity of a comparative catalyst composition using the same catalyst components, such as a metallocene compound and a cocatalyst, except that the comparative catalyst composition typically uses a different support-activator or activator, such as a pillared clay, or the clay component used in the catalytic reaction is not a heteroagglomerated clay. For example, increased or enhanced activity according to the present disclosure includes using a standard set of ethylene homopolymerization conditions based on the activity of the calcined clay heteroadduct being greater than or equal to about 300 grams polyethylene polymer per gram of calcined heteroagglomerated clay per hour (g/g/h). 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 to about 500 f rpm, and slurry polymerization conditions including 1L of purified isobutane diluent, a polymerization temperature of 90 ℃, a total ethylene pressure of 450psi, a typical run length of 30 or 60 minutes, comprising (1-Bu-3-MeCp) ₂ ZrCl ₂ And Triethylaluminum (TEAL) cocatalyst, optionally using a metallocene as a stock solution containing TEAL to provide about 7X 10 ^-5 The amount of metallocene-clay ratio of mmol metallocene/mg calcined clay was added. An alkylaluminum cocatalyst is generally used in the polymerization batch and is generally selected from TEAL or Triisobutylaluminum (TIBAL).

The product is contacted. The term "contact product" is used herein to describe a composition in which components are combined or "contacted" in any order and for any duration, unless the context of the present disclosure states or requires or implies a particular order in any way. Although "contact product" may include reaction products, there is no requirement that the individual components react with each other, and this term is used regardless of any reaction that may or may not occur upon contact of the listed components. To form the contact product, for example, the listed components can be contacted by blending or mixing, or can be contacted by adding the components to the liquid vehicle in any order or simultaneously. Further, unless otherwise indicated 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 enumerated 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 were used to determine pore size and pore volume distributions using the BJH method. The classification system of porous materials based on the International Union of Pure and Applied Chemistry (IUPAC) (see Pure and applied chemistry (Pure)&Chem.), 1994,66,1739-In National Institute of Standards and Technology Special Publication 960-17, pore sizes are defined as follows. 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 less than that present in the catalyst or catalyst support

The hole of (a). As used herein, "mesopores" and "mesopores" refer to the diameters present in a catalyst or catalyst support produced according to the process of the present disclosure

To less than

(i.e., 2nm to<50 nm). As used herein, "macropore" and "macropore" refer to a diameter equal to or greater than that present in a catalyst or catalyst support produced according to the process of the present disclosure

(50nm) pores.

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

"d 50" means the median pore diameter as measured by porosimetry. Thus, "d 50" corresponds to the median pore diameter calculated based on the pore size distribution, and half of the pore diameters are greater than the median. The d50 values reported herein are based on Nitrogen desorption, calculation of The Determination of i. Nitrogen Isotherms of The Pore Volume and Area distribution of Porous materials (The Determination of Pore Volume and Area distribution in pores from Nitrogen Isotherms) american chemical society (j.am.chem.soc.), 1951,73(1), page 380, using well-known calculation methods described by e.p.barrett, l.g.joyner and p.p.halenda ("BJH").

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

A transition metal catalyst. By "transition metal catalyst" is meant a transition metal compound or composition that, when contacted with the support-activator of the present disclosure, can act as or be converted to an active olefin polymerization catalyst, either in its present form or when contacted with a cocatalyst capable of transferring or imparting a polymerizable activation to the transition metal catalyst. The use of the term "catalyst" is not intended to reflect any particular mechanism or that the "transition metal catalyst" itself represents an active site for catalyzing polymerization when the "transition metal catalyst" is activated or is rendered polymerizable activated ligand. The transition metal catalyst is 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.

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. Polymerizable activated ligands include, but are not limited to, hydrocarbyl groups such as alkyl groups, such as methyl or ethyl groups, aryl and substituted aryl groups, such as phenyl or tolyl groups, substituted alkyl groups such as benzyl or trimethylsilylmethyl (-CH) ₂ SiM ₃ ) Hydride, silyl, and substituent groups such as trimethylsilyl and the like. Thus, it is possible to provideIn one aspect, the co-catalyst can be an alkylating agent, a hydrogenating agent, a silylating agent, and 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 may 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 a 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, 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, as understood by those skilled in the art. According to another aspect, the term "cocatalyst" can refer to an "activator", or can 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 (substance) 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. An "activator" can convert the contact product of a metallocene component and a component that provides the metallocene with an activatable ligand (such as an alkyl or hydride) to a catalyst system that can polymerize olefins, for example, when the metallocene compound does not already contain such a ligand. This term is used regardless of the actual activation mechanism. Exemplary activators can include, but are not limited to, support-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 which a support-activator is present, can be referred to as an "activator" or "co-activator," but the catalyst composition is supplemented with one or more aluminoxanes, organoborons, organoborates, ionizing compounds, or other co-activators.

A support-activator. As used herein, the term "support-activator" refers to an activator in solid form, such as ion-exchanged clay, protonic acid-treated clay, or pillared clay, and similar insoluble supports that also serve as activators. The support-activator, when combined with a metallocene having an activatable ligand or, alternatively, a metallocene and a cocatalyst which can provide an activatable ligand, provides a catalyst system for polymerizable olefins.

An ion-exchange clay. As used herein, the term "ion-exchanged clay" is understood by those skilled in the art as a clay (also referred to as a "mono-ionic" or "mono-cationic" clay) in which the exchangeable ions of a naturally occurring or synthetic clay have been replaced or exchanged with another selection of one or more ions. Ion exchange can be carried out by treating a naturally occurring or synthetic clay, usually from a concentrated ionic solution (such as a 2N aqueous cation solution), with a selected cation source, which treatment comprises passing through a plurality of exchange steps, for example, 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, e.g., Sanchez et al colloid and surface a: physicochemical and Engineering Aspects (Colloids and Surfaces A: physical and Engineering Aspects), 2013,423,1-10 and Kawamura et al, Clay and Clay minerals, 2009,57(2), 150-. Typically, centrifugation is used to separate the clay from the 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 that includes at least one substituted or unsubstituted cycloalkadienyl-type ligand or alkadienyl-type ligand, including heteroatom analogs thereof, regardless of the particular bonding mode, e.g., regardless of whether the cycloalkadienyl-type ligand or alkadienyl-type ligand is η ⁵ -、η ³ -or η ¹ Bonding modes to metals, and whether or not more than one of these bonding 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 η ³ Allyl is not of cycloalkadienyl type or alkadienylAs part of a type ligand, which compound is useful as a transition metal compound component of the catalyst compositions described herein. Thus, "metallocene" includes compounds having a substituted or unsubstituted η ³ To eta ⁵ Cycloalkadienyl type and eta ³ To eta ⁵ -alkadienyl ligands,. eta ³ Compounds of allylic ligands, including heteroatom analogues thereof, and including but not limited to cyclopentadienyl ligands, indenyl ligands, fluorenyl ligands, η ³ -allyl ligands, pentadienyl ligands, borato-anion hetero-phenyl ligands, 1, 2-aza-bora-heteropentadienyl ligands, 1, 2-diaza-3, 5-diboron-yl ligands, substituted analogues thereof and partially saturated analogues thereof. The partially saturated analogs include ⁵ -compounds of cycloalkadienyl-type ligands, examples of which include, but are not limited to, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl, partially saturated fluorenyl, substituted analogs thereof, and the like. In some instances, the metallocene is referred to simply as a "catalyst" in much the same way as the term "cocatalyst" is used herein to refer to, for example, an organoaluminum compound. Thus, a metallocene ligand may be considered in this disclosure to include at least one substituted or at least one unsubstituted cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, allyl, borato-ionic heteroaryl, 1, 2-azaborodienyl, or 1, 2-diaza-3, 5-diboronoyl ligand, including substituted analogs thereof. For example, any substituent may be independently selected from halide, C ₁ -C ₂₀ Hydrocarbyl radical, C ₁ -C ₂₀ Heterohydrocarbyl radical, C ₁ -C ₂₀ Organic hetero group, condensed C ₄ -C ₁₂ Carbocyclic moiety or fused C having at least one heteroatom independently selected from nitrogen, oxygen, sulfur or phosphorus ₄ -C ₁₁ A heterocyclic moiety.

Organoaluminum compounds and organoboron compounds. As used herein, the terms "organoaluminum compound" and "organoboron compound" include, for example, AlMe ₃ And BEt ₃ Also included are neutral compounds such as LiAlMe ₄ 、LiAlH ₄ 、NaBH ₄ And LiBEt ₄ And the like. Thus, it is possible to provideUnless otherwise indicated, aluminum and boron hydride compounds are included in the definition of organoaluminum and organoboron compounds, respectively, whether the compounds are neutral or anionic.

Pillared clay. In the present disclosure, "pillared clays" are defined as those in which the spacing between the ordered layers is substantially greater than the substrate spacing

To

The clay material of (1). When a silty clay sample is analyzed using an X-ray diffraction apparatus capable of scanning 2 ° or greater 2 θ angles, it is generally observed that materials containing such pillared sequences have a significant peak at 2 θ values between 2 ° and 9 °. These are typically prepared by the introduction of 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 a pillaring agent with 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 can be contrasted with support-activator preparations according to the present disclosure, where the support-activator 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 pillaring agent used to form the pillared clay can be selected from the same heterocoagulation reagents used to form the heterocoagulation clays of the present disclosure. As explained herein, some pillared clay species may be formed even during the preparation of the montmorillonite heteroadducts disclosed herein.

And (4) inserting. The term "intercalation" or "intercalation" is a term of art which refers to the 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.

The substrate pitch. The terms "substrate spacing", "substrate d001 spacing" or "d 001 spacing" when used in the context of a montmorillonite clay, 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 smectite 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 the intermediate octahedral sheet, with or without modification or pillaring. The substrate spacing value was measured using X-ray diffraction analysis (XRD) of the d001 plane. Natural montmorillonite as found in bentonite has about

To about

The substrate pitch range of (1). (see, for example, Table 1 at the Fifth National Conference on Clays and Clay Minerals, National Academy of Sciences, National Research Council, publication 566,1958, Conference notes Heterogeneity of Montmorillonite (Heterogeneity In Montmorillonite), J.L.McAntee, Jr, pages 279-88 and 282.) XRD test methods for determining the spacing of substrates are described In: pillared Clays and Pillared Layered Solids (Pillared Clays and Pillared Layered Solids), R.A. Schoonheydt et al, Pure applied. chem., 71(12), 2367-; and U.S. patent No. 5,202,295 (McCauley) column 27, lines 22-43.

Zeta potential. As used herein, the term "zeta potential" refers to the potential difference between the junction of the fixed layer (Stern layer) (the strongly attached layer of counterions formed to neutralize the surface charge of the colloidal particles) and the diffusion layer (the loosely attached ionic groups, which reside further away from the particle surface than the fixed 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 sonic amplitude effect" (ESA) which is the generation of ultrasonic waves due to the application of an electrical potential on a colloidal suspension, as described in U.S. patent No. 5,616,872, which is incorporated herein by reference.

A hydrocarbyl group. As used herein, the term "hydrocarbyl" is used according to the art-recognized IUPAC definition as a monovalent, straight, branched, or cyclic group formed by removing a single hydrogen atom from a parent hydrocarbon compound. Unless otherwise specified, 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 nomenclature catalog (Compendium of Chemical technology), 2 nd edition (1997), page 190. Examples of hydrocarbyl groups include, but are not limited to, aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, cycloalkadienyl, alkynyl, aralkyl, aralkenyl, and aralkynyl groups, and the like.

A heterohydrocarbyl group. The term "heterocarbyl" is used in this disclosure to encompass monovalent, straight chain, branched, or cyclic groups formed by the removal of 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 produce a free valence. Examples of heterocarbyl groups include, but are not limited to, -CH ₂ OCH ₃ 、-CH ₂ SPh、-CH ₂ NHCH ₃ 、-CH ₂ CH ₃ NMe ₂ 、-CH ₂ SiMe ₃ 、-CMe ₂ SiMe ₃ 、-CH ₂ (C ₆ H ₄ -4-OMe)、-CH ₂ (C ₆ H ₄ -4-NHMe)、-CH ₂ (C ₆ H ₄ -4-PPh ₂ )、-CH ₂ CH ₃ PEt ₂ 、-CH ₂ Cl、-CH ₂ (2,6-C ₆ H ₃ Cl ₂ ) And the like.

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

Organoheteryl (Organoheteryl). The term "organoheteryl" is also used according to the art-recognized IUPAC definition as a monovalent group containing carbon, and thus is organic, but has a free valence at an atom other than carbon. See IUPAC Total chemical nomenclature catalog, 2 nd edition (1997) page 284. The organoheteryl group may be linear, branched, or cyclic, and includes common groups such as alkoxy, aryloxy, organothio (or organothio), organogermanium (or organogermanium), acetamido, acetonylacetamido, alkylamido, dialkylamido, arylamido, diarylamido, trimethylsilyl, and the like. Radicals such as-OMe, -OPh, -S (tolyl), -NHMe, -NMe ₂ -N (aryl) ₂ 、-SiMe ₃ 、-PPh ₂ 、-O ₃ S(C ₆ H ₄ )Me、-OCF ₂ CF ₃ 、-O ₂ C (alkyl), -O ₂ C (aryl), -N (alkyl) CO (alkyl), -N (aryl) CO (aryl), -N (alkyl) C (O) N (alkyl) ₂ Hexafluoroacetonyl acetate, and the like.

An organic group. Organic group, as used in this disclosure according to the IUPAC definition, refers to any organic substituent having a free valence at a carbon atom, regardless of functional type, e.g., CH ₃ CH ₂ -、ClCH ₂ C-、CH ₃ C (═ O) -, 4-pyridylmethyl, and the like. The organo groups may be linear, branched, or cyclic, and the term "organo" may be used in conjunction with other terms, such as in the organo thio- (e.g., MeS-) and organo oxy groups.

A heterocyclic group. The IUPAC general catalogue compares organic groups with other groups such as heterocyclic and organoheteryl groups. These terms are set forth in IUPAC catalog 2 nd edition (1997) which demonstrates the convention of attaching an "-yl" suffix to the moiety of a molecule or group that bears a valence from the missing hydrogen. Thus, a heterocyclyl group is defined as a monovalent group formed by removing a hydrogen atom from any ring atom of a heterocyclic compound. For example, piperidin-1-yl and piperidin-2-yl groups shown below are both heterocyclic groups in which the line drawn from a nitrogen atom or a carbon atom represents an open valency other than methyl.

However, piperidin-1-yl is also considered an organic hetero-group, and piperidin-2-yl is also considered a heterohydrocarbyl group. Thus, the valency of the "heterocyclyl" can occur on any suitable ring atom, while the valency of the "organoheteryl" occurs on a heteroatom, and the valency of the heterohydrocarbyl group occurs on a carbon atom.

Alkylene and alkylene. As described in IUPAC general list of chemical terms, 2 nd edition (1997), "alkylene" 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 a double bond. Examples of the alkylene group include, for example, 1, 2-phenylene, 1, 3-propanediyl (-CH) ₂ CH ₂ CH ₂ -) cyclopentylene (-CC), cyclopentylene (-CO-O-C) ₄ H ₈ ) Or bridge (-CH) ₂ -) and does not form a methylene group of the double bond. Alkylene groups in which the free valences do not participate in the double bond are different from hydrocarbylene groups such as alkylidene.

A "partial hydrocarbyl" is a divalent group formed by removing two hydrogen atoms from the same carbon atom of a hydrocarbon, the free valences of which are part of a double bond. Alkylidene is an exemplary partial hydrocarbon group and is defined as a divalent group formed by removing two hydrogen atoms from the same carbon atom of an alkane, the free valences of which are part of a double bond. Examples of alkylidene groups are such as ═ CHMe, CHEt, ═ CMe ₂ CHPh or where the methylene carbon forms a double bond (═ CH) ₂ ) Of (a) is (b).

Heterohydrocarbylene and heterohydrocarbylene groups. Similar to hydrocarbylene, the term "heteroalkylene" refers to a divalent group formed by removing two hydrogen atoms from a parent heterocarbon molecule, the free valence of which does 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 free valences do not participateA double bond. Examples of "heterocarbyl" include, but are not limited to, -CH ₂ OCH ₂ -、-CH ₂ NPhCH ₂ -、-SiMe ₂ (1,2-C ₆ H ₄ )SiMe ₂ -、-CMe ₂ SiMe ₂ -、-CH ₂ NCMe ₃ -、-CH ₂ CH ₂ PMe-、-CH ₂ [1,2-C ₆ H ₃ (4-OMe)]CH ₂ -and the like.

Like the partial hydrocarbon group, a "heteropartial hydrocarbon group" is a divalent group formed by removing two hydrogen atoms from the same carbon atom of a heterohydrocarbon, the free valences of which are part of a double bond. Examples of heterohydrocarbyls include, but are not limited to, compounds such as ═ CHNMe ₂ 、＝CHOPh、＝CMeNMeCH ₂ Ph、＝CHSiMe ₃ 、＝CHCH ₂ Cl, etc.

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

A polymer. The term "polymer" is used generically herein to include olefin homopolymers, copolymers, terpolymers, etc. Copolymers are derived from one olefin monomer and one olefin comonomer, while terpolymers are 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 comonomers such as propylene, 1-butene, 1-hexene or 1-octene. If the monomer and comonomer are ethylene and 1-hexene respectively, the resulting polymer will be classified as an ethylene/1-hexene copolymer. Likewise, the term "polymerization" includes homopolymerization, copolymerization, terpolymerization, and the like. For example, the copolymerization process includes contacting an olefin monomer such as ethylene and an olefin comonomer such as 1-hexene to produce a copolymer. Well known abbreviations for polyolefin types such as "HDPE" may be used herein to represent high density polyethylene.

The term "polymer" is used herein to refer to the inorganic compositions used in the preparation and formation of the pillars in the modified clay, as the context permits or requires. For example, it is known to form columns in montmorillonite clays based on the use of polymeric cationic hydroxy metal complexes of metals such as aluminum, zirconium and/or titanium, such as aluminum chlorohydrate complexes (also known as "chlorohydroxy" or "chlorohydroxide"). 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 otherwise specifically stated, 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.

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

Additional explanation of the terms. The following additional explanations of terms are provided to fully disclose aspects of the disclosure and claims.

Unless otherwise indicated or the context requires otherwise, the chemical formula of the multimetal salts disclosed herein for use as heterocoagulants are empirical formulas. Thus, for example, (Al, Mg) ₂ Si ₄ O ₁₀ (OH) ₂ (H ₂ O) ₈ Is an empirical formula of a multimetal salt, which can be considered to encompass oligomeric or polymeric species, and is such as FeO _x (OH) _y (H ₂ O) _z ] ⁿ⁺ The formula (ii) can also be considered to encompass oligomers or polymers where the variable subscript need not be an integer.

Several types of numerical ranges are disclosed herein, including but not limited to numerical ranges of atomic numbers, substrate spacing, weight ratios, mole ratios, percentages, temperatures, and the like. When any type of scope is disclosed or claimed,it is the intention of the applicants to disclose or claim individually each possible number that such a range can reasonably encompass, consistent with the written description and context, and to include the endpoints of the range and any subranges and combinations of subranges encompassed therein. For example, when applicants disclose or claim a chemical moiety having a certain number of carbon atoms, such as C1 through C12 (or C ₁ To C ₁₂ ) Alkyl, or in other words having from 1 to 12 carbon atoms, applicants' intent is to refer to moieties that may 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 these two numbers (e.g., C1 to C6 alkyl), and also including any combination of ranges between these two numbers (e.g., C2 to C4 and C6 to C8 alkyl). If for any reason the applicant chooses to claim less than the full extent of the disclosure, for example in view of a reference that the applicant may not be aware of at the time of filing an application, the applicant reserves the right to limit or exclude any individual member of any such range or group, including any sub-ranges or combinations of sub-ranges within said group, which may be claimed by range or in any similar manner.

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

R＝RL+k(RU-RL)，

where k is a variable ranging from 1% to 100% in 1% increments, e.g., k is 1%, 2%, 3%, 4%, 5% … … 50%, 51%, 52% … … 95%, 96%, 97%, 98%, 99% or 100%. In addition, any numerical range represented by any two values of R as calculated above is also specifically disclosed.

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

Unless otherwise indicated, a value or range may be indicated in this disclosure using the term "about" to mean, for example, "about" to specify a value, greater than or less than "about" to specify a value, or within a range from "about" one value to "about" another value. When such values or ranges are expressed, other embodiments disclosed include the specifically recited values, ranges between the specifically recited values, and other values proximate to the specifically recited values. In one aspect, use of the term "about" means ± 15% of the stated value, ± 10% of the stated value, ± 5% of the stated value, or ± 3% of the stated value. For example, when the term "about" is used as a modifier of, or in combination with, a variable, characteristic, or condition, it is intended that the numbers, ranges, characteristics, and conditions disclosed herein are sufficiently flexible that one of ordinary skill in the art can practice the disclosure with temperatures, rates, times, concentrations, amounts, contents, attributes (such as substrate spacing, dimensions, including pore size, pore volume, surface area, and the like) slightly outside the specified ranges or different from a single specified value to achieve the desired results as described in the application, such as the preparation of porous catalyst carrier particles having the defined characteristics and their use in the preparation of active olefin polymerization catalysts and in olefin polymerization processes using such catalysts.

Unless otherwise specified, the terms "a", "an", "the", and the like (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 than one of a catalyst support-activator, organoaluminum compound, or metallocene compound, respectively.

As used in the transitional phrase or specification, the term "comprising" and variations thereof, such as "comprises", "comprising", "has", "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 exclude any element, step, or ingredient not specified in the claims. The transitional phrase "consisting essentially of … …" limits the scope of the claims to specific components or steps and 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" as this phrase is intended to describe the listed components, including materials, which do not materially alter the compositions or methods to which the term is applied. For example, a precursor or catalyst component may consist essentially of a material that, when prepared by a procedure, may include impurities that are common in samples of its commercial production. When the claims include different features and/or classes of features (e.g., method steps, 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 may have different transitional terms or phrases utilized in conjunction with the different features within the claims. For example, a process can comprise several of the recited steps (and other non-recited steps), but be prepared using a catalyst system that "consists of" or "consists essentially of" the particular steps, but utilizes a catalyst system that comprises the recited components and other non-recited components. When compositions and processes are described in terms of "comprising" various components or steps, the compositions and processes may also "consist essentially of" or "consist of" the various components or process steps.

Unless otherwise defined with respect to a particular attribute, characteristic, or variable, the term "substantially" as applied to any criteria such as an attribute, characteristic, or variable means that the specified criteria are met to a sufficient degree such that one skilled in the art will understand the benefits 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 alumoxane, borate activators, protonic acid-treated clays, or pillared clays. In other words, the terms "substantially" and "essentially" are used reasonably to describe the subject matter so that its scope will be understood by those skilled in the relevant art and to distinguish the claimed subject matter from any prior art. In one aspect, "substantially free" can be used to describe a composition wherein none of the listed components that the composition is substantially free of are added to the composition and only impurity amounts, such as amounts derived from purity limits of other components or amounts produced as byproducts, are present. In another aspect, when a composition is referred to as being "substantially free of" a particular component, the composition can have less than 20 wt.% of the component, less than 15 wt.% of the component, less than 10 wt.% of the component, less than 5 wt.% of the component, less than 3 wt.% of the component, less than 2 wt.% of the component, less than 1 wt.% of the component, less than 0.5 wt.% of the component, or less than 0.1 wt.% of the component.

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

Reference to the periodic table or groups of elements in the periodic table refers to the version of the periodic table of elements published by the International Union of Pure and Applied Chemistry (IUPAC) on http:// old.iupac.org/reports/periodic _ table/online on 19 months 2010. As reflected in the periodic table of elements, reference to one or more "groups" of the periodic table is used to number the group of elements as groups 1-18 using the IUPAC system. If any group is identified by a Roman numeral according to the periodic Table of the elements as published, for example, in Hawley's Condensed Chemical Dictionary (2001) (CAS System), it will further identify the element or elements of the group to avoid confusion and provide a cross-reference to the numerical IUPAC identifier.

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

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

gu, b.; doner, H.E., Clay and Clay minerals, 1991,38(5), 493-500;

covarrubias et al, "apply catalysis a edition: general introduction (Applied Catalysis A: General), 347(2), 2008, 9, 15, 223-;

tayano et al, Clay Science 2016,20, 49-58;

tayano et al, Macromolecular Reaction Engineering (Macromolecular Reaction Engineering), 2017, (11), 201600017;

molecular catalysis journal 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, 2007,77(12), 2265-2271;

bibi, Singh and silver, Applied Geochemistry 2014,51, 170-;

sharma et al, Journal of Material Science (Journal of Material Science), 2018,53, 10095-;

okada et al, Clay science 2003,12, 159-;

sucha et al, Clay Minerals (Clay Minerals), 1996,31, 333-;

vlasova et al, Science of Sintering, 2003,35, 155-;

kline and Fogler, Industrial & Engineering Chemistry Fundamentals, 1981,20(2), 155-;

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

kooli, "Microporous and Mesoporous Materials (microporus and mesoporus Materials"); 2013,167, 228-;

pergher and Bertella, "Materials", 2017,10, 712; and

tsvetkov et al, Clay and Clay minerals, 1990,38(4), 380-;

each reference is incorporated by reference herein in its entirety.

B. Overview

The support-activator of the present disclosure may be formed by: starting with a slurry of an expanded clay in a liquid carrier such as a montmorillonite or dioctahedral smectite clay, and contacting the clay in the slurry with a heterocoagulation agent comprising at least one cationic multimetal salt produced under the conditions specified herein. The heteroagglomerated clay is 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 clay heteroadducts in good yield can be achieved by controlling the proportion or amount of heterocoagulating 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 smectite clay, such as a colloidal smectite clay, and [2] a heterocoagulating agent in a liquid carrier, the heterocoagulating agent comprising at least one cationic multimetal salt, and the amount of the heterocoagulating agent being sufficient to provide a slurry of the resulting clay heteroadduct having a zeta potential in the range of about positive 25mV (millivolts) to about negative 25 mV.

When montmorillonite clay is contacted with the heterocoagulation agent in a liquid vehicle using a mole number per gram of cationic multimetal salt of clay greater than the mole number directly specified above, such that the resulting slurry has a zeta potential of greater than about +25mV, which is likely to occur with cationic multimetal salts such as Aluminum Chlorohydrate (ACH) and colloidal montmorillonite clay when using formulations of 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 (millimole of aluminum per gram of clay). Although it was observed by powder X-ray diffraction (XRD) that the slurry of the desired montmorillonite heteroadduct may include some of the corresponding pillared clay, and that some of the pillared clay formation is secondary to or incidental to the support-activator formation, a support-activator with too high a concentration of pillared clay results in a loss of ready filterability of the slurry as compared to the clay heteroadduct, such that the ease of support-activator separation is compromised. When the smectite clay is contacted with the heterocoagulation agent in the liquid carrier using a smaller mole of cationic multimetal salt per gram of clay such that the resulting slurry has a zeta potential of less than about-25 mV, which can 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 (mmol aluminum/g clay) when using the cationic multimetal salt Aluminum Chlorohydrate (ACH) and the colloidal smectite clay, a small amount of clay heteroadduct is formed and a large amount of the colloidal clay is retained.

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

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

a) providing a colloidal montmorillonite clay;

b) contacting the colloidal smectite clay with a heterocoagulation agent in a liquid carrier, the heterocoagulation agent comprising at least one cationic multimetal salt and the amount of heterocoagulation agent being sufficient to provide a slurry of a smectite heteroadduct having a zeta potential in the range of about positive 25mV (millivolts) to about negative 25 mV.

The method may further comprise the step of c) separating the smectite heteroadduct from the slurry.

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

b) optionally, at least one co-catalyst; and

In another aspect, there is provided a process for preparing an olefin polymerization catalyst, the process comprising contacting, in any order:

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

b) optionally, at least one co-catalyst; and

c) at least one support-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 and a catalyst composition under polymerization conditions to form a polyolefin, wherein the catalyst composition comprises:

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

b) optionally, at least one co-catalyst; and

c) at least one support-activator comprising a calcined montmorillonite heteroadduct as described herein.

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

C. Colloidal montmorillonite clay

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

An expanded clay (such as a montmorillonite or a 2:1 dioctahedral smectite clay) or a combination of expanded clays can be used to prepare the carrier-activator described herein. These expanded clays can be described as phyllosilicates or phyllosilicate clays, since certain members of the clay mineral family of phyllosilicates can be used. Suitable starting clays may include layered, naturally occurring or synthetic smectites. The starting clay may also comprise a dioctahedral smectite clay. In addition, suitable starting clays can 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 can include, for example, monocationic exchanged dioctahedral smectites, such as lithium-exchanged clays, sodium-exchanged clays, or potassium-exchanged clays, or combinations thereof.

Water may also be coordinated to the layered clay structural units, either bound to the clay structure itself, or coordinated to the cations as a hydration layer. When dehydrated, the repeat distance or d001 substrate spacing of the 2:1 layered clay is about in powder X-ray diffraction (XRD)

(Angstrom) to about

(angstrom); or alternatively, in powder X-ray diffraction (XRD) at about

From (angstroms) to about

(angstrom) range.

Layered smectite clays are referred to 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 silicone sheet. Therefore, these structures are also referred to as "TOT" (tetrahedron-octahedron-tetrahedron) structures. These sandwich structures are stacked one on top of the other to produce clay particles. This arrangement may provide about five angstroms per nine points compared to pillared or intercalated clays produced by inserting "pillars" of inorganic oxide material between the layers to provide more space between the layers of the natural clay

The repeating structure of (2).

In one aspect, the clay used to prepare the support-activator can be a colloidal montmorillonite clay. Thus, the smectite clay can have an average particle size of less than about 10 μm (micron), 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 75 nm. That is, any range of clay particle sizes between these referenced numbers is disclosed. Although clays that do not produce a colloidal suspension can 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 support-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 smectite clay can further comprise structural units characterized by the formula:

(M ^A IV) ₈ (M ^B VI) _p O ₂₀ (OH) ₄ (ii) a Wherein

a)M ^A IV is four-coordinate Si ⁴⁺ In which is not Si ⁴⁺ Optionally partially substituting Si with a tetra-coordinated cation of ⁴⁺ (e.g., non-Si) ⁴⁺ The cations of (A) may be independently selected from Al ³⁺ 、Fe ³⁺ 、P ⁵⁺ 、B ³⁺ 、Ge ⁴⁺ 、Be ²⁺ 、Sn ⁴⁺ Etc.);

b)M ^B VI is hexa-coordinated Al ³⁺ Or Mg ²⁺ In which is not Al ³⁺ Or Mg ²⁺ Optionally partially replacing Al with a hexacoordinated cation of (2) ³⁺ Or Mg ²⁺ (e.g., non-Al) ³⁺ Or Mg ²⁺ The cations of (A) may be independently selected from Fe ³⁺ 、Fe ²⁺ 、Ni ²⁺ 、Co ²⁺ 、Li ⁺ 、Zn ²⁺ 、Mn ²⁺ 、Ca ²⁺ 、Be ²⁺ Etc.);

c) p is four for cations charged with the +3 form, or 6 for cations charged with the +2 form; and is

d) From at M ^A non-Si at IV ⁴⁺ Any charge deficiency resulting from partial substitution of the cation at M and/or ^B non-Al at VI ³⁺ Or Mg ²⁺ Any charge deficit resulting from partial substitution of the cations of (a) is balanced by cations inserted between the building blocks (e.g., the cations inserted between the building blocks may be selected from monocationals, biscationals, tricationials, other polycations, or any combination thereof.

Examples, data, and aspects of the present disclosure section provide additional detail on the montmorillonite clay aspects and embodiments.

D. Cationic multimetal salts for heterocoagulation reagents

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

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

The heterocoagulation reagents of the present disclosure can be positively charged species that, when combined with a colloidal suspension of clay in the appropriate ratio, form a coagulum that is easily filtered and easily washed. Positively charged species include soluble polyoxometallate, polyhydroxymetallate and polyhydroxymetallate cations, as well as related cations that are partially halide substituted, such as polyaluminum chlorohydrate or aluminum chlorohydrate or polyaluminum chloride species of linear, cyclic or cluster compounds. These compounds are collectively referred to as multimetal salts. The latter aluminum compounds may contain from about 2 to about 30 aluminum atoms.

Useful heterocoagulation agents also include any colloidal substance characterized by a positive zeta potential when dispersed in an aqueous solvent or a mixed aqueous and organic (e.g., alcohol) solvent. For example, useful dispersions of heterocoagulation agents can exhibit a zeta potential of greater than (> +20mV (plus 20mV), greater than +25mV, or greater than +30 mV. While 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 a heterocoagulating agent in forming an easily 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 support-activator, such as in examples 40 and 41.

Furthermore, unlike the treatment of leaching Al ions from montmorillonite using concentrated strong acid, the formation of clay heteroadducts does not leach Al ions from clay. When using an aluminum-containing heterocoagulation reagent such as ACH or PAC, the support-activator, although having an aluminum content much lower than that of the corresponding pillared clay, is actually higher than that of the starting clay.

In one aspect, the heterocoagulation reagent can 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 can comprise a chemically modified or 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 can be produced by treating a metal oxide or metal oxide hydroxide or the like with a reagent in a fluidized bed, which will provide a positive zeta potential when the reagent is dispersed in a suspension. The heterocoagulants may exhibit positive values of greater than +20mV prior to combination with the phyllosilicate clay component.

In one aspect, the cationic multimetal salt can include a first metal oxide 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 with a positive zeta potential, for example a zeta potential of greater than positive 20mV (millivolts). That is, the chemically treated first metal oxide is the first metal oxide with [1 ]]A second metal oxide, i.e. another different metal oxide, [2]Metal halide, [3 ]]Metal oxyhalides or [4]A contact product of a combination thereof. For example, the chemically-treated first metal oxide can 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 selected from metal oxides, hydroxides, oxyhalides or halides (such as ZrOCl ₂ 、ZnO、NbOCl ₃ 、B(OH) ₃ 、AlCl ₃ Or a combination thereof) in an aqueous solution or suspension. For example, the treatment may consist of dispersing the vapor phase oxide in an aluminum chlorohydrate solution. In the case where the fumed silica may exhibit a negative zeta potential in suspension, the suspension of chemically treated fumed silica, after treatment with aluminum chlorohydrate, exhibits a positive zeta potential of greater than about +20 mV.

In another aspect, the cationic multimetal salt composition can comprise or be selected from [1] fumed silica, fumed alumina, fumed silica-alumina, fumed magnesium oxide, fumed zinc oxide, fumed titania, fumed zirconia, fumed ceria, or any combination thereof, said cationic multimetal salt composition being chemically treated with [2] polyaluminum chloride, aluminum chlorohydrate, or any combination thereof. For example, the cationic multimetal salt composition can 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 fumed metal oxides, such as fumed alumina, may already exhibit a positive zeta potential prior to chemical treatment. However, fumed metal oxides having no or a positive zeta potential of less than about +20mV may also be chemically treated with a material such as aluminum chlorohydrate, after which a colloidal suspension having a zeta potential of greater than about +20mV may be obtained.

In another aspect, the heterocoagulation agent can include a mixture of metal oxides formed during or after the fuming process, the mixture exhibiting a positive zeta potential as a result of the metal oxide composition. An example of this type of fumed oxide is fumed silica-alumina.

In another embodiment, the heterocoagulation reagent may comprise any colloidal inorganic oxide particle, such as particles described in U.S. patent No. 4,637,992 to Lewis et al (such as colloidal ceria or colloidal zirconia or any positively charged colloidal metal oxide disclosed therein), which is incorporated herein by reference. In another aspect, the heterocoagulation reagent can comprise magnetite or ferrihydrite. 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 can include a cationic oligomeric or polymeric aluminum species in solution, such as aluminum chlorohydrate, also known as Aluminum Chlorohydrate (ACH), polyaluminum chloride (PAC), aluminum sesquichlorohydrate, or any combination or mixture thereof. For example, the cationic multimetal salt heterocoagulation reagent can include or be selected from the group consisting of aluminum species or any combination of species having the empirical formula:

Al ₂ (OH) _n Cl _m (H ₂ O) _x ，

Where n + m is 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 a group having the formula [ AlO ₄ (Al ₁₂ (OH) ₂₄ (H ₂ O) ₂₀ ] ⁷⁺ Is so-called "Al ₁₃ Mer polycation and considered as Al ₁₃ A precursor of a pillared clay.

When aluminum chlorohydrate is used as a heterocoagulation reagent or chemical treatment reagent for treating other metal oxides, a solution or solid powder of Aluminum Chlorohydrate (ACH) from a commercial source may be used. The aluminum chlorohydrate solution may be referred to as a polymeric cationic aluminum hydroxy complex or aluminum chlorohydrate, which is referred to as a polymeric cationic aluminum hydroxy complex having the general empirical formula 0.5[ Al [ ] ₂ (OH) ₅ Cl(H ₂ O) ₂ ]A polymer formed from the monomer precursor of (1). 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 alumina (Al) may be used ₂ O ₃ ) Aluminum nitrate, chloride or other aluminum salts and treated with an acid or base to obtain an aluminum chlorohydrate solution. Many substances that may be present in such solutions (including deca-trimeric [ AlO ]) ₄ (Al ₁₂ (OH) ₂₄ (H ₂ O) ₂₀ ] ⁷⁺ (Al ₁₃ Mer) polycations) are described in Perry and Shafran, Journal of Inorganic Biochemistry (Journal of Inorganic Biochemistry) 2001,87,115-124, which is incorporated herein by reference. The materials disclosed in this study that were present in such solutions, either alone or in combination, can be used as cationic multimetal salts of montmorillonite clay heterocoacervation.

In one aspect, the aqueous aluminum chlorohydrate solution used in accordance with the present disclosure may have a composition of Al ₂ O ₃ May range from about 15 wt.% to about 55 wt.%, although more dilute concentrations may be usedAnd (4) degree. As understood by one of ordinary skill in the art, other reaction conditions, such as time and temperature, may be adjusted simultaneously using more dilute solutions. With Al ₂ O ₃ Alternative aluminum concentrations in aqueous solutions of multimetal aluminum salts such as aluminum chlorohydrate, expressed in weight percent, may include: about 0.1 wt.% to about 55 wt.% Al ₂ O ₃ (ii) a About 0.5 wt.% to about 50 wt.% Al ₂ O ₃ (ii) a About 1 wt.% to about 45 wt.% Al ₂ O ₃ (ii) a About 2 wt.% to about 40 wt.% Al ₂ O ₃ (ii) a About 3 wt.% to about 37 wt.% Al ₂ O ₃ (ii) a About 4 wt.% to about 35 wt.% Al ₂ O ₃ (ii) a About 5 wt.% to about 30 wt.% Al ₂ O ₃ (ii) a Or about 8 wt.% to about 25 wt.% Al ₂ O ₃ (ii) a Each range includes every single concentration expressed as a tenth (0.1) of the weight percent and includes any subrange subsumed therein. For example, about 0.1 wt.% to about 30 wt.% Al ₂ O ₃ The reference includes 10.1 wt.% to about 26.5 wt.% Al ₂ O ₃ Reference to (3). When convenient, a solid multimetal salt, such as solid aluminum chlorohydrate, may be used and added to the slurry of colloidal clay when preparing the heterocoagulate. Accordingly, the concentrations disclosed above are not limiting, but rather 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 combinations 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 combinations thereof. In one aspect, the heterocoagulation reagent can comprise a lanthanide and Al ₁₃ Aqueous solutions of Keggin ions, such as described by McCauley in U.S. patent No. 5,059,568. However, the calcined clay heteroadducts of the present disclosure prepared using McCauley-type multimetallic salts do not provide substrate spacings greater than

Uniformity of (angstrom)And (4) 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 agent to colloidal clay used in accordance with the present disclosure. This minor amount results from the contacting conditions of the smectite clay and the heterocoagulation agent in an amount sufficient to provide a slurry of the smectite heteroadduct having a zeta potential in the range of about +25mV (millivolts) to about-25 mV.

In further aspects, exemplary multimetallic salts of the present disclosure may comprise: [1]epsilon-Keggin cation [ epsilon-PMo ] ₁₂ O ₃₆ (OH) ₄ {Ln(H ₂ O) ₄ } ₄ ] ⁵⁺ Wherein Ln can be La, Ce, Nd or Sm; and [2 ]]Has the general formula [ Ln ₂ V ₁₂ O ₃₂ (H ₂ O) ₈ {Cl}]A lanthanide-containing cationic heterovanadyl cluster of Cl, wherein Ln can be Eu, Gd, Dy, Tb, Ho or Er.

In another aspect, the heteroagglomerant may be a layered double hydroxide, such as in Colloid and polymer science (Colloid Polymer. Sci.) 1998,276,730-731, Abend et al, or synthetic hematite, hydrotalcite, or other positively charged layered double hydroxide, including but not limited to those described in U.S. Pat. No. 9,616,412, which is 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 the 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 aluminium magnesium hydroxide nitrate, aluminium magnesium hydroxide sulphate, aluminium magnesium hydroxide chloride, Mg _x (Mg,Fe) ₃ (Si,Al) ₄ O ₁₀ (OH) ₂ (H ₂ O) ₄ (x is a number from 0 to 1, e.g., about 0.33 for steatite), (Al, Mg) ₂ Si ₄ O ₁₀ (OH) ₂ (H ₂ O) ₈ Synthesizing hematite, hydrozincite (basic zinc carbonate) Zn ₅ (OH) ₆ (CO ₃ ) ₂ Hydrotalcite [ Mg) ₆ Al ₂ (OH) ₁₆ ]CO ₃ ·4H ₂ O, diaspore [ Ni ] ₆ Al ₂ (OH) ₆ ]CO ₃ ·4H ₂ O, hydrocalumite [ Ca ] ₂ Al(OH) ₆ ]OH·6H ₂ O, Mg plus Al [ Mg) ₁₀ Al ₅ (OH) ₃₁ ](SO ₄ ) ₂ ·mH ₂ O, lepidocrocite [ Mg ₆ Fe ₂ (OH) ₁₆ ]CO ₃ ·4.5H ₂ O, ettringite [ Ca ₆ Al ₂ (OH) ₁₂ ](SO ₄ ) ₃ ·26H ₂ O or any combination thereof.

In yet another aspect, the heterocoagulation reagent may comprise an aqueous solution of Fe polycations, such as in Oads, Clay and Clay minerals, 1984,32(1),49-57, or Cornell and Schwertmann, iron oxides: structures, attributes, responses, events and Uses (The Iron Oxides: structures, Properties, Reactions, Occurents and Uses), 2003, second edition, Wiley VCH. The cationic multimetal salt may contain or may be selected from those having an empirical formula of FeO _x (OH) _y (H ₂ O) _z ] ⁿ⁺ Wherein 2x + y is less than<)3, z is a number from 0 to about 4, and n is a number from 1 to 3.

The use of cations such as protons, lithium ions, sodium ions, or potassium ions, such as those described in examples 40 and 41, do not provide the clay heteroadducts provided by the cationic multimetallic 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 from HCl or H in aqueous solution ₂ SO ₄ Such as described in U.S. patent No. 6,531,552 to Nakano et al and references thereto, which are incorporated herein by reference, do not form stable, readily filterable heterocoacervate clay adducts using dilute or concentrated acids. 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 low pH (b:, although not intending to be bound by theory <3) The potential of the colloidal dispersion of montmorillonite becomes less negative and may even approach a zeta potential of about negative 30mV (-30 mV). (Ginseng radixSee Duran et al, Journal of Colloid and Interface Science, 2000,229, pp.107-117, which is incorporated herein by reference. ) However, before the colloidal clay is able to approach or reach a neutralized or near-neutralized surface charge, it is believed that the clay structure itself is destroyed by the peptization of the octahedral aluminum oxide layer. (see Tayano et al; "macromolecular reaction engineering", 2017,11,201600017 and Clay science ", 2016,20,49-58, all incorporated herein by reference.) for example, leaching of octahedral alumina layers from TOT structures and dissolution of clays into strongly acidic solutions is described in: U.S. patent No. 3,962,135; bibi, Singh and Silvester, "dissolution kinetics of kaolinite, illite and montmorillonite under acid-sulfate conditions: a comparative study (dispersions of kaolin, illite and montmorillonite under acid-sulfate conditions): a comparative study, Chapter 4 (manuscripts available from htps:// ses. library. used. au. bitstream/handle/2123/8647/channel. Chapter.204. Dissolution.20 of 20% 20of 20kaolin,% 20 monomeric. pdfsuess. 5) and also from htps:// pdpdps. molecular. org. 6836/3 c.9c.293 d 2004 d 4255558867817c 633833. pdf, and Dudkin et al, Sustainable chemical Development (Chemistry Development) Chemistry variant 327, 330; and Okada et al, Clay science, 2003,12,159-165, all of 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 point where the colloidal montmorillonite particles may flocculate is thought to be due to shielding and reducing the niobium repulsion between the montmorillonite particles. The concentration of monocationic ions at which coagulation occurs is referred to as the critical coagulation concentration, and the concentration of monovalent cations required to achieve coagulation is generally significantly greater than that required when divalent or trivalent cations are used. Also, while not wishing to be bound by theory, the monovalent cation-clay product remains 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 does not produce a metallocene support-activator catalyst of sufficient practical activity. Furthermore, for simple ionic 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 by-products, or result from incomplete reaction of colloidal clay with the multimetallic salt.

In another aspect, the colloidal montmorillonite clay may comprise or be selected from colloidal montmorillonite, such as

HPM-20 Bentonite. The heterocoagulation reagent may comprise or be selected from aluminium chlorohydrate, polyaluminium chloride, or aluminium chlorohydrate.

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-x M(III) _x (OH) ₂ ]A _x/n ·m L (I)

[LiAl ₂ (OH) ₆ ]A _1/n ·m L (II)

wherein:

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

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

a is at least one inorganic anion;

l is an organic solvent or water;

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

x is a number from 0.1 to 1; and is

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, further, 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 a carbonate.

In one aspect, the cationic multimetal salt can comprise polyaluminum chloride, aluminum chlorohydrate, or a combination thereof. In yet another aspect, the cationic multimetal salt can comprise a linear, cyclic, or cluster aluminum compound containing, for example, 2 to 30 aluminum atoms. In the formulation used to prepare the smectite heteroadduct, the ratio of millimoles (mmol) of aluminum (Al) in the polyaluminum chloride, aluminum chlorohydrate, or aluminum chlorohydrate to grams (g) of colloidal montmorillonite clay 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 smectite heteroadduct, the millimoles (mmol) of aluminum (Al) per gram (g) of colloidal smectite clay in the polyaluminum chloride, aluminum chlorohydrate or aluminum chlorohydroxide can 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 the formulation used to prepare the isolated or calcined montmorillonite heteroadduct, the ratio of millimoles (mmol) of aluminum (Al) in the polyaluminum chloride, aluminum chlorohydrate, aluminum sesquichlorohydrate, or aluminum chlorohydroxy-oxychloride to grams (g) of the colloidal clay can be about 90% or less, about 80% or less, about 70% or less, about 60% or less, about 50% or less, about 45% or less, about 40% or less, or about 35% or less of the comparative ratio of millimoles (mmol) of aluminum to grams of colloidal clay used in preparing the pillared clay using the same colloidal gelatin clay and heterocoagulating agent.

In this regard, in the pillared formulation, the ratio of aluminum reagent to clay is expressed as mmol Al/g clay, which represents the number of millimoles of Al in the aluminum chlorohydrate reagent relative to the grams of clay in the formulation. Specifically, this ratio reflects the ratio employed in the synthesis formulation, not the ratio in the final pillared clay product. As an example, consider Al described in Ocelli, Clay and Clay minerals, 2000,48(2),304- ₁₃ Type Keggin ions, the amount of Al used in the preparation of pillared clays far exceeds the amount of Al that eventually intercalates between the solid layers of the final pillared clay. The use of excess aluminum reagent is employed in order to provide maximum column content in the final product and to obtain the desired porosity and surface area of the final calcined material. Kooli in microporous and mesoporous materials; 2013,167,228-236 discloses that typically about 6mmol Al/g clay is required in the formulation to optimize pillaring. In recent years to Al ₁₃ In scale-up studies and optimization of Keggin ion pillared clays, Pergher and Bertella in Materials, 2017,10,712 disclose that to obtain pillaring with the desired substrate spacing and surface area, a dilute dispersion of 15mmol Al/g clay and about 1 wt.% clay is required.

E. Preparation and Properties of Clay heteroadducts (heterocoacervated Clays)

Unlike pillared clays, the heteroagglomerated clays of the present disclosure are amorphous solids. Thus, the preparation of heteroagglomerated 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 is not merely swollen upon contact with the cationic multimetal salt, but is collapsed upon preparation of the clay heteroadduct to provide a non-crystalline, non-regular, non-lamellar amorphous material. Factors that can influence the formation of an amorphous three-dimensional structure include reaction time, reaction temperature, purity and clay particle size of the starting clay, drying method, etc., and these factors as described herein are readily determinable for each heterocoagulation reagent and clay system.

In preparing the clay heteroadduct, the heterocoagulant may be added to a slurry of the colloidal clay, the colloidal clay may be added to a slurry or solution of the heterocoagulant, or the heterocoagulant and the colloidal clay may be added to the liquid vehicle simultaneously or over an overlapping period of time. Alternatively, the heterocoagulant and colloidal clay may be added simultaneously to the residue of the heteroadducted product, such as by adding the heterocoagulant and clay as a solid or suspension to a vessel or reactor containing water or an aqueous residue.

In one aspect, the liquid carrier for preparing the clay heteroadduct may be water or aqueous based, to which additional components may be added, such as ethanol and/or at least one surfactant. Suitable surfactants may include anionic, cationic, or nonionic surfactants. Specific examples of liquid carriers or "diluents" and specific examples of surfactants are provided in aspects of this disclosure.

As noted above, the ratio of heterocoagulation reagent to clay used in the formulation is defined as the ratio that provides a coagulated product mixture such as a slurry having a zeta potential in the range of about plus (+)25mV (millivolts) to about minus (-)25 mV. Thus, the amount of heterocoagulation reagent added to a known clay sample, i.e., the ratio of cationic multimetal salt (heterocoagulation reagent) to clay, is determined by titrating the clay with the heterocoagulation reagent. 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 ratio of the heterocoagulation reagent to clay. The actual amount of cationic multimetal salt used to form the clay heteroadduct, i.e., the ratio of heterocoagulating agent to clay, can 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 formed heterocoagulation clay 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 formed heterocoagulation clay exhibits a zeta potential of about +22mV to about-22 mV, about +20mV to about-20 mV, about +18mV to about-18 mV, about +15mV to about-15 mV, about +10mV to about-10 mV, about +5mV to about-5 mV, or about 0 mV.

As described in the examples, colloidal dynamic Zetaprobe Analyzer ^TM For measuring zeta potential, including dynamically tracking changes in zeta potential during titration of colloidal clay dispersions with cationic multimetal salt titrant. Exemplary results of zeta potential titration are shown in the figures and described in the examples, e.g., data are presented in tables 4-6. For example, FIG. 3 depicts the use of Aluminum Chlorohydrate (ACH) pairs

The zeta potentials of a series of dispersions formed during titration with HPM-20 montmorillonite are plotted against the cumulative titrant volume (x) of aqueous ACH added versus the zeta potential of the dispersion (mV, (y)). Similarly, FIG. 4 plots cumulative mmol Al/g clay for the same titration against zeta potential (mV) of the dispersion. A sample of some of the solid product formed during the zeta potential titration of HPM-20 clay with ACH was collected and figure 2 provides the powder XRD patterns of this series of calcined products collected during the zeta potential titration of HPM-20 clay with ACH. Thus, a comparison and correlation of filterability of mmol Al/g clay having a zeta potential and the resulting product was examined, and from this analysis, it was unexpectedly found that when clay and a heterocoagulation reagent comprising at least one cationic multimetal salt are contacted with each other in a liquid carrier in an amount or ratio that provides a slurry of a smectite heteroadduct having a zeta potential in the range of about positive 25mV (millivolts) to about negative 25mV, the resulting product is readily filterable, can be used as a support-activator with no or minimal washing, and confers high polymerization activity to the supported metallocene catalyst.

In a synthesis reaction or titration using a cationic multimetallic salt, calculating the ratio of the number of millimoles of metal atoms in the multimetallic salt per piece of clay provides a useful metric for comparing multimetallic saltsAnd (4) standard. For example, in zeta potential titration using aluminum cationic multimetal salts as heterocoagulation reagents, the ratio of millimoles of aluminum per clay allows for more direct comparison of different Al-containing heterocoagulation reagents, as shown in the titration curve of fig. 4. Derivation of this value is done by obtaining the aluminum weight percent of the heterocoagulant, which is typically provided directly by the manufacturer, or as alumina (e.g., Al) ₂ O ₃ ) The equivalent weight percent is provided. In the latter case, the weight percent of aluminum may be derived from the product of the weight percent of alumina and the weight proportion of aluminum in the empirical formula. From this aluminum weight percentage, the molar amount of aluminum heterocoagulation reagent can be determined and the aluminum/clay molar mass ratio can be obtained.

For example, FIG. 4 shows Aluminum Chlorohydrate (ACH) in mmol Al/g clay with a desired zeta potential range

One ratio of HPM-20 was 1.76mmol Al/g clay. The actual ratio may vary slightly depending on the batch, method of preparation, degree of contamination or aging of the aluminum chlorohydrate, and/or the particular batch

HPM-20. FIG. 2 shows colloid company of America

Zeta potential titration of HPM-20 (with 22 wt.% aluminum chlorohydrate from GEO Specialty Chemicals). Thus, mmol Al/g clay can be determined as the point at which the zeta potential of the colloidal species in the mixture drops below +25mV and above-25 mV, for example between about +10mV and-10 mV, thereby providing a heterocoagulated 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 heteroadduct may be carried out with or without vacuum assistance, belt filters, and the like.

The resulting dispersion of the heterocoacervate 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 without wishing to be bound by theory, excellent yields and filterability of clay heteroadducts can be obtained when the amount of heterocoagulation agent associated with a colloidal montmorillonite (such as the dioctahedral smectites herein) provides a dispersion of particles having a zeta potential close to zero, such that the particles in the dispersion have little or no electrophoretic mobility. This zero zeta potential point can be considered as the nominal target ratio of cationic multimetal salt to colloidal clay. For example, aspects of electrophoretic mobility are described in Gu et al clay and clay minerals 1990,38(5), 493-500.

The ratio of the experimentally derived heterocoagulation agent (cationic multimetal 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 in portions to the dispersion, and the zeta potential of the dispersion was measured after each addition. The ratio of cationic multimetal salt to colloidal clay used to prepare the filterable clay heteroadduct is calculated by determining from the resulting zeta potential titration curve the ratio of heterocoacervating agent 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), an extrapolation of the point closest to zero zeta potential can be used to estimate the intersection of the zeta potential curve from negative to positive zeta potential, thereby 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 limit of zeta potential (e.g., ± 20mV or ± 25mV), linear extrapolation between points on the titration curve just before and after the discontinuity can be used to estimate the heterocoacervate 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 heterocoacervation agent to clay are provided in the figures and examples section of the present disclosure. See, for example, fig. 2-8, example 8-12, and example 38.

Aluminum mmol (mmol Al) of aluminum chlorohydrate for preparing Clay heteroadducts with

The 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, using the same cationic multimetal salt and colloidal clay, 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 heteroadduct dispersion, will form a pillared clay. Thus, the ratio of cationic multimetal salt to colloidal clay that forms the clay heteroadducts of the present disclosure differs 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 clays as support-activators.

In contrast, when too low a ratio of heterocoagulating agent to clay 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 0.30mmol Al/g clay formulation of a clay heteroadduct was prepared using Aluminum Chlorohydrate (ACH) and HPM-20 clay, and the predicted zeta potential was-44 mV when deduced from the zeta potential titration in FIG. 2. Filtration of the resulting contact product is difficult and separation and preparation of the sample requires centrifugation to separate the product. For convenience, products such as these may be referred to herein as "heteroadducts" that are readily filterable even outside the zeta potential range. Similarly, in example 26, the use of powder was used

A formulation of 0.30mmol Al/g clay of 51P aluminum chlorohydrate (Parchem Fine and Specialty Chemicals) provided a contact product heteroadduct that was difficult to handle and isolate, and required centrifugation to isolate the product.

Due to isomorphous substitution of ions into one of the "TOT" layers, e.g. with Mg ²⁺ Replacement of Al in octahedral aluminum oxide layers ³⁺ And thereby a negative charge is imparted to the alloy,the starting clay particles such as montmorillonite therefore carry a permanent negative charge. Thus, when negatively charged clay particles repel each other and are stable in a polar aqueous environment, the starting clay forms a dispersion or suspension in water. While not wishing to be bound by theory, it is believed that contact of cations, such as the cationic multimetal salts disclosed herein, with the negatively charged colloidal clay initially promotes the agglomeration of the colloidal clay by coulomb attraction of heterogeneous charge types and neutralization of the clay surface. This neutralization results in the clay heteroadduct precipitating out of the polar aqueous carrier as large agglomerated or coagulated particles that are easily filtered. When additional cationic multimetal salts are added in excess to the coacervate composition, such as when preparing ion-exchanged, protonic acid-treated, or pillared clays, some or all of the coalesced surfaces can be "recharged" as positively charged species, thereby being resuspended in a polar carrier, such as water. This re-suspension provides a dispersion of highly charged species that are difficult or impossible to filter out and can clog the filter media. The clay heteroadducts of the present disclosure are formed at less than these high ratios, and thus it is believed that reloading and resuspension of the clay heteroadducts is avoided. Thus, the near zero zeta potential surface of the clay heteroadduct provides a product that is easy to filter and at the same time substantially avoids pillaring of the clay and further avoids homogeneous intercalated clay structures of the pillared clay and the starting clay. Surprisingly, even without pillaring, these structures form thermally stable, robust structures that can be used as very active support-activators for metallocenes.

In one aspect, FIG. 1 provides an illustration of the actual and desired aspects of producing a neutral or weakly charged dispersion having a low magnitude, near zero or zero zeta potential. Filtration of clay heteroadducts having these attributes proceeds quickly and typically requires little continuous filtration to produce a support having 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 easily filterable and must be processed using relatively more expensive and cumbersome methods to obtain useful support-activators.

Also in contrast to other materials such as those described by Jensen et al in U.S. patent application publication nos. 2018/0142047 and 2018/0142048, assigned to w.r.grace, the clay heteroadducts of the present disclosure, after filtration and calcination at 300 ℃ or higher, may exhibit no or substantially no d001 peak in the powder XRD scan at 2 theta (2 theta) of less than 10 degrees. This characteristic is illustrated by the example in figure 2, which shows the powder XRD (x-ray diffraction) pattern of a series of calcined products from the reaction of Aluminum Chlorohydrate (ACH) and Aluminum Chlorohydrate (ACH)

HPM-20 montmorillonite combination, each sample differing by the amount of cationic multimetal salt used to prepare the heteroagglomerated 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 Al ₁₃ Typical preparation of pillared clays (see example 5). The XRD signature of the starting clay itself (bottom) was from 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 major peaks that change as the proportion of cationic multimetal salt in the preparation formulation increases. First, the XRD peak at about 9 degrees 2 theta (2 theta) corresponding to the starting clay disappears, and as the ratio of the cationic multimetal salt increases, one peak gradually increases from about 9 degrees (2 theta) to about 10 degrees (2 theta). The disappearance of the 9 degree (2 theta) peak appears to indicate a reaction process that forms a largely amorphous, heteroagglomerated clay, and the subsequent 9-10 degree (2 theta) peak may represent simple ionic intercalation, such as Al ³⁺ Ion intercalation characterized by smaller basal spacing than the initial ion-exchanged clay. As more multimetallic salt was added to the slurry, a peak increased from about 4 degrees (2 θ) to about 6 degrees (2 θ), and this peak represented the major product of 6.4mmol Al/g clay. This 4-6 degree (2 theta) ) The peaks may correspond to Keggin ion intercalation pillared structures that form as the concentration of added multimetallic salt increases. At concentrations of clay not highly diluted (i.e., not less than 1 wt.% clay) for these experiments, the 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 the Volclay HPM-20 montmorillonite is colloidal clay, the zeta potential data and XRD data indicate that a zeta potential range of 25mV corresponds to a range of about 1mmol Al/g clay to 1.8mmol Al/g clay. Similarly, the zeta potential range of. + -. 15mV for the clay heteroadduct with less charge corresponds to the range from about 1.3mmol Al/g clay to 1.7mmol Al/g clay. These data also show that a zeta potential of 0 (zero) mV, where the clay heteroadduct is close to zero charge, corresponds to about 1.5mmol Al/g clay. Figure 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 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 20-30 degrees 2 theta.

While not wishing to be bound by theory, when aluminum chlorohydrate and colloidal montmorillonite are used, the near-zero charge of the heteroadduct provided by the 1.5mmol Al/g clay formulation corresponds to the possible actual incorporation of Al ₁₃ Less than half the amount (ratio) of aluminium in the pillared montmorillonite, also corresponding to a smaller fraction of aluminium used in the pillared formulation. See, for example, Schoonheydt et Al, Clay and Clay minerals 1994,42(5),518-525, which describes this amount as about 3-4mmol Al/g clay actually incorporated. As mentioned above, the amount of heterocoagulation reagent that provides a zeta potential of 0 (zero) mV heteroadduct (which can be considered to be a preferred amount of about 1.5mmol Al/g clay) is an order of magnitude less than the amount used for an optimized pillaring 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, whereas the clay heteroadducts are metallocenesThe metal support-activator provides activity comparable to and generally higher than that of pillared clays.

The clay heteroadducts 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 regularly complex ionically intercalated ("irregular intercalation"), the microporous catalytic component comprising a layered colloidal clay having a plurality of pillars intercalated between expanded 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 pillaring and/or consistent intercalation of aluminum oxides or hydroxides, such as derived from Al in U.S. patent application publication nos. 2018/0142047 and 2018/0142048 ₁₃ poly-Al centered on Keggin ions or lanthanides ₁₃ And (3) a column. However, particularly in some instances of multiple washes and filters, powder XRD peaks indicating some pillaring could be detected. For example, the XRD pattern for the 1.76mmol Al/g clay sample corresponds approximately to +23mV zeta potential, but the intensity of the peak is significantly less than that of the pillared formulation, e.g., using 6.4mmol Al/g and higher clay.

Thus, in another aspect, the calcined clay heteroadducts of the present disclosure lack ordered domains as evidenced by the lack of XRD peaks between 0-12 degrees 2 theta. This observation highlights one difference from a simple monoatomic ion exchange process or a complex polyatomic ion exchange process by which sodium ions (e.g., in the starting sodium montmorillonite) are exchanged for divalent, trivalent, or multivalent ions, which upon drying provides a reflection of simple monoatomic ion size or polyatomic ions (such as Al) ₁₃ Keggin ions or other pillared species evidenced by the associated d001 group spacing in XRD) sizes.

In one aspect, the isolated clay heteroadduct is collected, for example by filtration, and not washed. In another aspect, the isolated clay heteroadduct is minimally washed, e.g., once or twice with a suitable washing liquid such as water, e.g., just sufficient to provide some purification benefit. While not wishing to be bound by theory, it has been observed that washing promotes pillaring, as described by Schoonheydt et al, Clay and Clay minerals 1994,42(5),518-525, which is incorporated herein by reference. Thus, washing to the extent that pillaring occurs appears to sacrifice the isolated desired clay heteroadduct, forming an undesirable by-product pillared clay.

In another aspect of the 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 disclosure until a washed water is obtained that exhibits negative AgNO ₃ The test (chloride test) is not necessary to impart high polymerization activity to the clay heteroadduct. In contrast, a single filtration of the direct heteroadduct mixture containing about 5 wt.% solids provided 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, example 22 and example 23 differ in the preparation of ACH-clay heteroadduct in whether the product is prepared using one or two filtrations, the latter comprising one wash between each filtration. Thus, in example 22, where a single filtration was used to prepare the clay heteroadduct, the filtrate obtained from the filtration of the slurry was characterized by an electrical conductivity of 1988. mu.S/cm. In contrast, example 23 prepared the clay heteroadduct using two filtrations with washes between the two filtrations, providing a filtrate characterized by a conductivity of 87 μ S/cm, almost 23-fold difference. However, the polymerization activity of catalysts prepared using these support-activators varies by only 10%, which the skilled person would consider to be within the variability of the laboratory scale polymerization experiments.

Similarly, the use of example 24 and example 25 support-activator polymerization batches further indicate the economic benefit of the support-activator, wherein one filtration of the clay heteroadduct and two filtrations again provided essentially the same polymerization activity. Specifically, the catalyst formed from a single filtration of the support-activator exhibited an activity of 3581g/g/h, whereas the activity observed for the catalyst formed from two filtration of the support-activator was 3547 g/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 double filtered product (example 25) was 180. mu.S/cm. Thus, it was unexpectedly found that extensive washing of the clay heteroadduct was 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 catalyst activities of 1404g/g/h and 1513g/g/h, respectively. In this comparison, the single filtration heteroadduct slurry of example 29, having a conductivity of 1750 μ S/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 and the slurry conductivity was 169 μ S/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 heteroadduct slurries of the present disclosure at room temperature or elevated temperature for at least 10 days prior to isolation and use. In contrast, the clay heteroadduct slurries of the present disclosure can be immediately filtered and then dried or calcined, thereby providing more efficient support-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 temperatures ranging from almost 0 ℃ to the boiling point of the slurry of the clay-containing heteroadduct may be used.

The pH of the solution containing the heterocoagulant may be adjusted to provide a minimum zeta potential of the heterocoagulation product, as readily determined by the experiments described by Goldberg et al, Clay and Clay minerals, 1987,35, 220-270. The resulting heteroadducts isolated by this process can also be used in olefin polymerization together with metallocenes. Furthermore, this method of adjusting zeta potential can be used where the ratio of the heterocoagulant to clay does not itself provide a zeta potential within and including the range of ± 25mV (or alternatively, ± 22mV, ± 20mV, etc.) disclosed in this document. However, this pH adjustment method requires additional steps in the synthesis and isolation of the clay heteroadduct and it has been observed that this method does not guarantee ready filterability or optimal final polymerization activity. While not wishing to be bound by theory, it is believed that pH adjustment in this case may result in protonated or hydroxylated clays, heterocoagulating agents, and/or clay heteroadducts, which may affect the properties and ultimate catalytic activity of the clay heteroadducts.

In another aspect, the present disclosure provides for the removal of salts and small amounts of non-condensed colloidal species formed in the preparation of the heterocoagulation product. For example, soluble by-products such as sodium chloride and the like can be easily removed from the heterocoagulation product in addition to a small amount of colloidal substances by washing with water and then simply filtering the heterocoagulation product. Washing may be accomplished by resuspending the separated heterocoacervate 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 pillaring-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 adduct from impurities including its starting components, nano-or micro-sized quartz and other inorganic metal oxides, and the like. In contrast, the filtration of the clay heteroadduct may be carried out batchwise by means of sintered glass frits, metal frits, ordinary filter paper, felts or other filter media, or continuously using a moving belt filter. Filtration is practical because it is rapid, e.g., 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 heteroadduct can be monitored using a commercially available conductivity meter. In one aspect, when the concentration of the slurry ranges from about 1 wt.% to about 10 wt.% solids, from about 2.5 wt.% to about 10 wt.% solids, or from about 5 wt.% to about 10 wt.% solids, the clay heteroadduct slurry can be characterized by a conductivity ranging from about 100 μ S/cm (0.1mS/cm) to about 50,000 μ S/cm (50mS/cm), from about 250 μ S/cm to about 25,000 μ S/cm, or from about 500 μ S/cm to about 15,000 μ S/cm, or from about 1,000 μ S/cm (1mS/cm) to about 10,000 μ S/cm (10 mS/cm).

If desired, the heterocoacervate solid can be dried via azeotropic methods, as is done in some examples. In contrast to simply heating the heterocoacervate solid, it is believed that azeotropic drying maintains pore volume and surface area during drying. For example, the filtered smectite heteroadduct can be resuspended in a slurry with a solvent that will lower the boiling point of water in the heterocoagulated product. This water lost during drying is characterized as free water or chemically bound water. That is, the water lost during drying may come from free water in the pores of the heteroadduct or on the outer surface, as well as chemically bound water generated by dehydration of surface hydroxyl groups during the drying and calcination processes. Various alcohols are used as the entrainer, 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 during the dehydration process, 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 support-activator and supported catalyst particle morphology. For example, suspensions of the clay heteroadduct in an aqueous or organic solvent or a combination of water and organic solvent may be spray dried. Dry or wet grinding and sieving may be employed to refine the morphology, particle size and particle size distribution of the heteroagglomerated clay. These methods may be employed alone or in combination to achieve the desired support-activator particle morphology, particle size and particle size distribution of the clay heteroadduct. Spray drying and/or sieving of the clay heteroadduct may be used, as may other methods known to those skilled in the art for removing fines or larger particles that may be problematic when transporting or using the heteroadduct as a carrier-activator.

The heteroagglomerated solids can be calcined or heated in a fluidized bed, for example, at a temperature in the range of from about 100 ℃ to about 900 ℃. For example, the heteroagglomerated montmorillonite clay can 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 ℃. The calcination may be carried out in an atmospheric environment (air), for example, the calcination may be carried out in dry air at a temperature in the range of at least 110 ℃, for example, 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 ℃ and 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 ℃ and 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 heteroadduct may also be calcined at a temperature of about 225 ℃ to about 700 ℃ for a time period in the range of about 1 hour to about 10 hours, and most preferably at a temperature of about 250 ℃ to about 500 ℃ for a time period in the range of about 1 hour to about 10 hours. Alternatively, the temperature range for 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 noted above, calcination temperatures selected from any single temperature or a range between two temperatures, e.g., 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 carried out in an ambient atmosphere or under other conditions that favor the removal of water, for example, calcination may be carried out in a carbon monoxide atmosphere. The use of such atmospheres can remove surface hydroxyl groups more efficiently at lower temperatures than temperatures used in ambient air calcination processes, thereby maintaining greater pore volume and surface area during surface dehydration. After calcination, the heteroagglomerated product can be described as a continuous, non-crystalline combination of clay and inorganic oxide particles, which we refer to herein as activator-support or support-activator.

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

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

A comparison of BJH porosities of the clay and clay heteroadducts is presented in fig. 10, 11 and 12. BJH pore volume analysis of the calcined but not azeotroped starting montmorillonite treated with heterocoagulant is presented in fig. 11 (example 1). Pore volume analysis of the starting montmorillonite sheared, then azeotroped and calcined but not treated with heteroagglomerant is presented in fig. 12 (example 3). Finally, the pore volume analysis of the Aluminum Chlorohydrate (ACH) heteroagglomerated clay of example 18 (1.76mmol Al/g clay) is presented in FIG. 10. Thus, in the absence of a heterocoagulation agent, the calcined montmorillonite (such as bentonite) BJH porosity can be from about 0cc/g to about 0.2 cc/g.

The cumulative pore volume between specific pore size limits can be determined using the pore volume distribution derived by the BJH method. Pore size X nm (nanometers) and Y nm (V) _X-Ynm ) The cumulative pore volume (where X nm is the lower limit of the pore diameter and Y is the upper limit of the pore diameter) therebetween: the total cumulative pore volume of pore sizes from 0nm to Y nm was subtracted by the total cumulative pore volume of pore sizes from 0nm to X nm. In the event that the total cumulative pore volume for the upper or lower pore size limits 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 pore volume or cumulative pore volume (V) of pores having a diameter of 3 to 10nm _3-10nm Or "small mesopores") can occupy a cumulative pore volume (V) of pores ranging from 3 to 30nm _3-30nm ) Is/are as follows<And 55 percent. In another aspect, V _3-10nm Can account for the cumulative pore volume V _3-30nm Is/are as follows<50% or alternatively, V _3-10nm Can account for the cumulative pore volume V _3-30nm Is/are as follows<40 percent. This is illustrated by the data in FIG. 10, which shows a BJH pore volume analysis of the montmorillonite heteroadduct of example 18, where V is _3-10nm Has a value of about 0.33 (V) _3-30nm ). This pore volume analysis is in contrast to BJH pore volume analysis of untreated, non-azeotropic clay (example 1, fig. 11) and of azeotropic clay (example 3, fig. 12), both of which are characterized by V _3-10nm Greater than 0.55 (V) _3-30nm )。

These pore volume characteristics of the clay heteroadducts in FIG. 10 of the present disclosure are in contrast to the pore volume characteristics of the acid-treated clays in U.S. Pat. No. 9,751,961 to Murase et al, which discloses "2 nm to 10nm (V) diameter _2-10nm ) The sum of the volumes of the pores of (a) to (b) accounts for 60% -100% of the total volume of mesopores (i.e., all pores from 2nm to 50 nm). (see FIG. 1 and Table 1 of U.S. Pat. No. 9,751,961). Specifically, Murase et al disclose that smaller mesopores of 2nm to 10nm account for a large total mesopore volume (2nm to 50nm) Part(s) in which the total mesopore volume can be determined by, for example, V _2-10nm +V _10-30nm +V _30-50nm And (4) calculating. In contrast, the clay heteroadducts of the present disclosure are characterized by V alone _10-30nm Exceeds the volume V of the smaller mesopores _3-10nm . While not wishing to be bound by theory, it is believed in this disclosure that the increased proportion of larger mesopores to total porosity facilitates the diffusion of metallocene compounds and access to ionization sites on the surface of the clay heteroadduct. It is believed that this is in contrast to smaller mesopores which may impede or even preclude diffusion of the metallocene to surfaces containing ionization sites, particularly for metallocenes having radii of gyration exceeding the smallest end of the mesopore diameter.

Further, as shown, for example, in U.S. patent No. 6,677,411 to Uchino et al, the pore size distribution determined by the BJH method can be plotted by plotting dv (log d) against pore size. The diameter showing the highest value of this function may be represented by D _M Represents, and is considered to be, the most commonly occurring aperture. That is, D _M Is corresponding to

And

the diameter of the point with the highest DV value (log D) in the region between the pore diameters. D _M The ordinate value of (A) is the maximum value, termed D _VM And (4) showing. In one aspect, this log differential pore volume distribution generally has a pore volume distribution of about

To about

Local maximum in (angstroms). This local maximum density may also be the global maximum density D _VM . In one aspect, D _VM The intensity of

And

between dv (log d) of about 200% of the intensity of the maximum. Alternatively, D _VM The intensity of

And

between dv (log d) of about 120% of the intensity of the maximum. Alternatively, D _VM The intensity of

And

between dv (log d) maximum of about 100% of the intensity. On the other hand, in between

And

the maximum value of dV (log D) between exceeds

And

all dV (log D) values in between. This is in contrast to, for example, the acid-treated clays of Uchino et al in U.S. Pat. No. 6,677,411, which is incorporated herein by reference, where the maximum D observed in the logarithmic differential pore size distribution of the ideal example is _VM Has a value between

And

relative diameter D between _M 。

Similarly, the treated clay activator described by Casty et al in U.S. patent No. 7,220,695 identifies a preferred embodiment in which the maximum D is shown _VM Diameter D of value _M Between

And

(angstroms) between. In contrast, the most commonly occurring pore size D of the clay heteroadducts of the present disclosure _M In that

To

Within a range of or

To

Within the range of (1).

Furthermore, the differential log pore volume distribution in U.S. Pat. No. 6,677,411 is demonstrated by

To is that

In comparison with the range of the compound (A),

and

the intensity in the range is significantly lower.

And

the maximum value of dV (log D) in the range is usually less than

And

within the range dV (log D) 10% of the maximum value. In contrast, the clay heteroadducts of the present disclosure may provide

And

maximum value of dV (log D) in the range, which is usually greater than

And

100% 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 the larger mesopores be present in the clay heteroadducts of the present disclosure because the metallocene diffuses more readily to the ionization site of the support-activator.

F. Filterability of montmorillonite heteroadducts

The clay heteroadducts prepared in slurry form over the zeta potential range according to the present disclosure unexpectedly exhibit improved ease of separation compared to similar pillared clays prepared using the same smectite clay and heterocoagulating agent. In particular, unlike pillared clays, 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 lists the slurry settling rate comparisons between pillared and heteroagglomerated clays (each prepared with 5 wt.% of an aqueous HPM-20 clay dispersion). Each slurry was prepared as in the reference example and added to a graduated cylinder and the settling rate was measured as a function of time based on the observed volume of the substantially transparent layer (no turbidity of visible colloidal particles at the top of the slurry). In this comparison, the settling rate of the heteroagglomerated 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 heterocoagulated clay dispersion with a zeta potential in a relatively narrow range of about 0mV, for example in the range of about ± 10mV, relative to the pillared clay particles, favors flocculation, whereas the pillared clay particles tend to remain dispersed.

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

Thus, one method employed to evaluate filterability of a heterocoagulated clay slurry as "easy to filter" is to "check the settling rate of the slurry compared to the settling rate of a pillared clay slurry". In one aspect, if the 2.5 wt.% aqueous-based heteroadduct slurry has a settling rate (as explained in this disclosure) that 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 a 2.5 wt.% aqueous-based pillared clay slurry (prepared using the same colloidal smectite clay, the same heterocoalescing agent, and the same liquid carrier), the composition (such as a clay heteroadduct) is easy or easy to filter, comparing the settling rates for 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 start of the settling test.

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

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

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

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

[b] upon evaporation, the filtrate in the heteroadduct slurry yields solids comprising < 20%, < 15%, or < 10% of the initial total weight of clay and heterocoagulant.

The feature of filtration between 0 hours and 2 hours after initial formation is specified because 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 examples used to generate the data of table 2, the heteroadduct slurry and the 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 the vacuum filtration, substantially all of the water in the heteroadduct slurry had been filtered off, while at 10 minutes after the start of the vacuum filtration, substantially no water in the pillared clay slurry was filtered off. By using a combination of the two features described above to evaluate "ease of filtration", it is not necessary to specify a filter pitch (e.g., 20 μm), nor is it necessary to specify whether filtration is to be used, either 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 allows the clay heteroadduct to meet both criteria, but the absence of a filter size allows the pillared clay to meet both criteria.

As an example of applying this "easy filtration" test, if a filter with too large openings between the filter media is used such that pillared clay filtration meets the requirements of criteria section [ a ] above, it will not meet the requirements of section [ b ] and is not considered easy filtration. The clay heteroadduct also does not meet the requirements of section [ b ] with such larger filter sizes, but reducing the filter size (e.g., to about 20 μm) will allow the clay heteroadduct to meet both standards [ a ] and [ b ], while the pillared clay does not meet the requirements of section [ a ] when the filter size is reduced, because the filter will plug and be almost unable to filter the liquid carrier.

Also, gravity filtration or vacuum filtration can be used for the "ease of filtration" test, since at the point in time specified for the measurement of the filtrate (10 minutes after the start of filtration), the skilled person can easily determine the appropriate filter size, which will allow the clay heteroadduct to meet the criteria [ a ] and [ b ], while the pillared clay will not meet at least one of the criteria [ a ] and [ b ].

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

[a] When filtering 2.0 wt.% of the aqueous heteroadduct slurry over a period of 0 hours to 2 hours after contacting step b) to provide a first filtrate, the weight ratio of a 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 2.0 wt.% pillared clay slurry prepared by filtering using colloidal montmorillonite clay, a heterocoagulation agent, and a 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

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

G. Metallocene compound

The calcined clay heteroadduct can be used as a matrix or catalyst support-activator for one or more suitable polymerization catalyst precursors (such as metallocenes), other organometallic compounds, and/or organoaluminum compounds, among others, or other catalyst components, to prepare an olefin polymerization catalyst composition. Thus, in one aspect, an active olefin polymerization catalyst or catalyst system is provided when a clay heteroadduct is prepared as disclosed herein and combined with an organo main group metal (such as an alkylaluminum compound) and a group 4 organo 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), and the resulting composition exhibits catalytic polymerization activity in the absence or substantial absence of ion exchange, protonic acid treatment, or pillared clay, or alumoxane or borate activators. Previously, it has been believed that activators such as alumoxane or borate activators are necessary to achieve polymerization catalytic activity with metallocene or single site or coordination catalyst systems. However, if it is desired to impart an activatable alkyl ligand to the metallocene, the combination of the heteroadduct support-activator, the metallocene and the cocatalyst (e.g., an alkylaluminum compound) will result in an active catalyst that requires additional activator (e.g., alumoxane or borate activator).

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

In one aspect, the metallocene can be a group 3 to 6 transition metal containing metallocene or a lanthanide series 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 can comprise, consist of, consist essentially of, or consist of a compound or combination of compounds, each independently having the formula:

(X ¹ )(X ² )(X ³ )(X ⁴ ) M, wherein

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

b)X ¹ selected from the group consisting of substituted or unsubstituted cyclopentadienyl, indenyl, fluorenyl, pentadienyl, allyl, borato-ionic heteroaryl, 1, 2-azaborodienyl or 1, 2-diaza-3, 5-diboronoyl, wherein any substituent is independently selected from the group consisting of halide, C ₁ -C ₂₀ Hydrocarbyl radical, C ₁ -C ₂₀ Heterohydrocarbyl radical, C ₁ -C ₂₀ Organic hetero group, condensed C ₄ -C ₁₂ A carbocyclic moiety or a fused C having at least one heteroatom independently selected from ₄ -C ₁₁ Heterocyclic moiety: nitrogen, oxygen, sulfur orPhosphorus;

c)X ² selected from: [1]Substituted or unsubstituted cyclopentadienyl, indenyl, fluorenyl, pentadienyl, or allyl, wherein any substituent is independently selected from the group consisting of halide, C ₁ -C ₂₀ Hydrocarbyl radical, C ₁ -C ₂₀ Heterohydrocarbyl or C ₁ -C ₂₀ An organic hetero group; or [2 ] ]Halides, hydrides, C ₁ -C ₂₀ Hydrocarbyl radical, C ₁ -C ₂₀ Heterohydrocarbyl radical, C ₁ -C ₂₀ Organic hetero group, condensed C ₄ -C ₁₂ A carbocyclic moiety or a fused C having at least one heteroatom independently selected from ₄ -C ₁₁ Heterocyclic moiety: 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 each bridging atom may be unsubstituted (bonded to H) or substituted with a non-bridging valence, wherein any substituents are independently selected from halide, C ₁ -C ₂₀ Hydrocarbyl radical, C ₁ -C ₂₀ Heterohydrocarbyl or C ₁ -C ₂₀ An organoheteryl group, and wherein any hydrocarbyl, heterohydrocarbyl or organoheteryl substituent may form a bridging atom or X ¹ Or X ² A saturated or unsaturated cyclic structure of (a);

e)[1]X ³ and X ⁴ Independently selected from halide, hydride, C ₁ -C ₂₀ Hydrocarbyl radical, C ₁ -C ₂₀ Heterohydrocarbyl or C ₁ -C ₂₀ An organic hetero group; [2][GX ^A _k X ^B _4-k ]-, where G is B or Al, k is a number from 1 to 4, and X ^A Independently at each occurrence, selected from H or halide, and X ^B Independently at each occurrence is selected from C ₁ -C ₁₂ Hydrocarbyl radical, C ₁ -C ₁₂ Heterohydrocarbyl radical, C ₁ -C ₁₂ An organic hetero group; [3]X ³ And X ⁴ Together are C ₄ -C ₂₀ A polyene; or [4 ]]X ³ And X ⁴ Together with M form a substituted or unsubstituted, saturated or unsaturated C ₃ -C ₆ A metal ring compound moiety thereof Wherein any substituents on the metallocycle moiety are independently selected from the group consisting of halide, C ₁ -C ₂₀ Hydrocarbyl radical, C ₁ -C ₂₀ Heterohydrocarbyl or C ₁ -C ₂₀ An organic hetero group.

According to another aspect, X, if desired ¹ And X ² May be bridged by a linker substituent selected from:

a)>EX ⁵ ₂ 、-EX ⁵ ₂ EX ⁵ ₂ -、-EX ⁵ ₂ EX ⁵ EX ⁵ ₂ -or>C＝CX ⁵ ₂ Wherein E is independently at each occurrence selected from C or Si;

b)-BX ⁵ -、-NX ⁵ -or-PX ⁵ -; or

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

Wherein X ⁵ Independently at each occurrence, selected from H, halide, C ₁ -C ₂₀ Hydrocarbyl radical, C ₁ -C ₂₀ Heterohydrocarbyl or C ₁ -C ₂₀ An organic hetero group;

and wherein any X selected from hydrocarbyl, heterohydrocarbyl or organoheteryl substituents ⁵ The substituent being able to be bound to the bridging atom, another X ⁵ Substituent group, X ¹ Or X ² Forming a saturated or unsaturated cyclic structure.

Can bridge X ¹ And X ² Examples of suitable linker substituents include C ₁ -C ₂₀ Alkylene group, C ₁ -C ₂₀ Partial hydrocarbon group, C ₁ -C ₂₀ Heterohydrocarbyl radical, C ₁ -C ₂₀ Heterocarbyl radical, C ₁ -C ₂₀ Hetero alkylene radicals or C ₁ -C ₂₀ A heterocarbyl group. For example, X ¹ And X ² May be bridged by at least one substituent having the formula:>EX ⁵ ₂ ，-EX ⁵ ₂ EX ⁵ ₂ -, or-BX ⁵ -, where E is independently C or Si, X ⁵ Independently at each occurrence selected from halide, C ₁ -C ₂₀ Aliphatic radical, C ₆ -C ₂₀ Aromatic radical, C ₁ -C ₂₀ Heteroaliphatic radical, C ₄ -C ₂₀ Heteroaromatic radical or C ₁ -C ₂₀ An organic hetero group.

Aspects of the disclosure are set forth in part with respect to X ¹ And X ² Between connecting parts, with respect to X ⁵ And with respect to specific linker substituents or X ⁵ Additional description and selection of substituents.

Aspects of the disclosure also recite X ¹ And X ² Additional descriptions and alternatives of, including X ¹ And X ² The specific substituents above.

Aspects of the disclosure also recite X ³ And X ⁴ Additional descriptions and alternatives of, including X ³ And X ⁴ The specific substituents above.

Aspects of the present disclosure also provide some specific examples of metallocene compounds used 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 methods for 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 No; 5,436,305 No; 5,401,817 No; 5,631,335, 5,571,880; 5,191,132, No. 5,191,132; 5,480,848 No; U.S. Pat. No. 5,399,636; no. 5,565,592; 5,347,026 No; 5,594,078 No; 5,498,581 No; 5,496,781 No. C; 5,563,284 No; 5,554,795 No; 5,420,320 No; 5,451,649 No. C; 5,541,272 No; 5,705,478 No; 5,631,203 No; 5,654,454 No. C; 5,705,579 No; 5,668,230 No; 9,045,504 and 9,163,100 and U.S. patent application publication No. 2017/0342175, the entire disclosures of which are incorporated herein by reference.

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 co-catalyst; and c) at least one support-activator as described herein. Cocatalysts include compounds such as trialkylaluminums, which are believed to impart to the metallocene a ligand that can initiate polymerization when the metallocene is otherwise activated with a support-activator. The cocatalyst may be considered optional, for example, in the case where the metallocene may already include a polymerizable activating/initiating ligand (such as a methyl or hydride). It should be understood that even when the metallocene compound includes, for example, a polymerizable activating/incipient ligand, the cocatalyst may be used for other purposes, such as scavenging moisture from the polymerization reactor or process. Thus, the co-catalyst may comprise or be selected from, for example, an alkylating agent, a hydrogenating agent or a silylating agent. The metallocene compound, support-activator, and cocatalyst can be contacted in any order.

The co-catalyst may comprise or may 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 disclosure set forth additional descriptions and selections of organoaluminum compounds, organoboron compounds, organozinc compounds, organomagnesium compounds, and organolithium compounds.

In one aspect, for example, the co-catalyst can comprise, consist essentially of, or be selected from at least one organoaluminum compound, which can independently have the formula Al (X) ^A ) _n (X ^B ) _m 、M ^x [AlX ^A ₄ ]、Al(X ^C ) _n (X ^D ) _3-n 、M ^x [AlX ^C ₄ ]That is, it may be a neutral molecular compound of aluminumOr an ionic compound/salt, wherein each variable of these formulae is defined in the aspects section of the present disclosure. For example, the co-catalyst can comprise, consist essentially of, or be selected from 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 cocatalyst can comprise, consist of, consist essentially of, or be selected from at least one organoboron compound, which can independently have the formula B (X) ^E ) _q (X ^F ) _3-q Or M ^y [BX ^E ₄ ]I.e. may be a neutral molecular compound or an ionic compound/salt of boron, wherein each variable of these formulae is defined in the aspects section of the present disclosure. For example, the co-catalyst may comprise, consist essentially of, or be selected from trimethylboron, triethylboron, tripropylboron, tributylboron, trihexylboron, trioctylboron, diethylethoxyboron, diisobutylhydroboron, triisobutylboron, diethylboron chloride, di-3-pinanyl borane, pinacolborane, catechol borane, lithium borohydride, lithium triethylborohydride, and the like, including Lewis base adducts thereof, or any combination or mixture thereof. In another aspect, the cocatalyst can comprise or can be an organoboron halide compound, such as an organoboron fluoride 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]Borate, triphenylcarbenium tetrakis [3, 5-bis (trifluoromethyl) phenyl]Borates, and any combination or mixture thereof.

In another aspect, for example, the cocatalyst can comprise, consist essentially of, or be selected from at least one organozinc or organomagnesium compoundThe substance may independently have the formula M ^C (X ^G ) _r (X ^H ) _2-r Wherein each variable of this formula is defined in the aspects section of this disclosure. For example, the co-catalyst can comprise, consist of, consist essentially of, or be selected from dimethylzinc, diethylzinc, diisopropylzinc, dicyclohexylzinc, diphenylzinc, butylethylmagnesium, dibutylmagnesium, n-butyl-sec-butylmagnesium, biscyclopentadienylmagnesium, ethylmagnesium chloride, butylmagnesium chloride, and the like, including any combination thereof.

In another aspect, for example, the co-catalyst can comprise, consist essentially of, or be selected from at least one organolithium compound, which can independently have the formula Li (X) ^J ) Wherein each variable of formula is defined in the aspects section of the present disclosure. For example, the co-catalyst may comprise, consist essentially of, or be selected from methyllithium, ethyllithium, propyllithium, butyllithium (including n-butyllithium and t-butyllithium), hexyllithium, isobutyllithium, the like, or any combination thereof.

I. Optional co-activator

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

Additional description and selection of each of the optional co-activators are detailed in the aspects section of this disclosure.

An aluminoxane. Alumoxanes (also known as poly (hydrocarbylaluminum oxides) or organoalumoxanes) can be used to contact other catalyst components, for example, in any solvent that is substantially inert to the reactants, intermediates and products of the activation step, such as a saturated hydrocarbon solvent or a solvent, such as toluene. If desired, the catalyst composition formed in this way can be isolated or introduced into the polymerization reactor without isolation.

As understood by those skilled in the art, alumoxanes are oligomers, wherein the alumoxane compound may comprise a linear structure, a cyclic or cage structure, or mixtures thereof. For example, the cyclic aluminoxane compounds have the formula (R-Al-O) _n Wherein R may be a linear or branched alkyl group having from 1 to about 12 carbon atoms and n may be an integer from 3 to about 12. (AlRO) _n Moieties also constitute repeating units of linear aluminoxanes, for example having the formula: r (R-Al-O) _n AlR ₂ Wherein R may be a linear 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 chain C ₁ -C ₈ Alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, wherein n may represent an integer from 1 to about 50. Depending on how the organoaluminoxane is prepared, stored, and used, the value of n may vary in a single sample of aluminoxane, and combinations or populations of such organoaluminoxane species are typically present in any sample.

Organoaluminoxanes can be prepared by various procedures known in the art, for example, the organoaluminoxanes 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 may be prepared by reacting water in an inert organic solvent with an alkylaluminum compound such as AlR ₃ To produce a reaction to form the desired organoaluminoxane compound. Alternatively, the organoaluminoxane may 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, isopropylaluminoxane, n-butylaluminoxane, t-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 cocatalysts, and these aluminoxanes may be prepared from trimethylaluminum, triethylaluminum or triisobutylaluminum, respectively. These compounds can 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 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 alumoxane can be, for example, from about 1:10mol Al per mole of metallocene (mol Al per mol metallocene) to about 100,000:1mol Al per mol metallocene or from about 5:1mol Al per mol metallocene to about 15,000:1mol Al per mol metallocene. When used in combination with the disclosed support-activators, the relative amount of alumoxane can be reduced. For example, the amount of optional aluminoxane added to the polymerization zone can be less than the typical amounts heretofore described in the range of about 0.01mg/L to about 1000mg/L, about 0.1mg/L to about 100mg/L, or about 1mg/L to about 50 mg/L. Alternatively, alumoxanes may be used in amounts typically used in the art, but additionally with the support-activator of the present disclosure to obtain further advantages of such combinations.

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

Thus, the term fluoroorganoboron compound is used herein to refer to BY ₃ Neutral compound of the form, the term fluoroorganoborate compound being used herein to refer to [ cation] ⁺ [BY ₄ ] ^- Monoanionic salt of a fluoroorganoboron compound of the form wherein Y represents a fluorinated organic group. For convenience, the fluoroorganoboron and fluoroorganoborate compounds are generally referred to collectively as organoboron compounds, or either name may be used as the context requires.

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

Aspects of the disclosure detail additional descriptions and options for alternative fluoroorganoboron and fluoroorganoborate compound co-activators.

While not intending to be bound by theory, it is believed that these fluoroorganoborate 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.

Generally, any amount of organoboron compound can be used as optional co-activator. For example, in one aspect, the molar ratio of the organoboron compound to the metallocene compound in the composition can be from about 0.1:1 moles of organoboron or organoborate compound per mole of metallocene (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 is understood that if a clay heteroadduct support-activator is present, the amount may be reduced or adjusted downward.

Ionizing the compound. In another aspect, optional co-activators that may be used may comprise or may be selected from ionizing compounds in addition to the listed components of the catalyst composition of the present disclosure. 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 selections of optional ionizing compound co-activators.

The term ionizing compound is a term of art that refers to a compound, particularly an ionizing compound, that may function to enhance the activity of the 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 fluoroorgano borate compounds, such as compounds encompassed by ionizing compounds, such as fluoroorgano aluminates.

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 cation or an 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 ionized compound may function by fully or partially extracting the anionic ligand from the metallocene, particularly a non-cycloalkadienyl ligand or a non-alkadienyl ligand, such as the metallocene formula (X) disclosed herein ¹ )(X ² )(X ³ )(X ⁴ ) M of (X) ³ ) Or (X) ⁴ ) To form a cationic or initially cationic metallocene. However, the ionizing compound may act as an activator (co-activator), regardless of the mechanism by which it acts. For example, ionizing compounds which ionize metallocenes and abstract X in such a way that ion pairs are formed ³ Or X ⁴ Ligands, weakening of metal-X ³ Or metal-X ⁴ A bond, or simply with X ³ Or X ⁴ Ligand coordination, or any other mechanism by which activation may occur. Furthermore, the ionizing compound does not have to activate (co-activate) the metallocene only, since the ionizing compound has a work of activation compared to a catalyst composition comprising a catalyst composition that does not comprise any ionizing compoundThe enhanced activity of the catalyst composition as a whole is more significant.

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

Optionally a support-activator. In another aspect, in addition to the enumerated 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, co-activator-supports. Examples of optional co-activator-carriers 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 from about 1:1 to about 100:1, or from about 2:1 to about 20: 1. The at least one electron-withdrawing anion can comprise or be selected from fluoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate, and the like, or combinations thereof.

In one aspect, the optional co-activator-support can 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 of which, or any combination thereof, can 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 section of the present disclosure.

J. Preparation of the catalyst composition

In the catalyst system, the metallocene is of the formula (X) ¹ )(X ² )(X ³ )(X ⁴ ) The relative concentration or ratio of the group 4 metallocene of M to the calcined clay heteroadduct can be expressed as moles of M (metal) per gram of calcined clay heteroadduct (mol M/g heteroadduct). In one aspect, it has been found that the molar ratio of M per gram of calcined clay heteroadduct can range from about 0.025mol M/g heteroadduct to about 0.000000005mol M/g heteroadduct. In another aspect, the M moles of heteroadduct per gram of calcined clay can be used in a range of from about 0.0005mol M/g heteroadduct to about 0.00000005mol M/g heteroadduct, or alternatively, in a range of from about 0.0001mol M/g heteroadduct to 0.000001mol M/g heteroadduct. As in all ranges disclosed herein, the recited ranges include the endpoints and the intermediate values and subranges within the recited ranges. These ratios reflect the catalyst formulation, i.e., they are based on the combined component amounts that result in the catalyst composition, regardless of the ratio in the final catalyst.

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

The catalyst composition can be produced by contacting under suitable conditions a transition metal compound (e.g., metallocene, calcined clay heteroadduct) and a cocatalyst (e.g., organoaluminum compound). The contacting can be performed in a variety of ways, such as by blending, by contacting in a carrier liquid, by adding the components to the reactor individually or in any order or combination. For example, the components or various combinations of compounds may be contacted with each other prior to further contact with the remaining compounds or components in the reactor. Alternatively, all three components or compounds may be contacted together prior to introduction to the reactor. With respect to additional optional components that may be used in the catalyst systems disclosed herein, such as co-activators, ionizing ionic compounds, and the like, 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 about 1 minute to about 1 hour, at a contact temperature that can range 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, which can then 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 can be precontacted prior to introduction into the reactor. For example, the precontacting step can 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 period 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, it can be said that the catalyst composition comprises the contacted components. For example, the catalyst composition can comprise a post-contacted metallocene, a post-contacted cocatalyst (e.g., an organoaluminum compound), and a post-contacted 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 not be precisely known. While not intending to be bound by theory, the majority by weight of the catalyst composition may be considered to comprise the post-contacted calcined clay heteroadduct, based on the relative weight of the individual components. Because the nature of the active sites and the post-contact components are not precisely known, the catalyst composition may be described simply in terms of its components, or as comprising post-contact compounds or components.

The polymerization activity of the catalyst composition can be expressed as the weight of support-activator comprising the calcined montmorillonite heteroadduct per weight of polymer polymerized per unit time, e.g., g polymer/g (calcined) support-activator/h (g/g/h). That is, the activity may be calculated based on the support-activator alone, without the presence of any metallocene or cocatalyst component. This measurement allows for a comparison of various activator supports, including comparisons with other activators where 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, a polymerization temperature of about 50 ℃ to about 150 ℃ (e.g., at a temperature of 90 ℃), and a combined ethylene and isobutane pressure range of about 300psi to about 800psi, e.g., a total pressure of 450psi for the combined ethylene and isobutane. Activity data are reported as the weight of polymer produced per hour divided by the weight of calcined clay heteroadduct.

Catalyst activity can be a function of the metallocene and calcined clay heteroadducts as well as other components and conditions. Under the above conditions, 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 can 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 50,000 g/g/h. Each upper limit of these activities may be about 70,000g/g/h, and as such activities may range from greater than these disclosed values to less than about 75,000 g/g/h.

For example, in one aspect and using the conditions described herein, the activator-support can have 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, A polymerization activity of about 50,000g/g/h, about 60,000g/g/h, about 70,000g/g/h, or about 75,000g/g/h, including any range therebetween. Higher polymerization activity values may be associated with clay supports having very high site densities, and these activity values may also be metallocene dependent. Thus, by applying the teachings herein, activity levels in the range between the two recited values can be obtained, e.g., activity levels in the range of 500-. Unless otherwise indicated, the activities in the examples and data tables were 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) ₂ ZrCl ₂ And a triethylaluminum catalyst composition.

In one aspect, an aluminoxane (e.g., methylaluminoxane) is not required to activate the metallocene and form the catalyst composition. Methylaluminoxane (MAO) is an expensive activator compound and can add significantly to the cost of production of the polymer. In addition, in another aspect, no organoboron compounds or ionizing compounds (e.g., borate compounds) are required to activate the metallocene and form the catalyst composition. Furthermore, ion exchange, protonic acid treatment or pillared clays, which require similar multistep preparations that add cost, are not required to activate the metallocene and form the catalyst composition. Thus, in the absence of any aluminoxane compounds, boron compounds or borate compounds, ion exchange, protonic acid treatment or pillared clays, the active heterogeneous catalyst composition can also be produced easily and inexpensively and used for polymerizing olefin monomers, including comonomers if desired. Although MAO or other alumoxanes, boron or borate compounds, ion exchange clays, protonic acid treated clays or pillared clays are not necessary in the disclosed catalyst system, these compounds may 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 and 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, a polymer of two or more olefin monomers is simply referred to as a copolymer. Thus, the catalyst composition may be used to polymerize at least one monomer to produce a homopolymer or a copolymer.

In one aspect, the homopolymer comprises monomeric 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 by the present disclosure. On the other hand, copolymers of ethylene and at least one comonomer, as well as less commonly copolymers of two non-ethylene copolymers, are also encompassed by the present disclosure.

When a copolymer is desired, each monomer can have from about 2 to about 20 carbon atoms per molecule. Ethylene comonomers may include, but are not limited to, aliphatic 1-olefins having from 3 to 20 carbon atoms per molecule such as, for example, propylene, 1-butene, 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. The comonomer may be introduced into the reactor zone in an amount sufficient to produce a copolymer that may comprise from about 0.01 wt.% to about 10 wt.% or even more comonomer than this range, based on the total weight of monomers and comonomers in the copolymer; alternatively, about 0.01 wt.% to about 5 wt.% comonomer; still alternatively, about 0.1 wt.% to about 4 wt.% comonomer; still alternatively, any amount of comonomer may be introduced into the reactor zone to provide the desired copolymer. In general, the catalyst composition can be used to homopolymerize ethylene or propylene, or to copolymerize ethylene with a comonomer, or to copolymerize ethylene and propylene. In another aspect, several comonomers may be polymerized with the monomers in the same or different reactor zones to achieve desired polymer attributes.

Other useful comonomers may include polar vinyl, conjugated and non-conjugated diene, acetylene and acetaldehyde monomers, which may be included in minor amounts in the terpolymer composition, for example. For example, the non-conjugated diene useful as a comonomer can be a straight chain 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) monocyclic alicyclic dienes such as 1, 4-cyclohexadiene; 1, 5-cyclooctadiene and 1, 7-cyclododecadiene; (d) polycyclic alicyclic fused and bridged ring dienes such as tetrahydroindene; norbornadiene; methyl tetrahydroindene; dicyclopentadiene (DCPD); bicyclo- (2.2.1) -hepta-2, 5-diene; alkenyl, alkylene, cycloalkenyl and cycloalkylidene norbornenes such as 5-methylene-2-norbornene (MNB), 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5- (4-cyclopentenyl) -2-norbornene, 5-cyclohexylidene-2-norbornene and 5-vinyl-2-norbornene (VNB); and (e) cycloalkenyl-substituted alkenes 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 compositions can be used to polymerize olefins to produce oligomeric 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 are 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. According to certain aspects of the present disclosure, densities of less than 0.91g/cc and even as low as 0.860g/cc may be achieved. When the density is described as being less than a particular density, one lower limit of such density may be about 0.860 g/cc. The copolymer resin may contain at least about 65 wt.% (weight percent) of ethylene units, that is, the weight percent of ethylene monomer actually incorporated into the copolymer resin. In another aspect, the copolymer resins of the present disclosure may contain at least about 0.5 wt.%, e.g., 0.5 wt.% to 35 wt.% of an alpha-olefin (a-olefin), which refers to the weight percent of the a-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 copolymers are randomly distributed along the polymer backbone or chain; (b) "propylene random copolymer", wherein the random copolymer of propylene and ethylene comprises about 60 wt.% of polymer derived from propylene units; and (c) "impact copolymer" means two or more polymers, wherein one polymer is dispersed in another polymer, typically one polymer comprising a matrix phase and the other polymer comprising an elastomer phase. The catalyst compositions described herein can further be used to prepare polyalphaolefins having monomers wherein the monomers contain more than three carbons. Such oligomers and polymers are particularly useful, for example, in lubricants.

Any number of polymerization methods or processes can be used with the catalyst compositions of the present disclosure. For example, slurry polymerization, gas phase polymerization, solution polymerization, and the like, including multiple reactor combinations thereof, may be used. Depending on the desired polymerization sequence, multiple reactor combinations can be configured in series or in parallel, or a combination thereof. Examples of reactor systems and combinations can include, for example, a dual slurry loop in series, multiple slurry tanks in series, or a slurry loop in combination with a gas phase, or various combinations of these processes, wherein the polymerization of ethylene, propylene, and alpha-olefins can be carried out separately 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 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 may be used. 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.

Catalyst compositions comprising the enumerated components may polymerize olefins in the presence of a diluent or liquid carrier, and these two terms are used interchangeably herein even though the catalyst components are not soluble in the diluent or liquid carrier. Suitable diluents for slurry and solution polymerization are known in the art and include hydrocarbons that are liquid under the reaction conditions. Further, the term "diluent" as used in this disclosure does not necessarily mean that the material is inert, as the diluent may facilitate 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 so on. Isobutane works well as a diluent in slurry polymerizations. Examples of such slurry polymerization techniques are described 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 herein in their entirety. When polymerizing propylene or other alpha-olefins, the propylene or alpha-olefin itself may contain 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 feedstock 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 can 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 30000 psig. In another aspect, the polymerization pressure can be from about 50psig to about 800 psig.

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; thus, no water is present at the start of the reaction. Therefore, a dry inert atmosphere, such as dry nitrogen or dry argon, is generally used in the polymerization reactor.

In one aspect, hydrogen can be used in the polymerization process to control polymer molecular weight. In another aspect, a process for deactivating a catalyst by adding carbon monoxide to a polymerization zone, as described in U.S. patent No. 9,447,204, which is 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 carried out in a loop reaction zone using a slurry polymerization process or a batch process, or in a gas phase zone using a fluidized or stirred bed.

A 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 combinations thereof.

The polymerization reactor system may comprise at least one loop slurry reactor, and may comprise a vertical or horizontal loop, 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 can 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 comonomers can be continuously fed to the loop reactor where polymerization occurs. The reactor effluent may be flashed to separate solid polymer particles.

A gas phase. In one aspect, the method of producing a polyolefin polymer 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-0802202, Belgian patent No. 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.

Gas phase polymerization systems may employ a continuous recycle stream containing one or more monomers that is continuously recycled through a fluidized bed under polymerization conditions in the presence of a catalyst. The recycle stream may be withdrawn from the fluidized bed and recycled back to the reactor. At the same time, polymer product may be withdrawn from the reactor and fresh monomer may be added in place of polymerized monomer. Such gas phase reactors may comprise a multi-step gas phase polymerization process of olefins, wherein 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 process include series 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-0794200, EP-B1-0649992, EP-A-0802202, and EP-B-634421, all of which are incorporated herein by reference.

In gas phase polymerizations according to the present disclosure, the ethylene partial pressure may vary within a range suitable to provide actual polymerization conditions, such as within a range of 10psi to 250psi, such as 65psi to 150psi, 75psi to 140psi, or 90psi to 120 psi. On the other hand, 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 from 0.0 to 0.70, from 0.0001 to 0.25, more preferably from 0.005 to 0.025 or from 0.025 to 0.05. According to an aspect, the reactor pressure may be maintained within a range suitable to provide actual polymerization conditions, such as within a range from 100psi to 500psi, from 200psi to 500psi, or from 250psi to 350psi, and the like.

According to other aspects, in a fluidized bed process for producing polymers, a gas stream containing one or more monomers under reaction conditions in the presence of a catalyst may be continuously circulated through the fluidized bed. The gas stream may be withdrawn from the fluidised bed and recycled back to the reactor, whilst polymer product may be withdrawn from the fluidised bed and from the reactor, and fresh monomer may be added in place of the 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 5,228; each of which is incorporated herein by reference in its entirety.

In another aspect, the antistatic compound can be fed to the polymerization zone simultaneously with the finished catalyst. Alternatively, antistatic compounds such as those described in U.S. Pat. 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 heteroadduct may be contacted with or impregnated with one or more antistatic compounds. The antistatic compounds can be added at any point, for example, they can be added at any time after calcination, such as until (including) final post-contact catalyst preparation.

In another aspect, so-called "self-limiting" compositions can be added to the clay heteroadduct to inhibit caking, fouling or uncontrolled reaction 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 catalyst poisons above a threshold temperature. Generally, such compositions can be added at any time after calcination in order to limit or stop polymerization activity above a desired temperature.

And (3) solution. The polymerization reactor may also comprise a solution polymerization reactor wherein the monomer is contacted with the catalyst composition by suitable agitation or other means. The solution polymerization can be carried out in a batch mode or a continuous mode. A support comprising an inert organic diluent or excess monomer may be employed and the polymerization zone maintained at a temperature and pressure which will result in the formation of a polymer solution in the reaction medium. Agitation may be employed during the polymerization process to obtain better temperature control and to maintain a uniform polymerization mixture throughout the polymerization zone and to dissipate the exothermic heat of polymerization using suitable means. The reactor may also contain a series of at least one separator that uses high and low pressures to separate the desired polymer.

Tubular reactors and high pressure LDPE. In yet another aspect, the polymerization reactor can comprise a tubular reactor, which can produce a polymer by free radical initiation or alternatively by employing the disclosed catalyst. 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 region of the reactor, and the initiator, catalyst composition and/or catalyst components may be entrained in a gas stream and introduced in another region of the reactor. These gas streams can then be mixed for polymerization, wherein the heat and pressure can be suitably adjusted to obtain optimal polymerization conditions.

Combinations 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 may be used in a multiple reactor system, which may comprise a combined or connected reactor to perform the polymerization, or a plurality of 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 to be polymerized 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 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 polymer produced by a first polymerization reactor to a second reactor, wherein the polymerization conditions in each reactor are different. Alternatively, polymerization in multiple reactors may include manually transferring 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 loops and gas reactors, autoclave reactors or solution reactors in combination 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 fouling 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 range from about 10 microns (μm) to about 1000 microns, from about 25 microns to about 500 microns, from about 50 microns to about 200 microns, or from about 30 microns to about 100 microns to provide good control over polymer particle production during polymerization.

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

In other polymerization reactor systems, whether single or multiple systems in series, the appropriate particle size may be a function of the overall productivity of the catalyst and the optimal 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 by the fluidizing gas, which could lead to downstream filter plugging. Also, when the catalyst-polymer composite particles are melted and extruded into pellets, the optimal size and size distribution in the polymerization system can be balanced with the ease of transporting or handling them in storage warehouses or extrusion facilities.

Polymers produced using the catalyst compositions of the present disclosure can be formed into various articles, such as household containers and appliances, film products, automotive bumper assemblies, drums, fuel tanks, pipes, geomembranes, and liners. 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 attributes obtained from polymers produced using the transition metal or metallocene catalyst compositions disclosed herein.

Provided is a concrete embodiment. 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 easily filtered and washed to a conductivity of less than 10mS/cm, or less than 5mS/cm, or between 1mS/cm and 50 μ S/cm, or between 500 μ S/cm and 50 μ S/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 heteroagglomerated clay adduct composition that does not exhibit or does not substantially exhibit a 2 θ d001 peak of less than 8 degrees, preferably does not exhibit or does not substantially exhibit a 2 θ d001 peak of less than 10 degrees. A peak in which the main peak is not less than 4 degrees 2 θ if present in a region of less than 10 degrees 2 θ, or a peak having an intensity greater than that exhibited by the clay mineral itself after calcination at 300 ℃, such as from 8 degrees 2 θ to 12 degrees 2 θ;

(3) combining the calcined heterocoagulation 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 between 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.

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

Examples of the invention

The foregoing description is intended to illustrate and not to 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. Rather, it should be understood that resort may be had to various other embodiments, aspects, modifications, and equivalents thereof which, based on the written description, suggest themselves to those of ordinary skill in the art without departing from the spirit of the 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 procedures

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

Produced by colloid company of America

HPM-20 aqueous bentonite dispersions (montmorillonites), abbreviated as HPM-20 or HPM-20 clays, obtainable from McCullough &Associates. 50% aqueous polyaluminum chloride solution (abbreviated as "ACH") and

290 (polyaluminium chloride, known as Al) ₂ (OH) _2.5 Cl _3.5 ). Aluminum chlorohydrate powder obtained from Parchem Fine and Specialty Chemicals (

51P, commonly known as Al ₂ Cl(OH) ₅ ) And a solution of aluminum sesquichloride: (

31L). Fumed silica from Evonik Industries AG (a)

200) And gas phaseAqueous alumina dispersion (A)

W400). Colloidal alumina was obtained from Nano Technologies, Inc. (

AL 27).

Unless otherwise indicated, in the specification and examples, clay dispersions, clay heteroadducts, pillared clays and other compositions may be prepared using a two speed Conair equipped timer ^TM Waring ^TM A commercial laboratory blender model 7010G. The "low" speed versus "high" speed blending of blender speeds is as follows: the 7010G blender was connected to a Staco energy variable transformer (model 3PN1010B) and the blender speed 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.

The conductivity was measured using a Eutech pcststr 35 or radiometric conductivity meter according to the instrument instruction manual and the references provided for each instrument. The pH of the solution or slurry was measured using a Eutech PCSTstr 35 or Beckmann φ 265 laboratory acidimeter.

Water was initially pretreated by using a Prepak 1 pretreatment package, followed by Millipore Milli-

The Advantage A10 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 dichloromethane were dried over activated molecular sieves and degassed with nitrogen before use. Instrument grade isobutane used as the ethylene homopolymerization solvent was purchased from Airgas and passed through an activated carbon column, oxidizedPurification was performed on an aluminum column, a 13X molecular sieve column, and finally by OxyClear, model RGP-R1-500, available from Diamond Tool and Die, Inc ^TM And purifying by using a gas purifier. Ultra-high purity grade ethylene and hydrogen were obtained from Airgas. UHP (ultra-high purity) ethylene passes through an activated carbon column, an alumina column, a 13X molecular sieve column and an OxyClear with the model number of RGP-R1-500 ^TM The gas purifier is used for further purification. UHP Hydrogen passes OxyClear model RGP-R1-500 ^TM And purifying by a gas purifier. Purified propylene was obtained as a slip stream from a commercial polypropylene plant.

All preparations involving treatment of organometallic compounds are under nitrogen (N) ₂ ) Performed under atmosphere using Schlenk techniques or in a glovebox.

Zeta potential measurement

The zeta potential of the colloidal suspensions disclosed herein is obtained by measuring the electroacoustic effect when an electric field is applied across the suspension. The apparatus used to make these measurements is a colloid dynamics Zetaprobe Analyzer ^TM . For example, zeta potential measurements are used to determine the dispersion between 0.5 wt.% and 1wt. -% ]

The HPM-20/aqueous dispersion is as follows. Samples of 250g to 300g of the dispersion to be tested are transferred into a measuring vessel containing an axial bottom stirrer. The stirring speed is set fast enough to prevent sedimentation or substantial sedimentation of the dispersion, but slow enough to allow complete immersion of the electroacoustic probe into the mixture when fully lowered. Typically the agitation speed is set between 250rpm and 350rpm, most commonly 300 rpm.

The Colloid dynamic Zetaprobe Analyzer ^TM The measurement parameters were as follows: 5 readings at a rate of 1 reading/minute; the particle density was 2.6 g/cc; the dielectric constant was 4.5. The initial estimated colloidal weight percentage is 0.7 wt.% to 1.0 wt.% (concentration) _{Estimated value} ) Usually inputted to a Zetaprobe Analyzer ^TM In software. Measuring 5wt. -%)

HPM-20/aqueous dispersion to give a zeta potential of-46 mVAnd (4) performing potential treatment. If the final dispersed clay concentration is referred to as "concentration" in the following equation, the final dispersed clay concentration can be calculated from the initial estimated concentration according to the following equation.

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

Zetaprobe Analyzer ^TM And also for dynamically tracking the zeta potential developed during titration of clay dispersions, whether colloidal dispersions or non-colloidal solutions. Typically, the cationic multimetal salt titrant (or other cationic titrant) is added to 0.5 wt.% to 5.0 wt.%

HPM-20/water dispersion, concentration per titration point from 0.25mL to 2.0mL, equilibration delay time from 30 seconds to 120 seconds.

Zetaprobe software calculates the zeta potential using the weight percentage of colloidal particles not counted in the colloidal titrant. Thus, in the case 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 titrated clay and titrant cationic species is determined by the following equation (where x represents the multiplication, W is the weight and V is the volume).

W _Titrant ＝V _Titrant Density of change _Titrant Solid% _Titrant

W _{Clay clay} ＝V _{Total amount of} Density of _{Dropped article} Particle concentration _{Measured value}

Determined as 5%

The density of the HPM-20 aqueous dispersion (instilled drop) was about 1.03 g/mL. According to the particle density of the titrant relative to the dripped matter

Particle density of HPM-20 (montmorillonite) to convert titrant weight to provide an effective titrant weight (W) _{Effective titrant} ) Which in this example is calculated as follows.

W _{Effective titrant} ＝W _Titrant Particle density _Titrant Particle Density _{Dropped article}

Then calculating the effective colloidal particle weight percent (wt. -%) _{Is effective} ) 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.％ _{Is effective} ＝(W _{Effective titrant} +W _{Clay clay} )/V _t

A＝wt.％ _{Measured value} /wt.％ _{Is effective}

ZP _{Adjusting value} ＝ZP _{Measured value} *A

In the zeta potential titration of clay dispersions using cationic multimetal salts, e.g. Aluminum Chlorohydrate (ACH) couple

HPM-20 montmorillonite was titrated and the zeta potential was measured before and during titration as a function of titrant volume and mmol Al/g clay. Samples of the solid material formed at different 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 plots the results obtained by pairing Aluminum Chlorohydrate (ACH) with Aluminum Chlorohydrate (ACH)

Titration of HPM-20 montmorillonite provides a series of zeta potentials of the dispersion, plotting titrant volume versus zeta potential (mV) of the dispersion, and fig. 4 plots mmol Al/g clay for the same titration versus zeta potential (mV) of 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 using standard X-ray powder diffraction techniques on a Bruker D8 daVinci instrument with a Bragg Brentano geometry of the "theta-theta" scan type and using a afterloaded holder with zero background silicon chips. The detector used was a linear silicon strip (LynxEYE) PSD detector. The test specimen is placed in a specimen holder of a two-circle goniometer enclosed in a radiation safe housing. The X-ray source is a 2.0kW Cu X-ray tube, and the working current is kept at 40kV and 25 mA. The X-ray optics is a standard Bragg-Brentano secondary focus mode, with X-rays diverging from a DS slit (0.6mm) on the tube to impinge on the sample, and then converging on a position sensitive X-ray detector (Lynx-Eye, Bruker-AXS). The double circle 250mm diameter goniometer was computer controlled by independent stepper motors and optical encoders. The flat compressed powder sample was scanned at a rate of 0.8 ° (2 θ) per minute (2-30 ° 2 θ in 35 minutes). The software suite for data collection and evaluation is Windows (Windows) based. Data was automatically collected using the command program by using the BSML file, and analyzed by the program diffrac.

For example, McCauley, in U.S. patent No. 5,202,295 (e.g., column 27, lines 22-43), describes an XRD test method applied to the calcined clay heteroadducts disclosed herein to determine the spacing of the substrates. The bragg equation or law applied to clay is: n λ is 2d sin θ, where n is the number of repeats, λ is 1.5418, d is the d001 pitch, and θ is the angle of incidence.

Pore volume and pore volume distribution

The pore volume of the clay heteroadduct is reported as the cumulative volume of all pores discernible by the nitrogen desorption method in cc/g (cm) ³ Per gram, cubic centimeter per gram). For catalyst supports or carrier particles such as alumina powders, and for the clays and clay heteroadducts of the present disclosure, the pore size distribution and pore volume are calculated by b.e.t. (or BET) techniques with reference to nitrogen desorption isotherms (assuming cylindrical pores), as described in s.brunauer, p.emmett, and e.teller, journal of the american chemical society, 1939,60, 309; see also ASTM D3037, which defines the procedure for determining surface area using the nitrogen BET method.

Pore Volume distribution is helpful in understanding catalyst performance, and Pore diameters corresponding to dv (log d) and local maxima of Pore size distribution are described, as well as "Pore mode", obtained from Nitrogen adsorption-desorption Isotherms according to The methods described in e.p. barrett, l.g. joyner and p.p. halenda ("BJH") in The calculation of defined i. Nitrogen Isotherms for Pore Volume and Area distribution of Porous materials (The Determination of Pore Volume and Area distribution in pores substations.i. computations from Nitrogen Isotherms). Journal of the national chemical Association, 1951,73(1), pp.373-380.

Surface area of

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

Polymerisation reaction

Homopolymerization of ethylene was performed in a dry 2L stainless steel Parr autoclave reactor using 1L isobutane diluent. Table 3A reports the use of (1-n-butyl-3-methyl-cyclopentadienyl) ₂ ZrCl ₂ And triethylaluminium (AlEt) ₃ ) Performance and polymerization data as comparative support for metallocene and cocatalyst and the heterocoacervated clay support of the invention. The selected pressure in the reactor used to calculate the activities reported in table 3A was 450 total psi, the temperature was 90 ℃, maintained either 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 heteroagglomerated clay supports of the present invention.

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

When hydrogen is used, a premixed 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 change the ratio of ethylene to hydrogen in the reactor feed. The addition of hydrogen will affect the melt index of the polymer obtained with any given catalyst.

Before proceeding with the polymerization batch, the moisture inside the reactor was first removed by preheating the reactor to at least 115 ℃ under a stream of dry nitrogen, which process lasted at least 15 minutes. Stirring is carried out by an impeller and a Magnadrive ^TM The set point is provided, for example, at 600 rpm. The metallocene catalyst used in the polymerization batch of Table 3A was (1-n-butyl-3-methyl-cyclopentadienyl) ₂ ZrCl ₂ And using triethylaluminium (AlEt) ₃ Or TEA) as cocatalyst or alkylating agent, 1.8mmol of AlEt ₃ (3mL of 0.6m TEA in hexane) was typically used for the polymerization batches 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 addition tube or vessel. The reactor contents were then charged to the catalyst addition vessel by flushing with 1L of isobutane. The reactor temperature control system is then turned on to reach 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 the manual feed valve for ethylene and the polymerization batch was run for the time reported in table 3A, e.g. 30 minutes or 60 minutes.

Table 3a. compare the properties and polymerization data of the support and the heterocoacervated clay support of the invention. Use is made of (1-n-butyl-3-methyl-cyclopentadienyl) ₂ ZrCl ₂ And triethylaluminium (AlEt) ₃ ) As the metallocene and cocatalyst, the polymerization was carried out at a reactor pressure of 450psi and a temperature of 90 ℃. ^A

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

Table 3b. compare the surface area and porosity properties of the support and the heteroagglomerated clay supports of the present invention. ^A

^A Abbreviations: NA, unavailable; DVlogDmax 30-40max/DvlogD200-500max, also abbreviated D _VM(30-40) /D _VM(200-500) Is prepared from

And

a maximum value of dV (log D) between and

and

the ratio of the maximum values of dV (log D) in between; and DVlogDmax200-500max/DvlogD60-200max, also abbreviated as D _VM(200-500) /D _VM(60-200) Is prepared from

And

a maximum value of dV (log D) between and

and

the ratio of the maximum values of dV (log D) in between.

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

Catalyst and Polymer characterization

Collecting the metallocene compound at room temperature by placing a 20mg sample of the metallocene in a 10mm NMR tube ¹ H NMR Spectroscopy, to which 3.0mL of CDCl was added ₃ . In Bruker AVANCE ^TM Obtained by 400NMR (400.13MHz) ¹ H NMR spectrum. Chemical shifts are reported in ppm (δ) relative to TMS, or with reference to the chemical shift of the residual solvent proton resonance. Coupling constants are reported in hertz (Hz).

Polypropylene (PP)NMR determination of the isotactic pentad content in olefins was obtained by placing a 400mg sample of the polymer in a 10mm NMR tube, to which 1.7g of tetrachloroethane-d 2 and 1.7g of o-dichlorobenzene were added. ¹³ C NMR spectra at Bruker AVANCE ^TM Obtained at 400NMR (100.61MHz, 90 ℃ pulse, 12 seconds delay between pulses). Each spectrum stored about 5000 transients with mmmm pentad peak (21.09ppm) used as reference. Microstructure analysis was performed as described in Busico et al, Macromolecules (Macromolecules), 1994,27, 4521-.

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

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

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

EXAMPLE 1 comparative example prepared by calcining Clay

Mixing 700mg of the raw powder

The HPM-20 clay sample was 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 yield 620mg of a gray powder. Nitrogen adsorption/desorption BJH pore volume analysis is plotted in fig. 12.

EXAMPLE 2 comparative example of azeotropic Clay preparation

Mixing 5.16g

A sample of HPM-20 clay powder was placed in a round bottom flask and combined with 40mL to 60mL n-butanol. Violent stirringThe mixture was stirred and then evaporated to dryness at 45 ℃ with rotation. This drying step was stopped shortly after significant evaporation of the alcohol. After this process, the odor of the n-butanol of the sample is generally clearly audible. A5.39 g sample of wet clay was obtained, and then 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 and then azeotroped Clay

A133 g sample of 5 wt.% HPM-20/water dispersion was passed over

The blend was prepared by slowly adding HPM-20 clay to deionized water with stirring, initially rotary evaporating at 45-55 ℃ to remove most of the water, followed by the addition of 50mL of n-butanol. The rotary evaporation at 45 ℃ was continued and drying was stopped shortly after significant evaporation of ethanol. A3.2 g sample of this material was then calcined at 300 ℃ for 6 hours to give 2.6g of a grey powder. BJH pore volume analysis of this material is provided in fig. 11.

EXAMPLE 4 preparation of colloidal Clay Dispersion

To the direction of

570g of deionized water were added to the blender and 30.0 g of HPM-20 were added in portions with stirring. This mixture was stirred at a high rate (revolutions per minute, rpm) to give a substantially lump-free or lump-free dispersion, 5 wt.% of HPM-20 suspension. When prepared using 20g HPM-20 and 394g water

4.8 wt.% dispersion of HPM-20 clay and use

The blender was stirred at high rpm to give a non-blocking dispersion characterized by a conductivity of 908 μ S/cm and a pH of 9.39.

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

100g of the colloidal clay dispersion prepared according to example 4 were charged

Blender, followed by the addition of 6.9g of 50% GEO aluminum chlorohydrate solution with stirring, reported to have an alkalinity of 83.47%. After the addition of aluminum chlorohydrate, the mixture was stirred at high speed (rpm) for an additional 3 minutes. The pH of the mixture was measured to be pH 4.23. Attempted by Fisherbrand ^TM The resulting mixture was filtered through a P8 filter paper, but without success. 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 was repeated multiple times (typically 4 to 8 times) until the supernatant of the centrifuged sample reached a conductivity of 67. mu.S/cm and a pH of 6.0. The supernatant was then decanted and the solid was transferred to an erlenmeyer flask with a minimum amount of deionized water along with approximately 70mL of n-butanol. Rotovap 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 preparation of aluminum chlorohydrate (Al) Using aluminum chlorohydrate solution (6.4mmol Al/g clay) ₁₃ Reproducibility of Keggin-ion) -pillared clays

30g of HPM-20 clay was slowly added to a solution containing 570g of deionized Milli-

Of water

While stirring at low speed in a blender, a grey colloidal dispersion is obtained that is free or substantially free of visible lumps or lumps. 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 a 5 wt.% aqueous dispersion of HPM-20 clay。

150g of a portion of this 5 wt.% aqueous dispersion of HPM-20 was transferred to

In the blender, 9.35g of a 50 wt.% aqueous solution of GEO aluminum chlorohydrate was pipetted into a vial and added to the dispersion at once. The mixture was blended at high speed for 5 minutes and then dispensed into four 50mL centrifuge tubes and centrifuged at 3000rpm to 3500rpm for 30 minutes to 60 minutes. The pH and conductivity of the supernatant was measured (Eutech pcststr 35). The supernatant was decanted and the remaining wet solids were resuspended in deionized Milli-

In water. The centrifugation process (centrifugation, measurement of the pH/conductivity of the supernatant, removal of the supernatant, resuspension in deionized Milli-

Water) until the conductivity of the supernatant reached 100. mu.S/cm to 300. mu.S/cm. A total of six centrifugations were performed, at which time the supernatant was discarded the last time. To the remaining wet solid, 200mL of 1-butanol was added, 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) Using powdered aluminum chlorohydrate (6.4mg Al/g clay) ₁₃ Comparative examples of Keggin-ion) -pillared clays

A30 g sample of HPM-20 clay was slowly added to a sample containing 570g of deionized Milli-

Of water

In a blender with low agitation, a gray colloidal dispersion is obtained that is free or substantially free of visible lumps or lumps. After the addition is completed, the mixture is divided intoThe dispersions were blended at high speed for 5 minutes to 10 minutes to give a slightly viscous mixture of a 5 wt.% aqueous dispersion of HPM-20 clay.

A100 g sample of this 5 wt.% HPM-20 aqueous dispersion was transferred to

In the blender, 3.42g of Parchem were weighed

51P powder into vials with 35g to 40g of deionized Milli-

Diluted with water and then added to the dispersion all at once. The mixture was blended at high speed for 5 minutes, then dispensed into four 50mL centrifuge tubes and centrifuged at 3000rpm to 3500rpm for 30 minutes to 60 minutes. The pH and conductivity of the supernatant was measured (Eutech pcststr 35). The supernatant was decanted and the remaining wet solids were resuspended in deionized Milli-

Water) until the conductivity of the supernatant reached 100 to 300. mu.S/cm (six centrifugations in total, final supernatant pH 4.25, conductivity 225. mu.S/cm), at which time the supernatant was discarded the 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. A1.8 g portion 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 colloidal Clay content in HPM-20 aqueous Dispersion

A60 g sample of a 5 wt.% dispersion of HPM-20 clay in water was mixed with 240g Milli-

Deionized water was combined to give 300g of a 1 wt.% HPM-20 aqueous dispersion. After standing for some 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 process yielded 900mg of collected HPM-20 clay, corresponding to a colloidal 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, and the resulting diluted dispersions had colloidal content values of 0.77 wt.% and 0.69 wt.%.

Example 9 aluminum chlorohydrate in Clay heteroadduct

Zeta potential determination of the HPM-20 ratio

30g of HPM-20 clay was slowly added to a solution containing 570g of Milli-

Of deionized water

In the blender, a grey colloidal dispersion free or substantially free of visible lumps or lumps was obtained. After the addition was complete, the dispersion was stirred at high speed for 5 to 10 minutes to give a slightly viscous mixture of a 5 wt.% aqueous dispersion of HPM-20 clay. 42g of a portion of this 5 wt.% HPM-20 aqueous dispersion were mixed with 258g Milli-

Deionized water was combined to give a 0.7 wt.% HPM-20 aqueous dispersion. Then, 280g of this 0.7 wt.% Colloidal dispersion was transferred to a Colloidal dynamic Zetaprobe Analyzer containing an axial bottom stirrer ^TM In the measuring vessel of (2). The stirring speed was set at 250rpm and 35Between 0 rpm.

According to the colloid dynamics Zetaprobe Analyzer attached to the instrument ^TM The procedure outlined in the manual, zeta potential measurements were performed on the diluted HPM-20 aqueous dispersion using an initial colloid content estimate of 0.7 wt.% to determine the actual colloid content of the clay dispersion. The 5 wt.% HPM-20 aqueous dispersion was measured to give a zeta potential measurement of-46 mV (minus 46 millivolts). The initial colloid content estimate was adjusted to match this zeta potential. In this case, the HPM-20 colloidal content of the dispersion was determined to be 0.62%. The colloid dynamic zetaprobe measurement parameters were as follows: 5 readings at a rate of 1 reading/minute; the particle density was 2.6 g/cc; the dielectric constant was 4.5.

By diluting the 50 wt.% aluminum chlorohydrate solution (GEO), a 2.5 wt.% aqueous solution of Aluminum Chlorohydrate (ACH) was obtained. This 2.5 wt.% ACH solution was then volumetric titrated into 0.7 wt.% HPM-20 aqueous dispersion. Titration was set at 0.5mL per titration point and equilibration was delayed for 30 seconds, that is, after addition of 0.5mL of aqueous ACH solution, 30 seconds was delayed before zeta potential measurement to allow equilibration.

Fig. 3 and table 4 report zeta potential titration results of 2.5 wt.% Aluminum Chlorohydrate (ACH) in water added to 0.7 wt.% HPM-20 in water, plotted as a function of measured zeta potential and titrant volume (mL). The titrant volume represents the cumulative volume of the aqueous solution of aluminium chlorohydrate added. The ACH molar aluminum/clay mass ratio for achieving-20 mV, neutral and +20mV zeta potentials is summarized in table 4 based on the amount of ACH solution and the measured density of the ACH solution of 1.075 g/mL.

TABLE 4 addition of ACH to

Zeta potential titration results of HPM-20 aqueous dispersions

EXAMPLE 10 polyaluminum chloride in Clay heteroadducts

290/

Zeta potential determination of HPM-20 ratio

30g of HPM-20 clay was slowly added to a solution containing 570g of Milli-

Of deionized water

In a blender with low agitation, a gray colloidal dispersion is obtained that is free or substantially free of visible lumps or lumps. 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 a 5 wt.% aqueous dispersion of HPM-20 clay.

60g portions of this 5 wt.% HPM-20 aqueous dispersion were mixed with 240g Milli-

Deionized water was combined to give a 1 wt.% HPM-20 aqueous dispersion. Approximately 280g of this 1 wt.% Colloidal dispersion was transferred to a Colloidal dynamic Zetaprobe Analyzer containing an axial bottom stirrer ^TM In the measuring vessel of (2). The stirring speed was set as described above.

Zeta potential measurements were made on this diluted HPM-20 aqueous dispersion using an initial colloid content estimate of 1 wt.% to determine the actual colloid content of the clay dispersion. The 5 wt.% HPM-20 aqueous 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%. The colloid dynamic zetaprobe measurement parameters were as follows: 5 readings at a rate of 1 reading/minute; the particle density was 2.6 g/cc; the dielectric constant was 4.5.

Use of Milli-

Deionized Water 4.58g of polyaluminum chloride (abbreviated as "PAC") was sampledArticle (A)

290(Al ₂ O ₃ Content 17.1%) into a 100mL volumetric flask. Then this 4.58wt. -%)

The 290 volume of solution was titrated into the 1 wt.% HPM-20 clay dispersion described above. Titration was set at 1mL per titration point and equilibration delayed for 30 seconds.

Fig. 5 and table 5 report these zeta potential measurements, where titrant volume represents 4.58 wt.% aqueous added

290, and plotting the measured zeta potential against titrant volume (mL). Table 5 summarizes the zeta potentials used to achieve-20 mV, neutrality and +20mV

290 amount of dispersion.

TABLE 5. will

290 to be added to

Results of zeta potential titration of HPM-20 aqueous dispersions

EXAMPLE 11 Clay heteroadducts

AL27 colloidal alumina-

Zeta potential determination of HPM-20 ratio

By mixing about 60g5 wt.% HPM-20 aqueous Clay Dispersion to 240g of Milli-

In water, a 1 wt.% HPM-20 clay dispersion was prepared. A portion of 285g to 300g of the 1 wt.% dispersion was transferred to a measurement vessel of a Zetaprobe and an initial zeta potential measurement was made to estimate the true particle wt.% of the solution.

Zeta potential measurements were made on this diluted HPM-20 aqueous dispersion to determine the actual colloidal content of the clay dispersion. The 5 wt.% HPM-20 aqueous dispersion was measured, yielding 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%. The colloid dynamic zetaprobe measurement parameters were as follows: 5 readings at a rate of 1 reading/minute; the particle density was 2.6 g/cc; the dielectric constant was 4.5.

Will be sold on the market

AL27 colloidal alumina dispersion (20 wt.% AL) ₂ O ₃ ) 100g of sample and 100g of Milli-

Combining with deionized water to obtain

10 wt.% Al of AL27 ₂ O ₃ A dispersion. This 10 wt.% dispersion capacity was then titrated into the 1 wt.% HPM-20 clay dispersion described above. (the concentration designation of 1 wt.% HPM-20 is based on the formulation, not an estimate of zeta potential, which was determined to be about 0.92 wt.%, since not all clays were colloidal upon dilution.) the titration settings were as follows: from 0mL to 27mL, 1mL per titration point followed by 3mL per titration point, equilibration was delayed for 60 seconds.

These measurements are reported in FIG. 6 and Table 6, where the titrant volume represents the addition

Cumulative volume of AL27 alumina dispersion. In this example, the titrant is also a colloidal substance. The zeta potential was adjusted using the method described previously to provide the data in fig. 6. . For achieving zeta potentials of-20 mV, neutral and +20mV

The amounts of AL27 dispersions are summarized in table 6.

TABLE 6. will

AL27 colloidal alumina to

Results of zeta potential titration in HPM-20

EXAMPLE 12 preparation of aluminum chlorohydrate Clay heteroadduct (1.76mmol Al/g clay)

In that

475.22 grams of deionized water was added to the blender. 25.09 grams of HPM-20 clay from colloid company, USA, was slowly added with stirring. After the clay addition was complete, the mixture was stirred at high speed for 5 minutes to give a homogeneous suspension without lumps, after which 9.53 g of a 50 wt.% aqueous solution of aluminum chlorohydrate were added with stirring and stirring was continued for 9 minutes. The mixture was poured into a high density polyethylene bottle. 42.5 g deionized Milli-

Washing with water

The flask and the rinse water was transferred to the bottle. The flask was shaken to thoroughly mix the contents and the conductivity of the slurry was measured to be 4.03mS/cm and the pH was measured to be 5.89.

Use 380.26 gDeionization Milli-

A second batch of aluminum chlorohydrate clay heteroadduct (GEO) was prepared in the same manner with water, 20.03 grams of HPM-20 clay, and 7.70 grams of aluminum chlorohydrate 50 wt.% aqueous solution. The batch was measured to have a conductivity of 3.64mS/cm and a pH of 5.58. The contents of the second batch were transferred to a bottle containing the contents of the first batch, along with 30 grams of deionized water, to transfer the remaining slurry. The bottle 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 preparation of a comparative example of a Clay heteroadduct of aluminum sesquichlorohydrate Using powdered aluminum sesquichlorohydrate (ASCH, 6.4mmol Al/g clay)

In this comparative example, the aluminum chlorhydrol clay heteroadduct was synthesized using powdered aluminum chlorhydrol (ASCH), indicating that multiple washes and centrifuges were required to separate the product compared to the procedures and products of examples 31 and 32.

Of water

In a blender with low agitation, a gray colloidal dispersion is obtained that is free or substantially free of visible lumps or lumps. After the addition was complete, the dispersion was blended at high speed for 5 to 10 minutes to give a slightly viscous mixture of a 5 wt.% aqueous dispersion of HPM-20 clay.

100g portions of this 5 wt.% HPM-20 clay aqueous dispersion were transferred to

In a blender. To a separate vial was added 3.53g

31P powder and 35-40 mL deionized Milli-

Water and this mixture is poured into the stirred dispersion in one portion. The mixture was blended at high speed for 5 minutes and then dispensed into four 50mL centrifuge tubes and centrifuged at 3000 to 3500rpm for 30 to 60 minutes. The pH and conductivity of the supernatant (Eutech PCSTestr 35) was measured at pH 4.0 and conductivity 7300. mu.S/cm. The supernatant was decanted and the remaining wet solids were resuspended in deionized Milli-

Water) until the conductivity of the supernatant reached 100. mu.S/cm to 300. mu.S/cm. Six centrifugation runs were performed in total to achieve this conductivity, and the final supernatant pH was found to be 4.3 and the conductivity was found to be 286. mu.S/cm. At this point, the supernatant was discarded for the last time, and 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 aluminum chlorohydrate clay heteroadduct retained on a 325 mesh screen (1.76mmol Al/g clay)

A portion of the aluminum chlorohydrate clay heteroadduct (1.76mmol 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 heteroadduct was sieved through a 325 mesh screen. Two grams of the material retained on the 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 aluminum chlorohydrate clay heteroadduct (1.76mmol Al/g clay) on a 325 mesh screen

A portion of the aluminum chlorohydrate clay heteroadduct (1.76mmol 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 heteroadduct was sieved through a 325 mesh sieve. Two grams of the sieve-through material was charged into an oven at 300 ℃ 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 calcining washed aluminum chlorohydrate clay heteroadduct (1.76mmol Al/g clay)

Passing through Fisherbrand using Buchner funnel and vacuum ^TM A portion of the aluminum chlorohydrate clay heteroadduct (1.76mmol Al/g clay) slurry prepared according to example 12 was filtered through a P8 filter paper. 158g of the filter cake was then transferred to an HDPE bottle and resuspended in about 1.2L of deionized water by shaking. The thus-obtained slurry had an electric conductivity of 114. mu.S/cm and a pH of 6.25. The slurry was again passed through a Fisherbrand ^TM The P8 filter paper was filtered and left on the filter under vacuum overnight to give 109.03 g of a gray solid. An 97.07 gram sample of this solid was charged into an HDPE bottle along with 452 grams of deionized water and shaken until no lumps were visible in the slurry. The slurry had a conductivity of 112. mu.S/cm and a pH of 6.33. A portion of this aluminum chlorohydrate clay heteroadduct slurry was spray dried using a Buchi B290 laboratory spray dryer. A 1.77 gram sample of the spray dried material was loaded into a 300 ℃ oven and calcined in air for 6 hours. While hot, the material was then transferred to a vacuum chamber and cooled to room temperature under vacuum.

EXAMPLE 17 Single filtration, azeotropic and calcination of aluminum chlorohydrate Clay heteroadduct (1.76mmol Al/g clay)

By Fisherbrand ^TM A slurry of aluminum chlorohydrate clay heteroadduct (1.76mmol Al/g clay) prepared according to example 12, 543g, was vacuum filtered through a filter paper designated P8. 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. Then passing through Fisherbrand ^TM The slurry was vacuum filtered through paper brand P8,11.5 g of the filter cake from the clay heteroadduct retained on the filter paper was charged to an erlenmeyer flask equipped with a stir bar. 200mL of n-butanol are then added and the mixture is stirred until a slurry with no visible lumps or lumps is obtained. The stir bar was removed and the erlenmeyer flask was rotary evaporated in a 45 ℃ bath. The off-white powder containing 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 material was transferred into an inert atmosphere glove box.

EXAMPLE 18 reproducibility of Single filtration, azeotropic and calcination of aluminum chlorohydrate Clay heteroadduct according to example 17 (1.76mmol Al/g clay)

Of water

This 5 wt.% aqueous dispersion of 100g of a portion of HPM-20 clay was transferred to

In the blender, 1.91g of a 50 wt.% aqueous solution of GEO aluminum chlorohydrate was pipetted into a vial and added to the dispersion in one portion. The mixture was rapidly coagulated and 70mL of deionized Milli-

Water to facilitate stirring. 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 pcsttes)tr 35), giving a pH of 6.1 and a conductivity of 1516. mu.S/cm. The filtrate was discarded and the remaining wet solids were resuspended in 50mL to 100mL deionized Milli-

In water.

The filtration process was repeated again (suspension of wet solids in deionised Milli-

Water, vacuum filtration, filtrate pH/conductivity measurement). The remaining wet solids were resuspended in 150mL to 200mL of 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. A1.90 g portion 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 (0.3mmol Al/g Clay)

Of water

While stirring at low speed in a blender, a grey colloidal dispersion is obtained that is free or substantially free of visible lumps or lumps. After the addition was complete, the dispersion was blended at high speed for 5 to 10 minutes to give a slightly viscous mixture of a 5 wt.% aqueous dispersion of HPM-20 clay.

100g portions of this 5 wt.% HPM-20 clay aqueous dispersion were transferred to

In a blender. A sample of 0.325g of aqueous GEO ACH dispersion (50 wt.%) was pipetted into a vial and mixed with 20mL of deionized Milli-

The water was combined and then poured into the clay dispersion all at once. The resulting mixture was then blended at high speed for 5 minutes and then vacuum filtered through a Fisher P8 qualitative grade filter paper (coarse porosity). Filtration is slow (<1 drop/second). After allowing a filtration process of 15 to 30 minutes, the pH and conductivity of the filtrate (Eutech pcststr 35) were measured, giving a pH of 7.3 and a conductivity of 487 μ S/cm. The filtrate was discarded and the remaining wet solids were resuspended in 50mL of deionized Milli-

In water, and centrifuged once at 3000rpm to 3500rpm for 30 minutes to 60 minutes. After removal of the supernatant (conductivity measured as 180. mu.S/cm), the remaining wet solids were resuspended in 50mL to 100mL of 1-butanol and rotary evaporated at 45 ℃. The resulting solid was then ground with a pestle and mortar, and 1.7g of the ground solid was then 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 heteroadduct (1.17mmol Al/g clay)

Under stirring, 30g of the mixture is added in 1 to 2 minutes

HPM-20 clay was slowly added to a solution containing 570g of deionized Milli-

Of water

100g portions of this 5 wt.% HPM-20 clay aqueous dispersion were transferred to

In a blender. Then, 1.27g of a 50 wt.% aqueous solution of GEO aluminum chlorohydrate was pipetted into a vial and added to the dispersion in one portion. The mixture was rapidly coagulated and 70mL of deionized Milli-

Water to facilitate stirring. 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 (Eutech PCSTTestr 35) were measured, giving a pH of 6.25 and a conductivity of 1166. mu.S/cm. The filtrate was discarded and the remaining wet solids were resuspended in 50mL to 100mL deionized Milli-

In water.

The filtration process was repeated (suspension of wet solids in deionised Milli-

Water, vacuum filtration, filtrate pH/conductivity measurement) until the conductivity of the resuspended slurry reaches 100 to 300 μ S/cm. In this case, an additional filtration was performed to obtain a slurry with pH 6.2 and conductivity 188. mu.S/cm. The remaining wet solids were resuspended in 150mL to 200mL of 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. A1.7 g portion 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 FIG. 2.

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

Under stirring, 30g of the mixture is added in 1 to 2 minutes

HPM-20 clay was slowly added to a solution containing 570g of deionized Milli-

Of water

100g portions of this 5 wt.% HPM-20 clay aqueous dispersion were transferred to

In a blender. A 1.66g sample of a 50 wt.% aqueous solution of GEO aluminum chlorohydrate was pipetted into a vial and added to the dispersion in one portion. The resulting mixture was rapidly condensed and 80mL of deionized Milli-

Water to facilitate stirring. This 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 (Eutech PCSTest 35) were measured, giving a pH of 6.2 and a conductivity of 1518. mu.S/cm. The filtrate was discarded and the remaining wet solids were resuspended in 50mL to 100mL deionized Milli-

In water.

This filtration process was repeated (suspension of wet solids in deionised Milli-

Water, vacuum filtration, measurement of filtrate pH/conductivity) until the conductivity of the resuspended slurry reaches 100 to 300 μ S/cm. In this case, one additional filtration was performed to obtain a slurry having a pH of 6.1 and an electrical conductivity of 199. mu.S/cm. The remaining wet solids were resuspended in 150mL to 200mL of 1-butanol and rotary evaporated at 45 ℃. The resulting solid was then ground with a pestle and mortar,3.19g of a pale gray powder are obtained. 1.65g of this solid sample was transferred to a ceramic crucible and calcined at 300 ℃ for 6 hours to obtain 0.9g of a gray black powder. The powder XRD pattern of this sample is shown in fig. 2.

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

Of water

In a blender. A 2.71g sample of a 50 wt.% aqueous solution of GEO aluminum chlorohydrate was pipetted into a vial and added to the dispersion in one portion. The mixture quickly became viscous and 100mL of deionized Milli-

Water to facilitate stirring. This 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 PCSTest 35) to give a pH of 4.72 and a conductivity of 1988. mu.S/cm. A portion of the wet solid cake was resuspended in 50mL to 100mL of 1-butanol and rotary evaporated at 45 ℃. The dry solid was then ground with a pestle and mortar to give 0.66g of a light gray powder. A0.64 g portion 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 with additional washing/filtration compared to example 22(2.5mmol Al/g Clay)

Of water

Water to facilitate stirring. The mixture was then blended at high speed for 5 minutes and then vacuum filtered through a 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 pcsttetr 35). The filtrate was discarded and the remaining wet solids were resuspended in 50mL to 100mL deionized Milli-

In water.

Water, vacuum filtration, measurement of filtrate pH/conductivity) until the re-suspended slurryThe conductivity of (a) is 100 to 300. mu.S/cm. In this case, one additional filtration was performed to obtain a slurry having a pH of 4.67 and an electrical conductivity of 87. mu.S/cm. The remaining wet solids were resuspended in 50mL to 100mL of 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. A1.37 g portion 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 fig. 2.

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

Of water

In a blender. A3.80 g GEO aluminum chlorohydrate sample of 50 wt.% in water was pipetted into a vial and added to the dispersion in one portion, and 20mL deionized Milli-

Water to facilitate stirring. This 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 PCSTTest 35) to give a pH of 4.34 and a conductivity of 1500. mu.S/cm. Resuspending a portion of the wet solids in 50mL to 100mL of 1-butanolAnd rotary evaporated at 45 ℃. The dry solid was then ground with a pestle and mortar to give 0.74g of a light gray powder. A0.62 g portion 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 with additional washing/filtration compared to example 24(3.5mmol Al/g Clay)

Of water

100g of this 5 wt.% aqueous dispersion of a portion of HPM-20 clay was transferred to

In a blender. A 3.80g sample of a 50 wt.% aqueous solution of GEO aluminum chlorohydrate was pipetted into a vial and added to the dispersion in one portion. The mixture quickly became viscous and 20mL of deionized Milli-

Water to facilitate stirring. 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 pcsttetr 35). The filtrate was discarded and the remaining wet solids were resuspended in 50mL to 100mL deionized Milli-

In water.

Repeating the filtration process (to solidifySuspension in deionized Milli-

Water, vacuum filtration, measurement of filtrate pH/conductivity) until the conductivity of the resuspended slurry reaches 100 to 300 μ S/cm. In this case, one additional filtration was performed to obtain a slurry having a pH of 4.5 and an electrical conductivity of 180. mu.S/cm. The remaining slurry was resuspended in 50mL to 100mL of 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. A1.36 g portion 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 fig. 2.

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

30g of HPM-20 clay was slowly added to the solution containing 570g of deionized Milli-

Of water

In a blender. To a separate vial was added 0.160g

51P powder and 20mL deionized Milli-

And (3) water.This mixture was poured into the stirred dispersion in one portion and 40mL of deionized Milli-

Water to facilitate stirring. The mixture was then blended at high speed for 5 minutes and then passed through a Fisherbrand ^TM P8 qualitative grade filter paper (coarse porosity) was vacuum filtered. Filtration is slow (<1 drop/second). After allowing to filter for 15 to 30 minutes, the pH and conductivity of the filtrate (Eutech PCSTest 35) were measured, giving 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 centrifuged once at 3000rpm to 3500rpm for 30 minutes to 60 minutes. After removal of the supernatant (conductivity 180. mu.S/cm), the remaining wet solids were resuspended in 50mL to 100mL of 1-butanol and rotary evaporated. The resulting solid was then ground with a pestle and mortar and then transferred to a ceramic crucible and calcined at 300 ℃ for 6 hours to give a gray black powder.

EXAMPLE 27 comparative example to prepare Aluminum Chlorohydrate (ACH) -clay heteroadduct using powdered ACH reagent (0.6mmol Al/g clay)

Of water

In a blender. To a separate vial was added 0.4g

51P powder and 20mL deionized Milli-

And (3) water. This mixture was poured into the stirred dispersion all at once. Adding 40mL of deionized Milli-

Water to facilitate stirring. 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 PCSTTest 35) 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 centrifuged once at 3000rpm to 3500rpm for 30 minutes to 60 minutes. After removal of the supernatant (conductivity 180. mu.S/cm), the remaining wet solids were resuspended in 50mL to 100mL of 1-butanol and rotary evaporated at 45 ℃. The resulting solid was then ground with a pestle and mortar to give 2g of a 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 heteroadduct using powdered ACH reagent in comparison to example 29(1.52mmol Al/g Clay)

Of water

In a blender while stirring at low speed to obtain a blend free or substantially free of visible lumps or lumpsA grey colloidal dispersion. After the addition was complete, the dispersion was blended at high speed for 5 to 10 minutes to give a slightly viscous mixture of a 5 wt.% aqueous dispersion of HPM-20 clay.

In a blender. To a separate vial was added 0.812g

51P powder and 20mL deionized Milli-

And (3) water. This mixture was poured into the stirred dispersion all at once. Adding 20-40mL of deionized Milli-

Water to facilitate stirring. 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 pcsttetr 35). Resuspending the remaining wet solids in 50mL to 100mL deionized Milli-

In water.

Water, vacuum filtration, measurement of filtrate pH/conductivity) until the conductivity of the supernatant reached 100 to 300 μ S/cm. In this case, filtration was performed twice to give 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 of 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 heteroadduct using powdered ACH reagent in comparison to example 28(1.52mmol Al/g Clay)

Of water

In a blender. To a separate vial was added 0.812g

51P powder and 20mL deionized Milli-

And (3) water. This mixture was poured into the stirred dispersion in one portion and 20-40mL of deionized Milli-

Water to facilitate stirring. The resulting mixture was then blended at high speed for 5 minutes and then passed through a Fisher ^TM Qualitative grade P8 filter paper for vacuum filtration. After allowing to filter for 15 to 30 minutes, the pH and conductivity of the filtrate were measured (Eutech PCSTTest 35) 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 of 1-butanol and rotary evaporated at 45 ℃. The solid was then ground with a pestle and mortar to give 1g of a grey powder, which was then transferred toIn a ceramic crucible and calcined at 300 ℃ for 6 hours, 0.6g of a gray black powder was obtained.

EXAMPLE 30 preparation of Aluminum Chlorohydrate (ACH) -clay heteroadduct using powdered ACH reagent (1.76mmol Al/g clay)

Of water

In a blender. To a separate vial was added 0.940g

51P powder and 20mL deionized Milli-

And (3) water. This mixture was poured into the stirred dispersion all at once. Adding 20mL to 40mL of deionized Milli-

Water to facilitate stirring. The mixture was then blended at high speed for 5 minutes and passed through a Fisherbrand machine ^TM Qualitative grade P8 filter paper vacuum filtered and treated with 100mL deionized Milli-

And (4) washing with water. After allowing to filter for 15 to 30 minutes, the pH and conductivity of the filtrate were measured (Eutech PCSTTestr 35) to give 6.1pH and conductivity of 1799. mu.S/cm. A portion of the remaining wet solid was resuspended in 50mL to 100mL of 1-butanol and rotary evaporated at 45 ℃. The solid was then ground with a pestle and mortar to give 1.07g of a gray powder, which was then transferred to a ceramic crucible and calcined at 300 ℃ for 6 hours to give 0.9g of a gray black powder.

EXAMPLE 31 preparation of aluminum sesquichlorohydrate-Clay heteroadduct (1.52mmol Al/g clay)

Of water

In a blender. Weigh 1.30g

31L of the solution sample, placed in a vial and mixed with enough deionized Milli-

Water is added to the dispersion together to facilitate stirring. The mixture was then blended at high speed for 5 minutes and the conductivity measured (Eutech PCSTst 35) to give a conductivity of 2600. mu.S/cm. Then passing through Fisherbrand ^TM P8 qualitative grade filter paper vacuum filter mixture, and use 100mL deionization Milli-

And (5) simply washing with water. Allow forAfter filtration for 15 to 30 minutes, a portion of the remaining wet solids was resuspended in 50 to 100mL of water and the conductivity was again measured, typically in the range of 100 to 500. mu.S/cm (in this case, 70. mu.S/cm). The suspension is then combined with 100 to 200mL of 1-butanol and rotary evaporated at 45 ℃. The solid was then ground with a pestle and mortar to give 6.2g of a 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 a gray black powder.

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

Of water

In a blender. Weigh 2.79g

Water is added to the dispersion together to facilitate stirring. The mixture was then blended at high speed for 5 minutes and the conductivity measured (Eutech PCSTstr 35) to give a conductivity of 2800. mu.S/cm. Then passing through Fisherbrand ^TM P8 qualitative grade filter paper vacuum filtrationThe mixture was combined with 100mL of deionized Milli-

And (5) simply washing with water. After allowing to filter for 15 to 30 minutes, a portion of the remaining wet solids was resuspended in 50 to 100mL of water and the conductivity (320. mu.S/cm) was again measured, typically between 100 to 500. mu.S/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 a 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 a gray black powder.

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

5.0 wt.% prepared according to the procedure in example 4

177.28 g of a HPM-20 suspension were sampled and loaded

In a blender. Under stirring, add 1.32g

The 290 solution (GEO) was added to the HPM-20 clay slurry, which was then stirred at high speed for 9 minutes. The gray heteroadduct sticky mass was then transferred in 2 portions to HDPE polyethylene bottles with 210g of deionized water. 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. By Fisherbrand ^TM The slurry was filtered through a P8 coarse filter paper to give 28.03g of a wet filter cake, which was transferred to a HDPE bottle, to which 308g of deionized water was also added. The bottle was shaken to make the slurry free of lumps, pH 4.76, and conductivity 200. mu.S/cm. Passing said slurry through a Fisherbrand ^TM The filter paper P8 was filtered to give 22.30g of a wet cake which was transferred to an Erlenmeyer flask equipped with a stir bar along with 200mL of n-butanol and stirred until no lumps were visible. Removing the stirring rod, and mixingRotary evaporation in a 45 ℃ bath yielded 9.49g of an off-white powder which was lightly ground to a fine powder using a mortar and pestle. 1.10 g of the off-white powder was charged into a ceramic crucible, which was then charged into an oven at 300 ℃ and calcined for 6 hours, yielding 0.8960g of a dark gray powder. This 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 heteroadduct (1.01mmol Al/g Clay)

A sample of 201.23 g of a 5.0 wt.% HPM-20 clay suspension as prepared in example 4 was charged

In a blender. Under stirring, 3.036g

290 solution (GEO) was added to the HPM-20 slurry. The obtained paste cannot be used

The blender was stirred but transferred to a HDPE bottle, double ground with deionized water, and a total of 185g of the bottle was shaken by hand until no lumps or lumps were visible. The pH of the resulting slurry was 3.8 and the conductivity was 26 mS/cm. Said slurry is passed through a Fisherbrand ^TM Coarse filter paper No. 8 filtration, the conductivity of the clear filtrate was 5.2 mS/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 resulting conductivity was 1116. mu.S/cm, and the pH was 3.93. Then passing through Fisherbrand ^TM The slurry was filtered through a P8 filter paper. The conductivity of the clear filtrate was 1200. mu.S/cm. A9.95 g sample of the filter cake was transferred to an Erlenmeyer flask. The remaining filter cake was resuspended in a fresh HDPE bottle in 281g of deionized water while shaking, resulting in a slurry with a pH of 4.11 and a conductivity of 150. mu.S/cm. After standing overnight, the mixture was passed through Fisherbrand ^TM The slurry was filtered through a P8 filter paper and 18.25g of the filter cake was transferred to a conical flask along with 100mL of n-butanol. The flask was shaken to break up the chunks, which were then rotary evaporated in a 40 ℃ bath to give 9.08g of an off-white powderAnd (3) grinding. A sample of 2.384g of off-white powder was loaded into a ceramic crucible and placed in an oven at 300 ℃ for 6 hours to give 1.72g of 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 (1.46mmol Al/g Clay)

199.31g of a 5.0 wt.% HPM-20 clay suspension prepared according to example 4 was loaded with a sample

In a blender. 4.36g of a product from GEO Specialty Chemicals were mixed under stirring

290 solution is added to the HPM-20 clay slurry. The flask was removed from the stirrer and swirled until the viscous gray mass 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 deionized water totaling 85g to give a total of 275g of gray heteroadduct slurry, which was then shaken by hand for about 1 minute to give a slurry with a pH of 3.73 and a conductivity of 6.79 mS/cm. By Fisherbrand ^TM The P8 coarse filter paper filtered the slurry, and the filter cake was then resuspended in approximately 200mL of deionized water to give a slurry with a conductivity of 1 mS/cm. The slurry was filtered and 34g of a portion of the filter 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 stir 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 to an inert atmosphere glove box.

EXAMPLE 36 preparation of Nano alumina Clay-heteroadduct (0.49g alumina/g clay, 4.8mmol Al/g clay)

With stirring, 30g of HPM-20 are bound in 1 to 2 minutesSoil was slowly added to the solution containing 570g of deionized Milli-

Of water

Then 80g of a 5 wt.% colloidal suspension of HPM-20 clay was added to the calibrated addition funnel. 9.7g of

AL-27 Dispersion (20% Al) ₂ O ₃ ) Add to a separate addition funnel and dilute the suspension to 80mL volume level. The solution was added simultaneously to a solution containing 137g of Milli-

Of water

In a blender. The resulting mixture was then blended at high speed for approximately 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 PCSTstr 35) were measured, giving a pH of 9.1 and a conductivity of 451. mu.S/cm. A portion of the remaining wet solid was resuspended in 50mL to 100mL of 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, and 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 a novel cationic colloidal multimetal salt system that can be used as a heterocoagulation reagent such that when contacted with a colloidal clay, a heterocoagulation clay can be formed.

In a beaker 15g

200 fumed silica sample with 277g deionized Milli-

And (4) mixing water. Use of ULTRA-

The dispersion tool dispersed the mixture at 5400rpm for 10 minutes and further redispersed at 7000rpm for 5 minutes, resulting in a 5 wt.% (calculated as silica) dispersion. 270g of this dispersion were transferred to a colloid dynamic Zetaprobe Analyzer ^TM The measuring vessel of (1), which vessel comprises an axial bottom stirrer. The stirring speed was 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 usually set between 250rpm and 350rpm, most often at 300 rpm.

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. Then proceed to add this 2.5 wt.% ACH solution to the aforementioned 5 wt.%

Volumetric zeta potential titration of 200 dispersions. Titration was set at 1mL per titration point and equilibration delayed for 60 seconds. The resulting data are depicted in FIG. 7ACH-

200。

The comparison of zeta potential to titrant volume data in FIG. 7 was converted to zeta potential and

a comparison of 200 fumed silica masses is plotted in fig. 8. From FIG. 8, an arbitrary point is selected, the ratio of which is higher than 0.04g ACH/g

200, corresponding to a zeta potential of about +30mV and below about the monolayer ratio, to prepare a heterocoacervation reagent. The ratio of heterocoagulation reagent to clay was then determined in a conventional manner as described in examples 8 to 11, specifically by titration with the zeta potential of the clay and this ACH-fumed silica heterocoagulation reagent.

Example 38 zeta potential titration of Clay with ACH-fumed silica, and ACH-SiO ₂ Determination of the Clay ratio

15g of the mixture

200 fumed silica sample with 277g deionized Milli-

The water is combined in a beaker. Use of ULTRA-

The dispersing means disperses the mixture at 6000rpm to 7000rpm for 10 minutes, after which 7.86g of GEO Aluminum Chlorohydrate (ACH) solution are added. This mixture was then redispersed at 7000rpm for 5 minutes to give 5 wt.% (based on silica) ACH-

200 fumed silica dispersion.

Separately, 30g of HPM-20 clay was slowly added over a period of 1 to 2 minutes to a solution containing 570g of deionized Milli-

Of water

In a blender, while stirring at a low speed, to obtain a free or substantially free ofA gray colloidal dispersion containing visible lumps or agglomerates. After the addition was complete, the dispersion was stirred at high speed for 5 to 10 minutes to give a slightly viscous mixture of a 5 wt.% aqueous dispersion of volcalay.

A60 g sample of this 5 wt.% HPM-20 aqueous dispersion was mixed with 240g of deionized Milli-

Water was combined and shaken to give a 1 wt.% HPM-20 aqueous dispersion. Approximately 280g of this Colloidal dispersion was transferred to a Colloidal dynamic Zetaprobe Analyzer containing an axial bottom stirrer ^TM In the measuring vessel of (2). The stirring speed was set as described above. According to Zetaprobe Analyzer ^TM The manual, zeta potential measurements were performed on the diluted HPM-20/water dispersion to determine the actual colloidal content of the clay dispersion. The 5 wt.% HPM-20 aqueous 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%. The colloid dynamic zetaprobe measurement parameters were as follows: 5 readings at a rate of 1 reading/minute; the particle density was 2.6 g/cc; the dielectric constant was 4.5.

Then proceeding ACH-

Volumetric titration of 200 fumed silica dispersion added to clay dispersion. Titration was set from 0 to 1.2mL, 0.2mL per titration point, and 0.5mL per titration point up, with a 30 second delay in equilibration, to provide 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 previously described in example 11 to obtain the graph in fig. 9. Thus, ACH-

AEROSIL in 200 fumed silica Dispersion

The amount of fumed silica is summarized inIn table 7.

Table 7.

Results of zeta potential titration of 200 and ACH compared to HPM-20

EXAMPLE 39 preparation of ACH-aerosil/clay heteroadduct (3.31mmol Al/g clay)

15g of the mixture

200 fumed silica sample with 277g deionized Milli-

The water was combined in a beaker and ULTRA-

The dispersion tool dispersed the mixture at 6000-. A sample of 7.86g GEO aluminum chlorohydrate solution was then added, followed by redispersion at 7000rpm for 5 minutes.

Of water

57mL of

200 Dispersion sample packInto a graduated addition funnel and 80g of hpm-20 clay dispersion was transferred to a separate graduated addition funnel. While stirring

135g deionised Milli-

The 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 passed through a Fisherbrand mixer ^TM Qualitative grade P8 filter paper for vacuum filtration. After allowing to filter for 15 to 30 minutes, the pH and conductivity of the filtrate were measured (Eutech pcsttetr 35). Resuspending the remaining wet solids in 50mL to 100mL deionized Milli-

In water.

Water, vacuum filtration, measurement of filtrate pH/conductivity) until the conductivity of the filtrate reaches 100 to 300 μ S/cm. In this case, two additional filtrations were performed. The remaining wet solids were resuspended in 150mL to 200mL of 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 were 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 (5.28mmol H +/g clay)

Of water

Blending machineWhile stirring at low speed, a grey colloidal dispersion free or substantially free of visible lumps or lumps is obtained. After the addition was complete, the dispersion was blended at high speed for 5 to 10 minutes to give a slightly viscous mixture of a 5 wt.% aqueous dispersion of HPM-20 clay.

80g of this 5 wt.% aqueous dispersion of the HPM-20 clay sample was transferred to

In a blender. 42.2mL aliquots of 0.5M aqueous HCl were metered into a graduated cylinder 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 of deionized Milli-

In water. The pH and conductivity of the resulting suspension (Eutech PCSTst 35) were measured to give a pH of 2.27 and a conductivity of 1560. mu.S/cm.

The suspension is again filtered under vacuum for 2 to 3 hours. The filtrate was discarded again and the remaining wet solids were resuspended in 80mL of deionized Milli-

In water. The pH and conductivity of the resulting suspension were measured (Eutech PCSTstr 35) to give a pH of 3.09 and a conductivity of 217. mu.S/cm. The remaining wet solids were resuspended in 150mL to 200mL of 1-butanol and rotary evaporated at 45 ℃. The solid was then ground with a pestle and mortar to give 0.58g of a light gray flake. This solid was transferred to a clay crucible and calcined at 300 ℃ for 6 hours to give 0.45g of a gray powder.

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

Of water

This 5 wt.% aqueous dispersion of an 80g sample of HPM-20 clay was transferred to

In a blender. 12mL aliquots of 0.5M aqueous HCl solution were metered into a graduated cylinder and then added to the clay dispersion in one portion, and 30mL deionized Milli-

Water to facilitate stirring. This 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 of deionized Milli-

In water. The pH and conductivity of the resulting suspension (Eutech PCSTst 35) were measured, giving 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 of deionized Milli-

In water. The pH and conductivity of the resulting suspension (Eutech PCSTst 35) were measured to give a pH of 3.25 and a conductivity of 213. mu.S/cm. The remaining wet solids were resuspended in 150mL to 200mL of 1-butanol and rotary evaporated at 45 ℃. The resulting solid was then ground with a pestle and mortar to give 1.73g of a light gray flake. This solid was transferred to a clay crucible and calcined at 300 ℃ for 6 hours to give 1.2g of a gray powder.

EXAMPLE 42 slurry Settlement test of heterocoagulated Clay (1.52mmol Al/g clay)

40g of HPM-20 clay was slowly added to a mixture containing 760g of deionized Milli-

Of water

100g portions of this 5 wt.% HPM-20 clay aqueous dispersion were transferred to

In a blender. Then, 1.66g of a 50 wt.% aqueous solution of GEO aluminum chlorohydrate was pipetted into a vial and added to the dispersion in one portion. An additional 28mL of deionized Milli-

Water to facilitate stirring. The mixture was blended at high speed for 5 minutes and then transferred to a bottle. Deionization of Milli-

The stirrer was washed with water, and 184g of slurry was obtained.

The slurry was added to 250mL

In a graduated cylinder until 183mL mark was reached, and the slurry was allowed to stand. Over time, the slurry settles and forms a layer that is substantially free of visible colloidal particles. The volume of this clear layer was recorded periodically and after a settling time of 95h (hours) the volume of the clear layer, referred to as the settled volume, was 15 mL.

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

A5 wt.% aqueous dispersion of HPM-20 clay was prepared by slowly adding 40g of HPM-20 clay over a period of 1 to 2 minutes to a solution containing 760g of deionized Milli-

Of water

In a blender with low speed agitation, resulting in a gray colloidal dispersion that is free or substantially free of visible lumps or lumps. After the addition was complete, the dispersion was blended at high speed for 5 to 10 minutes to give a slightly viscous 5 wt.% aqueous dispersion of HPM-20 clay.

100g portions of this 5 wt.% HPM-20 clay aqueous dispersion were transferred to

In a blender. A 6.18g sample of a 50 wt.% aqueous solution of GEO aluminum chlorohydrate was pipetted into a vial and added to the dispersion in one portion. An additional 13.8mL of deionized Milli-

Water, then blended at high speed for 5 minutes, then transferred to a bottle. With an additional 30g of deionised Milli-

The mixer is washed with water. Then 50g portions of Milli-

Deionized water was added to the mixture to yield 194g of slurry.

The slurry was added to 250mL

In a graduated cylinder until 183mL mark was reached, and the slurry was allowed to stand. Over time, the slurry settles and forms a foundationThere is essentially no layer of visible colloidal particles. The volume of this clear layer was recorded periodically and after a settling time of 95h (hours), the volume of the clear layer, referred to as the settled volume, was 3 mL.

EXAMPLE 44 filtrate quantification of heterocoacervated clays (1.52mmol Al/g clay)

A 5 wt.% aqueous dispersion of HPM-20 clay was prepared as described in example 42.

100g portions of this 5 wt.% HPM-20 clay aqueous dispersion were transferred to

In a blender. Then, 1.66g of a 50 wt.% aqueous solution of GEO aluminum chlorohydrate was pipetted into a vial and added to the dispersion in one portion. An additional 38mL of deionized Milli-

Water to facilitate stirring. The mixture was blended at high speed for 5 minutes and then transferred to a bottle. A total of 110g of deionized Milli-

Water to give a slurry having a total mass of 250 g.

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

EXAMPLE 45. comparative example to quantitative testing of the filtrate of ACH-pillared Clay (5.7mmol Al/g clay)

A 5 wt.% aqueous dispersion of HPM-20 clay was prepared as described in example 43. 100g portions of a 5 wt.% aqueous dispersion of HPM-20 clay were transferred to

In a blender. A 6.18g sample of a 50 wt.% aqueous solution of GEO aluminum chlorohydrate was pipetted into a vial and added to the dispersion in one portion. Adding additional agent to the mixture44g deionization Milli-

Water, then blended at high speed for 5 minutes, then transferred to a bottle, and then 100g of Milli-

Deionized water to give a total mass of 250g of slurry.

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

EXAMPLE 46.7 preparation of phenyl-2-methyl-indene

To a mixture of phenylboronic acid (3.05g, 25.0mmol), Pd under nitrogen atmosphere ₂ (dba) ₃ (229mg, 0.25mmo, dba is dibenzylideneacetone) and K ₃ PO ₄ (15.9g, 75.0mmol) in toluene (50mL) was added P (t-Bu) ₃ (202mg, 1.00mmol) and 7-bromo-2-methyl-1H-indene (5.23g, 25.0mmol) the reaction mixture was stirred vigorously 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 removal of 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 (4.41g, 86%). CDCl ₃ The product of (1) contains traces of dichloromethane and water and the NMR spectrum of the product is shown in fig. 13.

EXAMPLE 47 preparation of ansa-metallocene ligand Dimethylsilanebis (2-methyl-4-phenylindenyl)

In N ₂ n-BuLi (8.56mL, 2.5M in hexanes, 21.4mmol) was added to 60mL of anhydrous toluene under atmosphere, then added to a solution of 7-phenyl-2-methyl-1H-indene (4.41g, 21.4mmol) at room temperature with stirring. In the roomAfter stirring at room temperature for a period of 6 hours, the reaction mixture was cooled to-35 ℃ and a solution of dichlorodimethylsilane (1.29mL, 10.7mmol) in THF (5mL) 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 the volatiles were removed from the filtrate by rotary evaporation. By column chromatography (Hexane and Et) ₂ The resulting crude product was purified at a ratio of 200:1 (vol: vol)) to give a yellow solid (2.65g, 53% yield).

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

A portion of the yellow solid dimethylsilylenebis (2-methyl-4-phenylindenyl) ligand (410mg, 0.875mmol) from the previous example was dissolved in methyl tert-butyl ether (2mL) and diluted with diethyl ether (2 mL). The solution was cooled to-35 ℃ and a portion of n-butyllithium (0.7mL, 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 ℃. Then the cold ligand solution is added with ZrCl-containing solution which is pre-cooled to-35 DEG C ₄ (THF) ₂ (333mg, 0.875mmol) in hexane (10 mL). 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 was extracted with Dichloromethane (DCM). After passing the dichloromethane extract through the 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 (280mg, 51% yield). The product was recrystallized from Dichloromethane (DCM)/hexane (1/1(v: v)) to give 145mg of crystals, which were recrystallized once more from DCM to give 60mg of rac-dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride in substantially isomeric purity. CDCl ₃ The recrystallized product of (1) contains a trace amount of methylene chloride, and the product of ¹ The H NMR spectrum is shown in FIG. 14.

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

To a solution of 6.0. mu. mol 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 aluminum chlorohydrate clay heteroadduct (1.76mmol Al/g clay) which had been single filtered, azeotroped and calcined according to example 17. The resulting slurry was shaken for 2 minutes and held at room temperature for several hours before use.

Propylene polymerization was carried out in a 2L reactor on a laboratory scale according to the following procedure. The reactor was first preheated to at least 100 ℃ with a nitrogen purge 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 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 proceed 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 contents, and the resulting mixture was stirred for 5 minutes, and then filtered to give a polymer product. The obtained polymer was dried under vacuum 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. The propylene polymerization results of this example are summarized in table 8 below.

TABLE 8 propylene polymerization batches were run according to examples 46 and 47, catalyzed by rac-dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, calcined clay heteroadduct, and trialkylaluminum

EXAMPLE 50 polymerization of propylene catalyzed by rac-Dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride, calcined Clay heteroadduct 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 the polymerization was carried out at a temperature of 80 ℃ instead of 70 ℃ (as in example 49). Table 8 summarizes the propylene polymerization results for this example.

EXAMPLE 51 ethylene homopolymerization catalysis the present and comparative Supports and metallocene catalysts

Homopolymerization of ethylene was carried out at 450 total psi and 90 ℃ using the reaction procedures and conditions described previously. 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 heterocoacervated clay activator support, as well as 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 compounds or compositions 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, may be selected independently of each other and combined or contacted in any order to provide a heterocoacervate 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, can be selected independently of each other and combined or contacted with each other and with the heterocoacervated 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 heterocoacervate clay activator support and olefin polymerization catalyst.

In table 9, certain abbreviations are used as can be understood by those of ordinary skill in the art, such as TEA (triethylaluminum), TnOA (tri-n-octylaluminum), TiBA (triisobutylaluminum), MAO (methylaluminoxane), EAO (ethylaluminoxane), and the like. Unless otherwise specified, groups such as "hydrocarbyl" or "silicon-containing hydrocarbyl" can 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 substituents, each "Q" group is selected independently of any other Q groups, and so forth.

Also with respect to table 9, the co-catalyst 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 halide-substituted and cocatalysts may provide polymerizable activating/initiating ligands, such as methyl or hydride.

Aspects of the disclosure

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

a) at least one metallocene compound;

b) optionally, at least one co-catalyst; and

Aspect 2. 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 co-catalyst; 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 co-catalyst; and

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

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

a) providing a colloidal montmorillonite clay;

c) separating the smectite heteroadduct from the slurry.

Aspect 6. the catalyst composition, process for polymerizing an olefin, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator of any one 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 a surfactant 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 sulfosuccinates, 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 metal (such as lithium, sodium or potassium), alkaline earth metal (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, dioctadecyldimethylammonium chloride, cetyltrimethylammonium chloride, octadecylammonium chloride, trimethyloctadecylammonium chloride or cetyltrimethylammonium 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 t-octylphenyl ether, polymers of methyl ethylene oxide with 1,2, -ethylenediamine and ethylene oxide, or polymers of 1, 2-ethylenedinitrotetrapropanol with ethylene oxide and methyl propylene oxide; or

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

Aspect 7. the support-activator or the method for producing a support-activator according to any one of aspects 5 in aspect 4, wherein the isolated montmorillonite heteroadduct [1] is 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 smectite heteroadduct:

a) separating from the slurry by filtration or by an azeotropic process; and/or

b) No ultrafiltration, centrifugation or settling tank is used for separation from the slurry.

Aspect 9. the support-activator or the method of producing a support-activator according to any one of aspects 4 to 5, wherein the smectite heteroadduct is separated from the slurry by ultrafiltration, centrifugation or settling tank.

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

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

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

Aspect 13. 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 12, wherein:

a) the smectite clay is colloidal; and/or

b) The smectite 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 75 nm.

Aspect 14. the catalyst composition, process for polymerizing an olefin, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator of any one of aspects 1 to 13, wherein the smectite 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 of polymerizing an olefin, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator according to any of the preceding aspects, such as aspects 1-13, wherein the smectite clay comprises structural units characterized by the formula:

(M ^A IV) ₈ (M ^B VI) _p O ₂₀ (OH) ₄ (ii) a Wherein

a)M ^A IV is tetra-coordinated Si ⁴⁺ In which Si is ⁴⁺ Is not Si ⁴⁺ Of (2) is a four coordinate systemThe cation is optionally partially substituted;

b)M ^B VI is hexa-coordinated Al ³⁺ Or Mg ²⁺ In which Al is ³⁺ Or Mg ²⁺ Is not Al ³⁺ Or Mg ²⁺ Optionally partially substituted with a hexacoordinate cation of (a);

d) At M ^A IV is composed of non-Si ⁴⁺ Any charge produced by partial substitution of the cation of (a) is deficient and/or at M ^B VI is made of a material other than Al ³⁺ Or Mg ²⁺ Any charge deficit resulting from partial substitution of the cation(s) is balanced by the cation(s) inserted 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 of aspect 15, wherein:

a) in each case, non-Si ⁴⁺ Is independently selected from Al ³⁺ 、Fe ³⁺ 、P ⁵⁺ 、B ³⁺ 、Ge ⁴⁺ 、Be ²⁺ 、Sn ⁴⁺ Etc.;

b) in each case, not Al ³⁺ Or Mg ²⁺ Is independently selected from Fe ³⁺ 、Fe ²⁺ 、Ni ²⁺ 、Co ²⁺ 、Li ⁺ 、Zn ²⁺ 、Mn ²⁺ 、Ca ²⁺ 、Be ²⁺ Etc.; and/or

c) The cations interposed between the structural units are selected from monocationals, biscationals, tricationials, other polycations, or any combination thereof.

Aspect 17. 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 15, wherein:

a) In each case, non-Si ⁴⁺ Is independently selected from Al ³⁺ Or Fe ³⁺ (ii) a And is

b) In each case, not Al ³⁺ Or Mg ²⁺ Is independently selected from Fe ³⁺ 、Fe ²⁺ 、Ni ²⁺ Or Co ²⁺ 。

c) The cations inserted between the structural units are selected from monocationals.

Aspect 18. the catalyst composition, process for polymerizing olefins, method of making an olefin polymerization catalyst, support-activator, or method of making a support-activator of any of aspects 1 to 17, wherein the smectite clay has been monocationally exchanged with at least one of lithium, sodium, or potassium.

Aspect 19. 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 18, wherein the cationic multimetal salt comprises, consists essentially of, or is selected from the group consisting of a cationic oligomeric aluminum species or a cationic polymeric aluminum species.

Aspect 20. the catalyst composition, process for polymerizing an olefin, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator of any of aspects 1 to 18, wherein the cationic multimetal salt comprises, consists essentially of, or is selected from the group consisting of: polyaluminum chloride, aluminum chlorohydrate, or aluminum chlorohydrate.

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 the polyaluminum chloride, aluminum chlorohydrate or aluminum chlorohydroxy-chloride to grams (g) of colloidal montmorillonite clay is in the range: from about 0.2mmol Al/g clay to about 2.5mmol Al/g clay, from about 0.5mmol Al/g clay to about 2.2mmol Al/g clay, from about 0.75mmol Al/g clay to about 2.0mmol Al/g clay, or from 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 the polyaluminum chloride, aluminum chlorohydrate or aluminum chlorohydrate 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 comparative ratio of millimoles of aluminum to grams of colloidal clay used in preparing a pillared clay using the same colloidal montmorillonite clay and heterocoagulating agent.

Aspect 23. 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 18, wherein the cationic multimetal salt comprises a linear, cyclic, or cluster aluminum compound containing from 2 to 30 aluminum atoms.

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

Aspect 25. 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 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, process for polymerizing an olefin, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator of aspect 24, wherein:

the first metal oxide comprises SiO ₂ Or Al ₂ O ₃ And wherein the second metal oxide, metal halide or metal oxyhalide is selected from the group consisting of metal oxides, hydroxides, oxyhalides or halides (such as ZrOCl ₂ 、ZnO、NbOCl ₃ 、B(OH) ₃ 、AlCl ₃ Or a combination thereof); or

The first metal oxide comprises SiO ₂ Wherein the second metal oxide, metal halide or metal oxyhalide comprises Al ₂ O ₃ 、ZnO、AlCl ₃ Or a combination thereof.

Aspect 27. 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 18, wherein the cationic multimetal 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; it is composed of

Chemical treatment with polyaluminum chloride, aluminum chlorohydrate, aluminum chlorohydroxy, aluminum oxychloride, or any combination thereof.

Aspect 28. the catalyst composition, process for polymerizing an olefin, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator of any of aspects 1 to 18, wherein:

a) colloidal montmorillonite clays include colloidal montmorillonite such as HPM-20 Volclay; and is provided with

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

Aspect 29. 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 18, wherein the cationic multimetal salt comprises, consists essentially of, or is selected from the group consisting of: boehmite, fumed silica-alumina, colloidal ceria, colloidal zirconia, magnetite, ferrihydrite, any positively charged colloidal metal oxide, or any combination thereof.

Aspect 30 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 18, wherein the cationic multimetal 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 an olefin, method of making an olefin polymerization catalyst, support-activator, or method of making a support-activator of any one of aspects 1 to 18, wherein the cationic multimetal 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:

Al ₂ (OH) _n Cl _m (H ₂ O) _x ，

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

Aspect 32. 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 18, wherein the cationic multimetal salt comprises, consists essentially of, or is selected from the group consisting of: having an empirical formula of 0.5[ Al ₂ (OH) ₅ Cl(H ₂ O) ₂ ]Or [ AlO ] ₄ (Al ₁₂ (OH) ₂₄ (H ₂ O) ₂₀ ] ⁷⁺ (“Al ₁₃ Mer ") polycationic aluminum species.

Aspect 33. the catalyst composition, process for polymerizing olefins, method for preparing an olefin polymerization catalyst, support-activator, or method for preparing a support-activator of any of aspects 1 to 18, wherein the cationic multimetal salt comprises, consists of, consists essentially of, or is selected from an oligomer 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 combinations 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 of 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 an olefin, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator of any of aspects 1 to 18, wherein the cationic multimetal salt comprises, consists essentially of, or is selected from the group consisting of: a complex of formula I or formula II according to the formula or any combination of complexes of formula I or formula II:

[M(II) _1-x M(III) _x (OH) ₂ ]A _x/n ·m L (I)

[LiAl ₂ (OH) ₆ ]A _1/n ·m L (II)

wherein:

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

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

a is at least one inorganic anion;

l is an organic solvent or water;

x is a number from 0.1 to 1; and is

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 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 essentially of, or is selected from the group consisting of: iron, chromium, manganese, bismuth, cerium or aluminum;

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

n is a number from 1 to 3; and is

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

Aspect 37. 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 35, wherein the cationic multimetallic salt is selected from a complex of formula I wherein m (ii) is magnesium, m (iii) is aluminum, and a is a carbonate.

Aspect 38. the catalyst composition, process for polymerizing an olefin, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator of any of aspects 1 to 18, wherein the cationic multimetal 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 of polymerizing an olefin, method of making an olefin polymerization catalyst, support-activator, or method of making 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 of aspect 39, wherein the layersThe double hydroxide or mixed metal layered hydroxide comprises, consists essentially of, or is selected from the group consisting of: aluminum magnesium hydroxide nitrate, aluminum magnesium hydroxide sulfate, aluminum magnesium hydroxide chloride, Mg _x (Mg,Fe) ₃ (Si,Al) ₄ O ₁₀ (OH) ₂ (H ₂ O) ₄ (x is a number from 0 to 1, e.g., the amount of steatite is about 0.33), (Al, Mg) ₂ Si ₄ O ₁₀ (OH) ₂ (H ₂ O) ₈ Synthesizing hematite, hydrozincite (basic zinc carbonate) Zn ₅ (OH) ₆ (CO ₃ ) ₂ Hydrotalcite [ Mg) ₆ Al ₂ (OH) ₁₆ ]CO ₃ ·4H ₂ O, diaspore [ Ni ] ₆ Al ₂ (OH) ₆ ]CO ₃ ·4H ₂ O, hydrocalumite [ Ca ] ₂ Al(OH) ₆ ]OH· ₆ H ₂ O, Mg plus Al [ Mg) ₁₀ Al ₅ (OH) ₃₁ ](SO ₄ ) ₂ ·mH ₂ O, lepidocrocite [ Mg ₆ Fe ₂ (OH) ₁₆ ]CO ₃ ·4.5H ₂ O, ettringite [ Ca ₆ Al ₂ (OH) ₁₂ ](SO ₄ ) ₃ ·26H ₂ O or any combination thereof.

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

Aspect 42. the catalyst composition, process for polymerizing an olefin, method of making an olefin polymerization catalyst, support-activator, or method of making a support-activator of any of aspects 1 to 41, wherein the slurry of montmorillonite heteroadduct is characterized by an electrical conductivity in the range of: about 20,000 to about 100, about 10,000 to about 200, or about 1000 to about 300 μ S/cm, with the slurry concentration being greater than or equal to about 1 wt.%, or greater than or equal to about 2.5 wt.%, or with the slurry concentration ranging from: about 1 wt.% to about 10 wt.% solids, about 2.5 wt.% to about 10 wt.% solids, about 5 wt.% to about 10 wt.% solids.

Aspect 43. the catalyst composition, process for polymerizing olefins, method for preparing an olefin polymerization catalyst, support-activator, or method for preparing a support-activator of any of aspects 1 to 41, wherein the slurry of montmorillonite heteroadduct is characterized by an electrical conductivity of less than 10mS/cm, less than 5mS/cm, or less than 1mS/cm, or wherein the slurry of montmorillonite heteroadduct is characterized by an electrical conductivity in the range of about: 2mS/cm to 10 μ S/cm, 1mS/cm to 50 μ S/cm, 500 μ S/cm to 100 μ S/cm, the slurry concentration thereof being greater than or equal to about 1 wt.%, or greater than or equal to about 2.5 wt.% solids, or the slurry concentration thereof ranging from: about 1 wt.% to about 10 wt.% solids, about 2.5 wt.% to about 10 wt.% solids, about 5 wt.% to about 10 wt.% solids.

Aspect 44. the catalyst composition, process for polymerizing an olefin, method of making an olefin polymerization catalyst, support-activator, or method of making a support-activator of 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 time period 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

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 an olefin, method of making an olefin polymerization catalyst, support-activator, or method of making a support-activator of any of aspects 1 to 43, wherein the montmorillonite heteroadduct is calcined in air at a temperature in the following 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 an olefin, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator of 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 an olefin, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator of any of aspects 1 to 45, wherein the montmorillonite heteroadduct is calcined in air or carbon monoxide in a fluidized bed.

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

Aspect 49. the catalyst composition, process for polymerizing an olefin, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator of any of aspects 1 to 43, wherein the calcined montmorillonite heteroadduct is calcined at a temperature of 250 ℃ or greater.

Aspect 50 the catalyst composition, process for polymerizing an olefin, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator of any one of aspects 1 to 43, wherein the calcined montmorillonite heteroadduct is calcined at a temperature of 300 ℃ or greater.

Aspect 51. the catalyst composition, process for polymerizing an olefin, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator of any of aspects 1 to 43, wherein the calcined montmorillonite heteroadduct is calcined at a temperature of 350 ℃ or greater.

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

Aspect 53 the catalyst composition, process for polymerizing an olefin, method of making an olefin polymerization catalyst, support-activator, or method of making a support-activator of any of aspects 1 to 51, wherein the calcined montmorillonite heteroadduct is characterized by any of the following characteristics:

a) a d001 substrate spacing greater than or equal to about in the presence or substantial absence of powder X-ray diffraction (XRD)

Homogeneous intercalation structure of (angstrom);

b) the d001 substrate spacing range is about in the presence or substantial absence in powder X-ray diffraction (XRD)

From (angstroms) to about

In the (angstrom) range, or alternatively in the powder X-ray diffraction (XRD) range at about

From (angstroms) to about

Homogeneous intercalation structures in the range of (angstroms); or

c) a combination of a) and b).

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

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

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

Aspect 57. the catalyst composition, process for polymerizing olefins, method of making an olefin polymerization catalyst, support-activator, or method of making a support-activator of any of aspects 1 to 56, wherein the calcined montmorillonite heteroadduct exhibits a log differential pore volume distribution (dv (log d) and pore diameter) having a pore size ranging from that of aspect 1 to aspect 56

(angstrom) to

(D _VM(30-40) ) Local maximum within the range.

Aspect 58 catalysis according to any of aspects 1-57A catalyst composition, 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 calcined montmorillonite heteroadduct is characterized by a log differential pore volume distribution (dV (log D) and pore diameter) having a molecular weight from that of the calcined montmorillonite heteroadduct

(angstrom) to

(D _VM(30-40) ) Within or from

(angstrom) to

(D _VM(200-500) ) Highest value in the range (D) _M Indicating the most frequently occurring aperture).

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 the 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 maximum in between.

Aspect 61. the catalyst composition, process for polymerizing an olefin, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator of aspect 58, wherein the log differential pore volume distribution(dV (log D) vs. pore size) appears to be in

(Angstrom) and

(D _VM(200-500) ) In excess of the local maximum between

(Angstrom) and

all dv (log d) values in between.

Aspect 62 the catalyst composition, process for polymerizing an olefin, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator of any one of aspects 1 to 61, wherein the heterocoalescing agent comprises aluminum in a concentration in the range of:

a) Based on Al ₂ O ₃ Calculated about 1 wt.% to about 60 wt.%;

a) based on Al ₂ O ₃ Calculated about 5 wt.% to about 50 wt.%;

b) based on Al ₂ O ₃ Calculated about 10 wt.% to about 45 wt.%; or

c) Based on Al ₂ O ₃ Calculated about 15 wt.% to about 35 wt.%.

Aspect 63. the catalyst composition, process for polymerizing olefins, method of making an olefin polymerization catalyst, support-activator, or method of making a support-activator of any of aspects 1 to 62, wherein the contacting amounts of [1] the colloidal smectite clay and the [2] heterocoagulating agent are sufficient to provide a smectite heteroadduct slurry having a zeta potential in the range:

a) about positive (+)22mV (millivolts) to about negative (-)22 mV;

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

c) about positive (+)18mV (millivolts) to about negative (-)18 mV;

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

e) about positive (+)12mV (millivolts) to about negative (-)12 mV;

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

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

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

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 smectite clay and the [2] heterocoagulating agent are contacted at 25 ℃ ± 5 ℃ for a period 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, method of preparing an olefin polymerization catalyst, support-activator, or method of preparing a support-activator of any of aspects 1 to 64, wherein the smectite heteroadduct is separated from the slurry by filtration after contacting [1] the colloidal smectite clay and the [2] heterocoagulating agent without the use of ultrafiltration, centrifugation or a settling tank.

Aspect 66. the catalyst composition, process for polymerizing an olefin, method of making an olefin polymerization catalyst, support-activator, or method of making a support-activator of any of aspects 1 to 65, wherein the montmorillonite heteroadduct 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-exchanged clay, a protonic acid-treated clay, a pillared clay, an alumoxane, 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 absent of ion-exchanged clay, protonic acid-treated clay, pillared clay, alumoxane, 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 heteroadduct is subsequently dried and/or calcined.

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

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

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

Aspect 73. the method of making a support-activator according to any one of aspects 5 to 71, wherein the montmorillonite heteroadduct 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 making a support-activator of any of aspects 5 to 71, wherein the montmorillonite heteroadduct 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 entrapped air from the dried or calcined montmorillonite heteroadduct by: [1] placing the dried or calcined montmorillonite heteroadduct in a vacuum, followed by an inert atmosphere such as nitrogen or argon, and optionally repeating the vacuum and inert gas cycles one or more times; or [2] when the smectite heteroadduct 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 making a support-activator of any of aspects 5-75, wherein the concentration of the smectite heteroadduct solids in the slurry is at least about 5 wt.%.

Aspect 77. the method of making a support-activator according to any one of aspects 5 to 76, wherein the concentration of the smectite heteroadduct solid in the slurry is up to about 30 wt.%, up to about 25 wt.%, up to about 20 wt.%, up to about 15 wt.%, up to about 10 wt.%, up to about 5 wt.%, or wherein the concentration of the smectite heteroadduct solid in the slurry is in the range of about 2 wt.% to about 30 wt.%, about 3 wt.% to about 20 wt.%, or about 5 wt.% to about 15 wt.%.

Aspect 78. the method of making a support-activator of any one of aspects 5-77, wherein the contacting step is performed in the substantial absence of an ion-exchange clay, a protonic acid-treated clay, an alumoxane, a borate co-activator, or any combination thereof.

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

Aspect 80. the support-activator or the method of making a support-activator of any of aspects 4 to 79, wherein the slurry of the smectite heteroadduct is characterized by the following filtration behavior:

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

Aspect 81. the support-activator or the method of making a support-activator of any of aspects 4 to 79, wherein the slurry of the smectite heteroadduct is characterized by the following filtration behavior:

[a] when filtering the heteroadduct slurry having a 2.0 wt.% aqueous based heteroadduct concentration over a period of time 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 2.0 wt.% pillared clay slurry prepared by filtering using a colloidal montmorillonite clay, a heterocoagulation agent, and a 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

[b] upon evaporation, the filtrate in the heteroadduct slurry produced solids comprising < 20%, < 15%, or < 10% of the initial total weight of clay and heterocoagulant.

Aspect 82. the support-activator or the method of making a support-activator of any of aspects 4 to 79, wherein the montmorillonite heteroadduct slurry is characterized by a settling rate of 2.5 wt.% aqueous heteroadduct slurry composition that is 3 times, 3.5 times, 4 times, 4.5 times, 5 times, 6 times, 7 times, 8 times, 9 times, or 10 times greater than the settling rate of a 2.5 wt.% aqueous pillared clay slurry made using colloidal montmorillonite clay, a heterocoagulating agent, and a 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 the start of the settling test.

An aspect 83. the catalyst composition, process for polymerizing olefins, or method of making an olefin polymerization catalyst 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 is active for olefin polymerization when activated with an ion-exchanged clay, a protonic acid-treated clay, a pillared clay, an alumoxane, a borate co-activator, or any combination thereof.

Aspect 84. the catalyst composition, process for polymerizing olefins, or method of making an olefin polymerization catalyst according to any one 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: an unbridged (non-ansa-metallocene) compound or a bridged (ansa-metallocene) compound.

Aspect 85. the catalyst composition, process for polymerizing olefins, or method of making an olefin polymerization catalyst 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: a compound or combination of compounds, each independently having the formula:

(X ¹ )(X ² )(X ³ )(X ⁴ ) M, wherein

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

b)X ¹ selected from the group consisting of substituted or unsubstituted cyclopentadienyl, indenyl, fluorenyl, pentadienyl, allyl, borato-hetero-phenyl, 1, 2-azaboropentadienyl, or 1, 2-diaza-3, 5-diboronoyl, wherein any substituent is independently selected from halide, C ₁ -C ₂₀ Hydrocarbyl radical, C ₁ -C ₂₀ Heterohydrocarbyl radical, C ₁ -C ₂₀ Organic hetero group, condensed C ₄ -C ₁₂ A carbocyclic moiety or a fused C having at least one heteroatom independently selected from ₄ -C ₁₁ Heterocyclic moiety: nitrogen, oxygen, sulfur or phosphorus;

c)X ² selected from: [1]Substituted or unsubstituted cyclopentadienyl, indenyl, fluorenyl, pentadienyl, or allyl, wherein any substituent is independently selected from the group consisting of halide, C ₁ -C ₂₀ Hydrocarbyl radical、C ₁ -C ₂₀ Heterohydrocarbyl or C ₁ -C ₂₀ An organic hetero group; or [2 ]]Halides, hydrides, C ₁ -C ₂₀ Hydrocarbyl radical, C ₁ -C ₂₀ Heterohydrocarbyl radical, C ₁ -C ₂₀ Organic hetero group, condensed C ₄ -C ₁₂ A carbocyclic moiety or a fused C having at least one heteroatom independently selected from ₄ -C ₁₁ Heterocyclic moiety: nitrogen, oxygen, sulfur or phosphorus;

e)[1]X ³ and X ⁴ Independently selected from the group consisting of halides, hydrides, C ₁ -C ₂₀ Hydrocarbyl radical, C ₁ -C ₂₀ Heterohydrocarbyl radicals or C ₁ -C ₂₀ An organic hetero group; [2][GX ^A _k X ^B _4-k ]-, where G is B or Al, k is a number from 1 to 4, and X ^A Independently at each occurrence, selected from H or halide, and X ^B Independently at each occurrence is selected from C ₁ -C ₁₂ Hydrocarbyl radical, C ₁ -C ₁₂ Heterohydrocarbyl radical, C ₁ -C ₁₂ An organic hetero group; [3]X ³ And X ⁴ Together are C ₄ -C ₂₀ A polyene; or [4 ]]X ³ And X ⁴ Together with M form a substituted or unsubstituted, saturated or unsaturated C ₃ -C ₆ A metallocycle moiety, wherein any substituent on the metallocycle moiety is independently selected from halide, C ₁ -C ₂₀ Hydrocarbyl radical, C ₁ -C ₂₀ Heterohydrocarbyl or C ₁ -C ₂₀ An organic hetero group.

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 Bridged by a linker substituent selected from:

b)-BX ⁵ -、-NX ⁵ -or-PX ⁵ -; or

and wherein any X is selected from the group consisting of hydrocarbyl, heterohydrocarbyl, or organoheteryl substituents ⁵ The substituent may be bonded to the bridging atom, another X ⁵ Substituent group, X ¹ Or X ² Forming a saturated or unsaturated cyclic structure.

Aspect 87. 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 By selecting from C ₁ -C ₂₀ Hydrocarbylene group, C ₁ -C ₂₀ Meta-hydrocarbon group, C ₁ -C ₂₀ Heterohydrocarbon radical, C ₁ -C ₂₀ Heterocarbyl radical, C ₁ -C ₂₀ Heterohydrocarbylene radicals or C ₁ -C ₂₀ Linker substituents bridging heterocarbyl groups.

Aspect 88. 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 By at least one having the formula>EX ⁵ ₂ 、-EX ⁵ ₂ EX ⁵ ₂ -or-BX ⁵ Bridging of substituents of (A) wherein E is independently C or Si, X ⁵ Independently selected in each case from halides, C ₁ -C ₂₀ Aliphatic radical, C ₆ -C ₂₀ Aromatic radical, C ₁ -C ₂₀ Heteroaliphatic radical, C ₄ -C ₂₀ Heteroaromatic radical or C ₁ -C ₂₀ An organic hetero group.

Aspect 89. the catalyst composition, process for polymerizing olefins, or method of making an olefin polymerization catalyst according to any of aspects 86 to 88, wherein X ⁵ Independently selected in each case from halides, C ₁ -C ₁₈ Or C ₁ -C ₁₂ Alkyl radical, C ₂ -C ₁₈ Or C ₂ -C ₁₂ Alkenyl radical, C ₆ -C ₁₈ Or C ₆ -C ₁₂ Aromatic radical, C ₄ -C ₁₈ Or C ₄ -C ₁₂ Heteroaromatic radical, C ₁ -C ₁₈ Or C ₁ -C ₁₂ Heterohydrocarbyl radical, C ₁ -C ₂₁ Or C ₁ -C ₁₅ Organosilicon radicals, C ₁ -C ₁₈ Or C ₁ -C ₁₂ Halogenoalkyl (haloalkyl) radical, C ₁ -C ₁₈ Or C ₁ -C ₁₂ Organic phosphorus radical, or C ₁ -C ₁₈ Or C ₁ -C ₁₂ An organic nitrogen group.

Aspect 90. 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 By a reaction of a compound selected from the group consisting of silylene, methylsilylene, dimethylsilylene, diisopropylsilylene, dibutylsilylene, methylbutylsilene, methyl-tert-butylsilylene, dicyclohexylsilylene, methylcyclohexylsilylene,A linker substituent of methylphenylsilylene, diphenylsilylene, ditolysilylene, methylnaphthylsilylene, dinaphthylsilylene, cyclodimethylsilylene, cyclotrimethylsilylene, cyclotetramethylsilylene, cyclopentylmethyl silylene, cyclohexylmethylsilylene or cycloheptylmethyl silylene.

Aspect 91. the catalyst composition, process for polymerizing olefins, or method of making an olefin polymerization catalyst according to any of aspects 85 to 90, wherein X ¹ 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 -C ₂₀ Aliphatic radical, C ₆ -C ₂₀ Aromatic radical, C ₁ -C ₂₀ Heteroaliphatic radical, C ₄ -C ₂₀ Heteroaromatic radical or C ₁ -C ₂₀ An organic hetero group.

Aspect 92. the catalyst composition, process for polymerizing olefins, or method of making an olefin polymerization catalyst according to any of aspects 85 to 90, wherein X ¹ 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 -C ₁₈ Or C ₁ -C ₁₂ Alkyl radical, C ₂ -C ₁₈ Or C ₂ -C ₁₂ Alkenyl radical, C ₆ -C ₁₈ Or C ₆ -C ₁₂ Aromatic radical, C ₄ -C ₁₈ Or C ₄ -C ₁₂ Heteroaromatic radical, C ₁ -C ₂₁ Or C ₁ -C ₁₅ Organosilicon radicals, C ₁ -C ₁₈ Or C ₁ -C ₁₂ Halogenoalkyl (haloalkyl) radical, C ₁ -C ₁₈ Or C ₁ -C ₁₂ Organic phosphorus radical, or C ₁ -C ₁₈ Or C ₁ -C ₁₂ An organic nitrogen group.

Aspect 93. the catalyst composition, process for polymerizing olefins, or method of preparing an olefin polymerization catalyst according to any of aspects 85 to 90, wherein X ¹ 、X ² Or X ¹ And X ² Independently selected from the group consisting of substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl, any of which is substitutedThe radicals are independently selected from:

a) having the formula-SiH ₃ 、-SiH ₂ R、-SiHR ₂ 、-SiR ₃ 、-SiR ₂ (OR)、-SiR(OR) ₂ or-Si (OR) ₃ Silicon base of (a);

b) having the formula-PHR, -PR ₂ 、-P(O)R ₂ 、-P(OR) ₂ 、-P(O)(OR) ₂ 、-P(NR ₂ ) ₂ or-P (O) (NR) ₂ ) ₂ A phosphorus group of (a);

c) having the formula-BH ₂ 、-BHR、-BR ₂ -BR (OR) or-B (OR) ₂ A boron group of (a);

d) having the formula-GeH ₃ 、-GeH ₂ R、-GeHR ₂ 、-GeR ₃ 、-GeR ₂ (OR)、-GeR(OR) ₂ or-Ge (OR) ₃ A germanium group of (a); or

e) Any combination thereof;

wherein R is independently selected at each occurrence from C ₁ -C ₂₀ A hydrocarbyl group.

Aspect 94. the catalyst composition, process for polymerizing olefins, or method of making an olefin polymerization catalyst according to any of aspects 85 to 90, wherein X ¹ 、X ² Or X ¹ And X ² 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 method of preparing an olefin polymerization catalyst according to any of aspects 85 to 92, wherein X ² Selected from: [1]Substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl, wherein any substituent is independently selected from the group consisting of halide, C ₁ -C ₂₀ Aliphatic radical, C ₆ -C ₂₀ Aromatic radical, C ₁ -C ₂₀ Heteroaliphatic radical, C ₄ -C ₂₀ Heteroaromatic radical or C ₁ -C ₂₀ An organic hetero group; or [2 ]]Halide, C ₁ -C ₂₀ Aliphatic radical, C ₆ -C ₂₀ An aromatic group,C ₁ -C ₂₀ Heteroaliphatic radical, C ₄ -C ₂₀ Heteroaromatic radical or C ₁ -C ₂₀ An organic hetero group.

Aspect 96. the catalyst composition, the process for polymerizing olefins, or the method for preparing an olefin polymerization catalyst according to any of aspects 85 to 92, wherein X ² Selected from the group consisting of: [1]Substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl, wherein any substituent is independently selected from the group consisting of halide, C ₁ -C ₁₈ Or C ₁ -C ₁₂ Alkyl radical, C ₂ -C ₁₈ Or C ₂ -C ₁₂ Alkenyl radical, C ₆ -C ₁₈ Or C ₆ -C ₁₂ Aromatic radical, C ₄ -C ₁₈ Or C ₄ -C ₁₂ Heteroaromatic radical, C ₁ -C ₂₁ Or C ₁ -C ₁₅ Organosilicon radicals, C ₁ -C ₁₈ Or C ₁ -C ₁₂ Halogenoalkyl (haloalkyl) radical, C ₁ -C ₁₈ Or C ₁ -C ₁₂ Organic phosphorus radical, C ₁ -C ₁₈ Or C ₁ -C ₁₂ An organic nitrogen group; or [2 ]]Halide, C ₁ -C ₁₈ Or C ₁ -C ₁₂ Alkyl radical, C ₂ -C ₁₈ Or C ₂ -C ₁₂ Alkenyl radical, C ₆ -C ₁₈ Or C ₆ -C ₁₂ Aromatic radical, C ₄ -C ₁₈ Or C ₄ -C ₁₂ Heteroaromatic radical, C ₁ -C ₂₁ Or C ₁ -C ₁₅ Organosilicon radicals, C ₁ -C ₁₈ Or C ₁ -C ₁₂ Halogenoalkyl (haloalkyl) radical, C ₁ -C ₁₈ Or C ₁ -C ₁₂ Organic phosphorus radical, or C ₁ -C ₁₈ Or C ₁ -C ₁₂ An 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 X ¹ 、X ² Or X ¹ And X ² At least one of the connecting substituents between is represented by the formula- (CH) ₂ ) _n CH＝CH ₂ C of (A) ₃ -C ₁₂ Alkenyl, wherein n is 1-10.

Aspect 98. the catalyst composition, process for polymerizing olefins, or method of making an olefin polymerization catalyst according to any of aspects 85 to 97, wherein: [1]X ³ And X ⁴ Independently selected from halide, hydride, C ₁ -C ₂₀ Aliphatic radical, C ₆ -C ₂₀ Aromatic radical, C ₁ -C ₂₀ Heteroaliphatic radical, C ₄ -C ₂₀ Heteroaromatic radical or C ₁ -C ₂₀ An organic hetero group; [2]X ³ And X ⁴ Together are a substituted or unsubstituted 1, 3-butadiene having from 4 to 20 carbon atoms; or [3 ]]X ³ And X ⁴ Together with M form substituted or unsubstituted, saturated or unsaturated C ₄ -C ₅ (ii) a metallocycle moiety, wherein any substituents on the metallocycle moiety are independently selected from the group consisting of halide, C ₁ -C ₂₀ Aliphatic radical, C ₆ -C ₂₀ Aromatic radical, C ₁ -C ₂₀ Heteroaliphatic radical, C ₄ -C ₂₀ Heteroaromatic radical or C ₁ -C ₂₀ An organic hetero group.

Aspect 99. the catalyst composition, process for polymerizing olefins, or method of preparing an olefin polymerization catalyst according to any of aspects 85 to 97, wherein: [1]X ³ And X ⁴ Independently selected from halide, hydride, C ₁ -C ₁₈ Or C ₁ -C ₁₂ Alkyl radical, C ₂ -C ₁₈ Or C ₂ -C ₁₂ Alkenyl radical, C ₆ -C ₁₈ Or C ₆ -C ₁₂ Aromatic radical, C ₄ -C ₁₈ Or C ₄ -C ₁₂ Heteroaromatic radical, C ₁ -C ₂₁ Or C ₁ -C ₁₅ Organosilicon radicals, C ₁ -C ₁₈ Or C ₁ -C ₁₂ Halogenoalkyl (haloalkyl) radical, C ₁ -C ₁₈ Or C ₁ -C ₁₂ Organic phosphorus radical, C ₁ -C ₁₈ Or C ₁ -C ₁₂ An 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 -C ₅ (ii) a metallocycle moiety, wherein any substituents on the metallocycle moiety are independently selected from the group consisting of halide, C ₁ -C ₁₈ Or C ₁ -C ₁₂ Alkyl radical, C ₂ -C ₁₈ Or C ₂ -C ₁₂ Alkenyl radical, C ₆ -C ₁₈ Or C ₆ -C ₁₂ Aromatic radical, C ₄ -C ₁₈ Or C ₄ -C ₁₂ Heteroaromatic radical, C ₁ -C ₂₁ Or C ₁ -C ₁₅ Organosilicon radicals, C ₁ -C ₁₈ Or C ₁ -C ₁₂ Halogenoalkyl (haloalkyl) radical, C ₁ -C ₁₈ Or C ₁ -C ₁₂ Organic phosphorus radical, or C ₁ -C ₁₈ Or C ₁ -C ₁₂ An organic nitrogen group.

Aspect 100. the catalyst composition, process for polymerizing olefins, or method of preparing an olefin polymerization catalyst according to any of aspects 85 to 97, wherein X ³ And X ⁴ Independently selected from [1]Halides, hydrides, borohydrides, aluminum hydrides; or [2 ]]Substituted or unsubstituted C ₁ -C ₁₈ Aliphatic radical, C ₁ -C ₁₂ Alkoxy radical, C ₆ -C ₁₀ Aryloxy radical, C ₁ -C ₁₂ Alkylthio radical, C ₆ -C ₁₀ Arylthio, wherein any substituent is independently selected from halide, C ₁ -C ₁₀ Alkyl or C ₆ -C ₁₀ An aryl group; or [3 ]]Amido or phosphido radicals, wherein any substituents are independently selected from C ₁ -C ₁₀ Alkyl or C ₆ -C ₁₀ And (3) an aryl group.

Aspect 101. the catalyst composition, process of polymerizing an olefin, or method of making an olefin polymerization catalyst of any one 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, zirconium (I) zirconium (II) chloride, zirconium (III) chloride, zirconium (IV) chloride, and mixtures thereof, 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 (fluorenyl) zirconium dichloride, Bis (trimethylsilylcyclopentadienyl) zirconium dichloride, bis (trimethylgermylcyclopentadienyl) zirconium dichloride, bis (trimethylstannacyclopentadienyl) 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, and (trimethylgermyl) zirconium dichloride, (cyclopentadienyl) (pentaethylcyclopentadienyl) 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-tert-butylfluorenyl) zirconium dichloride, (dimethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (dimethylcyclopentadienyl) (4-methoxyfluorenyl) zirconium dichloride, (ethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (ethylcyclopentadienyl) (2, 7-di-tert-butylfluorenyl) zirconium dichloride, (ethylcyclopentadienyl) - (octahydrofluorenyl) zirconium dichloride, (ethylcyclopentadienyl) (4-methoxyfluorenyl) zirconium dichloride, (diethylcyclopentadienyl) - (fluorenyl) zirconium dichloride, (diethylcyclopentadienyl) (2, 7-di-tert-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 making 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 support-activator with a cocatalyst in any order.

Aspect 104 the catalyst composition, process for polymerizing an olefin, or method of making an olefin polymerization catalyst of any one 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 method of making an olefin polymerization catalyst according to any one 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 method of making an olefin polymerization catalyst according to any one 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 combination of organoaluminum compounds, each independently having the formula:

Al(X ^A ) _n (X ^B ) _m Or M ^x [AlX ^A ₄ ]In which

a) n + m is 3, where n and m are not limited to integers;

b)X ^A independently selected from: [1]Hydrides, C ₁ -C ₂₀ Hydrocarbyl or C ₁ -C ₂₀ A heterohydrocarbyl group; [2]Hydrides, C ₁ -C ₂₀ Aliphatic radical, C ₆ -C ₂₀ Aromatic radical, C ₁ -C ₂₀ Heteroaliphatic radicals or C ₄ -C ₂₀ A heteroaromatic group; or [3 ]]Two X ^A Together contain C ₄ -C ₅ Alkylene, remainder X ^A Independently selected from hydride, C ₁ -C ₂₀ Hydrocarbyl or C ₁ -C ₂₀ A heterohydrocarbyl group;

c)X ^B independently selected from: [1]Halide or C ₁ -C ₂₀ An organic hetero group; or [2 ]]Halide, C ₁ -C ₁₂ Alkoxy or C ₆ -C ₁₀ An aryloxy ether group; and

d)M ^x selected from Li, Na or K.

Aspect 107. the catalyst composition, process of polymerizing olefins, or method of making 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 combination of organoaluminum compounds, each independently having the formula:

Al(X ^C ) _n (X ^D ) _3-n or M ^x [AlX ^C ₄ ]In which

a) n is a number from 1 to 3, inclusive;

b)X ^C independently selected from hydride or C ₁ -C ₂₀ A hydrocarbyl group;

c)X ^D is a form of an anionic species independently selected from: a fluoride compound; chlorination ofAn agent; bromide; an iodide; a bromate salt; a chlorate salt; a perchlorate salt; a hydrocarbyl sulfate; a hydrocarbyl sulfite; a sulfamate salt; hydrocarbyl sulfides, hydrocarbyl carbonates; bicarbonate (bicarbonate); a carbamate; a nitrite salt; a nitrate salt; a hydrocarbyl oxalate; dihydrocarbyl phosphate; a hydrocarbyl selenite; a sulfate salt; a sulfite; a carbonate salt; an oxalate salt; a phosphate salt; a phosphite salt; selenite; a selenide; a sulfide; an oxide; a sulfamate salt; an azide; an alkoxide; an amido group; a hydrocarbyl amide group; a dihydrocarbylamido group; r ^A [CON(R)] _q (ii) a Wherein R is ^A Independently at each occurrence is H or substituted or unsubstituted C ₁ -C ₂₀ A hydrocarbyl group, q is an integer from 1 to 4, inclusive; and R ^B [CO ₂ ]R, wherein R ^B Independently at each occurrence is H or substituted or unsubstituted C ₁ -C ₂₀ A hydrocarbyl group, r is an integer from 1 to 3, inclusive; and

d)M ^x selected from Li, Na or K.

Aspect 108. the catalyst composition, process for polymerizing olefins, or method of making an olefin polymerization catalyst according to any one 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-alkylcyclopentadiyl) aluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, Triisobutylaluminum (TIBAL), diethylaluminum chloride, or any combination or mixture thereof; or [2] ethyl- (3-alkylcyclopentadiyl) aluminum, Triisobutylaluminum (TIBAL), trioctylaluminum, or any combination or mixture thereof; or [3] any combination of any one or more of the cocatalysts [1] and any one or more of the combinations of the cocatalysts [2 ].

Aspect 109. the catalyst composition, process for polymerizing an olefin, or method of making an olefin polymerization catalyst of 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 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 independently selected from: [1]Hydrides, C ₁ -C ₂₀ Hydrocarbyl or C ₁ -C ₂₀ A heterohydrocarbyl group; [2]Hydrides, C ₁ -C ₂₀ Aliphatic radical, C ₆ -C ₂₀ Aromatic radical, C ₁ -C ₂₀ Heteroaliphatic radicals or C ₄ -C ₂₀ A heteroaromatic group; [3]Fluorinated C ₁ -C ₂₀ Hydrocarbon radicals, or fluorinated C ₁ -C ₂₀ A heterohydrocarbyl group; or [4 ]]Fluorinated C ₁ -C ₂₀ Aliphatic radical, fluorinated C ₆ -C ₂₀ Aromatic radical, fluorinated C ₁ -C ₂₀ Heteroaliphatic radicals or fluorinated C ₄ -C ₂₀ A heteroaromatic group;

c)X ^F independently selected from: [1]Halide or C ₁ -C ₂₀ An organic hetero group; or [2]]Halide, C ₁ -C ₁₂ Alkoxy or C ₆ -C ₁₀ An aryloxy ether group; and

d)M ^y selected from Li, Na or K.

Aspect 110 the catalyst composition, process for polymerizing an olefin, or method of making an olefin polymerization catalyst according to any one 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, diethylethanolboron, diisobutylboorohydride, triisobutylboron, diethylboron chloride, di-3-pinanyl borane, pinacolborane, 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 an olefin, or method of making an olefin polymerization catalyst according to any one 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 independently selected from: [1]Hydrides, C ₁ -C ₂₀ Hydrocarbyl or C ₁ -C ₂₀ A heterohydrocarbyl group; or [2]]Hydrides, C ₁ -C ₂₀ Aliphatic radical, C ₆ -C ₂₀ Aromatic radical, C ₁ -C ₂₀ Heteroaliphatic radicals, or C ₄ -C ₂₀ A heteroaromatic group; and

c)X ^H independently selected from: [1]Halide or C ₁ -C ₂₀ An organic heteroaryl group; or [2]]Halide, C ₁ -C ₁₂ Alkoxy or C ₆ -C ₁₀ An aryloxide group.

Aspect 112. the catalyst composition, process of polymerizing an olefin, or method of making an olefin polymerization catalyst of any one 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, biscyclopentadienyl 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 an olefin, or method of making an olefin polymerization catalyst of any one 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 ) Wherein

X ^J Independently selected from: [1]Hydrides, C ₁ -C ₂₀ Hydrocarbyl radicals or C ₁ -C ₂₀ A heterohydrocarbyl group; or [2 ]]Hydride compound, C ₁ -C ₂₀ Aliphatic radical, C ₆ -C ₂₀ Aromatic radical, C ₁ -C ₂₀ Heteroaliphatic radicals, or C ₄ -C ₂₀ A heteroaromatic group.

Aspect 114. the catalyst composition, process for polymerizing olefins, method of making 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: methyllithium, ethyllithium, propyllithium, butyllithium (including n-butyllithium and t-butyllithium), hexyllithium, isobutyllithium, or any combination thereof.

Aspect 115. the catalyst composition, process for polymerizing olefins, or method of making an olefin polymerization catalyst according to any of aspects 1 to 3, 6 to 68, or 83 to 104, wherein the catalyst composition further comprises a catalyst selected from the group consisting of ion-exchanged clays, protonic acid-treated clays, pillared clays, aluminoxanes, borate co-activators, aluminate co-activators, ionizing ionic compounds, solid oxides treated with electron-withdrawing anions, or any combination thereof.

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

Aspect 117 the catalyst composition, process of polymerizing olefins, or method of making an olefin polymerization catalyst of aspect 116, wherein the ionically ionized 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, tetrakisphosphonium tetraphenylborate, triphenylcarbonium tetraphenylborate, triphenylphosphonium tetraphenylborate, triethylsilyltetraphenylborate, benzene (diazo) tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (N-butyl) ammonium tetrakis (pentafluorophenyl) borate, Tris (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N-dimethyl- (2,4, 6-trimethylanilinium) tetrakis (pentafluorophenyl) borate, tetrakisphosphonium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, triethylsilyltetrakis (pentafluorophenyl) borate, benzenediazonium tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (2,3,4, 6-tetrafluorophenyl) borate, triethylammoniutetrakis (2,3,4, 6-tetrafluorophenyl) borate, tripropylammoniutetrakis (2,3,4, 6-tetrafluorophenyl) borate, tri (N-butyl) ammoniutetrakis (2,3,4, 6-tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2,3,4, 6-tetrafluorophenyl) borate, N-dimethylanilinium tetrakis- (2,3,4, 6-tetrafluorophenyl) borate, N-diethylanilinium tetrakis- (2,3,4, 6-tetrafluorophenyl) borate, N-dimethyl- (2,4, 6-trimethylanilinium) tetrakis- (2,3,4, 6-tetrafluorophenyl) borate, phosphonium tetrakis- (2,3,4, 6-tetrafluorophenyl) borate, triphenylcarbenium tetrakis- (2,3,4, 6-tetrafluorophenyl) borate, triphenylphosphonium tetrakis- (2,3,4, 6-tetrafluorophenyl) borate, triethylsilyltetrakis (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 (tert-butyl) ammonium tetrakis (perfluoronaphthyl) borate, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate, N-diethylanilinium tetrakis (perfluoronaphthyl) borate, N-dimethyl- (2,4, 6-trimethylaniline) tetrakis (perfluoronaphthyl) borate, tetrakistrinium (perfluoronaphthyl) borate, triphenylcarbonium tetrakis (perfluoronaphthyl) borate, triphenylphosphonium tetrakis (perfluoronaphthyl) borate, triethylsilyltetrakis (perfluoronaphthyl) borate, Benzene (diazonium) tetrakis (perfluoronaphthyl) borate, trimethylammonium tetrakis (perfluorobiphenyl) borate, triethylammonium tetrakis (perfluorobiphenyl) borate, tripropylammonium tetrakis (perfluorobiphenyl) borate, tri (N-butyl) ammonium tetrakis (perfluorobiphenyl) borate, tri (tert-butyl) ammonium tetrakis (perfluorobiphenyl) borate, N-dimethylanilinium tetrakis (perfluorobiphenyl) borate, N-diethylanilinium tetrakis (perfluorobiphenyl) borate, N-dimethyl- (2,4, 6-trimethylanilinium) tetrakis (perfluorobiphenyl) borate, phosphonium tetrakis (perfluorobiphenyl) borate, triphenylcarbonium tetrakis (perfluorobiphenyl) borate, triphenylphosphonium tetrakis (perfluorobiphenyl) borate, triethylsilyltetrakis (perfluorobiphenyl) borate, benzene (diazonium) tetrakis (perfluorobiphenyl) borate, trimethylammoniutetrakis (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 (tert-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, phosphonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, zirconium oxide, or a mixture of any of the type, any of the group, Triphenylcarbenium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, triphenylphosphonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, triethylsilyltetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, benzene (diazo) 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 an olefin, or method of making an olefin polymerization catalyst according to any one 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, process for polymerizing olefins, or method of making an olefin polymerization catalyst of aspect 118, wherein:

a) the solid oxide comprises, 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 making an olefin polymerization catalyst of aspect 118, wherein the co-activator comprises, consists essentially of, or is selected from the group consisting of: fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, or any combination thereof.

Aspect 121. the catalyst composition, process for polymerizing olefins, or method of making an olefin polymerization catalyst according to any one 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 the carrier or diluent in any order.

Aspect 122. the catalyst composition, process of polymerizing olefins, or method of making 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 of polymerizing olefins, or method of making 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.

The catalyst composition, process of polymerizing olefins, or method of making 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 of polymerizing an olefin, or method of making an olefin polymerization catalyst according to 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 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]Is about 7X 10 ^-5 mmol metallocene compound/mg calcined montmorillonite heteroadduct, and [2]Other standard conditions described in the specification.

Aspect 126. the catalyst composition, process for polymerizing an olefin, or method of making an olefin polymerization catalyst according to any one 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 relative concentrations, expressed 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 of 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 of polymerizing olefins according to any of aspects 1-3, 6-68, or 83-127, 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 of polymerizing olefins 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: an olefin homopolymer or an olefin copolymer.

Aspect 130. the process of 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 olefin monomer residues having from 2 to about 20 carbon atoms per monomer molecule.

Aspect 131. the process of 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 of 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 of polymerizing olefins according to aspect 132, wherein the olefin comonomer is selected from aliphatic C ₃ To C ₂₀ Olefins, conjugated or non-conjugated C ₃ To C ₂₀ Dienes or any mixture thereof.

Aspect 134. the process of polymerizing olefins of 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 method of preparing an olefin polymerization catalyst according to any one of aspects 3, 6 to 68, or 83 to 126, wherein:

a) Contacting a metallocene compound and a cocatalyst [1] for a time period of 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 the

b) Contacting the first mixture with a support-activator comprising a calcined montmorillonite heteroadduct to form the catalyst composition.

Aspect 136. the method of 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 the calcined montmorillonite heteroadduct 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. a catalyst composition prepared according to any one of aspects 3, 6 to 68, 83 to 126, or 135 to 136.

Aspect 138. a process of polymerizing an olefin 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 an olefin, method for preparing an olefin polymerization catalyst, support-activator, or method for preparing a support-activator of 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 support-activator comprising an isolated smectite heteroadduct comprising the contact product of [1] colloidal smectite clay and [2] a heterocoagulating agent comprising at least one cationic multimetal salt in a liquid carrier, the heterocoagulating agent being in an amount sufficient to provide a slurry of the smectite heteroadduct having a zeta potential in the range of about positive (+)25mV (millivolts) to about negative (-)25 mV.

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

3. The support-activator of claim 1, wherein the cationic multimetal salt comprises a cationic polyaluminate selected from polyaluminum chloride, aluminum chlorohydrate, or any combination thereof.

4. The support-activator of claim 1, wherein the cationic multimetal salt comprises a cationic polyaluminate selected from the group consisting of polyaluminum chloride, aluminum chlorohydrate, or any combination thereof, and a ratio of millimoles (mmol) of aluminum (Al) to grams (g) of colloidal montmorillonite clay in the cationic polyaluminate is in a range from about 0.2mmol Al/g clay to about 2.5mmol Al/g clay.

5. The support-activator of claim 1, wherein the cationic multimetal salt comprises a first metal oxide 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 plus (+)20mV (millivolts).

6. The support-activator of claim 1, wherein the cationic multimetal salt comprises fumed silica, fumed alumina, fumed silica-alumina, fumed magnesium oxide, fumed zinc oxide, fumed titania, fumed zirconia, fumed ceria, or any combination thereof, chemically treated with polyaluminum chloride, aluminum chlorohydrate, polyaluminum hydroxychloride, or any combination thereof.

7. The support-activator of claim 1, wherein the slurry of the smectite heteroadduct is characterized by an electrical conductivity in a range of 2mS/cm to 10 μ S/cm when the concentration of the slurry is in a range of about 1 wt.% to about 10 wt.% solids, and wherein the isolated smectite heteroadduct is calcined.

8. The support-activator of claim 1, wherein the calcined montmorillonite heteroadduct exhibits a total cumulative pore volume (V) for pores with a BJH porosity from about 0.2cc/g to about 3.0cc/g and a diameter of 3-10nm _3-10nm ) Total cumulative pore volume (V) of pores less than 3-30nm _3-30nm ) 55% of the total.

9. The support-activator of claim 1, wherein the colloidal smectite clay and the heterocoagulation agent are contacted in amounts sufficient to provide a slurry of the smectite heteroadduct having a zeta potential in the range of about positive (+)20mV (millivolts) to about negative (-)20 mV.

10. The support-activator of claim 1, wherein the colloidal smectite clay and the heterocoagulation agent are contacted in amounts sufficient to provide a slurry of the smectite heteroadduct having a zeta potential in the range of about positive (+)15mV (millivolts) to about negative (-)15 mV.

11. The support-activator of claim 1, wherein the montmorillonite heteroadduct is isolated from the slurry by filtration without the use of ultrafiltration, centrifugation, or settling tanks, and wherein the isolated montmorillonite heteroadduct [1] (optionally) is washed with water and [2] dried and/or calcined.

12. The support-activator of claim 1, wherein the slurry that provides the smectite heteroadduct is characterized by the following filtration behavior:

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

(b) when evaporated, the filtrate from the heteroadduct slurry produces a solids comprising less than 20% of the initial total weight of clay and heterocoagulant.

13. A catalyst composition for olefin polymerization, the catalyst composition comprising:

a) at least one metallocene compound;

b) optionally, at least one co-catalyst; and

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

14. The catalyst composition of claim 13, wherein the at least one metallocene compound has the formula:

(X ¹ )(X ² )(X ³ )(X ⁴ ) M, wherein

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

b)X ¹ selected from the group consisting of substituted or unsubstituted cyclopentadienyl, indenyl, fluorenyl, pentadienyl, allyl, borato-ionic heteroaryl, 1, 2-azaborodienyl or 1, 2-diaza-3, 5-diboronoyl, wherein any substituent is independently selected from the group consisting of halide, C ₁ -C ₂₀ Hydrocarbyl radical, C ₁ -C ₂₀ Heterohydrocarbyl radical, C ₁ -C ₂₀ Organic hetero group, condensed C ₄ -C ₁₂ A carbocyclic moiety or a fused C having at least one heteroatom independently selected from ₄ -C ₁₁ Heterocyclic moiety: nitrogen, oxygen, sulfur or phosphorus;

c)X ² selected from: [1]Substituted or unsubstituted cyclopentadienyl, indenyl, fluorenyl, pentadienyl, or allyl, wherein any substituent is independently selected from the group consisting of halide, C ₁ -C ₂₀ Hydrocarbyl radical, C ₁ -C ₂₀ Heterohydrocarbyl or C ₁ -C ₂₀ An organic hetero group;

or [2 ]]Halides, hydrides, C ₁ -C ₂₀ Hydrocarbyl radical, C ₁ -C ₂₀ Heterohydrocarbyl radical, C ₁ -C ₂₀ Organic hetero group, condensed C ₄ -C ₁₂ A carbocyclic moiety or a fused C having at least one heteroatom independently selected from ₄ -C ₁₁ Heterocyclic moiety: 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-bridging valence, wherein any substituents are independently selected from halide, C ₁ -C ₂₀ Hydrocarbyl radical, C ₁ -C ₂₀ Heterohydrocarbyl radicals or C ₁ -C ₂₀ An organoheteryl group, and wherein any hydrocarbyl, heterohydrocarbyl or organoheteryl substituent may form a bridging atom or X ¹ Or X ² A saturated or unsaturated cyclic structure of (a);

e)[1]X ³ and X ⁴ Independently selected from the group consisting of halides, hydrides, C ₁ -C ₂₀ Hydrocarbyl radical, C ₁ -C ₂₀ Heterohydrocarbyl or C ₁ -C ₂₀ An organic hetero group; [2][GX ^A _k X ^B _4-k ]-, where G is B or Al, k is a number from 1 to 4, and X ^A Independently at each occurrence, selected from H or halide, and X ^B Independently at each occurrence is selected from C ₁ -C ₁₂ Hydrocarbyl radical, C ₁ -C ₁₂ Heterohydrocarbyl radical, C ₁ -C ₁₂ An organic hetero group; [3]X ³ And X ⁴ Together are C ₄ -C ₂₀ A polyene; or [4 ]]X ³ And X ⁴ Together with M form a substituted or unsubstituted, saturated or unsaturated C ₃ -C ₆ A metallocycle moiety, wherein any substituent on the metallocycle moiety is independently selected from halide, C ₁ -C ₂₀ Hydrocarbyl radical, C ₁ -C ₂₀ Heterohydrocarbyl radicals or C ₁ -C ₂₀ An organic hetero group.

15. The catalyst composition of claim 13, wherein X ¹ And X ² Bridging by a linker substituent selected from:

b)-BX ⁵ -、-NX ⁵ -or-PX ⁵ -; or

Wherein X ⁵ At each time of dischargeIndependently at the occurrence is selected from H, halide, C ₁ -C ₂₀ Hydrocarbyl radical, C ₁ -C ₂₀ Heterohydrocarbyl or C ₁ -C ₂₀ An organic hetero group;

16. The catalyst composition of claim 13, wherein the co-catalyst comprises an alkylating agent, a hydrogenating agent, or a silylating agent.

17. The catalyst composition of claim 13, wherein the co-catalyst comprises an organoaluminum compound, an organoboron compound, an organozinc compound, an organomagnesium compound, an organolithium compound, or any combination thereof.

18. 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 co-catalyst; and

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

19. The process for polymerizing olefins according to claim 18, wherein the at least one olefin monomer is selected from [ a ] ethylene or propylene, or [ b ] ethylene in combination 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.

20. The process for polymerizing olefins according to claim 18, wherein the process comprises polymerization in a gas phase reactor, a slurry loop, a double slurry loop in series, a plurality of slurry tanks in series, a slurry loop in combination with a gas phase reactor, a continuously stirred reactor in a batch process, or a combination thereof.

21. A method of producing a support-activator, the method comprising:

a) providing a colloidal montmorillonite clay;

b) contacting the colloidal smectite clay with a heterocoagulation agent in a liquid carrier, the heterocoagulation agent comprising at least one cationic multimetal salt in an amount sufficient to provide a slurry of a smectite heteroadduct having a zeta potential in the range of about positive (+)25mV (millivolts) to about negative (-)25 mV; and

c) Separating the smectite heteroadduct from the slurry.

22. The method for producing a support-activator of claim 21 wherein the colloidal smectite clay and the heterocoagulating agent are contacted in amounts sufficient to provide a slurry of the montmorillonite heteroadduct having a zeta potential in the range of about positive (+)20mV (millivolts) to about negative (-)20 mV.

23. A method of producing a support-activator according to claim 21, wherein the colloidal montmorillonite clay and the heterocoagulation agent are contacted in amounts sufficient to provide a slurry of montmorillonite heteroadduct having a zeta potential in the range of about positive (+)15mV (millivolts) to about negative (-)15 mV.